Water-based fluorescent ink, method of image printing, and printed image

FIELD: printing materials.

SUBSTANCE: invention relates to printing ink containing first colorant and second colorant, at least one of the colorants including fluorescent color. First and second colorants are located separately on a printing medium while printing ink ensure obtaining printed image with improved fluorescent properties. Invention further relates to printed image and a method of forming printed image utilizing such ink. Invention solves the problem of reducing fluorescence and improving fluorescent properties by way of separating fluorescence region and colored region as well as by way of formation of area on printing medium wherein points of coagulated first colorant are spread in the region of fixed second colorant so that absorption of fluorescent emission energy from fluorescent colorant is considerably reduced by coexisting colorant involving corresponding technologies. The latter are based on a novel technical conception residing in improvement of characteristics of fluorescent emission of a second colorant used in printing ink including a first fluorescent colorant, which, being excited at specified excitation wavelength, fluoresces within specified wavelength range.

EFFECT: improved fluorescent properties of printed image.

15 cl, 31 dwg, 4 tbl, 33 ex

 

The technical field

The present invention relates to inks for printing containing a first coloring agent and the second coloring substance, with at least one coloring substance comprises a fluorescent coloring matter, and a first coloring agent and the second coloring substance are in a divided state on the media, printed information, and printing ink to provide a printed image with improved fluorescence properties. The present invention also relates to a printed image and method of image formation, involving the use of such inks. More specifically, the present invention relates to appropriate technology, based on a new technical idea, which allows to solve the problem of reducing fluorescence and improve the fluorescent properties by dividing the fluorescent area and the painted area, more specifically, by education on the media of printed information, in which dots of coagulated first coloring matter dispersed in the sphere of the fixed second colorants, thereby significantly reducing the energy absorption of the fluorescent radiation from the fluorescent colorants coexisting coloring substance. Image is eenie also refers to the interrelated technologies, based on a new concept of improvement of characteristics of the fluorescent emission of the second fluorescent colorants used in the ink for printing, including the first fluorescent coloring matter, which upon excitation at a predefined wavelength of the fluorescent excitation in the wavelength range including the predetermined wavelength used for measurement or determination.

The level of technology

As colorants for water-based inks typically used coloring substances, soluble in water, resulting in most of the inks exhibit excellent manifestation of color and satisfactory resistance to coagulation or Association of coloring substances, and acceptable reliability, for example, in relation to resistance to clogging and stability in time. On the other hand, the ink is poor in durability of the printed image, such as the resistance. Relative fluorescence properties, in particular good solubility of the coloring substance satisfactory fluorescence, but cannot increase the intensity due to concentration quenching (the phenomenon of decrease of fluorescence in the case where the content of the coloring substances exceeds some is the ROI size). For example, in U.S. patent No. 6176908 (patent reference 1) proposed ink using a polymeric dispersant, a pigment and a fluorescent dye.

However, in the above sentence, when a drop of ink is applied on the carrier printed information, a polymeric dispersant, a pigment and a fluorescent dye deposited in the solid coagulated condition (figure 2) throughout the system, resulting in image density in the image is increased, and the property of the manifestations of colors, including fluorescent radiation, not improved as much as expected, due to the aforementioned phenomenon of concentration quenching.

This drawback could be overcome by limiting the increase in PMU (indicator characterizing the intensity of fluorescence), described in the above-mentioned proposal, by adjusting the area of the fingerprint measured to determine the intensity of fluorescence, but it would be difficult to do during normal operation.

Meanwhile, to improve the water resistance, it is proposed to use the dye having a carboxyl group as a water-soluble group. This proposal is based on the usage characteristics of the dissociation of carboxylic acid, forming water-soluble group, and when the media printed information is pH cher the sludge towards the acidic solution, the solubility of the coloring matter in the water decreases, and the dye coagulates, increasing the resistance.

However, in this proposal, the resistance increases due to coagulation or Association colorants due to the low solubility of the coloring matter in the water, resulting in the problem, namely, that deteriorate the properties of the degree of color development coloring matter. In particular, due to coagulation or Association colorants difficult to enhance the fluorescent radiation.

In addition, in order to avoid the above-mentioned concentration quenching (the phenomenon of decrease of fluorescence in the case where the content of the coloring substance exceeds a certain value) and increase the density of the image in a print, for example, in the publication WO 02/092707 (patent reference 2) method combined application of several coloring substances so that the wavelength range of the fluorescent radiation colorants as little as possible overlap the wavelength range of absorption of coexisting colorants to enhance the fluorescent radiation of the printed image.

Such proposals may contribute to the increase in fluorescence intensity and density of the printed image to some the second degree, but this is not enough. In addition, the durability of the printed image according to the publication WO 02/092707 (patent reference 2) is still unsatisfactory, resulting in the need of significant improvement of the water resistance and light fastness.

In recent years, to improve the stability of the printed image, such as water resistance and light fastness, the proposed water-based ink, which use a combination of water-dispersible colored substances, such as carbon black or organic pigment, and painted resin comprising a water-soluble coloring matter. For example, in Japanese laid out application No. 8-239610 (patent reference 3) discloses water-based ink containing the water-dispersible coloring substance dispersed in the system water-based due to the impact of resins and emulsions of water-soluble colorants, emulsified with the emulsifier or resin to improve the properties of the degree of color development. In addition, in the publication WO 02/092707 (patent reference 2) the proposed use of the pigment, including fluorescent coloring matter.

When such inks are printed on the media information, water or a liquid medium evaporates from the media printed information or penetrates and diffuses into him, causing coagulation dispergirovannogo substances, resulting in better durability of the printed image, for example, the water resistance or light resistance. At the same time, water-soluble coloring matter, which is introduced into the resin, etc. itself will not be easy to coagulate or associate, providing, thereby, a satisfactory property manifestations of color, in particular, the fluorescent radiation. However, since the ink contains a large amount of resin, emulsifier, etc., the viscosity of the ink tends to increase, and the use of such coloring substances in larger quantities tends to deteriorate the fixing-drying the printed image.

In addition, these inks suffer from the lack of resistance to freezing and tend to demonstrate solidification of the pigment component, when they are left on for a long time in the environment of normal temperature. For example, when such ink is used in the head for ink-jet printing, creates a tendency to decomposition stable dispersion colorants due to evaporation of water or liquid ink in the vicinity of the nozzle head, which causes the coagulation of the coloring substances, which can cause hardening of the ink or clogging of the nozzle. In addition, when the ejection of ink droplets under the action of thermal energy applied is th ink, dispersed coloring matter in the printhead inkjet tends to deposition on the heater, so that the reliability of the head in relation to the property release ink drops significantly.

Thus, the aforementioned suggestions might help improve water resistance and light fastness water-soluble dye in the print, but may impair the property of the fixing-drying the printed image and its resistance to freezing, when the print density of the image increases. In addition, when such inks are used in the process of inkjet printing may occur nozzle clogging or failure of the ejection of ink.

In recent years there has arisen a demand for various applications of ink. In such applications, in addition to forming a beautiful color images, it is proposed, for example, to use fluorescent ink to provide information (such as protected information), in addition to visual information, by printing information such as letters, numbers, symbols or bar codes, such ink printed on the media information and irradiation with ultraviolet light of the appropriate wavelength to generate a colored fluorescence of the fluorescent ink. Specifically, in the system for reading information authentication is being used is then intended for the fight against counterfeiting) or protected information using a device for fluorescence excitation and readout of the intensity of the radiation, fluorescent coloring agent excite stimulating light of a predetermined wavelength (for example, 254 nm) for the occurrence of fluorescence, and determine or measure the fluorescence.

As for the coloring substances in the ink, the dye can easily provide a predetermined color, but often have poor water resistance, and pigments can impart excellent water resistance, but are sometimes unable to provide a predetermined color tone. In view of the foregoing, the proposed ink containing a dye and a pigment, to obtain an ink capable of providing an image excellent in water resistance and color tone. For example, in the examined Japanese patent publication S60-45669 (patent reference 4) discloses a liquid for printing containing the water-soluble red dye (for example, Acid Red 52) and red pigment as a means for printing, and a polymeric dispersant for dispersing the pigment in a liquid medium.

In the postal systems of the United States distributed printing fluorescent red dye, and as a fluorescent dye using such a dye, Acid Red 52 (AR52), which is described in the aforementioned publication. In U.S. patent No. 6176908 (patent reference 1) discloses an ink containing fluore the interest dye, the pigment and the polymer as a dispersant for pigment, as an example of a fluorescent dye described AR52. It should be noted that the color shading correction final color in accordance with the visual perception of a person by a combination of dyes was well known design technique long before the filing of U.S. patent No. 6176908.

In U.S. patent No. 6176908, as in Japanese patent publication JP-S60-V (patent reference 4), the proposed ink for ink-jet printing containing pigment in addition to the fluorescent dye to improve the water resistance of the ink, and also described the addition of fluorescent dyes two species known to correct the visible color (visual color correction), and also described additives to give the system high fluorescence intensity (high level PMU). Specific examples of the ink with increased fluorescence intensity (high level PMU) include solvents such as water, 2-pyrrolidone, and tetraethylene glycol, and the following fluorescent colorants, non-component-based pigment comprising pigment, polymer and tetraethyleneglycol or diethylene glycol. As fluorescent coloring substances are described, for example, the combination of AR52 (0.4 wt.%, the range from 0.5 wt.%, to 3.0 wt.%) and one of these dyes, it is to AY7, AY73 and DY96, as well as the combination of basic violet dye (RHDB) and basic yellow dye (BY40).

In JP H11-80632A (patent reference 5) discloses invisible fluorescent water-based ink containing three different fluorescent coloring matter (fluorescent bishopshostel, yellow fluorescent dye, a derivative of coumarin, and a red fluorescent dye (rhodamine b or rhodamine-6G), and also print postcards using these inks. In the description of this document indicates that each of these three fluorescent coloring substances emits light under the action of irradiation with ultraviolet light for excitation of the other colorants, consistently leading to the resulting fluorescent emission having a peak at wavelength component of 587 nm. However, in this publication, there is no specific description of excitation wavelengths, and the description is given using the result that the ink and the printed image show the same characteristics of fluorescence. Basically, the water absorbs ultraviolet light, so that the fluorescence of the printed image is different from the fluorescence of ink used. Thus, the invention described in the publication, technically implausible. the publication WO 02/092707 (patent reference 2) discloses ink, forming a dark image, and also showing the fluorescence of a predetermined color when exposed to excitation radiation. These inks contain many dyes (for example, red and yellow fluorescent dye, blue dye and black dye), as the ink in the patent reference 5, but differ from ink patent reference 3 the fact that the dyes are selected so that the absorption band at longer wavelengths and the emission band at shorter wavelengths do not overlap. In this publication the relationship between fluorescent coloring substances have not been analysed sufficiently, so that it is not always possible to obtain the desired intensity of the fluorescence. In JP 2003-113331A (patent reference 6) discloses an invention aimed at improving the fluorescence characteristics of the ink in terms of the ratio between the solvents and fluorescent coloring substances. In other words, in patent reference 6, are disclosed ink for printing, which include two fluorescent colorants of the same color (see the example in which add not fluorescent coloring matter), two different organic solvent (for example, glycerol and non-ionic surfactant), which have no compatibility with each on the natives and clean water for dissolving these components.

Patent reference 1: U.S. patent No. 6176908;

Patent reference 2: WO 02/092707;

Patent reference 3: not held the examination of Japanese patent publication No. 8-239610;

Patent reference 4: passed examination Japanese patent publication No. 60-45669;

Patent reference 5: not held the examination of Japanese patent publication No. 11-80632;

Patent reference 6: not held the examination of Japanese patent publication No. 2003-113331.

As explained above, it is still not proposed water-based ink, which can provide excellent water resistance, the density of the printed image and, in particular, the degree of color development properties, including fluorescence with high reliability. The present invention is to develop an ink that gives the opportunity to solve the above problem.

In particular, the present invention proposed the ink is less influenced by the characteristics of the absorption colorants used in the ink that allows you to clarify "the problem of loss of fluorescence in accordance with the characteristics of the absorption coloring matter used in conjunction with them (i.e. light absorption because of the color of colorants), which is one of the main factors that suppress fluorescence) shall increase, by analyzing the fixed state of the ink printed on the media information based on a new technical concept, as a result it was possible to provide the printed image with a satisfactory fluorescent radiation and methods of forming such images.

Summary of the invention

The above-mentioned problems can be solved by the present invention in the following variants of its implementation.

More specifically, the present invention proposed a separate fluorescent water-based ink that enables the formation of the first region in the Central part, where the first coloring substance, including a second coloring matter, and the formation of the second region along the periphery of the first region including the inside of the carrier printed information, where there is only a second coloring substance, distinct fluorescent water-based ink containing a first coloring substance, the second coloring substance, and the liquid medium and water for dissolving or dispersing these coloring substances, with at least one of the first colorants and the second coloring substance is a fluorescent coloring matter.

The present invention also is radlogin the printed image, which contains a first region formed in the Central part, where first the dye with the second coloring substance, and a second area formed on the entire periphery of the first region including the inside of the carrier printed information, where there is only a second coloring substance, with at least one of the first coloring substance and the second coloring substance is a fluorescent coloring matter.

The present invention also proposed a separate fluorescent water-based ink containing a first coloring substance, the second coloring substance, and the liquid medium and water for dissolving or dispersing these coloring substances, with at least one of the first coloring substance and the second coloring substance is a fluorescent coloring matter, and the aforementioned ink provide education on the media printed information fixed field containing many scattered bystrorezhuschej spots of the first coloring matter in the coagulated state in the region where the fixed second coloring substance.

The present invention also suggested that the printed image formed on the medium of printed information, which is contains a plot of the fixed colorants, in which there are many bystrorezhuschej spots of coagulated first colorants, scattered on a fixed part of the second coloring substance, with at least one of the first coloring substance and the second coloring substance is a fluorescent coloring matter.

In the present invention is also a method of forming a printed image, comprising the stage of formation on the media printed information image with many pixels by applying a separate fluorescent water-based inks, which provide the opportunity of education printed on the media information of the first area in which first concentrated the dye with the second coloring substance, and a second area in which there is only a second coloring material and which surrounds the entire periphery of the first area, including the area in the printed media of information with at least one of the first coloring substance and the second coloring substance is a fluorescent coloring matter, and a separate fluorescent water-based ink is applied so that the first region of each pixel is not in contact with each other.

In the present invention is also a method of forming on the printed image, including the stage of applying a separate fluorescent water-based inks on printed media information to form the image, and these inks provide education on the media printed information of the first area in which first concentrated the dye with the second coloring substance, and a second area in which there is only a second coloring material and which surrounds the entire periphery of the first area, including the area in the medium of printed information, the image has a different resolution in the longitudinal direction and the transverse direction.

In the present invention is also a method of forming a printed image, comprising the stage of formation on the media printed information image with many pixels by applying a separate fluorescent water-based inks, ensuring education on the printed media point information containing the first fixed region within the second fixed region, and the first fixed region contains many scattered bystrorezhuschej spots of coagulated first colorants, fixed it, and the second fixed region includes a second coloring substance, fixed it, at the same time, man is our least one of the first coloring substance and the second coloring substance is a fluorescent coloring matter, and the first coloring material is a water-dispersible coloring agent, and point form so that the first region of each pixel is not in contact with each other, and the vertical resolution is different from the horizontal resolution.

In addition, in the present invention proposed a separate fluorescent water-based ink containing a first coloring matter having a free carboxyl group as the main water-soluble group, the second coloring substance with a free sulfonylurea group as the main water-soluble group, a surfactant, providing the opportunity to hold the second coloring substance in larger amounts as compared with the first coloring agent.

Such separate fluorescent water-based ink preferably include a water-soluble kristallenen a substance which is solid in the environment of normal temperature.

Brief description of drawings

Figure 1 - schematic view illustrating the structure of the dots formed on the medium of printed information with ordinary ink.

Figure 2 - schematic diagram, illustrated is yuusha structure point, formed on the printed media information with ordinary ink, including several coloring substances.

Figure 3 - schematic diagram illustrating the structure of the dots formed on the medium of printed information ink according to the present invention.

4 is a schematic diagram of the structure of the dots formed on the medium of printed information ink according to the present invention.

5 is a schematic diagram illustrating the arrangement of ink dots in the image formed by the ink according to the present invention.

6 is a schematic diagram illustrating the arrangement of ink dots in the image formed by the ink according to the present invention.

7 is a diagram illustrating the formation of an Assembly in the ink according to the present invention.

Fig diagram illustrating the formation of a coagulated mass of the water-dispersible coloring matter.

Fig.9 is a diagram illustrating a state in which the Assembly water-dispersible colouring substance according to the present invention deposited on the carrier printed information.

Figure 10 is a chart illustrating the state of education coagulated mass of the water-dispersible coloring substances when combined, woodysproduce the CSOs colorants and water-soluble coloring matter.

11 is a chart illustrating the state of the ink in which the dye dispersible forms an Assembly with crystals as nuclei in the presence of water-soluble coloring substances with a solubility that is higher than the solubility of the water-dispersible coloring material, the solvent ink.

Fig is a schematic diagram illustrating the state of the ink in which the dye dispersible forms an Assembly with crystals as nuclei in the presence of water-soluble coloring substances with a solubility that is higher than the solubility of the water-dispersible coloring material, the solvent ink.

Fig diagram illustrating the condition of education Assembly of water-soluble colorants according to the present invention when combined, dispersed colorants and water-soluble coloring matter.

Fig illustrates the spectrum of the fluorescent radiation C.I. Acid Red 52 when the wavelength of the excitation component 254 nm.

Fig illustrates the excitation spectrum C.I. Acid Red 52 for the fluorescent radiation at a wavelength component 600 nm.

Fig illustrates the spectrum of the fluorescent radiation of the water-soluble fluorescent coloring matter And n and the wavelength of excitation, component 254 nm.

Fig illustrates the comparison of the spectrum of the excitation C.I. Acid Red 52 for the fluorescent radiation at a wavelength component 600 nm, and the spectrum of the fluorescent radiation of water-soluble colorants And when the wavelength of the excitation component 254 nm.

Fig illustrates the comparison of the spectrum of the excitation C.I. Acid Red 52 for fluorescent emission at 600 nm and the absorption spectrum of water-soluble colorants A.

Fig illustrates the comparison of the spectrum of the fluorescent radiation of water-soluble colorants And at 254 nm and the absorption spectrum of C.I. Acid Red 52.

Fig illustrates the spectrum of the fluorescent radiation of the mixed ink of C.I. Acid Red 52 and a water-soluble colorants A.

Fig illustrates the fluorescence spectrum imprint formed by the ink containing C.I. Acid Red 52 and a water-soluble coloring matter A.

Fig illustrates the spectra of the excitation C.I. Acid Red 52 at 580, 600 and 620 nm.

Fig illustrates the spectrum of the fluorescent radiation C.I. Acid Yellow 73 when the wavelength of the excitation component 254 nm.

Fig illustrates the comparison of the spectrum of the excitation C.I. Acid Red 52 for the fluorescent radiation at a wavelength component 600 nm, and the spectrum of the fluorescent radiation C.I. Acid Yellow 73 with wavelength excitation component 254 nm.

Fig the illustration is any comparison of the spectrum of the excitation C.I. Acid Red 52 for the fluorescent radiation at a wavelength component 600 nm, and the absorption spectrum of C.I. Acid Yellow 73.

Fig illustrates a comparison of the absorption spectrum of C.I. Acid Red 52 and the spectrum of the fluorescent radiation C.I. Acid Yellow 73 at 254 nm.

Fig is a diagram schematically illustrating the situation added dropwise vododispersionnaya coloring substances in the solution of surface-active substances in a vessel such as a Petri dish: directly after the add (left) and after some time (right).

Fig is a diagram schematically illustrating the situation added dropwise vododispersionnaya coloring substances in the solution of surface-active substances in a vessel such as a Petri dish: directly after the add (left) and after some time (right).

Fig is a diagram schematically illustrating the situation added dropwise vododispersionnaya coloring substances in the solution of surface-active substances in a vessel such as a Petri dish: directly after the add (left) and after some time (right).

Fig is a diagram schematically illustrating the situation of adding dropwise water-dispersible colouring substance in a container such as a Petri dish containing a solution of surface-active substances, etc is this shows the state immediately after the add (left) and the status after some time (right).

Fig illustrates the difference in contrast between the ink of example 12 and comparative example 3.

The best option of carrying out the invention

In the following text provides a more detailed explanation of the present invention in preferred embodiments of its implementation.

First of all, explains the mechanism by which the individual water-based inks according to the present invention increases the resistance, in particular resistance, the manifestation of colors, including fluorescent radiation, and the image quality including image density in the printed image. Comprehension explain in the following text mechanism achieved by the analysis of various phenomena on the basis of experimental data and after numerous trial and error, but the following still does not cover all aspects, because the present invention provides a complex interaction.

The authors of the present invention have conducted studies and confirmed that the proposed ink have satisfactory reliability and safety and allow for increased image resistance, in particular resistance, and can also improve the properties of the manifestations of colors, including fluorescent radiation and the density of the image. As a result, the authors found that h is on a separate fluorescent water-based ink, enables the formation of the first region, in which first the dye is concentrated with the second coloring substance in the Central part, and education second area in which there is only a second coloring substance on the periphery of the first region including the inside of the carrier printed information, can increase the resistance, in particular resistance and print quality, as well as property manifestations of colors, including fluorescent radiation and the density of the image. Thus was established the present invention.

First, a comparison with the known ink. Figure 1 shows the model. Figure 1 represents a point formed by the ink drop, where the solid black area represents the area in which the dye is fixed. Top view figure 1 is a schematic top view point, i.e. the region in which the dye is fixed, formed by a drop of ink on the media, printed information, and which is viewed from above. Figure 1 also shows a schematic cross section of a point.

To increase the density of the printed image, you can use the method of increasing the content of coloring matter in a solid black area, or way to deter penetration of ink in the printed media inform the tion. In this situation, when the dye in solid black round area has satisfactory resistance to water, the dye in this area aggregates and associated decreasing solubility in water, which leads to satisfactory water resistance. However, in this case, the dye is fixed on the printed media information in the associated, coagulated or assembled condition. Such associate, coagulated or mixed condition worsens the degree of color development property inherent coloring substance, resulting ink indicates a poor property of the degree of color development on the media printed information.

