Printing ink containing a plurality of fluorescent coloring materials and a method of jet application of ink

FIELD: print engineering.

SUBSTANCE: invention provides ink containing first fluorescent color material emitting fluorescence at specified emission wavelength used for measurement or determination of excitement at specified excitement wavelength; and second fluorescent color material emitting fluorescence when excited at specified excitement wavelength, said second color material being contained in larger amount than said first color material. To obtain fluorescence at desired emission wavelength, excitement spectrum of the first color material in ink should have peak wavelength range adjoining specified fluorescent wavelength, and emission fluorescence spectrum of the second color material has emission wavelength range that includes at least above-mentioned peak wavelength range.

EFFECT: enhanced fluorescence intensity due to presence of several fluorescent coloring substances.

9 cl, 26 dwg, 3 tbl, 6 ex

 

The invention relates to a printing ink containing multiple fluorescent coloring materials, applicable for such printing devices, such as inkjet printers, printing machines, plotters and line by line printers, and others; and printing ink are designed to improve the fluorescent properties of the image printed this paint; and to a method of spray application of the printing ink. In particular, the present invention provides a non-novel method of improving characteristics of the fluorescence of the second fluorescent coloring material in the printing ink containing the first fluorescent coloring material; and the first coloring material creates fluorescence with light radiation of a given wavelength of excitation, and the values of the wavelength of the fluorescence include a given wavelength of fluorescence to measure or definition.

The LEVEL of TECHNOLOGY

In recent years, from the colors you want the possibility of their various applications. Among them: in addition to the aesthetic formation of color images is proposed, for example, the use of fluorescent paint to provide information (such as security information) - in addition to visual information by printing information such as characters, figures, symbols or barcodes E. the second ink on the recording medium, and by the irradiation of UV light of the appropriate wavelength for the formation of the color of fluorescence of the fluorescent paint. In particular, in the system information reading authentication (anti-counterfeiting) or information security using the device for fluorescence excitation and read its intensity fluorescent dye is excited by exciting light radiation of a given wavelength (for example, 254 nm) for fluorescence, and the fluorescence is determined or measured.

As coloring materials in the ink dyes can easily provide the desired color, but sometimes they have a low resistance; and pigments can provide good water resistance, but not the desired shade of color. In view of the foregoing proposed paint containing both dye and pigment to receive paint, providing the image with good perspective and water resistance, and color hue. For example, patent publication Japan No. S60-45669 (Patent document 1) discloses damaging the paint-liquid that contains water-soluble red dye (for example, Acid Red 52) and red pigment as applied substances, and a polymeric dispersant for dispersing the pigment in a liquid medium.

In the postal systems of the United States distributed printing fluorescent to what asnau paint; and this dye Acid Red 52 (AR52)described in the above publication is used as a fluorescent dye. U.S. patent No. 6176908 (Patent document 2) discloses an ink containing a fluorescent dye, a pigment and a polymer as a dispersant of the pigment, whereby AR52 is a fluorescent dye. It should be noted that before the advent of U.S. patent No. 6176908 was well known technical solution to control the final color shade using a combination of dyes according to visual perception.

U.S. patent No. 6176908 (Patent document 2) proposes the ink for ink-jet printing containing pigment, in addition to the fluorescent dye, to improve the water resistance of the paint - as in accordance with the patent publication Japan No. S60-45669 (Patent document 1); this patent proposes the introduction of two kinds of fluorescent dyes for known object visual color control, and also additives for increasing fluorescence intensity (level of photometric units) of the system. Specific examples of the dye with high fluorescence intensity (level of photometric units) contains solvent, such as water, 2-pyrrolidone, tetraethylene glycol, and the following fluorescent coloring materials, non-pigment component, the polymer and tetraethyleneglycol, or diethylene glycol. As fluorescent coloring materials are available, for example, a combination of AR52 (0,4; 0,5 - 3,0 wt.%) and one substance from the following groups: AY7, AY73 and AU, and a combination of basic violet (RHDB) and basic yellow (BY40).

Lined patent application No. H11-80632 (Patent document 3) discloses an invisible fluorescent water-based paint containing three different fluorescent coloring material (increasing the brightness of a fluorescent substance, a yellow fluorescent dye is a derivative of coumarin and red fluorescent dye: rhodamine b or rhodamine-6G); and discloses a method of printing postcards with this paint. According to the description of this publication, each of these three fluorescent coloring material emits light under ultraviolet radiation for excitation of another coloring material sequentially to the final fluorescence with a peak wavelength equal to 587 nm. But this publication does not have a specific description of the values of the wavelength of excitation, and this description is based on the fact that the ink and the printed image have the same characteristics of fluorescence. In General: water absorbs UV light radiation, and therefore the fluorescence caused by the image will be different from the fluorescence used for paints. According to this invention with the under mentioned publication is technically false.

WO 02/092707 (Patent document 4) discloses a paint made with the possibility of the formation of a dark image and also with the possibility of fluorescence of a given color when exposed to stimulating rays. Paint contains many dyes (for example, red and yellow fluorescent dye, blue dye and black dye) is similarly laid patent publication Japan No. H11-80632, but differs from this publication that the dyes are selected such that the absorption band of greater wavelength and an emission band with a shorter wavelength will not be each other to overlap. In the above-mentioned publication, the relationship between the fluorescent coloring materials not analyzed sufficiently, and therefore the desired intensity of the fluorescence is not always possible to get.

Lined patent application of Japan No. 2003-113331 (Patent document 5) discloses the invention to enhance the performance of the fluorescence dye in the relationship between solvents and fluorescent coloring materials. That is, Patent document 5 discloses designed for applying paint, which contains two fluorescent coloring material of the same color (the example of the introduction afluorescent coloring material), two different organic solvent (for example, the R, glycerol and non-ionic surfactant), incompatible with each other, and clean water for dissolving these components.

Patent documents

1. Patent publication Japan No. S60-045669.

2. U.S. patent No. 6176908.

3. Lined patent application of Japan No. H11-080632.

4. WO 02/092707.

5. Lined patent application of Japan No. 2003-113331.

The INVENTION

Conventional paints containing the combination of many fluorescent dyes, combine only some of their characteristics, in order to increase the intensity of fluorescence at a given wavelength fluorescence (for example, a band in the range of 580-620 nm or a wavelength of fluorescence in this range). That is, the above-mentioned publications do not provide a way that could increase the intensity of fluorescence of the first fluorescent coloring material in the specified area of the wavelength (for example, 580 - 620 nm) when exposed to a given excitation by light radiation in conjunction with other fluorescent coloring material (hereinafter - "the second coloring material"). Therefore, the technical problem solved by this invention include the analysis of the relationship between multiple fluorescent dyes, the characteristics of the paint, the paint composition and the formed image. Therefore, the main objective of the present invention zaklyuche is to create a new way of ensuring the fluorescence intensity of the most effective way with many fluorescent dyes based on substantial analysis of the phenomenon of "fluorescence". Accordingly, the authors of the present invention have conducted fundamental and technical study of the phenomena of fluorescence and its mechanism. For example, the authors investigated the following phenomenon: despite the fact that the above-mentioned fluorescent dye AR52 emits sufficient red fluorescence even in the ink containing water, which absorbs UV light radiation, the image obtained with this dye shows weak fluorescence when excited using UV-light radiation. The study of this phenomenon found that the wavelength of the excitation AR52 for emitting red fluorescence is distributed not only in the UV region, but also in the field of visible light, and the fluorescence intensity affects the locking state of the dye in the medium of paint. Therefore, the main objective of the present invention is to conduct technical analyses to the development of the method of the maximum of the exciting light beam, and to develop ways of bringing in the locking state of the dye in the deposited image so that it is suitable for fluorescence.

If AR52 is used as the first coloring material, a significant fluorescence intensity is provided after the evaporation of water from a paint containing 0.01 to the AC.% AR52 or less. But there are other issues that need to be considered: loss of the coloring material in the medium of the applied ink to a sheet of paper or envelope, not fixed on the surface of the fibers; and the problem of concentration quenching, when the fluorescence intensity of the coloring material is reduced with the increase of the first and second coloring materials in the ink. You should also note that the energy source is limited to the specified light radiation excitation. Other calculations will be understood from the following description.

Therefore, the present invention solves at least one of the formulated tasks (preferably multiple tasks) to increase the intensity of fluorescence compared to the usual technical standard.

The first task of the present invention is to provide a printing ink made with the possibility of increasing the intensity of its fluorescence at a standard wavelength of excitation, resulting in its energy efficiency is improved due to the fact that the utmost attention is paid to the correlation between the fluorescence of the second coloring material generated by the impinging light radiation with a given wavelength excitation wavelength of excitation of the first coloring material to obtain the specified wavelength (gave the e - "given a single wavelength or range of fluorescence").

The second objective of the present invention is to provide a printing ink made with the possibility of increasing the intensity of its fluorescence at a given wavelength excitation, resulting in its energy efficiency is significantly increased due to the fact that the utmost attention is paid to the absorption spectrum of the first coloring material and the fluorescence of the second coloring material, generated by exposure to light radiation having a given wavelength excitation.

