JP2005307209A - Colored resin microparticle and method for producing aqueous colored resin dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare an aqueous colored resin dispersion which enables the preparation of an ink capable of giving high-density recording being free from bleeding, excellent in fastnesses such as water resistance and light resistance, and good in long-term storage stability. <P>SOLUTION: The method for obtaining the aqueous colored resin dispersion comprises dissolving or dispersing in a polymerizable unsaturated monomer a colorant having an affinity for the polymerizable unsaturated monomer and emulsion-polymerizing the solution or the dispersion in the presence of anionic and/or nonionic reactive emulsifiers to obtain colored resin microparticles, and dispersing the colored resin microparticles in an aqueous medium. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to colored resin fine particles. The present invention also relates to an aqueous colored resin dispersion prepared using the colored resin fine particles. More specifically, the present invention relates to an aqueous colored resin dispersion used for ink for inkjet printers, water-based ink for printing presses, water-based ink for writing instruments, water-based paints, cosmetics and the like.

Solvent-based inks in which oil-soluble dyes are dissolved in organic solvents are problematic in terms of environment and safety because they use solvents, and in recent years, water-soluble inks have been frequently used.
On the other hand, a water-soluble ink using a water-soluble dye has a problem that water resistance, bleeding, light resistance, and the like are inferior, while the solvent is water and the hue is clear and the number of colors is easy to use.

A water-based ink in which a pigment is dispersed in an aqueous medium has problems that the water resistance and light resistance are good, but the number of colors is small, the color tone is not clear and transparent, and long-term storage is not sufficient.
In recent years, many developments of water-based inks using colored resin fine particles have been reported in order to improve these drawbacks. (For example, refer to Patent Documents 1 to 4 and 5.) Among them, the colored resin fine particles by emulsion polymerization have a fine particle diameter of 1 μm or less and have been evaluated to be extremely high in utility value for inks and the like.

However, since a large amount of an emulsifier and a dispersant used in emulsion polymerization remain in the aqueous medium, there is a problem that the water-based ink itself has a large permeability and a decrease in surface concentration. Furthermore, since long-term storage stability is inferior due to dispersion deterioration by this emulsifier, it has not been put into practical use yet.
JP 61-19651 A Japanese Examined Patent Publication No. 4-54685 JP-A-8-81647 JP-A-5-247108 JP-A-4-170402

It is an object of the present invention to provide an aqueous colored resin dispersion having improved long-term storage stability that is improved in terms of bleeding, water resistance and other reductions in surface concentration, and colored resin fine particles for producing the same. It is.
Another object of the present invention is to provide a high-concentration aqueous ink that is useful for water-based paints, cosmetics, writing inks, printing inks, and the like, and that is particularly useful for inkjet recording liquids and has excellent temporal stability. .

As a result of intensive studies to achieve the above object, the present inventors have completed the present invention.
That is, the gist of the present invention is as follows.
1. By dissolving or dispersing a colorant having an affinity for the polymerizable unsaturated monomer in the polymerizable unsaturated monomer, followed by emulsion polymerization using an anionic and / or nonionic reactive emulsifier. A method for producing colored resin fine particles, comprising obtaining colored resin fine particles.
2. 2. The method for producing colored resin fine particles as described in 1 above, wherein the colorant is a water-insoluble dye and / or pigment.
3. 2. The method for producing colored resin fine particles as described in 1 above, wherein the colorant is a water-soluble dye.
4). 4. The method for producing colored resin fine particles according to any one of 1 to 3, wherein the average particle diameter of the colored resin fine particles is in the range of 0.01 to 10 μm.
5). A colorant having an affinity for the polymerizable unsaturated monomer is dissolved or dispersed in the polymerizable unsaturated monomer, and then an anionic and / or nonionic reactive emulsifier is used in an aqueous medium. A method for producing an aqueous colored resin dispersion, characterized in that an aqueous colored resin dispersion in which colored resin fine particles are dispersed in an aqueous medium is obtained by emulsion polymerization.
6). 6. The method for producing an aqueous colored resin dispersion as described in 5 above, wherein the aqueous colored resin dispersion is an aqueous ink.
7). 6. The method for producing an aqueous colored resin dispersion as described in 5 above, wherein the aqueous colored resin dispersion is an inkjet recording liquid.