On the other hand, when using, for example, several coloring substances, one can increase the resistance, one can increase the density of the image, and one can improve the color, so that they are recorded in a mixed state on the media, printed information, as shown in figure 2. For example, when using the dye, which provides the possibility of increasing the water resistance, the resistance may increase, but the colorants are recorded in a mixed state, and colorants tend to take the form of a coagulated associated or assembled state, so that it is difficult to improve the properties is about the degree of color development. When the ability of the ink to penetrate into the media printed information is reduced to increase the density of the image, several coloring substances are recorded on the media printed information in the same mixed state, as described above, so that the degree of color development property deteriorates. In particular, in the case of fluorescent colorants for fluorescent radiation, colorants from coagulated associated or assembled condition significantly reduce fluorescent radiation.

In figure 2 the black diamonds show the first the dye and the white diamonds display the second coloring substance. Figure 2 top view is a schematic top view of the point formed by the drop of ink on the media printed information and consider the top and the bottom view is a schematic cross-section point, illustrating the inside of the carrier printed information.

On the other hand, figure 3 presents a schematic illustration of a dot formed by a separate water-based inks according to the present invention. Figure 3 solid black area denotes the region where the fixed, at least the first coloring matter, and the white area indicates the region where the marks only the second coloring substance. Figure 3 top the th schematic view to illustrate the point, formed by a drop of ink on the media printed information and discussed above. In addition, the cross-section figure 3 is a schematic illustration of the point, showing the inside of the carrier printed information.

In accordance with a preferred embodiment of the present invention, a separate water-based ink containing the liquid medium is water-based (usually water and water-soluble organic solvent), the first coloring agent and the second coloring substance before settling on the medium of printed information, but immediately after deposition of a separate water-based inks printed on the media information, a liquid medium ink droplets evaporates and penetrates or diffuses into the medium of printed information, resulting in fixation of the coloring substances.

When colorants separate water-based inks according to the present invention are recorded on the media printed information, forming the image, first the dye forms an image at the position at which the ink drop is deposited or slightly diffuses from the initial position, while the second the dye forms an image, diffundere on and in the printed media information. Thus, a separate water-based ink according to the present which the invention form the printed image, as shown in figure 3, through the first and second coloring substances, diffusion properties of which and in the printed media information differ from each other. In this image formation is first the dye comes in coagulated associated or mixed state, thereby increasing the resistance, for example, water resistance and light fastness. In addition, when the media printed information is generated combined image, the dye is fixed in a concentrated manner, thereby to obtain the density of the image with a striking force, or images of high density.

On the other hand, the second the dye forms an image area, clearly surrounding the first coloring agent. Second, the dye has a lower tendency to coagulate, Association or picking up on and in the printed media information than the first coloring matter and recorded media printing information in almost monomolecular state in comparison with the first coloring substance, which is considered to improve the properties of the degree of color development. In addition, there is a tendency, according to which the more diffusion of the second coloring substance in the medium of printed information, the better the characteristics of the image is to be placed.

In addition, the first coloring substance separate water-based inks is preferably water-dispersible coloring agent, and the second coloring substance is a water-soluble coloring matter.

When first the dye is a water-dispersible colouring substance, easily obtained satisfactory property coagulation, which can increase the local density of the image, and the density of the printed image. It can also increase the resistance.

When the second coloring substance is a water-soluble coloring matter, it is water-soluble, the dye diffuses to and in the printed media information together with water, which is the main component of the ink. It can be foreseen that this state of fixation of the coloring matter on the media printed information in almost monomolecular state with improved properties manifestations color.

In addition, because the fixed image (e.g. point) drops of ink deposited on the medium of the printed information includes a first region formed coagulated coloring matter, mainly in the Central part, and a second area formed diffundiruyushchim coloring substance, fixed in the her the periphery of the first region, including the inside of the carrier printed information, there is a density gradient, decreasing from the center to the peripheral zone. Therefore, when the image formed by dots, these dots are less visible, and granular appearance of the resulting image is smoothed, thereby simplifying the formation of excellent images.

In addition, the inventors have found that when certain water-based ink is fluorescent ink, the fluorescent property of radiation becomes excellent, in particular, in the case where the fluorescent radiation in the region formed by the second coloring substance, is stronger than in the field, educated, mainly, the first coloring agent. The inventors also found that a high image density and a satisfactory fluorescent radiation can be achieved by applying a water-dispersible colouring substance as the first coloring matter and water-soluble coloring substances as a second colorants. When the fluorescent coloring matter is the second coloring substance, it diffuses in the medium of printed information, causing a small Association or coagulation fluorescent coloring matter, as a result ensure the satisfactory W fluorescent radiation. On the other hand, first the dye may increase the density of the image, as mentioned above. As a result, can be obtained printed image with high density and a satisfactory property of the fluorescent radiation around the printed image. You can also get satisfactory resistance due to the property of coagulation of the first coloring matter.

The inventors also found that when an image is formed from a set of points using a separate water-based inks in such a way that each region, where first the dye in the presence of the second coloring substance, is not in contact with another area (see figure 4), this leads to the formation of the second areas, where there is only a second coloring substance, resulting in quite a satisfactory printed image. In figure 4, each of the solid black areas is an area where the first coloring substance, and each of the white areas is a region where only the second coloring substance. Top view figure 4 is a schematic top view of two points, consisting of fixed coloring substances, each of which is formed to the play of ink, deposited on the carrier surface of printed information, and is viewed from above. Figure 4 also shows the cross-section, schematically illustrating the point, consisting of a fixed coloring substances in the medium of printed information. The symbol "a" in figure 4 denotes the distance between the areas where concentrated, mainly, the first coloring agent.

In addition, the inventors found that when the printed image on the printed media information generated by a separate water-based inks according to the present invention so that the resolution in the vertical direction is different from the resolution in the horizontal direction, is guaranteed a place for the diffusion of the second coloring substance, which further enhances the effect of some water-based inks according to the present invention.

In the present description, the phrase "for the application of multiple drops of ink on the media printed information in such a way that each region, where first the dye in the presence of the second coloring substance, is not in contact with another area"means, for example, as shown in figure 5 that the ink is applied in such a way that between two points there are areas where ink is deposited. Figure 5 presents schematizes the th surface for printing media printed information, each of the black circles represents a zone in which a drop of ink deposited, and white circles represent the area in which ink droplets are not deposited.

When a separate water-based ink according to the present invention is used in the implementation of the method of printing as shown in figure 5, the resulting printed image is as shown in Fig.6, facilitating the formation of regions where only the second coloring substance. As a result, the effect of the present invention is fully represented. Figure 6 black circle indicates the area where concentrated, first the dye, and the peripheral zone is the area in which is recorded, mainly the second coloring substance.

When the image is formed as described above, to obtain the image shown in Fig.6, a method of forming images according to the principle of "point to point" is not preferred. When forming images on the principle of "point to point", the first region, where mainly the first coloring substance, and the second region where only the second coloring substance, undergoing an unwanted imposition.

The authors of the present invention have found that the effect of the present invention monomolecular to demonstrate through a separate water-based inks, containing water-dispersible coloring substance, a water-soluble coloring agent, surfactant and water, and surfactant enables retention (dissolved) water-soluble coloring substances in large quantities, but almost does not hold water-dispersible coloring material. 7 schematically illustrates the case in which the use of such surface-active substance.

7 black dots show the area where the fixed first the dye and the white portions indicate the area where fixed second coloring substance.

Top view figure 7 is a schematic view of the points discussed above, the dot consists of areas in which the coloring matter and which are formed by the deposition of ink droplets on the surface of the print medium printed information. Figure 7 also shows the cross-section, schematically illustrating the point, consisting of a fixed coloring substances in the medium of printed information.

When the ink contains a surfactant, which can hold or dissolving a water-soluble coloring matter in a large number in comparison with the water-dispersible coloring agent, surface Natai which the ink is reduced, and the wettability of the carrier printed information increases, resulting in easier penetration and diffusion of the ink in the printed media information. When ink is applied to the printed media information, surface-active substance is distributed in printed media information in the vicinity of the surface of the carrier printed information, where the deposited ink drop, and diffuses with the simultaneous adsorption. If the surfactant is such that it may hold or dissolving a water-soluble coloring matter, but ill withhold or dissolves the water-dispersible coloring matter, water-soluble, the dye diffuses into the medium of printed information together with surface-active agent and water, the main component of the ink, forming a wide area, where the fixed second coloring substance. In other words, water-soluble, the dye diffuses and penetrates together with the solvent of the ink and the surface-active substance in the medium of printed information. In this state, the separation of the coloring substances takes place on and in the carrier of printed information, resulting in fixation of the ink is as shown in Fig.7.

On the other hand, surface-active substance is still present in OCD the particular zone, where the deposited ink drop due to adsorption or the like, so that the water-dispersible coloring substance is less diffusible in comparison with the water-soluble coloring matter, and the inherent water-dispersible substance tendency to agglomeration is enhanced. In this state, the water-dispersible coloring material is not coagulates instantly, and coagulates in the diffusion process, forming a distribution of units in the whole area where concentrated water-dispersible colouring substance, i.e. in the area, "tainted" by agglomerates of water-dispersible coloring material. In other words, first the dye forms an Assembly of many agglomerates in the field of media printed information, as shown in Fig.7, and this area corresponds to the first region, where the water-dispersible coloring agent.

When using such a surfactant, the area occupied by the first coloring agent and per unit area of the first region is reduced, so that the area occupied by the second coloring substance in the first area, where first the dye increases, thereby improving the property of the manifestations of colors at the same time maintaining the apparent density of the image. In particular, the GDS second coloring substance has the property of fluorescence, fluorescent emission increases (see Fig.7). In this state, the first region of the image, where the first coloring matter, including the second coloring substance, contains areas where fixed mainly first the dye, and areas where the fixed mainly second coloring substance, that is, the first coloring agent and the second coloring substance creates a region in a mutually separated state. Thus, it becomes possible to obtain a satisfactory density of the printed image and satisfactory properties, the degree of color development, such as the property of fluorescence, when the first coloring material is a coloring substance, providing the ability to increase image density, and the second coloring substance is a substance that provides the possibility of improving the properties of the degree of color development, in particular, the fluorescent coloring matter. Due to the characteristics of the coagulation of the first coloring substances can also get satisfactory water resistance.

In this case, first the dye forms numerous small coagulation, as shown in Fig.7, but such coagulation recognized as one by visual observation, because these coagulation too small to the eye of a person who could recognize them, so the density of the printed image with such bystrorezhuschej conurbations is comparable with the density of the image at which such agglomeration are not formed. In addition, when the image formed by dots, these dots are less visible, so that it is possible to obtain images of high density. In addition, if the content of the surfactant in the ink support is equal to or above the critical concentration of micelles, diffusion of ink on and in the printed media information increases, as a result, the effect of the present invention.

In a preferred embodiment, the difference between the dynamic surface tension and the static surface tension of the applied surfactant is small. This means increased speed orientation of the surfactant to the surface section, which accelerates the diffusion of liquid ink and media, printed information, and in the case of water-dispersible colouring substance in this invention, such surface-active substance is instantly absorbed and focused on the water-dispersible coloring agent in the state bystrorezhuschej agglomerations, while bystrorezhuschej agglomeration water-dispersible coloring substances are distributed on the carrier pecat the second information, additionally enhancing the effect of the present invention.

The preferred combination of surfactants and water-dispersible coloring substances can be determined, for example, in the following way: when a solution of the desired water-dispersible coloring substances, such as aqueous dispersion at a concentration of 15 wt.% (for example, about 0.1 g), dropwise served from a syringe into a solution of the selected surfactants, if water-dispersible colouring substance floating in the coagulated state on the surface of the solution of surface-active substances, and when he is left standing for long periods of time or at 60°C, coagulated coloring substance will not dissolve, turning into the solution of surface-active substances, and will settle at the bottom of the solution, this combination is preferred.

Fig-30 illustrate such testing conceptual. Each drawing schematically illustrates the state immediately after the drip feed (left) and the status after some time (right)when the water-dispersible coloring material is fed dropwise into a solution of surfactant in a Petri dish or similar container.

On Fig shown specifically preferred is a combination where water dispersible abrasivos the e substance is separated in a floating state on the surface of the solution of surface-active substance immediately after the drip feed and separated in the besieged state at the bottom after a certain amount of time. On Fig shows the following preferred combination, in which the water-dispersible coloring substance separated in the besieged state at the bottom of a solution of surfactant immediately after the drip feed and separated also in the besieged state at the bottom after some time.

On the other hand, Fig and 30 shows an undesirable combination. On Fig shown that water-dispersible colouring substance is separated in the besieged state at the bottom of a solution of surfactant immediately after the drip feed, but diffuses into the solution entirely after some time, forming a dissolved state. On Fig shown that water-dispersible colouring substance is separated in a floating state on the surface of the solution of surface-active substance immediately after the drip feed, but diffuses into the solution entirely after some time, moving in a dissolved state.

In the present invention the choice of nonionic surfactants as the above-mentioned surfactants can minimize problems when taking into account various properties of the ink and the applied coloring substances. This is because the polarity can facilitate the formation of salts with various anionic and cationogenic the mi components, contained in the ink, resulting in achieving preferred status orientation to the surface of the section and, therefore, satisfactory coagulation water dispersible colorants can be difficult.

In addition to the above-mentioned surfactant, a separate water-based ink according to the present invention preferably include a water-soluble kristallenen substance (kristalloobrazuyushchikh component), which is solid in the environment of normal temperature. The ink according to this preferred variant implementation represent a stable mixture of water-dispersible colorants, water-soluble colorants, liquid environment (environment water-based, surface-active substances performing the above function, and water-soluble kristalloobrazuyushchikh component. When such inks allow to settle, the water in the ink decreases due to evaporation, and water-soluble kristalloobrazuyushchikh component reaches the saturation concentration in the ink and begins to precipitate. At the same time, water-dispersible colouring substance concentration reaches saturation, and the state of dispersion becomes unstable, easily causing coagulation.

Due to the simultaneous development of the two is akih States, namely, the deposition of crystals in the ink and unstable dispersion of water-dispersible coloring substances, leading to coagulation, formed the Assembly dispersed aggregates water-dispersible colouring substance in which the water-dispersible coloring matter collected around precipitated crystals in the ink as around the nuclei (Fig). The presence of the Assembly dispersed coloring substances, including crystals as nuclei in the ink, inhibits the formation of the grid (figure 9) water-dispersible coloring substances, which will occur in the ink, which uses ordinary water-dispersible coloring agent.

In addition, since the concentration of surfactant that performs the above function, increases water-dispersible colouring substance manifests the property of enhanced coagulation, facilitating the formation of dispersed bystrorezhuschej agglomerates water-dispersible coloring material. Agglomerates dispersed coloring substances, including crystals as cores do not provide easy formation of the grid, not leading, thus, to intense cold, as if there are only dispersed colorants, and not increasing, thereby, the resistance to freezing and clogging.

Next, p is since such Assembly includes a water-soluble core, even in the case of clogging, for example, in the vicinity of a nozzle head for ink-jet printing, the recovery operation, such as injection pressure by suction, can easily solve the problem of clogged condition by influences from inside and outside the Assembly water dispersible colorants having such a crystal as a nucleus present in the vicinity of the nozzle and forming such a blockage.

In addition, the ink deposited on the medium of printed information, lose water due to evaporation and infiltration, resulting in the Assembly of the water-dispersible coloring matter formed around the nucleus of the crystalline component, manifested in part of the surface of the carrier printed information, at the same time water-dispersible colouring substance carries out intensive chemical and physical interaction with cellulose fibers, etc. that make up the media printed information that provides satisfactory resistance, such as resistance (figure 10).

In addition, although the ink coexist water-dispersible coloring material and a water-soluble coloring matter, the printed image is improved in respect of the degree of color development properties and resistance to freezing. This mechanism is discussed below. In the case of conventional h is rnil, in which coexist water-dispersible coloring material and a water-soluble coloring matter, although the ink deposited on the medium of printed information, lose water and fixed on the carrier, a water-soluble coloring matter is introduced into the coagulation mesh water-dispersible colouring substance, and it is water-soluble coloring matter coagulates with the water-dispersible coloring agent and is captured in coagulation grid, becoming unable to develop a satisfactory property of the degree of color development (11). On the other hand, in accordance with the present invention, water-dispersible colouring substance is not coagulates locally due to the above-described functions of surfactants, and coagulates in the diffusion process, forming a state in which bystrorezhuschej agglomerates water-dispersible coloring matter, whether or not containing crystalline core formed from kristalloobrazuyushchikh component are dispersed without forming large local coagulation of the water-dispersible coloring material. As a result, the net water-dispersible colouring substance is not formed, and a water-soluble coloring substance is present in a part of the solvent in addition to the agglomerates in the ink, and this moderator is my the dye can exhibit a satisfactory property manifestations color (Fig).

The mechanism for improving the properties of anti freezing is discussed below. Assembly water-dispersible coloring matter formed around the crystal nuclei can be present in a satisfactory dispergirovannom condition due to buffer interaction between units. Furthermore, since the solvent of the ink is a water-soluble coloring matter, better soluble than water-dispersible colouring substance is acceptable collecting water dispersible colorants around the crystal nuclei due to the difference in solubility of these two coloring substances in the ink (Fig).

The use of fluorescent colorants as a water-soluble coloring substances effectively, in particular, by increasing the intensity of fluorescence images. It is believed that the fluorescent coloring substance is present in a monomolecular state and is seamless to the coagulation of the water-dispersible coloring matter, as explained above, with a water-soluble coloring matter, demonstrating thereby a high fluorescence intensity. In this case, the content of the fluorescent coloring matter must be smaller than the content, which causes concentration quenching n is the carrier of printed information. For example, this content is defined as less than the content of the fluorescent coloring matter, which causes concentration quenching in water-based inks, i.e. the composition of water-based inks, of which the evaporated water. The term "concentration quenching" refers to the phenomenon of decrease in fluorescence intensity with increasing content of the fluorescent coloring matter in the ink.

As described above, the ink according to the present invention contain as their constituents, at least, the environment water-based, water-dispersible coloring material and kristalloobrazuyushchikh component. In addition, to give the preferred effect ink may contain an organic solvent, providing the possibility of dissolution kristalloobrazuyushchikh component.

The ink according to the invention comprising such an organic solvent, facilitate not only the formation of assemblies around crystals as nuclei, but education is not associated agglomerates in the ink, resulting in effectively developing Assembly water-dispersible coloring material. Preferred as such an organic solvent is, in particular, the solvent is very volatile at ordinary temperature, for example glycerol or triethyleneglycol, if such an organic solvent can dissolve the water-soluble coloring matter, it is additionally improved properties manifestations of colors, including fluorescence in the printed image. This is due to the ability to guarantee satisfactory dissolved state of the water-soluble coloring substances using such an organic solvent.

In addition, the ratio of organic solvent and kristalloobrazuyushchikh component it should be noted that specifically preferred is the ratio at which the content kristalloobrazuyushchikh component in the ink is equal to or more than the saturation concentration with respect to the content of organic solvent in the ink. This is necessary to facilitate educational Assembly water-dispersible colouring substance, having a core crystal kristalloobrazuyushchikh component. Therefore, the preferred mechanism according to the present invention is, in particular, the situation when the concentration of saturation kristalloobrazuyushchikh component in an organic solvent does not exceed the saturation concentration in water.

In addition, the effect of the present invention can also be demonstrated when the content kristalloobrazuyushchikh component in the ink is equal to or less concentrate the radio saturation in water, used in the ink, and is equal to or greater than the saturation concentration in the organic solvent used in the ink. The reason is that kristalloobrazuyushchikh component satisfactorily dissolved in the ink, but quickly crystallizes when evaporate volatile components present in the ink.

On the other hand, the authors of the present invention found that it is possible to increase the density and durability of the printed image, as well as to improve the degree of color development property and image quality, by using separate water-based inks containing the dye, having a free carboxyl group as the main water-soluble group, the dye having free sulfonylurea group as the main water-soluble group, a surfactant that is able to contain the dye having free sulfonylurea group more than the dye having a free carboxyl group, and water.

In particular, referring to figure 3, it can be noted that if the first coloring material is a coloring matter having a free carboxyl group as the main water-soluble group, and the second coloring material is a coloring matter having free is ing sulfonylurea group as the main water-soluble group, the printed image is satisfactory density, durability and the degree of color development property, and in the case of forming the printed image point, the point becomes less and less distinct, so it printed the image of satisfactory quality. The carboxyl group is less hydrophilic, so that the dye having a carboxyl group, coagulates lighter than the dye having sulfonylurea group. In addition, in the case of surface-active substances which may contain the dye having free sulfonylurea group as the main water-soluble group, more than the dye having a free carboxyl group as the main water-soluble group, it becomes possible to increase the density and durability of the printed image due to the colorants having free sulfonylurea group as the main water-soluble group, and obtaining satisfactory properties manifestations color and image quality at the expense of colorants having a free carboxyl group as the main water-soluble group. In addition, these effects can be further enhanced by the introduction of the aforementioned kristallogr the ith component.

Below is an explanation of the components of the ink according to the present invention can provide excellent effects via the above mechanisms.

It is important that the first coloring agent and the second coloring substance, the fundamental components of the present invention, were in such a combination, so that they can be separated from each other on the printed media information. For their separation on the media printed information can be applied, for example, a method using the difference in solubility of the coloring substances with a pH of media surface of the printing information, the method of introduction into the ink component, providing the possibility of reducing the solubility of one of the coloring substances so that when ink is applied to the printed media information, and the water content decreases, this component acts on the dye, reducing its solubility, or method of introduction into the ink volatile component, providing an opportunity to increase the solubility of one of the coloring substances and decrease the solubility of the coloring matter, when ink is precipitated on the carrier printed information and the volatile component evaporates. In these cases, first the dye preferably has a lower solubility in/var shall giramonti, than the second coloring substance.

As coloring substances used in the ink, it is preferable to use water-dispersible coloring material and a water-soluble coloring matter.

The term "water-dispersible coloring agent" means the dye, which is hardly soluble or not dispersed in water alone, but is dispersed in water by chemical or physical effect of the compound having a water-soluble group, such as a surfactant or a polymer, or means the dye formed from the dye substances, not dispersible in water by chemical binding of the hydrophilic group, such as sulfonylurea or carboxyl group by oxidation or surface treatment colorants low-molecular compound having a hydrophilic group.

