Aqueous dispersion of particles comprising water-insoluble pigment and method for its preparing, particles comprising water-insoluble pigment and method for their preparing and ink

FIELD: dyes and pigments.

SUBSTANCE: invention relates to a method for preparing an aqueous dispersion wherein water-insoluble dye is dispersed stable in an aqueous medium containing water and that is used as ink, respectively. Invention describes an aqueous dispersion comprising particles including water-insoluble dye and a polymeric compound or surface-active substance wherein its hydrophilic moiety is formed by at least one group taken among the group consisting of carboxyl, sulfonic, phosphorus, hydroxyl and alkylene oxide group. Particles are dispersed in water-containing medium and dispersion shows intensity of light scattering 30000 imp/s, not above, when it comprises sufficient amount of particles and to provides value of absorption peak with respect to visible light = 1 and particles give the same color as a water-insoluble dye in crystalline state. Also, invention relates to a method for its preparing involving the following stages: (1) preparing a solution containing water-insoluble dye and a dispersing agent dissolved in aprotonic water-soluble organic solvent in the presence of alkali; (2) mixing the solution with water and preparing the dispersion containing particles comprising water-insoluble dye and dispersing agent. Also, invention describes particles comprising water-insoluble dye and polymeric compound or surface-active substance wherein its hydrophilic moiety is formed by at least one group taken among the group consisting of carboxyl, sulfonic, phosphorus, hydroxyl and alkylene oxide group provides the same color as water-insoluble dye in crystalline state and having colored moiety with water-insoluble dye and non-colored moiety wherein non-colored moiety exists in the round region with radius 40 nm and wherein its center is the required point in a particle. Also, invention relates to a method for their preparing that involves the following stages: (A) preparing an aqueous dispersion; (B) formation of aggregate consisting of dispersion particles and isolation of aggregate from the dispersion; (C) conferring to particles in aggregate the capacity for repeated dispersing and wherein the stage (B) involves sub-stage of addition of acid to the dispersion to form aggregate, and the stage (C) involves sub-stage of treatment of aggregate with alkali to confer particle in aggregate the capacity for repeated dispersing, and ink containing particles described above. Proposed ink provides printing with excellent quality by color and clearness that are resistant to water and light.

EFFECT: improved preparing method, improved and valuable properties of dispersion and ink.

19 cl, 16 tbl, 1 dwg, 24 ex

 

This invention relates to a water dispersion which contains particles containing a water-insoluble dye in a water-containing environment in dispergirovannom condition and the way they are received, and to particles that contain water-insoluble pigment and have good dispersibility in water, and the way they are received.

Inkjet recording method is a method in which droplets of ink are formed using any of a variety injects ink systems, and some or all of them are applied on the recording medium, such as paper, processed paper, film, plastic, fabric or the like, conducting thereby record. Water liquid for recording, formed mainly from paint and water-soluble additives are used as fluids for inkjet recording. Although they are excellent in stability during storage as a printing ink, that is obtained by printing with these liquids for the record, may not have satisfactory properties in terms of resistance to water, resistance to light or the like, depending on their use in some cases, and therefore, further improvement is desirable. So, an attempt was made to improve the stability in water and light resistance by changing the coloring matter from dye to pigment. However, the pigment is s ink are often poor stability of ejection from the outlet heads for inkjet printing in comparison with the ink from the dye. In addition, since the pigment is not a dye derived from a single molecule, such as a dye, and consists of particles, the absorption spectrum becomes broad due to scattering of light by the pigment and reflected by the pigment light compared with the dye so that the dye image formed with the pigment ink, mainly tends to be weak compared with the image formed by the ink from the dye. The way to solve the problems associated with such coloring properties, includes such a method in which a pigment is finely ground. Thus, there is a need for fine grinding of pigment to 100 nm or less, to reduce the effect of light scattering and transmittance property was comparable with the transmission of the dye. Fine grinding of the pigment is mainly produced by the mechanical force using a dispersing device such as a sand mill, a roller mill or ball mill. In accordance with this method, however, fine grinding of the pigment is limited in size to about 100 nm from the degree of their primary particles. Accordingly, this method is difficult to apply when there is need for further grinding (Japanese patent application publication No. 10-110111). It takes more time for dispersion, taktak particle diameter of the pigment is reduced, so the price increases to a greater extent and, in addition, faced with the difficulty in obtaining a pigment having a uniform property. As it is very difficult to grind the pigment to a smaller particle than the primary particles, with this method, the pigment primary particles which are large, cannot be used as raw material for reception of pigment particles having a diameter less than 100 nm. On the other hand, suggested ways in which the pigment is first dissolved and then re-precipitated to obtain finely ground particles of pigment. In Japanese patent application No. publishing 9-221616 proposed pulverisation process acid pastravanu, in which the organic pigment is first dissolved with sulfuric acid. However, this method cannot obtain the pigment particles having a diameter less than 100 nm. In Japanese patent publication No. 4-29707 and 6-4776 described such a method, by which an organic pigment is dissolved in aprotonin polar solvent in the presence of alkali, and then neutralized with acid, to obtain particles of the finely ground pigment. Although thin grinding pigment and stabilizing the dispersion processing is not carried out at the same time with this method, however, the pigment particles, first finely ground, are Agra is then already at variance, and so it is difficult to obtain a pigment dispersion essentially nanometer order. Japanese patent publication No. 5-27664, 6-33353 and 6-96679 and Japanese patent application No. publishing 11-130974, finely ground particles of pigment obtained by dissolving an organic pigment and a dispersing agent such as surfactant or resin, together aprotonin solvent in the presence of alkali, and then neutralizing the acid solution to precipitate the pigment. However, research in the framework of this invention it was found that the resulting particles of the pigment is insufficient for stability of a dispersion in an aqueous solvent containing water, for use in, for example, in ink, water based, for example, inkjet printing. Because this method involves the step of adding drops of acid to the solution pigment (a water content of 20% or below) for the sedimentation and separation of the pigment from the solution by neutralization, re-deposition is also done at the same time, it is impossible to sufficiently prevent the Association of the pigment particles, and therefore concluded that the pigment dispersion of nanometer-order particles having the same diameter, it is impossible to obtain a stable, even when then conducted a dispersing treatment using a ball mill the like.

Incidentally, when inkjet printing using the ink containing the pigment, it is considered that the ink is excellent in stability during storage, obtained by fine grinding of the pigment particles, and the viscosity of the ink and the change of the particle diameter of the pigment dispersion is negligible, even when the ink is not used over an extended period, and therefore, a good ejection properties can easily be obtained by examining the properties of the finite speed of sedimentation of the ink, when considering the property ejection of ink from nozzles (ejection holes) heads for inkjet printing. However, the finer the particle size of the pigment, the greater the increase in surface area per unit mass of particles. Thus, the usual way of stabilizing the dispersion may be insufficient to ensure that the dispersion contained particles having a diameter of nanometer order.

As for the pigment coated with resin only by physical adsorption forces, there remain concerns about its resistance to solvents. When using a pigment such a structure as a component of the ink for inkjet printing, in some cases, the pigment may create a situation where not only the various types of additives added to the ink is limited, but also the situation when the image quality of whutcha is raised due to the change in the viscosity of ink depending on the temperature, tend to become large, and the amount of ink ejected from a nozzle head for ink-jet printing, changing.

Accordingly, an object of this invention to provide a water dispersion in which the water-insoluble colorant stably dispersed in an aqueous medium containing water, and which accordingly is used as an ink, which can provide printing, excellent color and transparency, and to a method capable of effectively obtaining such water dispersion.

Another object of this invention to provide particles which contain water-insoluble dye and possess excellent stability of dispersion in water, and the way they are received.

An additional object of this invention is to obtain an ink, which can respectively be used to obtain high-quality images.

In accordance with this invention, accordingly, the aqueous dispersion comprising particles containing a water-insoluble dye, and particles dispersed in a medium containing water, and the dispersion has the intensity of light scattering is not more than 30000 pulses/sec, when the dispersion contains a sufficient number of particles, such that gives the value of the peak absorption for visible light, is equal to 1.

In compliance the with this invention presents a method of obtaining a water dispersion, incorporating the following stages:

(1) a solution containing water-insoluble colorant and the dispersing agent dissolved in aprotonin organic solvent in the presence of alkali, and

(2) mixing the solution with water to obtain a dispersion comprising particles containing the water-insoluble colorant and a dispersing agent.

According to this invention, moreover, the particles containing the water-insoluble dye, exhibiting the same color as the color of insoluble dye in the crystalline state, and having painted part with a water-insoluble dye and unpainted part, and an unpainted part exists within a circular area having a radius of 40 nm, the center of which is a predetermined point in the particle.

This invention also presents ink containing particles described above, in the aquatic environment in dispergirovannom condition.

This invention also presents a method of producing particles containing water-insoluble dye, which consists of stages:

(A) obtaining a water dispersion in accordance with the method described above;

(C) forming a unit consisting of particles of the dispersion for the extraction of aggregates from the dispersion and

(C) give the ability to re-dispergirujutsja in the water particles in EPR the gate.

The drawing is a schematic image representing typical particle according to this invention.

Next will be described embodiments of the present invention. However, this invention is not limited to these embodiments. Aqueous dispersion according to this invention includes particles containing a water-insoluble dye, which are dispersed in a medium containing water. The intensity of light scattering dispersion is not more than 30000 counts/sec (cps), when the dispersion contains a sufficient number of particles, such that the variance gives the value of the peak absorption for visible light, such as light having a wavelength equal to from about 380 to 700 nm, is equal to 1. This means that the intensity of light scattering in dispersion is extremely low, such as not more than 30000 pulses/sec, even when the dispersion contains enough dye to demonstrate the value of absorption equal to 1 for visible light. With respect to conventional pigment ink containing pigment particles, the average diameter of which is equal to about 150 nm, the intensity of light scattering ink ranges from 150,000 to 250,000 pulses/sec, when the value of the peak absorption of the conventional pigment ink in the visible region is 1. From this fact it will be clear that the visual transparency of the water dispersion according to this invention the value is positive above, than conventional pigment inks. Particles in such aqueous dispersions consist of finely ground particles of water-insoluble colorant, such as pigment, and finely ground particles are formed by mixing Rarotonga organic solvent in which is dissolved dispersing agent and water-insoluble colorant, such as pigment, with water. Preferably the particle has many parts, painted finely ground particles of water-insoluble colorant, each of the painted parts separated unpainted part formed by the dispersing agent. The aqueous dispersion according to this invention is obtained by dispersing such finely dispersed particles in the aqueous medium consisting mainly of water.

This aqueous dispersion can be obtained, for example, through the stages of (1) dissolving the organic pigment in the form of a water-insoluble colorant and the dispersing agent in aprotonin organic solvent containing the alkali, and (2) mixing the solution of the pigment obtained in stage (1) with water to form a water dispersion in which the dispersed particles containing the pigment. In accordance with this method the solution of the pigment obtained in stage (1), mixed with water, whereby the solubility of the pigment is reduced, and the solution formed a thin part of the s pigment, having a diameter of from 0.5 to 40 nm. If the dispersing agent is not present at this time, fine particles together with the formation of a large aggregate. In the above composition, however, believe that at least part of the fine particles formed in the solution, covered with a dispersing agent, due to the simultaneous presence of dispersing agent in solution, and the coating dispersing agent, at least part of the fine pigment particles effectively prevents the formation of a large aggregate of finely ground particles. In accordance with this invention, even when the unit is formed of finely ground particles, the number of fine particles in the aggregation, as is, does not exceed 1×109. Observation using an electron microscope of the transmission type, it is concluded that containing the pigment particle in the aqueous dispersion obtained by this method has many of the painted parts 1, painted with fine particles of water-insoluble dye, and dyed part 1 divided unpainted parts 2 dispersing agent, the typical form of which is illustrated, for example, in the drawing, and it is believed that the painted parts stably present in the dispersion, and the size of the colored parts are small enough not to scatter light in the visible region. The other is the capture, containing the pigment particle, as it is written, has the unpainted parts in a circular region with a radius of 40 nm, whose center is given by a point in the particle.

That is, the dispersion of this invention has a small number of painted parts to scatter visible light, unlike conventional ink in which the pigment particles was obtained by mechanical milling method. Therefore, the dispersion containing particles having an average particle diameter equal to, for example, 150 nm or less, as determined by dynamic measurement of light scattering, weakly scatters the light and has a high transparency compared with the dispersion of pigment particles having the same diameter and received in the usual way of grinding. When the pigment is first dissolved and then precipitated in a manner similar to this invention, it is generally considered that the crystallization of the pigment develops insufficient, and therefore the pigment, which is good to use for painting, when he takes a particular crystalline structure, has a disadvantage from the viewpoint of coloring ability. However, containing the pigment particles obtained by the method of the present invention, given the same color as the pigment in the crystalline state and, more specifically, are such coloring ability, the color difference (ΔN°) from the color covered the CSOs by the pigment in the crystalline state, is within a 30°however, the reason is unclear.

The dispersion according to this invention exhibits the effect of staining, comparable to the dispersion containing the pigment particles obtained by the method of grinding the same weight as the dispersion according to this invention, so far as containing pigment particles enclosed in the dispersions of this invention have an average particle diameter in the range of 3 nm or more, as measured when determining the dynamic scattering of light.

In this aqueous dispersion comprising pigment particles contained in the aqueous dispersion with the above intensity light scattering, have an average particle diameter equal to not more than 150 nm, since the aqueous dispersion may accordingly be used as an ink for inkjet printing.

As described above, a method of obtaining a water dispersion of this invention involves the following stages:

(1) a solution containing water-insoluble colorant and the dispersing agent dissolved in aprotonin solvent in the presence of alkali, and

(2) mixing the solution with water to form a water dispersion containing particles comprising water-insoluble colorant and the dispersing agent is dispersed in the aqueous environment.

A method of obtaining a water dispersion according to this invention will be then is written in detail. In this regard, in the following description, an example is presented as a concrete example, water-insoluble dye is taken pigment. However, water-insoluble dyes in this invention are not limited to organic pigments.

The first option exercise

The first stage in the method of obtaining a water dispersion according to the first embodiment of the present invention is the stage of dissolving the organic pigment in aprotonin organic solvent to obtain a solution of the pigment, and the second stage is a stage play containing pigment particles having the same diameter, in the form of aqueous dispersions.

As the organic pigment used in this invention, it is possible to use any pigment, as long as it is soluble in aprotonin solvent in the presence of alkali and allows you to achieve the technical result of the present invention. More preferably, when it is not reactive under these conditions and is stable. More specifically, it is possible to use organic pigments used in inks for printing, paints or the like. Examples of organic pigments include insoluble azo, diazo, condensed azo, antrahinonovye, diantaranya, intraperitonealy, anthanthrene, thioindigo, naftalie, benzoine asalouyeh, philanthropie, phthalocyanine, flavanonol, chinaredorbit, desiccative, diketopiperazine, indanthrene, isoindolines, isoindoline, chieftancy, perinova and perylenebis pigments, pigments, VAT dyes, pigments of metal complexes, pigments, basic dyes, fluorescent pigments and pigments, fluorescent in daylight. Specific examples of this include S (color index) pigment yellow 1, 3, 12, 13, 14, 17, 42, 55, 62, 73, 74, 81, 83, 93, 95, 97, 108, 109, 110, 128, 130, 151, 155, 158, 139, 147, 154, 168, 173, 180, 184, 191 and 199; S pigment red 2, 4, 5, 22, 23, 31, 48, 53, 57, 88, 112, 122, 144, 146, 150, 166, 171, 175, 176, 177, 181, 183, 184, 185, 202, 206, 207, 208, 209, 213, 214, 220, 254, 255, 264 and 272; S pigment blue 16, 25, 26, 56, 57, 60, 61 and 66; S pigment violet 19, 23, 29, 37, 38, 42, 43 and 44; S pigment orange 16, 34, 35, 36, 61, 64, 66, 71 and 73; S pigment brown 23 and 38. These pigments can be used either one by one or in any combination thereof.