The present invention will be described in detail below.
As a result of various studies, the present inventors first fixed an anionic and / or nonionic reactive emulsifier (hereinafter referred to as a reactive emulsifier) on the surface of the colored resin fine particles, whereby the hydrophilic groups are densely formed. The particles that uniformly cover the surface are the most stable in an aqueous medium, and the dispersion stability and long-term storage stability when converted to ink are considered to be particularly excellent, and the invention has been completed based on this idea. is there.

  The feature of these colored resin fine particles is that the reactive emulsifier is integrally fixed on the surface of the colored resin fine particles, and the hydrophilic groups such as immobilized sulfonic acid groups, carboxylic acid groups, and alkyleneoxy groups are densely formed on the surface of the particles. In other words, the particles themselves have extremely stable dispersibility.

  Therefore, the aqueous dispersion of colored resin fine particles is particularly excellent in long-term storage stability when converted into an ink. In addition, in emulsion polymerization using a normal emulsifier, a large amount of the emulsifier remains in the aqueous medium, and when this is converted into an ink, the effect of the emulsifier increases the permeability, which causes problems such as bleeding and a decrease in surface concentration. . However, when the colored resin fine particles of the present invention using this reactive emulsifier are used, since the emulsifier hardly remains in the aqueous medium, an ink having a small surface blur and a high surface concentration can be obtained.

By using the aqueous colored resin dispersion of the present invention obtained by using the colored resin fine particles of the present invention, it is possible to prepare an ink that has good storage stability and can be recorded at a high density without bleeding. In addition, this ink is excellent in the abrasion resistance of the printed matter, has good print quality of the recorded matter, and can record with good light resistance, water resistance and other various fastness properties. Thus, since the water-based colored resin dispersion of the present invention has the above-mentioned properties, it can be used as ink for many other purposes as well as for inkjet and writing instruments.

  The colored resin fine particles of the present invention are obtained by dissolving or dispersing a colorant having an affinity for the polymerizable unsaturated monomer in a polymerizable unsaturated monomer and then emulsion polymerization using a reactive emulsifier. . The emulsion polymer particles obtained by emulsion polymerization using a reactive emulsifier have an average particle size of 0.01 or more, preferably 0.01 or more, and 10 μm or less, preferably 1 μm or less. It can be manufactured by the method. In general, an emulsion polymerization method using a reactive emulsifier is obtained by emulsifying and dispersing a polymerizable unsaturated monomer in submicron particles in an aqueous medium and emulsion polymerization in the presence of a radical polymerization initiator.

As the polymerizable unsaturated monomer for the emulsion polymerization, vinyl aromatic hydrocarbons, (meth) acrylic acid esters, (meth) acrylamide, alkyl-substituted (meth) acrylamide, N-substituted maleimide, maleic anhydride, (meth ) Acrylonitrile, methyl vinyl ketone, vinyl acetate, vinylidene chloride and the like. Preferably, oil-soluble vinyl aromatic hydrocarbons and (meth) acrylic acid esters are desirable. The vinyl aromatic monomer has the formula (1)

(Wherein R ¹ is a hydrogen atom, a lower alkyl group or a halogen atom, and R ² is a hydrogen atom, a lower alkyl group, a halogen atom, an alkoxy group, a nitro group or a vinyl group). .

Specific examples of the vinyl aromatic hydrocarbon include, for example, styrene, α-methylstyrene, o, m, p-chlorostyrene, p-ethylstyrene, divinylbenzene and the like alone or in combination of two or more. However, the present invention is not limited to this.
The (meth) acrylate monomer is represented by the formula (2)

(Wherein R ³ is a hydrogen atom or a lower alkyl group, R ⁴ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyalkyl group or a vinyl ester group)
Can be shown.

  Specific examples of (meth) acrylic acid ester monomers include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, methacrylic acid. Hexyl, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-hydroxyacrylate, butyl δ-hydroxyacrylate, ethyl β-hydroxymethacrylate, ethylene glycol dimethacrylate, or tetraethylene glycol dimethacrylate Examples include, but are not limited to, acid esters.