Water-dispersible colouring substance may be an inorganic pigment, for example, carbon black, furnace carbon black, lamp black, acetylene black or channel gas soot, specific examples include commercially available products such as Raven 700, Raven 5750, Raven 5250, Raven 5000 ULTRA, Raven 3500, Raven 2000, Raven 1500, Raven 1250, Raven 1200, Raven 1190 ULTRA-II, Raven 1170, Raven 1255 (product Colombian Chemicals Co.); Black Pearls L, Regal 400R, Regal 330R, Regal 660R, Mogul L, Monarch 700, Monarch 800, Monrch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, and Valcan XC-72R (the above products are manufactured by Cabot Corp.); Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Printex 140V, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 (the above products are manufactured by Degussa Corp.); № 25, № 33, № 40, № 47, № 52, № 900, № 2300, MCF-88, MA600, MA7, MA8 and MA (the above products are manufactured by Mitsubishi Chemical Co.); you can also use any of the new resulting product. These products can be used separately or in combination, consisting of products of two or more types.

Specific examples of the organic pigment include insoluble azo pigment, such as toluidine red, toluidine chestnut, Hansa yellow, benzidine yellow and pyrazolinones red; soluble azo-pigment, such as lithology red, Helio Bordeaux, pigment scarlet and invariably red 2B; derivatives of VAT dyes, as alizarin, indanthren and thioindigo chestnut; phtalocyanine pigment, such as phtalocyanine blue and phtalocyanine green; genocidally pigment, such as genocidally red or genocidally purple; perylenebis pigment, such as perylenebis red or perylenebis scarlet; isoindoline pigment, such as isoindoline yellow or isoindoline Oran is the song data; imidazolinones pigment, such as benzimidazolone yellow, benzimidazolone orange or benzimidazolone red; philanthropy pigment, such as philanthropy red or philanthropy orange; thioindigo pigment; condensed azo pigment; diketopiperazines pigment; and other pigments such as plantronic yellow, acylamide red, chieftancy yellow, Nickel azo yellow, copper azomethine yellow, purinovy orange, astronomy orange, ventriculography red and dioxazine purple. These pigments can be used singly or in combination of two or more types.

Examples of the organic pigment, denoted by numbers color index (C.I.)include C.I. Pigment Yellow (pigment yellow) under the numbers 12, 13, 14, 17, 20, 24, 55, 74, 83, 86, 93, 97, 98, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185; C.I. Pigment Orange (pigment orange) the 16, 36, 43, 51, 55, 59, 61, 71; C.I. Pigment Red (pigment red) under the numbers 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 175, 176, 177, 180, 192, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, 254, 255, 272; C.I. Pigment Violet (pigment violet) under the numbers 19, 23, 29, 30, 37, 40, 50; C.I. Pigment Blue (pigment blue) under the numbers 15, 15:1, 15:3, 15:4, 15:6, 22, 60, 64; C.I. Pigment Green (pigment green No. 7, 36; C.I. Pigment Brown (brown pigments) 23, 25, 26, etc) what are the different ways dispersion, for example, other pigments such as C.I. Pigment Yellow 13, 17, 55, 74, 93, 97, 98, 110, 128, 139, 147, 150, 151, 154, 155, 180, 185; C.I. Pigment Red 122, 202, 209; C.I. Pigment Blue 15:3, 15:4, etc. posted In Japanese patent application No. S46-52950, U.S. patent No. 5200164 and 5554739 lined Japanese patent application No. N8-3498 and U.S. patent No. 5571311 disclosed is a method of binding a hydrophilic groups with surface coloring substances through a group, page, ensuring, thus, the dispersion in water as samodopomoga pigment; a method of surface oxidation colorants hypochlorous acid and so on, with the formation of the hydrophilic group and the guarantee of a dispersion in water; how the introduction of coloring matter in the surface-active agent or polymer, thereby ensuring dispersion in water in the form of an emulsion or capsules; and posted in Japanese patent applications No. N-179183, N-136311, N-053841, N10-87768, H11-043639, H11-236502 and H11-269418 disclosed a method of dispersion in water using physical adsorption of a dispersant such as a surfactant or polymer on the surface of the coloring substances that are not dispersible in water.

The dispersant may be, for example: resin, such as statistical or block copolymer of polymerized styrene and acrylic acid or a copolymer of styrene and maleic acid; nonionic or Aminogen the fired surface-active substance, ensure the dispersed state in water using micellar or emulsion state; or a block copolymer, a statistical copolymer, graft copolymer or its salt, at least two monomers selected from styrene, a derivative of styrene, vinylnaphthalene, derived vinylnaphthalene, complex ester of aliphatic alcohol and α,β-Ethylenediamine carboxylic acid, acrylic acid, a derivative of acrylic acid, maleic acid, a derivative of maleic acid, the basis of itaconic acid, derived on basis of itaconic acid, fumaric acid, derived fumaric acid, vinyl acetate, vinylpyrrolidone, acrylamide and their derivatives (in this case, at least one of the two monomers is hydrophilic). Among these substances are specifically preferred for implementing the present invention is a block copolymer. Water-dispersible coloring matter obtained using the block copolymer is homogeneous and facilitates obtaining a stable ink.

The block copolymer has a structure represented by the links AB, VAV, ABC, etc. In particular, when implementing the present invention, it is preferable block copolymer having a hydrophobic block and a hydrophilic block sizes that are appropriate about the time balanced to contribute to the stability of the dispersion. In the hydrophobic block, which is associated with the pigment, it is also possible to introduce some functional group, resulting in enhanced special interaction between the dispersant and the pigment to improve the stability of dispersion. In addition, the mass-average molecular weight of the polymer is preferably less than 30000, preferably less than 20000 and more preferably is in the range of 2000-10000.

Ways to obtain such a polymer is described in Japanese laid bids No. N-179183, N-136311, N-053841, N10-87768, H11-043639, H11-236502 and H11-269418.

Below are examples of typical hydrophobic monomer used in the block copolymer, but such examples are not restrictive: benzoylacrylate, bezelmaterial, methyl methacrylate (MMA), ethyl methacrylate (EMA), propylbetaine, n-butylmethacrylate (BMA or NBMA), hexyllithium, 2-ethylhexylacrylate (ENMA), octylacrylate, laurenmarie (LMA), sterilisability, fenilsalicilat, hydroxyethylmethacrylate (DUMB), hydroxypropylmethacrylate, 2-ethoxyethylacetate, Methacrylonitrile, 2-trimethylsilylmethyl, glycidylmethacrylate (GMA), n-trimethacrylate, sorelmetal, methyl acrylate, acrylate, propylacetate, butyl acrylate hexylaniline, 2-ethyl hexyl acrylate, octylacrylate, laurelcrest, stearylamine, pinelake is at, 2-fenilatilmalonamid, hydroxyethylacrylate, hydroxypropylmethacrylate, Acrylonitrile, 2-trimethylsilylmethylamine, glycidylmethacrylate, p-tolylacetate and corelacelal. Preferred hydrophobic monomers are benzoylacrylate, bezelmaterial, 2-fenilatilmalonamid, methyl methacrylate, butylmethacrylate or 2-ethylhexylacrylate; also, it is preferable to obtain a block copolymer using homopolymer or derived from a copolymer such as a copolymer of methyl methacrylate and butyl methacrylate.

In addition to the above, the following are typical examples of hydrophilic monomers used in the block copolymer, but such examples are not restrictive: methacrylic acid (MMA), acrylic acid, dimethylaminoethylmethacrylate (DMAEMA), diethylaminoethylmethacrylate, tert-butylmethacrylate, dimethylaminoethylacrylate, diethylaminoethylamine, dimethylaminoethylmethacrylate, methacrylamide, acrylamide and dimethylacrylamide. It is preferable to obtain a block copolymer using homopolymer or derived from a copolymer of methacrylic acid, acrylic acid or dimethylaminoethylmethacrylate.

Acid polymer can be obtained either directly or from the blocked monomer having a blocking group that is removed after which olymerization. Examples of blocked monomer, allowing to obtain acrylic acid or methacrylic acid after removal of the blocking groups include trimethylsilylmethyl (TMS-MAA), trimethylsilyltriflate, 1-biotoxicological, 1-ethoxyethylacetate, 1-butoxyethanol, 1-ethoxyethylacetate, 2-tetrahydropyranyloxy and 2-tetrahydropyranyloxy.

The content of the pigment as the dispersible colorants in the ink is not specifically limited. However, the separation of the first colorants and second colorants printed on the media information is important for the present invention, when the content of the coloring substances too large, water-dispersible coloring substance will be recorded on the media printed information in a coagulated state, undesirable for the present invention. Therefore, the content of water-dispersible coloring matter in the ink is preferably less than 10 wt.%, more preferably less than 4 wt.% and even more preferably less than 2.5 wt.% for commonly used media of printed information, although this parameter may vary depending on the media type of printed information, for example, from the type of adhesive and quantity in which it is added to the composition of the media. The lower limit of the content so the second pigment can be determined in accordance with the desired density of the image.

It should also be noted that in the case when the dispersion of water-dispersible colouring substance added to a dispersant, a resin as a dispersant or surface-active dispersant, for example, by physical adsorption, it is possible to use one such resin dispersant or surface-active dispersant, or a combination of such dispersant two or more kinds, and the amount of the dispersant is preferably 0.5 to 10 wt.% from the total ink weight, more preferably 0.8 to 8 wt.% and even more preferably 1-6 wt.%. If the content of the dispersant exceeds such a range, it will be difficult to maintain the desired viscosity of the ink.

In addition, when the content of water-dispersible coloring matter in the ink is too large, will remain free coloring substance, which will not gather around the crystal nucleus, thereby weakening the effect of the present invention. You can use one water-dispersible colouring substance or combination of such substances two or more types.

The term "water-soluble coloring agent" means the dye having a water-soluble group such as a sulfonic group, a free carboxyl group, or a group of phosphoric acid, Hydra is xylina group or amino group, can stably be present in the water without the influence of the auxiliary component such as a surfactant or resin. As compounds having the property of fluorescence or fluorescent colorants used as a component of the ink according to the present invention, it is possible to use various compounds or coloring substances that emit light when excited. For example, you can use the connection that is excited by ultraviolet light and emits light in the ultraviolet, visible or infrared wavelength range, or compound that is excited by visible light and emits light in the visible or infrared wavelength range, or a compound which is excited by infrared light and emits light in the visible or infrared wavelength range. Specifically preferred are compounds having the following groups of atoms or basic structure.

(Chemical formula)

Specific examples include a compound with the structure of Xanten, such as Acid Red 52, Acid Red 92, Acid Red 289 or Acid Yellow 73; derived pyranine, such as Solvent Green 7; coumarin derivative such as Acid Yellow 184; derived oxazole, proizvoditeli, a derivative of imidazole, derived imidazolone, pyrazolone derivative, a benzidine derivative, diaminodiphenylsulfone acid; and dyes with the structures shown in the following table, and their water-soluble derivatives. Water-soluble fluorescent dye can exhibit the effect of the present invention are most strongly.

pink
Table
DyeStructureColor in daylightFluorescent color
Diamond sulfophenyl FF (C.I. 56205)yellowfrom green to yellow-green
Basic yellow HG (C.I. 460400yellowfrom green-yellow to yellow
Eosin (C.I. 45380)redfrom yellow to orange
Rhodamine 6G (C.I. 45160)redfrom yellow to orange
Rhodamine B (C.I. 45170)from orange to red
PigmentStructure
Lumogen L

yellow
Lumogen L

diamond yellow
Lumogen L

yellow-orange
Lumogen L

red-orange

As compounds having the property of fluorescence, it is also possible to use conventional fluorescent whitening agent. In particular, the following water-soluble fluorescent coloring matter (which may be referred to below as the "fluorescent compound (A)or a fluorescent substance (s)") is one of the specifically satisfactory fluorescent coloring matter.

Water-soluble fluorescent coloring matter And

(chemical formula)

The content of the fluorescent dye in the ink is preferably 0.01 to 30 wt.% from the total mass cher the sludge, more preferably 0.05 to 20 wt.%. In addition, if for printed content (printed image) requires the property of fluorescence, it is preferable that the content was not determined concentration quenching (the phenomenon of decrease in fluorescence intensity when the contents of the ink exceeds a certain limit) when performing printing by ink deposition according to the present invention on the media printed information. If the most important is the strengthening properties of fluorescence, specifically preferred is a content not exceeding 3 wt.%, but, depending on the media printed information or properties of the fluorescent coloring matter, the content is not limited to this value.

In addition, the substance having the above basic structure for fluorescent radiation in the numerous links within this structure, for example, the dye having the structure of the dimer or trimer through a connecting group, exhibits an excellent effect in terms of properties of the fluorescent radiation, in particular, due to resistance to concentration quenching.

When the purpose of the present invention is the achievement of the fluorescent characteristics of the present invention is preferred also respect what their conditions, taking into account the following points.

Now, explanation will be given "numerous fluorescent dyes" for the purposes of this invention. The term "multiple fluorescent dyes", explain in the following text refers to technology that can significantly increase the intensity of the fluorescence of the first dye substance in a predefined control the wavelength range of fluorescence (e.g., 580-629 nm by excitation at a reference wavelength of excitation, interconnected with other fluorescent coloring matter (hereinafter referred to as the second coloring material).

For example, the authors of the present invention investigated the phenomenon that, although the above-mentioned fluorescent dye AR52 provides radiation with a satisfactory red fluorescence even in the ink containing water, which absorbs ultraviolet light, the printed image with this dye shows weak fluorescence when excited by ultraviolet light. This study found that the wavelength of the excitation AR52 with fluorescent red radiation is distributed not only in the ultraviolet region, but also in the field of visible light, and the fluorescence intensity affects the fixed state is of the dye in the medium of printed information. Therefore, there was conducted a technical analysis, which allowed to determine how to provide as much of the exciting light and how to make a fixed state of the dye in the printed image suitable for fluorescent radiation.

In addition, when using AR52 as the first coloring substance satisfactory fluorescence intensity obtained by the evaporation of water from the ink containing AR52 in an amount of 0.01 wt.% or less. However, there are additional circumstances that should be included in the review: this loss colorants that are not preserved in the surface fibers in the media of printed information, such as a sheet of paper or envelope, and the problem of concentration quenching, namely, that the intensity of the fluorescence colorants decreases with increase in the content of the first and second coloring substances in the ink. It should also be noted that the energy source is limited to a predefined excitation light. Other tests will become apparent from the following description.

Therefore, the present invention solves at least one of the following tasks (preferably a combination of these tasks) to enhance the intensity of fluorescence compared to the usual technical standard.

The first purpose of this is th invention consists in the fact, to develop inks for printing, providing the possibility of increasing the intensity of their fluorescence at a standard wavelength of excitation so that their energy efficiency is increased by focusing on the correlation between the fluorescence emission of the second coloring substance, which is made light, and the wavelength of excitation of the first coloring substances for obtaining a predetermined wavelength (hereinafter referred to as a predefined wavelength fluorescence for a single wavelength or wavelength interval).

The second objective of the present invention is to develop an ink for printing, providing the possibility of increasing the intensity of their fluorescence at a predefined wavelength of the radiation in such a way that their energy efficiency is greatly increased, by focusing on the absorption spectrum of the first dye substance and the fluorescent radiation of the second coloring substance, which is deposited by the light having the predetermined wavelength excitation.

The third objective of the present invention is to develop an ink for printing, providing the possibility of increasing intense is vnesti their fluorescence at a predefined wavelength, by focusing on information obtained through analysis of the structural differences between fluorescent dyes (i.e., the amount of added fluorescent dyes can be increased by judicious prevent the formation of assemblies fluorescent dyes).

In addition to the third objective, the fourth objective of the present invention is to develop an ink for printing, providing the possibility of increasing the intensity of their fluorescence at a predefined wavelength, by focusing on the presence of the fluorescent radiation of the second coloring substance, which is deposited by the light having the predetermined wavelength of the excitation, and the characteristics of the wavelength of excitation required for obtaining a predetermined wavelength of the fluorescent radiation of the first coloring matter.

The fifth objective of the present invention is to develop an ink for printing, providing a more stable increase in the intensity of their fluorescence at a predefined wavelength due to the characteristics of ink, which contain multiple fluorescent coloring matter.

The sixth objective of the present from which retene is to develop inks for printing, providing the possibility of increasing the intensity of their fluorescence at a predefined wavelength radiation without significant dependence on the type or characteristics of the media printed information on which to form an image, and the aforementioned increase is achieved thanks to the information obtained by analyzing the generated image.

In addition to the first goal, the seventh objective of the present invention is to develop an ink for printing, providing the possibility of increasing the intensity of their fluorescence at a predefined wavelength, by focusing on the correlation between the characteristics of the excitation of the first coloring matter and the absorption spectrum of the second coloring substance. Other goals and objectives of the present invention will become apparent from the following description.

To achieve the above objectives the present invention offers the following options for implementation. The ratio between the wavelengths in the invention can be briefly described as follows: the wavelength range of the fluorescent radiation (see Fig described below) of the second fluorescent coloring matter comprises at least the wavelength range of PI is a (see Fig described below) of the spectrum of wavelengths of excitation of the first fluorescent coloring matter to obtain the fluorescence at a predefined wavelength radiation (e.g., 600 nm) and, optionally, the wavelength range of absorption in the visible light of the first fluorescent coloring matter (see lower graph Fig described below).

First of all, in accordance with the first embodiment of the present invention, to achieve at least the first objective of the proposed ink for printing, which contain

the first fluorescent coloring substance that is fluorescent in a predefined wavelength of radiation used for measurement or determination upon excitation at a predefined wavelength excitation, and

the second fluorescent coloring matter, which is fluorescent when excited at a given predefined wavelength excitation,

moreover, the excitation spectrum of the first coloring matter in the ink to obtain the fluorescence at a predefined wavelength radiation has a wavelength range peak following this pre-determined wavelength fluorescence, and the fluorescence spectrum of the radiation of the second coloring substance is the area of the lengths of AlN radiation, essentially, comprising at least the wavelength range of the peak.

Here, the phrase "the wavelength range of the peak, which corresponds to the area of the peak that follows this pre-determined wavelength of fluorescence of the fluorescent emission from the first fluorescent coloring matter according to the present invention has practical implications when considering the efficiency of energy conversion of this radiation. In other words, in the spectrum of the excitation wavelengths for obtaining a predetermined wavelength of fluorescence of the first fluorescent coloring matter, an area that has a peak following this pre-determined wavelength fluorescence, and in which the intensity is 100 or more, is defined as the region of the peak, and the wavelength range corresponding to this area is defined as the wavelength range of the peak.

Predefined wavelength excitation is preferably 254 nm, and the wavelength range of the peak is preferably from 430 nm to 600 nm, including both extreme values. In a preferred embodiment, the wavelength range of the emission of the second fluorescent coloring matter includes a predefined wavelength (600 nm) fluorescence and extends from 425 nm to 600 nm, including about who and extreme values. In addition, in the ink corresponding to the first variant implementation of the present invention, it is preferable that the absorption spectrum of the first fluorescent coloring matter was the region of the peak in the visible light and the wavelength range of the fluorescent emission of the second fluorescent coloring matter encompassed the region of shorter wavelengths than the above region of the peak of the absorption spectrum.

In accordance with the second embodiment of the present invention, for achieving at least the second objective, the proposed ink for printing, containing the first fluorescent coloring substance that is fluorescent in a predefined wavelength fluorescence used to measure or determine when excitation light of a predefined wavelength of excitation, and the second fluorescent coloring matter, which fluorescent due to the excitation at a given predefined wavelength excitation, the wavelength of emission of the second fluorescent coloring matter includes at least a main wavelength region of absorption in the spectrum of the light absorption of the first fluorescent coloring matter in the field of excitation wavelengths to produce radiation when specified the seat reservation at the specific wavelength of fluorescence of the first fluorescent coloring matter in the ink.

In the ink corresponding to the second variant of implementation of the present invention, it is preferable that the main wavelength region of absorption of the first fluorescent coloring matter was in the range of from 500 nm to 590 nm, including both extreme values, and the main region of the wavelength of the second fluorescent coloring matter was in the range of from 450 nm to 600 nm, including both extreme values.

In addition, in the ink corresponding to each of the first and second embodiments of the present invention, it is preferable that the second fluorescent coloring matter was the dye having a structure with many fluorescent groups.

In accordance with a third embodiment of the present invention, for achieving at least the third objective of the proposed ink for printing, containing the first fluorescent coloring substance that is fluorescent in a predefined wavelength fluorescence, used for measuring or determining upon excitation at a predefined wavelength of excitation, and the second fluorescent coloring matter, which is fluorescent when excited at a given predefined wavelength excitation and increases the intensity of halogen with exceptiona the radiation at a given predefined wavelength fluorescence, and the second fluorescent coloring matter has many fluorescent groups.

In the ink corresponding to the third variant of implementation of the present invention, it is preferable that the wavelength of emission of the second fluorescent coloring matter has been in the area of excitation wavelengths to obtain the specified predefined wavelength fluorescence of the first fluorescent coloring matter in the ink.

In accordance with the fourth embodiment of the present invention, for achieving at least the fourth objective of the proposed ink for printing, containing the first fluorescent coloring substance that is fluorescent in a predefined wavelength fluorescence, used for measuring or determining upon excitation at a predefined wavelength of excitation, and the second fluorescent coloring matter, which is fluorescent when excited at a given predefined wavelength excitation, and the second fluorescent substance has many fluorescent groups, and the wavelength of emission of the second fluorescent coloring matter overlaps at least part of the region of wavelengths of radiation to obtain radiation in the criminal code which marks a predefined wavelength of fluorescence of the first fluorescent coloring matter in the ink.

In the ink corresponding to each of the third and fourth embodiments of the present invention, it is preferable that each of the multiple fluorescent groups in the second fluorescent coloring matter had the basic structure to give the brightness of its fluorescence. In addition, the second fluorescent coloring substance preferably has a lot of sulfonic groups.

In the ink corresponding to any of the embodiments of the present invention with first through fourth, many fluorescent groups in the second fluorescent coloring matter is preferably presented in the form of dimers. Incidentally, in embodiments implementing the present invention with the first to the fourth, the second fluorescent coloring matter is preferably a direct dye.