Nephrotomy organic solvent used in this invention can be any solvent so far as it can dissolve the organic pigment in the presence of alkali and can achieve the technical result of the present invention. However, it is preferable to use those which have a solubility in water of at least 5%. Those that are able to be freely mixed with water, are more PR is doctitle. If the pigment is dissolved in a solvent having a solubility in water below 5%, such a solution has the disadvantage that contains the pigment particles are difficult to precipitate when the solution is mixed with water, and are easily formed larger particles. In addition, it also has the disadvantage that there is a tendency adverse effects on the stability of the resulting aqueous dispersion. Specific examples of the preferred solvent include dimethyl sulfoxide, dimethylimidazolidine, sulfolane, N-organic, dimethylformamide, acetonitrile, acetone, dioxane, tetramethylrhodamine, hexamethylphosphoramide, hexamethylphosphorotriamide, pyridine, propionitrile, butanone, cyclohexanone, tetrahydrofuran, tetrahydropyran, etilenglikolevye and γ-butyrolactone. Among them, dimethyl sulfoxide, N-organic, dimethylformamide, dimethylimidazolidine, sulfolane, acetone and acetonitrile are preferred. These solvents can be used alone or in any combination thereof. No particular limitations on the amount used Rarotonga organic solvent does not impose. However, the solvent preferably used in the range from 2 to 500 parts by weight, more preferably from 5 to 100 parts by weight per 1 part by weight of the organic pigment from the point C the program state of good dissolving an organic pigment, the ease of formation of finely ground particles having a desired diameter and good color density obtained aqueous suspension.

As the dispersing agent, it is possible to use a dispersing agent which is soluble in aprotonin organic solvent in the presence of alkali, soluble in water, and which can provide a dispersing effect by education containing pigment particles, organic pigment in an aqueous solution of dispersing agent. Preferably used surfactant or polymeric compound, the hydrophilic Deputy which is formed of at least one of carboxyl, sulphonic, phosphate and hydroxyl groups and accelerated. The preferred dispersing agent is stably dissolved with an organic pigment in aprotonin organic solvent in the presence of alkali. When the hydrophilic part of the dispersing agent is formed only by other groups, not those described above, such as primary, secondary and tertiary amino groups and Quaternary ammonium group, the degree of stability of the dispersion may be relatively low in some cases, although it is sufficient in water dispersion of organic pigment containing alkali. The usual process is dispergirovanija pigment requires the use of some techniques, such as the choice of dispersing agent, able to effectively come into contact with the surface of the pigment in the state of dispersion in the environment. Although as a dispersing agent and the pigment exist in the environment in a dissolved state in the present invention, and easily achieve the desired effect between them, however, there are no restrictions in respect of dispersing agent on the effectiveness of contact on the surface of the pigment, in contrast to the usual process of dispersion of the pigment, and therefore, you can use a wide range of dispersing agents.

In particular, the surfactant may be appropriately selected from conventional well-known surfactants such as anionic surfactants, including alkylbenzenesulfonate, alkylnaphthalenes, salts of higher fatty acids, salt sulfonate acid esters of higher fatty acids, sulfate salts ethers of higher alcohols, alkylcarboxylic salts of higher alkylsulfonamides and alkylphosphates; nonionic surfactants, such as polyoxyethyleneglycol ethers, polyoxyethyleneglycol ethers, esters of polyoxyethylene and fatty acids, esters sorbitan and fatty acids, ethyleneoxide adducts of glycerol and esters of polyoxyethylenesorbitan igornych acids, and, in addition, amphoteric surfactants, such as alkylbetaine and aminobutane, silicone surfactants, and fluorine-containing surfactants and their derivatives.

Specific examples of the polymer compound used as the dispersing agent include block polymers, random copolymers and graft copolymers formed of at least two monomers (at least one of them is a monomer having a functional group formed by any of a carboxyl, sulphonic, phosphate and hydroxyl groups, and accelerated)selected from styrene, styrene derivatives, vinylnaphthalene, vinylnaphthalene derivatives, esters of aliphatic alcohols and α,β-Ethylenediamine carboxylic acids, acrylic acid, derivatives of acrylic acid, methacrylic acid, derivatives of methacrylic acid, maleic acid, derivatives of maleic acid, alkanesulphonic acids, vinylamine, allylamine, basis of itaconic acid, derivatives of basis of itaconic acid, fumaric acid derivatives, fumaric acid, vinyl acetate, vinylphosphonic acid, vinylpyrrolidone, acrylamide, N-vinylacetate, N-vinylformamide and their derivatives, and the like, and modified products and salts of these copoly the development. Alternatively, it is preferable to use natural polymer compounds such as albumin, gelatin, rosin, shellac, starch, gum Arabic and sodium alginate, and their modified products. These dispersing agents can be used either one by one or in any combination thereof. No special restrictions to the amount of dispersing agent is not installed. However, the dispersing agent is preferably used in amounts in the range of from at least 0.05 part by weight per 1 part by weight of organic pigment and up to 50 parts by weight per 100 parts by weight Rarotonga organic solvent. If the amount of dispersing agent is higher than 50 parts by weight per 100 parts by weight Rarotonga organic solvent, in some cases, it may be difficult to completely dissolve the dispersing agent. If the amount of dispersing agent is below 0.05 part by weight per 1 part by weight of organic pigment, in some cases, it may be difficult to achieve an appropriate dispersing effect.

As the alkali used in the first stage, you can use any lye, which can dissolve the organic pigment in aprotonin organic solvent and to ensure the achievement of the technical result of the present invention. However, GI is rockside alkali metals, alkoxides of alkali metals, hydroxides of alkaline earth metals, alkoxides of alkaline earth metals, and strong organic bases are preferred from the point of view of their high ability to dissolve organic pigment. Specifically, you can use the lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, tert-piperonyl potassium methoxide, potassium ethoxide potassium, sodium methoxide, ethoxide sodium, Quaternary ammonium compounds such as tetrabutylammonium hydroxide, 1,8-diazabicyclo-[5,4,0]-7-undecene, 1,8-diazabicyclo-[4,3,0]-7-nonen and quinidine. These alkalis can be used either separately or in any combination thereof. No particular restrictions on the quantity used of the base is not installed. However, it is preferable to use it in the range from 0.01 to 1000 parts by weight per 1 part by weight of organic pigment. If the amount of alkali below 0.01 part by weight per 1 part by weight of organic pigment, a difficulty that can be encountered in some cases, is that there is a tendency that it becomes difficult to completely dissolve the organic pigment together with a dispersing agent in aprotonin organic solvent. If the amount exceeds 1000 parts by mass, obstruction, which can occur in some cases, is that a hundred is ulitsa difficult to dissolve the lye in aprotonin organic solvent, and increase the solubility of the organic pigment becomes impossible to expect.

To completely dissolve the lye in aprotonin organic solvent, to deprotonate organic solvent may be added a certain amount of solvent having a high ability to dissolve the alkali, such as water or a lower alcohol. These solvents act as solubilizers alkali auxiliary agent for improving the solubility of the alkali in aprotonin organic solvent, and therefore the dissolution in an organic solvent becomes easy. Because there is a risk of reducing the solubility of the organic pigment, when the degree of the addition is 50 mass% or higher to the number of all solvent, the degree of adding from about 0.5 to 30% by weight is usually the most effective. The reason is that the solubility of alkali only aprotonin the solvent is relatively low. Specifically, it is possible to use methanol, ethanol, n-propanol, isopropanol, butyl alcohol and the like. To quickly dissolving an organic pigment by reducing the quantity of alkali used at least for dissolving the organic pigment, it is preferable to add the alkali in the form of a solution in a lower alcohol or the like in nephrotomy organic rest ritel, in which was suspended organic pigment, up until the pigment is dissolved. At this time can easily be spent removing foreign substances or the like, since the pigment is in the form of a solution. When choosing these solubilizing alkali additives it is important to ensure compatibility with dispersing agent, so it is especially preferable to use a lower alcohol, such as methanol or ethanol, from the viewpoint of compatibility with the dispersing agent is preferably used in this invention.

When an organic pigment is dissolved in aprotonin organic solvent for the organic pigment and the dispersing agent may be added, at least one of preventing the crystal growth agent, ultraviolet absorber, antioxidant, polymer additives, etc. when necessary. Examples of agents that prevent the growth of crystals include phthalocyanine derivatives and chinaredorbit derivatives, are well known in the art. Concrete examples include phthalimidomethyl phthalocyanine derivatives, derivatives of sulfonic acids and phthalocyanine derivatives, N-(dialkylamino)methyl derivatives of phthalocyanine, N-(dialkylaminoalkyl)sulfonamidnuyu derivatives of phthalocyanine, phthalimidomethyl derivative chinagreen, derived sulfosalicylate and chinagreen, N-(dialkylamino)methyl derivative chinagreen and N-(dialkylaminoalkyl)sulfonamidnuyu derivative chinagreen.

Examples of the ultraviolet absorber include metal oxides, aminobenzoate absorbers of ultraviolet radiation, salicylate absorbers of ultraviolet radiation, benzophenone absorbers of ultraviolet radiation, benzotryazolyl absorbers of ultraviolet radiation, cinnamate absorbers of ultraviolet radiation, nicergoline absorbers UV absorbers of ultraviolet radiation with a spatial dull amines, ultraviolet absorbers from Eurocasinobet acid and vitamin absorbers of ultraviolet radiation.

Examples of antioxidants include spatial employed phenolic compounds, esters Tolkunova acid, organophosphorus compounds and aromatic amines.

Examples of polymer additives include synthetic polymers, such as bionanotechnology polyvinyl alcohol, nationaldirectory polyvinyl alcohol, polyurethane, carboxymethyl cellulose, polyester, polyarylate, polyvinylpyrrolidone, polyethylenimine, primisulfuron, polyvinylene, hydroxyethylcellulose, hydroxypropylcellulose, melanin resins and modified products. All of these prevent the growth of crystals agents, ultraviolet absorbers, antioxidants and polymer additives mo is but used separately or in any combination thereof.

The amount of water used in mixing with aprotonin solvent, in which were dissolved in the presence of alkali, an organic pigment and a dispersing agent, hereafter called "the solution of the pigment with water in the first stage for the deposition of the organic pigment is from about 0.5 to 1000 parts by weight, more preferably from 1 to 100 parts by weight per 1 part by weight solution of a pigment from the viewpoint of further improving the stability of a dispersion containing pigment particles deposited in the aquatic environment and improving the color density obtained water dispersion.

The temperature of the slurry of the pigment and water when mixed is preferably regulated in the range from -50 to 100°S, more preferably from -20 to 50°C. as the temperature of the solution in the mixing strongly affects the particle size of precipitated organic pigment, the temperature of the solution is preferably maintained in the range from -50 to 100°in order to obtain a water dispersion containing pigment particles having a particle diameter of nanometer order. For reliable flow solution at this time can be added widely known for reducing the temperature of the freezing agent, such as ethylene glycol, propylene glycol or glycerin before adding water with which to mix.

To n in order to obtain containing pigment particles of nanometer order, with uniformity in size, the mixing of the solution of the pigment with water is preferably carried out as quickly as possible, and you can use conventional, well-known device used for stirring, mixing, dispersion and crystallization, such as ultrasonic emitter, panosovna paddle stirrer, internal mixing device of the circulation type, external mixing device of the circulation type, and the device that regulates the flow rate and concentration of ions. Mixing can also be produced in a continuous flow of water. As a way of infusion of a solution of the pigment in water can be used any conventional, known methods of infusion fluid. However, preferably, when the solution is poured or serve it in water in the form of an input stream from a nozzle of a syringe, needle or tube, or the like. The solution can also be injected through many nozzles in order to complete the infusion within a short period of time. To steadfastly to obtain the aqueous dispersion containing the pigment particles to the water, which must be mixed with a solution of pigment, you can also add the lye and additives including dispersing agent.

Consider that the pigment is dissolved in aprotonin solvent, is undergoing rapid growth of crystals or aggregates of amorphous forms when mixed with water is and the second stage, and at the same time, stabilization of the dispersion is performed using a dispersing agent contained in the solution of the pigment. When necessary, can be produced by heat treatment in the range that does not violate the stability of the dispersion during and immediately after the second stage to adjust the crystal system and the aggregate state water dispersion containing pigment particles.

The aqueous dispersion thus obtained, can be used for different applications, such as ink for inkjet printing, as is, or by adjusting the concentration of the dye as needed. Incidentally, the aqueous dispersion obtained by the above process, may be too diluted concentration of the dye in some cases it can be used in inks for inkjet printing. Although the concentration can be increased by concentrating the dispersion or the like, this method is not practical from a manufacturing standpoint. In this case containing the pigment particles are first separated from the aqueous dispersion, and then dispersing in water results containing pigment particles, and then a certain number containing such pigment particles are again dispersed in water, whereby it may be manufactured aqueous dispersion having the desired concentration of dye. The EU is ü the third stage is formed unit from containing pigment particles from the dispersion, obtained in the second stage.

For the formation of the unit preferably is processed by adding acid. The treatment with an acid preferably includes stages of aggregation containing pigment particles using an acid, separating the unit from the solvent (dispersion medium), its concentration, desolvatation and desalination (removal of acid). By acidification of the dispersion obtained in the second stage, the strength of the static repulsion dispersing agent is reduced, so that the particles containing the pigment aggregate. When aggregation was carried out using an acid in the normal dispersion of the pigment, there was an increase in particle diameter, and was hard again fully dispersing aggregated, even when then were processed with alkali. When using the aqueous dispersion containing the pigment particles obtained in the second stage in the method of receiving according to the first embodiment of the present invention, the diameter of the particles does not increase after re-dispersion, even when aggregation is performed using acid.

As the acid used for aggregation containing pigment particles, you can use any acid, which can aggregate containing pigment particles in the aqueous dispersion present in the form of finely ground particles that work is about to besiege, for the formation of a thick slurry, paste, powder, granules, dense sediment (loose weight), of the reservoir, the low layer, flakes or the like, so as to effectively separate them from the solvent and to obtain the objects of the present invention. To separate the alkali used in the first stage, at the same time, it is more preferable to use an acid capable of forming soluble salts with alkali, used in the first stage. Preferably, the solubility of the acid in water was also high. For the effective conduct desalting preferably, the amount of acid used was as small as possible within, which contains the pigment particles in the water dispersion of aggregate. Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, triperoxonane acid, dichloracetic acid and methansulfonate acid, and hydrochloric acid, acetic acid and sulfuric acid are particularly preferred. Containing the pigment particles in the aqueous dispersion, is addressed in the state in which they are easily distinguished using acid can be easily separated using conventional, well-known centrifugal separator, a filter, a separator for a thick suspension of solids in liquids, and the like At this time, the degree of demineralization and desolvatation can be adjusted by adding a diluent, water or rinsing water.

The aggregates obtained in the third stage, can be used effectively in the form of a paste or thick slurry with a high water content. However, they can also be used in the form of finely ground powder by drying the conventional well-known methods of drying, such as spray drying method, the method of the centrifuge drying, a method of filtering and drying or drying by freezing when necessary.

The fourth stage in the process according to the first implementation of this invention is the stage giving the ability again to dispergirujutsja in the aquatic environment units, selected from aqueous dispersions in the third stage, and the preferred treatment includes treatment with alkali. In other words, the fourth stage includes treatment with an alkali is a stage of neutralization containing pigment particles, aggregated, for example, by applying acid at the third stage, alkali, to re-dispersing them in water with a particle diameter close to the diameter containing the pigment particles in the water dispersion obtained in the second stage. As desalting and desolately already performed at the third stage, can be obtained concentrated aqueous dispersion containing pigment particles with minor impurities. As the alkali used in chetvert the stage, you can use any lye, which acts as a neutralizer for the dispersing agent having acidic hydrophilic part to enhance water solubility, and can contribute to the implementation of the present invention. Specific examples include various organic amines, such as aminomethylpropanol, dimethylaminopropanol, dimethylethanolamine, dietitian, monoethanolamine, diethanolamine, triethanolamine, butyldiethanolamine and morpholine; hydroxides of alkali metals such as sodium hydroxide, lithium hydroxide and potassium hydroxide, and ammonia. These alkalis can be used separately or in any combination thereof.

No special restrictions are not set in relation to the amount of alkali used, if it falls within those limits, which contains the pigment particles in the unit can be re-attached stable dispersibility. However, when considering the use of a dispersion obtained by re-dispersing unit, hereinafter referred to as "re-dispersion", as printing inks, inks for inkjet printing, etc., the alkali is preferably used in such amounts that the resulting dispersion has a pH from 6 to 12, preferably from 7 to 11.

