Dispergated coloring agent and the method of its production, the water ink, the container for the ink, the ink-jet inscriber, the method of the ink-jet recording and the ink-jet recorded images produced at its application

FIELD: nonferrous metallurgy industry; aircraft industry; other industries; production of the heat-resistant alloys on the basis of the nickel.

SUBSTANCE: the invention is pertaining to the dispergated coloring agents intended for the ink-jet recording. The invention describes the dispergated coloring agent containing the coloring agent and the pseudo-finely-dispergated particles of the polarizable polymer having the dimension less, than the particles of the coloring agent. In the dispergated coloring agent the coloring agent itself and the particles of the polarizable polymer are attached to each other. At that the pseudo-finely-dispergated particles of the polarizable polymer contain the interpolymer consisting of the monomeric components containing, at least, one type of the hydrophobic monomer and, at least, one type of the hydrophilic monomer, where the hydrophobic monomer contains, at least, the monomer having the methyl group in α - position and the radically-polymerizable non-saturated double bond. The invention also describes the method of production of the indicated dispergated coloring agent and the water ink produced on its basis. The presented dispergated coloring agent has the high stability for a long time and practically in the absence of the surface-active substance or the dispergator. The ink produced on its basis has stability of blowout in the ink-jet printing method.

EFFECT: the invention ensures, that the ink produced on the basis of the presented dispergated coloring agent has the high stability of blowout in the ink-jet printing method.

20 cl, 14 dwg, 7 tbl, 15 ex

 

The technical field to which the invention relates.

This invention relates to a dispersible dye and the method thereof, the aqueous ink for inkjet recording, inkjet recording device, method of inkjet recording and inkjet recorded by recording images obtained during its application.

The level of technology

In the inkjet recording are different principles for acquiring images, letters, or similar marks by ejection of small droplets of ink from nozzles onto the medium (substrate) to record (paper or similar material). Inkjet recording has rapidly spread in various fields due to their advantages such as: high speed, low noise, ease of obtaining multicolor images, the high flexibility of the recorded samples and the absence of symptoms/fixation. In particular, in methods of full-color inkjet printing using aqueous ink recently there has been considerable progress, and at present it is possible to obtain a multicolor image, which are not worse than those obtained by conventional methods of printing or pictures. Such techniques are widely spread in the field of full-color images, as they allow to obtain images with less cost than the conventional methods of printing or pictures, if the number of copies is limited.

Inkjet recording device and recording method using aqueous ink was improved to meet the requirements of the improved printing characteristics, such as higher speed, more crisp images and full color images. In General, inkjet ink for inkjet recording device must meet the following characteristics: (1) images must be high resolution and high density, must not contain any stains or samotney, (2) the ink must be discarded without drying at the edges of the nozzle to prevent clogging at the same time maintaining good characteristics of emissions and sustainability, (3) the ink should have a good foothold on paper, (4) images must be resistant (i.e. resistant to weather, water or similar phenomena) and (5) images must be sustainable for a long time. In connection with the recent increase in printing speed is especially popular inks that dry quickly and are fixed, as well as provide high quality printing even on plain paper for printing, such as paper for copying.

Dyes for inkjet recording using aqueous ink mainly composed of a dye or pigment. Basically apply water-soluble dyes, as they are easy to use is good show color. Recently, however, widely used for water ink is practically insoluble in water paints, in particular pigments, which can provide higher resistance of the image obtained by the method of inkjet recording, to weather and water. If in the aqueous ink for inkjet recording is used water-insoluble dye, in particular, a pigment, it must be stably dispersible in water. The high stability of dispersions of water-insoluble dyes is primarily achieved by adding a surfactant or polymer dispersant (hereinafter referred to as "dispersant resin"). Other methods for producing stable dispersions of water-insoluble dyes include chemical modification of their surfaces (for example, published patent application of Japan No. N10-195360). On the other hand, was offered a pigment-based microcapsules, for example, the pigment with the shell of the resin (for example, published patent application of Japan No. N8-183920 and 2000-34770). In lined with the application for the Japan patent No. 2003-34770 described "thin-dispersed aqueous dispersion of the colored particles, which polymerizes in the presence of vinyl monomer after it introduced a water-insoluble dye is dispersed in water using a dispersant, where the dispersion exhibits stable the guard when the dispersant helps dispersing water-insoluble dye, and when the vinyl monomer is polymerized in the presence of the dispersant, the resulting latex is not stable, and described that "the dispersion of water-insoluble dye can be obtained by emulsion polymerization with a high yield in the absence of agglomeration thin-dispersed particles of the pigment in the shell, because the affinity of the dispersant to vinyl monomer and its polymer: not so high and thereby gain a limited separation from the surface of the pigment particles, and the polymerization takes place on the surfaces of the pigment particles adsorbed dispersant". The authors of this invention offer ink for inkjet recording, which have excellent stability of dispersion and print, give a slight metallic Shine and have excellent resistance to water, light and scratches regardless of the type of paper.

The invention

These techniques, however, are not always simultaneously and sufficiently satisfy the characteristics of the stability of the dispersion and stability when stored for long periods of time. The authors of the present invention believe that in order to be stably dispersible in ink, the dye must have a functional GRU is PU high density on the surface. In the application of conventional methods, which use a polymer dispersant, and the techniques described in application laid on the Japan patent No. N8-183920, which uses the pigment with the polymer membrane, the increase in acid number of the polymer to improve the stability of dispersion, sometimes may not provide sufficient stability during storage for a long time, because it is accompanied by increased hydrophilicity of the polymer and has a tendency to cause desorption of the polymer from the dye over time. On the other hand, modification of the surface of the water-insoluble dye chemical methods described in application laid on the Japan patent No. N10-195360, also faces challenges. For example, modifiable functional groups and their density is limited. Direct chemical modification, in particular, if the colorant is an organic pigment, can bind hydrophilic group 12 to the molecules of the pigment, which is initially insoluble in water and has a crystalline form, turning them into molecules hydrophilic pigment 13, which are separated from the molecules of the original pigment, significantly changing color, this phenomenon is called stratification color (Figa and 6B). Therefore, such conventional techniques have not been developed to the extent that meets modern requirements.

the Purpose of this invention is a dispersible dye, having a sufficiently high stability of the dispersion, in which there is no separation of the polymer component from the dye, and which is stable over a long period of time, which solves the problems of conventional techniques. Another purpose of this invention is the simple way to obtain the dye. Other objectives of this invention are aqueous inks containing excellent dispersible colorant for ink-jet recording, ink tank, ink-jet recording device, method of inkjet recording, and an image obtained by ink jet recording.

The authors of this invention have developed after a comprehensive study of the ways of solving the above problems, a new dispersible colorant having a new form, which can maintain a high stability of the dispersion is practically in the absence of surfactant or polymer dispersant containing polymer component, initially adsorbed to the colorant to achieve stability during storage over a long period of time. They have also developed the aqueous ink for inkjet recording having sufficient for the purposes of inkjet recording, the ejection stability and the stability of the dispersion, giving a printed image of high quality and durability that is achieved in the connection in their composition described above dispersible dye. More specifically, objects of this invention can be described as follows.

1. Dispersible dye containing a dye and pseudolocalization polarizable particles of polymer having a size smaller than the particles of the dye, where the colorant particles are attached to each other.

2. Dispersible dye containing a dye and pseudolocalization polarizable particles of polymer having a size smaller than the particles of the dye, where many particles are distributed on the dye and attached.

3. Dispersible colorant according to items 1 or 2, which has a density of surface functional groups of at least 250 µmol/g and not more than 1000 µmol/g

4. Dispersible colorant according to any one of items 1 to 3, which has a surface energy of 70 MJ/m2or less.

5. Dispersible colorant according to any one of items 1 to 4, in which the component is a copolymer containing pseudolocalization particles polarizable polymer has a glass transition temperature of not less than -40°s and 60°C.

6. Dispersible colorant according to any one of items 1 to 5, in which pseudolocalization polarizable particles of the polymer include a copolymer of monomer components containing at least one type of hydrophobic monomer and at least one type of hydrophilic monomer.

7. The var is geremy dye according to claim 6, in which the hydrophobic monomer contains at least a monomer having a methyl group in position α and the radical-curable unsaturated double bond.

8. Dispersible colorant according to any one of PP or 7, in which the hydrophobic monomer contains at least the connection type (meth)acrylic ester.

9. Dispersible colorant of claim 8, in which the hydrophobic monomer contains at least one compound selected from the group including bezelmaterial and methyl methacrylate.

10. Dispersible colorant according to any one of PP-9, in which the hydrophilic monomer contains at least anionic monomer.

11. Dispersible colorant of claim 10, in which the anionic monomer contains at least one compound selected from the group consisting of acrylic acid, methacrylic acid and n-styrelseledamot salts.

12. Dispersible colorant according to any one of PP-9, in which the hydrophilic monomer is used, at least a cationic monomer.

13. A method of obtaining a dispersible colorant comprising a stage of carrying out the polymerization process of deposition in the aquatic environment, capable of radical polymerization of the monomer in the aqueous dispersion of water-insoluble dye using a radical polymerization initiator in water to combine insoluble what about the dye in water with pseudoconditioning particles polarizable polymer.

14. A method of obtaining a dispersible colorant comprising a stage (1) carrying out the polymerization process of deposition in the aquatic environment, capable of radical polymerization of the monomer in the aqueous dispersion of water-insoluble dye using a radical polymerization initiator in water to combine water-insoluble dye with pseudoconditioning polarizable particles of the colorant; and

(2) cleaning of the product.

15. A method of obtaining a dispersible colorant according PP or 14, in which the aqueous dispersion of water-insoluble colorant is an aqueous solution containing a pigment dispersed with a polymer dispersant having an acid number of not less than 100 and not more than 250.

16. A method of obtaining a dispersible colorant according to § 15, in which the dispersant is a copolymer of monomer components containing at least one type of monomer selected from the group consisting of acrylic acid, methacrylic acid and styrene monomer.

17. A method of obtaining a dispersible colorant according PP or 16, in which the initiator of radical polymerization in water is anionic or ampholytic.

18. A method of obtaining a dispersible colorant according PP or 14, in which the aqueous dispersion of water-insoluble colorant is an aqueous solution containing the second pigment, dispersed with a polymeric dispersant having an acid number of not less than 150 and not more than 300.

19. A method of obtaining a dispersible colorant according p, in which the initiator of radical polymerization in water is a cationic or ampholytic.

20. A method of obtaining a dispersible colorant according to any one of PP-19, in which the radical-curable monomer component is added to the polymerization system.

21. A method of obtaining a dispersible colorant according to any one of PP-20, in which the radical-curable monomer component contains at least one type of hydrophobic monomer and at least one type of hydrophilic monomer.

22. A method of obtaining a dispersible colorant according to any one of PP-21, in which the initiator of radical polymerization in water is called an initiator atenonol polymerization in water.

23. Dispersible colorant obtained by the method according to any of PP-22.

24. Aqueous ink containing the dispersible colorant according to any one of items 1 to 12 and 23.

25. Aqueous ink containing a dispersible dye containing a dye and pseudolocalization polarizable particles of polymer having a size smaller than the particles of the dye, where the colorant particles are attached to each other, and optionally containing at least one type encodebegin the data particles satismarriages polymer.

26. Water ink on A.25, in which a polymer component that is pseudolocalization polarizable particles, and a polymeric component which comprises at least one type of particles satismarriages polymer containing a polymerization product mixture comprising at least one type of the total monomer component.

27. Aqueous ink for p, in which the polymer component is at least one type pseudoconditioning polarizable particles, and a polymeric component which comprises at least one type of particles satismarriages polymer contains a polymerization product of a mixture comprising at least one type of the total monomer component.

28. Aqueous ink containing a dispersible dye containing a dye and a negative polarizable pseudolocalization polarizable particles of polymer having a size smaller than the particles of the dye, where the colorant particles are attached to each other, and where the dispersible colorant has an average Zeta-potential of the surface is not less than -80 mV and not more than -15 mV in an aqueous environment, which is included in the aqueous ink, and the distribution of the Zeta-potential of the surface of less than 50, expressed as standard deviation.

29. Aqueous ink containing a dispersible dye, is holding a dye and a positive polarizable pseudolocalization particles polarizable polymer, having a size smaller than the particles of the dye, where the colorant particles are attached to each other, and where the dispersible colorant has an average Zeta potential of the surface of at least +10 mV and not more than +60 mV in an aqueous environment, which is included in the aqueous ink, and the distribution of the Zeta-potential of the surface of less than 50, expressed as standard deviation.

30. The aqueous ink according to any one of PP-29, where the dye, part of the dispersible colorant is a pigment, and where the ratio of the total polymer component to pigment (polymer/pigment or/R mass.) is not less than 0.3 and not more than 4.0.

31. The ink tank containing the aqueous ink according to any one of PP-30.

32. Inkjet recording device for acquiring images using the ink according to any one of PP-30.

33. The way inkjet recording for acquiring images using aqueous ink according to any one of PP-30 using an inkjet recording device.

34. The image obtained by the method of inkjet recording using aqueous ink according to any one of PP-30 using an inkjet recording device.

The present invention presents dispersible dye, which has a sufficiently high stability of the dispersion, with a high density of functional groups on the surface, contains on the surface of the polymer whom onent and has virtually no tendency to separate from the surface, and way easier to get a dispersible dye.

The present invention also presents dispersible colorant having other advantages, for example, a property fast drying on the substrate for recording, high scratch resistance on the substrate for recording and excellent emission characteristics shown in the inkjet recording device.

Other advantages of the dispersible colorant in accordance with this invention are excellent properties manifestations of colors and suitable for operation in environments with high or low pH. The present invention also presents a simple way of obtaining dispersible dye, which is another advantage of the present invention.

The present invention also presents aqueous ink suitable for use on highly glossy or glossy substrate for recording with high scratch resistance on a glossy substrate for recording and has excellent storage stability for a long period of time, which is another advantage of the present invention.

The present invention presents aqueous ink having a sufficient ejection stability and the stability of the dispersion for the purposes of the ink-jet recording and which allows to obtain a printed form with the high image quality and durability thanks to the introduction into them dispersible dye, and the capacity for storing ink, an inkjet recording device, method of inkjet recording, and an image obtained by the method of inkjet recording using aqueous ink.

Brief description of drawings

On Figa and 1B schematically shows the basic structure of the dispersible colorant in accordance with this invention with attached pseudoconditioning particles polarizable polymer.

Each of Figa, 2B, 2C and 2D presents a characteristic stage of the method in accordance with this invention.

Figure 3 schematically represents the stage of education pseudoconditioning particles polarizable polymer and another stage of the accession of these particles to the colorant in accordance with the method according to this invention.

4 shows an enlarged pseudolocalization polarizable particles of the polymer in accordance with this invention, located on the contact surface of the dye to which they are attached.

Figure 5 shows an enlarged contact surface on which pseudolocalization polarizable particles of polymer attached to the dye in accordance with this invention.

In Fig 6A and 6B schematically illustrates the phenomenon of disconnection of the pigment, as in the modification of organic p is gment with hydrophilic group, which is described in application laid on the Japan patent No. N10-195360.

On Figa, 7B and 7C schematically shows the agglomeration dispersible dye on the substrate for recording.

Best mode for carrying out the present invention

The invention is described in more detail in the variants of its implementation, which are considered the best ways. The term "dispersible dye"used in this description, assume the dye, which can be substantially dispersed in water or environment for liquid ink in the absence of a surfactant or a polymeric dispersant, for example, samogiciensis dye.

The first variant of implementation of the present invention is a dye and pseudolocalization polarizable particles of the polymer, where the particles of dye attached to the polymer particles. On Figa and 1B schematically shows the dye 1, attached particles 2, which is a feature of this invention. On FIGU shown schematically pseudolocalization polarizable particles of polymer 2, attached to the surface of the dye 1, being partially condensed in part 2'.