The third objective of the present invention is to provide a printing ink made with the possibility of increasing the intensity of its fluorescence at a given wavelength due to the fact that the primary focus is on information obtained by analyzing the structural difference between fluorescent dyes (i.e. the number of relevant input fluorescent dyes can be increased by appropriate prohibition combining fluorescent dyes).

The fourth objective of the present invention is to provide a printing ink made with the possibility of increasing the intensity of its fluorescence at a given wavelength due to the fact that the paramount consideration is the use of paid connection with the fluorescence of the second coloring material, generated by exposure to light radiation of a given wavelength excitation with a given wavelength characteristics of the wavelength of the excitation to obtain a given wavelength fluorescence radiation of the first coloring material in addition to the third task.

The fifth objective of the present invention is to provide a printing ink made with the possibility of increasing the intensity of its fluorescence at a given wavelength a more stable image quality characteristics of the paints containing multiple fluorescent coloring materials.

The sixth objective of the present invention is to provide a printing ink made with the possibility of increasing the intensity of its fluorescence at a given wavelength, no significant depending on the type or characteristics of the recording medium (the material on which you get the picture); that is, thanks to information obtained by analyzing the generated image.

The seventh objective of the present invention is to provide a printing ink made with the possibility of increasing the intensity of its fluorescence at a given wavelength, due to the fact that the utmost attention is paid to the correlation between the characteristics of the excitation of the first coloring material is the absorption spectrum of the second coloring material - in addition to the first invention. Other problems and objectives of the present invention will be apparent from the following description. Therefore, the present invention is directed to solving at least one of the tasks listed above (preferably multiple tasks), and to provide printing inks with good intensity of fluorescence. In addition, the present invention is also directed to a method of inkjet printing the image by using the ink according to the present invention.

The present invention for solving the above-mentioned problems provides the following options for implementation. The relationship between the wavelengths in accordance with the present invention, briefly, is as follows: the wavelength range of fluorescence (see figure 3) of the second fluorescent coloring material includes at least a peak wavelength range (see Figure 2) range of wavelengths of excitation of the first fluorescent coloring material to obtain fluorescence at a given wavelength (for example, 600 nm), and, alternatively, the wavelength range of absorption in the visible region of light of the first fluorescent coloring material (see lower graph 6, we explain below).

First, according to the first implementation of the present invention to solve at least the first problem is especen printing ink, contains:

the first fluorescent coloring material that emits fluorescence at a given wavelength of radiation used for measurement or determination upon excitation at a given wavelength excitation; and

the second fluorescent coloring material that emits fluorescence upon excitation at a given wavelength excitation;

moreover, the excitation spectrum of the first coloring material in the ink to obtain the fluorescence at a given wavelength radiation has a peak wavelength range adjacent to a given wavelength of fluorescence, and the fluorescence spectrum of the radiation of the second coloring material is a region of the wavelength of the radiation, essentially containing at least the peak wavelength range.

In this case, the expression "peak wavelength range, which correspond to the peak area adjacent to a given wavelength of the fluorescence radiation of fluorescence from the first fluorescent coloring material according to the present invention has practical value in terms of efficiency of energy conversion. In other words, in the spectrum of wavelengths of excitation to obtain a given wavelength of fluorescence of the first fluorescent coloring material region having a peak adjacent to a given wavelength fluorescence, intensives the ü which is 100 or more, is defined as the peak region, and the wavelength range corresponding to this area, defined as the peak wavelength range.

Given the wavelength of excitation is preferably 254 nm, the peak wavelength range is preferably 430-600 nm, including limits. The range of the emission wavelength of the second fluorescent coloring material preferably includes a given wavelength (600 nm) of fluorescence is 425-600 nm, including limits. In addition, in the ink according to the first implementation of the present invention, the absorption spectrum of the first fluorescent coloring material preferably has a peak area in the region of visible light, and the length range of the fluorescence of the second fluorescent coloring material includes a region of shorter wavelength than the peak area of the absorption spectrum.

According to the second implementation of the present invention, which solves at least the second above-mentioned objective, provided the printing ink contained: the first fluorescent coloring material that emits fluorescence at a given wavelength fluorescence used to measure or determine when excited by light radiation of a given wavelength excitation; and a second fluorescent coloring material, which is uchet fluorescence upon excitation at a given wavelength excitation; when this region of the wavelength of the second fluorescent coloring material includes at least a main wavelength of absorption in the spectrum of the light absorption of the first fluorescent coloring material in the area of wavelength excitation to produce radiation at a given wavelength of fluorescence of the first fluorescent coloring material in the ink.

In the ink according to the second implementation of the present invention, it is preferable that the wavelength of absorption of the first fluorescent coloring material is in the range of 500-590 nm, including limits; and the wavelength of the second fluorescent coloring material has been in the area 450-600 nm, including limits.

In the ink according to the first and second implementations of the present invention the second fluorescent coloring material preferably is a coloring material having a structure with many groups fluorescence.

According to a third implementation of the present invention, a decisive third goal, provided with printing ink containing: a first fluorescent coloring material that emits fluorescence at a given wavelength fluorescence, used for measuring or determining upon excitation at a given wavelength excitation; and the second f is uorescently coloring material, which emits fluorescence upon excitation at a given wavelength excitation and increases the intensity of radiation at a given wavelength fluorescence; and the second fluorescent coloring material has many groups fluorescence.

In the ink according to the third implementation of the present invention, it is preferable that the area of the emission wavelength of the second fluorescent coloring material was a region of wavelength of excitation to obtain a given wavelength of fluorescence of the first fluorescent coloring material in the ink.

According to a fourth implementation of the present invention, decisive, at least a fourth objective, provided with printing ink containing: a first fluorescent coloring material that emits fluorescence at a given wavelength fluorescence, used for measuring or determining upon excitation at a given wavelength excitation; and a second fluorescent coloring material that emits fluorescence upon excitation at a given wavelength excitation; the second fluorescent coloring material has many groups fluorescence; and the area of the emission wavelength of the second fluorescent coloring material overlaps at least part of the region of the wavelength of excitation to provide radiation n is given wavelength fluorescence the first fluorescent coloring material of this paint.

In the ink according to the third and fourth implementation of the present invention it is preferable that each group of the multiple groups of fluorescence of the second fluorescent Crusades the material had the basic structure to ensure the brightness of its fluorescence. And the second fluorescent coloring material preferably has a lot of sulfonic groups.

In the ink according to any of the accomplishments from the first to the fourth set of bands of fluorescence of the second fluorescent Crusades material preferably are dimers. In implementations of this invention, first to fourth second fluorescent coloring material preferably is a direct dye.

Printing ink according to the third and fourth implementation of the present invention is preferably water-based paint that emits fluorescence at a given wavelength excitation; and aqueous printing ink is in the state after evaporation of water and/or condition of the printed image and spectrum of its radiation has a first peak, including the specified wavelength fluorescence, and the second peak in the region of wavelengths, the corresponding region of the wavelength of the excitation of the first fluorescent coloring material to provide radiation at a given wavelength is by fluorescence in paint.

According to the fifth implementation of the present invention to solve at least the fifth above-mentioned tasks are provided aqueous printing ink containing: a first fluorescent coloring material that emits fluorescence at a given wavelength fluorescence, used for measuring or determining upon excitation at a given wavelength excitation; and a second fluorescent coloring material that emits fluorescence upon excitation at a given wavelength excitation, which emits fluorescence of a given wavelength excitation, and water printing ink is in the state after evaporation of water and/or condition of the printed image and spectrum of its radiation has a first peak, including the specified length wave fluorescence, and the second peak in the wavelength corresponding to the region of the wavelength of the excitation of the first fluorescent coloring material to produce radiation at a given wavelength fluorescence in the paint. In the ink according to the fifth implementation of the present invention the second fluorescent coloring material may preferably have a structure with many groups fluorescence.

According to the sixth implementation of the present invention to solve at least the sixth mentioned above tasks provided with printed red is a, containing: a first fluorescent dye that emits fluorescence at a given wavelength fluorescence, used for measuring or determining upon excitation at a given wavelength excitation; the second fluorescent dye to emit fluorescence when excited at a given wavelength excitation and increase the intensity of radiation at a given wavelength fluorescence; and a solvent comprising a first solvent which has a relatively high solubility for the first fluorescent dye, and low solubility for the second fluorescent dye; and a second solvent, which provides a relatively high solubility of the second fluorescent dye, and is compatible with the first solvent.

In the ink according to the sixth implementation of the present invention, the first and second fluorescent dyes preferably may contain a sulfonic group. In addition, it is preferable that the area of the emission wavelength of the second fluorescent dye is essentially included the peak wavelength range adjacent to a given wavelength fluorescence excitation spectrum of the first fluorescent dye, to ensure that the fluorescence of a predetermined wavelength fluorescence in the paint. In the ink according to the sixth implementation is July of the invention field of the emission wavelength of the second fluorescent dye may preferably be within the scope of the wavelength of the excitation of the first fluorescent dye to provide fluorescence on a given wavelength fluorescence, except for the area corresponding to the core area of the wavelength of the absorption in the spectrum of the light absorption of the first fluorescent dye.