Re-dispersion may be added water-soluble organic solvent in order to facilitate re-dis is ergonovine aggregated, containing pigment particles. No special restrictions are not set specifically for the used organic solvent. However, his examples include lower alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, Isobutanol and tert-butanol; aliphatic ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone and datetoday alcohol, and, in addition, ethylene glycol, diethylene glycol, triethylene glycol, glycerin, polypropylenglycol, onomatology (or monotropy) simple ether of ethylene glycol, methyl simple ether of propylene glycol, methyl simple broadcast dipropyleneglycol, methyl simple broadcast tripropyleneglycol, phenyl simple ether of ethylene glycol, phenyl simple ether of propylene glycol, onomatology (or monotropy) simple ether of diethylene glycol, monobutyl simple ether of diethylene glycol, onomatology (or monotropy) simple ether of triethylene glycol, N-organic, 2-pyrrolidone, dimethylformamide, dimethylimidazolidine, dimethylsulfoxide and dimethylacetamide. These solvents can be used singly or in any combinations thereof. The amount of water in the water dispersion obtained by repeated dispersion containing pigment particles can be adjusted from 99 to 20% by weight, preferably from 95 to 30% by weight. The amount of water-soluble organic the second solvent can be adjusted from 50 to 0.1% by weight, preferably from 30 to 0.05% by weight.

When to get re-dispersion is water, alkali or water soluble organic solvent, it is possible to use conventional, well-known device for stirring, mixing and/or dispersion, if necessary. When, in particular, use paste or thick slurry of the organic pigment having a high water content, there is no need to use water; heating, cooling, distillation and the like can be carried out in order to increase the effectiveness of re-dispersion and removal of water-soluble organic solvent, which has become useless or excess alkali.

Also, can be carried out modification containing the colorant particles in the aqueous dispersion according to this invention using any method selected from the methods in the following embodiments with the second to the fourth.

The second option exercise

The method according to the second variant embodiment of the invention can be carried out in the same manner as in the first and second stages of the method of receiving according to the first embodiment, except that the polymerized substance contained in the pigment solution. Curable compound in the obtained containing pigment particles is polymerized, and p is gment in containing the pigment particles is fixed. By this fixation is possible to effectively prevent the destruction or loss of dispersive ability of the pigment even when the aqueous medium added to different substances such as a surfactant and the like, in order, for example, regulation of the physical properties of the ink. It should be noted that the very curable substance may be dispersibility, if containing pigment particles having the desired dispersibility, get through their joint use with the dispersing agent, but you can use the polymerized connection with dispersing ability in relation to pigment. In addition, can be used both from the polymerized compounds with dispersing ability in relation to pigment without it. At the same time you can also optionally use another dispersing agent, and not polymerisation connection with dispersing ability, when necessary. As specific preferable examples of when the use of the polymerized compound, may be mentioned the following combinations of the respective components:

(a) (polymerized dispersing agent) + (curable compound) + (other dispersing agent, and not the polymerized dispersing agent);

(b) (polymerized dispersing agent) + (polymerized connection);/p>

(C) polymerized dispersing agent and

(d) (curable compound) + (other dispersing agent, and not polimerizarii dispersing agent).

In the second stage of the method of obtaining a water dispersion according to the second embodiment of the present invention the pigment is dissolved in a solution of a pigment, quickly crystallizes or forms similar to amorphous unit when replacing Rarotonga organic solvent with water, and are formed simultaneously containing pigment particles, which are given stable dispersibility by using at least one of the dispersing agents and polymerizing connection with dispersing ability.

As the pigment used in the process according to the second embodiment, it is possible to use any pigment, if it is soluble together with the components of the solution of the pigment in aprotonin organic solvent and can achieve the technical result of the present invention. Concrete examples include pigments mentioned earlier, for the process according to the first variant embodiment of the invention.

As Rarotonga solvent can also use the ones shown in the example for the process according to the first variant of implementation, and the mixing ratio of the pigment with aprotonin organic solvent, etc. can also be set which go the same way as for the process according to the first variant implementation.

As polymerised compounds used in the process according to the second variant implementation, the connection is used, which has the polymerized part, can be dissolved in aprotonin organic solvent and can save polimerizuet, at the same time, being obtained containing pigment particles. Preferably, you can use the monomer used in the radical polymerization or ionic polymerization.

No particular limit is not set for the specific type of monomer, if he can lead the technical results of this invention. However, their examples include α-olefinic aromatic hydrocarbons having from 8 to 20 carbon atoms, such as styrene, 4-methylsterol, 4-atillery, styrelseledamot acid and their salts; vinyl esters having from 3 to 20 carbon atoms, such as wikiformat, vinyl acetate, finalproject and isopropenylacetate; galogensoderjasimi vinyl compounds having from 2 to 20 carbon atoms, such as vinyl chloride, vinylidenechloride, vinylidenefluoride, tetrafluoroethylene and tetrachlorethylene; olefinic carboxylic acids having from 4 to 20 carbon atoms and their esters such as methacrylic acid and its salts, methyl methacrylate, ethyl methacrylate, prop is methacrylat, butylmethacrylate, 2-ethylhexylacrylate, sterilisability, acrylic acid and its salts, methyl acrylate, acrylate, butyl acrylate, 2-ethyl hexyl acrylate, euroelectric, stearylamine, militant, utilityand, maleic acid and its salts, maleic anhydride, methylmaleic, etilalaat, fumaric acid and its salts, methylvalerate, ethylfuran, crotonic acid and its salts, methylcrotonate and etildronat; cyanocobalamin vinyl compounds having from 3 to 20 carbon atoms, such as Acrylonitrile, Methacrylonitrile and allisland; vinylamide compounds having from 3 to 20 carbon atoms, such as acrylamide, methacrylamide, 2-acrylamide-2-methylpropanesulfonic acid and their salts; retinaldehyde having from 3 to 20 carbon atoms such as acrolein and CROTONALDEHYDE; vinyl aromatic amines having from 8 to 20 carbon atoms, such as 4-vinylpyridine and 4-Finlayson; reinventory having from 8 to 20 carbon atoms, such as 4-vinylphenol, and diene compounds having from 4 to 20 carbon atoms, such as butadiene and isoprene. In addition, the polymerized monomer can be appropriately selected from polyfunctional monomers, macromonomers, other known monomers and their derivatives. These curable compounds can be used either separately or in any combination thereof. No persons shall limit is not set for the number (when used such two or more polymerized compounds, described in (a) and (b)their total number) of the polymerized compounds used within, which can make the object of the present invention. However, the curable compound is preferably used in the range from 0.001 to 10 parts by mass, more preferably 0.005 to 2.0 parts by weight per 1 part by weight of the organic pigment from the viewpoint of more improving the stability of the dispersion containing pigment particles and improve the color intensity of the resulting aqueous dispersion.

When using a curable compound, functioning as a dispersing agent, its amount is regulated to the amount necessary as a dispersing agent and to obtain the effect, given the addition of the polymerized compounds. When the polymerized compound, dispersing agent from which you want, and the polymerized compound, functioning as a dispersing agent are used in combination, their total amount is preferably set in the above-mentioned interval.

As the dispersing agent was added into the solution of pigment, it is possible to use reactive emulsifier in addition to the emulsifiers mentioned for the method according to the first variant implementation. This reactive emulsifier suitable as the above polimerizuet the connection. When using a reactive emulsifier, functions as a dispersing agent and curable compounds can be performed by this emulsifier, and therefore the number of components used is reduced. As described above, the curable compound and a reactive emulsifier having a function of dispersing agent can be used in combination or three components of the reactive emulsifier, polymerisation connection and dispersing agent can also be used in combination. The number of added dispersing agent can be selected in the range above for the process according to the first variant implementation. When the polymerized compound capable of functioning as a dispersing agent, and dispersing agent, unable to polimerizuet, used in combination, their number is preferably selected so that the total number fell in the interval provided for the method according to the first variant implementation.

The polymerized compound, functioning as a dispersing agent capable of imparting dispersibility is obtained containing pigment particles during their formation by mixing a solution of the pigment with water. Specific preferred examples include reactive emulsifier having a hydrophobic part, hydrophilous part and the polymerized part in their molecules. Preferably used are those hydrophilic part which is formed at least one carboxylic, sulfonic, phosphoric and a hydroxyl group and alkalization. No special restrictions are not set specific examples of the reactive emulsifier, if they can obtain the objects of this invention, and used vinylsulfonic acid, 4-vinylbenzenesulfonic acid, arylsulfonate acid, 3-(meth)acryloylmorpholine acid, 2-medicalinsurance acid, 2-(meth)acryloyloxyhexyloxy acid, 2-acrylamide-2-methylpropanesulfonic acid, phosphate mono{2-(meth)acryloyloxy} acid, sulphates allyl alcohol and their salts, vinyl esters having different polyester chain in their respective side chains, such as polyoxyethylenesorbitan esters, esters of polyoxyethylene and of higher fatty acids and polyoxyethyleneglycol ethers, allyl ethers, and monomers of acrylic esters or methacrylic esters. Available for purchase typical reactive emulsifiers include "ADEKA REASOAP SE-10N", "ADEKA REASOAP SE-20N", "ADEKA REASOAP SE-30N", "ADEKA REASOAP NE-10", "ADEKA REASOAP NE-20" and "ADEKA REASOAP NE-30" (products of Asahi Denka Kogyo K.K.), "AQUALON HS-05", "AQUALON HS-10", "AQUALON HS-20", "AQUALON HS-30", "H-3330PL", "AQUALON RN-10", "AQUALON RN-20", "AQUALON RN-30" AND "AQUALON RN-50" (all products of Daiichi Kogyo Seiyaku Co., Lt.), "LATEMUL S-120", "LATEMUL S-120A", "LATEMUL S-180", "LATEMUL S-180A" and "LATEMUL ASK" (all products of Kao Corporation), "ELEMINOL JS-2" and "ELEMINOL RS-30 (both products of Sanyo Chemical Industries, Ltd.), and RMA-564", "RMA-568", "RMA-1114", "ANTOCS MS-60", "ANTOCS MS-2N", "RN-1120" and "RA-2614 (products of Nippon Nyukazai Co., Ltd.). These emulsifiers can be used either separately or in any combination thereof.

When necessary, when the process according to the second variant implementation, you can use the polymerization initiator. The polymerization initiator can be added to one or both of: water for solution preparation of pigment and deprotonate organic solvent. As the method of polymerization can be used radical polymerization, ionic polymerization, or the like. However, polymerization, it is preferable to perform polymerization using free radicals from the point of view of control, ease and wide variety of used polymerized compounds. The polymerization can also be triggered and cause the development by using heat or light, or a combination thereof, or by use of a polymerization initiator generating an active group by heating or light, or a combination thereof.

Specific examples of the above-described polymerization initiators include soluble in oil initiators for the initiator, thermal polymerization, such as initiators of azopolymers the AI, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) and 2,2'-azobis(methyl-2-methylpropionate), and peroxide polymerization initiators such as benzoyl peroxide, eurailpress, bis(4-tert-butylcyclohexyl)peroxocarbonate, tert-butyl peroxy-2-ethylhexanoate, di-tert-butylperoxide, tert-butyl peroxybenzoate and 1,1-bis(tert-BUTYLPEROXY)-3,3,5-trimethylcyclohexane. Water-soluble initiators include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate; peroxide compounds such as hydrogen peroxide; water-soluble initiators azopolymers, such as 2,2'-azobis(2-amidinopropane) dihydrochloride and atomiclongarray acid; redox initiators such as a combination of a peroxide and a reducing bisulfite, such as ammonium persulfate and sodium bisulfite, a combination of peroxide and amino compounds, such as ammonium persulfate and dimethylaminoethanol, and combinations of peroxide ions and polyvalent metal, such as hydrogen peroxide and Fe2+. The photopolymerization initiators include hydrogen abstract type photopolymerization initiators such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylamine, isopropylthioxanthone, dietitican and ethyl-4-(IER is ylamino)benzoate, and the initiators of photopolymerization type intramolecular cleavage, such as benzoylacetone esters, benzyldimethylamine, 1-hydroxycyclohexyl, 2-hydroxy-2-methyl-1-phenylpropane-1-he, alkylphenolethoxylate and diethoxyacetophenone. Fotonation polymerization initiator, such as triphenylsulfonium hexafluoroantimonate or triphenylsulfonium phosphate, can also be used in accordance with the method of polymerization. These initiators can be used alone or in any combination.

The number of these used polymerization initiators is preferably appropriately adjusted in accordance with the physical properties and the like of the polymer that intend to obtain, in addition to the method of polymerization, the polymerization conditions, types of the used polymerization initiators, etc. But usually it is desirable that the number was chosen in the range from 0.05 to 10% by weight of the monomer used.

As the alkali used for the manufacture of a solution of the pigment used in the method according to the second embodiment may be used any of what is specified for the method according to the first embodiment, and the quantity added may be selected from the interval provided for the process according to the first implementation.

When the method according to the second embodiment of the stage of obtaining aq is th dispersion, containing containing pigment particles, by mixing a solution of the pigment with water can be performed in the same way that stage in the method according to the first variant implementation.

The third step in the method according to the second variant implementation is the stage of polymerization of the curable compounds contained in the water dispersion. It is believed that with the help of this third stage of the curable compound in the containing pigment particles polymerized with an increase in the adhesion of the pigment to the dispersant agent, and therefore the stability of the dispersion is improved. Initiation and development of polymerization can properly be controlled by the method of polymerization using a polymerization initiator. However, the process in which polymerization is initiated and its development is caused by heat or light, or combination thereof, is preferred. When used as a radical polymerization initiator, particularly preferably used in this invention, the polymerization preferably is carried out in conditions temperature above approximately 10 to 20°than 10-hour half-period temperature, which usually, as mentioned, is an indicator of activation of the initiator of polymerization. The polymerization is preferably performed under appropriate conditions, taking into account the physical and the definition of the properties of the obtained water dispersion. The polymerization can also be initiated at the same time as the deposition containing pigment particles to obtain a water dispersion by setting the water temperature, which was poured a solution of the pigment in the second stage, at a temperature suitable for polymerization. Curing time required for the polymerization reaction may also be adjusted accordingly, using the method of polymerization, the degree of activation of the used polymerization initiator and/or the like. In General, the polymerization is preferably carried out under such conditions that the polymerization is completed in from about 2 to about 24 hours. In addition, the solution is subjected to the polymerization reaction may also be first purged with an inert gas such as nitrogen.

Aqueous dispersion obtained by the above process by which containing dispersed pigment particles containing a pigment and a polymer of polymerized compounds, can be used for various applications, such as ink for inkjet printing, by itself or by adjusting the concentration of the dye. Alternatively, the aqueous dispersion can also be subjected to the same processes as in the third stage and the fourth stage in the process in the first embodiment of implementation. More specifically, the fourth stage in the process in Oromo implementation is the stage of selection containing pigment particles, processed by polymerization in the third stage, in the form of aggregates of an aqueous dispersion. The formation and evolution of aggregates can be carried out in the same manner as in the method used in the process according to the first embodiment. When using a curable compound which is insoluble or poorly soluble in water, unreacted curable compound, suspended or precipitated in water dispersion, can be washed by washing aggregates water.

Aqueous dispersion containing pigment particles are concentrated in the fourth stage, can actually be used in the form of a paste or thick slurry with a high water content. However, it can also be used in the form of finely ground powder, subjecting the drying conventional known method such as spray drying method, the method of the centrifuge drying, a method of filtering and drying, or a method of freeze-drying when necessary.

The fifth stage in the process according to the second embodiment is the stage of giving ability again to dispergirujutsja in the aquatic environment particles containing a pigment, forming aggregates. To give the ability again to dispergirujutsja similarly, you can use the treatment with alkali, as in the process according to the first implementation. The units, which given the ability again dispersional the Xia, re-dispersed in aqueous medium, whereby it is possible to obtain an aqueous dispersion suitable for different uses.

A third option exercise

Containing pigment particles obtained by the method of the third implementation, have such a structure that at least part of their surface coated with the polymer of Ethylenediamine connection. The method according to the third variant of implementation as a way of containing such pigment particles can be performed in the same manner as in the first and second stages of the method of receiving according to the first implementation, except that, as a dispersing agent is used reactive emulsifier in addition to the surfactant and polymer connection.

To obtain, therefore, the water dispersion containing pigment particles, at least some part of the surface containing the pigment particles are covered with a polymer of Ethylenediamine connection at the third stage. As surface-active substance and a polymeric compound as the dispersing agent in the method according to the third implementation, you can use the ones that are named for the method according to the first implementation. As the reactive emulsifier can be used those which are named for the method according to the second implementation. As this is a reactive emulsifier can be used, which can also function as Ethylenediamine connection. The amount of dispersing agent can also be selected in the interval provided for the method according to the first embodiment.