The dye is provided by the charge, which is determined pseudoconditioning particles polarizable polymer, attached keychain, four button is certain to its surface, so that the dye can be dispersed in water or environment for water ink. So get dispersible dye. At the same time he has a high degree of adhesion with the substrate for recording by the presence on its surface of the polymeric component. Moreover, the dispersible colorant in accordance with this invention has a high stability during storage over a long period of time due to pseudoconditioning polarizable particles of polymer attached to the surface of the dye, not the physical adsorption of the polymer component, which is also the hallmark of the dispersible colorant in accordance with this invention, which is hardly separates from the surface.

Pseudolocalization polarizable particles of the polymer in accordance with this invention are composed of polymer agglomerate, in which the polymer components are strongly agglomerated with each other, preferably have plenty of cross-linking in the polymer agglomerate consists of a polymer component, is constantly present in the form of a thin-dispersed particles, which can be agglomerated in other thin-dispersed particles. Pseudolocalization polarizable particles of polymer are described in detail below.

Pseudomonad piergiovanni polarizable particles of the polymer are attached to the dye in accordance with this invention due to the strong interaction between them. I believe that it is achieved due to the following phenomenon. Figure 4 schematically shows an enlarged contact surface on which pseudolocalization polarizable particles come into contact with the dye. It is necessary, first, to note that pseudolocalization polarizable particles of polymer are formed from a polymer consisting of compositions of different Monomeric units, woven with each other. The polymer in certain places accepts a variety of patterns on the surface of contact with the dye and, therefore, has a surface energy that is distributed locally. The dye and the polymer are firmly bound to each other in certain places, in which their surface energy, defined chemical and surface structure, match with each other (dark circles in figure 4). There are many places on the surface where they coincide with each other (designated 10 in figure 4). Consider that the particles attached to the dye in such places due to the strong interaction in accordance with this invention.

Each of pseudoconditioning particles polarizable polymer comprises polymers, strongly interacting with each other with the conventional formation of physical cross-linking. This prevents separation of the particles from the dye or the polymer component is a, having a hydrophilic group, and the constant washing away of particles, even if the particles contain many hydrophilic groups. On the contrary, the dye obtained by encapsulating (described, for example, posted in the patent application of Japan No. N8-183920) is not always demonstrates a sufficient storage stability for a long period of time, as strongly hydrophilic polymer may not be firmly connected with the dye.

Pseudolocalization polarizable particles of polymer attached to the dye to obtain a dispersible colorant in accordance with this invention have another advantage, which lies in the increased specific surface area due to the morphology of fixation. Increased specific surface very effectively contributes to the charge on the particles and on the surface of the dye. As a result, the surface of the dispersible colorant is a very highly charged. In other words, the dispersible colorant in accordance with this invention has a morphology in which the surface charge is more efficient and more strongly, and he has a higher stability of the dispersion as compared with the dye-coated with a polymer shell that is described in application laid on the Japan patent No. N8-183920, even if the polymer component has a lower to the PCI-e slot or amine number.

In General, organic pigments are resolubilization (suitable pigments), when bearing the color molecules are crystallized by the strong interaction. When using an organic pigment as the colorant for the dispersible colorant in accordance with this invention, pseudolocalization polarizable particles of the polymer are attached to the pigment particles over several dye molecules, as shown in Figure 5, due to the many interactions at the contact surface between pseudoconditioning polarizable particles and the colorant as described above. Therefore, the detachment of the pigment" (shown in Figa and 6B) caused by dye, becoming locally hydrophilic, should not occur in this invention. When using an organic pigment as the colorant preferably pseudolocalization particles polarizable polymer had a smaller size than the particles of the dispersed pigment, but larger than the molecules of the dye that gives dispersible dye containing highly dispersible pigment, without destroying the crystalline structure of the pigment.

The terms "fastener" pseudoconditioning polarizable particles of the polymer to the dye in this invention may be the simply confirmed by the following method, including split in three stages. At the first stage of the test dye is separated from the other water-soluble components (including water-soluble polymer)that is present in the ink or water dispersion. In the second stage, the dye and the water-insoluble polymer component is separated from the precipitate obtained in the first stage. The third stage is divided weakly adsorbed polymer component and dispersible dye, attached pseudolocalization polarizable particles of the polymer, for the quantitative analysis of polymer component in the supernatant solution obtained in the third stage, and compare the precipitate obtained in the second stage with the sediment obtained in the third stage. This method can confirm the conditions in which pseudolocalization polarizable particles of the polymer are attached to the dye.

More specifically, the conditions can be confirmed by the following methods. Get ink or aqueous dispersion (20 g), in which the dispersed dye in an amount of about 10 wt.% by weight of the total solids, and centrifuged at 12,000 rpm for 60 minutes in the first stage. The precipitate containing the dye deposited in the lower layer, re-dispersed in almost triple the amount of pure water and centrifuged at 80000 rpm for 90 min is t in the second stage. Then the precipitate containing the dye deposited in the lower layer, re-dispersed in triple the amount of pure water and again centrifuged at 80000 rpm for 90 minutes in the third stage. The precipitate containing the dye deposited in the lower layer is collected from the system. The precipitate obtained at the second and third stages, dried in vacuum at a temperature of 30°C for 18 hours and studied by scanning electron microscope with a magnification of 50,000, with each resulting sample contains about 0.5 g of solids. If the study dispersible dye has many thin-dispersed particles or similar agglomerates attached to the surface, and the precipitate obtained at the second and third stages, has the same morphology, it is considered that pseudolocalization polarizable particles of polymer attached to the dye. In addition, about half of the upper supernatant layer obtained in the third stage, slowly collected from the system and dried at a temperature of 60°C for 8 hours to determine the content of solids based on the difference of weight before and after drying. If it is less than 1%, believe that pseudolocalization polarizable particles of the polymer are not separated from the dispersible colorant and the particles attached to the dye.

Conditions of separation described above, I have considered the preferred example, but can be used any methods to assess whether the dye dispersible dye in accordance with this invention, if it satises the conditions of division three stages. More specifically, the first stage separates the dye present in the ink or water dispersion, and the polymer components adsorbed thereon from the water-soluble components. In the second stage separates the dye and the polymer component attached to it, from the other polymer component(s)adsorbed in the dye. In the third stage, confirm that the polymer component is attached to the dye, is not separated from the dye. Needless to say, that can be applied to any method that can satisfy the objectives of each stage, whether it is known or new. They may include more or less than three stages.

A second embodiment of the present invention is a dispersible dye, which is satisfacgermany, with pseudoconditioning polarizable particles of polymer 2, attached to a water-insoluble dye 1. As described above, the dispersible colorant in accordance with this invention is satisfacgermany, i.e. he can steadily dispergirujutsja in water and aqueous ink, especially in the absence of surface-Akti the different substances or polymer dispersant. Definition and evaluation method described below. Dispersible colorant in accordance with this invention can be distributed without polymeric dispersant, other polymeric component or surface-active substances that can be separated from the dye in for longer periods and which are traditionally used to stabilize the dispersion of the dye. As a result, the dispersible colorant in accordance with this invention gives another advantage of the aqueous ink, namely a greater degree of freedom in selection of components, non-dispersible dye. Therefore, the aqueous ink containing the dispersible colorant in accordance with this invention, can provide a sufficiently high concentration of printing even on permeable to ink the substrate for recording, for example, plain paper for printing.

Satisfaroriamente dispersible colorant in accordance with this invention may be confirmed, for example, by the following method. Ink or aqueous dispersion in which the dispersed dye, a tenfold diluted with pure water and concentrate to the initial concentration using ultrafilter catching a molecular weight of 50000. The concentrated solution was centrifuged at 12000 rpm for 2 hours, and the precipitate sobi is try and re-dispersed in pure water. The dye is satisfacgermany, if the sediment is well re-dispersed. Good or bad, whether it is dispersed, evaluate, taking into account the following observations; visually, the dispersion is homogeneous, after maturation of the solution within 1-2 hours no visible precipitate is observed, or the residue, if any, may be dispersed with a light shake of the solution, and the diameter of the dispersed particles, a certain dynamic svetorasseyanie, not more than 2 times the diameter of the particles before processing.

As described above, the dispersible colorant in accordance with this invention has a large specific surface area, which is obtained by attaching pseudoconditioning polarizable particles of the polymer to the dye, and has excellent stability during storage, being strongly charged over a large area. More preferable results can be obtained by applying pseudoconditioning polarizable particles of the polymer in a large number attached to the dye at uniform distribution. Particularly preferably, these particles were at a certain distance from each other and, preferably, uniformly distributed. Even more preferably, the surface of the dye between such particles should be open. Such is morfologii can be confirmed by transmission or scanning electron microscope. In other words, research microscopes can confirm whether the particles at a certain distance from each other, or opened if the surface of the dye between such particles. Such particles can be places closer to each other or fused with each other in some cases. However, in the art it is obvious that such particles attached to the dye, if in General they are at a certain distance from each other or the surface of the dye between such particles is open, and these conditions prevail.

Moreover, it was found that the aqueous ink containing the dispersible colorant in accordance with this invention, dry quickly on the substrate for recording, presumably due to the following mechanism, which, however, is not fully confirmed. Dispersible colorant is dispersed in the ink attached to the surface pseudoconditioning polarizable particles of the polymer, as described above. When the ink into the substrate for recording, the solvent in the ink is absorbed into the fine pores of the substrate (the space between the cellulose fibers of the paper, or small pores in the receiving layer for coated paper or glossy paper), due to the phenomenon of capillarity. Then dispersible colorant in accordance with the data and the acquisition makes a lot of small gaps on the square, where the dye is in contact with each other, and uniformly distributed pseudolocalization polarizable particles of polymer that is the result of its morphological characteristics. Therefore, the ink solvent is present between the particles of the dye, is rapidly absorbed in the substrate for recording due to the phenomenon of capillarity. The aqueous ink in accordance with this invention have the preferred characteristics of fast drying, if they contain dispersible dye containing pseudolocalization particles polarizable polymer uniformly distributed on the surface. This observation confirms the above mechanism for fast drying.

Dispersible colorant in accordance with this invention preferably has a surface functional group density of at least 250 µmol/g and not more than 1000 μmol/g, more preferably not less than 290 µmol/g and not more than 900 µmol/g. He may have the worst characteristics of stability during storage over a long period of time if the density is less specified. At much higher density, on the other hand, it can be difficult to withstand high concentrations of printing due to excessive stability of the dispersion and, consequently, the permeability of the substrate for recording. The raft is ity of surface functional groups, more preferably not less than 350 µmol/g and not more than 800 µmol/g when used as a colorant carbon black, since carbon black has a higher specific weight, the higher the stability of the dispersion and a higher concentration of black on the substrate for recording. The density of the surface functional groups can be determined, for example, by the following method, if the dispersible colorant is charged negatively. The water dispersion or the ink containing the dispersible colorant, diluted with excess hydrochloric acid (HCl) and centrifuged at 20,000 rpm for 1 hour. The precipitate is collected and re-dispersed in pure water, and the concentration of solids in the sediment is determined by the method of drying. Re-dispersed residue is weighed and then added a known amount of sodium bicarbonate. The mixture is stirred to obtain a dispersion, which is centrifuged at 80000 rpm for 2 hours. The supernatant solution is weighed and titrated with 0.1 G. of hydrochloric acid for neutralization, allowing you to determine the density of the surface functional group (mol/g - dye) by subtracting a known quantity of sodium bicarbonate from quantity to neutralize. If the dispersible colorant charged cationic group as the polar group, the density of the surface functional groups is determined by a similar method except that hloristovodorodnykh acid and sodium bicarbonate is substituted for the sodium hydroxide (NaOH) and ammonium chloride, respectively.

Dispersible colorant having a surface energy of 70 MJ/m2or less, is one of the preferred variants of the present invention. The authors of this invention have found that the dispersible colorant can provide adequate fixation on the substrate for recording, if the surface energy is in the specified interval. The dye having a surface energy substantially in excess of 70 MJ/m2can impede the uniform allocation of the dye from the aqueous medium of the ink due to excessive hydrophilicity of the surface of the dispersible colorant and may impede uniform drying of the printed image. In addition, the dried image may be insufficiently resistant to water, presumably due to the strong hydrophilicity of the surface dispersible dye that causes the re-dispersion of the dye on the substrate for recording after sintering, if the image is in contact with water or water with a marker. The surface energy dispersible colorant in accordance with this invention can be controlled surface charge of the dye, the structure of the functional groups and chemical and surface structure pseudoconditioning polarizable particles of polymer attached to the dye. Also what about the, chemical and surface structure pseudoconditioning polarizable particles of polymer can be controlled by any polymerization initiator and monomer components in the synthesis of particles.

"Surface energy" in this description means the free energy at the contact surface between the material and depends on the chemical structure of the contact surface. Material with a higher surface energy is more wettable and is compatible with water. The surface energy dispersible dye is defined as the value determined using inverse gas chromatograph from Surface Measurement System. More specifically, it is determined by extrapolation to the retention time of gas for dispersible dye, the cured powder, as stationary phase, and an organic gas with different polarity of the mobile phase.

The following describes each component of the dispersible colorant in accordance with this invention.

Dye

Described dye, which is one of the components of the dispersible colorant in accordance with this invention. This can be any known or new dye. However, preferably, it was a hydrophobic dye, inorganic pigment, organic pigment, a metal colloid is whether colored polymer powder, insoluble in water and can be stably dispersed in water in the presence of dispersant. Preferably, the diameter of its particles is, in the dispersion, from 0.01 to 0.5 μm (10 to 500 nm, more preferably from 0.03 to 0.3 μm (from 30 to 300 nm). Dispersible colorant in accordance with this invention, the particles of which, in the dispersion have a diameter in the above range, an excellent dispersible dye to the aqueous ink, such as dye has a high ability to staining and gives images a high degree of resistance to the environment. The diameter in the dispersion is defined as the cumulative average diameter, determined by a dynamic scattering.

Inorganic pigments used for the coloring agent include carbon black, titanium oxide, white zinc, zinc oxide, tripon, iron oxide, aluminum oxide, silicon dioxide, kaolinite, montmorillonite, talc, barium sulfate, calcium carbonate, silica, alumina, cadmium red, red iron oxide, molybdenum red, chrome vermillion, molybdate orange, yellow lead, chrome yellow, cadmium yellow, yellow iron oxide, yellow titanium, chromium oxide, peridian, green, cobalt green, titanium cobalt green, chromium-cobalt, deep blue, ultramarine blue, Prussian blue, cobalt blue, cerulean blue, fioletowypartner, purple cobalt and mica.

Organic pigments used in this invention include pigments based on azo compounds of h, poliuto, phthalocyanine, chinagreen, anthraquinone, Indigo, thioindigo, hinaplanon, benzimidazolone, isoindoline and isoindoline.

Organic, water-insoluble dyes used in accordance with this invention include hydrophobic dyes, for example, on the basis of azo compounds, anthraquinone, Indigo, phthalocyanine, carbonyl, hennipin, Metin, quinoline and nitro. Among them, particularly preferred dispersible dyes.

Pseudolocalization particles polarizable polymer

Pseudolocalization polarizable particles of polymer which are another component of the dispersible colorant in accordance with this invention, defined as small agglomerates of polymer with a sufficiently high degree of polymerization having a small dispersible units (diameter in dispersion in water (or ink), which are attached to the dye. Fine sinter morphologically close to the field in pseudowire or in the form of a thin-dispersed agglomerated particles (pseudolocalization particles polarizable polymer)having the same size in a certain interval. Polymer component pseudoman dispergirovannykh particles polarizable polymer preferably consists of particles, physically or chemically cross stitched with each other. Whether they are cross-linked with each other, can be checked using, for example, the following method. A polymer component that consists of pseudoconditioning polarizable particles, appreciate in advance by a known method of analysis and synthesized by polymerization in the solution of a linear polymer with the same chemical structure or composition of the Monomeric units). Then pseudolocalization polarizable particles of the polymer and the polymer are mixed in an organic solvent, which is a good solvent for the polymer, to compare their solubility. Pseudolocalization polarizable particles of polymer are cross-linked within, if they have a lower solubility compared to the polymer.