On the other hand, the printing ink according to the sixth implementation of the present invention may preferably be a water-based paint, in which the spectrum of radiation emitting fluorescence of a given wavelength excitation, when printing water-based paint is in a state after evaporation of the water content and/or condition of the printed image has a first peak, including the radiation at a given wavelength fluorescence, and the second peak in the region of wavelength of excitation to produce radiation at a given wavelength of fluorescence of the first fluorescent coloring material in the ink.

According to the seventh implementation of the present invention, decisive at least the seventh task, provided with printing ink containing: a first fluorescent coloring material that emits fluorescence at a given wavelength fluorescence, used for measuring or determining upon excitation at a given wavelength excitation; and a second fluorescent coloring material that emits fluorescence upon excitation at a given wavelength excitation; however, the range of which he is the wavelength of the second fluorescent coloring material includes at least a peak wavelength range, the corresponding peak area adjacent to a given wavelength of fluorescence in the wavelength range of the excitation of the first fluorescent coloring material, for a given wavelength of fluorescence, and the main range of absorption wavelength in the spectrum of the light absorption of the second fluorescent coloring material is in a shorter wavelength range than the wavelength range of the excitation of the first fluorescent coloring material. In the ink according to the seventh implementation of the present invention, a given wavelength of excitation is preferably 254 nm, and the peak wavelength range of the first fluorescent coloring material is in the range 430-600 nm, including the extent and scope of the wavelength of absorption of the second fluorescent coloring material is 440 nm or less than this value.

In the ink according to any of the accomplishments from the first to the fifth and seventh implementation of the present invention: more preferably, the printing ink contains a first solvent with a relatively high solubility with respect to the first fluorescent dye and low solubility with respect to the second fluorescent dye; and a second solvent with a high solubility with respect to the second fluorescent dye, and compatible with the TEW with the first solvent; and the third solvent that is not compatible with the second solvent and the second solvent fluorescent dye. This requirement for solvent may also improve the intensity of fluorescence of different fluorescent coloring material in accordance with the present invention.

When one of the mentioned printing inks used for inkjet printing the image, from the point of view of the fluorescence intensity of good printed image. Method of inkjet printing the image according to the present invention for the implementation of this advantage is the way in which perform ejection of ink through the discharge outlet and carry the paint to the media, which is applied to the image to perform image; the paint is one of the printing inks according to one of the above-mentioned implementations.

BRIEF DESCRIPTION of DRAWINGS

Figure 1 shows the fluorescence spectrum of the dye C.I. Acid Red 52 c excitation at 254 nm;

Figure 2 shows the excitation spectrum of the dye C.I. Acid Red 52, plotted on a wavelength of 600 nm;

Figure 3 shows the fluorescence spectrum of the Compound (A) with excitation at 254 nm;

Figure 4 shows the comparison between the spectrum of the excitation C.I. Acid Red 52 deposited on the emission wavelength of 600 nm, and the range fluoresc is ncii compounds (A) upon excitation at 254 nm;

Figure 5 shows the comparison of the spectrum of the excitation C.I. Acid Red 52, printed at 600 nm, and the absorption spectrum of the compound (A);

Fig.6 shows the comparison between the fluorescence spectrum of the compound (A) with excitation at 254 nm and the absorption spectrum of the C.I. Acid Red 52;

Fig.7 shows the fluorescence spectrum of a paint containing a mixture of C.I. Acid Red 52 and connections (A);

Fig shows the fluorescence spectrum of printed material with a paint containing a mixture of C.I. Acid Red 52 and connections (A);

Fig.9 shows the excitation spectra C.I. Acid Red 52, applied at the wavelength of fluorescence equal to 580, 600 and 620 nm, respectively;

Figure 10 shows the fluorescence spectrum C.I. Acid Yellow 73 with excitation at 254 nm;

11 shows a comparison between the spectrum of the excitation C.I. Acid Red 52, printed at 600 nm, and the fluorescence spectrum C.I. Acid Yellow 73 with excitation at 254 nm;

Fig shows the comparison between the spectrum of the excitation C.I. Acid Yellow 73, printed at 600 nm, and the absorption spectrum of the C.I. Acid Yellow 73;

Fig shows the comparison between the spectrum of fluorescence C.I. Acid Yellow 73 with excitation at 254 nm and the absorption spectrum of the C.I. Acid Red 52;

Fig shows the fluorescence spectrum C.I. Basic Violet 10 with excitation at 254 nm;

Fig shows the excitation spectrum C.I. Basic Violet 10 printed at 600 nm;

Fig shows the comparison between the spectrum of the excitation C.I. Basic Violet 10 to 600 nm, and the spectrum of the phosphor is ascentii compounds (A) with excitation at 254 nm;

Fig shows the comparison between the spectrum of the excitation C.I. Basic Violet 10 printed at 600 nm, and the absorption spectrum of the compound (A);

Fig shows a comparison between the fluorescence spectrum of the compound (A) with excitation at 254 nm and the absorption spectrum of the C.I. Basic Violet 10;

Fig shows the emission spectrum of fluorescence C.I. Solvent Green 7 with excitation at 254 nm;

Fig shows the comparison between the spectrum of the excitation C.I. Acid Red 52, printed at 600 nm, and the emission spectrum of fluorescence C.I. Solvent Green 7 with excitation at 254 nm;

Fig shows the comparison between the spectrum of the excitation C.I. Acid Red 52, printed at 600 nm, and the absorption spectrum of the C.I. Solvent Green 7;

Fig shows the comparison between the spectrum of fluorescence C.I. Solvent Green 7, excited at 254 nm and the absorption spectrum of the C.I. Acid Red 52;

Fig shows the fluorescence spectrum C.I. Acid Yellow 184, with excitation at 254 nm;

Fig shows the comparison between the spectrum of the excitation C.I. Acid Red 52, printed at 600 nm, and the absorption spectrum of the C.I. Acid Yellow 184 with excitation at 254 nm;

Fig shows the comparison between the spectrum of the excitation C.I. Acid Red 52, printed at 600 nm and the absorption spectrum of the C.I. Acid Yellow 184; and

Fig shows the comparison between the spectrum of fluorescence C.I. Acid Yellow 184, excited at 254 nm, and the absorption spectrum of the C.I. Acid Red 52.

Embodiments of the INVENTIONS

The invention relates to printing the Noah paint which contains a first fluorescent coloring material with a specific fluorescent intensity at a given wavelength fluorescence used for measurement or determination of the excitation at a given wavelength excitation, defining the relationship of the first fluorescent coloring material with a second fluorescent coloring material that is fluorescent with excitation at a given wavelength excitation according to the above.

In addition to the above tasks, the authors of the present invention have studied the fluorescence intensity of the image formed of the fluorescent coloring materials, studied the influence of different fluorescent coloring materials and intensities of fluorescence of printing ink that has been formed by using their images. A study of factors affecting the fluorescence intensity of fluorescent coloring materials such as fluorescent dyes, found that the arrangement of molecules of the coloring material strongly affects their fluorescence intensity. That is, in the case of AR52 sufficient fluorescence intensity was observed in the visible area of water-based paints containing only the dye with a concentration of 0.01 wt.% or less, because the dye molecules were dispersed in a monomolecular state. On the other hand, when in the hydrated solution contained 0.2 to 0.3 wt.% dye AR52, observed concentration quenching (reduction of fluorescence intensity with increasing concentration). This means that a sufficient intensity of fluorescence was obtained when the molecules of the coloring material was present singly and in significant concentrations, resulting remained molecular state, but if there is an Association, aggregation or Association of molecules, or the convergence of the molecules due to the high concentration, the efficiency of light emission of the excitation of each of the molecules decreases, or the fluorescence of each molecule prevents other molecules, reducing the intensity of fluorescence as a whole.

Therefore, if a paint containing a fluorescent coloring material that can cause concentration quenching, is used for applying to the medium, the molecules of the fluorescent coloring material will not be able to save its state of single molecules (monomolecular state) when the diffusion or penetration of dye on the surface of the carrier image or inside it. Therefore, Association, aggregation, Association and other molecules occur rapidly, resulting in a reduced fluorescence intensity. In this case, the fluorescent coloring material penetrated and established within the media image, hardly contributes to the intensity f is uorescence. In addition, when the concentration of the fluorescent coloring material in the ink to improve the fluorescence intensity of Association, aggregation, Association and other molecules of the coloring material in the carrier of image increases, and therefore the intensity of the fluorescence may not increase in proportion to the increase of the coloring material.

With regard to the conduct of the fluorescent coloring material, the authors have studied the question of how to attain a monomolecular or a similar condition to obtain sufficient fluorescence intensity on the media, which is applied to the image. The authors have conducted extensive research and found that this problem can be solved by using a specific combination of the first fluorescent coloring material and the second fluorescent coloring material, and developed the present invention. According to the present invention monomolecular state of the fluorescent coloring material, fluorescing at a given wavelength, is provided in accordance with the properties of the solvent and/or coloring material, even on the media that is applied to the image. Moreover, the combination of the first and second fluorescent coloring material according to the present invention allows to increase the concentration of the fluorescent coloring material in Raske, to increase the intensity of the fluorescence. In addition, the energy interaction between the first fluorescent coloring material and the second fluorescent coloring material can increase the intensity of the fluorescence. These effects can be achieved in the image formed by the ink on the media image, and also a solvent.