The third stage of the method according to the third embodiment is the stage of coating at least certain parts of the surface containing the pigment particles obtained in the first and second stages, the polymer of Ethylenediamine connection.

More specifically, Ethylenediamine connection is added to aqueous dispersion under stirring, and then polimerizuet to cover the entire surface or a part of a surface of each of the containing pigment particles, in the form of grains (shell)formed by the polymer, whereby significantly improves the stability of the dispersion. The polymerization is preferably performed using a radical polymerization from the viewpoint of management capability, lightness and wide variety of used polymerised compounds for cover.

No specific restrictions are not set in relation to Ethylenediamine compound (monomer), if it has at least one curable carbon-carbon double bond in its molecule and can provide objects of the present invention. Taking into account the properties of the obtained at the end of the cha is TIC, however, it is preferable that the polymer of Ethylenediamine compounds (monomer) was used as the dispersing agent, which is a material for forming the seed, and the same or a connection similar to that used in the seed, was used to form the shell. Specific examples of the compounds having Ethylenediamine bond in the molecule include styrene, derivatives of styrene, vinylnaphthalene, derivatives vinylnaphthalene, vinyl esters, acrylic acid, derivatives of acrylic acid, methacrylic acid, derivatives of methacrylic acid, maleic acid, derivatives of maleic acid, taconova acid derived on basis of itaconic acid, fumaric acid derivatives, fumaric acid, crotonic acid, derivatives of crotonic acid, alkylsulfonyl acid and its derivatives, vanillin and its derivatives, allylamine and its derivatives, vinylchloride, vinylcyanide, vinylphosphonic acid and its derivatives, vinyl pyrrolidone and its derivatives, methacrylamide and its derivatives, N-vinylacetate and its derivatives, N-vinylformamide and its derivatives, retinaldehyde, vinylaromatic amines and reinventory. Specific examples of compounds having two Ethylenediamine communication in the molecule include etilenglikolevykh, glycerol who methacrylate, trimethylolpropane, triallylisocyanurate, vinylmethyl, vinylacetat, divinylbenzene, butadiene and isoprene. In addition, ethyleneamine the connection can be properly selected from polyfunctional monomers, macromonomers, other commonly known monomers and their derivatives. These curable compounds for coating can be used either separately or in any combination thereof. No specific limitation is not installed on the amount of the polymerized compounds. However, the curable compound is preferably used in the range of from 0.001 to 10 parts by mass, more preferably 0.005 to 2.0 parts by weight per 1 part by weight of organic pigment, in order to increase the effect of improving the stability of the dispersion is obtained containing the pigment particles in the aqueous medium by coating polymer, and saves or further improves cartridge strength by using the pigment solid substances in water dispersion.

Curing the curable compound to cover can be initiated, and may be caused by its development by heat or light, or a combination thereof, or the use of a polymerization initiator generating active elements during heating or lighting, or their combination. The polymerization initiator may be appropriately selected in accordance with the tvii overlooking used Ethylenediamine compound (monomer) and a dispersing agent. The polymerization preferably is carried out near beans, so that no new particles are generated in the aqueous phase during the seed polymerization. At this time, preferably, in the system water dispersion obtained in the first and second stages, adding not only the initiator of the polymerization, but also soluble in oil, the polymerization initiator, dissolved in advance in aprotonin solvent in the presence of alkali in the first stage. The polymerization initiator may also be added as in the first and in the second stage. In any case, the amount added of the polymerization initiator is installed so as to ensure that you receive the expected covered condition. When both stages add the polymerization initiator, the amount can be set so that the total amount falls within the above interval.

Specifically, as the polymerization initiator can be used, at least one of the above-mentioned process according to the second implementation.

The number of these used polymerization initiators is preferably appropriately adjusted in accordance with the physical properties and the like of the polymer, which is intended to receive, in addition to the method of polymerization, the polymerization conditions, the type of polymerization initiators, etc. Od is ako usually desirable that number was chosen in the range from 0.05 to 10% by weight of the monomer used. When using a radical polymerization initiator, particularly preferably used in this invention, the polymerization is preferably performed under conditions of a temperature above about 10-20°and 10-hour half-period temperature, which usually, as mentioned, is an indicator for activation of the initiator of polymerization. However, the polymerization is usually performed in appropriate conditions, taking into account the physical properties of the obtained water dispersion. Curing time required for the polymerization reaction may also appropriately be adjusted by means of the method of polymerization, the degree of activation of the used polymerization initiator and/or the like. In General, the polymerization is preferably carried out under such conditions that it is completed within from about 2 hours to about 24 hours. In addition, the solution is subjected to the polymerization reaction, can also pre-purging with an inert gas such as nitrogen.

When containing the pigment particles are not sufficiently covered with the first seed polymerization, the polymerization process can optionally be repeated. This time use a different Ethylenediamine connection, whereby you can also get compo is etnie particles, having a multi-layer coating.

After the third stage of the process according to the third implementation of the aqueous dispersion containing pigment particles having the coating layer formed from a polymer, can be further processed using an operation such as desalting, desolate or concentration in accordance with the scope, which will be used. When this processing can be applied generally known method of desalting method desolvatation or method concentration, such as the selection using acid, ultrafiltration, centrifugation or distillation under reduced pressure. However, the allocation acid, in which the system is acidified and thereby reduces the strength of the static repulsion acid hydrophilic part with aggregation containing pigment particles, is preferred. As the acid used in this method, you can use any acid, since it can cause aggregation containing the pigment particles in the aqueous dispersion of those particles that are present in the form of finely ground particles that are difficult to precipitate, in the form of a thick slurry, paste, powder, granules, dense sludge (mass), a layer of short fibers, flakes or the like, so as to effectively separate them from the solvent. To highlight the alkali, and is used in the first stage at the same time, it is more preferable to use the acid, forming water-soluble salt with the alkali used in the first stage. The solubility of the acid in water is also preferably is high. In order to effectively carry out desalting the amount of added acid is preferably as small as possible within the limits in which the aggregate containing the pigment particles. Specific examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, triperoxonane acid, dichloracetic acid and methansulfonate acid, and hydrochloric acid, acetic acid and sulfuric acid are particularly preferred. Containing pigment particles, turned into a state in which easily separated using acid can be easily separated by using commonly known centrifugal separator, a filter, a separator for a thick mist from the liquid-solids or the like. At this time, the degree of demineralization and desolvatation can be adjusted by adding diluent is water or an increase in the number of times decantation and washing with water. The washing water unreacted Ethylenediamine connection, insoluble or difficultly soluble in water, and the like, are suspended or dropped into the sediment in water dispersion, can is to be washed and removed. A concentrated aqueous dispersion can actually be used in the form of a paste or thick slurry with a high water content. However, it can also be used in the form of finely ground powder, subjecting its commonly known drying method such as spray drying method, the method of the centrifuge drying, a method of filtering and drying, or a method of freeze-drying when necessary. Containing pigment particles, aggregated by allocating acid thus neutralized with alkali and can dispergirujutsja water for use. As the alkali used here, you can use any alkali, since it acts as a neutralizer for dispersing substances having acidic hydrophilic part, and can increase the solubility in water. Namely, it is possible to use the same bases, as used in the process according to the first implementation, in the same way. The units, which again gives the dispersibility, is dispersed in an aqueous medium, whereby can be obtained dispersion, suitable for different uses.

The fourth option exercise

The method of obtaining containing pigment particles according to the fourth embodiment can be performed in the same manner as in the method according to the first embodiment, except that the connection is out, having a functional group capable of cross-stitching, optionally contained in the first and second stages of the process according to the first embodiment. The compound having a functional group capable of cross-linking, may itself not be dispersible, insofar as containing pigment particles having dispersible receive by using it in combination with a dispersing agent. When the compound having a functional group capable of cross-linking, has a function of dispersing agent, a compound having a functional group capable of cross-linking, can be used as a dispersing agent.

In addition, you can also use one or both of the compounds having a functional group capable of cross-stitching, and compounds having a functional group capable of cross-stitching, and functioning as a dispersing agent. At the same time, you can also use other dispersing agent, and not the compound having a functional group capable of cross-links. Alternatively, the polymer of the curable compound in the second embodiment or the polymer of Ethylenediamine connections in the third embodiment may be structured.

In the second stage by the sa obtain aqueous dispersions according to a third embodiment of the present invention, the pigment, dissolved in a solution of a pigment, quickly crystallizes or forms a unit of the amorphous form by replacing Rarotonga organic solvent and water simultaneously formed containing pigment particles, which are attached to a stable dispersibility by using at least one dispersing agent and a compound having a functional group capable of cross-linking, with dispersing ability.

As the pigment used in the process according to the fourth variant embodiment of the invention, it is possible to use any pigment, as soon as it can be dissolved together with the components of the solution of the pigment in aprotonin organic solvent and can achieve the technical result of the present invention. As its specific examples are the previously mentioned pigments for the method according to the first embodiment of the invention.

As Rarotonga organic solvent can also be used a solvent which is given as an example for the process according to the first variant of implementation, and the mixing ratio of the pigment and Rarotonga solvent and the like may be installed in the same way as for the process according to the first variant implementation.

As a dispersing agent, applicable in the way that p is the fourth draft of the implement, you can use any of these for the method according to the first variant implementation in the same mixed number.

When using a compound having a functional group capable of forming cross-links, functioning as a dispersing agent, its amount is regulated to the amount necessary as a dispersing agent and achieve the effect imparted by adding a compound having a functional group capable of crosslinking. When the compound having a functional group capable of crosslinking, which requires a dispersing agent, and a compound having a functional group capable of crosslinking, functioning as a dispersing agent, used in combination, their total number is preferably set in the range that will be shown next.

The compound having a functional group capable of crosslinking used in the method according to the fourth variant of implementation, is a compound having a functional group, directly contributing to the crosslinking reaction in the molecule, and this crosslinking reaction is commonly used in industries such as rubber, plastics, paints, glue the (binders), sealants, fibers, lithograph, in the manufacture of integrated circuits. To obtain a crosslinked structure, it is possible to use a crosslinking agent, when necessary. A crosslinking agent is a compound capable of interacting with the functional group capable of crosslinking, with the formation of the crosslinked structure, and this may be included macromolecular structure forming agent. Forms of knitting include hydrogen bonds, ionic bonds, coordinate communications, and chemical bonding. When received containing pigment particles are used as dye ink liquid, it is preferable to joining with chemical or coordinate relationships from the viewpoint of stability when stored in conditions. No specific restrictions are not set on a particular combination of functional groups capable of crosslinking with crosslinking agents, if they can lead to the technical result of the present invention. However, as their examples the following combinations: (functional group capable of crosslinking = hydroxyl group; a crosslinking agent = dialdehyde), (hydroxyl group, aminoformaldehyde), (hydroxyl group; diepoxybutane), (hydroxyl group; dibenyline connection), (g is drexeline group; phosphoric dichloride compound), (hydroxyl group; N ethylbis(2-chloroethyl)amine), (hydroxyl group; an N-methylol compound), (hydroxyl group; diisocyanate compound), (hydroxyl group; difunctional acid anhydride), (hydroxyl group; dimethylamine compound), (hydroxyl group; diepoxybutane), (hydroxyl group; a compound of boric acid), (hydroxyl group; a phosphoric compound), (hydroxyl group; Ti alkoxide), (hydroxyl group; Al alkoxide), (hydroxyl group; Zr the alkoxide), (hydroxyl group; an alkoxysilane), (hydroxyl group; difunctional diazoketone), (hydroxyl group; a compound of carboxylic acid), (carboxyl group; dimethylformaldehyde resin), (carboxyl group; triethylenemelamine), (carboxyl group; diaminoethane), (carboxyl group; polyamidoamine), (carboxyl group; isocyanate compound), (carboxyl group; an epoxy compound), (carboxyl group; oxazolinone connection), (carboxyl group; dicyclopentadienyl dihalogenide), (carboxyl group; chromium salt triperoxonane acid), (carboxyl group; carbodiimide compound), (carboxyl group; diazomethane connection), (sulfonic group; a salt of Quaternary Ammon is I), (sulfonic group; a halide of the metal), (sulfonic group; dibutylamine oxide), (sulfonic group; zinc acetate), (the amino group; isocyanate), (the amino group; dialdehyde connection), (the amino group; dehalogenase connection), (the amino group; operations connection), (the amino group; isothiocyanate connection), (the amino group; sulphonylchloride), (the amino group; N-halide compound), (the amino group; dichlorotriazines connection), (aldehyde group; hydrazine powered connection), (ketone group; hydrazine powered connection), (isocyanate group; spirit connection), (isocyanate group; a compound of dicarboxylic acid), (isocyanate group; paleologou connection), (isocyanate group; the connection with oxazolidone rings (nitrile group; bipolar connection), (isocyanate group; copper sulfide), (isocyanate group; tin chloride), (isocyanate group; zinc chloride), (epoxy group; phenolic resin, and epoxy group; aminosidine), (epoxy group; an alcohol compound, and an epoxy group; a compound of dicarboxylic acid), (silanol group, silane connection), (silanol group, silicon dioxide), (silanol group, titanate connection), (pyridine structure; dehalogenase connection), (pyridine structure; the chloride of the metal), (amidoxime group; dichloride dialkylated the La), (the acetate group; dialkoxy aluminum), (acetylacetonate; aluminum stearate), (acetylacetonato; chromium stearate), (mercaptopropyl; phenolic resin), (mercaptopropyl; financialtimes connection), (mercaptopropyl; diisocyanate connection), (mercaptopropyl; furfural), (mercaptopropyl; diepoxybutane), (mercaptopropyl; zinc oxide), (mercaptopropyl; lead oxide), (mercaptopropyl; alkylhalogenide connection), (mercaptopropyl; maleimide connection), (mercaptopropyl; aziridine connection), (ester group; aminosilanes linking agent), (structure with acid anhydride; aminosidine), chlorosulfonic group; diaminoethane), (chlorosulfonic group; dialogue connection), (chlorosulfonic group; diepoxybutane), (chlorosulfonic group, a metal oxide), (amide bond; iron chloride (III)and (diacetonitrile group; dihydrazide connection).

These combinations can be used either separately or in any combination thereof.

Can also be preferably used a compound undergoing reaction samolepky. Zameshivaem connection in this exercise is a compound having as functional groups capable of cross-relations, and the structure of the cross-linking agent in its molecule, or compound with many camassia the relevant functional groups in its molecule. Examples samoszhimayuschihsya functional groups include mercaptopropyl (disulfide bonds), ester bond (condensation Claisen) and silanol group condensation dehydration). The compounds having functional groups capable of crosslinking, and the effect of dispersing the organic pigment in an aqueous solution, may also be used as a dispersing agent and can produce a system that is not added separately to any other dispersing agent. In addition, the compounds having smossyvesa functional group, and the effect of dispersing the organic pigment in an aqueous solution, can also be used as a dispersing agent, and it can form a system that is not added separately nor dispersing agent or a crosslinking agent.

These compounds with functional groups capable of crosslinking, and structure of substances used, when necessary, can be used separately one by one or in any combination. No specific limitation is set for the number of used compounds having functional groups capable of crosslinking, if it turns out the desired cross-linked structure. However, the connection with f the purpose ground receiving stations group, capable of crosslinking, preferably used in the range of from at least 0.01 to 10 parts by weight per 1 part by weight of organic pigment, in order to further increase the effect of improving the stability of the dispersion is obtained containing the pigment particles in the aqueous medium by formation of a crosslinked structure and to maintain or further improve the ink capacity of the pigment solid substances in water dispersion.

The operation of mixing the solution of the pigment with water can also be carried out in the same manner as in the method according to the first embodiment. When necessary, it is possible to perform heat treatment or microwave irradiation within, so as not started neither stitching nor does not deteriorate the stability of the dispersion during and immediately after the first and second stages to adjust the crystal system and the aggregate state water dispersion.

Preferably, no reaction of the crosslinking did not occur before the formation of aqueous dispersions of the first and second phases. When the crosslinking reaction occurs before the formation of the aqueous dispersion, the dispersion stability of the particles in the water dispersion may become insufficient in some cases.