Other preferred are particles having a cumulative average diameter of not less than 10 nm and not more than 200 nm, when measured by a dynamic scattering. More preferably, the particles have a coefficient of polydispersity diameter in the dispersion is not less than 0.2, from the standpoint of stability during storage dispersible dye for a long period of time. Stabilization of fine-dispersed dye, which is one of the main purposes of this invention, cannot be postign is the if the dispersed particles have an average diameter of more than 200 nm or coefficient of polydispersity is more than 0.2. On the other hand, pseudolocalization polarizable particles of polymer having an average diameter of less than 10 nm, may not have the advantages of the present invention, as they will not be able to sufficiently maintain the morphology pseudoconditioning polarizable particles of the polymer, and the polymer will be more easy to dissolve in water. Dispersed particles having an average diameter of not less than 10 nm and not more than 200 nm, can effectively give a stable dispersion of the dye, which is achieved by attaching pseudoconditioning polarizable particles of the polymer to the dye, since they are smaller than the particles of dye. The above preferred options are valid for cases where the diameter of the dispersed pseudoconditioning particles polarizable polymer cannot be measured. In this case, the diameter can be determined using an electron microscope. The preferred spacing diameter should be such as specified above, or close to it.

If the colorant is an organic pigment, particularly preferably dispersed pseudolocalization particles polarizable polymer had an average diameter shown in the above range and, at the same time, were smaller than the particles dispersible pigment, and more than molecules dispersed dye, since the satisfaction of these conditions, you can get a very stable structure and vysokodispersnyi dye.

The polarizable particles in accordance with this invention are particles that have some kind of an ionized functional group in an aqueous medium, preferably, samodoprinos due to its polarizability. Whether pseudolocalization polarizable particles can confirm one of the following known methods; measurement of Zeta-potential of the surface of the particles, potentiometric titration to determine the density of functional groups, described below, confirm the dependence of stability of the dispersion pseudoconditioning particles polarizable polymer concentration of the electrolyte after the aqueous dispersion of particles is mixed with the electrolyte, and the analysis of the chemical structure pseudoconditioning particles polarizable polymer to confirm the presence of ionic functional groups.

Polymer component pseudoconditioning particles polarizable polymer is not limited and may be selected from any natural or synthetic polymeric compounds, and that the same polymer compound, obtained in accordance with this invention. The polymers used as the polymeric component in accordance with this invention include acrylic, styrene/acrylic, polyester, polyurethane and polyurea polymer, as well as polysaccharides and polypeptides. In particular, preferred polymers and copolymers having a radical-curable unsaturated bond, which are characterized by acrylic, styrene/acrylic polymers, since they can be widely applied and can be easily processed to obtain characteristics pseudoconditioning polarizable particles.

Monomers having a radically-curable unsaturated bond (hereinafter called "radical-curable monomers or just monomers), preferably used in accordance with this invention include hydrophobic monomers such as (meth)acrylic esters such as methyl acrylate, acrylate, isopropylacetate, n-propylacetate, n-butyl acrylate, tert-butyl acrylate, benzoylacrylate, methyl methacrylate, ethyl methacrylate, isopropylacetate, n-propylbetaine, n-butylmethacrylate, ISO-butylmethacrylate, tert-butylmethacrylate, tridecylamine and bezelmaterial; based monomers styrene, for example styrene, α-methylsterol, o-methylsterol, m methylsterol, p-methylsterol and p-tert-butalbiral; SL is the author esters basis of itaconic acid, for example benzylmalonate; esters of maleic acid, such as dimethylmaleic; esters of fumaric acid, such as dimethylfumarate; and Acrylonitrile, Methacrylonitrile and vinyl acetate.

The following compounds, which are classified as hydrophilic monomers are also preferably used in accordance with this invention include monomers having anionic group, such as monomers having a carboxyl group, for example, acrylic acid, methacrylic acid, crotonic acid, etakrinova acid, propylacetate, isopropylacrylamide acid, fumaric acid and their salts; monomers having a sulfonic acid group, for example, styrelseledamot, 2-propyltrichlorosilane, (acrylic acid)-2-ethylsulfonyl, (methacrylic acid)-2-ethylsulfonyl, butylacrylamide sulfonate and their salts; and monomers having a phosphonic acid group, for example (methacrylic acid)-2-ethylphosphonate and (acrylic acid)-2-ethylphosphonate. Among them, more preferred are acrylic acid and methacrylic acid.

Monomers having a cationic group include monomers having a primary amino group, such as aminoaciduria, aminopropylsilyl, amylmetacresol, aminoacylation, aminopropionitrile; monomers having a secondary amino group, such as methylaminoethanol methylaminopropyl, acylaminoalkyl, ethylenepropylene, methylaminomethyl, methylaminopropyl, ethylaminomethyl and ethylenepropylene; monomers having a tertiary amino group, such as dimethylaminoethylacrylate, diethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dimethylaminoethylmethacrylate, diethylaminoethylmethacrylate, dimethylaminoethylmethacrylate and diethylaminopropylamine; monomers having a Quaternary ammonium group, for example, chloride dimethylaminoethylmethacrylate chloride dimethylaminoethylmethacrylate chloride dimethylaminoethylmethacrylate chloride dimethylaminoethylmethacrylate; and vinyl imidazoles.

Non-ionic hydrophilic monomers include compounds having a radical-curable unsaturated bond and a hydroxyl group, which have a strong hydrophilicity. They include hydroxymethyl(meth)acrylate, hydroxyethyl(meth)acrylate and hydroxypropyl(meth)acrylate. Other known or new oligomers and micronaire different types can be used without restrictions.

The use of cross-linked monomer is yet another preferred option. Such monomers include divinylbenzene, allyl(meth)acrylate and methylenebisacrylamide. Can be applied to other known or new cross-linked m is the numbers of different types.

Various characteristics of the dispersible colorant and pseudoconditioning polarizable particles of polymer can be appropriately controlled according to the number of control parameters such as the type and the ratio of copolymerization of the monomer, which is pseudolocalization polarizable particles of the polymer, and the type and concentration of the polymerization initiator for polymerization of the monomer. The use of a copolymer consisting of at least one type of hydrophobic monomer and at least one type of hydrophilic monomer selected from the above, for pseudoconditioning particles polarizable polymer is one of the most preferred options. The use of at least one type of hydrophobic monomer gives particles with excellent properties attached to the dye and thermal stability, and the use of at least one type of hydrophilic monomer gives good control of the morphology and the stability of the dispersion. Therefore the introduction of such monomers can give pseudolocalization polarizable particles of polymer which are well attached to the dye and have a good stability of the dispersion. Pseudolocalization particles polarizable polymer attached to each other, to disperser is the reception of the colorant and/or dye in accordance with this invention, can have one or more additional functions, by choosing the right type of monomer and copolymerization ratio for the polymer component, which has one or more functions in addition to those described above.

For example, in one preferred options used at least one type of hydrophobic monomer, which has a methyl group in position α and the radical-curable unsaturated bond. Aqueous ink containing the dispersible colorant with pseudoconditioning polarizable particles of polymer attached to the dye, have very good vybrasyvaet, in particular, when thermal inkjet recording, the ink are ejected using thermal energy, if the polarizable particles used radical-curable monomer having a methyl group in position α. Improved vybrasyvaet is considered as a result of depolymerization of a polymer consisting of a radical-curable monomer having a methyl group in position αat high temperatures, to prevent adhesion of the polymer to the inside of the holes for ejection, when the ink is exposed to thermal energy, although this concept has not been fully established.

In another preferred embodiment, use of hydrophobic monomial is, which contains at least alkilany ester of acrylic or methacrylic acid (hereinafter designated as alkilany ester of (meth)acrylic acid). Alkilany ester of (meth)acrylic acid has a high degree of attachment to the dye and to a large extent lightly copolymerized with a hydrophilic monomer component and, therefore, gives a favorable characteristics pseudoconditioning particles polarizable polymer, for example, homogeneous surface characteristics and uniform attachment of the dye.

Among the preferred hydrophobic monomers are more preferred are bezelmaterial and methyl methacrylate, and particularly preferable to apply at least one of them, as they give, in addition to the above characteristics, the favorable characteristics of heat resistance and transparency pseudoconditioning polarizable particles of the polymer. As a result, the dispersible colorant containing such particles, has a superb degree of manifestation of color.

As described above, the characteristics pseudoconditioning polarizable particles of polymer attached to the dispersible colorant in accordance with this invention and/or dye for him, can properly be controlled by selecting the type and ratio of copolymerizate the monomer, which is particles. Copolymer component particles preferably has a glass transition temperature of not less than -40°s and 60°S, more preferably not less than -30°and not more than 55°S, even more preferably, not less than -25°and not more than 53°that is another preferred option. For such particles, the monomer which gives a homopolymer having a low glass transition temperature, are selected from the preferred monomers described above. The combination of n-butyl acrylate and acrylic acid in an appropriate ratio is one of the preferred Monomeric components. The combination of ethyl methacrylate and methacrylic acid in an appropriate ratio is also one of the preferred Monomeric components. The glass transition temperature pseudoconditioning polarizable particles of polymer can be determined by analysis on a differential scanning calorimeter. For example, it is determined on the analyzer (METTLER, DSC822e). The analysis is described in detail in the examples.

Dispersible colorant-containing component is a copolymer having a glass transition temperature of not less than -40°s and 60°get in the film formed with the dye on the substrate for recording with obtaining durable, colored film with excellent for skinning t what you pseudoconditioning polarizable particles of the polymer. Therefore, the dispersible colorant having the above structure, the image gives great strength to scratches, even if it is formed on a glossy substrate for recording, which is not very preferable from the viewpoint of stability of the image to scratches.

Aqueous ink containing the dispersible colorant in accordance with this invention containing the component is a copolymer having a glass transition temperature in the above range, given an image, highly resistant to scratches, even if it is deposited on the substrate for recording temperatures not much different from room temperature. The reason for this phenomenon is not clear, but the authors of the present invention involve the following mechanism. The glass transition temperature of the polymer, determined by analysis on a differential scanning calorimeter, in General, is characteristic of the polymer in the dried state, and it is known that it is lower for the polymer, which contains absorbed water. In pseudoconditioning particles polarizable polymers that are dispersible colorant in accordance with this invention, the polymer contains absorbed water in at least that part of it, which is around the ionic functional group. Pseudolocalization polarizable particles of the polymer having the t lower glass transition temperature compared to the measured if they are dispersible dye, in aqueous medium to obtain aqueous ink. Therefore, such particles may exhibit characteristics of film forming and adhesion when they are on the substrate for recording. The authors of this invention have found that such particles exhibit these characteristics, if the glass transition temperature is in the range of not less than -30°and not more than 55°S, more preferably not less than -25°and not more than 53°and give a more favorable result if the polymer component for such particles contains at least one type of hydrophilic monomer.

Composition with an anionic monomer as the hydrophilic monomer is yet another preferred option pseudoconditioning particles polarizable polymer comprising a copolymer containing at least one type of hydrophobic monomer and at least one type of hydrophilic monomer. In particular, the introduction of the anionic monomer may specify a higher number of anionic groups in pseudolocalization polarizable particles of the polymer, and therefore, it is also good practice to control the density of the surface functional groups on the surface of the dye to the desired level, as described above. Dispersible paints the eh may exhibit a higher stability of the dispersion at high pH, if it contains anionic monomer.

Anionic monomer used in accordance with this invention, is not limited if it has a functional group that is anionic in water. Particularly preferred examples include acrylic acid, methacrylic acid, p-styrelseledamot and their salts, considered from the point of view of ability to copolymerization with another monomer component, availability and anionic strength.

If the above composition also contains at least a cationic monomer as a hydrophilic monomer, dispersible dye will have a higher stability of dispersion in the environment with low pH. Such compositions, therefore, are another preferred choice. The cationic monomer used in accordance with this invention, is not limited if it has a functional group that is cationic in the water. From a radically-curable monomers mentioned above, preferably used are those which have a cationic group.

Synthesis pseudoconditioning polarizable particles of polymer and their attachment to the dye.

Pseudolocalization polarizable particles of polymer can be synthesized by known methods or methods and can be attached to the dye-known method of producing dye. And the Torah of the present invention was developed, as a result of extensive studies, the simple way to obtain a dispersible colorant with specified characteristics containing the dye and pseudolocalization polarizable particles of polymer having a size smaller than the dye, where the colorant particles are attached to each other. A method of obtaining a dispersible colorant in accordance with this invention, which preferably is carried out in this invention, below.

The authors of this invention have found that the dispersible colorant having the above characteristics, can be very simply obtained by polymerization by precipitation in water, carried out under the following conditions.

Firstly, water-insoluble dye is dispersed in the presence of a dispersant to obtain an aqueous solution dispergirovannogo dye. Then polimerizuet radical-curable monomer in the presence of a radical polymerization initiator in an aqueous dispersion by polymerization of deposition for attaching pseudoconditioning polarizable particles of the polymer to the dye. Dispersible colorant obtained by polymerization by precipitation in water, contains pseudolocalization polarizable particles of polymer that are well received in this way, uniformly distributed, attached to the dye. aspergery dye has excellent stability of the dispersion itself. The above-described desirable characteristics pseudoconditioning polarizable particles of polymer can be easily controlled during polymerization by precipitation in water, simultaneously reaching specified in this invention the characteristics attached to the dye. Preferred variants of the above method of obtaining described in detail below.

Dispersion of water-insoluble dye.

Firstly, water-insoluble dye selected from the preferred options in accordance with this invention, is dispersed in the presence of a dispersant with obtaining a water dispersion. Dispersant for dispersing the dye in an aqueous medium is not limited and may be ionic or non-ionic. However, it is preferable to use a polymer dispersant or a water-soluble polymeric compound to maintain the stability of the dispersion at a later stage of polymerization. Especially preferred is the radical-curable monomer that is soluble in water and must be entered into the surface of the particles of colorant and at the stage of polymerization. Even more preferably, it has a hydrophobic segment, which provides the centers for adsorption of hydrophobic monomer on the surface of the oil drops. Even more preferably, it contains at least one type of guy who riobravo monomer, applied at a later stage of polymerization, as it can strengthen the attachment pseudoconditioning polarizable particles of the polymer to the dye at this stage.

A method of obtaining a polymer dispersant or a water-soluble polymer compound, is used as the dispersant in accordance with this invention, is not limited. For example, it may be obtained by the interaction of the monomer having an ionic group with other polymerized monomer in directionspanel solvent in the presence or in the absence of catalyst. Found that good results can be obtained with dispersant based on styrene/acrylic polymer compound obtained by polymerization of the above monomer having an ionic group and a styrene monomer as main components, or based on acrylic polymer compound having an ionic group, obtained by polymerization of a monomer having an ionic group and a monomer based on a complex ester of (meth)acrylic acid having at least 5 carbon atoms as main components. It is preferable to use anionic dispersant, if you get dispersible dye containing an anionic group, and a dispersant having a cationic or non-ionic group, if you get dispersible dye, the ima is the overall cationic group.

If attaching pseudoconditioning polarizable particles of the polymer to the dye should be increased in the process of polymerization by precipitation in water and, at the same time, the stability of the dispersion should be maintained at the stage of polymerization, it is preferable to use anionic dispersant having an acid number of not less than 100 and not more than 250, or cationic dispersant, having an amine number of at least 150 and not more than 300. In the presence of a dispersant having an acid or amine number below the above limits, pseudolocalization polarizable particles of polymer may not preserve a good dispersibility, as the hydrophobic monomer is more compatible with the dispersant, than with the dye in the polymerization process of deposition in water, resulting dispersant is separated from the surface of the dye before pseudolocalization particles polarizable polymer will be attached to the dye. On the other hand, in the presence of a dispersant having an acid or amine number higher than the above limits, attaching pseudoconditioning polarizable particles of the polymer to the surface of the dye can be slow, as it is very strong in the surround replacement or static repulsion on the surface of the dye. If the application is aetsa anionic dispersant, he preferably should have a carboxyl group as the anionic group, from the viewpoint of preventing deceleration attach pseudoconditioning polarizable particles of the polymer to the dye.

At the stage of dispersion of water-insoluble colorant with obtaining a water dispersion, the dye preferably has a diameter of not less than 0.01 μm and not more than 0.5 μm (not less than 10 nm and not more than 500 nm, especially preferably not less than 0.03 μm and not more than 0.3 μm (not less than 30 nm and not more than 300 nm), after dispersion. The diameter in the dispersion at this stage greatly affects the diameter in the dispersion obtained dispersible dye. Therefore, it is preferable that he was above the limits from the point of view of the control capabilities of the dye image stability to the environment and the stability of the dispersion.