According to the below description: printing ink according to the present invention with the optimal combination of dyes can increase the luminosity level of the printed image (measured aramara LM-2C, described in patent US 6,176,908) at least two times compared with conventional fluorescent paint (three times if the solvent is selected according to Aspect 3, described below).

Next, the printing ink according to the present invention is described with reference to the drawings. If there are images or printed products not specifically discussed, the results are given for a paint in which water is removed by evaporation, and a coloring material dispersed in an organic solvent. Printing ink according to each implementation of the present invention includes: a first fluorescent coloring material that emits fluorescence of a predetermined wavelength used for measurement or determination, became the group on a given wavelength excitation; the second fluorescent coloring material that emits fluorescence with excitation at the same wavelength excitation; and a liquid medium for dissolving or dispersing these materials.

The first and second fluorescent coloring material according to the present invention may be pigments or dyes subject to each of the realizations. Dyes are preferred as there is less spread out and have a higher intensity of fluorescence on the media application.

Some examples of dyes:

C.I. Basic Red 1, 2, 9, 12, 13, 14, 17;

C.I. Basic Violet 1, 3, 7, 10, 11:1 and 14;

C.I. Acid Yellow 73, 184 and 250;

C.I. Acid Red 51, 52, 92 and 94;

C.I. Direct Yellow 11, 24, 26, 87, 100 and 147;

C.I. Direct Orange 26, 29, 29:1 and 46;

C.I. Direct Red 1, 13, 17, 239, 240, 242 and 254.

The total number of the respective first and second fluorescent coloring material in the ink should preferably be 0.01 wt.% or more and 15 wt.% or less, more preferably to 0.05 wt.% or more and 10 wt.% or less of the total amount of paint for practical use. In accordance with these coloring materials: if the total amount of coloring materials in the ink does not exceed 0.01 wt.%, the fluorescence intensity sufficient for printed products, it is impossible to get. If this paint is intended for inkjet printing the image, eharacteristic from the point of view of ease of ejection may be worse if the total amount of these materials will be 15 wt.% or more. In practice, it is preferable that the number of the first fluorescent coloring material was selected in the range from 0.01 to 1 wt.%, and the number of the second fluorescent coloring material may preferably be greater than the number of the first fluorescent coloring material in the ink to improve the efficiency of excitation energy.

Some of the dyes listed above have more weak fluorescence at concentrations above a certain value, having a certain range of concentration of high fluorescence intensity. Therefore, it is preferable to use the dye in this area of concentration.

To increase the intensity of the fluorescence preferably, the first and second fluorescent coloring materials corresponded to at least one of Aspects 1 to 3. The combination of the first and second fluorescent coloring material can be selected from among the aforementioned coloring materials according to the Aspects.

According to the present invention, the most preferred example of a combination of fluorescent coloring material is a combination of C.I. Acid Red 52 as the first fluorescent coloring material, and specify the following compounds (A) as the second fluorescent coloring the first material. In the following description, among other things, the desired wavelength for measuring or determining the amounts to 600 nm, although it may be a band or any wavelength in the range of 580-620 nm.

According to Figure 1, upon excitation at 254 nm of the first fluorescent coloring material - AR52: fluorescence spectrum has a wide range of fluorescence from 550 nm to about 675 nm, with a peak at 600 nm. That is, AR52 emits fluorescence not only at a given wavelength of 600 nm, as defined above, but also in the range of 580-620 nm, including limits. On the other hand, the absorption band of the dye AR52 in the visible region is in the range 460-610 nm, with a peak at 565 nm as shown in figure 6.

The structure of the compound (A) is as follows:

The compound (A) has a dimeric structure with several groups of radiation. That is, the compound (A) performs the function of preventing the Association; and the intensity of fluorescence can be increased by increasing the number of connections (A). The compound (A) is a direct dye having a sulfonic group and a low solubility in water (less than 2 wt.% in pure water), but good solubility in organic solvents. According to Figure 3: fluorescence spectrum of the compound (A) upon excitation at 254 nm has a wide range phosphorescence approximate within 425-650 nm, with a peak at 510 nm. Therefore, with increasing the insertion amount of the compound (A), the intensity of its fluorescence increases, and therefore, the energy of excitation of the first fluorescent coloring material is increased. In addition, according to the lower graphics Figure 5 absorption in the visible region of the compound (A) comes to 440 nm, with a peak at 380 nm, and also has a UV absorption. Therefore, even if the connection is (A) entered in significantly large quantities, it will not damage the characteristics of the fluorescence of the compound (A): fluorescence intensity in the field, the appropriate wavelength for excitation of the first fluorescent coloring material, or characteristic fluorescence of the first fluorescent coloring material.

Preferred solvents for paint: pure water, which can dissolve the first fluorescent coloring material in large quantities, and the organic solvent which can dissolve the second fluorescent coloring material in large quantities. More preferred is the introduction of surfactants in a liquid environment. This liquid medium is used for imaging, in which the first fluorescent coloring material is fixed in a monomolecular state, and the first and second coloring materials uniformly dispersed and fixed. The poet is, upon excitation at 254 nm, the characteristics of the fluorescence caused by the image (Fig) is much improved compared with the characteristics of the ink, from which the evaporated water (Fig.7). Therefore, the compound (A) is a preferred example, having the structure and characteristics for the various tasks of the present invention.

Below is a description of a combination of C.I. Acid Red 52 as the first fluorescent coloring material, and the compound (A) as the second fluorescent coloring material; using the standard definition of a given wavelength of 600 nm, and a given wavelength of excitation equal to 254 nm, including implementation of the present invention (Aspect 1).

Aspect 1 is characterized by the fact that the region of the wavelength of the fluorescence of the second fluorescent coloring material includes at least the peak wavelength range of the spectrum of the excitation of the first fluorescent coloring material, measured for the emission at 600 nm (see Figure 2), and/or values of the wavelength of the absorption in the visible region of the first fluorescent coloring material (see the lower part 6). According to the Aspect 1: the relative relationship of the areas wavelength is complementary, or increases efficiency. First, caused by evaporation of the paint was prepared as follows: about the a certain number (in this case - 0.3 wt.% solvent) dye C.I. Acid Red (AR52) as the first fluorescent coloring material was dissolved in aqueous solution (organic solvent, such as glycerin, and pure water); and the solution was heated to 60°to completely evaporate the water. When done by evaporation of the paint was subjected to excitation at 254 nm using a measuring device (FP-750, manufactured by JASCO Corp.), was obtained fluorescence spectrum according to Figure 1, and the range of wavelength of excitation for a given wavelength of 600 nm, as shown in the drawing of figure 2. Figure 2 shows that the UV-region of 380 nm or shorter value has a peak region with a peak at about 265 nm, and the peak area peak around 360 nm and also one of the peak area in the region of visible light. Typically, the wavelength of UV vznuzdanie is 254 nm or 365 nm. When studying the efficiency of energy conversion was found that when the intensity of the excitation, shown on the vertical axis of figure 2, is 100 or more, the determination is effective, i.e. intensity sufficient for use. Therefore, the expression "peak wavelength range corresponding to the peak area adjacent to a given wavelength of radiation fluorescence of the first fluorescent coloring material in the present invention has practically the practical meaning when considering mentioned the efficiency of energy transformation. That is, in the spectrum of wavelengths of excitation to produce radiation at a predetermined wavelength of the first fluorescent coloring material "peak region" is a region, the intensity of which is 100 or more in a spectrum having a peak adjacent to a given wavelength fluorescence. The wavelength range corresponding to this area is the peak wavelength range. Therefore, in the drawing Figure 2: if the specified wavelength fluorescence at AR52 is 600 nm (specified wavelength excitation: 254 nm), the peak wavelength range is from 430 nm to 600 nm. On the other hand, according to Figure 3: compound (A)provided as the second fluorescent coloring material has a main fluorescent radiation in the range of 450-600 nm, including limits, almost including the peak wavelength range from 430 to 600 nm, including limits. From these drawings, when the above-mentioned fluorescence intensity is set at a value of 100, it is necessary that the compound (A) fluorescent in accordance with this range.

Figure 4 shows a plot of the relationship between the characteristics of the wavelength of fluorescence of the compound (A) and wavelength excitation to produce radiation of the dye AR52 at 600 nm, where the range of the wavelength of excitation (Figure 2) of the first fluorescent coloring material and the emission spectrum (Figure 3) is showing fluorescent coloring material shall be imposed. From the drawing of Figure 4, it follows that compared to the fluorescent intensity of dye AR52 at a wavelength of 600 nm, where the emission intensity of the dye AR52 maximum - according to Figure 1, the maximum emission intensity of the compound (a) is 800 or more at a wavelength of 510 nm. This exercise explains these above-mentioned drawings. Therefore, the wavelength of the second fluorescent coloring material includes the peak wavelength range of the first fluorescent coloring material, and this means that the energy conversion can be efficiently carried out; and the intensity of fluorescence at a given wavelength fluorescence can be improved synergistically with the excitation at a given wavelength excitation.