The third step in the method according to the fourth variant of the implementation stage is the reaction of crosslinking with the use with the unity, having a functional group capable of crosslinking included in containing the pigment particles. Containing pigment particles, comprising a compound having a functional group capable of crosslinking, improve their thermal stability and resistance to solvent through cross-linking. The crosslinking reaction can be initiated by adding a crosslinking agent or by using heat or light, or combinations thereof. At this time you can add the usual well-known catalyst or the like to facilitate crosslinking.

After the reaction, the crosslinking can be carried out processing by centrifugation or filtration to remove large particles formed by the reaction of cross-linking between the particles and the compound having a functional group capable of crosslinking, which was dissolved in the solvent and stitched in excess.

After the third stage in the method according to the fourth implementation is obtained containing the pigment particles can be processed using an operation such as desalination, desolvation or concentration, in accordance with the use. With this treatment you can apply any method, such as allocating acid, ultrafiltration, centrifugation or distiller what I under reduced pressure, if the containing pigment particles are separated from the solvent to the data of the conventional known method selection. To separate the alkali used in the first stage at the same time as the solvent, it is preferable to use an acid capable of forming soluble salts with alkali, used in the first stage. The solubility of the acid in water is also preferably is high. In order to effectively carry out desalting, the amount of added acid is preferably as small as possible within those limits in which the aggregate containing the pigment particles. As specific examples of such acids may be mentioned those which are used in the method according to the third implementation. The amount of acid used, its use and process can be the same as in the method according to the third implementation.

Containing pigment particles, converted into a state where they can be easily identified with the help of acid can be easily separated by using commonly known centrifugal separator, a filter, a separator for dense suspensions of solids in liquids, or the like. At this time, the degree of demineralization and desolvatation can be adjusted by adding diluent is water or an increase in the number of times decantation, premiani the water. By washing with water, unreacted compounds having a functional group capable of crosslinking, insoluble or sparingly soluble in water, or the like, which are suspended or dropped into the sediment in water dispersion, can be washed and removed. Concentrated aqueous dispersion can be used effectively in the form of a paste or thick slurry with a high water content. However, it can also be used in the form of finely ground powder, subjecting them to the usual well-known drying method such as spray drying method, a method of drying by centrifugation, a method of filtering and drying and drying by freezing when necessary. Containing pigment particles, aggregated by selection acids are neutralized in this way alkali and again dispersed in water for further use. As used herein, the alkali can be any of those mentioned for the method according to the first, second or third options for implementation. Quantity and processing method using the same can be the same as in the method according to the first, second or third options for implementation. The units, which was given the ability again to dispergirujutsja, is dispersed in an aqueous medium, whereby can be obtained by water on sparse, suitable for different uses.

Ink

Containing pigment particles according to this invention preferably can be used as dyes for ink for inkjet printing. The aqueous dispersion containing containing pigment particles according to this invention, can be used as a water coloring liquid for coloring products or raw materials for them and, in addition, as the ink for ink-jet printing or raw materials for them. As for the ink (hereinafter simply referred to as "ink") for inkjet printing, the concentration containing pigment particles in the ink is preferably communicated in such a way that the content of the pigment is from 2.0 to 10.0 parts by weight per 100 parts by weight of the ink, based on terms of staining intensity. The ink according to this invention it is possible to add water-soluble organic dye in order to prevent drying out and to move the ink in the solid state in the holes and regulation of their viscosity. Specific examples of water-soluble organic solvent include alkalemia alcohols having from 1 to 4 carbon atoms (e.g. methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and so on), ketones and ketone alcohols (for example, acetone, datetoday alcohol etc), amides (for example dimethylformamide, dimethylacetamide, etc.), ethers (e.g. tetrahydrofuran, dioxane, etc.), polyalkylphenol (for example, polyethylene glycol, polypropyleneglycol etc), alkalophile, Allenova part of which has from 2 to 6 carbon atoms (e.g. ethylene glycol, propylene glycol, butyleneglycol, triethylene glycol, hexyleneglycol, diethylene glycol, etc.), 1,2,6-hexanetriol, alkalemia ethers of polynuclear alcohols (for example, methyl ether of ethylene glycol, ethyl ether of ethylene glycol, onomatology ether of triethylene glycol, monotropy ether of triethylene glycol, etc.), N-organic, 2-pyrrolidone, dimethylimidazolidine. The total amount of water-soluble organic solvent in the ink is in the range from 2 to 60 parts by weight, preferably from 5 to 25 parts by weight of the total ink weight. To adjust the permeability of the paper and to improve the stability of the dispersion containing the pigment particles in the ink can be added surfactant in accordance with this invention. As surfactants can be used any of known conventional surface-active substances (surfactants), such as nonionic surfactants, cationic surfactants, amphoteric surfactants, fluorinated surfactants and silicone surfactants. The amount of surfactant in the ink is in the range from 0.05 to 10 parts by weight, preferably is t 0.1 to 5 parts by weight of the total ink weight. The ink according to this invention may contain additives such as substances that protect against mold, antioxidant and pH regulator in addition to the water dispersion containing pigment particles, water-soluble organic solvent and surfactant.

Containing pigment particles or their aqueous dispersions of this invention can be used in a wide variety of water colorants for printing inks, toners, inks, ink for writing, coating materials for films, ferroelectric printers, liquid developers, electrophotographic materials, plastics, rubber, fibers, etc. in addition to the ink for inkjet printing.

The invention will then be described more specifically by the following examples and comparative examples. In this regard, all designations of "part" or "parts" and "%", which will be used in the following examples mean part or parts by weight and % by weight unless specifically stated. The average diameter of the particles in each example represents the value measured by DLS-7000 (trade name, produced by Otsuka Denshi K.K.), after dilution of the sample water dispersion of purified water (ion exchange column) and filtering the diluted dispersion through a membrane filter having a pore size of 0.45 μm. In the following examples containing the pigment h, Stacy, creating each of the aqueous dispersion may also be referred to as "pigment".

EXAMPLE 1

Ten parts of a copolymer of styrene/acrylic acid (acid number 250; molecular weight 5000) as a dispersing agent was dissolved in 80 parts of dimethyl sulfoxide and 10 parts hinkreonsok pigment (S pigment red 122) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then dropwise slowly added 30% methanolic solution of potassium hydroxide for dissolving hinkreonsok pigment. After the solution of the pigment was stirred for 3 hours, it was quickly poured into purified with ion exchange water (400 parts of purified water to 10 parts of a pigment; 0°C), stirred using a paddle stirrer impeller-type (800 rpm) and cooled, the temperature was maintained with the help of two systemic dosing device (produced by Musashi Engineering K.K.; needle with an inner diameter of 0.57 mm; feed pressure of 4.0 kgf/cm2) to obtain a water dispersion containing genocidally pigment particles having an average particle diameter of 27.6 nm.

Then, to this aqueous dispersion of the pigment drops) was added 5% aqueous solution of sulfuric acid to bring the pH of the dispersion to 4.0, thereby aggregating containing pigment particles of the dispersion hinkreonsok pigment. Then the obtained aggregates hoteltravel is whether under reduced pressure through a membrane filter (diameter detained particles 0.45 µm) and three times washed with 500 ml of purified with ion exchange water to obtain a paste of an aqueous dispersion containing pigment genocidally particles, demineralized and desolvation.

After this paste was added 2.0 g of potassium hydroxide was added purified with ion exchange water so as to obtain a weight to 100 g, followed by stirring for 1 hour. Then add the potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing genocidally pigment particles having a pigment content of 10%. The average diameter of the particles contained in the water dispersion was 26.5 nm, and the dispersion had high transparency.

EXAMPLE 2

The aqueous dispersion containing azopigments (S pigment yellow 74) particles were obtained in the same manner as in example 1 except that the organic pigment was replaced with S pigment red 122 on S pigment yellow 74. The average diameter of the particles containing the pigment particles enclosed in aqueous suspension, was $ 48.6 nm before aggregation and 46.5 nm after re-dispersion, and the dispersion had a high light transmission.

EXAMPLE 3

The aqueous dispersion containing azopigments (S pigment yellow 128) particles were obtained in the same manner as in example 1 except that the organic pigment was replaced with S pigment red 122 on S pigment yellow 128. The average diameter of the particles containing the pigment particles, prisoners in aqueous suspensions amounted to 38.8 n is before aggregation and 39.6 nm after re-dispersion, the dispersion had a high light transmission.

EXAMPLE 4

The aqueous dispersion of particles comprising particles containing a solid solution of diketopiperazines/hinkreonsok pigment was obtained in the same manner as in example 1, except that 10 parts hinkreonsok pigment (S pigment red 122) was replaced with 5 parts diketopiperazines pigment (S pigment red 254) and 5 parts hinkreonsok pigment (S pigment violet 19). The average diameter of the particles comprising pigment particles contained in the aqueous suspension amounted to 25.2 nm before aggregation and 26.4 nm after re-dispersion, and the dispersion had a high light transmission.

EXAMPLE 5

The aqueous dispersion containing phtalocyanine pigment particles was obtained in the same manner as in example 1, except that 10 parts hinkreonsok pigment (S pigment red 122) was replaced by 10 parts S pigment blue 16. The average diameter of the particles comprising pigment particles contained in the aqueous suspension, was 32.5 nm before aggregation and to 31.7 nm after re-dispersion, and the dispersion had a high light transmission.

EXAMPLE 6

Ten parts of terpolymer of methyl methacrylate/ethyl acrylate/acrylic acid (5/4/1; molar ratio) (acid number 58; molecular weight 40000) as a dispersing agent p who was storyli in 80 parts of dimethylimidazolidine and 7 parts isoindoline pigment (S pigment yellow 110), and 3 parts of another isoindoline pigment (S pigment yellow 109) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then dropwise slowly added 30% methanolic solution of potassium hydroxide to dissolve isoindoline pigments. After the solution of the pigments was stirred for 3 hours, it was quickly poured into purified with ion exchange water (400 parts of purified water to 10 parts pigment; 0°C)mixed flow impeller-type stirrer and cooled, the temperature was maintained using two system distributors (produced by Musashi Engineering K.K.; inner needle diameter of 0.57 mm; feed pressure of 4 kgf/cm2) to obtain the aqueous dispersion of particles containing solid solution isoindoline pigment having an average particle diameter equal to 50,6 nm.

To this aqueous dispersion of pigment and then drops) was added 10% hydrochloric acid to bring the pH of the dispersion to 4.0, thereby aggregating the aqueous dispersion of particles containing solid solution isoindoline pigment. Then the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter detained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste of an aqueous dispersion of particles containing solid solution isoing innovage pigment, desalted and desolvation.

After this paste was added 2.0 g of potassium hydroxide was added purified with ion exchange water to obtain a total weight of 100 g, followed by stirring for 1 hour. Then add the potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining the aqueous dispersion of particles containing solid solution isoindoline pigment having a pigment content of 10%. The average diameter of the particles including the pigment particles contained in this aqueous dispersion, represented 50.1 nm, and the dispersion had a good light transmission.

COMPARATIVE EXAMPLE 1

Ten parts of a copolymer of styrene/acrylic acid (acid number 250; molecular weight 5000) as a dispersing agent was dissolved in 80 parts of dimethyl sulfoxide and 10 parts hinkreonsok pigment (S pigment red 122) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then dropwise slowly added 30% methanolic solution of potassium hydroxide to dissolve genocidally pigment. After the solution of the pigment was stirred for 3 hours, it was quickly poured into 5% aqueous sulfuric acid solution (400 parts of 5% aqueous solution of sulfuric acid to 10 parts of a pigment; 0°C)mixed flow impeller-type stirrer and cooled, the temperature of the Roux was supported by two system distributors (produced by Musashi Engineering K.K.; the inner diameter of the needle 0,57 mm; feed pressure of 4 kgf/cm2to obtain aggregates containing genocidally pigment.

Then the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter detained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste containing genocidally pigment, desalted and desolvation.

After this paste was added 2.0 g of potassium hydroxide was added purified with ion exchange water to obtain a total weight of 100 g, followed by stirring for 1 hour. Then add the potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining the aqueous dispersion hinkreonsok pigment having a pigment content of 10%. The average diameter of the particles contained in the pigment dispersion was 145,8 nm, and the dispersion badly missed the light.

COMPARATIVE EXAMPLE 2

Ten parts of a copolymer of styrene/acrylic acid (acid indicator 250; molecular weight 5000) as a dispersing agent was dissolved in 80 parts of dimethyl sulfoxide and 10 parts hinkreonsok pigment (S pigment red 122) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then dropwise slowly added 30% methanolic solution of potassium hydroxide that is s to dissolve genocidally pigment. After the solution of the pigment was stirred for 3 hours, the pH quickly brought up to 4,0 50% aqueous sulfuric acid solution, at the same time cooling the solution pigment and keeping the temperature at 0°C, under stirring paddle impeller-type stirrer (800 rpm) to produce aggregates containing genocidally pigment.

Then the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter detained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste containing genocidally pigment, desalted and desolvation. After this paste was added 2.0 g of potassium hydroxide was added purified with ion exchange water to obtain a total weight of 100 g, followed by stirring for 1 hour. Then add the potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining the aqueous dispersion hinkreonsok pigment having a pigment content of 10%. The average diameter of the particles contained in the pigment dispersion was 328,7 nm, the distribution of particle size, she had wide, and variance badly missed the light.

The measurement results of average diameters of the particles contained in the aqueous dispersions obtained in examples 1 to 6 and comparative examples 1 and 2, are presented in tables 1 and 2. adnie dispersion, obtained in the examples had a small average particle diameter, were monodisperse and had a narrow distribution of particle size. On the other hand, aqueous dispersions obtained in comparative examples had a large average particle diameter, were polydisperse and had a wide distribution of particle size.

328,7
Table 1
SampleDiameter (nm) particles in aqueous dispersion
Before aggregationAfter re-dispersion (after aggregation)
Example 127,626,5
Example 248,646,5
Example 338,839,6
Example 425,226,4
Example 532,531,7
Example 650,650,1
Table 2
SampleDiameter (nm) particles in aqueous dispersion
EUR. example 1145,8
EUR. example 2

TEST PRINT. EXAMPLE 1

Each of the aqueous dispersions obtained as described above was mixed with the following components. The resulting mixture was then filtered under reduced pressure through filter paper holding particle diameter of 1.0 μm to obtain ink for inkjet printer. In this regard, "acetylene YONG" is a trading name ethyleneoxide adduct of acetylenics, produced by Kawaken Fine Chemicals Co., Ltd.

Aqueous dispersion (pigment content of 10%)50 pieces
Diethylene glycol7.5 parts
Glycerin5 pieces
Trimethylolpropane5 pieces
Acetylene EN0.2 parts
Purified by using ion-exchange water32,3 part

The ink used to print the color of the recorded image on the sheet NRO and paper for photocopies using a commercially available inkjet printer (BJF 900, trade name, manufactured by Canon Inc.). The transparency of the image from the form of a light haze on the sheet NRO and density of the color image to the value of OP solid printed part of the paper for photocopies were evaluated in accordance with the following standard. Results p is estaline in table 3.

Evaluation of light transmittance (sheet NRO)

Ink, manufactured as described above was used to print a solid part of the image on the sheet available for purchase NRO (CF-301, trade name, product of Canon Inc.), the smoky appearance of the printed part was measured by using a turbidity meter (Direct Reading Haze Meter, trade name, produced by Toyo Seiki Seisakusho, Ltd.), in order to assess the transmission of light in accordance with the following standard:

And: assessment smoky printing was less than 10;

In: assessment of grey seal was at least 10 but less than 20;

From: assessment of grey seal was not less than 20.

Estimation of the density of the color (O.D. value)

Manufactured as described above, the ink used to print a solid image area on the sheet available for purchase paper copies (paper PB, trade name, product of Canon Inc.). After 1 hour, the optical density of the image was measured using Macbeth RD915 (trade name, produced by Macbeth Company)to estimate the density of a color in accordance with the following standard:

A: the density was not less than 1.25;

In: the density was less than 1.25 but not below 1,15;

C: the density was lower than 1,15.

td align="center"> Example 1
Table 3
SampleLight transmission (sheet NRO)Color density (smooth paper)
AndAnd
Example 2AndAnd
Example 3AndAnd
Example 4AndAnd
Example 5AndAnd
Example 6AndAnd
EUR. app.1
EUR. PR

For ink, respectively, using the aqueous dispersions of examples 1 through 6, the projection image printed on the sheet NRO, were bright and clear. For ink, respectively, using aqueous dispersions of comparative examples 1 and 2 on the other hand, the projection image printed on the sheet NRO was dark and dim. With regard to density color printing on smooth paper, inks, which are respectively used for the pigment dispersion of examples 1 to 6 had a high OD value. However, the ink, which respectively employ dispersion of the pigment of comparative examples 1 and 2 gave low OD value.