Water-insoluble dye in accordance with this invention preferably has a size of dispersed particles is close to monodisperse distribution. In General, the dispersible colorant with pseudoconditioning polarizable particles of polymer attached to the dye, usually has a distribution of particle diameter is narrower than this figure in water dispersion, processed at the stage of polymerization, as shown in Figv, although mainly depends on more than n the late distribution. It is important to narrow the diameter distribution of the particles of the dye, as it allows you to call the attach pseudoconditioning polarizable particles of the polymer to the dye by heteroallyl. The authors of this invention have found that the use of a dye having a coefficient of polydispersity 0.25 or less, gives dispersible dye with excellent dispersion stability.

Various analytical methods give different diameter particles dispersible dye. In particular, the particles of the organic pigment are rarely spherical. In this description, the diameter of the particles presents the average particle size and coefficient of polydispersity measured by a dynamic scattering (analyzer: Otsuka Electronics ELS-8000) and a specific cumulative analysis.

The method of dispersing water-insoluble dye in water is not limited, while it is the choice of methods, giving a stable dispersion of the dye in water under the conditions described above, in the presence of dispersant, as described above. He may be known or newly developed for this invention. If water-insoluble dye is a pigment, the polymeric dispersant is introduced in an amount not less than 10% and not more than 130 wt.% with respect to the pigment mass.

Water-insoluble dye in accordance with this is Subramaniam preferably is not satisfacgermany, because it allows you to control the characteristics of the dispersible colorant obtained described above, the preferred option for obtaining pseudoconditioning particles polarizable polymer.

The method of dispersing the dye in accordance with this invention is not limited insofar as it is widely used for dye may be selected from those methods that use machine for dispersion, for example, a shaker for dyes, sand mill, a mill with three shafts and the like, a high-pressure homogenizer, such as microfluidizer, denominator or MULTIMASTER, or machine for ultrasonic dispersion.

The radical polymerization initiator

The radical polymerization initiator in accordance with this invention is not limited if only it is well-known water-soluble initiator of radical polymerization.

Specific examples of the water-soluble initiator for radical polymerization include persulfates and water-soluble azo compounds. This can be the initiator of the reduction-oxidation, consisting of a combination of water-soluble initiator of radical polymerization and a reducing agent. More specifically, the optimal combination is created and applied depending on the characteristics of the IR dye, dispersant and monomer described above. Preferably, it is chosen from the initiators, giving a residue of the polymerization initiator having the same sign polarity, and surface characteristics of the resulting dispersible dye. For example, it is chosen from the initiators, giving a neutral or anionic residue of an initiator of polymerization, if you get a water-insoluble dye having anionic group. This allows more efficient to get the surface charge. Similarly, it is preferably selected from initiators, giving a neutral or cationic residue of the polymerization initiator, if you get dispersible dye having a cationic group.

The use of a water-soluble azo compounds as initiators of radical polymerization (hereinafter called ″initiator of radical polymerization in aqueous azo″) is another preferred variant of the present invention. The initiators of radical polymerization-based azo, including water, are compounds having at least one isogroup where Isograph decomposes with heat (or light) to produce radicals, thereby initiating polymerization. The radical polymerization initiator based on azo gives a reduction of pH in the polymerization system to the lower limit, as it maintains deistvuet with persulfate and therefore, more effectively control the formation of large particles as a result of the deterioration in the dispersive ability of the pigment system. The radical polymerization initiator based on the azo compounds used for the polymerization in accordance with this invention with certain organic pigment, in particular, pigment-based chinagreen as water-insoluble dye reduces the amount of unreacted monomer after polymerization and provides sufficient transformation. Therefore this option is especially preferred. Pigment-based chinagreen has a structure represented by General formula (1):

More specifically, these pigments include P.V (purple pigment) 19, P.R. (red pigment) 122, P.R. 192, P.R. 202, P.R. 206, P.R. 207 and P.R. 209, P.R. 122, as one of the preferred pigments in accordance with this invention, represented by General formula (1), where R2and R9each are CH3and R1, R3, R4, R8, R10and R11each are N.

The initiators of radical polymerization-based azo compounds are preferred in accordance with this invention include initiators commonly used for polymerization in emulsion or the like. In addition, they may be new, designed for the polymerization of e is Ulzii. More specifically, they include VA-080 (2,2'-azobis(2-methyl-N-(1,1-bis(hydroxymethyl)-2-hydroxyethyl)propionamide)), VA-086 (2,2'-azobis (2-methyl-N-(2-hydroxyethyl) propionamide)), VA-057 (2,2'-azobis(2-(N-(2-carboxyethyl)amidino)propane)), VA-058 (2,2'-azobis(2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane)dihydrochloride)), VA-060 (2,2'-azobis(2-(1-(2-hydroxyethyl)-2-imidazolin-2-yl)propane)dihydrochloride)), V-50 (2,2'-azobis(2-amidinopropane)dihydrochloride)and V-501 (4,4'-azobis(4-cyanobacteria acid)) (all supplied Wako Pure Chemical Industries). Among the initiators of radical polymerization-based initiator azo compounds having a carboxylic acid group and the amino group, for example, VA-057 (2,2'-azobis(2-(N-(2-carboxyethyl)amidino)propane)), gives another advantage in addition to those described previously. The remainder of the initiator associated with the surface pseudoconditioning particles polarizable polymer is ampholytic and gives a dispersible colorant having a good stability of the dispersion with a wide range of pH. The use of such initiator is further preferred in accordance with this invention.

Radical-curable monomer

Radical-curable monomer for the method in accordance with this invention is a component that is pseudolocalization particles polarizable polymer after about the of an unforgettable polymerization by precipitation in water, described above. He can be properly selected based on the characteristics pseudoconditioning polarizable particles of the polymer and the resulting dispersible dye, as described above for virtually insoluble in water and thin-dispersed particles of the polymer. Radical-curable monomer in accordance with this invention is not limited. He may be known or new.

Polymerization deposition in water

Next will be described the preferred options for polymerization by precipitation in water as a stage of synthesis pseudoconditioning polarizable particles of polymer and their attachment to the dye that is a feature of the present invention. It should be clear that this invention is not limited to the variants described below. On Figa-2D schematically illustrates this process. It is believed that the process includes the following stages of the dispersible colorant. First, dye 1 was dispersed in an aqueous solution in the presence of dispersant 3 with obtaining a water dispersion (Figa). Dispersion of dye 1 stabilize in the presence of adsorbed dispersant 3, and adsorption is thermally equilibrium. Then, the above aqueous dispersion is heated under stirring, and it adds a Monomeric component 4 together, for example, with water andnot what ecorom radical polymerization 5 (Pigv). The initiator 5 decomposes when heated emitting radicals, thereby enhancing the reaction between a hydrophobic monomer, dissolved in trace quantities in the aqueous phase, and water-soluble monomer present in the aqueous phase.

Figure 3 schematically shows a stage of polymerization of the monomer 4 with obtaining dispersible dye 6 (Figs). As the reaction of the monomer 4, described above, the oligomer 1, formed by polymerization of the Monomeric component, becomes insoluble in water and becomes sediment 8 after separation from the aqueous phase. Particles separated oligomer are not sufficiently stable in the dispersion, and they are combined with each other with obtaining pseudoconditioning polarizable particles of polymer 2. These thin-dispersed particles 2 undergo hetero-agglomeration with hydrophobic surfaces of the colorant in the water dispersion as nuclei, and a polymer component, which is pseudolocalization polarizable particles of polymer 2, strongly adsorbed on the surface of the dye 1 due to hydrophobic interactions, whereas in pseudoconditioning the polarizable particles of polymer 2 is the reaction of polymerization. As a result, these thin-dispersed particles 2 are transformed into a form more energetically stable morphology, the ri that increasing the number of adsorption centers. At the same time substantially form physical cross-links within pseudoconditioning polarizable particles of polymer 2, resulting in a thin-dispersed particles of 2 harden after reaching morphology, in which they adsorb more stable. On the other hand, the dye 1 is stabilized by attaching to it pseudoconditioning polarizable particles of polymer 2, which allows the dispersant adsorbed on it, to separate from the surface.

Figure 4 schematically presents both sides of the contact surface between pseudoconditioning particles polarizable polymer 2 obtained above, and dye 1. As shown, pseudolocalization polarizable particles of polymer 2, which are agglomerates of polymer component units have hydrophilic monomer 9-1 and the units of the hydrophobic monomer 9-2. They are distributed randomly, which gives the distribution of the local surface energy, and there are many centers of adsorption 10, in which the surface energy coincides with the surface energy of the dye.

Figure 5 schematically shows an enlarged contact surface on which pseudolocalization particles polarizable polymer 11 is attached to a part of the particles of dye 1A. Pseudomonades ergonovine particles polarizable polymer 11 adsorbed in the centre of adsorption 10, shown in figure 4, the contact surface being attached to the dye, with a stable morphology, which depends on the shape of the surface part of the dye 1A. As described above, the polymerization pseudoconditioning polarizable particles of the polymer takes place also at this stage, and the particles are attached to the dye after reaching morphology, in which they adsorb more stable. Dispersible dye composition described above can be easily obtained through these stages (Fig). In a system in which pseudolocalization particles polarizable polymer, charged on the surface sufficiently to be satismarriages, they are separated from each other by force (electro static repulsion, while they are absorbed by the dye and are attached to the dye in the process of heteroaromatic, uniformly spread on the surfaces of particles of the dye. As a result, they receive the preferred morphology described above.

The conditions of polymerization depend on the characteristics of the polymerization initiator, a dispersant and monomer. Examples of conditions include a reaction temperature must not exceed 100°S, preferably not less than 40°s and 80°C, reaction time: 1 hour or more, preferably not less than 6 hours and not more than 30 hours, and the speed of peremeci the project, not less than 50 rpm and 500 rpm, preferably not less than 150 rpm and not more than 400 rpm

In the above-described process, in particular when pseudolocalization polarizable particles of a polymer obtained by polymerization of a monomer component containing at least one type of hydrophobic monomer and at least one type of hydrophilic monomer, the monomer component is preferably placed in the water dispersion of water-insoluble dye, introduced in advance with an aqueous radical polymerization initiator. Or, on the contrary, the Monomeric component and the aqueous radical polymerization initiator are placed in the water dispersion of water-insoluble dye simultaneously or separately, which is also the preferred option. If the monomer mixture consists of various monomers, for example, hydrophobic monomers and hydrophilic monomers, it is preferable to maintain the ratio of copolymerization of the monomers at a constant level to achieve the desired uniform pseudoconditioning polarizable particles of the polymer. If a mixture of monomers introduced into the polymerization system in excess over the amount consumed by the polymerization reaction in a certain period of time, the particular monomer may preferably be dry out, leaving the other, which is polimerizuet after consumption of the first monomer. In this case, pseudolocalization polarizable particles of polymer can be considerably heterogeneous characteristics. Some of these particles, in particular those which contain most of hydrophilic Monomeric component may not be attached to the surface of the dye.

In addition, the polymer component containing a high proportion of hydrophilic Monomeric component, may not even stand out because of its high hydrophilicity, remaining as a water-soluble polymer component in the system, not forming pseudolocalization polarizable particles of the polymer. On the other hand, the ratio of the copolymerization of hydrophobic/hydrophilic monomer can be saved as a constant for the uniform receipt pseudoconditioning polarizable particles of the polymer in the desired ratio of copolymerization, if Monomeric component is placed in the water dispersion of water-insoluble colorant containing aqueous radical polymerization initiator.

Some hydrophilic monomers, in particular, anionic, for example, acrylic acid and methacrylic acid may be partially unstable against agglomeration, depending on the characteristics of the polymeric dispersant used for dispersing the dye. The preferred options is the ant of this invention is the introduction of anionic monomer in the form of sodium or potassium salts after neutralization to avoid the above problems.

The above method of obtaining pseudoconditioning particles polarizable polymer attached to a water-insoluble dye, preferably accompanied by a subsequent stage of purification with obtaining water ink containing the dye. To obtain the dispersible colorant with a high degree of stability during storage over a long period of time it is important to clean the mixture containing unreacted polymerization initiator, a Monomeric component or dispersant, or water-soluble polymer component or pseudolocalization particles polarizable polymer is not attached to the dye. Cleaning stage may be selected from well-known. Purification by centrifugation or ultrafiltration is the preferred option.

Dispersible colorant with pseudoconditioning particles polarizable polymer containing the desired copolymer attached to the surface of the dye can be obtained by using the above-mentioned stages, as they allow good control of many regulatory settings. If you enter anionic monomer, in particular, to obtain a high stability of the dispersion stage of the present invention allow a high density of surface functional groups and, thus, high St the stability of a dispersion of dispersible dye, even if the anionic monomer is used in relatively small quantities. Therefore, these stages can improve the stability of the dispersion pseudoconditioning polarizable particles of the polymer without affecting the storage stability dispersible dye for a long period of time.

The authors of the present invention suggest that the improved stability of the dispersion of the dispersible colorant obtained by the following mechanisms, which, however, is not fully confirmed. While pseudolocalization polarizable particles of polymer formed from oligomers released during polymerization, initiated by radicals formed in the water, oligomers comprising a component derived from an anionic monomer in large quantities, preferably oriented towards the aqueous phase, i.e. in proximity with pseudoconditioning polarizable particles of the polymer. This condition persists after attaching pseudoconditioning polarizable particles of polymer to dye with further concentration of the anionic group derived from an anionic monomer component, on the surface of the dispersible colorant in accordance with this invention, having a structure with a large specific surface area. As a result, dispergiruyushchei, obtained by the method in accordance with this invention may be stabilized with a small amount of anionic monomer component.

Water ink

The aqueous ink in accordance with this invention are content dispersible dye described above. If dye is used, the pigment, it is usually introduced in an amount not less than 0.1% and not more than 20 wt.% in relation to the weight of the ink, preferably no less than 0.3% and not more than 15 wt.%. Preferably, the aqueous medium for ink contains water or water-soluble organic solvent, if necessary. In the ink can be added penetrating agent to enhance their penetration into the substrate for recording, preservative and antifungal agent.

Dispersible colorant in accordance with this invention, which is present in the ink contains pseudolocalization polarizable particles of polymer 2, attached to the surface of the dye 1 (figa and 1B). Therefore, the particles of dye attached to the substrate for recording or to the adjacent particles of the substrate using pseudoconditioning particles polarizable polymer attached to its surface. Therefore, images obtained by using the aqueous ink in accordance with this invention, must be very scratch resistant. One is C preferred options are aqueous ink, in addition to the above characteristics, are composed of samodisciplina thin-dispersed particles of the polymer. This produces a very smooth image on a glossy substrate, which is usually difficult when using conventional water-insoluble colorant, such as pigment. More preferably, the ink contains pseudolocalization polarizable particles of polymer (A), attached to the dye, and samodisciplina thin-dispersed particles of polymer (B)present in the ink, where the Monomeric component particles (a) and Monomeric component particles (C) has at least one common monomer component. This ink composition gives greatly improved image stability to scratch on a glossy substrate for recording, as the particles (A), attached to the dye, and the particles (B) are more compatible with each other, which increases the viscosity of the ink.

Dispersible colorant in accordance with this invention has an average Zeta-potential of the surface is not less than -80 mV and -20 mV in an aqueous environment, which is included in the aqueous ink, in particular if it contains anionic group and at least +10 mV and not more than +60 mV, if it contains a cationic group. It is also the preferred option. Water ink can they the be the excellent storage stability for a long period of time, if part of their structure dispersible colorant has a Zeta-potential of the surface of the above limits. Dispersible colorant having a Zeta-potential of the surface is not less than -15 mV and not more than +10 mV may not have inherent high dispersion stability when exposed to water, which makes water ink with insufficient dispersion stability for a long period of time. On the other hand, the dispersible colorant having a Zeta-potential of the surface of less than -80 mV and +60 mV, can give images having insufficient resistance to water, although the ink will have excellent storage stability.