Thus to account for the losses it is necessary to take into account the absorption spectrum of the dye material. Figure 5 shows the excitation spectrum of the dye AR52 for fluorescence 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 in the same scale of the wavelength. While the absorption and excitation cannot be compared with each other quantitatively, but it is possible to determine the relationship between them. As a rule, the absorption band overlaps the emission band, but is shifted to a shorter length in the wave. Range of light absorption of the compound (A) also covers the region of the wavelength of fluorescence shown in the drawing, Figure 3, showing absorption at the wavelength of 440 nm or shorter wavelength. Absorption spectrum has a practical value in the vicinity of these peaks. Therefore, it is preferable that the region of the wavelength, including the maximum absorption wavelength (380 nm) of the compound (A), does not overlap the main wavelength of the excitation of the dye AR52 in the range 425-600 nm, including the limits, if the fluorescence intensity of 100 or more; and more preferably, to avoid overlap between the main area of absorption equal to 425 nm or shorter value, and the main field excitation of the dye AR52. The absorption band of the compound (A) does not overlap with a peak wavelength range of the dye AR52, and therefore the absorption band has no direct effect on the mentioned energy conversion.

If a large fraction of the radiation of the second fluorescent coloring material corresponding to the area of the wavelength of the excitation of the first fluorescent coloring material, is absorbed by the second coloring material, the increase in fluorescence intensity is smaller.

Since the wavelength range of the fluorescence of the compound (A) covers the wavelength range of the excitation is of rasites AR52 with receiving radiation at a given wavelength, therefore, the radiation of the compound (A) is used for excitation of the dye AR52. In addition, the absorption of the compound (A) does not reduce the efficiency of energy conversion. Therefore, the fluorescence of the second fluorescent coloring material becomes new energy excitation of the first fluorescent coloring material to enhance fluorescence.

From the comparison between Figure 1 and Figure 3 it is apparent that the fluorescence of the dye AR52 and the fluorescence of the compound (A) overlap in the wavelength range comprising at least 580 nm or more and 620 nm or less. The overlap provides a more effective relationship to determine at a given wavelength of radiation.

What follows is a description of the features of the present invention in relation to the absorption spectrum of the first fluorescent coloring material. 6 shows a graph of the absorption spectrum of the dye AR52 (lower graph) and fluorescence spectrum of the compound (A) (upper graph) on the same scale of the wavelength. Absorption spectrum of the dye AR52 can be considered as showing the energy loss in the fluorescence of the compound (A). Absorption spectrum of the dye AR52 has a primary peak near 560 nm: 600 to 460 nm, including limits, in the region of visible light. The range of significant absorption of the dye AR52 narrower than mentioned above: 500-590 nm, including the I limits. As to the range of fluorescence dye AR52 (550 nm or more) and its intensity according to Figure 1, it is considered that the absorption takes place in the range of 500-560 nm, including limits. Since this absorption band is present in the region of visible light, it is not considered relative to the fluorescence of the dye AR52. However, since the present invention uses different fluorescent coloring materials, this absorption band was an important moment in the two-stage conversion of excitation energy. That is, after determining that the absorption band concludes that the fluorescence of the second fluorescent coloring material is in the range that includes the wavelength of the excitation AR52 to provide radiation at a given wavelength fluorescence, but not including, the range of absorption. 6 shows this relationship. According to the upper and lower graphs 6: the main fluorescence of the compound (A) is in the range 430-515 nm, including the limits, but it does not influence the absorption band. The fluorescence of the compound (A) includes a range of fluorescence specified asin the drawing 6 (430 nm< 500 nm) in the wavelength range not overlapping significant absorption band of the dye AR52 range 500-590 nm, including limits, with the peak at 560 nm. The energy of light in this areaused as extra energy for excitation of the first fluorescent coloring material. Therefore, you can increase all the intensity of fluorescence at a given wavelength. That is, the areaincreases the fluorescence intensity of dye AR52, since at least the areaoverlaps the second wavelength excitation of the dye AR52.

Below in the example of the combination of the dye C.I. Acid Yellow 73 (AY73) and AR52 with reference to Figure 10-13: the combination described in U.S. patent 6,176,908 Century According to these drawings was used caused by evaporation of the dye using UV set, and the absorption was measured with a conventional paint. According to Figure 10: AY73 emits fluorescence in the approximate region of wavelengths from 500 to 600 nm, including limits (peak: 530 nm)upon excitation at a given wavelength excitation 254 nm.

According to 11 fluorescence spectrum of the dye AY73 shown on Figure 10, is imposed on the excitation spectrum of the dye AR52 shown in figure 2. According to Figure 2 fluorescence dye AY73 is in the approximate wavelength range of 500-600 nm, including limits (peak: 530 nm), and the wavelength range with effective intense the ability to narrow radiation. The range of fluorescence dye AY73 is a peak wavelength range of the excitation of the dye AR52 (475-600 nm). So AY73 does not emit fluorescence, which would be sufficient to AR52 was fluorescamine.

Fig shows a comparison between the excitation spectrum of the dye AR52 to provide radiation at 600 nm and a light absorption spectrum of the dye AY73. Strip light absorption of the dye AY73 in the visible light does not exceed 525 nm and has a peak at a wavelength of 490 nm. If the paint contains a compound (a) and both dye AR52 and AY73, then, as an example of the present invention, AY73 decreases the effect of the compound (A) in accordance with the absorption spectrum of the light. Therefore, it is necessary to increase an extra amount of compounds (A) to the extent necessary (see Aspect 2 below) and to compensate the loss caused by the absorption of the dye AY73. According Fig: maximum absorption wavelength (490 nm) of the dye AY73 is located in the region of wavelength of absorption (450-600 nm, including limits) dye AR52.

Fig shows the combination of the absorption spectrum of the dye AR52 in the bottom graph drawing 6 and fluorescence spectrum of the dye AY73. According to this drawing Fig: the band fluorescence AY73 is essentially in the field of absorption (500-590 nm, including limits) dye AR52, and radiation at a wavelength shorter than said about the art of absorption, is not observed. Therefore, the combination of dyes AR52 and AY73 does not disclose the configuration described above of the present invention and does not provide the advantage of this izobreteniya.

Referring to Fig.7 and 9: the invention is further illustrated by the example of the ink and the printed image. Fig.7 shows the measurements obtained in the preparation of the applied paint and dye AR52, the compound (A), pure water and an organic solvent; and then applied the paint stir as caused by evaporation of the ink at a given wavelength excitation 254 nm device FP-750. Fig shows the measurements obtained by the excitation of the image printed on the medium using a put paint on a given wavelength excitation 254 nm device FP-750. That is, Fig.7 shows the results of a study of the characteristics of the paint for application according to the present invention done by evaporation of the paint; and Fig shows the characteristics of the applied image with paint for coating according to the present invention; and application of paints for coating according to the present invention it is possible to prove in respect of the applied image.

The effects of the present invention are confirmed by comparing Fig.7 and Fig, because according to these drawings use the same paint for the effectiveness apostal the deposits. Each of Fig.7 and Fig graph has two peaks near 500 nm and 590 nm, respectively. From illustrated in figure 1 above and Figure 3 it follows that the compound (A) has a peak at approximately 500 nm; and dye AR52 provides peak at 590 nm. Comparison 7 and Fig shows that in respect of the drawing Fig.7 showing the dye AR52 the compound (A), in perfect working condition dissolve, damage the image gets further increase in fluorescence intensity, in particular the increase in the fluorescence intensity of a given wavelength (600 nm, or a range from 580 to 620 nm). These facts prove the following: in the deposited image of each coloring material effectively uses the specified wavelength excitation; and you can receive radiation from the compounds (A), provided as the second fluorescent coloring material, and the emission from the first fluorescent coloring material using radiation from compounds (A). Generally, if the fluorescent coloring materials associated with each other, the peak wavelength shifts to longer wavelengths. But in comparison between 7 and Fig such movement no. Therefore, the absence of this bias means that prevents the Association of the action in accordance with the present invention and according to other technical Acknowledgements the am proven as a result. Fig.7 shows the result obtained when studying the characteristics of the paint for application according to the present invention done by evaporation of the paint. Fig shows the characteristics of a depiction of the paint coating according to the present invention, showing the application of paints for coating according to the present invention in relation to the printed image.

Caused by evaporation of the ink containing the dye AR52, the compound (A)has two peaks, shown in Fig.7. It is obvious that the compound (A) compensates for the characteristics of the dye AR52 even in the case of inks for the application and the fluorescence of the compound (A) has characteristics sufficient to increase the preset wavelength. According to Fig caused the image has two peaks: it is shown that the fluorescent dye, in which to create the concentration quenching is difficult, completed and provided the strength of the continuing rise in long-term fluorescence intensity.