EXAMPLE 7

Five parts of a copolymer of styrene/acrylic acid (acid number 250; molecular weight 5000) as a dispersing agent was dissolved in 80 parts of dimethyl sulfoxide and 10 parts kinokritikov what about the pigment (S pigment red 122) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then drops gradually added 30% methanolic solution of potassium hydroxide for dissolving hinkreonsok pigment. After the solution of the pigment was stirred for 3 hours, there was added styrene in the quality of the polymerized compounds and 2,2'-azobisisobutyronitrile as a polymerization initiator, was dissolved in a solution of pigment in the proportions of 5 parts and 0.05 parts, respectively, per 10 parts of the pigment, the resulting solution was quickly poured into purified water (400 parts of purified water to 10 parts of a pigment; 0°C)mixed flow impeller-type stirrer (800 rpm), was purged with nitrogen and cooled, the temperature was maintained using 2 systems distributors (produced by Musashi Engineering K.K.; the inner diameter of the needle 0,57 mm; feed pressure of 4 kgf/cm2) to obtain the aqueous dispersion of particles containing genocidally pigment having an average particle diameter equal to 29.7 nm.

The aqueous dispersion was transferred into a reaction vessel equipped with a heater casing, a cooling tube, stirrer and thermometer, and heated until the internal temperature is 80°that the reaction continued for 2 hours while maintaining the temperature at 80°C. After the reaction is conducted during the one hour at a temperature increased to 90°C, the reaction mixture was again cooled to room temperature. Then to this reaction mixture was added dropwise a 5% aqueous solution of sulfuric acid to bring the pH of the dispersion to 4.0, thereby aggregating containing genocidally pigment particles in the aqueous dispersion. Then the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter of retained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste of an aqueous dispersion containing genocidally pigment particles, demineralized and desolvation.

After this paste was added 1.0 g of potassium hydroxide was added purified with ion exchange water so as to gain overall mass of 100 g, followed by stirring for 1 hour. Then add the potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing genocidally pigment particles having a pigment content of 10%. The average diameter of the particles including the pigment particles contained in the water dispersion was equal to 38.5 nm, and the aqueous dispersion had a high light transmission.

EXAMPLE 8

Five parts of a copolymer of styrene/acrylic acid (acid number 250; molecular weight 15000) as a dispersing agent was dissolved in 80 parts of dimethyl sulfoxide and 10 parts of azopigments (who .I. pigment yellow 74) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then dropwise slowly added 30% methanolic solution of potassium hydroxide, to dissolve azopigments. After the solution of the pigment was stirred for 3 hours, there was added styrene in the quality of the polymerized compounds, seminal RS-30 (trade name, product of Sanyo Chemical Industries, Ltd.) as a reactive surfactant (curable compound and a dispersing agent) and 2,2'-azobisisobutyronitrile as a polymerization initiator, was dissolved in a solution of pigment in the ratio 2 parts, 3 parts, and 0.05 parts, respectively, per 10 parts of the pigment, and the resulting solution was quickly poured into purified with ion exchange water (400 parts of purified water to 10 parts of a pigment; 0°C)mixed flow impeller-type stirrer (800 rpm), was purged with nitrogen and cooled, the temperature was maintained using 2 systems distributors (produced by Musashi Engineering K.K.; inner needle diameter of 0.57 mm; feed pressure of 4 kgf/cm2) to obtain the aqueous dispersion of particles containing azopigments having an average particle diameter equal to 32.4 nm.

The aqueous dispersion was transferred into a reaction vessel equipped with a heater casing, a cooling tube, a stirrer and a thermometer and were heated to within Enna temperature, 80°that the reaction continued for 2 hours while maintaining the temperature at 80°C. After the reaction is carried out for a further one hour if the temperature is increased to 90°C, the reaction mixture was again cooled to room temperature. Then to this reaction mixture (aqueous dispersion) was added dropwise a 5% aqueous solution of sulfuric acid to bring the pH of the dispersion to 4.0, thereby aggregating containing azopigments particles in aqueous dispersion. Then the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter of retained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste of an aqueous dispersion containing azopigments particles, demineralized and desolvation.

After this paste was added 1.0 g of potassium hydroxide was added purified with ion exchange water so as to gain overall mass of 100 g, followed by stirring for 1 hour. Then add the potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing azopigments particles having a pigment content of 10%. The average diameter of the particles including the pigment particles contained in the water dispersion was equal to or 42.8 nm, and the aqueous dispersion had a high light transmission.

EXAMPLE 9

Ten parts of phthalocyanine is first pigment (S pigment blue 16) suspended in 80 parts of dimethyl sulfoxide in a flask at 25°in an atmosphere of air. Then drops gradually added 30% methanolic solution of potassium hydroxide to dissolve phtalocyanine pigment. After the solution of the pigment was stirred for 3 hours, there was added styrene in the quality of the polymerized compounds, seminal RS-30 (trade name, product of Sanyo Chemical Industries, Ltd.), aqualon HS-20 (trade name, product of Daiichi Kogyo Seiyaku Co., Ltd.) and aqualon RN-20 (trade name, product of Daiichi Kogyo Seiyaku Co., Ltd.) as reactive surfactants (polymerised compounds and dispersing agents) and 2,2'-azobisisobutyronitrile as a polymerization initiator, was dissolved in a solution of pigment in the ratio of 5 parts, 2 parts, 2 parts, part 1 and 0.05 parts, respectively, per 10 parts of the pigment, and the resulting solution was quickly poured into purified water (400 parts of purified water to 10 parts of a pigment; 0°C)mixed flow impeller-type stirrer (800 rpm), was purged with nitrogen and cooled, the temperature was maintained using 2 systems distributors (produced by Musashi Engineering K.K.; inner needle diameter of 0.57 mm; feed pressure of 4 kgf/cm2) to obtain the aqueous dispersion of particles containing phtalocyanine pigment having an average particle diameter equal to 33.5 nm. Water Vara is this tolerated in the reaction vessel, equipped with a heater casing, a cooling tube, stirrer and thermometer, and heated until the internal temperature is 80°that the reaction continued for 2 hours while maintaining the temperature at 80°C. After the reaction is carried out for a further one hour if the temperature is increased to 90°C, the reaction mixture was again cooled to room temperature.

Then to this reaction mixture (aqueous dispersion) was added dropwise a 5% aqueous solution of sulfuric acid to bring the pH of the dispersion to 4.0, thereby aggregating containing azopigments particles in aqueous dispersion. Then the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter of retained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste of an aqueous dispersion containing phtalocyanine pigment particles, demineralized and desolvation.

After this paste was added 1.0 g of potassium hydroxide was added purified with ion exchange water so as to gain overall mass of 100 g, followed by stirring for 1 hour. Then add the potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing phtalocyanine pigment particles having a pigment content of 10%. The average diameter of the particles including the pigment is astiz, contained in this aqueous dispersion was 41.5 nm, and the aqueous dispersion had a high light transmission.

EXAMPLE 10

Five parts of a copolymer of styrene/acrylic acid (acid number 250; molecular weight 15000) as a dispersing agent was dissolved in 80 parts of dimethyl sulfoxide, and 5 parts hinkreonsok pigment (S pigment red 122) and 5 parts of another hinkreonsok pigment (S pigment violet 19) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then dropwise slowly added 30% methanolic solution of potassium hydroxide for dissolving chinagruzovik pigments. After the solution of the pigments was stirred for 3 hours, there was added styrene and dipropyleneglycol dimethacrylate as the polymerized compounds, and 2,2'-azobisisobutyronitrile as a polymerization initiator, was dissolved in a solution of pigment in the proportions of 2 parts, 3 parts, and 0.05 parts, respectively, per 10 parts of the pigment and the resulting solution was quickly poured into purified with ion exchange water (400 parts of purified water to 10 parts pigment; 0°C)mixed flow impeller-type stirrer (800 rpm), was purged with nitrogen and cooled, the temperature was maintained with the help 2 systems distributors (produced by Musashi Engineering K.K.; inner needle diameter of 0.57 mm; feed pressure 4 to the s/cm 2) to obtain the aqueous dispersion of particles containing solid solution chinagruzovik pigments having an average particle diameter equal of 27.8 nm.

The aqueous dispersion was transferred into a reaction vessel equipped with a heater casing, a cooling tube, stirrer and thermometer, and heated until the internal temperature is 80°that the reaction continued for 2 hours while maintaining the temperature at 80°C. After the reaction was conducted for one hour if the temperature is increased to 90°C, the reaction mixture was again cooled to room temperature. Then to this reaction mixture (aqueous dispersion) was added dropwise a 5% aqueous solution of sulfuric acid to bring the pH of the dispersion to 4.0, thereby aggregating containing solid solution chinagruzovik pigment particles in the aqueous dispersion. Then the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter of retained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste of an aqueous dispersion containing solid solution chinagruzovik pigment particles, demineralized and desolvation.

After this paste was added 1.0 g of potassium hydroxide was added purified with ion exchange water so as to gain overall mass of 100 g, followed by peremeci what W for 1 hour. Then add the potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing solid solution chinagruzovik pigment particles having a pigment content of 10%. The average diameter of the particles including the pigment particles contained in the water dispersion was equal to 32.4 nm, and the aqueous dispersion had a high light transmission.

EXAMPLE 11

Seven parts of terpolymer of methyl methacrylate/ethyl acrylate/acrylic acid (5/4/1 molar ratio; acid number 58; molecular weight of 140000) as a dispersing agent was dissolved in 80 parts of dimethylimidazolidine and 10 parts of azopigments (S pigment yellow 128) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then dropwise slowly added 30% methanolic solution of potassium hydroxide for dissolving azopigments. After the solution of the pigment was stirred for 3 hours, there was added divinylbenzene and bezelmaterial as polymerized compounds, seminal RS-30 (trade name, product of Sanyo Chemical Industries, Ltd.) as a reactive surfactant (curable compound and a dispersing agent) and 2,2'-azobisisobutyronitrile as a polymerization initiator, was dissolved in a solution of pigment in the ratio of 2 parts 2 parts and 0.05 parts respectively on 10 parts pigment the a and the resulting solution was quickly poured into purified with ion exchange water (400 parts of purified water to 10 parts of the pigment; 0°C)mixed flow impeller-type stirrer (800 rpm), was purged with nitrogen and cooled, the temperature was maintained using 2 systems distributors (produced by Musashi Engineering K.K.; inner needle diameter of 0.57 mm; feed pressure of 4 kgf/cm2) to obtain the aqueous dispersion of particles containing azopigments having an average particle diameter equal to 45.6 nm. The aqueous dispersion was transferred into a reaction vessel equipped with a heater casing, a cooling tube, stirrer and thermometer, and heated until the internal temperature is 80°that the reaction continued for 2 hours while maintaining the temperature at 80°C. After the reaction was conducted for one hour if the temperature is increased to 90°C, the reaction mixture was again cooled to room temperature.

Then to this reaction mixture (aqueous dispersion) was added dropwise a 5% aqueous solution of sulfuric acid to bring the pH of the dispersion to 4.0, thereby aggregating containing azopigments particles in aqueous dispersion. Then the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter of retained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste of an aqueous dispersion containing azopigments particles, demineralized and desolvation.

The village is e as to this paste was added 1.0 g of potassium hydroxide, added purified with ion exchange water so as to gain overall mass of 100 g, followed by stirring for 1 hour. Then add the potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing azopigments particles having a pigment content of 10%. The average diameter of the particles including the pigment particles contained in the water dispersion was equal to a 51.2 nm, and the aqueous dispersion had a high light transmission.

The results of measurements of the average diameter of the particles contained in the aqueous dispersions obtained in examples 7 to 11, jointly presented in table 4. These water dispersion had a small average particle diameter, were monodisperse and had a narrow distribution of particle size.

Table 4
SampleDiameter (nm) particles in aqueous dispersion
Before aggregationAfter re-dispersion

(after aggregation)
EXAMPLE 729,7a 38.5
EXAMPLE 832,442,8
EXAMPLE 933,541,5
EXAMPLE 1027,832,4
EXAMPLE 1145,6

TEST PRINT. EXAMPLE 2

Aqueous dispersions obtained in examples 7 to 11 were evaluated as colorants for ink in the same manner as in the TEST PRINT. EXAMPLE 1, except that used aqueous dispersions obtained in examples 7 to 11. The results are presented in table 5.

Table 5
SampleLight transmission (sheet NRO)Color density (smooth paper)
Example 7AndAnd
Example 8AndAnd
Example 9AndAnd
Example 10AndAnd
Example 11AndAnd

For ink, respectively, using the water dispersion, the projection image printed on the sheet NRO, were bright and clear. With regard to density color printing on smooth paper, ink, respectively, using ink aqueous dispersions of examples 7 through 11, manifested a high OD value.

THE TEST DURATION OF EJECTION. 1

Aqueous dispersions obtained in examples 7 to 11 were subjected to an endurance test of ejection. Each of the aqueous suspensions were mixed with SL is blowing components. The resulting mixture was then filtered under pressure through a filter paper, which keeps the particle diameter of 1.0 μm to obtain ink for inkjet printer. These inks were subjected to an endurance test of ejection. In this regard, "surfynol 420" and "surfynol 465" are trade names of ethyleneoxide adducts of acetylenics manufactured by Air Products Japan Co., Ltd.

Aqueous dispersion

(pigment content of 10%)
50 pieces
Diethylene glycol7.5 parts
Glycerin5 pieces
Trimethylolpropane5 pieces
Surfynol 4200.1 part
Surfynol 4658 pieces
Purified by using ion-exchange water24,4 part

Thermal head for inkjet printing (produced by Canon Inc.), in which thermal energy is used for ejection of the liquid, were used to conduct ejection (5×108pulsations) ink, whereby estimated ink in respect of changes in the quantity of ejection of ink between before and after the test. The measurement of the amount of ejection is carried out by collecting droplets of particles ejected from the recording head in the container for every 5×10 pulsations, and weighing container on electronic scales. The average number of droplets ejected during a 5×108ripple was calculated as the increase in weight of the container. In this regard, continuous ejection was performed up to 5×109pulsations in order to evaluate the ink in relation to the duration of ejection in accordance with the following standard. The results are presented in table 6.

A: the average number of ejection drops from 4,95×108up to 5×108pulsation was not less than 90% of the average amount of ejection of droplets from 0 to 0.05×108pulsations;

In: average number of ejection drops from 4,95×108up to 5×108pulsation was not less than 60%but less than 90% of the average amount of ejection of droplets from 0 to 0.05×108pulsations;

With: the average number of ejection drops from 4,95×108up to 5×108pulsation was not less than 30%but less than 60% of the average amount of ejection of droplets from 0 to 0.05×108pulsations;

D: the average number of ejection drops from 4,95×108up to 5×108ripple was less than 30% from the average number of ejection drops from 0 to 0.05×108pulsations;

E: no ejection was manifested in the middle of the test.

Table 6
Sample The ejection duration
EXAMPLE 7And
EXAMPLE 8And
EXAMPLE 9In
EXAMPLE 10And
EXAMPLE 11And

Ink, in which, respectively, are aqueous dispersions of examples 7 through 11, showed a good stability of ejection.

EXAMPLE 12

Five parts of a copolymer of styrene/acrylic acid (acid number 250; molecular weight 5000) as a dispersing agent was dissolved in 80 parts of dimethyl sulfoxide, and 10 parts hinkreonsok pigment (S pigment red 122) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then drops gradually added 30% methanolic solution of potassium hydroxide for dissolving hinkreonsok pigment. After the solution of the pigment was stirred for 3 hours, there was added octanolwater as a polymerization initiator, was dissolved in a solution of pigment in the ratio of 0.1 part to 10 parts of the pigment, the resulting solution was quickly poured into purified with ion exchange water (400 parts of purified water to 10 parts pigment; 0°C)mixed flow impeller-type stirrer (800 rpm), was purged with nitrogen and cooled, the temperature was maintained using 2 systems distributors (produced is led by Musashi Engineering K.K.; the inner diameter of the needle 0,57 mm feed pressure of 4 kgf/cm2) to obtain the aqueous dispersion of particles containing genocidally pigment having an average particle diameter equal to 35.5 nm. This aqueous dispersion was transferred into a reaction vessel equipped with a heater casing, a cooling tube, a stirrer, thermometer and nitrogen purge. While blowing with nitrogen and stirring at 300 rpm then drops for 3 hours was added styrene and acrylic acid as Ethylenediamine compounds in the ratio of 5.5 parts and 0.5 parts, respectively, per 10 parts of the pigment. This system was then heated to an internal temperature of 80°that the reaction continued for 8 hours while maintaining the temperature at 80°C. After the reaction was carried out for another 1 hour if the temperature is increased to 90°C, the reaction mixture was again cooled to room temperature.