The term "Zeta (ξ) capacity"used in this description, sometimes called "dynamic" potential at the phase boundary, means the potential obtained on the topic of phases between solid and fluid in relative motion, when they are in contact with each other. It is used for analysis of the conditions of the surface of a solid substance present in the liquid. In the electric double layer obtained in section solid/liquid phases, a stationary phase (or adsorbed phase) is from the solid phase, where the stationary phase and the surface of the solids charged ions with opposite charges. When a solid substance and LM is the bone are in relative motion, stationary phase moves together with the solid substance. Therefore, there is a potential between the surface of the stationary phase and the inner part of the solution, which actually controls the movement, and this potential is called the Zeta-potential. The Zeta-potential can be positive or negative depending on the charge of stationary phase. If water-insoluble colorant stably dispersed in the ink, dye particles remain separated from each other and stably dispergirovannykh using Zeta-potential of the dye. Therefore, the Zeta-potential is a significant feature for the stability of the dispersion and stability during storage of the ink containing the water-insoluble colorant for ink-jet recording.

In addition, the absolute value of Zeta-potential in itself greatly affects the stability of the dispersion, and its distribution is also an important parameter. In a dispersion, which contains colloidal dispersions with different Zeta-potential, in particular, usually there is a force of attraction between the dispersion with higher potential and the other dispersion with a lower potential with their agglomeration, even if they have the same sign (positive or negative) potential. This phenomenon is known as heteroglossia. In other words, dispersable the dye in accordance with this invention, having a uniform absolute value of Zeta-potential, affects the stabilization of the dispersion in the ink in accordance with this invention. The authors of this invention have found that the dispersible colorant in accordance with this invention demonstrates the desired effect of stabilizing the dispersion, if the distribution of its Zeta-potential is less than 50 in relation to the standard deviation within the middle level.

Zeta-potential varies depending on various conditions, for example, the dielectric constant, the pH and the salt concentration in the aqueous medium, which contains a dye, and this is true for any other colloidal dispersion. Therefore, the Zeta-potential must be considered in terms of its absolute value and distribution, measured in certain conditions of the environment in which the dispersed dye. Zeta-potential dispersible dye in the aqueous ink may be determined by the conventional method. Zeta-potential in this invention is determined on the analyzer (Microtech Nitchion ZEECOM), where water mixed solvent to aqueous ink, which is added to the dye diluted in the appropriate ratio, placed in a constant electric field to monitor the motion of dispersed particles (dispersible colorant in accordance with the data which m invention), and determine the velocity of the particles by image processing.

However, it should be noted that the Zeta-potential can not be determined when applying the method of analysis described above, the ink containing a specific electrolyte in high concentrations, even in aqueous medium with the same composition, due to the very high conductivity of the medium. In this case, the Zeta-potential of the dispersible colorant can be determined after processing of the aquatic environment with getting the pH level corresponding to the level used in the ink, through removal or reduction of the electrolyte of 0.01 M above the ink actually contain the electrolyte in a high concentration, and tend to decrease in stability during storage. However, they may have improved storage stability when holding the Zeta-potential of the dye within in accordance with this invention.

If dye is used, the pigment, the preferred option is the introduction of pigment in a ratio of polymer component pseudoconditioning particles polarizable polymer, or the ratio of polymer/pigment (/R ratio) is not less than 0.3 and not more than 4.0 for superior resistance to scratching images obtained using aqueous ink. The saving ratio In a/R is not less than 0.3 can improve the degree of attachment between particles of dye and between which the particles of the dye and the substrate for recording and therefore, to improve the image stability to scratch. In particular, the aqueous ink containing the dispersible colorant, may be more suitable characteristics education film, if a copolymer component pseudoconditioning polarizable particles of polymer attached to the dye has a glass transition temperature of not less than -40°s and 60°Since, as described above, that also improves image stability to the scratches on glossy paper. When the ratio V/R, considerably in excess of 4.0, the ink can be sufficiently viscous and have degraded characteristics of the emission, in particular for ink-jet recording devices. In addition, such ink may be insufficient image density, since a very high content of the polymer affects the manifestation of the color of the dye on the substrate for recording. The saving ratio In/P in the above limits of not less than 0.3 and not more than 4.0 allows to obtain aqueous ink, which simultaneously possess excellent scratch resistance and good emission characteristics in the inkjet recording devices. The weight of the polymer, described above, represents the total number pseudoconditioning polarizable particles of the polymer and may include other polymeric components, which are strongly adsorbed on the surface of the PI is ment, however, it does not include the water-soluble polymer component, which is easily separated from the pigment.

The ratio V/R can be determined by differential thermogravimetric analysis and determined on the analyzer (METTLER, TGA/SDTA851) in accordance with this invention. More specifically, the dispersible colorant in accordance with this invention or its containing aqueous ink for inkjet recording centrifuged at 80000 rpm for 2 hours, dried, weighed and heated in nitrogen atmosphere or in air with getting the weight change of each of the pigment and polymer components before and after treatment at the decomposition temperature, which determine the ratio V/R.

The recorded image

Image in accordance with this invention, recorded on the substrate for recording using aqueous ink in accordance with this invention containing the dispersible colorant with the above composition was produced using the inkjet recording device, described below. The substrate for recording used in accordance with this invention, is not limited, if only he can get the image using an inkjet recording.

Dispersible colorant in accordance with this invention, has a function, due to its characteristic form, pokazanija Figa, 7B and 7C, to obtain an inkjet image in accordance with this invention. Among these functions are preferable to those that are shown on Figv and 7C, and they occur simultaneously in real account. The function, shown in Figa, occurs if an aqueous ink described above, also contain thin-dispersed particles satismarriages polymer (C), obtaining a very smooth image on the substrate for recording 14 where pseudolocalization polarizable particles of polymer or samodisciplina thin-dispersed particles are accumulated on the substrate to smooth out irregularities between the particles of the dye. On FIGU pseudolocalization polarizable particles of polymer 2 are present between adjacent particles of the colorant, and at the same time attached to these particles of the dye, to obtain a solid colored film for the recorded image with high scratch resistance. On Figs shows another preferred feature, where the ratio of the surface of the dye, which are attached to pseudolocalization particles polarizable polymer, partially reduced, which allows the agglomeration of particles of the dye, while realizing the function shown in Figv. Figs illustrates the agglomeration of particles of the dye in the ink forming the image is agenie on the substrate for recording, where the static repulsion between pseudoconditioning polarizable particles of polymer (represented by the arrow 15 in the figure) is balanced by the force of agglomeration of the pigment grains in the sintering process, controlling agglomeration. Such control of the agglomeration on the substrate for recording allows you to control image density and the spreading of ink.

The method of image capture and recording device. Dispersible colorant-containing aqueous ink in accordance with this invention demonstrate excellent performance when used in the inkjet head printing device and stored in tanks for ink. The ink is also useful for filling ink. This invention shows particularly excellent characteristics when used in the head for recording and a recording device, recording method Bubble Jet®.

Sample structure and principles of operation preferably based on the structure and the basic principles described in U.S. patent No. 4723129 and 4740796. This principle applies to pulse type ("request") and to the continuous type. It is particularly effective when applied in a pulse type, where at least one signal to the actuator is transmitted to the electrothermal transducer, placed in the position corresponding to whether each of the sites and channels for liquid, which hold the ink, for the rapid heating of the ink to a temperature above the temperature of the nucleate boiling, where the Converter generates enough heat to boil a film on the heated surface of the head for recording, which makes the formation of bubbles in the ink corresponding to the signal. Ink are ejected through the port of discharge under the action of growing and expanding bubbles, with the formation of at least one droplet. A pulse signal is preferred because it can immediately and adequately to cause the growth and expansion of the bubbles with the receipt ejection of ink with high response. In U.S. patent No. 4463359 and 4345262 described preferred pulse signals. Recording can be done more efficiently under the conditions described in U.S. patent No. 4313124, which describes the rate of temperature rise in the heated working surface of the head.

Preferred head include a combination of ports for output, channels for fluid (linear or right-angled channels for the liquid) and the electrothermal transducers, which are described in the above U.S. patents. This invention is also effective in structures, where the components are located on the wavy heated working surface, as described in U.S. patent No. 4558333 or 4459600. It is also effective in other structure the arts with many 2 electrothermal transducers, having one or more common ports to discharge ink, and a private ports to eject ink, such as described in application laid on the Japan patent No. S59-123670. The recording head of the type in the entire string, which covers the length corresponding to the maximum width to which the recording device can record images may have a combination of multiple recording heads described in the above descriptions, to cover the desired length, or may have a structure where they are collected on the same block. This invention allows these types to demonstrate the above procedure more efficiently.

This invention is also effective when attached to the chassis of the recording head replacement type, in which it can be electrically connected to the housing for supplying ink from it, as well as to the cartridge, in which it is mounted as an integral part on the recording head. This invention can exhibit its advantages more effectively if it contains, as one of the components of the recording head regenerating device, or other assistive devices, which is another advantage in accordance with this invention. More specifically, these devices include nozzles, cleaning or sealing or ducarouge device, electrothermal Converter or other heating device, pre-heaters, including a combination of such devices, and the combination of such devices, for the preview release, which is not used for recording.

Examples

This invention is described in more detail in the examples and comparative examples, which, however, do not limit the invention, which can be made variations not beyond the scope of this invention. In the examples and comparative examples, "part(s)" and "%" are mass, unless otherwise specified.

Example 1

The ink for recording 1 produced by the method described in example 1. First, a mixed solution having a composition of 10 parts of carbon black, 6 parts of glycerin, 10 parts of a dispersant based on styrene/acrylic acid and 74 parts of water to obtain a solution of the dispersion of pigment 1 by processing these components in a sand mill (Kaneda Scientific) with balls of zirconium dioxide with a diameter of 0.6 mm at 1500 rpm for 5 hours for dispersion of the pigment, where the container is filled with a fill rate of 70%. Soot is a Black Pearls 880 (hereinafter designated as VR), obtained from Cabot Co., USA. Dispersant based on styrene/acrylic acid has a copolymerization ratio 70/30, molecular weight (Mw) of 8,000 and an acid number of 170. It is a small town which defaults to an aqueous solution, obtained by mixing the dispersant with water and potassium hydroxide in an amount equivalent to the acid number, at a temperature of 80°C. the resulting solution of the dispersion of pigment 1 stably dispersed pigment particles having an average particle diameter in the dispersion of 98 nm and the coefficient of polydispersity 0,16.

Then, as described below, the mixed solution is slowly added dropwise to 100 parts of the dispersion of pigment 1 in electric stirring at a temperature of 70°C in nitrogen atmosphere for polymerization continued for 5 hours. A mixed solution containing 5.5 parts of methyl methacrylate, 0.5 parts of acrylic acid, 0.12 parts of potassium hydroxide, 0.05 parts of potassium persulfate and 20 parts of water. The obtained dispersion was diluted 10 times with water and centrifuged at 5000 rpm for 10 minutes to remove agglomerates. Further, it is purified by centrifugation at 12500 rpm for 2 hours to obtain a precipitate in the form of a dispersible colorant 1.

Dispersible colorant 1 was dispersed in water and purified by centrifugation at 12,000 rpm for 60 minutes. The precipitate is re-dispersed in water and dried for analysis by scanning electron microscope (JOEL Hightech, JSM-6700) at magnification of 50,000. The analysis showed that the dispersible colorant 1 contains thin-dispersed particles of the polymer, attached to the surface of carbon black. The dyes obtained in the other examples examined by the same method to confirm the morphology of the dye.

The following composition is added to the dye 1 and filtered over a membrane filter (pore size: 2.5 μm) under pressure to get the ink to records containing dye 1 in the amount of 4%.

Glycerin7 pieces
Diethylene glycol5 pieces
Trimethylol propane7 pieces
Acetylene YONG (trade
name: Kawaken Fine
Chemicals)0.2 parts
Ion-exchange waterbalance

Example 2

As described below, the mixed solution is slowly added dropwise to 100 parts of a solution of a pigment dispersion 1 obtained in example 1, when an electric stirring at a temperature of 70°C in nitrogen atmosphere for polymerization continued for 8 hours. A mixed solution containing 5.7 parts of styrene, 0.3 part of acrylic acid, 0.07 parts of potassium hydroxide, 0.05 parts of potassium persulfate and 20 parts of water. The mixture after polymerization purified by centrifugation according to the method of example 1 to obtain dispersible KRA is Italia 2. The ink for recording 2 containing the dispersible colorant 2 at the rate of 4%, receive according to the method of example 1.

Example 3

As described below, the mixed solution is slowly added dropwise to 100 parts of a solution of a pigment dispersion 1 obtained in example 1, when an electric stirring at a temperature of 70°C in nitrogen atmosphere for polymerization continued for 6 hours. A mixed solution containing 5.7 parts of methyl methacrylate, 0.3 parts of acrylic acid, 0.07 parts of potassium hydroxide, 0.05 parts of potassium persulfate and 20 parts of water. The mixture after polymerization purified by centrifugation according to the method of example 1 to obtain dispersible dye 3.

The polymerization is conducted according to the method of example 1 except that 100 parts of the dispersion of pigment 1 replace 100 parts of 2% aqueous solution of potassium hydroxide, in an amount equivalent to the dispersant based on styrene/acrylic acid used in example 1 and the polymerization mixture is centrifuged by the method of example 1, except that used 20000 rpm for 1 hour, to obtain the thin-dispersed particles of the polymer B1.

The ink for recording 3 containing the dispersible colorant 3 and thin-dispersed particles of the polymer B1 in the amount of 4% and 1.2%, respectively, receive according to the method of example 1.

Example 4

Described neither the e mixed solution is slowly added dropwise to 100 parts of the dispersion of pigment 1, obtained in example 1, when an electric stirring at a temperature of 70°C in nitrogen atmosphere for polymerization continued for 6 hours. A mixed solution containing 4.5 parts of benzylmethylamine, and 1.2 parts of butyl acrylate, 0.3 parts of acrylic acid, 0.07 parts of potassium hydroxide, 0.05 parts of potassium persulfate and 20 parts of water. The mixture after polymerization purified by centrifugation according to the method of example 1 to obtain dispersible dye 4.

Dispersible dye 4 analyzed by the method of example 1. The analysis confirms that the dye also contains finely dispersed particles attached to the surface of carbon black, but more condensed than in the dye obtained in example 1.

The polymerization is conducted according to the method of example 3 to obtain a thin-dispersed particles of the polymer B1, replacing the 100 parts of the dispersion of pigment 1 of example 1, to obtain the thin-dispersed particles of polymer B2. Ink for recording 4 containing the dispersible colorant 4 and thin-dispersed particles of polymer B2 in the amount of 4% and 1.2%, respectively, receive according to the method of example 1.

Example 5

As described below, the mixed solution is slowly added dropwise to 100 parts of a solution of a pigment dispersion 1 obtained in example 1, when an electric stirring at a temperature of 50°C in an atmosphere of azo is for polymerization, continued for 5 hours. A mixed solution containing 6 parts of butyl acrylate, 0.05 part of potassium persulfate, the same number of moles of sodium thiosulfate, and potassium persulfate and 20 parts of water. The mixture after polymerization purified by centrifugation according to the method of example 1 to obtain dispersible dye 5.

Dispersible dye 5 analyzed by the method of example 1. The analysis confirms that the dye also contains thin-dispersed particles attached to the surface of carbon black, but more condensed than in the dye obtained in example 1. The ink for recording 5 containing the dispersible colorant 5 4%receive according to the method of example 1.

Example 6

As described below, the mixed solution is slowly added dropwise to 100 parts of a solution of a pigment dispersion 1 obtained in example 1, when an electric stirring at a temperature of 70°C in nitrogen atmosphere for polymerization continued for 5 hours. A mixed solution containing 17.2 parts of methyl methacrylate, 0.8 parts of n-styrelseledamot sodium, 0.05 part of potassium persulfate and 20 parts of water. The mixture after polymerization purified by centrifugation according to the method of example 1 to obtain dispersible dye 6. The ink for recording 6 containing the dispersible colorant 6 4%receive according to the method of example 1.