In addition, the ink for printing corresponding to each of the third and fourth embodiments of the present invention, preferably are water-based inks for printing which fluoresce when excited at a specified predefined wavelength excitation, and water-based ink are in a state of evaporation of water and/or condition of the printed image, and the emission spectrum has a first peak, including tentative is but a specific wavelength of fluorescence, and the second peak in the wavelength corresponding to the wavelength of the excitation of the first fluorescent coloring matter, to produce radiation at a specified predefined wavelength fluorescence ink.

In accordance with the fifth embodiment of the present invention, for achieving at least the fifth goal of the proposed water-based ink for printing, containing the first fluorescent coloring substance that is fluorescent in a predefined wavelength fluorescence, used for measuring or determining upon excitation at a predefined wavelength of excitation, and the second fluorescent coloring matter, which is fluorescent when excited at a given predefined wavelength excitation, and water-based ink are in a state of evaporation of water and/or condition of the printed image, and the emission spectrum has a first peak, including the predetermined wavelength fluorescence, and the second peak in the wavelength corresponding to the wavelength of the excitation of the first fluorescent coloring matter, to produce radiation at a given pre-defined wave fluorescence ink. In the ink corresponding to the item is the fact a variant implementation of the present invention, the second fluorescent coloring substance may preferably have a structure with many fluorescent groups.

In accordance with the sixth embodiment of the present invention, for achieving at least the sixth goal of the proposed ink for printing, containing the first fluorescent dye that is fluorescent in a predefined wavelength fluorescence, used for measuring or determining upon excitation at a predefined wavelength excitation, the second fluorescent dye for the emitted fluorescence when excited at a given predefined wavelength excitation and increase the intensity of radiation at a given predefined wavelength fluorescence, and a solvent including a first solvent that exhibits a relatively high solubility with respect to the first fluorescent dye and low the solubility with respect to the second fluorescent dye, and a second solvent that exhibits high solubility with respect to the second fluorescent dye, and compatible with the first solvent.

In the ink corresponding to the sixth variant embodiment of the invention, each of the first fluorescent dye and vtoro what about the fluorescent dye preferably may have a sulfonic group. In addition, it is preferable that the wavelength of emission of the second fluorescent dye is essentially covered the wavelength range peak following this pre-determined wavelength fluorescence excitation spectrum of the first fluorescent dye for fluorescence at a predefined wavelength fluorescence ink. In addition, the ink corresponding to the sixth variant of implementation of the present invention, the wavelength of emission of the second fluorescent dye may preferably be in the region of wavelengths of excitation of the first fluorescent dye for fluorescence at a predefined wavelength fluorescence, except for the area corresponding to the main region of wavelengths of absorption in the spectrum of the light absorption of the first fluorescent dye.

On the other hand, the ink for printing corresponding to the sixth variant of implementation of the present invention, preferably, can be a water-based inks, and the emission spectrum of these inks that fluoresce under the influence of a predefined wavelength excitation, when the water-based ink are in a state of evaporation of the water content and/or condition of the printed image is Oia, shows the first peak, which causes the radiation at a given predefined wavelength fluorescence, and the second peak in the region of excitation wavelengths to produce radiation at a predetermined wavelength of fluorescence of the first fluorescent coloring matter in the ink.

In accordance with the seventh embodiment of the present invention, for achieving at least the seventh goal of the proposed ink for printing, containing the first fluorescent coloring substance that is fluorescent in a predefined wavelength fluorescence, used for measuring or determining upon excitation at a predefined wavelength of excitation, and the second fluorescent coloring matter, which is fluorescent when excited at a given predefined wavelength excitation, the wavelength of emission of the second fluorescent coloring matter includes at least the wavelength range of the peak corresponding to the area of the peak that follows a predefined length wave fluorescence in the wavelength range of the excitation of the first fluorescent coloring matter for this predefined wavelength fluorescence, and the main range of the lean wave absorption in the spectrum of the light absorption of the second fluorescent coloring matter is in the range of shorter wavelengths, than the wavelength range of the excitation of the first fluorescent coloring matter. In the ink corresponding to the seventh variant of implementation of the present invention, preferably, a predefined wavelength of excitation was 254 nm, the wavelength range of the peak of the first fluorescent coloring matter ranged from 430 nm to 600 nm, including both extreme values, and the wavelength region of absorption of the second fluorescent coloring matter was 440 nm or less.

In the ink corresponding to any of the embodiments from the first to the fifth and seventh variant of implementation of the present invention, more preferably, the ink for printing contained the first solvent exhibiting a relatively high solubility with respect to the first fluorescent dye and low solubility with respect to the second fluorescent dye, the second solvent having a high solubility with respect to the second fluorescent dye, and compatible with the first solvent and the third solvent, it does not show compatibility with the second solvent and the second solvent fluorescent dye. This condition for solvents can further increase the fluorescence intensity of different fluorescent dye is of exist according to the present invention.

When one of the above printing inks used for inkjet printing, is obtained printed image excellent in fluorescence intensity. Method of inkjet printing according to the present invention, allowing to obtain such advantage is the way, including the stage at which the ejection of ink through the discharge hole and the application of ink to the medium of printed information, in doing so, the seal ink are some of the ink for printing corresponding to the above options for implementation.

Ink for printing according to the present invention contain multiple fluorescent coloring substances, and the first fluorescent coloring matter provides emission of light, the wavelength range which includes the predetermined wavelength used for measurement or assessment upon excitation at a predefined wavelength of excitation, and the second fluorescent coloring fluorescent substance due to excitation at this predefined wavelength excitation, and the ratio between the first and second fluorescent substances are as defined in the above inventions.

As will be described below, ink for printing, the relevant extract is he to the invention, when the best combination of dyes provide the possibility of increasing the level PMU printed image (measured using measuring light model LM-2C, as described in U.S. patent No. 6176908), at least half compared with conventional fluorescent ink (and three times, when the solvent is selected according to aspect 3, described below).

In the following text ink for printing according to the present invention will be described with reference to the drawings. Regardless of whether on the printed image or printed content, the results will be shown for the case after evaporation of the ink in which water is removed by evaporation, and colorants dispersed in an organic solvent. Ink for printing corresponding to each of embodiments of the present invention contain a first fluorescent coloring substance that is fluorescent in a predefined wavelength, which is used for measuring or determining upon excitation at a predefined wavelength excitation, the second fluorescent coloring matter, which is fluorescent when excited at the same wavelength excitation, and a liquid medium for dissolution or dispersion therein of these substances.

The first and the WTO the second fluorescent coloring matter according to the present invention may be pigments or dyes to the extent that how satisfied the configuration of each version of the implementation. Dyes are preferred to achieve high speed diffusion and increased intensity of fluorescence on the media printed information.

Specific examples of dyes include: C.I. Basic Red (basic red) under the numbers 1, 2, 9, 12, 13, 14 and 17; C.I. Basic Violet (basic violet) under the numbers 1, 3, 7, 10, 11:1 and 14; C.I. Acid Yellow (acid yellow) under No. 73, 184 and 250; C.I. Acid Red acid red) under the numbers 51, 52, 92 and 94; C.I.Direct Yellow (direct yellow) under the numbers 11, 24, 26, 87, 100 and 147; C.I.Direct Orange (direct orange) numbers 26, 29, 29:1 and 46; and C.I. Direct Red (direct red) under the numbers 1, 13, 17, 239, 240, 242 and 254.

The total number of the respective first and second fluorescent coloring substances in the ink is preferably in the range from 0.01 wt.% or more to 15 wt.% or less, more preferably in the range of from 0.05 wt.% or more to 10 wt.% or less of the total amount of ink in the practical use. In accordance with coloring substances, when the total number of coloring substances in the ink does not exceed 0.01 wt.%, it is impossible to obtain the fluorescence intensity sufficient to printed content. When the ink is the ink for ink-jet printing, on the characteristics of the release can be affected when the total is number of the above substances is 15 wt.% or more. From a practical point of view, it is preferable that the number of the first fluorescent coloring matter selected in the range from 0.01 to 1 wt.%, and the number of the second fluorescent coloring matter may preferably be higher than the number of the first fluorescent coloring matter in the ink to improve the efficiency of excitation energy.

Some of the dyes in the above list are known as having less fluorescence at concentrations exceeding some certain concentration, and have an area of concentration that corresponds to high-intensity fluorescence. In this case, it is preferable to use a dye in an area of concentration.

To increase the intensity of the fluorescence, it is preferable that the first and second fluorescent colorants meet at least one of the following aspects of 1-3. The combination of the first and second fluorescent coloring substances can be selected from coloring substances described above and which is the coloring substances relevant to this aspect.

In the present invention the most preferred example of the combination of the fluorescent dye compound is a combination of C.I. Acid Red 52 as the first fluorescent coloring washes the VA and compounds (A), described below as the second fluorescent coloring matter. In the following description, but without limiting it, a predefined wavelength of radiation used for measurement or determination, is 600 nm, although these purposes you can use some band or any wavelength in the range from 580 nm to 620 nm, including both extreme values.

As shown in Fig when AR52, the first fluorescent coloring matter, is excited at 254 nm, the fluorescence spectrum shows a broad area of fluorescence from 550 nm to about 675 nm with a peak at 600 nm. In other words, AR52 fluorescent not only when a predefined wavelength radiation component 600 nm, but in the range from 580 nm to 620 nm, including both extreme values. On the other hand, the absorption band of AR52 in the field of visible light ranges from 460 nm to 610 nm with a peak at 565 nm, as shown in the bottom graph Fig.

The compound (A) has a dimeric structure with numerous radiating groups. Thus, the compound (A) has the function of preventing the Association; in addition, you can increase the intensity of the fluorescence by increasing the number of connections (A). The compound (A) is a direct dye having a sulfonic group and having poor solubility in water (less than 2 wt.% in pure water), at the same BP is me showing good solubility in organic solvents. As shown in Fig, fluorescence spectrum of the compound (A) upon excitation at 254 nm shows a broad area of the fluorescent radiation, extending from 425 nm to about 650 nm with a peak at 510 nm. Therefore, the more compounds (A) add, the higher is the intensity of its fluorescence, so that the energy of excitation of the first fluorescent coloring matter is increased. In addition, as shown in the bottom graph Fig, the absorption in the visible region of the compound (A) is up to 440 nm with a peak at 380 nm, and the absorption in the ultraviolet region. Therefore, even if the compound (A) add essentially in large quantities, it will not deteriorate the characteristics of the fluorescence of the compound (A), the fluorescence intensity in a region corresponding to the wavelength of the excitation of the first fluorescent coloring matter, or the characteristics of the fluorescence of the first fluorescent coloring matter.

Preferred solvents for the ink is pure water, which can dissolve the first fluorescent coloring matter in large quantities, and the organic solvent which can dissolve the second fluorescent coloring matter in large quantities. More preferably the liquid medium may be included stand is Resto-active substance. Such a liquid medium is used to form the image, where the first fluorescent coloring matter is recorded in a monomolecular state, and the first and second colorants are dispersed and fixed uniformly. As a result, upon excitation at 254 nm fluorescence characteristics of the printed image (Fig) significantly improved compared to the fluorescence characteristics of the ink after evaporation (Fig). Thus, the compound (A) is a preferred example, having the structure and characteristics to achieve different purposes of the present invention.

In the following text the combination of C.I. Acid Red 52 as the first fluorescent coloring substances and compounds (A) as the second fluorescent coloring matter described using the standard definition of a predefined wavelength radiation component 600 nm, and a predefined wavelength excitation component 254 nm, including a description of embodiments of the present invention.

[Aspect 1]

Aspect 1 is characterized by the fact that the wavelength of fluorescence of the second fluorescent coloring matter covers at least the region of the wavelength peak of the excitation spectrum of the first fluorescent coloring matter, measured on the I emission at 600 nm (see Fig), and/or wavelengths of the absorption in the visible light for the first fluorescent coloring matter (see lower graph Fig). According to the aspect 1 corresponding connection regions of wavelengths is complementary to, or increases efficiency. First of all, after evaporation of the ink was prepared as follows: a predetermined number (in this case 0.3 wt.% solution) S Acid Red 52 (AR52) as the first fluorescent coloring matter dissolved in aqueous solution (organic solvent (e.g., glycerol) and clean water), and the solution was heated at 60°C until complete evaporation of water. When the ink after evaporation was subjected to excitation at 254 nm using a measuring device (FP-750, manufactured by JASCO Corporation), the spectrum of the fluorescent radiation was as shown in Fig, and a range of excitation wavelengths for a predetermined wavelength, comprising 600 nm, shown in Fig. Fig shows that the region of ultraviolet light of 380 nm or shorter wavelength, has an area of a peak having a peak of about 265 nm, and the area of the peak having a peak around 360 nm, as well as one region of the peak in the region of visible light. Basically, the wavelength of the excitation UV light used to cause the desired effect is 254 nm or 365 n is. In the study of the efficiency of energy conversion was found that when the intensity of the excitation delayed along the vertical axis on Fig is 100 or more, the determination is effective, that is, the intensity is sufficient to cause the desired effect. Therefore, the phrase "the wavelength range of the peak corresponding to the area of the peak that follows a predefined wavelength radiation, fluorescence emission from the first fluorescent coloring matter according to the present invention has practical implications when considering the above efficiency of energy conversion. In other words, in the "range of excitation wavelengths to obtain a predefined wavelength of fluorescence of the first fluorescent coloring matter (Fig) "peak area" is the area in which the intensity is 100 or more in a spectrum having a peak following the pre-determined wavelength fluorescence. The wavelength range corresponding to this area is the wavelength range of the peak.

Therefore Fig shown that when a predefined wavelength fluorescence AR52 is 600 nm (predefined wavelength excitation: 254 nm), the wavelength range of the peak of this kasitlaetavat from 430 nm to 600 nm, including both extreme values. On the other hand, as shown in Fig, the compound (A)provided as the second fluorescent coloring matter, has a basic range of fluorescent radiation from 450 nm to 600 nm, including both extreme values, almost overlapping wavelength range peak 430 nm-600 nm, including both extreme values. Each drawing can also be understood that when the above fluorescence intensity set to 100, the compound (A) fluorescent, corresponding to this range.

On Fig presents a graph showing the relationship between the characteristics of the wavelength of the fluorescent radiation of the compounds (a) and wavelength excitation to produce radiation AR52 at 600 nm, where the imposition of a range of excitation wavelengths (Fig) of the first fluorescent coloring matter and radiation (Fig) of the second fluorescent coloring matter. As you can see from Fig, when compared with the fluorescence intensity AR52 at a wavelength of 600 nm, at which the radiation intensity AR52 is maximum, as shown in Fig, the maximum emission intensity of the compound (a) is 800 or more at a wavelength of 510 nm, referring to these drawings, it can be understood that an implementation option. Therefore, the wavelength of the second fluorescent who CSOs colorants includes the wavelength range of the peak of the first fluorescent coloring matter, so the energy conversion can be performed efficiently, and the intensity of fluorescence at a predefined wavelength fluorescence can synergistically to increase with the excitation at a predefined wavelength excitation.

Then you should take absorption spectrum used colorants taking into account losses. On Fig shows the excitation spectrum AR52 for fluorescent emission at 600 nm (upper graph) and the range of light absorption of the compound (A) (lower graph), where the upper and lower graphs are compared with each other using the same wavelength scale. In this case, the absorption and excitation cannot be quantitatively compared with each other, but it is possible to detect the relative relationship between them. In General, the absorption band overlaps the emission band, but is shifted towards shorter wavelengths. Range of light absorption of the compound (A) also overlaps the wavelength region of fluorescent radiation is shown in Fig, showing absorption at a wavelength of 440 nm or less. Absorption spectrum has a practical sense about the peaks. Therefore, it is preferable that the wavelength region including the wavelength of maximum absorption (380 nm) of the compound (A), does not overlap the main area of excitation wavelengths AR52 extending from 425 nm is about 600 nm, including both extreme values, where the fluorescence intensity is 100 or more, more preferably not overlap the gap between the main area of the absorption 425 nm or less and the main field excitation AR52. In any case, the absorption band of the compound (A) does not overlap with the wavelength range of the peak AR52, so that the absorption band has no direct effect on the above-mentioned energy conversion.

If a large percentage of the emission of the second fluorescent coloring matter, corresponding to the area of the wavelength of the excitation of the first fluorescent coloring matter is absorbed by the second coloring substance will be a loss in the increase of fluorescence intensity.

Since the wavelength range of the fluorescent radiation of the compound (A) is covered by the range of excitation wavelengths AR52, effective upon receipt of radiation at a predetermined wavelength, the radiation from the compound (A) is used for excitation of AR52. In addition, the absorption of the compound (A) does not reduce the efficiency of energy conversion. Therefore, the fluorescent emission from the second fluorescent coloring matter becomes a new energy for excitation of the first fluorescent coloring substances, which increase Fluor is stantsii.

As is clear from comparison between Fig and Fig, fluorescent radiation AR52 and fluorescence emission of the compound (A) overlap in the wavelength range extending at least from 580 nm or more and 620 nm or less. This overlap provides a more effective relationship to determine when a predefined wavelength radiation.

The following is a description of the characteristic of the present invention, associated with the absorption spectrum of the first fluorescent coloring matter. On Fig presents a graph that includes the absorption spectrum of AR52 (lower graph) and the spectrum of the fluorescent radiation of the compound (A) (upper graph) on the same wavelength. Absorption spectrum of AR52 can be considered as showing the energy loss of the fluorescent radiation of the compound (A). Absorption spectrum of AR52 has a main peak around 560 nm in the range from 600 nm to 460 nm, including both extreme values, in the region of visible light. The range of significant acquisitions AR52 is narrower than the above, and extends from 500 nm to 590 nm, including both extreme values. Taking into consideration the range of fluorescent radiation AR52 (550 nm or more) and its intensity, as shown in Fig, believe that the absorption is in the range from 500 nm to 560 nm, including both extreme values. Because this band is my absorption the Oia is located in the region of visible light, it is not applicable technical argumentation on the basis of the fluorescent radiation AR52. However, since the present invention uses a variety of fluorescent colorants, this absorption band is considered in the two-stage conversion of excitation energy. That is, immediately after the recognition of this absorption band, the solution lies in the fact that fluorescence emission of the second fluorescent coloring matter is in the range, covering the wavelength of the excitation AR52, to produce radiation at a predetermined wavelength fluorescence, but does not include the range of absorption. This dependence is illustrated Fig. As you can understand from the upper and lower graphs shown in Fig, the main fluorescence emission of the compound (A) is in the range of from 430 nm to 515 nm, including both extreme values, and has no effect on the absorption band. Fluorescence emission of the compound (A) includes a range of fluorescent radiation, indicated by the symbol α Fig (430 nm ≤ α < 500 nm)in the wavelength range not overlapping strip of significant acquisitions AR52, extending from 500 nm to 590 nm, including both extreme values, with a peak at 560 nm. The energy of light this area α used as additional energy is sbordone for the first fluorescent coloring matter. Therefore, when a predefined wavelength radiation can increase the intensity of the fluorescence as a whole. In other words, the region α improves the intensity of fluorescence AR52, because at least the region α overlaps the second wavelength region of the excitation AR52.

Further, as a reference example will be given an explanation of the combination of C.I. Acid Yellow 73 (AY73) and AR52 with reference to Fig-26; this combination is described in U.S. patent No. 6176908 Century On each drawing shows that the used ink after evaporation when applied ultraviolet light, while the absorption was measured using normal ink. As shown in Fig, AY73 fluorescent in the region of wavelengths of about 500-600 nm, including both extreme values (peak: 530 nm), when carried out agitation at a predefined wavelength of 254 nm.

On Fig fluorescence spectrum AY73 Fig. 23 superimposed on the excitation spectrum AR52 shown in Fig. As can be seen from this figure, the fluorescent radiation AY73 occurs in the region of wavelengths of about 500-600 nm, including both extreme values (peak: 530 nm)and the wavelength range with an effective radiation intensity narrow. A range of fluorescent radiation AY73 is within the range of the wavelength of maximum excitation AR52 (from 475 nm to 600 nm, including both extreme values). With edutella, dye AY73 not fluorescent in the extent sufficient to cause fluorescence of AR52.

On Fig shows the comparison between the spectrum of the excitation AR52 to produce radiation at 600 nm and the absorption spectrum of the light AY73. The absorption band of the light AY73 is located in the region of visible light is not higher than 525 nm and has a peak at 490 nm. When the ink contains the compound (a) and both AR52 and AY73, as an example of the present invention, AY73 effect, reducing the effect of compounds (A) in accordance with the absorption spectrum of the light. Therefore, it is necessary to increase the added amount of the compound (A) to the extent this is desirable (see the aspect 2, described below)to compensate for the loss due to absorption by the dye AY73. In addition, as shown in Fig, the wavelength of maximum absorbance (490 nm) AY73 is located in the region of excitation wavelengths (450 nm-600 nm, including both extreme values) AR52.

On Fig depicts the combination of the absorption spectrum of AR52, shown in the bottom graph Fig, and fluorescence spectrum AY73. As can be seen from Fig, band fluorescence AY73 enters the realm of significant acquisitions (500 nm-590 nm, including both extreme values) AR52, and the wavelength of the radiation is not observed at shorter wavelengths than the above range absorption. Therefore, the combination of only dyes AR52 and AY73 does not reveal the essence of a l the Bo of the configurations of the present invention, described above, and does not provide the advantage of the present invention.

Returning to Fig-22, the present invention will be further described with reference to ink and printed image. On Fig presents the measurements obtained by the preparation of printing inks, which contain and AR52, the compound (A), pure water and an organic solvent, followed by excitation with the help of the device FP-750 at a predefined wavelength excitation component 254 nm, printing inks in the ink after evaporation. On Fig presents test results obtained by excitation with the help of the device FP-750 at a predefined wavelength excitation component 254 nm, the images printed on the media information using the ink for printing. In other words, Fig shows the results of a study of the characteristics of the printing inks according to the present invention, carried out on the ink after evaporation, and Fig showing the characteristics of the printed image obtained with the use of ink for printing according to the present invention, allowing to characterize the use of ink for printing according to the present invention in terms of the printed image.