These polymerizable unsaturated monomers can be used alone or in combination of two or more. Of course, a small amount of a water-soluble monomer may be added and polymerized in order to improve the properties of the generated colored resin fine particles depending on the application.
Examples of the water-soluble monomer include those having an anionic group such as a sulfonic acid group, a phosphoric acid group, and a carboxylic acid group, and these acid groups include alkali metal salts such as sodium salts, ammonium salts, and amine salts. , Etc., or in the form of the free acid, suitable examples are styrene sulfonic acid, sodium styrene sulfonate, 2-acrylamido-2-methylpropane sulfonic acid, 2-hydroxymethyl methacryloyl phosphate, 2-hydroxyethyl methacryloyl phosphate 3-chloro-2-hydroxypropylmethacryloyl phosphate, acrylic acid, methacrylic acid, fumaric acid, crotonic acid, tetrahydroterephthalic acid, itaconic acid, maleic acid and the like.

Reactive emulsifier The anionic and / or nonionic reactive emulsifier used in the present invention may be any reactive emulsifier as long as it has an α, β-ethylenically unsaturated group capable of radical polymerization and a surface activity. The reactive emulsifier is usually an α, β-ethylenically unsaturated group such as a vinyl group, an allyl group or a (meth) acryloyl group, an ion dissociable group such as a sulfonic acid group or a salt thereof, or a hydrophilic group such as an alkyleneoxy group. It is an emulsifier having a group. The reactive emulsifier includes, for example, compounds represented by the following general formulas (3) to (6).

(In the formula, R ⁵ is an optionally substituted hydrocarbon group (for example, an aralkyl such as a linear or branched alkyl group having 4 to 18 carbon atoms, an alkenyl group having 4 to 18 carbon atoms, or a benzyl group). Group), R ⁶ represents a hydrogen atom or a methyl group, and M represents an organic base or an inorganic base (for example, an alkali metal, an ammonium group, an amine residue or an alkanolamine residue).

(Ra, Rb and Rc are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and R ⁷ is a hydrogen atom or a hydrocarbon group optionally having a substituent (for example, having 4 to 18 carbon atoms). A linear or branched alkyl group, an aralkyl group such as an alkenyl group having 4 to 18 carbon atoms or a benzyl group), A represents an alkylene group having 2 to 4 carbon atoms, m is an integer of 2 to 20, and M is Organic base or inorganic base (for example, alkali metal, ammonium group, amine residue or alkanolamine residue) is shown. )

(In the formula, R ⁶ has the same significance as in formulas (3) and (4), and R ⁸ is a hydrocarbon group which may have a substituent (for example, an alkyl group having 8 to 24 carbon atoms). , An alkenyl group having 8 to 24 carbon atoms, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group) or an acyl group, X represents a hydrogen atom, a nonionic or an anionic hydrophilic group, and A represents a carbon number of 2 -4 represents an alkylene group, and n is an integer of 0-100.)

Addition amount of reactive emulsifier The amount of reactive emulsifier can be selected within a range that does not impair polymerization stability, prevention of coarse particles, mechanical and chemical properties of emulsion, and water resistance of the coating. The amount is 0.1 to 10 parts by weight, preferably 0.5 to 7.5 parts by weight, more preferably 1 to 7 parts by weight, and most preferably about 2 to 7 parts by weight with respect to 100 parts by weight of the body. When the amount of the reactive emulsifier relative to 100 parts by weight of the polymerizable unsaturated monomer is less than 0.1 parts by weight, the polymerization stability, mechanical or chemical stability may be impaired, and the amount exceeds 10 parts by weight. In some cases, the water resistance of the film and the adhesion to the substrate may be reduced.

  As long as long-term storage stability and bleeding are not impaired during emulsion polymerization, surfactants such as anionic surfactants and nonionic surfactants, polyvinyl alcohol, water-soluble polymers, and the like are necessary. These protective colloids may be used in combination.

Polymerization method The polymerization method can be carried out in accordance with a conventional emulsion polymerization method. For example, a polymerization unsaturated monomer containing deionized water, a reactive emulsifier, a polymerization initiator and a colorant is charged all at once. A method in which the charged chemical is pre-emulsified and then continuously or intermittently supplied, a method in which the polymerizable unsaturated monomer and other chemicals are separately or continuously supplied, a reactive emulsifier, and Examples thereof include a method in which at least one component of the polymerization initiator is polymerized while continuously or intermittently supplied.

In the case of continuous supply, a pre-emulsion in which the polymerizable unsaturated monomer is pre-emulsified and polymerized, or a combination of the above methods can be employed. Conventional methods such as seed polymerization can also be employed.
In these methods, the colorant is usually present dissolved or dispersed in the polymerizable unsaturated monomer. The polymerization reaction temperature can be selected according to the type of the polymerization initiator, and is usually 40 to 100 ° C., preferably 50 to 90 ° C., more preferably about 50 to 85 ° C., and the reaction time is Usually, it is about 1 to 12 hours (for example, 3 to 10 hours).