The use of the 7

The ink for recording 7 produced by the method described in example 7. First, a mixed solution having a composition of 10 parts of carbon black, 6 parts of glycerin, 10 parts of a dispersant based on styrene/dimethylaminoethylacrylate copolymer and 74 parts of water to obtain a solution of dispersion of pigment 2 by processing these components in a sand mill (Kaneda Scientific Co.) with balls of zirconium dioxide with a diameter of 0.6 mm at 1500 rpm for 5 hours for dispersion of the pigment, where the container is filled with a fill rate of 70%. Soot is the same as in example 1 (VR). Dispersant based on styrene/dimethylaminoethylacrylate copolymer has a copolymerization ratio 70/30, molecular weight (Mw) 8000 and amine number 170. He is an aqueous solution obtained by mixing the dispersant with water and acetic acid in a quantity slightly in excess of amine number above at a temperature of 80°C. the resulting solution of the dispersion of pigment 2 stably dispersed with the pigment particles, having an average particle diameter in the dispersion of 105 nm and the coefficient of polydispersity 0,18.

Then, as described below, the mixed solution is slowly added dropwise to 90 parts of the dispersion of pigment 2 in electric stirring at a temperature of 55°C in nitrogen atmosphere for polymerization continued in t the value of 7 hours. The mixed solution contains 4,2 part of benzylmethylamine, 1,8 part of dimethylaminoethylacrylate, 0,3 parts of V-50 (Wako Pure Chemical Industries) and 20 parts of water. The obtained dispersion was diluted 10 times with water and centrifuged at 5000 rpm for 10 minutes to remove agglomerates. Further, it is purified by centrifugation at 12500 rpm for 2 hours to obtain a precipitate in the form of a dispersible dye 7. Get ink for recording 1 containing the dye 7 in the amount of 4%, where the dye 7 is filtered and combined with the composition according to the method of example 1.

Example 8

The ink for recording 8 produced by the method described in example 8. First, a mixed solution having a composition of 10 parts of a blue pigment (PB) 15:13 (Clariant Co.) as a dye, 6 parts of glycerin, 10 parts of a dispersant based on styrene/acrylic acid and 74 parts of water to obtain a solution of dispersion of pigment 3 by processing these components in a sand mill (Kaneda Scientific Co.) with beads of Zirconia with a diameter of 0.6 mm at 1500 rpm for 5 hours for dispersion of the pigment, where the container is filled with a fill rate of 70%. Dispersant based on styrene/acrylic acid has a copolymerization ratio 70/30, molecular weight (Mw) of 8,000 and an acid number of 170. The resulting solution of the dispersion of pigment 3 stably dispersed with the pigment particles having the average particle diameter in the dispersion of 108 nm and the coefficient of polydispersity 0,14.

Then, as described below, the mixed solution is slowly added dropwise to 100 parts of the dispersion of pigment 3 in electric stirring at a temperature of 70°C in nitrogen atmosphere for polymerization continued for 5 hours. The mixed solution contains of 5.7 parts of methyl methacrylate, 0.3 parts of acrylic acid, 0.07 parts of potassium hydroxide, 0.05 parts of potassium persulfate and 20 parts of water. The obtained dispersion was diluted 10 times with water and centrifuged at 5000 rpm for 10 minutes to remove agglomerates. Further, it is purified by centrifugation at 12500 rpm for 2 hours to obtain a precipitate in the form of a dispersible dye 8. Get ink for recording 8 containing a dye 8 in the amount of 3.5%, where the dye 8 is filtered and combined with the composition according to the method of example 1.

Example 9

The ink for recording 9 produced by the method described in example 9. First, a mixed solution having a composition of 10 parts of a yellow pigment (PY) 180 (Clariant Co.) as a dye, 6 parts of glycerin, 10 parts of a dispersant based on styrene/acrylic acid and 74 parts of water to obtain a solution of dispersion of pigment 4 by processing these components in a sand mill (Kaneda Scientific) with balls of zirconium dioxide with a diameter of 0.6 mm at 1500 rpm for 5 hours for dispersion of the pigment, where the capacity order shall comply with the fill rate of 70%. Dispersant based on styrene/acrylic acid has a copolymerization ratio 70/30, molecular weight (Mw) of 8,000 and an acid number of 170. The resulting solution of the dispersion of pigment 4 stably dispersed with the pigment particles, having an average particle diameter in the dispersion of 126 nm and the coefficient of polydispersity 0,16.

Then, as described below, the mixed solution is slowly added dropwise to 100 parts of the dispersion of pigment 4 in electric stirring at a temperature of 70°C in nitrogen atmosphere for polymerization continued for 5 hours. The mixed solution contains of 5.7 parts of methyl methacrylate, 0.3 parts of acrylic acid, 0.07 parts of potassium hydroxide, 0.05 parts of potassium persulfate and 20 parts of water. The obtained dispersion was diluted 10 times with water and centrifuged at 5000 rpm for 10 minutes to remove agglomerates. Further, it is purified by centrifugation at 12500 rpm for 2 hours to obtain a precipitate in the form of a dispersible dye 9.

Get ink for recording 9 containing dye 9 in the amount of 3.5%, where the dye 9 is filtered and combined with the composition according to the method of example 1.

Example 10

The ink for recording 10 produced by the method described in example 10. In the beginning get mixed solution having a composition of 10 parts of red pigment (PR) 122 (Ciba Specialty Chemicals Co.) as a dye, 6 parts of the glycerol 10 parts of a dispersant based on styrene/acrylic acid and 74 parts of water, in the form of a solution of dispersion of pigment 5 by processing these components in a sand mill (Kaneda Scientific) with balls of zirconium dioxide with a diameter of 0.6 mm at 1500 rpm for 5 hours for dispersion of the pigment, where the container is filled with a fill rate of 70%. Dispersant based on styrene/acrylic acid has a copolymerization ratio 70/30, molecular weight (Mw) of 8,000 and an acid number of 170. The resulting solution of the dispersion of pigment 5 stably dispersed with the pigment particles, having an average particle diameter in the dispersion of 96 nm and the coefficient of polydispersity 0,13.

Then, as described below, the mixed solution is slowly added dropwise to 100 parts of the dispersion of pigment 5 in electric stirring at a temperature of 70°C in nitrogen atmosphere for polymerization continued for 5 hours. The mixed solution contains of 5.7 parts of methyl methacrylate, 0.3 parts of acrylic acid, 0.07 parts of potassium hydroxide, 0.05 parts VA-057 (Wako Pure Chemical Industries) and 20 parts of water. The obtained dispersion was diluted 10 times with water and centrifuged at 5000 rpm for 10 minutes to remove agglomerates. Further, it is purified by centrifugation at 12500 rpm for 2 hours to obtain a precipitate in the form of a dispersible dye 10.

Get the Ernie to record 10, containing dye 10 in the amount of 3.5%, where the dye 10 was filtered and combined with the composition according to the method of example 1.

Characteristics dispersible dyes

Dispersible dyes obtained in examples 1-10, analyze methods, described below, to determine their properties. The results are given in table 1.

Fixation and the presence of thin-dispersed polymer particles.

Each dispersible colorant is dispersed in water and dried for analysis by scanning electron microscope (JOEL Hightech, JSM-6700) at magnification of 50,000. Status and characteristics of thin-dispersed particles attached to the dye, evaluate according to the following standards:

The state of attaching the thin-dispersed particles of the polymer to the dye Of: attaching a thin-dispersed particles of the polymer to the dye confirmed.

x: attaching thin-dispersed particles of the polymer to the dye is not verified.

The presence of thin-dispersed polymer particles.

A: finely dispersed particles of the polymer uniformly distributed.

x: thin-dispersed particles of polymer are distributed unevenly or attached to the dye unevenly.

The stability of the dispersion.

5% aqueous dispersion of each dye tenfold diluted with pure water and concentrate to the initial concentration at which travelite, catching a molecular weight of 50000. The concentrated solution was centrifuged at 12000 rpm for 2 hours, and the precipitate is collected and re-dispersed in pure water. Dye visually evaluated for uniformity of particle distribution and analyze the dynamic scattering for confirmation that the particle diameter is larger than the original diameter until it is processed in 2 or less times. The evaluation is conducted according to the following standards.

A: when the above conditions are satisfied.

x: the above conditions are not satisfied.

The storage stability for a long period of time.

The storage stability for a long period of time is assessed visually after water dispersion of each dye in a closed glass bottle and maturation at a temperature of 60°C for 1 month. The evaluation is made according to the following standards.

And: agglomeration or precipitation of solids is missing.

In: sedimentation of solids has to a small extent, but the solution is returned to the original dispergirovannom state when lightly shaken.

From: agglomeration or precipitation of solids occurs and the solution is not returned to the original dispergirovannom state when lightly shaken.

The average particle size.

Each dispersed through the p dye analyze dynamic scattering (analyzer: Otsuka Electronics ELS-8000), and average particle diameter are as cumulative average.

The glass transition temperature: Tg (°)

The glass transition temperature of thin-dispersed polymer particles attached to the dye, and analyzed by the analyzer (METTLER-TOLEDO's DSC822e), where the dried sample dispersible dye is heated at a rate of 0.5°C/minute.

The density of the surface functional groups

The density of the surface functional groups of each dispersible dye is determined in the following method. The water dispersion of dispersible dye diluted with excess hydrochloric acid (HCl) and centrifuged with a speed of 20,000 rpm for 1 hour. The precipitate is re-dispersed in pure water and determine the content of solids. Re-dispersed residue is weighed and then combined with a known amount of sodium bicarbonate and stirred, and then centrifuged at 80000 rpm for 2 hours. The supernatant solution is weighed and titrated with 0.1 G. of hydrochloric acid to neutralize to determine the density of surface functional groups by subtracting a known quantity of sodium bicarbonate and values for pure water the number for neutralization. If the dispersible colorant has a polar group to tianwu group, the density of the surface functional groups is determined by the same method except that instead of hydrochloric acid and sodium bicarbonate used sodium hydroxide (NaOH) and ammonium chloride, respectively.

The surface energy

Dried and powdered dispersible colorant is placed in a column and analyzed using inverse gas chromatography (Surfase Measurement System), in which the test gas is applied hexane, heptane, pentane, chloroform, ethanol or acetone. Surface energy is determined by extrapolation to the retention time of gas dispersible dye for each test gas. Compositions and evaluation results of the ink obtained in examples 1-8 are shown in table 1, where MMA: methyl methacrylate, AAS: acrylic acid, St:styrene, BzMA: bezelmaterial, BA: butyl acrylate, NaSS: p-styrelseledamot sodium, DMAEA: dimethylaminoethylacrylate, KPS: potassium persulfate and NaTS: sodium thiosulfate.

Methods of assessing water ink for inkjet recording and evaluation results.

Characteristics ink assessed using the following methods. Using each receive ink image on the substrate for recording using an inkjet recording device (Canon's BJ S600), and evaluate. The image is evaluated for optical density (OD), clarity, resistance to scratching, is tasciotti to the marker, stability when stored at ordinary temperature and stability release. The results are shown in table 2.

The mass ratio of polymer/pigment ratio (V/R).

The ratio V/R analyze differential thermogravimetric analysis (METTLER-TOLEDO TGA/SDTA851) and expect to dried ink.

Zeta (ξ) potential surface.

Dispersible colorant obtained in each example, diluted with about 100,000 times in aqueous solvent used in example 1 not containing the dispersible colorant and finely dispersed particles of the polymer, and ξ potential fixed cell surface measured on the analyzer (Microtech Nitchion ZEECOM) for 100 particles. The average potential and the standard deviation for 100 particles record.

The optical density (OD)

The optical density (OD) is determined for the black text image recorded using each of the ink for recording on paper Canon's PPC, and left for 1 day. Ink evaluated according to the following standards, except for the ink received in the accept 8, in which appreciate OD blue instead OD black, and mark "A"if it is not less than 1.0.

And: OD image of at least 1.3.

In: OD image is not less than 0.8 and less than 1.3.

From: OD image less than 0.8.

Scratch resistance.

The image cause scratches 5 times using silbano the second paper, to which is applied a pressure of 40 g/cm2for visual evaluation of image corruption, and evaluate according to the following standards.

A: Scratching does not damage the image or does not leave paint on a blank part.

In: Scratching damages the image or leaves the paint on the empty side, but not on a significant scale.

From: Scratching significantly damages the image or leaves the paint on a blank part.

Resistance to the token.

The image is applied strip fluorescent yellow highlighter (ZEBRA's OPTEX) for visual assessment of image corruption, and evaluate according to the following standards.

And: Drawing of the bands does not damage the image.

In: Application of strips damages the image to a limited extent, minor staining rod token.

With the Deposition of bands much damage the image, staining rod token.

The storage stability for a long period of time.

The storage stability for a long period of time is assessed visually after each sample ink in a closed glass bottle and aged at room temperature for 1 month. It is assessed according to the following standards.

And: Agglomeration or sedimentation of solids does not occur.

In: insignificant precipitation of the solid substances, but the ink is returned to the initial dispersed state with a slight shaking.

From: agglomeration or sedimentation of solids, and the ink is not returned in the original dispersed condition with slight shaking.

Stable release.

Certain black text record for 100 sheets to assess the stability of ejection through visual examination of the first and last pages in accordance with the following standards.

A: Lines, uneven image or similar phenomena is not observed, the differences between the images on the first and last pages.

In: the image is obtained without problems, although to a small extent, there are one or more lines, uneven image or distortion of the image.

With: the Image is significantly degraded, or printing is not possible.

Dispersible colorant obtained in each of examples 1-10, gives good results, which proves the stability of the dispersion, as shown in table 1. The ink for recording, obtained in each example, also exhibit excellent performance record, although the ink obtained in example 5, containing the dispersible colorant 5, have a lower density of surface functional groups and the lower L, the potential slightly lower than others who ernil when assessing the stability during storage over a long period of time and the stability of the emission, as shown in table 2. From the point of view of resistance to scratches, ink for recording, obtained in example 3, containing thin-dispersed particles of satismarriages polymer, exhibit higher stability, compared with the ink for recording 1, although dispersible dye, are synthesized from the same monomers for these dyes.

And
Table 1

The properties of the dispersible colorants 1-10 and the results of their evaluation
dispersible colorant 1dispersible dye 2dispersible dye 3dispersible dye 4dispersible dye 5dispersible dye 6dispersible dye 7dispersible dye 8dispersive-by krassi-tel 9variance

geremy dye 10
dyeWRWRWRWRWRWRWRRV:3PY180PR122
acid number

disperser
170170170170170170170170170
and similar monomersMMA AACSt AAeMMA AACBzMA VA AACVAMMA NaSSBzMA DMAEAMMA AACMMA

AAC
MMA

AAC
the degree of charge of monomers5,5 0,55,7 0,35,7 0,34,5 1,2 0,3617,2 0,84,2 1,85,7

0,3
5,7 0,35,7

0,3
the total content of monomers66666186666
initiator

polymerization
KPSKPSKPSKPSKPS/NaTSKPSV-50KPSKPSVA-057
the obtained results0aboutabout0000000
the presence encodedpayload-tion of polymer particles0aboutabout0about 00000
the stability of the dispersion0aboutabout0about00000
the average diameter of the dispersed seeded particles (km)126118123134121135130121141101
Tg [°C]10511010530-1511595105105105
density

the surface functional groups (µmol/g)
37029034232187274272286292261
the surface energy

(MJ/m2)
45,840,245,232,722,546,5a 38.543,746,844,1
the storage stability for a long period of timeAndAndAndAndInAndAndAndAnd

MMA: methyl methacrylate, AAS: acrylic acid, St: styrene

BzMA: bezelmaterial, BA: butyl acrylate, NaTS: sodium thiosulfate

NaSS: p-styrelseledamot sodium

DMAEA: dimethylaminoethylacrylate

And
Table 2
Properties of the ink for recording 1-10 and results

their entry characteristics
ink for writing 1the ink for recording 2ink

for entry 3
ink for recording 4the ink for recording 5ink for writing 6ink for writing

7
the ink for recording 8the ink for recording 9the ink for recording 10
dispersible dye12345678910
source mammaryMMA AACSt

AAC
MMA

AAC
BzMA VA AACVAMMA NaSSBzMA DMAEAMMA

AAC
MMA

AAC
MMA

AAC
the presence of anodiser-Giovanni of polymer particles 0000000000
condisder-giovannieMMABzMA

DA
particles of polymer InAACAAC
Tg [°C]10511010530-1511595105105105
the ratio of polymer/pigment ratio (V/R)0,20,20,50,50,40,80,40,30,40,3
ξ potential[mV]-30-25-28-26-12-31182830-26
standard
deviation

ξ
35373538253342322825
capacity
surface
energy

(MJ/m2)
45,840,245,232,722,546,5a 38.543,746,844,1
the optical density (OD)AndAndAndAndAndAndAndAndAndAnd
Scratch resistanceInInAndAndAndAndAndAndAnd
Resistance markerAndAndAndAndAndAndAndAndAndAnd
the storage stability during

long period

time
AndAndAndAndInAndAndAndAndAnd
stable releaseAndAndAndAndInAndInAndAndAnd

MMA: methyl methacrylate, AAS: acrylic acid, St: styrene

BzMA: bezelmaterial, BA: butyl acrylate

NaSS: p-styrelseledamot sodium

DMAEA: dimethylaminoethylacrylate

Example 11

As described below, the mixed solution is slowly added dropwise to 100 parts of a solution of a pigment dispersion 1 obtained in example 1, when an electric stirring at a temperature of 70°C in nitrogen atmosphere for polymerization continued for 5 hours. The mixed solution contains 4,28 parts of styrene, 1,42 part of hydroxyethylmethacrylate, 0,3 parts of acrylic acid, 0.07 part of potassium hydroxide, 0.05 part of potassium persulfate and 20 parts of water. The resulting dispersion is 10 times resbala the t water and centrifuged at 5000 rpm for 10 minutes to remove agglomerates. Further, it is purified by centrifugation at 12500 rpm for 2 hours to obtain dispersible dye 11. Ink for writing 11 containing the dispersible colorant 11 4%receive filtering dye 11 and his connection with the composition according to the method of example 1.