The effects of the present invention will be validated by comparison the s Fig and Fig. This is possible because the same ink used in these drawings that effectively at a relative comparison. Graph each of Fig and Fig has two peaks, in the vicinity of 500 nm and 590 nm, respectively. As evidenced by each of Fig and 16 described above, the compound (A) provides peak at approximately 500 nm, and AR52 provides peak at 590 nm. As can be seen in the comparison between Fig and Fig, relatively Fig showing AR52 the compound (A)are dissolved in perfect condition, the printed image receives an additional increase in fluorescence intensity, in particular, the increase in the intensity of fluorescence at a predefined wavelength (600 nm or in the range from 580 nm to 620 nm). These facts prove the following. The printed image of each of the coloring substances effectively uses a predefined wavelength excitation, and can receive radiation from the compound (A)provided as the second fluorescent coloring matter, and the emission from the first fluorescent coloring matter with the radiation from the compound (A). Basically, when fluorescent colorants associated with each other, the peak wavelength is shifted toward a more long the x waves. However, when comparing between Fig and 21 above shift is not observed. Thus, the absence of such a shift means that the result is proved by preventing the Association of the effect of the present invention, and other technological features. On Fig shows the result obtained by examining characteristics of the ink according to the present invention as applied to the ink after evaporation. On Fig showing the characteristics of the printed image obtained with the use of ink for printing according to the present invention, allowing to characterize the use of ink for printing according to the present invention in terms of the printed image.

In addition, after evaporation of the ink, which contain and AR52, the compound (A), has two peaks, as shown in Fig. It is therefore evident that the compound (A) compensates for all the characteristics of AR52 even in the case of using ink to print, and the fluorescence emission of the compound (A) has characteristics sufficient influence to increase the predetermined wavelength. In addition, as shown in Fig, the printed image has two peaks, so here it is demonstrated that the generated fluorescent ink, which hindered the emergence of concentration quenching, and provide the raised durability, to continue increasing the intensity of fluorescence for a long time.

It should be noted that the predetermined wavelength fluorescence in the present invention can be chosen depending on the application of the ink images formed with the ink. For example, on Fig shows the spectra of the excitation AR52 obtained using wavelength fluorescent radiation (predetermined wavelength) 580 nm, 600 nm and 620 nm, respectively. Thus, the wavelength range of the peak corresponding to the peak area for each predetermined wavelength fluorescence, can be determined in accordance with the present invention. As described above, when a predefined wavelength is defined as a strip extending from 580 nm to 620 nm, inclusive, preferably, the wavelengths of emission of the second fluorescent coloring matter upon excitation at a predefined wavelength excitation covered most of the wavelengths of the peak of the spectrum of the excitation. However, in this case, to obtain the level of performance that exceeds that for known technical solutions, the wavelength may be the only wave high efficiency, or that before occhialino it may be more wide strip, for example, 600 nm ± 5 nm or ± 10 nm, when a predefined wavelength is defined as a range of wavelengths. That is, the wavelength of the fluorescent radiation includes wavelengths in the spectrum of the excitation, which effectively turns a predetermined fluorescent radiation. For example, in the case of AR52, as shown in Fig, it is more efficient to match the wavelength range of the peak excitation spectrum for the emission wavelength of 600 nm, as described above, instead of the excitation spectra for 580 nm and 620 nm. Naturally, the effects of the above aspect 1 can be enhanced, if it is possible to increase the added amount of the second fluorescent coloring matter.

(Aspect 2)

Aspect 2 refers to the requirement is usually not recognized characteristics in the structure of the second fluorescent coloring matter, which provides more add a second fluorescent coloring matter in the ink. The conditions for wavelengths described in the aspect 1 of the second fluorescent coloring matter, simplified in such a way that at least part of the wavelength fluorescence overlaps the excitation spectrum of the first dye substances. The energy ratio between the wavelength of excitation and emission wavelength can is velocity by increasing the added amount of the second fluorescent coloring matter. More specifically, the added amount of the second fluorescent coloring matter can be increased by preventing the molecular Association of the first coloring matter with the principal structure of the second coloring substance, which complicates the molecular Association of coloring substances. As a result you can increase the intensity of fluorescence at a predefined wavelength. The intensity of the fluorescent emission of the first fluorescent coloring matter at a predefined wavelength excitation can be improved by using a combination of the first and second fluorescent coloring matter, at least one of which, preferably the second fluorescent coloring matter, has the basic structure of the following atoms or groups of atoms, or the following fluorescent group.

In particular, the structure of the colorants preferably has a lot of fluorescent groups. That is, the dye having a lot of fluorescent bands of the same molecular structure is structurally larger and shows more clearly the property of the three-dimensional structure compared to conventional fluorescent coloring matter. Thus, hampered regular aggregation or as solirovanie colorants compared with conventional fluorescent coloring matter. Therefore, even if the content of the fluorescent coloring matter in the ink is increased compared with the normal content of the fluorescent coloring matter, it is difficult to reduce the intensity of fluorescence. In addition, the dye having a lot of fluorescent bands of the same molecular structure, contains many fluorescent groups in one molecule colorants. Thus, the fluorescent radiation in terms of the molecule becomes strong, resulting in increased intensity of fluorescent radiation. In addition, as described above, compared to conventional fluorescent coloring agent, a fluorescent coloring matter according to the present invention is structurally larger and shows more clearly the property of the three-dimensional structure, so that the coloring substance can more easily absorbed on the components of the carrier printed information that leads to a good water resistance. In addition, when the fluorescent coloring material has substantively, its resistance can be increased, and substantively can contribute to the durability of fluorescent radiation. In addition, regular aggregation or Association colorants, with many fluorescent g the SCP same molecular structure, difficult compared with conventional coloring agent. So, for example, even if the ink contained lose them in the water by evaporation, regular aggregation of coloring matter is difficult. Accordingly, it is difficult to cause the onset of intense aggregation, thereby to obtain excellent resistance to sticking. This mechanism allows the ink according to the present invention have acceptable fluorescence intensity and resistance. In addition, the dye having a lot of fluorescent bands of the same molecular structure also enhances the effects of the present invention through the use of sulfonic acids having a strong affinity to water as the hydrophilic group.

Preferred fluorescent group that satisfies the above requirements and functionally effective, can be aminostilbene derived dissolvability. The structure of the compound (A) also contains derived.

In the case of fluorescent colorants, such as basic coloring matter, even if the concentration of this coloring matter in the ink increases, the intensity of the fluorescence of this dye substances cannot be increased, but can be reduced. In the case of the use of such an f is uorescence colorants applicable concentration range of content in the ink) is narrowed, and there is a limit to the increase in fluorescence intensity. On the other hand, in the combination of the first and second fluorescent coloring substances of the present invention and a color converting radiation into visible light, the intensity of fluorescence can be improved when the content of the fluorescent coloring matter is increased, depending on the increment of this content.

Examples of fluorescent groups, fluorescent colorants according to the present invention, groups of atoms and groups with features to ensure the brightness of fluorescence below. In this case, the fluorescent coloring matter according to the present invention may have a wavelength region of light absorption in the visible light or other areas, but it is important to fluorescinated in the field of visible light, in order to obtain the radiation corresponding to the region of excitation wavelengths.

As shown by the structural formulas shown above, the compound (A) has a dimeric structure with numerous fluorescent group and sulfonic group.

Thus, when the fluorescent coloring matter contains a fluorescent group, it increases the intensity of fluorescence of the first fluorescent abrasivos the th substance when excited at a predefined wavelength excitation because of the excellent fluorescent radiation, the corresponding pre-defined excitation of the first fluorescent coloring matter. In particular, aminostilbene derivatives desulfation, thanks to its wide field fluorescent radiation, are preferred.

(Aspect 3)

Aspect 3 effective by itself or in combination with each of the aspects 1 and 2. Aspect 3 is the technology of increase of fluorescence intensity by a suitable arrangement of the fluorescent coloring matter on the media printed information using a fluid, such as a mixture of a first solvent having high solubility with respect to the first coloring matter, and the low solubility with respect to the second coloring substance, and a second solvent having a high solubility with respect to the second coloring matter.

Some dyes cause a chemical phenomenon known as the Association to maintain energetically stable state. This phenomenon of Association in case of dye molecules having a relatively flat frame having two ring structures or less, two molecules facing each other, and the flow and energy loss occur between these molecules. Therefore, in the presence of a fluorescent dye such phenomenon may be a factor, m is the decisive manifestation of the fluorescence properties of the dye. Because this state overlay is supported not only in ink, but in the printed contents on the paper, you want the tool to prevent the Association of the dyes. Basically, you know adding urea, naphthalenesulfonate or so as to prevent the Association of substances used to prevent Association. If, however, prevents the Association of the substance itself has the property of fluorescence, increasing the intensity of fluorescence of the first fluorescent coloring matter, and possesses prevent the Association function, it is possible to achieve both effects increase the intensity of fluorescence and efficient generation of fluorescence based prevention Association.

Next, when receiving the ink containing the first fluorescent coloring material and the second fluorescent coloring matter, providing increased the fluorescence intensity of the first fluorescent coloring matter upon excitation at the same wavelength excitation, using a mixed solvent containing a first solvent having high solubility with respect to the first coloring matter, and the low solubility with respect to the second coloring substance, and a second solvent having a high dissolve the awn relative to the second coloring matter.

In this description, the term "high solubility" or "good solvent" means that the dye may be dissolved upon reaching a concentration of about 3 wt.% or more, and the term "low solubility" or "poor solvent" means that the dye may be dissolved upon reaching a concentration of less than about 3 wt.%.

For example, when water is chosen as the first solvent, and the glycerol is chosen as the second solvent, the water has a high solubility with respect to AR52 and low solubility with respect to the compound (A), and the glycerin has a high solubility with respect to the compound (A). Then the ink is prepared by adding AR52 and connections (A) in a solvent containing water and glycerin. In the ink compound (A) is in the environment that cause the excess in a poor solvent, so that the compound (A) is dissolved in the weak state of the Association, forming a stable system with AR52. However, when the inks are printed on the media information, the water, which is a poor solvent, rapidly diffuses and penetrates into the medium of printed information. On the other hand, glycerin slowly diffuses and penetrates into the medium of printed information due to its viscosity. At this point, the joint is (A) is not soluble in water which is a poor solvent and glycerol, which is a good solvent. Thus, the compound (A) slowly diffuses and penetrates into the medium of printed information together with glycerol. In addition, since glycerin is a good solvent, the compound (A) is absorbed in a monomolecular state components, media, printed information. Therefore, is acceptable fluorescent radiation. In addition, the compound (A) dissolved in a monomolecular state, so that the compound (A) can also prevent the Association AR52. In other words, the molecules of compounds (a) and AR52 recorded on the media printed information on the state of mixing and dispersion with each other to a suitable degree. Thus, the effect of increasing the fluorescence intensity of AR52 compound (A) becomes significant. In this case, the first fluorescent coloring material and the second fluorescent coloring matter, each preferably has a lot of sulfonic groups.

Furthermore, for the preferred expression of the above-mentioned phenomenon, the content of used fluorescent colorants preferably does not exceed the amount that can dissolve in a bad solvent.

On the other hand, when the prevention Association is considered from a point the of view of the molecular structure of the fluorescent coloring substances, if at least one of the first and second coloring substance has a molecular structure having three or more ring structures, the imposition of molecules of the first and second coloring substances is prevented, but they are present in the vicinity of each other, ensuring a simple transfer and reception of energy mentioned above. As a result, the fluorescence intensifying.

Thus, the second fluorescent coloring matter used in the present invention preferably has a lot of fluorescent groups. More preferably the second fluorescent coloring matter used in the present invention has a basic structure that is appropriate to give the brightness of fluorescence. In addition, fluorescent groups in the second fluorescent coloring matter is preferably represent a dimer.

Examples of the ring structure of the second fluorescent dye is an annular structure having a double bond or a conjugated double bond, the structure of the aromatic ring structure of the cyclic ring or heterocyclic structure, as described above.

When the first fluorescent coloring material and the second fluorescent coloring matter both are water soluble, these two fluorescent colorants prefer is Ino have the same group for solubility in water, with the aim of simplified prevention Association. More preferably the group ensuring solubility in water, is a sulfonic group, the solubility of which does not affect the pH of the ink.

In the present invention, the ink may contain a fluorescent or not the fluorescent coloring matter as the third coloring substances in addition to the above two fluorescent coloring agents.

Next will be described the environment water-based, which together with the above-described dye forms a fluorescent ink according to the present invention. Environment water-based, used in the present invention, preferably is water-based, containing mainly water. The water content in the ink is 10-95 wt.%, preferably 25-93 wt.%, more preferably 40-90 wt.% from the total mass of the ink. The water used in the invention is preferably ion-exchange water.

In addition, to obtain the ink according to the present invention it is possible to use only water as a medium for water-based or in combination with water-soluble organic solvent to further enhance the effects of the present invention.

Water-soluble organic solvents used in the present invention are solvents described above, so their womenan is e not repeated here.

The content of water-soluble organic solvent in the ink is basically equal to or less than 50 wt.%, is preferably 5-40 wt.%, more preferably 10-30 wt.% from the total mass of the ink.

Among these solvents, preferred are ethylene glycol, diethylene glycol, triethylene glycol, 2-pyrrolidone, glycerol and 1,2,6-hexanetriol.

The ink according to the present invention preferably contain urea, etilenmocevina or trimethylolpropane as a humidifier, the same solvent. Among them particularly suitable for the present invention are etilenmocevina and trimethylolpropane. Their content is preferably 1 wt.% or more and 20 wt.% or more of the total mass of the ink.

Fluorescent ink according to the present invention prepared as described above, practically effective when they are used in inkjet printing. As a method of inkjet printing, you can specify the printing method, providing mechanical energy to the ink to release liquid droplets, and a method of inkjet printing, providing for the flow of ink through the supply of heat energy for the production of liquid droplets. Fluorescent ink according to the present invention containing multiple fluorescent coloring substances sentence on the us, in particular, the quality of the ink to implement methods of inkjet printing.

Hereinafter the present invention will be more specifically described with reference to examples and reference examples. In this case, the measured values obtained by using prepared on the basis of pure water, diluents, coloring substances, was used to determine the wavelength of the absorption region of the wavelength of maximum absorption and the wavelength of fluorescence. The wavelengths of absorption was measured using an absorption spectrometer. The diluent prepared in such a way that its absorbing capacity was in the range of 0.5-0.7. The area above the baseline as absorption coloring matter was determined as the wavelength region of absorption, and the value corresponding to the peak, defined as the region of the wavelength of maximum absorption. In addition, for wavelengths of fluorescence measurement conditions were determined so that the fluorescence intensity did not exceed the measured threshold value. Next, the measurement of the wavelengths of fluorescence was performed using the diluent used in the measurement of absorptive capacity, and locking the wavelengths of excitation of the first and second coloring substances at predefined wavelengths. The area above the baseline was defined as the area is Lin waves fluorescent radiation.

Ink in the following examples, multiple fluorescence satisfy the configuration of one of the ink for printing corresponding to the above-described variants of implementation of the present invention from the first to the sixth.

Example 1 multiple fluorescence

To prepare the ink, the following components were added in the correct quantities to achieve a predetermined concentration, and then these components were mixed and stirred sufficiently, followed by filtration under pressure through a microfilter (manufactured by Fuji Photo Film Co., Ltd.) with pore size 0.2 μm formed.

C.I. Acid Red (the first fluorescent coloring matter):0,25. parts
Connection (A) (second fluorescent coloring matter):1 wt. part
Glycerin:7.5 wt. parts
Diethylene glycol5 wt. parts
Urea:5 wt. parts
Acetylene E100 (adduct of acetylenics and SW produced by Kawaken Fine Chemicals Co., Ltd.):1 wt. part
Water:80,25 wt. parts

Spectra of fluorescence emission and excitation spectra of the first and second fluorescent is different coloring substances were measured using fluorometry FP 750, manufactured by JASCO Corporation, respectively. Each sample consisted of the ink, from which the vaporized water to eliminate the effect of water on the dimension.

The wavelength of absorption of the first and second coloring substances was measured using a spectrophotometer U-3200, manufactured by Hitachi Ltd., then, the sample was diluted with clean water to 100,000 times. The wavelength of the first absorption colorants stretched from 450 nm to 620 nm, including both extreme values, and the wavelength of maximum absorption for this substance was 565 nm. In addition, the wavelength region of absorption of the second dye substances stretched from 300 nm to 450 nm, including both extreme values, and the wavelength of maximum absorption for this substance was 372 nm.

Reference example 1

To prepare the ink, the following components were added in the correct quantities to achieve a predetermined concentration, and then these components were mixed and stirred sufficiently, followed by filtration under pressure through a microfilter (manufactured by Fuji Photo Film Co., Ltd.) with pore size 0.2 μm formed

C.I. Acid Red (the first fluorescent coloring matter):0,25. parts
Glycerin:7.5 wt. the t
Diethylene glycol5 wt. parts
Urea:5 wt. parts
Acetylene E100 (adduct of acetylenics and SW produced by Kawaken Fine Chemicals Co., Ltd.):1 wt. part
Water:an 81.25 wt. parts

(Evaluation)

(1) the Intensity of fluorescence

Using the printing device inkjet (BJS600, manufactured by Canon Inc.), having a multi-printhead, triggered on demand, from which ink is produced under the influence of thermal energy depending on the signal printing ink, printed continuous picture mode 50% load plain paper (SW-101, manufactured by Canon Inc.) for inkjet printing. Then the following conditions measured intensity of the fluorescence using a fluorometer (FP-750, manufactured by JASCO Corporation). The results were evaluated based on the criteria described below, and these results are listed in table 1. Conditions for the measurement were as follows: the wavelength of excitation was set equal to 254 nm; the fluorescence intensity was measured at the wavelength of maximum fluorescence; and measured the fluorescence intensity normalized by determining the fluorescence intensity of ink of reference example 1 as 100, then spent OC the GCC in accordance with the following criteria:

AA: the measured fluorescence intensity was 150 or more;

A: the measured fluorescence intensity was 110 or more and less than 150; and

In: the measured fluorescence intensity was less than 110.

(2) the Manifestation of color

By using the inkjet printing device (BJS600, manufactured by Canon Inc.), having a multi-printhead, triggered on demand, from which ink is produced under the influence of thermal energy depending on the signal printing ink, printed continuous picture mode 50% load plain paper (SW-101, manufactured by Canon Inc.) for inkjet printing. After this, the measured property is the degree of color development using a Macbeth densitometer printing of information materials (RD-918, manufactured by Macbeth Co., Ltd.).

AA: 0.7 or more, with the printed content can be immediately discerned visually;

And: 0.5 or more and less than 0.7, while the printed content can be distinguished visually;

In: 0.3 or more and less than 0.5, while the printed content is difficult to distinguish visually;

With: less than 0.3, with the printed content cannot be distinguished visually.

(3) Resistance

By using the inkjet printing device (BJS600, manufactured by Canon Inc.), having a multi-printhead, triggered on demand, from which ink is produced by the influence of thermal energy depending on the signal printing ink, printed continuous picture mode 50% load plain paper (SW-101, manufactured by Canon Inc.) for inkjet printing. After this paper was allowed to stand for 24 hours and then immersed in running water for 5 minutes. After that evaluated the change in the print density using a Macbeth RD918 on the basis of the following criteria:

AA: the change in density of less than 50%, while the printed content can be immediately discerned visually;

A: 50% or more and less than 70%, while the printed content can be distinguished visually;

In: 70% or more, with sealed contents cannot be distinguished visually.

Table 1
(1) the Intensity of fluorescence(2)

Property manifestations color
(3)

Property resistance
Example 1 multiple fluorescenceAAAndAnd
Reference example 1InAndIn

Each ink prepared in accordance with the composition shown in table 2 in each of examples 2-6 multiple fluorescence and reference examples 2 and 3.

Here, in each of the above reference examples use a combination of obychayami substances, and conditions on the solvents used are the same as in the present invention. Thus, each of the above reference examples are presented as a reference example.

Table 2
Example 2Example 3Example 4Example 5Example 6Reference example 2Reference example 3
First the dyeAR52

0.25 wt.%
AR52

0.25 wt.%
BV10

0.25 wt.%
AR52

0.25 wt.%
AR52

0.25 wt.%
AR52

0.5 wt.%
AR52

0.25 wt.%
The second coloring substanceThe compound (A)

1 wt.%
The compound (A)

2 wt.%
The compound (A)

1 wt.%
SG7

0.3 wt.%
The compound (A)

1 wt.%
AY73

0.5 wt.%
AY18

41 wt.%
Third coloring substanceAR92

0.6%
AR92

0.6%
-----
The first solventglycerin 7.5 wt.%glycerin 7.5 wt.%triethylene-glycol
7.5 wt.%
xylitol

7.5 wt.%
-glycerin 7.5 wt.%glycerin 7.5 wt.%
Diethylene glycol5 wt.%5 wt.%5 wt.%5 wt.%5 wt.%5 wt.%5 wt.%
Urea5 wt.%5 wt.%5 wt.%5 wt.%5 wt.%5 wt.%5 wt.%
Acetylene E1001 wt.%1 wt.%1 wt.%1 wt.%1 wt.%1 wt.%1 wt.%
The second solvent (water)of 79.65 wt.%78,65 wt.%80,25 wt.%80,95 wt.%87,75 wt.%80,5 wt.%80,25 wt.%

Each of the inks prepared in accordance with the foregoing, was irradiated with light at a wavelength of excitation of 254 nm. Then received spectrum of the resulting fluorescent radiation. For inks of examples 2-4 multiple fluorescence were detected such effects as two large peak in the fluorescence intensities of Fig and 21, and was conducted comparing them. On the other hand, this relationship was not found in the ink of the reference examples 1-3.

In addition, the intensity is Yunosti fluorescence, etc. was evaluated in the same way as in the case of each of examples 1 multiple fluorescence and reference example 1. As shown in table 3, there were significant differences between the examples and the reference examples.

Table 3
(1) the Intensity of fluorescence(2)

The manifestation of color
(3)

Resistance
Example 2 multiple fluorescenceAAAAAA
Example 3 multiple fluorescenceAAAAAA
Example 4 multiple fluorescenceAAAndAnd
Example 5 multiple fluorescenceAAAndAnd
Example 6 multiple fluorescenceAndAndAnd
Reference example 2InAAIn
Reference example 3InAndIn

As described above, in accordance with the present invention proposed a fluorescent ink having a high fluorescence intensity, the property of a high degree of color development and its the creation of high resistance, which cannot be achieved in the prior art, and the method of inkjet printing using such fluorescent ink.

In some cases, not water-soluble fluorescent substance can be used in combination. In this case, it is possible to use, for example, a direct dye, acid dye, basic dye or VAT dye, and specific examples include direct dyes, Direct Black 168, Direct Black 154, Direct Yellow 142, Direct Yellow 86, Direct Red 227, Direct Blue 199, Direct Black 195, dye Food Black 1, 2, but such examples are not restrictive. Water-soluble coloring matter also can be used separately or in combination of two or more types.