It should be noted that a given wavelength fluorescence according to the present invention can be chosen depending on the application of paint and images generated by it. For example, Fig.9 shows the excitation spectra of the dye AR52 obtained with wavelengths of fluorescence (specified wavelength fluorescence) dlinoi, 600 and 620. Therefore, the peak wavelength range corresponding to the peak region near each given wavelength fluorescence, can be defined according to the present invention. As mentioned above, when a given wavelength is determined in the band 580-620 nm, including the limits, then it is preferable that the wavelength of the second fluorescent coloring material upon excitation at a given wavelength included most of the peak wavelengths of the excitation spectra. In this case, to guarantee a level of performance above prior art: wavelength radiation may be one wave high efficiency, or preferably it may have a wider strip, for example, 6005 nm or 60010 nm, if the specified wavelength is defined as a certain wavelength range. That is, the wavelength of fluorescence is essentially includes wavelengths in the spectrum of the excitation, which effectively provides the desired fluorescence. For example, in the case of AR52, as shown in the drawing Figures 9, will be more effective compliance with the peak wavelength range of the spectrum of the excitation of the emission wavelength of 600 nm, as mentioned above, and not the excitation spectra for the 580 and 620 nm. Results 1 Aspect you can understand what I increase if you increase the additional amount of the second fluorescent coloring material.

[Dimension 2]

Aspect 2 is not routinely applied to the characteristic requirement of the structure of the second fluorescent coloring material and which allows you to increase the introduction of the second fluorescent coloring material in the ink. That is, the conditions for wavelength according to Aspect 1 of the second fluorescent coloring material is facilitated so that at least part of the wavelength fluorescence overlaps the excitation spectrum of the first coloring material. The energy relationship between the wavelength of excitation and emission wavelength can be improved by increasing the insertion amount of the second fluorescent coloring material. In particular, input the number of the second fluorescent coloring material can be increased, and thus to exclude the Association of molecules of the first coloring material with the core structure of the second coloring material, which prevents the molecular Association of coloring materials. As a result of this you can increase the intensity of fluorescence at a given wavelength. The intensity of fluorescence of the first fluorescent coloring material at a given wavelength excitation can be improved by means of which Oceania the first and second fluorescent coloring materials, of which at least one, preferably the second fluorescent coloring material has a basic structure further atoms or groups of atoms, or subsequent groups fluorescence.

In particular, the structure of the coloring material preferably has a lot of groups fluorescence. That is, the coloring material having many groups of fluorescence in the same molecular structure is structurally large and has improved properties of volume compared to conventional fluorescent coloring material. Therefore, regular aggregation or Association of coloring materials is difficult as compared with ordinary fluorescent coloring materials. Therefore, even if the content of the fluorescent coloring material in the ink is increased in comparison with conventional coloring material, the decrease in fluorescence intensity is difficult. In addition, the coloring material with many groups fluorescence in the same molecular structure contains many groups of fluorescence in a single molecule of the coloring material. That is, the fluorescence per molecule increases, and therefore, the fluorescence intensity can be increased. As mentioned above, compared to conventional fluorescent coloring materials of the fluorescent coloring material according to the present from which retenu structurally large and has improved properties of volume, resulting pigments can easily be absorbed on the components of the material of the coating, resulting in improved water resistance. If the fluorescent coloring material has an affinity, its resistance can be improved; and also the affinity may contribute to the durability of fluorescence. In Crusades material having many groups of fluorescence in the same molecular structure, regular aggregation or Association difficult compared with conventional coloring material. So, for example, even if contained in the paint the water has evaporated, the aggregation in Crusades the material will be difficult. Consequently, the occurrence condition of strong aggregation will be difficult, and as a result you will be able to provide resistance against sticking together. This mechanism allows the paint according to the present invention good intensity and resistance. In addition, the coloring material having many groups fluorescence same molecular structure also improves the effects of the present invention using a sulfonic acid with a strong affinity with water as the hydrophilic group.

A preferred group of fluorescence that meet the above-mentioned requirements and functionally effective, can be aminostilbene derived on the sulfonic acid. The structure of the compound (A) also contains derived.

In the case of such a fluorescent coloring material, as usual coloring material, even if the concentration of the coloring material in the ink is increased, the intensity of the fluorescence of this dye material may not be increased, and the intensity of the fluorescence may be reduced. When using such a fluorescent coloring material applicable limits concentration (content in paint) narrow and there is a limit of increasing fluorescence intensity. On the other hand, in the combination of the first and second fluorescent coloring material according to the present invention, which introduced the color radiation into visible light, the fluorescence intensity can also be increased if the content of the fluorescent coloring material is increased depending on the increase of the content.

Examples of groups fluorescence in fluorescent Crusades material according to the present invention, groups of atoms, and groups having the function of brightness of fluorescence below. When this fluorescent coloring material according to the present invention may have an area of the wavelength of the light absorption in the visible light or in other areas, but it is important that it is fluorescent in the visible light radiation corresponding to about the Asti wavelength excitation.

<Groups fluorescence>

<a connecting group (1)>

<port group (2)>

In the above formulas (1)to(3): Z is independently NR1R2, SR3or or3;

Y represents H, Cl;

above Z represents SR4or or4;

E represents Cl or CN, where

each of R1, R2, R3and R4is independently H, alkyl group, substituted alkyl group, aryl group, substituted aryl group, aracelio group, substituted aracelio group, or a hydroxyl group; and

R1and R2may form a 5 - or 6-membered ring together with the nitrogen atom.

The connecting group (3)

In the above formula (4):

R5independently selected from the group consisting of hydrogen atom, alkyl group, substituted alkyl group, CNS group, halogen atom, CN, raidgroup and NHCOR6,

where R6selected from the group consisting of:

hydrogen atom, alkyl group, substituted alkyl group, aryl group, substituted aryl group, aranceles group and substituted aranceles group;

in the formula (5): T is alkyl GRU is PU, and

W is chosen from the group consisting of:

hydrogen atom, CN, CONR7R8, pyridinium group, and a carboxyl group;

where R7and R8independently selected from the group consisting of hydrogen atom, alkyl groups and substituted alkyl groups;

m represents alkylenes chain having from 2 to 8 carbon atoms; and

in the formula (6) is chosen from the group consisting of hydrogen atom, alkyl groups, and carboxyl groups.

Specific examples of each substituent in formulas (1)to(6) can be selected according to the properties of the fluorescence of a given radiation.

According to the above structural formula (a) compound (A) has a dimeric structure with several groups fluorescence and sulfonic groups.

Therefore, if the fluorescent coloring material contains a group of fluorescence, it increases the intensity of fluorescence of the first fluorescent coloring material with excitation at a given wavelength excitation due to good fluorescence corresponding to the area specified wavelength excitation of the first fluorescent coloring material. In particular, aminostilbene derivatives disulfonic acid are preferred due to their wide field fluorescence.

[3 aspect]

Aspect 3 effective alone or in combination with each of the Aspects 1 and 2. Aspect 3 is the technique of increasing the intensity of fluorescence by proper location of the fluorescent coloring material to the medium of drawing the image using such a liquid as a mixture of a first solvent having high solubility with respect to the first kasashima material, and low solubility with respect to the second kasashima material and a second solvent having a high solubility with respect to the second kasashima material.

Some dyes are chemical phenomenon, known under the name of the Association, to ensure energetically stable state. This phenomenon of the Association for dye molecules having a relatively flat frame with two or less ring-like structures, two molecules facing each other, and between these molecules is the supply of energy and loss of energy. Therefore, in the case of a fluorescent dye, this phenomenon can be vospreschyon factor for the properties of the fluorescence of this dye. Since this is the condition of the packaging is not only in the paint, but also in the imprinted material on paper, so you need a means of preventing the Association of the dye. It is known that the Association prevents the introduction of urea, naphtalenesulfonic acid or the like as a means to prevent the Oia Association. But if it prevents the Association of the substance has the property of fluorescence, which increases the intensity of fluorescence of the first fluorescent coloring material, and has a function of preventing the Association, it is possible to provide both the effect of increasing the fluorescence intensity and the effective formation of fluorescence by preventing the Association.

Then in the preparation of paints containing the first fluorescent coloring material and the second fluorescent coloring material capable of increasing the fluorescence intensity of the first fluorescent coloring material upon excitation at the same wavelength excitation, use a mixed solvent containing a first solvent has a high solubility with respect to the first kasashima material and a low solubility with respect to the second kasashima material, and the second solvent has a high solubility with respect to the second kasashima material.

In this description, the term "high solubility" or "good solvent" means that the coloring material can be dissolved at a concentration of about 3 wt.% or more; and the term "low solubility" or "poor solvent" means that the coloring material can be dissolved at a concentration of approximately less wt.%.