Example 12

As described below, the mixed solution is slowly added dropwise to 100 parts of a solution of a pigment dispersion 1 obtained in example 1, when an electric stirring at a temperature of 70°C in nitrogen atmosphere for polymerization continued for 5 hours. A mixed solution containing 45.6 parts of ethyl methacrylate, 2,4 parts of acrylic acid, and 0.6 part of potassium hydroxide, 0.1 part of potassium persulfate and 20 parts of water. The resulting mixture to polymerization purified by centrifugation according to the method of example 9 to obtain dispersible dye 12. The ink for recording 12 containing the dispersible colorant 12 4%, receive filtering dye 12 and his connection with the composition according to the method of example 1.

Example 13

As described below, the mixed solution is slowly added dropwise to 100 parts of a solution of a pigment dispersion 1 obtained in example 1, when an electric stirring at a temperature of 70°C in nitrogen atmosphere for polymerization, prod is lausana for 5 hours. The mixed solution contains 5,7 part of benzylmethylamine, 0,3 parts of methacrylic acid, 0.07 part of potassium hydroxide, 0.01 part of potassium persulfate and 20 parts of water. The resulting mixture to polymerization purified by centrifugation according to the method of example 1 to obtain dispersible dye 13 in the form of sediment. The ink for recording 13 containing the dispersible colorant 13 4%, obtained by filtration of the dye 13 and his connection with the composition according to the method of example 1.

Example 14

As described below, the mixed solution is slowly added dropwise to 100 parts of a solution of a pigment dispersion 1 obtained in example 1, when an electric stirring at a temperature of 70°C in nitrogen atmosphere for polymerization continued for 7 hours. A mixed solution containing 10 parts of methyl methacrylate, 8 parts of acrylic acid, 1,9 parts of potassium hydroxide, 0.05 part of potassium persulfate and 20 parts of water. The resulting mixture to polymerization purified by centrifugation according to the method of example 1 to obtain dispersible colorant 14. The ink for recording 14 containing the dispersible colorant 14 4%, obtained by filtration of the dye 14 and connect it to the composition by the method of example 1.

Example 15

As described below, the mixed solution is slowly added dropwise to 100 parts of the dispersion of pigment 1, received the CSOs in example 1, when electric stirring at a temperature of 70°C in nitrogen atmosphere for polymerization continued for 5 hours. A mixed solution containing 4.5 parts of benzylmethylamine, and 1.2 parts of butyl acrylate, 0.3 parts of acrylic acid, 0.07 part of potassium hydroxide, 0.05 part of potassium persulfate and 20 parts of water. The resulting mixture to polymerization purified by centrifugation according to the method of example 1 to obtain dispersible dye 15.

The polymerization is conducted according to the method of example 1, except that 100 parts of the dispersion of pigment 1 replace 100 parts of 2% aqueous solution of potassium hydroxide in a quantity equivalent to the quantity of dispersant based on styrene/acrylic acid used in example 1, the mixture for the polymerization of purified according to the method of example 1, except that it is carried out at 20,000 rpm for 1 hour, to obtain the thin-dispersed particles of polymer B3.

The ink for recording 15 containing the dispersible colorant 15 and thin-dispersed particles of polymer B3 4% and 19.2%, respectively, receive according to the method of example 1.

Properties of ink to record their assessment

Results

Dispersible colorant obtained in each of examples 11-15, estimated with application of different methodologies and analyze its properties according to the methods of analysis of examples 1-10. Results Yes the s in table 3, where St: styrene, DUMB: hydroxyethylmethacrylate, AAS: acrylic acid, EMA: ethyl methacrylate, Wt: methacrylic acid, BzMA: bezelmaterial, MMA: methyl methacrylate, BA: butyl acrylate and KPS: potassium persulfate.

The characteristics of the recording ink to the recording, obtained in examples 11-15, evaluate which parameters used for the samples obtained in examples 1-10. In addition, evaluate the following additional characteristics of the record.

The ability to fast drying.

The image is obtained using each of the ink according to the method of examples 1-10 and put scratches with your finger in a minute after recording, for assessing staining according to the following standards.

A: On an empty part of the staining is not observed.

In: Blank part slightly colored, but problems with the recognition of letters.

With the Letters blurred, and the empty part of a distinct colored.

Resistance to water.

The substrate for recording, which caused the black text image according to the method of examples 1-10, incline at an angle of 45° horizontal image up, it drops 1 ml of water from a height of 20 cm with a syringe and see smudges image. Resistance to water is assessed according to the following standards.

A: the Spreading of the image is practically absent.

Q: there Is a slight spreading of the image, but on an empty part is not in the bottom trace of him.

From: Dye dripping from the image and leaves traces on the empty part.

The results are given in table 4.

Table 4 features of the composition, properties and evaluation of the ink obtained in each example 11-15.

As shown in table 4, good results were achieved for all the ink that confirms the content satismarriages dye. However, the ink obtained in example 13, contain polymer particles, agglomerated with the surface of the pigment in more and less uniformly distributed. All the ink for recording demonstrate excellent performance record. However, the ink obtained in example 11, having a higher surface energy, a bit worse compared to the other in quick drying and water resistance. The ink obtained in example 13 containing thin-dispersed particles of the polymer are distributed less uniformly in comparison with the other, and slightly worse than the other in image density, the ability to quickly dry and stability release. The ink obtained in example 14, have a high density of functional surface groups and slightly worse than others in the resistance to the marker and, more notably, in resistance to water, even though they have sufficient image density and ejection stability. On the other hand, the ink obtained in example 15, have more high value In/R compared to the other and slightly worse than others in the stability of ejection, because they sometimes give a distorted image during the initial stage of ejection and high-speed printing, which presumably is due to the increased viscosity of ink, which impairs the response to a high-speed ejection.

Table 3

Composition and properties of the dispersible colorants 11-15 the results of their evaluation.
dispersible dye 11dispersible dye 12dispersible dye 13dispersible dye 14dispersible dye 15
dyeWRWRWRBP880WR
acid value of the dispersant170170170170170
raw materialsSt

DUMB

AAc
EMA

MAc
BzMA

AAc
MMA

AAc
BzMA

VA

AAc
the degree of charge of monomers4,28

1,42

0,3
45,6

2,4
5,7

0,3
10

8
4,5

1,2

0,3
the total content of monomers6486 186
the polymerization initiatorKPSKPSKPSKPSKPS
the obtained results00000
the presence of thin-dispersed polymer particles00X00
the stability of the dispersion00000
thin-dispersed particles of the polymer In----BzMA

VA

AAc
the average diameter

dispersed

particles (nm)
122170320152134
Tg [°C]604510810230
the density of the surface functional

groups (µmol/g)
2753021801086321
the surface energy (MJ/m2)82,7to 47.245,592,532,7
the storage stability during

long period of the time
AndAndAndAndAnd

St: styrene, DUMB: hydroxyethylmethacrylate, AAc: acrylic acid

EMA: ethyl methacrylate, MAc: methacrylic acid, BzMA:

bezelmaterial

MMA: methyl methacrylate, BA: butyl acrylate

Table 4

Properties of the ink for recording 11-15 and the results of their

entry characteristics
ink for writing 11the ink for recording 12the ink for recording 13the ink for recording 14the ink for recording 15
dispersible

dye
1112131415
the original monomersSt

DUMB

AAc
EMA

MAc
BzMA

AAc
MMA

AAc
BzMA

VA

AAc
thin-dispersed particles of the polymer In----BzMA

VA

AAc
the presence of thin-dispersed

the polymer particles
00×00
Tg [°C]6045108 10230
the ratio of polymer/pigment ratio (V/R)0,31,51,20,45,1
ξ

potential [mV]
-27-26-27-90-26
standard deviation

ξ

capacity
3332724538
the density of the surface functional groups (µmol/g)2753021801086321
the surface energy (MJ/m2)82,7to 47.245,592,532,7
the optical density (OD)AndAndInAndIn
Scratch resistanceAndAndAndInAnd
Resistance markerAndAndAndInAnd
the storage stability for a long period of timeAndAndInAndIn
the ability to fast you is yanyu InAndInAndAnd
resistance to waterAndAndAndAnd
stable releaseAndAndInAnd

St: styrene, DUMB: hydroxyethylmethacrylate, AAc: acrylic acid

EMA: ethyl methacrylate, MAc: methacrylic acid, BzMA: bezelmaterial

MMA: methyl methacrylate, BA: butyl acrylate

Comparative example 1

Comparative ink 1 containing a pigment in an amount of 4%receive according to the method of example 1, the pigment solution using dispersion 1 obtained in example 1. Comparative ink 1, obtained by the method of example 1 does not contain finely dispersed particles of the polymer attached to the dye.

Comparative example 2

Comparative ink 2 get by the method of example 1, except that the surface treated satisfacgermany soot (Cabot's Cabojet 200) is contained in an amount of 4% of the content of solids and thin-dispersed particles of the polymer B1 obtained in example 3, are contained in amounts of 1.6%. Comparative ink 2, obtained by the method of example 1, containing thin-dispersed particle of the polymer attached to the dye in places. However, u is adelene fixation of such particles is not uniform, and there is some agglomeration with each other.

The dyes obtained in each of comparative examples 1 and 2, are examined using various techniques and analyze their properties according to the methods of examples 1-15. The results are given in table 5. The ink for recording, obtained in each of comparative examples 1 and 2, evaluated according to the methods of examples 9-15. The results are given in table 6.

The dyes obtained in each of comparative examples 1 and 2, are examined using various techniques and analyze their properties according to the methods of examples 1-13. The results are given in table 5. The ink for recording, obtained in each of comparative examples 1 and 2, evaluated according to the methods of examples 9-13. The results are given in table 6.

It is obvious that the inks obtained in each of comparative examples 1 or 2, much worse compared to the ink in accordance with this invention obtained in each example, in particular, in image density, stability during storage over a long period of time and the stability of the release. The ink obtained in comparative example 2, significantly worse than the ink in accordance with this invention in resistance to scratching, resistance to water and the ability to rapid drying, as the dye, although it is samodoprinos, does not contain thin-dispersed particles is, attached to it sufficiently.

Table 5

Properties of the dyes obtained in comparative examples 1 and 2 and the results of their evaluation.
comparative example 1comparative example 2
dyeWRCabojet200
acid value of the dispersant170-
the obtained resultsXX
the presence of thin-dispersed polymer particles--
the stability of the dispersionX0
thin-dispersed particles of the polymer In-MMA

AAC
the average diameter of dispersed particles (nm)98102
Tg [°C]-105
the density of the surface functional groups (µmol/g)-270
the surface energy (MJ/m2)--
the storage stability for a long period of time

MMA: methyl methacrylate and AAS: acrylic is Aya acid

Table 6

Properties of the ink for recording, obtained in comparative

examples 1 and 2, and the results of the evaluation of their performance record
comparative ink 1comparative ink 2
dyecomparative example 1comparative example 2
the obtained resultsxx
the presence of thin-dispersed polymer particles--
thin-dispersed particles of the polymer In-MMA

AAC
Tg [°C]-105
the ratio of polymer/pigment ratio (V/R)-0,4
ξthe potential [mV]--25
standard deviation ξcapacity-37
the density of the surface functional groups (µmol/g)270
the surface energy (MJ/m2)--
the optical density (OD)
resistance to dust, shock, scratches the us InIn
resistance markerIn
the storage stability during

long period of time
the ability to fast dryingIn
resistance to water
stable release

MMA: methyl methacrylate and AAS: acrylic acid

In addition, the ink for recording, obtained in examples 1-4, 6, 12, and 15 were additionally evaluated using the following methods, and the results are presented in table 7. A continuous strip (5 square cm) is applied using black ink obtained in each of examples on glossy paper for inkjet recording (Canon's PR-101) by using a recording device and conduct the above studies for the evaluation of image density, resistance to scratches and gloss on glossy paper.

The density of the image on glossy paper.

Image exploring through day after application to determine the optical density (OD) and evaluated according to the following standards.

And: OD image of at least 2, 3.

In: OD image 1, 7 or more and less than 2, 3.

From: OD image is less than 1, 7.

Resistance to scratches on the gloss is th paper.

Image 5 times Scrabble with seljanovo paper, to which is applied a pressure of 40 g/cm2for visual evaluation of image corruption, and evaluate according to the following standards.

A: Scratching slightly damages the image and leaves little paint on a blank part.

In: the Image is corrupted, but at least 90% of the printed image remains.

With: the Image is severely damaged.

The gloss of the image

Visually assess the gloss of the image according to the following standards.

A: the Image gloss to almost the same extent as pure part.

In: the Image is quite glossy, although it shows more irregular reflection compared to a net part.

With: the Image is not glossy and doesn't reflect the light.

The ink obtained in example 2, containing styrene, and obtained in example 15, containing a higher ratio of In/R given an image with a slightly lower density of the image on glossy paper than other containing monomer, based on the methacrylic acid. The ink obtained in examples 2, 12, and 15, having a lower Tg and obtained in example 3, containing thin-dispersed particles of the polymer To give the image more good resistance to scratches on the glossy is Umag.

Table 7

Composition and properties of the ink for recording received examples 1-4, 6, 12 and 15 and the results of their evaluation
example 1example 2example 3example 4example 6example 12Example 15
dispersible dye123461215
Thin-dispersed particles of the polymer In--MMA

AAC
BzMA

VA

AAC
--BzMA

VA

AAC
Tg [°C]105110105301154530
the ratio of polymer/ pigment ratio (V/R)0,20,20,50,50,81,55,1
the density of the image on glossy

paper
AndInInAndInAndIn
resistance to scratches on glossy paperInIn AndAndInAndAnd
glossAndInAndAndAndAndIn

BzMA: bezelmaterial, AAS: acrylic acid

MMA: methyl methacrylate, BA: butyl acrylate.