In addition, among these water-soluble coloring substances are those that have a low solubility in water and behave like pigments, can be used as a water-dispersible coloring matter.

The amount of water-soluble colorants are not specifically limited, but it is generally preferably is in the range of 0.1-15 wt.% from the total ink weight, more preferably 0.1 to 10 wt.% and even more preferably 1-10 wt.%.

In addition, the dye having a carboxyl group as a water-soluble group may, in particular, to be di - or tri-azo-coloring matter with the school by substantively, such as Direct Black 195 or Direct Black 51, or coloring substance dimeric structure, which is connected via a connecting group; for example, it may be the coloring matter in the form of the free acid, as represented by the following General formulas (A)-(C), but this is not restrictive sign.

(1) Coloring matter in the form of free acid that is represented the following General formula (A):

Pc(SO3H)t(SO2-NR1-L-NR2-X-NR3-G)qGeneral formula (A),

[where: Pc is metallsoderjasimi phthalocyanine nucleus; R1, R2and R3each independently represents H, alkyl group, substituted alkyl group, alkenylphenol group, substituted alkenylphenol group, aracelio group or substituted aracelio group; L represents a divalent organic connecting group; X each time independently represents a carbonyl group or a group represented by the following formula(2)-(4);

(Z in formulas (2)to(4) independently represents NR4R5, SR6or or6Y in the formula (3) is H, Cl, the above Z, SR7or or7; E in the formula (4) represents Cl or CN; R4, R5, R6and R7each independently represents H, alkyl group, substituted alkyl group is, aryl group, substituted aryl group, aracelio group or substituted aracelio group, and R4and R5form a 5 - or 6-membered ring together with a nitrogen atom); G is a colorless organic residue substituted by one or two groups COSH or COOH, and t+q is 3 or 4.]

Example compounds represented by the General formula (A)is the following:

example colorants (1)

(2) Coloring matter in the form of the free acid represented by the following General formula (I):

Ar1=NJX(NR1LNR2X)nJN=NAr2

General formula (B)

[In the General formula (I) J represents the following formula:

In the General formula (V) each of the groups Ar1and Ar2independently represents an aryl group or substituted aryl group, and at least one of the groups Ar1and Ar2independently has at least Deputy selected from COOH and COSH; R1and R2each independently represents H, alkyl group, substituted alkyl group, alkenylphenol group or substituted alkenylphenol group; L represents a divalent organic connecting group; n represents 0 or 1; and X each time independently represents a carbonyl group or a group represented by the following form is Lamy (2)-(4);

(Z in formulas (2)to(4) independently represents NR3R4, SR5or or5Y in the formula (3) is H, Cl, the above Z, SR6or or6; E in the formula (4) represents Cl or CN; R3, R4, R5and R6each independently represents H, alkyl group, substituted alkyl group, alkenylphenol group, substituted alkenylphenol group, aryl group, substituted aryl group, aracelio group or substituted aracelio group; and R4and R5form a 5 - or 6-membered ring together with a nitrogen atom); and the compound represented by General formula (B)includes a group selected from COOH and COSH, in number equal to the number of groups SO3N.]

Examples of compounds represented by the General formula (I)are as follows:

example colorants (2)

example colorants (3)

example colorants (4)

the example of the colorants (5)

(3) colorants in the form of the free acid represented by the following General formula (C):

[In General formula (C) each of the groups Ar and Ar1independently present is employed, aryl group or substituted aryl group, and at least one of the groups Ar and Ar1has a Deputy selected from the group consisting of a sulfonic group, carboxyl group and dicarboxylic group; and each of the groups J and J1independently represents a group represented by the following General formula (2), (3) or (4):

(In the formula (2): R5selected from a hydrogen atom, alkyl group, substituted alkyl group, alkoxygroup, halogen atom, CN, raidgroup and NHCOR6; R6selected from a hydrogen atom, alkyl group, substituted alkyl group, aryl group, substituted aryl group, aranceles group and substituted aranceles group; in the formula (3): T represents an alkyl group; W is selected from a hydrogen atom, CN, CONR10R11, group Pisidia and carboxyl group; R10and R11each independently selected from a hydrogen atom, alkyl groups and substituted alkyl groups; m represents alkylenes chain with 2 to 8 carbon atoms; and in formula (4) is selected from a hydrogen atom, alkyl groups, and carboxyl groups.

In the General formula (C): R1, R2, R3and R4each independently selected from a hydrogen atom, alkyl groups and substituted alkyl groups; L represents a divalent organic connecting group; n represents 0 or 1; and X each time independently before the hat carbonyl group or a group represented by the following formula (5), (6) and (7):

(Z in formulas (5)-(7) selected from OR7, SR7and NR8R9; Y is selected from H, Cl, CN, and Z; E is selected from Cl and CN; R7, R8and R9each independently selected from a hydrogen atom, alkenylphenol group, substituted alkenylphenol groups, alkyl groups, substituted alkyl groups, aryl groups, substituted aryl groups, aranceles group or substituted aranceles group, and R8and R9may form a 5 - or 6-membered ring together with the United with him by a nitrogen atom).

When the compound of General formula (C) does not have a sulfonic group, provided that it contains at least two groups selected from carboxyl groups and dicarboxylic groups, and the compound of General formula (C) is a group selected from a carboxyl group and dicarboximido group, in number equal to the number of sulfonic groups.]

Examples of compounds represented by the General formula (C)are as follows:

example colorants (6)

(6)

example colorants (7)

(7)

example colorants (8)

example colorants (9)

(9)

<> example colorants (10)

(10)

example colorants (11)

(11)

Specific examples of water-soluble organic solvent used for the ink containing a second coloring substance according to the present invention, include Elgiloy alcohol with 1-5 carbon atoms, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-pentanol; amide such as dimethylformamide, dimethylacetamide; ketone or cytosport, such as acetone or datetoday alcohol; a simple ether, such as tetrahydrofuran or dioxane; product accession oxyethylene or oxypropylene, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropyleneglycol, tripropyleneglycol, polyethylene glycol or polypropyleneglycol; allenglish with 2-6 alkionovymi groups, such as ethylene glycol, propylene glycol, triethyleneglycol, butyleneglycol, pentanediol or hexyleneglycol; a triol such as glycerin, trimethylacetyl, trimethylolpropane or 1,2,6-hexanetriol; thiodiglycol; bishydroxyethyl; simple lower allylglycidyl ether, such as simple onomatology (or-ethyl or butyl) ether is of etilenglikola, simple onomatology (or-ethyl or butyl) ether of diethylene glycol or a simple onomatology (or-ethyl or butyl) ether of triethylene glycol; a simple lower dialkylglycerol ether, such as simple dimethyl (or ethyl) ether, triethylene glycol or simple dimethyl (or ethyl) ether of tetraethyleneglycol; alkanolamine, such as monoethanolamine, diethanolamine or triethanolamine; sulfolan, N-methyl-2-pyrrolidone, 2-pyrrolidone and 1,3-dimethyl-1-2-imidazolidinone. Such water-soluble organic solvent as mentioned above may be used alone or in a mixture solvent of two or more types.

The content of such water-soluble organic solvents is usually 50 wt.% or less of the total ink weight, preferably 5-40 wt.% and more preferably 10-30 wt.%.

Among these solvents, preferred are ethylene glycol, diethylene glycol, triethylene glycol, 2-pyrrolidone, glycerol or 1,2,6-hexanetriol.

Ink containing a second coloring substance according to the present invention also preferably include a humidifier, a similar solvent, such as urea, etilenmocevina or trimethylolpropane. In particular, etilenmocevina or trimethylolpropane are very suitable for the second coloring substances is in accordance with the present invention. The content of this humidifier is preferably 1 wt.% or more of the total ink weight, and preferably 20 wt.% or less.

In addition to the above components, the ink including a second coloring substance according to the present invention, can be added, if necessary, protivovospalitel, additives, pH adjustment, Supplement, correction, viscosity, fluorescence intensifier, an antioxidant, an evaporation accelerator, anti-corrosion additive, additive anti musty and helatoobrazovatel to provide the ink with the desired properties.

Ink including a second coloring substance according to the invention preferably have a viscosity within the range of 0.7-12 CPS (at 25°C. the viscosity of the ink outside the above range can prevent the normal production of ink for ink jet printing, and, in particular, the ink, the viscosity of which exceeds 12 JV demonstrate slow penetration into the media printed information due to the viscosity resistance and undesirable in respect of the retention properties.

In addition, the ink containing a second coloring substance according to the present invention have a surface tension is preferably adjusted in the range of 20 to 60 Dyne/cm at 25°C. the Surface tension of less than 20 Dyne/cm regulate is Ino, because the force of retraction of the meniscus is insufficient after the release of liquid droplets by the inkjet printing system, or Vice versa, the power drain is relatively small when the nomination of the meniscus, which may cause the inclusion of bubbles or wetting holes, leading to poor production. Ink, provided in the case of using second colorants according to the present invention and having the structure explained above, in particular, have excellent shelf life and provide excellent recording density, fiksiruet when dry and the print quality when used as an ink for inkjet printing on plain paper.

In particular, the structure of colorants, especially the second fluorescent coloring matter, preferably has a lot of fluorescent groups.

That is, the dye having a lot of fluorescent bands of the same molecular structure is structurally larger and shows more clearly the property of the three-dimensional structure compared to conventional fluorescent coloring matter. Thus, hampered regular aggregation or Association colorants compared with conventional fluorescent coloring matter. Therefore, even if the content of the fluorescent who CSOs colorants in the ink is increased compared with the content of conventional colorants, it is difficult to reduce the intensity of fluorescence. In addition, the dye having a lot of fluorescent bands of the same molecular structure, contains many fluorescent groups in one molecule colorants. Thus, the fluorescent radiation in terms of the molecule becomes strong, resulting in increased intensity of fluorescent radiation. In addition, as described above, compared to conventional fluorescent coloring agent, a fluorescent coloring matter according to the present invention is structurally larger and shows more clearly the property of the three-dimensional structure, so that the coloring substance can more easily absorbed on the components of the carrier printed information that leads to a good water resistance. In addition, when the fluorescent coloring material has substantively, its resistance can be increased, and substantively can contribute to the durability of fluorescent radiation.

In addition, regular aggregation or Association colorants, with many fluorescent bands of the same molecular structure, difficult compared with conventional coloring agent. So, for example, even if the ink contained lose them in the water when the COI is the situation, regular aggregation of coloring matter is difficult. Accordingly, it is difficult to cause the onset of intense aggregation, thereby to obtain excellent resistance to sticking.

This mechanism allows the ink according to the present invention to have sufficient fluorescence intensity and resistance. In addition, the dye having a lot of fluorescent bands of the same molecular structure also enhances the effects of the present invention through the use of sulfonic acids having a strong affinity to water as the hydrophilic group.

Preferred fluorescent element is aminostilbene derived dissolvability.

As a liquid environment, designed to enable components such as dispersed coloring matter, preferred is a mixture of water and a water-soluble organic solvent. Examples of water-soluble organic solvent include amide, such as dimethylformamide or dimethylacetamide; a ketone, such as acetone; a simple ether, such as tetrahydrofuran or dioxane; polyalkyleneglycols, such as polyethylene glycol or polypropyleneglycol; allenglish containing alkylenes group with 2-6 carbon atoms, such as ethylene glycol, about jinglian, butyleneglycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexyleneglycol or diethylene glycol; glycerin; simple lower alkilany ether of a polyhydric alcohol, such as simple onomatology (or-ethyl) ether of ethylene glycol, simple onomatology (or-ethyl) ether of diethylene glycol or a simple onomatology (or-ethyl) ether of triethylene glycol; N-methyl-2-pyrrolidone, 1,3-dimethyl-1-2-imidazolidinone, triethanolamine, sulfolan, dimethylsulfoxide, 2-pyrrolidone; and the connection with a crystalline property, such as urea, atilmotin, ε-caprolacton, succinimide, thiourea, dimethylamine or 2-pyrrolidone, and these compounds may have at least one Deputy, selected from ethylene oxide, propylene oxide and alkyl. For reasons of stability of the crystalline component in the ink, also preferred is the presence of a cyclic structure. Kristalloobrazuyushchikh component can be used separately or in combination of two or more kinds, if necessary.

In particular, a substance which is solid in the environment of normal temperature, can satisfactorily demonstrate the effect of the deposition of crystals according to the invention. The term "environment of normal temperature" means the temperature range 20-25°C. However, for the sake of convenience to use the project, beneficial to kristalloobrazuyushchikh component which is a solid substance in the environment of normal temperature, had a melting point of 30°C or higher, preferably 60°C or higher and more preferably 120°C or higher.

The content of such substances in the ink can be selected in accordance with the nature of this substance, but preferably this content is in the range of 1-30 wt.% from the total ink weight, and more preferably is 2-20 wt.%. Excessively low content does not allow for the effect of the present invention, and excessively high content disastrous effect on the characteristics of the issue in case of application of inkjet printing.

The water content in the ink is chosen in the range of 30-95 wt.%. The water content is less than 30 wt.% can not guarantee energy for dissolution of water-soluble components and increases the viscosity of the ink. On the other hand, the water content in excess of 95 wt.%, can lead to poor fixation due to excessively volatile component.

As a component of the ink according to the present invention preferably use a surfactant. You can use various surfactants, but in accordance with the purpose of the invention use a surfactant selected from the top of OSTO-active substances, providing greater retention of water-soluble coloring matter than water-dispersible coloring substances or surfactants, providing greater retention of colorants having free sulfonylurea group as the main water-soluble group than colorants having a free carboxyl group as the main water-soluble group.

Preferred surface-active agent is a nonionic or anionic surfactant. This conclusion because cationic activity can affect the degree of color development property and reliability. In particular, preferred is a nonionic surfactant. Preferred nonionic surfactant is a substance that does not show phase separation in the state of aqueous solution. Nonionic surfactant, showing phase separation in the state of aqueous solution, is undesirable, because if it is used in the ink, the ink becomes unstable. This means that it is preferable to use a surfactant, which obviously is in water in dissolved or uniformly dispergirovannom status is I. Specifically preferred is a nonionic surfactant, showing the status of the emulsion in aqueous solution. In addition, the content of the nonionic surfactant in the ink is preferably does not exceed the quantity, ensure the maintenance of the status emulsion in an aqueous solution, to eliminate concerns about the reduced stability of the ink.

Among the nonionic surfactants in the present invention, it is preferable surfactant having a HLB of not more than 15, for reasons of fiksiruesh ink on the media printed information. In General, the HLB value greater than 15, increases the solubility in water, resulting in unable to achieve satisfactory penetration of the ink in the printed media information.

As the surfactant used in the present invention, a surfactant having a smaller difference between the dynamic surface tension and the static surface tension, maybe due to the higher speed orientation of this surface-active substance to the surface of the partition, to accelerate the diffusion of the liquid ink in the printed media information. In addition, in the case of water-dispersible coloring washes the VA in the invention, this surfactant can quickly adsorb in such water-dispersible coloring substance, so that it will be oriented and adsorbed on the water-dispersible coloring matter is still able mystreamreader agglomeration. Bystrorezhuschej agglomerates water-dispersible colouring substance, formed on the printed media information, enhance the effects of the present invention. When the above-mentioned difference of the surface tension is high, essentially, is unable to achieve the advantages of the present invention.

The content of nonionic surfactants in the ink according to the present invention is, in particular 0.5 wt.% or more of the total ink weight, preferably 1-20 wt.%. When the content is less than 0.5 wt.% can not get the ink with the desired properties penetration or sputtering when forming the image, and when the content exceeds 20 wt.%, can not get satisfactorily balanced image quality, namely, a satisfactory balance in such operating characteristics as the density of the image, fiksiruet image, prevention of diffusion ("smooth" spreading).

Among the nonionic surfactants satisfying the above is the requirements, practically preferable for the ink according to the present invention are compounds represented by the following General formula (I)and compounds represented by the following General formulas (II)-(VII), but such examples are not restrictive.

[In the General formula (I), a and b each independently represents CnH2n-1(n is an integer from 1 to 10; and each of the components of X and Y independently represents a broken link ethylenoxide rings and/or link broken propylenoxide ring.]

(II)

Ester 1,5-sorbitan

(III)

Ester 1,4-sorbitane

(IV)

Ester of sorbitol

(VI)

(R: alkyl group of the fatty acid).

In addition, among the nonionic surfactants represented by the General formula (I), particularly preferred is a compound represented by the following General formula (VIII).

(VIII)

(m, n: integers).

For reasons of stability of the ink, the ink according to the present invention preferably also include polyhydric spirity alcohol prevents the growth of microbes, such as mold, which can cause blockages. Polyhydric alcohol also facilitates the efficient expression of the advantages of the present invention, because it enhances the evaporation of the ink or the penetration of them in the media printed information in the deposition on the media printed information. The content of the polyhydric alcohol in the ink according to the invention is 0.1-20 wt.% from the total ink weight, preferably 0.5 to 10 wt.%. Specific examples of polyhydric alcohol used as a component of the ink according to the invention include ethanol, isopropyl alcohol and n-butanol, and you can use this alcohol alone or in combination of two or more types.

If necessary, the ink according to the present invention may optionally include various additives such as water-soluble organic solvent, surfactant, anti-corrosion additive, antiseptic, anti musty additive, antioxidant, antibacterial, an evaporation accelerator, helatoobrazovatel, water-soluble polymer or additive, pH adjustment.

The ink according to the present invention preferably have a surface tension of 40 mn/m or less. This value is chosen because due to the effective expression of the mechanisms explained above, the liquid droplets of predpochtitel is but a manifestation of a spreading after printing. The ink according to the present invention preferably have a pH value of 6.5 or above for stability of the ink.

In addition, the ink according to the present invention preferably contain numerous alkali metal ions as the ions oppositely charged dye substance. The combined use them when inkjet printing improves the stability of the ink and improves the property release ink. Examples of alkali metal ions are Li+, Na+, K+etc.

Water-based ink according to the present invention, prepared as described above, can be used as ink for conventional fixed writing utensils, but the practical efficiency of the ink is achieved by inkjet printing. Method of inkjet printing method includes supplying mechanical energy to the ink, which ensures the production of liquid droplets, and a method of printing by supplying thermal energy to the ink for formation of a bubble that ensures the production of liquid droplets. In particular, these inks are suitable for the latest systems of ink jet printing, where ink is produced due to the phenomenon of bubble formation in the ink due to heat energy, which provides features which allow to achieve very stable release and to avoid clicks the education related points. However, in this case, it may be necessary to adjust thermal properties such as specific heat, thermal expansion coefficient, thermal conductivity and so on).

To solve the water resistance of the ink in the print, made, for example, on plain paper, and simultaneously improving compatibility with a head for inkjet printing, it is also preferable to adjust the physical properties of the ink according to the present invention so that the surface tension ranged from 30 to 40 mn/m at 25°C, and the viscosity was 15 JV or less, preferably 10 SP or less and more preferably 5 CPS or less. Therefore, for the correction ink with obtaining the above-mentioned physical properties and to solve fixation on plain paper water content in the ink according to the present invention is preferably 50-98 wt.%, preferably 60-95 wt.%.

On the other hand, kristalloobrazuyushchikh component included in the ink according to the present invention contains a water-soluble substance which is solid in the environment of normal temperature. This substance is crystallogeny substance having a crystallinity of non-circular, spherical, etc. form and diluted with additional water. With decreasing water content, for example, vsledstvii the heat, this substance also recrystallised from its aqueous solution. This substance may be, for example, urea, etilenmocevina, ε-caprolacton, succinimide, thiourea, dimethylamine or 2-pyrrolidone, and as a substituent, these compounds may be added, at least one of ethylene oxide, propylene oxide and alkyl. Preferred is also a cyclic structure, for reasons of stability of the crystalline component in the ink. Kristalloobrazuyushchikh component may be used separately or in combination of two or more kinds, if necessary. In addition, a substance which is solid in the environment of normal temperature, can satisfactorily demonstrate the effect of the image by crystallization of the crystalline component according to the present invention. The term "environment of normal temperature" means the temperature range 20-25°C, but for reasons of ease of use is beneficial to kristalloobrazuyushchikh component which is a solid substance in the environment of normal temperature, had a melting point of 30°C or higher, preferably 60°C or higher and more preferably 120°C or higher. The content of such substances in the ink can be selected in accordance with the nature of this substance, but in predpochtitelno version of this content is in the range of 1-30 wt.% from the total mass of the ink, more preferably 2-20 wt.%. Excessively low content does not allow for the effect of the present invention, and excessively high content has a detrimental effect on the release characteristics when applied to inkjet printing.

The present invention is effectively applied to the head for ink-jet printing as a means of obtaining replenishment of ink for her. Among the methods of inkjet printing, the present invention provides specific excellent effect with respect to the printhead and the system bubble-jet type.

Typical configuration and principle of operation are described, for example, in U.S. patent No. 4723129 and 4740796. This system is also applicable to the so-called process of print-on-demand and continuous printing process, but specifically applicable to the process of print-on-demand, in which at least one signal is supplied to the electrothermal converting element located under leaves or input channels containing ink, which causes a rapid temperature increase to above the boiling temperature of the cores, and thermal energy is generated in the electrothermal converting element, causes a film boiling on the surface, providing thermal effect, the printhead with the formation of a bubble in the liquid (ink), odnosno is about corresponding to the excitation signals, relevant printed information.

The ink is released through an outlet in the form of ink droplets in accordance with the inflation and cracking of the bubble. Due to the formation of excitation signals in the form of pulse signals, growth and cracking of the bubble can be done instantly and adequately to achieve the preferred release liquid (ink), in particular, find themselves excellent in response characteristics. As excitation signals are pulse signals suitable those described in U.S. patent No. 4463359 and 4345262. In addition, excellent printing can be performed by applying the conditions described in U.S. patent No. 4313124 and the corresponding invention relates to a speed increase of temperature above the heating surface.

As the configuration of the printhead, in addition to combinations outlet channel for fluid (linear channel for liquid or rectangular channel for the liquid) and the electrothermal converting element, characterized in descriptions to the aforementioned patents, in connection with the present invention is also effective configuration based on U.S. patent No. 4558333 and 4459600, revealing the configuration, having a heating part located in the curved area. In addition, the present from reenie also can be effectively applied to a configuration (not according to held examination of Japanese patent publication No. S59-123670 etc) using holes common to many of the electrothermal converting elements.