For example, if water is selected as the first solvent and glycerol selected as the second solvent, the water has a good solubility with respect to AR52 and low solubility with respect to the compound (A)and glycerol has good solubility with respect to the compound (A). Then the paint is prepared by the introduction of AR52 and connections (A) in a solvent containing water and glycerin. The dye compound (A) is in an environment of excess bad solvent, and therefore, the compound (A) is dissolved in the weak state of the Association, creating a stable system with AR52. However, if the paint is placed on the medium of drawing the image, the water being a poor solvent, rapidly diffuses and penetrates into the medium of drawing the image. On the other hand, glycerin slowly diffuses and penetrates into the medium of drawing the image due to its high viscosity. When the compound (A) is not soluble in water - poor solvent, and the glycerin is a good solvent. Thus, the compound (A) slowly diffuses and penetrates into the medium of drawing the image together with glycerol. In addition, because glycerin is a good solvent, therefore, the compound (A) is absorbed in a monomolecular state components of the media application. This is a good fluorescence. Over the CSOs, the compound (A) dissolved in a monomolecular state, and therefore, the compound (A) also may prevent the Association of the dye AR52. That is, molecules of compound (A) and dye AR52 fixed to the carrier of the printing image in a state of mixing and disperse along to the proper degree. That is, the effect of increasing the fluorescence intensity of the dye AR52 by connecting (A) becomes significant. In this case, and the first fluorescent coloring material and the second fluorescent coloring material can have a variety of sulfonic groups.

For the preferred manifestation of this phenomenon, the content of used fluorescent coloring material preferably does not exceed the amount that can dissolve in a bad solvent.

On the other hand, if the prevention Association to consider from the point of view of the molecular structure of the fluorescent coloring materials, if at least either the first or the second coloring material has a molecular structure with three or more ring structures, prevents packing of the molecules of the first and second coloring materials, but they are nearby, providing easy possibility mentioned above transmission and reception of energy. This fluorescence is enhanced.

Thus, the fluorescent dyeing the second material, used according to this invention, preferably has a lot of groups fluorescence. More preferably, the second fluorescent coloring material used according to the present invention, had the basic structure to increase the brightness of fluorescence. Groups fluorescence of the second fluorescent Crusades material preferably are dimers.

Examples of the ring structure of the second fluorescent dye: the ring structure having a double bond or a conjugated double bond, an aromatic ring structure, a cyclic structure or a heterocyclic structure. Specific examples of this structure include a benzene, thiophene, pyridine, pyrrole, coumarin, inden, benzthiazole, benzoxazole, benzimidazole, rensselear, naphthalene, Tinatin, quinoline, indole, naphthene, fluoren, diphenylsulfide, phenanthrene, anthracene, acridine, phenanthridine, carbazole, fluorene, Naftalan, fluoranthrene, pyrene, Xanten, chrysin, triphenylene, perylene, pyrene, pizen, chinagreen and phthalocyanine.

More preferred specific examples include coloring material having a multiring structure, selected as described above, of the following substances: pyrene, coumarin, oxazole, imidazole, thiazole, imidazole, pyrazole, benzidine, residencelife, diaminocarbenes, naphtalene ring, diaminostilbene the sulfonic acid, and derivatives thereof, linked together referred to above, the connecting group.

If the first fluorescent coloring material and the second fluorescent coloring material is both water-soluble, these two fluorescent coloring material preferably have the same group for water solubility in order to more easily prevent the Association. Group water solubility is preferred is a sulfonic group, the solubility of which the pH of the paint has no effect.

According to the present invention, the paint may contain fluorescent or afluorescent coloring material as the third coloring material in addition to the two mentioned fluorescent dye materials.

The foregoing sets forth aqueous medium, forming a fluorescent dye according to the present invention described above with dyes. Used in the present invention, the aqueous medium is preferably an aqueous medium mainly containing water. The water content of the paint is 10-95 wt.%, preferably: 25-93 wt.%, more preferably: 40-90 wt.% in relation to the total weight of the paint. Used in this invention, water is preferably ion-exchange water.

In addition, for the paint according to the present invention, water may be used only as aq is I Wednesday, or can be used in combination with water-soluble organic solvent to further improve the results of the present invention.

Specific examples of water-soluble organic solvent that can be used in the present invention: alkalemia alcohols of 1 to 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 and n-pentanol;

such amides as dimethylformamide and dimethylacetamide;

ketones or ketaspire, such as acetone and datetoday alcohol;

ethers, such as tetrahydrofuran and dioxane;

such oxyethylene and oxypropylene additive polymers such as diethylene glycol, triethylene glycol, tetraethyleneglycol, dipropyleneglycol, tripropyleneglycol, polyethylene glycol and polypropyleneglycol;

such alkalophile with alkylenes group with 2-6 carbon atoms as ethylene glycol, propylene glycol, triethyleneglycol, butyleneglycol, pentanediol and hexyleneglycol;

such trioli as glycerin, trimethylacetyl, trimethylolpropane and 1, 2, 6-hexanetriol;

thiodiglycol; bishydroxyethyl;

these lower Alkylglucoside esters, as etilenglikolevye (ethyl or butyl) ether, diethyleneglycol milovy (ethyl or butyl) ether and triethylenemelamine (ethyl or butyl) ether;

these lower diacylglyceride esters, as triethylenemelamine (or ethyl) ether and tetraethylethylenediamine (or ethyl) ether;

such alkanolamine as monoethanolamine, diethanolamine and triethanolamine; sulfolan; N-methyl-2-pyrrolidone; 2-pyrrolidone; and 1, 3-dimethyl-2-imidazolidinone. Mentioned water-soluble organic solvents can be used singly or in mixtures thereof.

The content of water-soluble organic solvent in the paint is essentially equal to or less than 50 wt.%, preferably 5-40 wt.% and more preferably 10-30 wt.% in relation to the total weight of the paint.

Among these solvents, it is preferable to use ethylene glycol, diethylene glycol, triethylene glycol, 2-pyrrolidone, glycerol and 1, 2, 6-hexanetriol.

The paint according to the present invention preferably contains urea, etilenmocevina or trimethylolpropane as a humidifier, the same solvent. This invention suitable etilenmocevina and trimethylolpropane. Their preferred content is 1 wt.% or more, 20 wt.% or less relative to the total weight of the paint.

In the ink according to the present invention, if necessary, in addition to the described above components, to ensure the paint properties of the specified radiation - can be added additives such as protivostaritel, the surface tension regulator, pH regulator, a viscosity modifier, an amplifier fluorescence, antioxidant, power evaporation, corrosion additive, fungicide and helatoobrazovatel.

When the viscosity of the ink according to the present invention preferably 0.7-17 CPS (at 25aboutC. If the viscosity of the ink is not in the specified limit, then in a jet application of the normal ejection of ink can be broken. Paint with a viscosity of more than 12 JV slowly penetrates into the material, which is applied to the image, because of its viscous resistance, which is undesirable from the viewpoint of fixing it.

In addition, the surface tension of the ink used in the present invention, preferably set in the range of 20 to 60 Dyne/cm at 25°C. the Surface tension of less than 20 Dyne/cm, it is undesirable for the following reason. After ejection of liquid drops in a jet application of force leads back meniscus may weaken or stress leads back projected meniscus can relatively move. Therefore, it can form bubbles and holes can become wet, resulting in reduced surface tension may cause bending. In the preparation of paints according to the above description, it can be prepared as ink used for inkjet application of the corresponding plain paper; in particular, the paint having excellent stability during storage, the concentration of the coating, with a dry recording and printing quality.

Fluorescent dye according to the present invention, prepared in accordance with this description, particularly effective in the jet application. As a method of spray application, there is a method comprising the application of mechanical energy to the ink to eject liquid droplets, and a method of spray application, provides for the expansion of the paint by adding thermal energy to the ink to eject droplets. Fluorescent dye according to the present invention is particularly useful for methods of spray application.

Examples

The invention is hereinafter described more specifically with reference to examples and reference examples. Here the measured values obtained by using diluents in the form of clean water for painting materials were used for the wavelength of the absorption maximum wavelength absorption region of the wavelength of fluorescence. With absorption spectrometer were measured wavelength absorption. Was prepared in a diluent, the spectral absorption capacity of which amounted to 0.5-0.7. The area above the baseline as the peak absorption was defined as the region of wavelength of absorption,and the peak value was defined as the region of the wavelength of maximum absorption. In addition, for wavelengths of fluorescence measurement conditions were determined such that the intensity of fluorescence did not exceed the threshold measurement. Then the measurement of the wavelengths of fluorescence was done using thinner used to measure absorbance, and by fixing the wavelength of the excitation of the first and second coloring materials at a specified wavelength. The area above the baseline was defined as the region of the wavelength of the fluorescence.

In the examples below, the colors correspond to the execution of one of the printing inks according to the described above accomplishments from the first to the sixth of the present invention.

Example 1

The following components were adjusted to a predetermined concentration, and then the components were mixed and stirred sufficiently and were filtered by a microfilter (manufactured by Fuji Photo Film Co., Ltd.) with a pore size of 0.2 μm under pressure to prepare an ink, parts by weight:

C.I. Acid Red 52 (first fluorescent coloring material)
0,25
Connection (A) (second fluorescent coloring material)
1
Glycerin7,5
Diethylene glycol5
Urea5
Acetylene E100 (acetylglycosamine product

attach the ethylene oxide production

the company Kawaken Fine Chemicals Co., Ltd.)
1
Water80,25

Fluorescence spectra and excitation spectra of the first and second fluorescent coloring materials were measured by fluorometry FP-750, manufactured by JASCO Corp. Each sample was paint, water content which was evaporated to eliminate the influence of water on the dimension.