Then to this reaction mixture (aqueous dispersion) drops) was added 5% aqueous solution of sulfuric acid to bring the pH of the dispersion to 4.0, thereby aggregating containing genocidally pigment particles in the aqueous dispersion. Then the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter of retained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water obtained is eating pasta out of the water dispersion containing genocidally pigment particles, desalted and desolvation. After this paste was added 1.0 g of potassium hydroxide was added purified with ion exchange water so as to gain overall mass of 100 g, followed by stirring for 1 hour. Then add the potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing genocidally pigment particles having a pigment content of 10%. The average diameter of the particles including the pigment particles contained in the water dispersion was equal 42,7 nm, and the aqueous dispersion had a high light transmission.

EXAMPLE 13

Four parts of a copolymer of styrene/acrylic acid (acid number 250; molecular weight 15000) and 1 part Seminole RS-30 (trade name, product of Sanyo Chemical Industries, Ltd.) as a dispersing agent was dissolved in 80 parts of dimethyl sulfoxide, and 10 parts isoindoline pigment (S pigment yellow 109) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then dropwise slowly added 30% methanolic solution of potassium hydroxide to dissolve isoindoline pigment. After the solution of the pigment was stirred for 3 hours, there was added laurelbrooke as a polymerization initiator, was dissolved in a solution of pigment in the ratio of 0.1 part to 10 parts of the pigment, the resulting solution was quickly howled the Ali purified with ion exchange water (400 parts of purified water to 10 parts of the pigment; 0°C)mixed flow impeller-type stirrer (800 rpm), was purged with nitrogen and cooled, the temperature was maintained using 2 systems distributors (produced by Musashi Engineering K.K.; inner needle diameter of 0.57 mm; feed pressure of 4 kgf/cm2) to obtain the aqueous dispersion of particles containing isoindoline pigment having an average particle diameter equal to 39.9 nm. This aqueous dispersion was transferred into a reaction vessel equipped with a heater casing, a cooling tube, a stirrer, thermometer and nitrogen purge. With continued blowing with nitrogen and stirring at 300 rpm then drops for 3 hours was added styrene and acrylic acid as Ethylenediamine compounds in the ratio of 5.5 parts and 0.5 parts, respectively, per 10 parts of the pigment. This system was then heated to an internal temperature of 80°that the reaction continued for 8 hours while maintaining the temperature at 80°C. After the reaction was carried out for another 1 hour if the temperature is increased to 90°C, the reaction mixture was again cooled to room temperature.

Then to this reaction mixture (aqueous dispersion) was added dropwise a 5% hydrochloric acid to bring the pH of the dispersion to 4.0, thereby aggregating containing isoindoline pigment particles in water, d is Persii. Then the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter of retained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste of an aqueous dispersion containing isoindoline pigment particles, demineralized and desolvation.

After this paste was added 1.0 g of potassium hydroxide was added purified with ion exchange water so as to gain overall mass of 100 g, followed by stirring for 1 hour. Then add the potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing isoindoline pigment particles having a pigment content of 10%. The average diameter of the particles including the pigment particles contained in the water dispersion was equal to 52.5 nm, and the aqueous dispersion had a high light transmission.

EXAMPLE 14

Five parts of a copolymer of styrene/acrylic acid (acid number 250; molecular weight 5000) as a dispersing agent was dissolved in 80 parts of dimethyl sulfoxide, and 10 parts phthalocyaninato pigment (S pigment blue 16) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then dropwise slowly added 30% methanolic solution of potassium hydroxide for dissolving phthalocyaninato pigment. After the solution of the pigment peremeshivayu for 3 hours, it was quickly poured into purified with ion exchange water (400 parts of purified water to 10 parts pigment; 0°C)mixed flow impeller-type stirrer (800 rpm), was purged with nitrogen and cooled, the temperature was maintained using 2 systems distributors (produced by Musashi Engineering K.K.; inner needle diameter of 0.57 mm; feed pressure of 4 kgf/cm2) to obtain the aqueous dispersion of particles containing phtalocyanine pigment having an average particle diameter equal to 44,3 nm. This aqueous dispersion was transferred into a reaction vessel equipped with a heater casing, a cooling tube, a stirrer, thermometer and nitrogen purge. With continued blowing with nitrogen and stirring at 300 rpm then added dropwise within 3 hours was added styrene, divinylbenzene and acrylic acid as Ethylenediamine compounds in a ratio of 5.0 parts of 0.3 and 0.7 part parts, respectively, per 10 parts of the pigment. This system was then heated to an internal temperature of 80°S, and was added a solution of 0.1 part of ammonium persulfate as a polymerization initiator in distillirovannoi water to continue the reaction for 8 hours while maintaining the temperature at 80°C. After the reaction was carried out for another 1 hour if the temperature is increased to 90°C, the reaction mixture is again a cooling gap is Ali to room temperature.

Then to this reaction mixture (aqueous dispersion) was added dropwise a 5% aqueous solution of sulfuric acid to bring the pH of the dispersion to 4.0, thereby aggregating containing phtalocyanine pigment particles in the aqueous dispersion. Then the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter of retained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste of an aqueous dispersion containing phtalocyanine pigment particles, demineralized and desolvation.

After this paste was added 1.0 g of potassium hydroxide was added purified with ion exchange water so as to gain overall mass of 100 g, followed by stirring for 1 hour. Then add the potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing phtalocyanine pigment particles having a pigment content of 10%. The average diameter of the particles including the pigment particles contained in the water dispersion was equal to 58.9 nm, and the aqueous dispersion had a high light transmission.

COMPARATIVE EXAMPLE 3

Ten parts of a copolymer of styrene/acrylic acid (acid number 250; molecular weight 5000) as a dispersing agent was dissolved in 80 parts of dimethyl sulfoxide and 10 parts hinkreonsok pigment (S pigment red 122) suspen Aravali in the resulting solution in the flask at 25° In an atmosphere of air. Then dropwise slowly added 30% methanolic solution of potassium hydroxide for dissolving hinkreonsok pigment. After the solution of the pigment was stirred for 3 hours, it was quickly brought to pH 4.0 50% aqueous solution of sulfuric acid with cooling and maintaining the temperature at 0°With mixing paddle impeller-type stirrer (800 rpm), to obtain aggregates containing genocidally pigment.

Then the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter of retained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste containing genocidally pigment, desalted and desolvation. After this paste was added 2.0 g of potassium hydroxide was added purified with ion exchange water so as to gain overall mass of 100 g, followed by stirring for 1 hour. Then add the potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing genocidally pigment particles having a pigment content of 10%. The average diameter of the particles including the pigment particles contained in the water dispersion was equal 291,5 nm, and the aqueous dispersion had a bad light transmission.

The results of measuring the average diameter of the particles contained in podnyavshijsya, obtained in examples 12 to 14 and comparative example 3 are presented in tables 7 and 8. Aqueous dispersions obtained in examples 12 to 14, had particles of small diameter, were monodisperse and had a narrow distribution of particle size. On the other hand, the aqueous dispersion obtained in comparative example 3 had particles of large diameter, was polydisperse and had a wide size distribution of particles.

Table 7
SampleDiameter (nm) particles in aqueous dispersion
Up aggregationAfter re-dispersion

(after aggregation)
EXAMPLE 1235,542,7
EXAMPLE 1339,952,5
EXAMPLE 1444,3of 58.9
Table 8
SampleDiameter (nm) particles in aqueous dispersion
EUR. PR291,5

TEST PRINT. EXAMPLE 3

Aqueous dispersions obtained in examples 12 to 14 and comparative example 3 were evaluated as colorants for ink in the same manner as in the Test print. Example 1"except that the used water dispersion, obtained in examples 12 to 14 and comparative example 3. The results are presented in table 9.

Table 9
SampleLight transmission (sheet NRO)Color density (smooth paper)
Example 12AndAnd
Example 13AndAnd
Example 14AndAnd
EUR. Ave 3

For ink, using aqueous dispersions of examples 12 through 14, the projection image printed on the sheet NRO, were bright and clear. For ink, using aqueous dispersions of comparative examples 1 and 2, on the other hand, the projection image printed on the sheet NRO was dark and dim. With regard to density color printing on smooth paper, inks, which are respectively used for the pigment dispersion of the examples had a high OD value. However, the ink, which respectively used aqueous dispersion of a pigment of comparative example 3, gave a low OD value.

THE STORAGE STABILITY AND THE EJECTION DURATION. TEST 1

Aqueous dispersions obtained in examples 12 to 14 and comparative example 3 were subjected to and what to test for stability during storage. Each of the aqueous dispersions was mixed with the following components. The resulting mixture was then filtered under pressure through filter paper holding particle diameter of 1.0 μm to obtain ink for inkjet printer. These inks were subjected to an endurance test of ejection. In this regard, "surfynol 465" is a trading name ethyleneoxide adduct of acetylenics manufactured by Air Products Japan Co., Ltd.

Aqueous dispersion

(pigment content of 10%)
50 pieces
Diethylene glycol5 pieces
Trimethylpropane5 pieces
Diethylene glycol7.5 parts
Glycerin5 pieces
Surfynol 4650.1 part
Purified by using ion-exchange

water
32,4 part

The ink was stored for 2 weeks in the chamber of thermostat is adjusted to 60°With determining the change in viscosity between before and after storage. Measurements were performed using a viscometer of type R100 ('RE the type manufactured by Toki Sangyo K.K.). The results of the measurements are presented in table 10.

Table 10
About Aziz Viscosity [MPa·)
Before storageAfter storage
EXAMPLE 12a 3.94,0
EXAMPLE 133,63,6
EXAMPLE 143,33,5
EUR. AVE. 32,97,2

In the ink, in which, respectively, were used aqueous dispersions of examples 12 to 14 was not almost observed changes in viscosity between the definitions before and after storage. However, in the ink, which used a dispersion of comparative example 3, the observed increase in viscosity after storage.

As for the ink, as described above, the ejection efficiency was evaluated in the same manner as in the TEST FOR the DURATION of EJECTION. EXAMPLE 1". The results are presented in table 11.

Table 11
SampleThe ejection duration
EXAMPLE 12And
EXAMPLE 13And
EXAMPLE 14And
EUR. AVE. 3E

Ink, in which, respectively, were used aqueous dispersions of examples 12 to 14, showed relatively what about the good ejection stability in comparison with the ink, using the dispersion of the pigment of comparative example 3.

EXAMPLE 15

Five parts of a copolymer of styrene/acrylic acid (acid number 250; molecular weight 5000) as a dispersing agent and 4 parts of polyvinyl alcohol (low degree of saponification; degree of polymerization 1000) as compounds having capable of crosslinking functional group, was dissolved in 80 parts of dimethyl sulfoxide and 10 parts hinkreonsok pigment (S pigment red 122) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then dropwise slowly added 30% methanolic solution of potassium hydroxide for dissolving hinkreonsok pigment. After the solution of the pigment was stirred for 3 hours, were added terephthalaldehyde as cross-linking agent was dissolved in the solution of the pigment in the ratio of 1 part to 10 parts of the pigment, the resulting solution was quickly poured into purified with ion exchange water (400 parts of purified water to 10 parts of a pigment; 0°C)mixed flow impeller-type stirrer (800 rpm), was purged with nitrogen and cooled, the temperature was maintained using 2 system distributors (produced by Musashi Engineering K.K.; inner needle diameter of 0.57 mm; feed pressure of 4 kgf/cm2) to obtain a water dispersion of astiz, containing genocidally pigment having an average particle diameter equal to 38,9 nm. This aqueous dispersion was transferred into a reaction vessel equipped with a heater casing, a cooling tube, stirrer and thermometer, and the system was purged with nitrogen under stirring at 300 rpm and heated to an internal temperature of 80°C. While maintaining the internal temperature equal to 80°C, was added dropwise 10% hydrochloric acid to bring the pH of the reaction mixture to 4.0. After the reaction was continued for additional 5 hours, the reaction mixture was cooled to room temperature. Then the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter of retained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste of an aqueous dispersion containing genocidally pigment particles, demineralized and desolvation. After the resulting suspension was filtered under reduced pressure through a filter paper (diameter of retained particles of 1.0 μm to remove coarse particles, was added potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing genocidally pigment particles having a pigment content of 10%. The average diameter of the particles including the pigment particles contained in the water dispersion is AI, was equal to 48.8 nm, and the aqueous dispersion had a high light transmission.

EXAMPLE 16

Nine parts of terpolymer (molecular weight 5000) styrene/acrylic acid/hydroxyethylmethacrylate (molar ratio 6/3/1) as a dispersing agent having a functional group capable of crosslinking, was dissolved in 80 parts of dimethyl sulfoxide and 10 parts hinkreonsok pigment (S pigment red 122) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then dropwise slowly added 30% methanolic solution of potassium hydroxide for dissolving hinkreonsok pigment. After the solution of the pigment was stirred for 3 hours, were added terephthalaldehyde as cross-linking agent was dissolved in the solution of the pigment in the ratio of 1 part to 10 parts of the pigment, the resulting solution was quickly poured into purified with ion exchange water (400 parts of purified water to 10 parts of a pigment; 0°C)mixed flow impeller-type stirrer (800 rpm), was purged with nitrogen and cooled, the temperature was maintained using 2 system distributors (produced by Musashi Engineering K.K.; inner needle diameter of 0.57 mm; feed pressure of 4 kgf/cm2) to obtain the aqueous dispersion of particles containing genocidally pigment having an average particle diameter, R is wny 29,7 nm. This aqueous dispersion was transferred into a reaction vessel equipped with a heater casing, a cooling tube, stirrer and thermometer, and the system was purged with nitrogen under stirring at 300 rpm and heated to an internal temperature of 80°C. While maintaining the internal temperature equal to 80°C, was added dropwise 10% hydrochloric acid to bring the pH of the reaction mixture to 4.0. After the reaction was continued for additional 5 hours, the reaction mixture was cooled to room temperature. Then the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter of retained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste of an aqueous dispersion containing genocidally pigment particles, demineralized and desolvation.

After this paste was added 1.0 g of potassium hydroxide was added purified with ion exchange water to obtain a total weight of 100 g, followed by stirring for 1 hour. After the resulting suspension was filtered under reduced pressure through a filter paper (diameter of retained particles of 1.0 μm to remove coarse particles, was added potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing genocidally pigment particles having the second pigment content of 10%. The average diameter of the particles including the pigment particles contained in the water dispersion was equal to 36.5 nm, and the aqueous dispersion had a high light transmission.

EXAMPLE 17

As a dispersing agent having a functional group capable of crosslinking, 9.5 parts of a copolymer of styrene/methacrylic acid (acid number of 290; molecular weight of 15,000) was dissolved in 80 parts of dimethyl sulfoxide, and 10 parts isoindoline pigment (S pigment yellow 109) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then dropwise slowly added 30% methanolic solution of potassium hydroxide for dissolving isoindoline pigment. After the solution of the pigment was stirred for 3 hours, there was added phenylenebis(ethyl)carbodiimide as cross-linking agent was dissolved in the solution of the pigment in the ratio of 1 part to 10 parts of the pigment, the resulting solution was quickly poured into purified with ion exchange water (400 parts of purified water to 10 parts of a pigment; 0°C)mixed flow impeller-type stirrer (800 rpm), was purged with nitrogen and cooled, the temperature was maintained using 2 system distributors (produced by Musashi Engineering K.K.; inner needle diameter of 0.57 mm; feed pressure of 4 kgf/cm2) to obtain a water dispersion of particles, aderrasi isoindoline pigment, having an average particle diameter equal to 35.6 nm. This aqueous dispersion was transferred into a reaction vessel equipped with a heater casing, a cooling tube, stirrer and thermometer, this system was purged with nitrogen under stirring at 300 rpm, drops) was added 10% hydrochloric acid to bring the pH of the reaction mixture to 4.75. After the reaction was continued for a further 5 hours, the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter of retained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste of an aqueous dispersion containing isoindoline pigment particles, demineralized and desolvation.