In addition, the present invention is effectively applicable to a printhead full-line type having a length corresponding to the maximum width of the carrier of printed information, which can carry out printing printing device, and such print head may have a configuration that implements such a length by a combination of multiple printheads, or configuration, built-formed only of the printhead.

In addition, the present invention is in the field of the above-mentioned printing devices of the series type, effective for the print head attached to the main body of the printing device, or the printhead cartridge type replaceable chip, ensuring electrical connection with the main body of the printing device or supply of ink from the main body by mounting on the main body, or for the printhead cartridge type, in which a built-in ink for ink provided in the printhead. In addition, in the configuration of the printer according to the present invention, it is preferable introduction recovery tools release for the print head, preliminary auxiliary means, etc., is Otomo that you can further stabilize the effect of the present invention. Specific examples of these funds may include, for example, capping means, cleaning means, a means of pressure or suction, means of pre-heating to effect the heating by the electrothermal converting element, another heating element, or a combination of these tools and preparation tools release for the implementation of the idle issue regardless of release for printing.

EXAMPLES

Below is a detailed explanation of the present invention based on examples, but these examples do not limit the scope of the claims of the present invention. The percentages indicated in the text, are percentages by weight, unless specifically indicated otherwise.

In the examples and comparative examples, the ink is prepared by mixing the following components, subsequent sufficient dissolving and/or dispersing them with sufficient stirring and implementation of filtration under pressure through a Fluoropore filter (manufactured by Sumitomo Denko Co.) with a pore size of 0.1 μm.

Example 1. The ink composition

Cabojet 300 (satisfacgermany the dye; the water-soluble group: the group of carboxylic acid, aqueous solution of 15 wt.%)6,7%
C.I. Acid Red 52 (water-soluble flu is restante the dye; the hydrophilic group: sulfonic group)0,2%
Diethylene glycol10%
Triethylene glycol10%
Surfactant of General formula (VIII) (20-mole adduct of ethylene oxide to stimulate coagulation of the water-dispersible coloring material)2%
Clean waterrest

Example 2. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)13,4%
C.I. Acid Red 520,2%
Diethylene glycol10%
Triethylene glycol10%
Surfactant of General formula (VIII) (20-mole adduct of ethylene oxide)2%
Clean waterrest

Example 3. The ink composition

Preparation of dispersion 1 pigment

The block copolymer of the type ABC, having an acid number 350 and srednecenovogo molecular weight of 5000, prepared in the usual way from benzylmethylamine, methacrylic acid and ataxiatelangiectasia, then neutralized with an aqueous solution of potassium hydroxide and diluted with ion exchange water to obtain a homogeneous 50% aqueous rest the RA polymer. 60 grams of a 50% solution of the polymer was mixed with 100 g of carbon black and 340 g of ion exchange water and mechanically stirred for 0.5 hours. This mixture was processed in microfluidizer, passing 5 times through a camera interaction under liquid pressure of about 10,000 psi (about 70 MPa) to obtain a dispersed liquid. This dispergirovannoyj fluid was centrifuged (12,000 rpm, 20 minutes) to remove coarse particles. The obtained dispersion 1 had a pigment concentration of 10% and the concentration of the dispersant of 3.5%.

The ink composition

Variance 1 pigment15%
C.I. Acid Red 289 (water-soluble fluorescent coloring matter; hydrophilic group: sulfonic group)0,1%
Glycerin8%
Triethylene glycol8%
Etilenmocevina9%
Surfactant of General formula (VIII) (0-molar adduct of ethylene oxide for coagulation water dispersible colorants)1,5%
Clean waterrest

Example 4. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)10,%
Cabojet 200 (satisfacgermany the dye; the water-soluble group: group carboxylic acid; aqueous solution of 15 wt.%)3,4%
C.I. Acid Red 520,15%
Diethylene glycol10%
Triethylene glycol10%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide for coagulation water dispersible colorants)2%
Clean waterrest

Example 5. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)6,7%
Variance 1 pigment6,7%
C.I. Acid Red 520,1%
Diethylene glycol10%
Triethylene glycol10%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide for coagulation water dispersible colorants)2%
Clean waterrest

Example 6. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)15,0%
Fluorescence is emesto And (hydrophilic group: sulfonic group) 2,0%
Glycerin8%
Triethylene glycol8%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide for coagulation water dispersible colorants)2%
Clean waterrest

Example 7. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)14,0%
C.I. Acid Red 520,1%
Fluorescent substance And2,0%
Glycerin8%
Etilenmocevina9%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)2%
Clean waterrest

Example 8. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)1,3%
C.I. Acid Red 520,1%
Fluorescent substance And2%
Diethylene glycol7%
Triethylene glycol7%
Etilenmocevina7%
Newpol GE600 (trade mark, and sotavlyaet Sanyo Chemical Co., intended for coagulation water dispersible colorants)1,0%
Clean waterrest

Example 9. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)10,0%
Cabojet 2003,4%
C.I. Acid Red 520,1%
Fluorescent substance And2%
Diethylene glycol7%
Triethylene glycol7%
Etilenmocevina7%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)2%
Clean waterrest

Example 10. The ink composition

Preparation of a dispersion of 2 pigment

The block copolymers of the type AB, having an acid number 250 and srednecenovogo molecular weight of 3000, prepared in the usual way from benzylmethylamine and methacrylic acid, then neutralized with an aqueous solution of potassium hydroxide and diluted with ion exchange water to obtain a homogeneous 50% aqueous solution of the polymer. 100 g of this 50% of the polymer solution, 100 g of the dye C.I. Pigment Red 122 and 300 g of ion exchange water were mixed and mechanically stirred for 0.5 cha is and. This mixture was processed in microfluidizer, passing 5 times through a camera interaction under liquid pressure of about 10,000 psi (about 70 MPa) to obtain a dispersed liquid. This dispergirovannoyj fluid was centrifuged to remove large particles (12,000 rpm, 20 minutes) to obtain the dispersion 2. The obtained dispersion 2 had a pigment concentration of 10% and the concentration of the dispersant 5%.

The ink composition

Variance 2 pigment6,7%
C.I. Acid Red 520,05%
C.I. Acid Red 92 (water-soluble fluorescent coloring matter; hydrophilic group: sulfonic group)0,6%
Fluorescent substance And2%
Glycerin7%
Etilenmocevina9%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)1,2%
Clean waterrest

Example 11. The ink composition

Preparation of dispersion 3 pigment

The block copolymers of the type AB, having an acid number 250 and srednecenovogo molecular weight of 3000, prepared in the usual way from benzylmethylamine and methacrylic acid, then neutral is savali aqueous solution of potassium hydroxide and diluted with ion exchange water to obtain a homogeneous 50% aqueous solution of the polymer. 180 grams of 50% of the polymer solution, 100 g of the dye C.I. Pigment Blue 15:3 and 220 g of ion exchange water were mixed and mechanically stirred for 0.5 hours. This mixture was processed in microfluidizer, passing 5 times through a camera interaction under liquid pressure of about 10,000 psi (about 70 MPa) to obtain a dispersed liquid. This dispergirovannoyj fluid was centrifuged to remove large particles (12,000 rpm, 20 minutes). The obtained dispersion 3 had a pigment concentration of 10% and the concentration of the dispersant 10%.

The ink composition

Dispersion 3 pigment0,05%
Cabojet 300 (aqueous solution of 15 wt.%)13,4%
C.I. Acid Red 520,1%
Fluorescent substance And2%
Glycerin7%
Etilenmocevina9%
Surfactant of General formula (VIII) (20-mole adduct of ethylene oxide)2%
Clean waterrest

Example 12. The ink composition

2%
Cabojet 300 (aqueous solution of 15 wt.%)13,4%
C.I. Acid Red 520,1%
Fluorescent substance And
Glycerin7%
Etilenmocevina9%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)2%
Newpol GE6001%
Clean waterrest

Example 13. The ink composition

IJX266 (water-dispersible colouring substance; water-soluble group: the group of sulfonic acids; aqueous solution of 15 wt.%)6,7%
C.I. Acid Red 520,1%
Fluorescent substance And2%
C.I. Solvent Green 7 (water-soluble fluorescent coloring matter; hydrophilic group: sulfonic group)1%
C.I. Acid Yellow 7 (water-soluble fluorescent coloring matter; hydrophilic group: sulfonic group)0,05%
Glycerin7%
Diethylene glycol5%
Triethylene glycol7%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)2%
Dodecylbenzenesulfonate sodium0,5%
Clean water rest

Example 14. The ink composition

Variance 1 pigment0,05%
Cabojet 300 (aqueous solution of 15 wt.%)13,4%
C.I. Acid Red 520,2%
C.I. Acid Red 289 (water-soluble fluorescent coloring matter; hydrophilic group: sulfonic group)0,05%
Fluorescent substance And1%
C.I. Solvent Green 71%
C.I. Acid Yellow 184 (water-soluble fluorescent coloring matter; hydrophilic group: sulfonic group)0,5%
Glycerin7%
Etilenmocevina9%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)1,5%
Clean waterrest

Example 15. The ink composition

The dispersion of the pigment12,0%
C.I. Acid Red 520,05%
C.I. Acid Red 2890,5%
Fluorescent substance And2%
Glycerin8%
Triethylene glycol8%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)1,2%
Clean waterrest

Example 16. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)13,4%
IJX253 (satisfacgermany the dye; the water-soluble group: the group of sulfonic acids; aqueous solution of 15 wt.%)0,05%
C.I. Acid Red 520,1%
Fluorescent substance And1%
C.I. Solvent Green 70,05%
Glycerin7%
Etilenmocevina9%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)2%
Clean waterrest

Example 17. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)13,4%
C.I. Acid Red 520,1%
Fluorescent substance And1,5%
Glycerin7%
Etilenmocevina9%
Ionet T60C (trade mark, manufactured Sanyo Chemical Co., p is adnanced for coagulation woodspring colorants) 2%
Clean waterrest

Example 18. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)13,4%
C.I. Acid Red 520,1%
Fluorescent substance And1,5%
Glycerin7%
Etilenmocevina9%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)2%
Isopropyl alcohol2%
Clean waterrest

Example 19. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)13,4%
C.I. Acid Red 520,1%
Fluorescent substance And1,5%
Glycerin7%
Etilenmocevina9%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)2%
Isopropyl alcohol2%
Triethanolamine0,1%
Clean waterrest

Example 20. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)13,4%
CD380 (water-soluble coloring matter; water-soluble group: group carboxylic acid; manufacturer Liedel de Haan)0,1%
Glycerin7%
Etilenmocevina9%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)2%
Clean waterrest

Example 21. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)13,4%
C.I. Acid Red 520,1%
Fluorescent substance And1,5%
Glycerin7%
Etilenmocevina9%
Surfactant of General formula (VIII) (20-mole adduct of ethylene oxide)2%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)1%
Clean waterrest

Example 22. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)13,4%
C.I. Acid Red 520,1%
Ethylene glycol10%
Triethylene glycol10%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)0,75%
Clean waterrest

Example 23. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)16,8%
C.I. Acid Red 520,1%
Ethylene glycol10%
Triethylene glycol10%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)0,75%
Clean waterrest

Example 24. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)20,0%
C.I. Acid Red 520,1%
Ethylene glycol10%
Triethylene glycol10%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)0,75%
Clean waterrest

Example 25. The ink composition

Cabojet 300 (aqueous solution of 15 wt.%)26,7%
C.I. Acid Red 520,1%
Ethylene glycol10%
Triethylene glycol10%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide)0,75%
Clean waterrest

The ink composition in comparative example 1

C.I. Acid Red 520,2%
C.I. Direct Black 154 (water-soluble fluorescent coloring matter; hydrophilic group: sulfonic group)2%
Glycerin10%
Ethylene glycol5%
Clean waterrest

The ink composition in comparative example 2

C.I. Acid Red 520,2%
C.I. Direct Black 1542%
Glycerin10%
Ethylene glycol5%
Surfactant of General formula (VIII) (10-mole adduct of ethylene oxide to dissolve the two above-mentioned dyes)1%
Clean waterOST is nioe

The ink composition in comparative example 3

Millijet Black 2000 (dye, polymer-modified)1,9%
Millijet Blue 18 (dye, polymer-modified)3%
C.I. Acid Red 520,4%
Pyranin 120 (water-soluble fluorescent coloring matter; hydrophilic group: sulfonic group)1,4%
C.I. Acid Yellow 70,2%
Simple monobutyl ether of triethylene glycol4,6%
4 methylmorpholin2,5%
Polyvinylpyrrolidone (K-12)6%
Dodecylbenzenesulfonate sodium1,1%
Clean waterrest

The ink composition in comparative example 4

Variance 2 pigment4,3%
C.I. Acid Red 520,5%
C.I. Acid Yellow 73 (water-soluble fluorescent coloring matter; hydrophilic group: the group of carboxylic acid)0,5%
2-Pyrrolidone8%
Triethylene glycol7%
Clean waterStalin is e

The ink composition in comparative example 5

Variance 2 pigment20%
C.I. Acid Red 521%
Ethylene glycol7%
Diethylene glycol7%
Triethylene glycol7%
2-Pyrrolidone8%
Clean waterrest

The ink composition in comparative example 6

C.I. Acid Red 520,5%
C.I. Acid Yellow 70,5%
Glycerin7%
Ethylene glycol7%
Diethylene glycol7%
Clean waterrest

The ink composition in comparative example 7

C.I. Food Black 2 (water-soluble fluorescent coloring matter; hydrophilic group: sulfonic group)2%
C.I. Acid Yellow 52 (water-soluble fluorescent coloring matter; hydrophilic group: sulfonic group)0,1%
Glycerin7%
Ethylene glycolDiethylene glycol7%
Clean waterrest

The ink composition in comparative example 8

Cabojet 300 (aqueous solution of 15 wt.%)13,4%
C.I. Acid Yellow 521%
C.I. Acid Yellow 731%
Glycerin7%
Ethylene glycol7%
Diethylene glycol7%
Clean waterrest

<Rating>

(Evaluation division 1 coloring substances)

Drip feed of 0.5 ml of each ink of examples and comparative examples in the industrial supply of paper for printing of documents for various purposes was performed using the industrial dropper from a height of 10 cm above the paper, and the change of the ink droplets on the paper was evaluated in accordance with the following criteria:

A: on the surface of the paper, which came a drop of ink, the first area of concentrated first coloring matter formed in the center, and a second area with a second coloring substance is clearly formed on the whole of its periphery; on the reverse side of the paper was observed the second diffusion region;

In: on the surface of the paper, where populaces ink, the first area of concentrated first coloring matter formed in the center, and a second area with a second coloring substance was weakly visible on the periphery is very close to the edge of the first region; on the reverse side of the paper was observed the second diffusion region;

With: the surface of the paper, which came a drop of ink, the area of the first coloring matter formed in the center but at the periphery were observed region of the second coloring substance; on the reverse side of the paper was observed diffusion of the second coloring substance;

D: on the surface of the paper, which came a drop of ink, the area of the first coloring matter formed in the center but at the periphery were observed region of the second coloring substance; on the reverse side of the paper was not observed diffusion of the second coloring matter.

(Evaluation division 2 of coloring substances)

Each ink of examples and comparative examples were used by the industrial supply of the printing device BJS600 (trade mark, produced by Canon Inc.) for inkjet printing, to print single-point image, which is irradiated by excitation light having a wavelength of 254 nm, using an industrial device for the irradiation of UV light (brand: Handy UV Lamp SLUV-4; izgotovleniyu Luchi), and examined the microscopic features of the image under the stereomicroscope.

The evaluation was performed in accordance with the following criteria:

A: within a point on the paper attended the fluorescent area and a large number of small coagulate without fluorescence; when examining the periphery of the point in terms of a smaller gain was observed fluorescence at the periphery of the point.

In: within point on paper attended the fluorescent area and a large number of small coagulate without fluorescence; however, the fluorescence was weak, and the separation of the first colorants and second colorants was unsatisfactory;

From: within the point on the paper there was no fluorescent area and observed the Assembly of coagulase without fluorescence.

(Evaluation of fluorescent radiation 1)

Every ink subjected to the above evaluation 1 division of coloring substances were irradiated with excitation light having a wavelength of 254 nm, using an industrial device for the irradiation of UV light (brand: Handy UV Lamp SLUV-4; produced by Luchi), subjected filed dropwise ink visually inspected and evaluated in accordance with the following criteria.

A: on the surface produced on an industrial scale paper for printing is Tania documents for various purposes, anywhere drop of ink was observed fluorescent radiation in the second region of the second coloring substance, more explicit than in the first area of the first coloring substances; in addition, the fluorescent radiation emitted by the second coloring substance was observed on the opposite surface;

In: on the surface produced on an industrial scale of paper for printing of documents for various purposes, which came a drop of ink, the fluorescence of the second coloring substance was not observed, and almost invisible fluorescence was observed in the first area of the first coloring matter; however, the fluorescent radiation emitted by the second coloring substance was observed on the opposite surface.

With: on the surface produced on an industrial scale of paper for printing of documents for various purposes, which came a drop of ink, the fluorescence of the second coloring substance was not observed, and almost invisible fluorescence was observed in the first area of the first coloring agents; fluorescent radiation of the second coloring substance on the opposite surface was not observed.

(Evaluation of fluorescent radiation 2)

Each ink of examples and comparative examples used in industrial supply printing device BJS600 (the trademark, produced by Canon Inc.) for inkjet printing, to print a solid image of 100% load and alphanumeric characters, which were subjected to a visual inspection in conditions of irradiation with excitation light having a wavelength of 254 nm, using an industrial device for the irradiation of UV light (brand: Handy UV Lamp SLUV-4; produced by Luchi) and evaluated in accordance with the following criteria:

A: in the continuous image mode, 100% load, and the alphanumeric characters was clearly observed fluorescent emission;

In: continuous image mode, 100% load, and the alphanumeric characters were slightly observed fluorescent emission;

With: a solid image mode, 100% load, and the alphanumeric characters hard to see fluorescent radiation.

(Evaluation of fluorescent radiation 3)

Each ink of examples and comparative examples used in industrial supply printing device BJS600 (trade mark, produced by Canon Inc.) for inkjet printing, to print a solid image of 100% load continuous image mode 50% load, and tested these images using industrial supply unit FP-750 (trade mark, produced by Nippon Keiko Co.) the La measurement of fluorescence intensity upon excitation at 254 nm. The evaluation was performed in accordance with the following criteria:

A: the maximum fluorescence intensity in the region of visible light (400-700 nm) was 200 or more;

In: the maximum fluorescence intensity in the region of visible light (400-700 nm) was 100 or more, but less than 200;

With: the maximum fluorescence intensity in the region of visible light (400-700 nm) was less than 100.

(Quality assessment)

Each ink of examples and comparative examples used in industrial supply printing device BJS600 (trade mark, produced by Canon Inc.) for inkjet printing, to print images and alphanumeric characters with different densities of the print produced on an industrial scale paper for printing of documents for various purposes, and visually evaluated prints in accordance with the following criteria:

A: the definition of alphanumeric characters was satisfactory, and the images obtained at different densities of the print, not observed grain size, which ensured the smooth and satisfactory print quality;

In: the clarity of alphanumeric characters was satisfactory, but in images obtained at different print densities were observed grain size;

From: clarity of alphanumeric characters was unsatisfactory is, in images obtained at different print densities were observed grain size.

(Density estimation)

Each ink of examples and comparative examples used in industrial supply printing device BJS600 (trade mark, produced by Canon Inc.) for inkjet printing, to print a solid image 50% load produced on an industrial scale paper for printing of documents for various purposes, and after a satisfactory fixation of the image for 1 day in an environment of normal temperature and normal humidity measured print density using a MacBeth densitometer RD918 in accordance with the following criteria:

A: the density was 1.0 or more;

In: the density was 0.8 or more but less than 1.0;

C: the density was less than 0.8.

(Evaluation of resistance)

Each ink of examples and comparative examples used in industrial supply printing device BJS600 (trade mark, produced by Canon Inc.) for inkjet printing, to print a solid image 50% load produced on an industrial scale paper for printing of documents for various purposes, which, after exposure for 24 hours, immersed in tap water for 5 minutes and evaluated the change in density is Ekati using a MacBeth RD918 in accordance with the following criteria:

A: the change in density was less than 20%;

In: the changing density was 20% or more but less than 50%;

With: the change in density was 50% or more.

(Measurement of contrast of print)

Each ink of examples 1-9, 11, 12, 14, 16-19 and comparative examples 1-3 and 6-8 used in industrial supply printing device BJS600 (trade mark, produced by Canon Inc.) for inkjet printing, to print a solid image 50% load produced on an industrial scale paper for printing of documents for various purposes, which, after exposure for 24 hours were subjected to density measurement in reflected light using a reflective densitometer SM (trade mark, produced by Minolta Ltd.). Ink examples provided satisfactory contrast across the wavelength range of 400-700 nm, but the contrast was poor in the case of the ink of comparative examples. On Fig shows the difference in contrast between the ink of example 12 and comparative example 3.

(Evaluation results)

The results of the estimations are shown in the following tables.