Neutralizing agent When acidic monomers are used, the polymerization stability, freezing stability, and mechanical stability of the emulsion can be improved by adjusting the pH by adding a basic substance at the appropriate stage from the start to the end of emulsion polymerization or after the end of polymerization. Property and chemical stability can be improved. The pH of the emulsion is often 5 or more, preferably 6 to 9, more preferably about 7 to 9 neutral or anionic (alkaline) in many cases. Basic substances include organic bases (eg, amines such as ethylamine, diethylamine and triethylamine, alkanolamines such as ethanolamine, diethanolamine and triethanolamine, morpholine) and inorganic bases (eg, ammonia, sodium hydroxide, water). Potassium oxide etc. can be used.

Particle diameter and particle shape The particle diameter of the colored resin fine particles can be selected within a range that does not impair the dispersion stability, ejection stability, etc., for example, 0.01 to 10 μm, preferably 0.01 to 2 μm, more preferably 1 μm or less. It is desirable that
Furthermore, the colored resin fine particles may be homogeneous or may have a heterogeneous structure (for example, a core / shell structure, a microdomain structure, etc.). Further, the shape of the resin fine particles may be spherical or irregularly shaped.

Polymerization initiator Emulsion polymerization can be performed using a polymerization initiator. Examples of the polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, and water-soluble polymerization initiators such as hydrogen peroxide. The polymerization initiator may constitute a water-soluble redox type polymerization initiator system. Alternatively, an oil-soluble polymerization initiator such as azobisdimethylvaleronitrile (V-60 manufactured by Wako Pure Chemical Industries, Ltd.) may be used.

  In order to adjust the molecular weight of the resin, various chain transfer agents such as alcohols such as catechols, thiols, and mercaptans may be used. The amount of chain transfer agent used is, for example, about 0.01 to 3 parts by weight, preferably about 0.05 to 2.5 parts by weight, based on 100 parts by weight of the total amount of polymerizable unsaturated monomers.

Coloring method A dye is dissolved or dispersed in a polymerizable unsaturated monomer, and the monomer containing the colorant is polymerized at once in a micelle of a reactive emulsifier to obtain water-dispersible colored resin fine particles.
Examples of the dye as a colorant having an affinity for the polymerizable unsaturated monomer to be used include oil-soluble dyes, disperse dyes, water-insoluble metal-containing dyes, vat dyes, other photochromic dyes, and resin colorants. From the viewpoint of good color developability, it is better that the solubility in the polymerizable unsaturated monomer is higher, for example, an oil-soluble dye or a disperse dye.

Of course, even water-soluble dyes, depending on the type of polymerizable unsaturated monomer, water-soluble dyes, such as acid dyes, cationic dyes, basic dyes, under the condition that there is no appreciable amount of dissolved dye in the aqueous medium, Water-soluble metal-containing dyes and reactive dyes can also be used.
Alternatively, a water-soluble dye having an ionicity opposite to that of the ionic polymerizable unsaturated monomer may be used to salt both, and this salt-formation product may be polymerized in a micelle of a reactive emulsifier.

The amount of the dye to be used depends on the solubility of the dye, but is generally 0.1 to 20% by weight, preferably 1 to 10% by weight based on the polymerizable unsaturated monomer.
For dyes and pigments that are difficult or insoluble in the polymerizable unsaturated monomer, a fine particle is obtained by the same emulsion polymerization method after fine dispersion using a polymer dispersant in the monomer. be able to.

  On the other hand, for the purpose of improving the fastness of the colorant, an ultraviolet absorber or an antioxidant can be added to the polymerizable unsaturated monomer together with the colorant, and colored resin fine particles can be obtained by the same emulsion polymerization method. . Similarly, a fragrance, an antifungal agent, and the like can be added to the polymerizable unsaturated monomer together with the colorant to obtain colored resin fine particles.

Particle content The aqueous colored resin dispersion produced according to the method of the present invention is generally 1 to 50% by weight, preferably 5 to 30% by weight of the colored resin fine particles dispersed in an aqueous medium, based on the total weight of the aqueous dispersion. Contain by concentration.
Of course, the water-based ink composed of the water-based colored resin dispersion can contain components such as a dispersant desirable for dispersion stability and blending components desirable for the ink in addition to the colored resin fine particles.