Industrial application

The present invention presents dispersible colorant having a sufficiently high stability of the dispersion, in which component polymer is separated from the dye, and which is stable over a long period of time, and a simple way to obtain the dye. The present invention also presents aqueous ink containing excellent dispersible dye, ink tank, a device for an inkjet recording method, inkjet recording and an image obtained by ink jet recording. Another advantage of the present invention is a dispersible dye, can quickly dry on the substrate for recording. Another advantage of the present invention is a dispersible colorant having high scratch resistance on the substrate for recording. Another advantage of the present invention is a dispersible colorant having excellent characteristics ejection device for an inkjet recording. Another becoming the PTO of the present invention is a dispersible dye, possessing excellent manifestation on the substrate for recording. Another advantage of the present invention is a dispersible dye, consistently applied in environments with a pH from high to medium and from medium to low. The method in accordance with this invention makes it easy to get a dispersible colorant having the above characteristics. Another advantage of the present invention are aqueous ink for recording, which can give a glossy image on a glossy substrate for recording. Another advantage of the present invention are aqueous ink for recording having excellent scratch resistance on a glossy substrate for recording. Another advantage of the present invention are aqueous ink for recording, which has excellent stability when stored for long periods of time.

1. Dispersible dye containing a dye and pseudolocalization polarizable particles of polymer having a size smaller than the particles of the dye, where the colorant particles are attached to each other, and pseudolocalization polarizable particles of the polymer include a copolymer of monomer components containing at least one type of hydrophobic monomer and at least one type of hydrophilic monomer, where GI is rotably monomer contains at least a monomer having a methyl group in α-position and a radical-curable unsaturated double bond.

2. Dispersible colorant according to claim 1, which has a density of surface functional groups of at least 250 µmol/g and not more than 1000 µmol/g

3. Dispersible colorant according to claim 1, which has a surface energy of 70 MJ/m2or less.

4. Dispersible colorant according to claim 1, in which component a copolymer containing pseudolocalization particles polarizable polymer has a glass transition temperature of not less than -40°s and 60°C.

5. Dispersible colorant according to claim 1, in which the hydrophobic monomer contains at least the compound (meth)acrylic ester.

6. Dispersible colorant according to claim 5, in which the hydrophobic monomer contains at least one compound selected from the group including bezelmaterial and methyl methacrylate.

7. Dispersible colorant according to any one of claims 1 to 6, in which the hydrophilic monomer contains at least anionic monomer.

8. Dispersible colorant according to claim 7, in which the anionic monomer contains at least one compound selected from the group consisting of acrylic acid, methacrylic acid and n-styrelseledamot salts.

9. Dispersible colorant according to any one of claims 1 to 6, in which the hydrophilic what about the monomer is used, at least a cationic monomer.

10. A method of obtaining a dispersible colorant comprising a stage of carrying out the polymerization process of deposition in the aquatic environment capable of radical polymerization of the monomer in the aqueous dispersion of water-insoluble dye, using a radical polymerization initiator in water, to combine water-insoluble dye with pseudoconditioning particles polarizable polymer.

11. The method of obtaining the dispersible colorant of claim 10 in which the aqueous dispersion of water-insoluble colorant is an aqueous solution containing a pigment dispersed with a polymer dispersant having an acid number of not less than 100 and not more than 250.

12. A method of obtaining a dispersible colorant according to claim 11, in which the dispersant is a copolymer of monomer components containing at least one type of monomer selected from the group consisting of acrylic acid, methacrylic acid and styrene monomer.

13. A method of obtaining a dispersible colorant according to claim 11, in which the initiator of radical polymerization in water is anionic or ampholytic.

14. The method of obtaining the dispersible colorant of claim 10 in which the aqueous dispersion of water-insoluble colorant is an aqueous solution containing a pigment, on sergiovanni with a polymeric dispersant, having an acid number of not less than 150 and not more than 300.

15. A method of obtaining a dispersible colorant according to 14, in which the initiator of radical polymerization in water is a cationic or ampholytic.

16. A method of obtaining a dispersible colorant according to claim 10, in which the radical-curable monomer component is added to the polymerization system.

17. The method of obtaining the dispersible colorant of claim 10, in which the radical-curable monomer component contains at least one type of hydrophobic monomer and at least one type of hydrophilic monomer.

18. The method of obtaining the dispersible colorant of claim 10, in which the initiator of radical polymerization in water is called an initiator atenonol polymerization in water.

19. Dispersible colorant obtained by the method according to any of PP-18.

20. Aqueous ink containing the dispersible colorant according to any one of claims 1 to 9 and 19.



 

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EFFECT: improved fluorescent properties of printed image.

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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.

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: special compositions.

SUBSTANCE: invention relates to compositions used in preparing heat-protective covers based on silicon-containing ceramic hollow microspheres and able to withstand strong temperature drops. Composition for preparing heat-protective cover comprising hollow ceramic microspheres as a filling agent, a polymeric binding agent, technological additive and water involves hollow ceramic microspheres of specific mass 450-750 kg/m3, hardness value by Mohs scale 5.0-6.0 as a filling agent and in the following distribution of particles by sizes, wt.-%: basis diameter 250-350 mcm, 30-62; diameter 5-10 mcm, 15.0-20.0; diameter 10-30 mcm, 5.0-30.0; diameter 30-50 mcm, 5.0-30.0; diameter 60-100 mcm, 8.0-10.0; diameter 100-250 mcm, 5.0-10.0; as a polymeric binding agent the composition comprises latex chosen from group involving: modified acryl acetate latex, 33-38% latex of copolymer of butadiene, acrylonitrile and methacrylic acid, copolymer of styrene and n-butyl acrylate in the ratio 1:1 by mass; as a technological additive the composition comprises a froth breaker chosen from group comprising: silicon froth breakers, tributyl phosphate, polyester derivatives of fatty acids in the following ratio of components, wt.-%: abovementioned microspheres, 18-32; abovementioned froth breaker, 0.01-1.0; abovementioned binding agent, 8.0-12.0, and water - up to 100. Invention provides expanding assortment of compositions for preparing heat-protective covers, enhancing heat-protecting, heat-physical indices of cover with high uniformity and cohesion strength of cover with a basis, expanding region of working temperature from -60°C to +260°C. Invention can be used in filed of building, machine engineering, aviation, railway transport wherein surfaces require conferring heat-protective properties in exploitation of covers under rigid temperature conditions.

EFFECT: improved and valuable technical properties of composition.

2 tbl

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

SUBSTANCE: the invention may be used in production of the optically changeable pigments. The optically changeable pigment includes the stratified set composed of the different materials, in which, at least, one of the layers represents the reflecting layer and, at least, one of the other layers represents the dielectric layer. At least, one of the surfaces of the indicated layers is subjected to the chemical action. The indicated materials also include, at least, one of the layers, which represents the semitransparent metallic layer made out of chromium and also one or more metals and-or their inorganic compounds. At that the metal and-or its inorganic compound are subject to corrosion. The subjected to the chemical action surface of the reflecting and dielectric layer along the edge of the layering block of the edge structure of the pigment is coated with the passivating agent, which is selected from the group consisting of the organic esters and the fluorinated organic esters of the phosphoric acid, having the following structural formula: (Rf-CH2-CH2-O)xP(O)(OH)y, where Rf=F-(CF2-CF2)z, х=1 or 2, у=2 or 1, х+у=3, z=l-7. The composition of the printing paint includes the binding system, water and the optically changeable pigment. The invention allows to diminish oxidation of the metallic layers and dissolution of the dielectric layers of the optically changeable pigment and to use it in the compositions of the printing paint.

EFFECT: the invention allows to diminish oxidation of the metallic layers and dissolution of the dielectric layers of the optically changeable pigment and to use it in the compositions of the printing paint.

22 cl, 7 ex

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

SUBSTANCE: proposed printing ink contains dyes or pigments of expanded or hyperchromatic color space which is not reproduced by means of standard 4-color reproducing equipment. Identification of marking includes mathematical conversion of non-processed spectral information into statically independent hyperchromatic coordinates and comparison of selected hyperchromatic coordinates with respective standard magnitudes. Specification gives also description of printing inks and method of marking and identification of articles.

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.

SUBSTANCE: proposed printing ink contains dyes or pigments of expanded or hyperchromatic color space which is not reproduced by means of standard 4-color reproducing equipment. Identification of marking includes mathematical conversion of non-processed spectral information into statically independent hyperchromatic coordinates and comparison of selected hyperchromatic coordinates with respective standard magnitudes. Specification gives also description of printing inks and method of marking and identification of articles.

EFFECT: enhanced efficiency.

25 cl, 6 dwg, 2 tbl, 4 ex

FIELD: polymer production.

SUBSTANCE: invention relates to production of polymeric binders for toner and can be used for copying appliances and printers. Process comprises separate preparation via emulsion polymerization of (i) low-molecule weight copolymer of styrene (α-methylstyrene), 2-ethylhexyl acrylate (or butyl acrylate) and methacrylic acid at monomer weight ratio (88-91.5):(8-11):(0.5-1.0) with intrinsic viscosity in toluene 0.08-1.2 dL/g and (ii) high-molecule weight copolymer of styrene (α-methylstyrene) and 2-ethylhexyl acrylate (or butyl acrylate) at monomer weight ratio (88-92):(8-12) with intrinsic viscosity in toluene 1.0-1.28 dL/g. In both cases, polymerization is carried out at 60-70% to monomer conversion close to 100%. Resulting latexes of low- and high-molecule weight copolymers are supplemented by stopper and antioxidant and then mixed with each other at "dry" weight ratio between 70:30 and 75:25 and coagulated intrinsic viscosity in toluene 1.0-1.28 dL/g. with electrolyte solutions to form polymer characterized by intrinsic viscosity in toluene 0.4-0.45 dL/g and polydispersity Mw/Mn, which ensures bimodal molecular weight distribution of copolymer. The latter has melting (spreading) point 125-137°C and softening temperature 70-75°C.

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: composite materials.

SUBSTANCE: invention relates to powdered composite filler for elastomer materials suitable for fabrication of articles operated under dry friction or increased wear conditions used in engine, compressor, and pump manufacturing industries. Particles of filler comprise at least one nucleus of inorganic material, in particular quasi-crystalline alloy Al-Cu-Fe or quasi-crystalline alloy Al-Cu-Cr and shell made from thermoplastic polymer with elasticity modulus 0.5 to 5.0 GPa and volume fraction of nuclei in a filler particle 1 to 10%. Process of preparing such composite filler resides in that inorganic material particles are activated in a mechanochemical activator with mechanical energy supply intensity 1 to 5 kW/kg and dose 30 to 1000 kJ/kg in a medium selected from a series: air, nitrogen, argon, and vacuum at pressure from 10-2 to 1 atm until particles with average size not larger than 15 μm are obtained, after which shell polymer is added to activator and inorganic material particles are modified at mechanical energy supply intensity 0,05 to 0.5 kW/kg and dose 3 to 100 kJ/kg in a medium selected from a series: air, nitrogen, argon, and vacuum at pressure from 10-2 to 1 atm.

EFFECT: lowered coefficient of friction under dry friction conditions and substantionally reduced summary rate of wear of friction pair under hydroabrasive wear conditions.

3 cl, 2 dwg, 3 tbl

FIELD: composite materials.

SUBSTANCE: invention relates to a process of manufacturing composite powder filler for elastomer compositions designed for fabrication of articles operated under increased wear and dry friction conditions. Process resides in that titanium carbide particles are activated in a mechanochemical activator with mechanical energy supply intensity 1 to 5 kW/kg and dose 100 to 1000 kJ/kg in a medium selected from a series: air, nitrogen, argon, and vacuum at pressure from 10-2 to 1 atm until particles with average size not larger than 15 μm are obtained, after which high-pressure polyethylene is added to activator and titanium carbide particles are modified at mechanical energy supply intensity 0,05 to 0.5 kW/kg and dose 3 to 100 kJ/kg in a medium selected from a series: air, nitrogen, argon, and vacuum at pressure from 10-2 to 1 atm.

EFFECT: lowered coefficient of friction under dry friction conditions and reduced summary rate of wear of friction pair under hydroabrasive wear conditions.

1 tbl

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to a method for preparing a filling agent used in manufacturing polymeric composition materials in making articles for structural and tribotechnical designation. Method involves mixing 0.5-10.0 mas. p. of epoxy diane resin with 100.0 mas. p. of sodium silicate aqueous solution (by dry matter) at temperature 40-60°C. Then the mixture is coagulated with mineral acid taken in the amount providing hydrogen index pH = 4.0-5.0, washed out with water and prepared solid substance as a precipitate is dried. Invention provides enhancing physicochemical and antifriction properties of the polymeric composition.

EFFECT: improved preparing method.

5 ex

FIELD: composite materials.

SUBSTANCE: invention concerns powderlike composite filler suitable for elastomer materials intended for manufacturing articles operated under elevated wear or dry friction conditions. Filler particles contain at least one core made from ceramic material (metal carbide) and exterior layer made from polytetrafluoroethylene, volume fraction of cores in filler particles ranging from 1 to 10%. Powderlike composite is prepared by activating metal carbide particles in mechanochemical activator at mechanical power supply intensity between 1 and 5 kW/kg and dose 30 to 1000 kJ/kg in a medium selected from: air, nitrogen, argon, vacuum between 10-2 and 1 atm until particles with average size not larger than 15 μm are obtained, after which polytetrafluoroethylene is added to mechanochemical activator and metal carbide particles are modified at mechanical power supply intensity between 0.05 and 0.5 kW/kg and dose 3 to 100 kJ/kg in a medium selected from: air, nitrogen, argon, vacuum between 10-2 and 1 atm.

EFFECT: addition of powderlike composite filler to rubber compound results in reduction in friction coefficient under dry friction conditions and significant reduction in summary friction pair wear under hydroabrasive wear conditions.

4 cl, 2 dwg, 3 tbl

FIELD: organic and physical chemistry; chemical modification of solid surfaces of highly dispersed amorphous silica for imparting hydrophobic properties; oil and gas industry; manufacture of building materials.

SUBSTANCE: proposed method consists in production of silica by chemical modification of surface with the aid of organic compounds at elevated temperature. Modification reaction is conducted in reactor at mechanical mixing and at boiling point of modifying agent. Modification of surface is performed with the aid of compound selected from group of higher α-olefins C10-C16 at elevated temperature; the procedure is continued for 3-10 h at the following ratio of mixture components, mass-%: α-olefin : dispersed silica (17-95) : (5-83), respectively. Proposed method may additionally include drying or dehydroxylation of silica at temperature of 120-300°C for 2 h.

EFFECT: avoidance of corrosion of equipment; enhanced ecological safety; low cost of final product.

2 cl, 1 tbl, 12 ex

FIELD: dyes.

SUBSTANCE: invention relates to stable mixtures comprising filling agents and condensing agents chosen in the indicated combinations and concentrations. These stable mixtures can be used as mixtures in a method for preparing dyes by using dye precursors or as a component in the covering material such as a dye, or for another final aim wherein pigments conferring the paints covering power are used.

EFFECT: improved and valuable properties of mixtures.

13 cl

The invention relates to mineral fillers used for the manufacture of polyurethane foams, in particular to the fillers of the type of carbonate, hydroxides, silicates, sulfates and similar mineral fillers

The invention relates to compositions containing micronized particles of inorganic material treated with a derivative of cellulose or cellulose, modified by at least one ionic or Deputy containing ion such Deputy

FIELD: chemistry of polymers, leather industry, chemical technology.

SUBSTANCE: invention relates to a method for preparing polymeric products that are used in processes for dressing leather or fur, in treatment and disinfection of natural and sewage waters. Method for preparing polymeric products involves the hydroxymethylation reaction of polyhexamethylene guanidine chloride with formaldehyde and arylation reaction of prepared product with aromatic compound comprising o-amino- or o-hydroxy-groups. The hydroxymethylation reaction is carried out in the presence of acetic acid or formic acid up to formation of trimethylol derivative of polyhexamethylene guanidine chloride. In some cases the arylation product is subjected for complex formation with transient metal salt or azo-coupling reaction with diazonium salt taken among group including sulfanilic acid, naphthionic acid, j-naphthyls, p-nitroaniline, 2,6-dichloro-4-nitroaniline. Invention provides simplifying, accelerating and enhancing the effectiveness of process in dressing leathers with derivatives of polyhexamethylene guanidine showing tanning effect, staining properties, flocculating capacity and high antibacterial activity.

EFFECT: improved preparing method.

3 cl, 1 tbl, 9 ex

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