EXAMPLES

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Division 1 coloring substancesAndAndAndAndAndAndAndAndAndAnd
Division 2 coloring substancesAndAndAndAndAndAndAndAndAndAnd
Evaluation of fluorescent radiation 1AndAndAndAndAndAndAndAndAndAnd
Evaluation of fluorescent radiation 2AndAndAndAndAndAndAndAndAndAnd
Evaluation of fluorescent radiation 3AndAndAndAndAndAndAndAndAndAnd
Quality assessmentAndAndAndAndAndAndAndAndAndAnd
The density estimationAnd AndAndAndAndAndAndAndAndAnd
Evaluation of water resistanceAndAndAndAndAndAndAndAndAndAnd

111213141516171819202122232425
Division 1 coloring substancesAndAndAndAndAndAndAndAndAndAndAndAndAnd±±
Division 2 coloring substancesAndAndAndAndAndAndAndAndAndAndAndAndAndAndAnd
Evaluation of fluorescent radiation 1AndAndAndAnd AndAndAndAndAndAndAndAndAndAndAnd
Evaluation of fluorescent radiation 2AndAndAndAndAndAndAndAndAndAndAndAndAndAndAnd
Evaluation of fluorescent radiation 3AndAndAndAndAndAndAndAndAndAndAndAndAnd±±
Assessment

quality
AndAndAndAndAndAndAndAndAndAndAndAndAndAndAnd
The density estimationAndAndAndAndAndAndAndAndAndAndAndAndAndAndAnd
Evaluation wodostock the STI AndAndAndAndAndAndAndAndAndAndAndAndAndAndAnd

COMPARATIVE EXAMPLES

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Division 1 coloring substances
Division 2 coloring substances
Evaluation of fluorescent radiation 1
Evaluation of fluorescent radiation 2InInB
Evaluation of fluorescent radiation 3In
Quality assessmentAndAndAndAndAndAndAndAnd
The density estimationAndAndAndAndAndAndAndAnd
Evaluation of water resistanceInInInIn

(Evaluation of resistance to freezing)

About 100 ml of each ink of examples was placed in a Petri dish, and then left to stand for about 1 month in an environment having a temperature of 25°C and humidity 55%, for evaporation of water in the ink. After this was added the amount of water lost and evaluated the property is re-dissolving ink. The ink, which used water-dispersible colouring substance samodopomoga type, re-dissolved, and in ink, using a polymeric dispersant, the property is re-dissolution proved unsatisfactory.

As explained above, the present invention proposed a separate fluorescent water-based ink, fluorescent printed image and a printing method that ensures the durability of the images, as well as the properties of color and fluorescence. In addition, satisfactory was the reliability, for example, resistance to freezing and property release.

In addition, the present invention ensures the recognition of the obtained printed image with multiple colors. In particular, the present image solves the problem of decrease in fluorescence intensity due to the overlap of the wavelength of light and the wavelength of light absorption, thereby providing a satisfactory fluorescent image.

In addition, the ink according to the present invention when they are used to implement the method of inkjet printing, show satisfactory reliability. In particular, the ink, in which the water-dispersible coloring agent is satisfacgermany the dye, can reduce the accumulation of ink around the nozzle during continuous production, as well as on the blade, which removes the ink adhered on the surface carrying the nozzle, that is a beneficial effect.

In addition, as shown by the assessment of the "contrast typo", ink according to the present invention provide sufficient contrast, and, as shown by the evaluation of the fluorescence of individual fluorescent water-based ink according to the present invention provide the more satisfactory fluorescent radiation.

In this application claimed priority claim of Japanese patent publication No. 2003-162988, filed may 2, 2003, which is incorporated herein by reference.

1. Fluorescent water-based ink containing a first coloring substance, a second coloring agent and a liquid medium and water for dissolving or dispersing these coloring substances, and at least one of the first coloring substance and the second coloring substance is a fluorescent coloring matter, and the aforementioned ink provide education on the media printed information of the first area in which first concentrated the dye with the second coloring substance, and a second area in which there is only a second coloring material and which surrounds the periphery of the first region, including the area in the medium of printed information, where the first the dye is water-dispersible colouring substance containing some amount of water-dispersible particles, and the second coloring substance is a water-soluble coloring matter, and where the first region includes many bystrorezhuschej spots first colorants, scattered spots on the second colorants, each of bystrorezhuschej toe is h contains some amount of water-dispersible particles of the first coloring matter in a coagulated state.

2. The ink according to claim 1, in which the fluorescent radiation from the second region is stronger than the fluorescent radiation from the first region.

3. The ink according to claim 1, additionally containing surfactant that provides dissolving or dispersing a water-soluble coloring substances in larger quantities than water-dispersible coloring matter.

4. The ink according to claim 3, in which the surfactant is nonionic.

5. The ink according to claim 1, in which the water-dispersible coloring material is a coloring substance, which is not fluorescent in the media, printed information, and a water-soluble dye as the coloring substance is a substance that is fluorescent in the media printed information.

6. The ink according to any one of claims 1 and 2, in which the second coloring substance has a wavelength range of fluorescent radiation within the wavelength range of absorption of the first coloring matter.

7. The printed image formed on a medium printed information containing the first region surrounded by the second area and the first area focuses first the dye with the second coloring substance, as specified in the second area, there is only a second coloring substance, surrounding the entire paragraph is RIVERIA first area, including the site in the media printed information, while at least one of the first coloring substance and the second coloring substance is a fluorescent coloring matter, where first the dye is a water-dispersible colouring substance containing some amount of water-dispersible particles, and the second coloring substance is a water-soluble coloring matter, and where the first region includes many bystrorezhuschej spots first colorants, scattered spots on the second colorants, each of bystrorezhuschej spots contains some amount of water-dispersible particles of the first coloring matter in a coagulated state.

8. The printed image according to claim 7, in which the fluorescent radiation from the second region is stronger than the fluorescent radiation from the first region.

9. The printed image according to claim 7, in which the second region is formed by diffusion of surface-active substances.

10. The printed image according to claim 9, in which the surfactant is nonionic.

11. The printed image according to claim 7, in which the water-dispersible coloring material is a coloring substance, which is not fluorescent in the media printed information is AI, and a water-soluble dye as the coloring substance is a substance that is fluorescent in the media printed information.

12. The printed image according to any one of claims 7 to 11, in which the second region has a wavelength range of fluorescent radiation within the wavelength range of absorption of the first region.

13. The method of forming the printed image, including the stage at which the media printed information form the image of the set of points by applying a fluorescent water-based inks containing a first coloring agent and the second coloring substance, method of inkjet printing, where the specified image contains the first area in which first the dye is concentrated with the second coloring substance, and a second area in which there is only a second coloring material and which surrounds the entire periphery of the first area, including the area in the printed media of information with at least one of the first colorants and second colorants is a fluorescent coloring matter, where first the dye is a water-dispersible colouring substance containing some amount of water-dispersible particles, and the second coloring substance is water the soluble coloring matter, where the first region includes many bystrorezhuschej spots first colorants, scattered spots on the second colorants, each of bystrorezhuschej spots contains some amount of water-dispersible particles of the first coloring matter in the coagulated state, and where the fluorescent water-based ink is applied so that the corresponding first region is not in contact with each other between the points.

14. The method of forming the printed image, including the stage at which the media printed information form the image of the set of points by applying a fluorescent water-based inks containing a first coloring agent and the second coloring substance, method of inkjet printing, where the specified image contains the first area in which first the dye is concentrated with the second coloring substance, and a second area in which there is only a second coloring material and which surrounds the entire periphery of the first area, including the area in the medium of printed information, and at least one of the first coloring substance and the second coloring substance is a fluorescent dye substance, where first the dye is photodisintegration substance, containing some amount of water-dispersible particles, and the second coloring substance is a water-soluble coloring matter, where the first region includes many bystrorezhuschej spots first colorants, scattered spots on the second colorants, each of bystrorezhuschej spots contains some amount of water-dispersible particles of the first coloring matter in the coagulated state, and where the fluorescent water-based ink is applied so that the corresponding first region is not in contact with each other between the points and the specified image has a different resolution in the longitudinal direction and the transverse direction.

15. Fluorescent water-based ink containing the water-dispersible coloring substance having a free carboxyl group as the main water-soluble groups, a water-soluble coloring matter having a free alphagroup in the quality of the main water-soluble group, a surfactant, providing the possibility of dissolving or dispersing a water-soluble coloring substances in larger quantities compared to the water-dispersible coloring material and water, where water-dispersible colouring substance isone the dye, which is not fluorescent in the media, printed information, and a water-soluble dye as the coloring substance is a substance that is fluorescent in the media printed information.



 

Same patents:

FIELD: printing engineering.

SUBSTANCE: invention, in particular, relates to a method of printing allowing protection of printing materials against counterfeit reprints, for instance in fabrication of banknotes, shares, checks, and other valuable paper documents. Invention provides printing liquid for printing through narrow nozzles onto objects, in particular when fabricating banknotes, shares, and checks, which liquid comprises carrying medium and nanoparticles of metal salts in the form of crystalline solid particles having average diameter less than 300 nm, which fluorescent and phosphorescent when excited by UV emission of the A, B, or C band, or visual light, while emitted fluorescent and phosphorescent waves do not lie in the visual light frequency region and excitation frequency region and emission frequency region are shifted in frequency scale. Nanoparticles contain enhancing additives of at least one type having excitation and emission frequency ranges corresponding to fluorescence and phosphorescence. Provided is also printing method including injecting of above-described liquid(s) through one or several narrow nozzles, which are regulated individually or by groups in relation to availability or lack of printing liquid and in relation to duration or intensity of flowing of printing liquid. Printing method is either piezoelectric method or jet printing one. Employment of proposed liquid for ink-pots and object marking, in particular when fabricating banknotes, shares, and checks involving printing equipment provided with one or several narrow nozzles is also described.

EFFECT: increased reliability of protection.

15 cl, 2 dwg

FIELD: chemical industry; printing industry; powder metallurgy industry; cosmetic industry; other industries; production and application of the highly anticorrosive metallic pigments.

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EFFECT: the invention ensures the increased anticorrosive resistance of the metallic pigments, saving the initial surface smoothness of the similar to the laminas metallic substrates, the increased homogeneity and density of the layers of the hydrated metals oxides.

40 cl, 9 ex, 4 tbl, 8 dwg

FIELD: chemical industry; computer industry; methods of production of the pigments used in the coatings of the registering medium of ink-jet systems.

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FIELD: special compositions.

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2 tbl

FIELD: chemical industry; printing industry; other industries; methods of production of the composition of the paint including the optically changeable pigments.

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22 cl, 7 ex

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EFFECT: enhanced efficiency.

25 cl, 6 dwg, 2 tbl, 4 ex

FIELD: marking and identification of protected articles, such as bank-notes, service papers, labels, foil, fiber, card or industrial products.

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EFFECT: improved quality of electrographic printing.

2 cl, 1 tbl, 4 ex

FIELD: chemical industry; methods of production of the coatings with the strong adhesion.

SUBSTANCE: the invention is pertaining to the method of production of the coatings with the strong adhesion on the inorganic or organic substrate, which provides, that one inorganic or organic substrate is subjected to the treatment with the low-temperature plasma, the corona discharge or the treatment with the gaseous flame, at the normal atmospheric pressure deposit on the inorganic or organic substrate one or several photoinitiating agents or the mixtures of the at least one ethylene- unsaturated with the monomers and-or the oligomers containing at least one ethylene- unsaturated group, or the solutions, suspensions or emulsions of the above indicated substances using the suitable methods; the above indicated substances are not necessary subjected to drying and-or to the electromagnetic irradiation; and either on the preliminary so treated substrate deposit the composition including at least one ethylene- unsaturated monomer or the oligomer and the coating is subjected to hardening under action of the UF/ the visual rays emission or the electron beam; or on the substrate with such a preliminary coating made out of the photoinitiating agent they apply the printing ink coating and dry it. The method has the high efficiency and allows to produce the coating with the good adhesion and is suitable for to production of the products made out of the various plastics materials and-or metals or the glass types with the coatings having the good adhesion.

EFFECT: the invention ensures the high efficiency of the method, production of the highly adhesive coatings suitable for manufacture of the products made out of the various plastics materials, metals or the glass types.

18 cl, 19 ex

FIELD: chemical industry; polygraphy; methods of the stencil printing.

SUBSTANCE: the invention is pertaining to the paint suitable for the stencil printing inside the pressurized castings. The invention describes the paint suitable for the printing films made out of the transparent thermoplastic, consisting predominantly of: a) one or several pigments; b) the binding in the solution in c) the organic solvent or in the mixture of the organic solvents, d) the routine auxiliary materials, if it is desirable, at that as the binding use the copolymer of the poly-(metha)-acrylate containing (м1) from 50 up to 90 % to the mass of alkylmethacrtlate having from 1 up to 6 atoms of carbon in the ethereal radical; (м2) from 5 up to 25 % to the mass, at least, one vinylaromatic compound; (м3) from 1 up to 25 % to the mass of maleic anhydride, and if it is desirable, (м4) from 0 up to 5 % to the mass of the alkylacrylate having from 1 up to 6 atoms of carbon in the ethereal radical or the copolymer of the poly-(metha)-acrylamide containing polymethylmethacrylate with the degree of imidization from 65 up to 80 %, to 1 up to 15 mass % of methacrylic acid and from 1 up to 15 mass % of methacrylic anhydrade. At that the indicated copolymer has the softening temperature by VIKA (ISO 306 B) at least of 115°С. As the dissolvents use aliphatic, cycloaliphatic and aromatic hydrocarbons, ketones, esters, ethers, alcohols, phenoles or their mixtures. The invention also describes the film made out of the thermoplastic printed by the above described paint; the pressurized casting consisting of the film made out of the thermoplastic printed on the opposite side with the above described paint and supplied on this side with the layer of the thermoplastic coating. At that the indicated layer is applied by the operation of pressure die casting on the inside and at that the film and-or the plastic material for operation of the pressure die casting on the inside represents the copolymer of polymethylmethacrylate; and the method of production of the pressurized castings includes the following stages: a) stencil printing of the thermoplastic films by the above described method, b) the film molding, c) the pressurized castings on the inside on the stencil printed film side in the casting mould with the thermoplastic, and d) removal of the pressurized casting from the casting mould. The technical result of the invention: the paint is resistant to the action of the high pressures and temperatures during the operation of the pressurized casting on the inside, the image stencil printed by the paint has the stable color after long-term action of the atmospheric conditions.

EFFECT: the invention ensures, that the paint is resistant to the action of the high pressures and temperatures during the operation of the pressurized casting on the inside, the image stencil printed by the paint has the stable color after the long-term action of the atmospheric conditions.

6 cl, 1 tbl

FIELD: image generation.

SUBSTANCE: image generation element includes chemical compound in crystalline form, which transforms to amorphous form, which has its own color, different from color of crystalline form. Image generation temperature mainly does not depend on time of heating.

EFFECT: increased efficiency.

2 cl, 8 app, 3 dwg

FIELD: image generation.

SUBSTANCE: image generation element includes chemical compound in crystalline form, which transforms to amorphous form, which has its own color, different from color of crystalline form. Image generation temperature mainly does not depend on time of heating.

EFFECT: increased efficiency.

2 cl, 8 app, 3 dwg

FIELD: method and device for colored flexography.

SUBSTANCE: method for applying multiple paint layers onto a substrate includes following stages: application onto a substrate of at least one painting layer of energy-hardened liquid paint with viscosity less than approximately 4000 centipoises, and including reaction-incapable paint thinner, where applied layer of energy-hardened paint has first viscosity; evaporation of at least a part of reaction-incapable paint thinner from applied paint layer for increasing viscosity of applied layer of energy-hardened paint; application onto substrate and applied layer of energy-hardened paint with increased viscosity of at least one layer of non energy-hardened liquid paint, viscosity of which is less than increased viscosity of previously applied layer of energy-hardened paint; and drying of both paint layers on the substrate. Another variant of method for applying multiple paint layers onto a substrate is differentiated by applied layer of energy-hardened paint having to be of increased viscosity compared to following layer of energy-hardened liquid paint with viscosity less than approximately 4000 centipoises, and containing reaction-incapable paint thinner, where viscosity of following layer is less than increased viscosity of energy-hardened paint layer applied beforehand. Also a method is suggested for printing multiple paint layers on a substrate, which includes stage of selection of first and second energy-hardened liquid flexography paint, where each paint contains viscosity controlling reaction-incapable paint thinner, consisting of water in amount of from 5% to 50% of thinner weight, where each paint has viscosity approximately ranging from 30 to 70 centipoises, and stage of serial application of first and second energy-hardened liquid flexography paint onto a substrate to create first and second paint layers, having overlapping parts, where second paint is applied only after at least a part of paint thinner is evaporated in first paint layer. Device for serial application of multiple overlapping paint layers onto a substrate contains substrate route and substrate drive for moving the substrate along a route, where paint application sections are adapted for applying paint onto substrate, which paint includes reaction-incapable paint thinner and has viscosity less than 4000 centipoises, and also management system, which manages transportation of substrate along a route. Viscosity of first layer of liquid paint, applied onto a substrate in one of paint sections, is increased due to evaporation of at least a part of paint thinner from first paint layer to higher viscosity compared to viscosity of second paint, applied on top of first paint layer in next paint section, located at a certain distance from first paint section, up to viscosity, sufficient for "crude" application of second liquid paint layer during transportation of substrate between paint sections.

EFFECT: in suggested methods, relief printing is achieved without insignificant modifications of printing equipment.

4 cl, 2 dwg

FIELD: chemical industry; computer industry; methods of production of the pigments used in the coatings of the registering medium of ink-jet systems.

SUBSTANCE: the invention is pertaining to production of the pigments suitable for usage in the compositions of the registering mediums used for the ink jet printing. The invention provides, that the surface of the pigmental loose material is subjected to action of the water-soluble salt of the polyvalent metal in the aqueous medium. The treated surface of the particles gains the sizeable cationic surface charge. The salt represents the metal salt of the Group II or the Group III of Periodic table. The registering mediums for the ink-jet printing treated with the coating composition containing the indicated pigment ensure the high density fast-drying and anti-bleeding colorful images with the sufficient water-resistance. The compositions used for creation of the coating also have the advantage pertaining to the net cost and to the improved rheology at the more higher content of the pigment in the coating as compared with the coatings based on the siliceous pigments.

EFFECT: the invention ensures production of the coatings with the indicated pigment having the high density, fast-drying and anti-bleeding colorful images with the sufficient water-resistance at the low net cost, the improved rheology at the more higher content of the pigment in the coatings, as compared with the coatings based on the siliceous pigments.

30 cl, 5 dwg, 7 tbl, 7 ex

FIELD: pulp-and-paper industry.

SUBSTANCE: coating composition consisting of ink-compatible pigment, binder, and cationic fixative is deposited onto one of the sides of based paper and the other side is covered with detwisting coating, after which coating is ennobled by means of supercalendering. As pigment, mixture of amorphous silicon dioxide with calcium carbonate or kaolin with outer specific surface 60-85 m2/g at ratio (25-50):(75-50). Binder is a mixture of polyvinyl alcohol with latex selected from class of styreneacrylic copolymers at ratio (20-25%):(7-18%) based on the weight of pigment. Cationic fixative is poly(diallyldimethylammonium chloride), which is directly incorporated into coating composition in amount 5-10%.

EFFECT: enabled image quality and paper surface strength control.

3 cl, 1 tbl, 13 ex

FIELD: pulp-and-paper industry.

SUBSTANCE: coating composition consisting of ink-compatible pigment, water-soluble binder, and cationic fixative is deposited onto one of the sides of based paper and the other side is covered with detwisting coating, after which glossy surface is formed. Coating composition is supplemented by wettability controlling agent based on polydimethylsiloxane resins in amounts 0.4 to 1.6% of the weight of pigment. Water-soluble binder is a mixture of polyvinyl alcohol with polyvinylpyrrolidone at ratio (90-50):(10-50) in amount 40-60% and styreneacrylic latex in amount 15-20% of the weight of pigment. When forming glossy surface, polyethylene oxide-based plasticizer is used in amount 7-15% of the weight of pigment followed by supercalendering at pressure in roll contact zone 20-25°C and temperature 50-90°C.

EFFECT: improved manufacturability of process.

5 cl, 1 tbl, 54 ex

FIELD: negative printing forms developed in printing machine, which may be exposed by ultraviolet, visible or infrared radiation.

SUBSTANCE: cover-forming composition is described, which includes (i) polymerization-capable compound and (ii) polymer binding agent, containing polyethylene-epoxide segments, where polymer binding agent is selected from group which consists of at least one added copolymer, containing polymer of the main chain and polyethylene-epoxide side chains, block copolymer, containing at least one polyethylene-epoxide block and least one non polyethylene-epoxide block, and combinations of these. Also described is an element, in which image may be formed, including base and polymerization-capable covering composition.

EFFECT: differentiation between image sections exposed and non-exposed by electromagnetic radiation, facilitating development of non-exposed sections in water developing agents, increased resistance to development of exposed sections, ensured coloration capacity of the latter when not heated before development.

5 cl, 3 dwg, 11 ex

FIELD: protective members for visual controlling of authenticity of printing product such as security papers, banknotes, identification cards.

SUBSTANCE: protective member is formed as color layer applied to substrate and having color-free portions produced by exposing color layer to laser radiation for forming of image detected by visual control. Substrate surface is provided with relief, said image being formed on at least one side of relief after exposing to laser radiation falling at predetermined angle to relief surface. Protected printing product is equipped with protective member for visual controlling of paper authenticity.

EFFECT: increased extent of protecting printing products due to creation of protective member more complicated for counterfeit and using optical variable image.

7 cl, 5 dwg

FIELD: self-copy papers.

SUBSTANCE: group of inventions relate to use of microcapsules containing color reaction component. Color reaction component is first dissolved in solvent, namely vegetal oil C1-C8-alkyl ester, and to thus obtained solution a non-solvent is admixed at rapid stirring, said non-solvent not dissolving or dissolving insignificantly color reaction component and being taken in amount as to form supersaturated solution. The latter is directly emulsified in water phase at rapid stirring and, immediately after that, resulting emulsion is processed so that encapsulation takes place therein. Microcapsules obtained in this way are further described as well as their employment in color reaction paper.

EFFECT: improved writing quality and economic and environmental advantages.

33 cl, 1 dwg, 4 ex

FIELD: the invention refers to a multiplayer body.

SUBSTANCE: the multi-layer body fulfilled as a carbon film preferably as hot stamping film or as laminated film consists of layer structure formed with a substrate, a layer sensitive to laser emission where layered structure has one background layer which serves for laser emission as reflective and/or opaque , and/or absorbent which is correlated with a layer sensitive to laser emission. The background layer is located in one partial field on the side inverted to the layer sensitive to laser emission and provides so that laser emission does not pass or pass in a very insignificant degree into the layers below the background layer so that sufficient destruction of the substrate is averted under influence of used laser emission.

EFFECT: creation of multi-layer element that ensures possibility of forming exceptionally accurate and many-sided marking induced with laser.

18 cl, 10 dwg

Printing device // 2256560

FIELD: printing devices.

SUBSTANCE: device has feeding section, meant for feeding paper for printing one sheet after another separately, and transporting route, passing, actually, linearly for transporting printed data carrier, having high rigidity. A portion of feeding section is overlapped with transporting route in vertical transverse direction, but does not in direction, perpendicular to direction of transporting of carrier of printed information.

EFFECT: simplified construction, lower costs, higher reliability, broader functional capabilities.

18 cl, 22 dwg

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