  For example, various surfactants and polymer stabilizers may be included for the purpose of assisting dispersion stability of colored resin fine particles and preventing sedimentation. Moreover, in order to improve the wettability and rewetability of the colored resin fine particles, ethylene glycol, glycerin, various polyhydric alcohols, and the like can be included. Furthermore, for the purpose of sequestering metal ions mixed in the ink, a metal sequestering agent such as various chelating agents is blended, and various bactericides, fungicides, perfumes, An ultraviolet absorber, an antioxidant, etc. can also be mix | blended.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

Example 1
Red oil-soluble dye oil red (Oil Red (Sudan IV) CI 26105) (product of Tokyo Chemical Industry Co., Ltd.) 0.8 parts by weight 20 parts by weight of methyl methacrylate, 20 parts by weight of n-butyl methacrylate and acrylic acid Dissolve in 0.8 parts by weight of the polymerizable monomer mixture, and add 2 parts by weight of the following reactive emulsifier (trade name: Terramul S-180A, product of Kao Corporation) to 20 parts by weight of deionized water. In addition to the dissolved aqueous solution, it was emulsified.
Product name: Terramuru S-180A

  This emulsified liquid was placed in a reactor (reactor equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet pipe) in which 40 parts by weight of deionized water was heated to 80 ° C. for 3 hours under a nitrogen stream. After the completion of the dropwise addition, the mixture was further heated for 2 hours and then cooled to room temperature to obtain colored resin fine particles. Subsequently, 0.8 weight part of 25% ammonia water was added and neutralized to obtain an aqueous colored resin dispersion.

Example 2
Emulsion polymerization was carried out in the same manner as in Example 1 except that 20 parts by weight of styrene, 20 parts by weight of n-butyl methacrylate, and 0.8 parts by weight of acrylic acid were used as the polymerizable unsaturated monomer to obtain colored resin fine particles. Then, an aqueous colored resin dispersion was obtained.

Example 3
It implemented except having used 2.0 weight part of reactive emulsifiers (trade name: Aqualon HS-10, Dai-ichi Kogyo Seiyaku Co., Ltd. product) represented by the following formula instead of the reactive emulsifier used in Example 1. Emulsion polymerization was carried out in the same manner as in Example 1 to obtain colored resin fine particles, and then an aqueous colored resin dispersion was obtained.
Product Name: Aqualon HS-10

Example 4
Example except that 2.0 parts by weight of a reactive emulsifier (trade name: Eleminol JS-2, product of Sanyo Chemical Industries, Ltd.) represented by the following formula was used instead of the reactive emulsifier used in Example 1. In the same manner as in Example 1, emulsion polymerization was performed to obtain colored resin fine particles, and then an aqueous colored resin dispersion was obtained.
Product name: Eleminor JS-2

Example 5
Instead of using the reactive emulsifier represented by the following formula instead of the reactive emulsifier used in Example 2 (trade name: Adekaria Soap SE-10N, Asahi Denka Kogyo Co., Ltd.) 2.0 parts by weight, Emulsion polymerization was carried out in the same manner as in Example 1 to obtain colored resin fine particles, and then an aqueous colored resin dispersion was obtained.
Product name: ADEKA rear soap SE-10N

Example 6
30 parts by weight of styrene, 30 parts by weight of methyl methacrylate, a polymer dispersant (trade name: Disper BYK 161, manufactured by Big Chemi Japan Co., Ltd.), 6 parts by weight of copper phthalocyanine blue pigment (CI Pigment Blue 15: 3) 6 Part by weight was added and milling was performed in 60 ml of glass beads (diameter 0.5 mm) for 16 hours to obtain a dispersion of copper phthalocyanine blue of 0.5 μm or less.

40 parts by weight of this dispersion was added to an aqueous solution obtained by adding 2 parts by weight of the reactive emulsifier Teramulu S-180A used in Example 1 to 20 parts by weight of deionized water, and this was emulsified. Parts were added.
40 parts by weight of deionized water was added to a reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inflow pipe and the temperature was raised to 80 ° C., and the emulsion was placed in this reactor for 3 hours under a nitrogen stream. After the completion of the dropwise addition, heating was continued for 2 hours, followed by cooling to room temperature to prepare colored resin fine particles, and then adding 0.8 parts by weight of 25% ammonia water to neutralize the aqueous blue resin dispersion Got.