The field of wavelength of absorption of the first and second coloring materials were measured by using a spectrophotometer U-3200 manufactured by Hitachi Ltd., after 100,000-fold dilution of the sample with clean water. The region of wavelength of absorption of the first coloring material was in the range of 450-620 nm, including limits, and its maximum absorption wavelength amounted to 565 nm. The region of wavelength of absorption of the second coloring material was in the range of 300-450 nm, including limits, and its maximum absorption wavelength amounted to 372 nm.

Reference example 1

The following components were adjusted to given concentrations, then the components the options were mixed and stirred sufficiently, and were filtered by a microfilter (manufactured by Fuji Photo Film Co., Ltd.) with a pore size of 0.2 μm under pressure to prepare an ink, parts by weight:

C.I. Acid Red 52 (first fluorescent coloring material)
0,25
Connection (A) (second fluorescent coloring material)
1
Glycerin7,5
Diethylene glycol5
Urea5
Acetylene E100 (acetylglycosamine product

attach the ethylene oxide production

the company Kawaken Fine Chemicals Co., Ltd.)
1
Wateran 81.25

(Evaluation)

(1) the Intensity of fluorescence

Using an inkjet damaging the paint device (BJS600 manufactured by Canon Inc.) with a special head multiple application from which ink is ejected at the expense attached to the paint of thermal energy depending on the signal applied, was printed solid sample 50% mode on plain paper inkjet (SW-101, manufactured by Canon Inc.). Then, when indicated by the provisions below, the intensity of fluorescence is orescence was measured using fluorometry (FP-750 production company JASCO Corp.). The results were evaluated according to the criteria specified below and listed in Table 1. The measurement conditions were as follows: wavelength of excitation was set at a value of 254 nm was measured fluorescence intensity at the maximum wavelength of fluorescence; and measured the fluorescence intensity was normalized by determining the fluorescence intensity of the dye of the Reference example 1 in 100; and an evaluation was made according to 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

Using an inkjet damaging the paint device (BJS600 manufactured by Canon Inc.) with a special head multiple application from which ink is ejected at the expense attached to the paint of thermal energy depending on the signal applied, was printed solid sample 50% mode on plain paper inkjet (SW-101, manufactured by Canon Inc.). Then the characteristic manifestations of color substances to print the application was measured by the Macbeth densitometer (RD-918 manufactured by company Macbeth Co., Ltd.).

AA: 0.7 or more visually very clear printed material;

p> And: 0.5 or more; and less than 0.7 - visually readable printed material;

In: 0.3 or more; and less than 0.5 is visually difficult to read printed material; and

With: less than 0.3 - printed material visually unreadable.

(3) Durability

Using an inkjet damaging the paint device (BJS600 manufactured by Canon Inc.) with a special head multiple application from which ink is ejected at the expense attached to the paint of thermal energy depending on the signal applied, was printed solid sample 50% mode on plain paper inkjet (SW-101, manufactured by Canon Inc.). Then the paper was left for 24 hours and then immersed in running water for 5 minutes Then change the optical density of the print was evaluated using device Macbeth RD 918 according to the following criteria:

AA: the change in density of less than 50% is visually very clear printed material;

A: 50% or more; and less than 70% of visually readable printed material;

In: 70% or more visually readable printed material.

Table 1
(1) the intensity of fluorescence(2) the characteristic manifestations color(3) the characteristic resistance
Example 1AA AndAnd
Reference example 1InAndIn

Each ink was prepared in accordance with the composition of Table 2 in each of Examples 2 to 6 and Reference examples 2 and 3. Fig-18 respectively show the relationship of fluorescence, excitation and absorption combination of the first and second coloring materials in Example 4. Fig-22 respectively show the relationship of fluorescence, excitation and absorption combination of the first and second coloring materials in Example 5. Fig-25 respectively show the relationship of fluorescence, excitation and absorption combination of the first and second coloring materials in the Reference example 3. Descriptions of these figures are not given, but these examples and reference examples will be clear from the description of the present invention and the description of the reference examples. Each of the above reference examples uses a combination of conventional coloring materials using the same solvent as in the present invention. Therefore, each of the above-mentioned reference examples is given as reference example.

The benchmark-ing Example 2
Table 2
Example 2Example 3Example 4Example 5Example 6The benchmark-ing Example 3
The 1st coloring material, wt.%AR52

0,25
AR52

0,25
BV10

0,25
AR52

0,25
AR52

0,25
AR52

0,5
AR52

0,25
2nd coloring material, wt.%Conn. (A)

1
Conn. (A)

2
Conn. (A)

1
SG7

0,3
Conn. (A)

1
AY73

0,5
AY18

41
3rd coloring material, wt.%AR92

0,6
AR92

0,6
-----
1st solvent, wt.%Glycerine

7,5
Glycerine

7,5
Triethylene

glycol

7,5
Xylitol

7,5
-Glycerine

7,5
Glycerine

7,5
Diethylene glycol, wt.%5555555
Urea, wt.%5555555
Acetylene E100, wt.%11111 11
2nd solvent (water), wt.%of 79.6578,6580,2580,9587,7580,580,25

Each of the above prepared ink was irradiated by light radiation at a wavelength of excitation of 254 nm. Then was determined range of the resulting fluorescence. Inks according to Examples 2-4 were two strong peak intensities of fluorescence: as shown in drawings 7 and 8 when comparing them with each other. And the relationship that takes place on the drawings 7 and 8, is not present in the inks according to the Reference examples 1-3.

Fluorescence intensity, etc. were evaluated in the same way as according to Example 1 and Reference example 1. Table 3 shows significant differences between the examples and reference examples.

Table 3
(1) the intensity of fluorescence(2) the manifestation of color(3) resistance
Example 2AAAAAA
Example 3AAAAAA
Example 4AAAndAnd
Example 5AA AndAnd
Example 6AndAndAnd
Reference example 2InAAIn
Reference

example 3
InAndIn

According to the above, the present invention provides: a fluorescent dye having a high fluorescence intensity; the good characteristics of the degree of color development and stability, which cannot be obtained in the prior art; and method of spray application using this fluorescent paint.

1. Printing ink containing the first fluorescent coloring material that emits fluorescence at a given wavelength of radiation used for measurement or determination upon excitation at a given wavelength excitation; and a second fluorescent coloring material that emits fluorescence upon excitation at a given wavelength excitation; in which the excitation spectrum of the first coloring material in the ink to obtain the fluorescence at a given wavelength radiation has a peak wavelength range adjacent to a given wavelength of the fluorescence; and a spectrum of the fluorescence emission of the second fluorescent coloring material has a region of wavelengths of radiation, colorallocate at least the peak wavelength range, moreover, the printing ink contains a second fluorescent coloring material in quantities greater than the first coloring material.

2. Printing ink according to claim 1, in which a given wavelength is 254 nm excitation; peak wavelength is in the range of from 430 nm or more and 600 nm or less; and the region of the wavelength of the second fluorescent coloring material is in the range 425-600 nm, including 600 nm, as given wavelength fluorescence.

3. Printing ink according to claim 1 or 2, in which the first fluorescent coloring material has a peak region in the absorption spectrum in the visible light, and the wavelength of the second fluorescent coloring material includes a region of a wavelength which is shorter than the peak area of the absorption spectrum.

4. Printing ink according to claim 1, in which the second fluorescent coloring material is a coloring material having a structure with many groups fluorescence.

5. Printing ink according to claim 1, additionally containing a first solvent having high solubility with respect to the first fluorescent kasashima material and low solubility with respect to the second fluorescent kasashima material; a second solvent having a high solubility with respect to the second fluorescent kasashima material and sovmestimosti with the first solvent; and

the third solvent that does not have compatibility with the second solvent and dissolving the second fluorescent coloring material.

6. Printing ink according to claim 1, in which the first and second fluorescent coloring materials selected from the group consisting of C.I. Basic Red 1, 2, 9, 12, 13, 14, 17;

C.I. Basic Violet 1, 3, 7, 10, 11:1 and 14;

C.I. Acid Yellow 73, 184 and 250;

C.I. Acid Red 51, 52, 92 and 94;

C.I. Direct Yellow 11, 24, 26, 87, 100 and 147;

C.I. Direct Orange 26, 29, 29:1 and 46;

C.I. Direct Red 1, 13, 17, 239, 240, 242 and 254 and the compound (A)having the following structural formula

7. Printing ink according to claim 6, in which the first fluorescent coloring material is C.I. Acid Red 52, and the second fluorescent coloring material is a compound (A).

8. Printing ink according to claim 1, in which the specified length is 254 nm excitation.

9. Method of spray paint, which includes stages of ejection of ink through the discharge outlet; and applying the paint to the media, which is applied to the image receiving printed images, and the ink is a printing ink according to any one of claims 1 to 8.



 

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The invention relates to ink for ink-jet printing, including personal printers

Printing device // 2318673

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