After this paste was added 1.0 g of potassium hydroxide was added purified with ion exchange water so as to gain overall mass of 100 g, followed by stirring for 1 hour. After the resulting mixture was filtered under reduced pressure through a filter paper (diameter of retained particles of 1.0 μm to remove coarse particles, was added potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing isoindoline pigment particles having a pigment content of 10%. The average diameter of the particles including the pigment particles contained in the water dispersion was equal to 39.5 is m, and aqueous dispersion had a high light transmission.

EXAMPLE 18

Five parts of a copolymer of styrene/acrylic acid (acid number 250; molecular weight 5000) as a dispersing agent and 4 parts of polyvinyl alcohol (low degree of saponification; degree of polymerization 1000) as compounds having capable of crosslinking functional group, was dissolved in 80 parts of dimethyl sulfoxide, and 10 parts phthalocyaninato pigment (S pigment blue 16) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then dropwise slowly added 30% methanolic solution of potassium hydroxide for dissolving phthalocyaninato pigment. After the solution of the pigment was stirred for 3 hours, it was quickly poured into purified with ion exchange water (400 parts of purified water to 10 parts of a pigment; 0°C)mixed flow impeller-type stirrer (800 rpm), was purged with nitrogen and cooled, the temperature was maintained using 2 system distributors (produced by Musashi Engineering K.K.; inner needle diameter of 0.57 mm; feed pressure of 4 kgf/cm2) to obtain the aqueous dispersion of particles containing phtalocyanine pigment having an average particle diameter 41.5 nm. This aqueous dispersion was transferred into a reaction vessel equipped with a heater casing is m, a cooling tube, stirrer and thermometer, and the system was purged with nitrogen under stirring at 300 rpm and heated to an internal temperature of 60°C. While maintaining the internal temperature is 60°C, was added dropwise ethylenediaminedisuccinate ether as a cross-linking molecules of the agent in the ratio of 1 part to 10 parts of the pigment, the mixing was continued for another 5 hours and the reaction mixture was then cooled to room temperature. Then was added dropwise 10% hydrochloric acid to bring the pH of the reaction mixture to 4.0, and the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter of retained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste of an aqueous dispersion containing phtalocyanine pigment particles, demineralized and desolvation.

After you add this paste 1.0 g of potassium hydroxide was added purified with ion exchange water so as to achieve the total mass of 100 g, followed by stirring for 1 hour. After the resulting suspension was filtered under reduced pressure through a filter paper (diameter of retained particles of 1.0 μm to remove coarse particles, was added potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing phtalocyanines egment particles, having a pigment content of 10%. The average diameter of the particles including the pigment particles contained in the water dispersion was equal to 50.1 nm, and the aqueous dispersion had a high light transmission.

EXAMPLE 19

Ten parts of terpolymer (molecular weight 5000) styrene/acrylic acid/glycidylmethacrylate (molar ratio 7/2/1) as samoszhimayuschegosya compounds were dissolved in 80 parts of dimethyl sulfoxide and 10 parts hinkreonsok pigment (S pigment red 122) suspended in the resulting solution in the flask at 25°in an atmosphere of air. Then dropwise slowly added 30% methanolic solution of potassium hydroxide for dissolving hinkreonsok pigment. After the solution of the pigment was stirred for 3 hours, it was quickly poured into purified with ion exchange water (400 parts of purified water to 10 parts of a pigment; 0°C)mixed flow impeller-type stirrer (800 rpm), was purged with nitrogen and cooled, the temperature was maintained using 2 system distributors (produced by Musashi Engineering K.K.; inner needle diameter of 0.57 mm; feed pressure of 4 kgf/cm2) to obtain the aqueous dispersion of particles containing genocidally pigment having an average particle diameter equal to 30.2 nm. This aqueous dispersion was transferred into a reaction vessel equipped with a heater casing, klaid the setup portion of the column, stirrer and thermometer, and the system was purged with nitrogen under stirring at 300 rpm and heated to an internal temperature of 60°C. While maintaining the internal temperature is 60°C, stirring was continued for another 5 hours and the reaction mixture is then cooled to room temperature. Then was added dropwise 10% hydrochloric acid to bring the pH of the reaction mixture to 4.0. The resulting aggregates were filtered under reduced pressure through a membrane filter (diameter of retained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste of an aqueous dispersion containing genocidally pigment particles, demineralized and desolvation.

After this paste was added 1.0 g of potassium hydroxide was added purified with ion exchange water to obtain a total weight of 100 g, followed by stirring for 1 hour. After the resulting suspension was filtered under reduced pressure through a filter paper (diameter of retained particles of 1.0 μm to remove coarse particles, was added potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing genocidally pigment particles having a pigment content of 10%. The average diameter of the particles containing the pigment particles in this water dispersion was equal to 37.2 nm, and in the Naya dispersion had a high light transmission.

The results of measuring the average diameter of the particles in including organic pigment particles contained in the aqueous dispersions obtained in examples 15 to 19, jointly presented in table 12. Aqueous dispersions obtained in examples 15 to 19, had a small average particle diameter, were monodisperse and had a narrow distribution of particle size.

Example 12
SampleDiameter (nm) particles in aqueous dispersion
Before aggregationAfter re-dispersion (after aggregation)
Example 1538,948,8
Example 1629,736,5
Example 1735,639,5
Example 1841,550,1
Example 1930,237,2

TEST PRINT. EXAMPLE 4

Aqueous dispersions obtained in examples 15 to 19, were evaluated as colorants for ink in the same manner as in the TEST PRINT. EXAMPLE 1, except that used aqueous dispersions obtained in examples 15 to 19. The results are presented in table 13.

Table 13
SampleLight transmission (sheet NRO)Color density (smooth paper)
Example 15AndAnd
Example 16AndAnd
Example 17AndAnd
Example 18AndAnd
Example 19AndAnd

For inks respectively containing aqueous dispersions of examples 15 to 19, the projection image printed on the sheet NRO, was bright and clear. With regard to density color printing on smooth paper, ink gave a high OD value.

THE STORAGE STABILITY AND THE EJECTION DURATION.

TEST 2

The storage stability and the duration of the ejection of ink at the corresponding use of the aqueous dispersions obtained in examples 15 to 19 were evaluated in the same manner as the storage Stability and the ejection duration. Test 1, except that used aqueous dispersions obtained in examples 15 to 19. The results of this are presented in tables 14 and 15.

Table 14
SampleViscosity [MPa·)
Before storageAfter storage
EXAMPLE 154,14,2
EXAMPLE 164,34,3
EXAMPLE 17a 3.94,0
EXAMPLE 183,7a 3.9
EXAMPLE 193,5a 3.9

In the ink, in which, respectively, are aqueous dispersions of examples 15 to 19, almost was not observed changes in viscosity between the tests before and after storage.

Table 15
SampleThe ejection duration
EXAMPLE 15And
EXAMPLE 16And
EXAMPLE 17And
EXAMPLE 18And
EXAMPLE 19And

Ink, in which, respectively, were used aqueous dispersions of examples 15 to 19, showed a good stability of ejection.

EXAMPLE 20

The aqueous dispersion containing genocidally pigment particles having an average diameter 142,6 nm, was obtained in the same manner as in example 1 except that the pressure supply system of the dispenser is changed to 0.5 kgf/cm2.

Then this in the ne dispersion drops) was added 5% aqueous solution of sulfuric acid, to bring the pH of the dispersion to 4.0, thus producing an aggregation containing genocidally pigment particles in the aqueous dispersion. Then the resulting aggregates were filtered under reduced pressure through a membrane filter (diameter of retained particles 0.45 μm) and washed 3 times with 500 ml of purified with ion exchange water to obtain a paste of an aqueous dispersion containing genocidally pigment particles, demineralized and desolvation.

After this paste was added 2.0 g of potassium hydroxide was added purified with ion exchange water to obtain a total weight of 100 g, followed by stirring for 1 hour. Then add the potassium hydroxide to bring the pH of the mixture to 9.5, thereby obtaining a water dispersion containing genocidally pigment particles having a pigment content of 10%. The average diameter of the particles containing the pigment particles in this water dispersion was equal 148,1 nm, and the aqueous dispersion had a high light transmission.

TEST THE INTENSITY OF THE SCATTERING. EXAMPLE 1

Water dispersion containing pigment particles obtained in examples 1, 7, 12, 15 and 20, and the dispersion of the pigment from S pigment red 122 having an average particle diameter of 50.5 nm and obtained by performing a typical grinding process over an extended period of time as comparative example 4, the subject is Ali the measurement of the intensity of scattering. In this case, the variance of each pigment was diluted to a concentration so that the value of the peak absorption of the dispersion in the visible region was equal to 1, and then filtered through a membrane filter that retains particles with a diameter of 1.0 μm for the measurement. The scattering intensity was shown as the average number (pulse/sec) for 3 minutes, which was calculated using the FPAR-1000 (produced by Otsuka Denshi K.K.) without using any ND filter. In this regard, the intensity of the dispersion aqueous dispersion (concentration 0,0163%) finely ground particles having a particle diameter equal to 88 nm, was measured by the same method described above. As a result, it was 69664 pulse/sec. The results thus obtained are presented in table 16.

Table 16
SampleThe intensity of dispersion (pulse/sec)Particle diameter (nm)
EXAMPLE 1683926,5
EXAMPLE 77202a 38.5
EXAMPLE 12776042,7
EXAMPLE 15788148,8
EXAMPLE 2016697148,1
EUR. AVE. 437620a 50.5

Aqueous dispersions of examples 1, 7, 12, 15 and 20 had a higher light transmission than the dispersion of the pigment of comparative example 4.

MEASUREMENT OF COLOR DIFFERENCES. EXAMPLE 1

The ink for ink-jet printing was obtained in the same manner as in the Test print. Example 1, except that used a water dispersion containing pigment particles obtained in examples 1, 7, 12, 15 and 20, and the content of the pigment was changed to 1%. In addition, the ink for ink-jet printing was obtained in the same manner as in the Test print. Example 1, except that used a dispersion S pigment red 122 having an average particle diameter equal to a 50.5 nm, and is made using a conventional grinding process, and the content of the pigment was changed to 1%. Each of these ink was used to print a solid image area on smooth paper (paper PB, product of Canon Inc.) using an inkjet printer, such as that used in the Test print. Example 1".

The color images obtained using each of the ink was determined using a spectral calorimeter (Spectro Photometer CM-2022, trade name, produced by Minolta Camera Co., Ltd.). As a result, the color difference (ΔN°) between the image obtained by using the ink containing containing pigment particles according to this invention, and the image obtained using the ink, containing pigment particles obtained by a simple grinding process were in the range of 30°C. this fact was confirmed that the containing pigment particles according to this invention give the same color, giving and S pigment red 122 (γ-chinagreen).

EXAMINATION WITH AN ELECTRON MICROSCOPE OF THE TRANSMISSION TYPE. EXAMPLE 1

The aqueous dispersion containing the pigment particles obtained in example 1 and the dispersion of the pigment IS pigment red 122 having an average particle diameter of 50.5 nm prepared using a conventional grinding process in Comparative example 4, was studied using the electron microscope of the transmission type. Each of the dispersions were fixed on microresist quickly and directly studied with the increase in 10000 and 100000. In the observed particles compared to particles with an average diameter on the measurement of dynamic light scattering, as in example 1, and comparative example 4. However, almost all particles in comparative example 4 was observed in the form of pigment particles having the same color, whereas it was confirmed that the particles of example 1, each dotted with a number of colored particles (colored parts) 1 in their inner parts, as shown in figure 1, and always have an unpainted part 2 in the area not exceeding 40 nm in radius from a given point of the particle, as a center.

In accordance with this invention presents a dispersion of finely ground pigment, which do not require processing by using a dispersant for an extended period of time and have uniformity in size regardless of the size of the primary particles of the pigment as a raw material, and the way they are received. Presents water coloring liquid, with an excellent stability in the water and an excellent stability to light, and the light transmittance property, in particular ink for inkjet printing.

1. Aqueous dispersion containing particles comprising water-insoluble colorant and a polymer compound or surfactant, the hydrophilic portion of which is formed by at least one group selected from the group consisting of carboxyl, sulphonic, phosphate, hydroxyl and alkalinising groups, with particles dispersed in a medium containing water, the dispersion is the intensity of light scattering is not more than 30,000 CPS, when it contains a sufficient number of particles, so that the peak value of the absorption with respect to visible light was equal to 1, and the particles give the same color that and water-insoluble dye in the crystalline state.

2. The dispersion according to claim 1, in which the average particle diameter of the composition is employed not more than 150 nm.

3. The dispersion according to claim 1, which is used for inkjet printing.

4. Particles containing the water-insoluble colorant and a polymer compound or surfactant, the hydrophilic portion of which is formed by at least one group selected from the group consisting of carboxyl, sulphonic, phosphate, hydroxyl and alkalinising groups, giving the same color as water-insoluble dye in the crystalline state, and having painted part with a water-insoluble dye and unpainted part, and an unpainted part exists in a circular region with a radius of 40 nm, the center of which is a predetermined point in the particle.

5. Ink containing particles according to claim 4 in the aquatic environment in dispergirovannom condition.

6. The ink according to claim 5, used for inkjet printing.

7. A method of obtaining a water dispersion, which includes the following stages:

(1) preparation of a solution containing water-insoluble colorant and the dispersing agent dissolved in aprotonin water-soluble organic solvent in the presence of alkali, and

(2) mixing the solution with water and obtaining a dispersion containing particles comprising water-insoluble colorant and a dispersing agent.

8. The method according to claim 7, in which the solution obtained in stage (1), Ni is sustained fashion includes a curable compound, and stage (2) further comprises the stage of inclusion of the polymerized compounds in particles and polymerization of the curable compounds in the particles.

9. The method according to claim 7, in which the dispersing agent is curable compound, and the method further includes a step of polymerization dispersing agent in the particles obtained in stage (2).

10. The method according to claim 8 or 9, in which the solution further comprises a polymerization initiator.

11. The method according to claim 7, which additionally includes a step of coating at least part of the surface of the particles in the dispersion polymer of Ethylenediamine connection after stage (2).

12. The method according to claim 11, in which the polymer is formed by using a seed polymerization.

13. The method according to item 12, in which the solution contains a polymerization initiator for the seed polymerization.

14. The method according to claim 7, in which the solution further comprises a compound containing a functional group capable of crosslinking, and stage (2) additionally includes the stage of inclusion compounds having a functional group capable of crosslinking, in particles and crosslinking compounds having a functional group capable of crosslinking included in the particle.

15. The method according to claim 7, in which the dispersing agent is soy is inanam, having a functional group capable of crosslinking, and stage (2) further includes a step of crosslinking dispersing agent in the particle.

16. The method according to claim 7, in which the solubility Rarotonga organic solvent in water is at least 5 mass%.

17. The method according to claim 7, in which the alkali, at least, is an alkali selected from the group consisting of hydroxides of alkali metals, alkoxides of alkali metals, hydroxides of alkaline earth metals, alkoxides of alkaline earth metals, and strong organic bases.

18. A method of producing particles containing water-insoluble dye providing stage:

(A) obtaining a water dispersion in accordance with the method according to claim 7;

(C) forming a unit consisting of particles of the dispersion, and the selection unit of the dispersion and

(C) imparting to the particles in the unit abilities again dispergirujutsja, and stage (B) includes a substage, MIS adding acid to the dispersion for the formation of the unit, and stage (C) includes a substage, MIS-handling unit with alkali to give the particles in unit of ability again to dispergirujutsja.

19. The method according to p, in which the acid is at least one selected from acids, are capable of forming soluble salts with alkali.

Priority items:

08.04.2003 according to claims 1-6;

21.05.2002 according to claims 7 to 19.



 

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FIELD: varnish-and-paint industry.

SUBSTANCE: invention proposes non-fluorescent typewriter ink composition, which includes non-fluorescent pigment preliminarily dispersed in alkyd resin and organic solvent with high boiling temperature. Composition may further contain resins, plasticizers, substance preventing formation of surface film, and lubricants.

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44 cl, 3 tbl, 2 ex

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