Comparative Example 1
Instead of the reactive emulsifier of Example 2, colored resin fine particles were obtained under the same conditions as in Example 2 except that 2 parts by weight of sodium lauryl sulfate was used, and then an aqueous colored resin dispersion was obtained.

Comparative Example 2
Instead of the reactive emulsifier of Example 1, 2 parts by weight of sodium dodecylbenzenesulfonate was used, and colored resin fine particles were obtained under the same conditions as in Example 1, and then an aqueous colored resin dispersion was obtained.

Comparative Example 3
Instead of the reactive emulsifier of Example 2, colored resin fine particles were obtained under the same conditions as in Example 2 except that 2 parts by weight of sodium dodecylbenzenesulfonate were used, and then an aqueous colored resin dispersion was obtained.

(Ink evaluation)
-Preparation of ink liquid Colored aqueous resin dispersion 70 parts Glycerin 10 parts Ethylene glycol 10 parts Isopropyl alcohol 10 parts The reaction product liquid of the aqueous colored resin dispersions of Examples 1 to 5 and Comparative Examples 1 to 3 was adjusted to 30% solids. The ink composition was used after being adjusted and converted into ink with the above recording liquid composition, and evaluated as follows.

Printing test Inkjet recording was performed on electrophotographic paper (Xerox product name: 4024 paper) with an ink jet printer (product name: Desk Writer C).

-Water resistance test The printed matter obtained in the printing test was immersed in tap water taken in a beaker for 5 seconds. After the printed matter was dried, the presence or absence of character smudge was visually evaluated. The results are classified as follows and are shown in Table 1 below.
○: Almost no smudges △: Slightly smudged characters but no problem in practical use × ... Slightly smudged characters

-Light resistance test The faded color after irradiating the printed matter for 100 hours with a xenon fade meter (product of Suga Test Instruments Co., Ltd.) was visually evaluated. The results are classified as follows and shown in Table 1 below.
○… Good △… There is discoloration but there is no practical problem ×… Discoloration is severe

-Ink storage stability test The ink liquid was sealed in a Teflon (registered trademark) container, stored at 60 ° C for 1 month, and visually evaluated for the presence of gelation and precipitation. The results are classified as follows and shown in Table 1 below.
○… Almost no gelation or precipitation △… Slight gelation or precipitation is observed, but there is no problem in practical use ×… Severe gelation or precipitation

-Rubbing resistance test The printed matter obtained in the printing test was visually judged for the presence of smudges when traced from above with a finger. The results are classified as follows and shown in Table 1 below.
○: Slightly soiled △: Slightly soiled but practically no problem ×: Scratched soiled

-Particle size distribution measurement The average particle diameter of the colored resin fine particles in the ink liquid obtained by the method described in the above example was measured using a MICROTORAC particle size distribution model 9230UPA (product of Nikkiso Co., Ltd.).
The measurement solvent used for this measurement was measured under the conditions of a refractive index of 1.81 and a specific gravity of 1.0.

Claims (7)

By dissolving or dispersing a colorant having an affinity for the polymerizable unsaturated monomer in the polymerizable unsaturated monomer, followed by emulsion polymerization using an anionic and / or nonionic reactive emulsifier. A method for producing colored resin fine particles, comprising obtaining colored resin fine particles. The method for producing colored resin fine particles according to claim 1, wherein the colorant is a water-insoluble dye and / or pigment. The method for producing colored resin fine particles according to claim 1, wherein the colorant is a water-soluble dye. The method for producing colored resin fine particles according to any one of claims 1 to 3, wherein the average particle diameter of the colored resin fine particles is in the range of 0.01 to 10 µm. A colorant having an affinity for the polymerizable unsaturated monomer is dissolved or dispersed in the polymerizable unsaturated monomer, and then an anionic and / or nonionic reactive emulsifier is used in an aqueous medium. A method for producing an aqueous colored resin dispersion, characterized in that an aqueous colored resin dispersion in which colored resin fine particles are dispersed in an aqueous medium is obtained by emulsion polymerization. The method for producing an aqueous colored resin dispersion according to claim 5, wherein the aqueous colored resin dispersion is an aqueous ink. The method for producing an aqueous colored resin dispersion according to claim 5, wherein the aqueous colored resin dispersion is an inkjet recording liquid.