JP2869812B2 - Method for producing colored aqueous resin dispersion - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a process for producing a colored aqueous resin dispersion having good dyeing properties and dispersion stability.

[Problems to be solved by conventional technology and invention]

Conventionally, coloring of an aqueous resin dispersion has been performed mainly by dispersing or dissolving a pigment or dye in the resin dispersion. However, the addition of pigments and the like to the aqueous resin dispersion causes the dispersion to become unstable, and may affect the water resistance, adhesion, adhesion, weather resistance, and mechanical strength of the coating even after drying. Was exerted.

As a method for solving these problems, a method of coloring the resin portion of the aqueous resin dispersion has been attracting attention. The coloring of the resin portion is mainly performed by adding a pigment to the resin and then forming a colored aqueous resin dispersion or by polymerizing a monomer in which the pigment is dispersed to form a colored aqueous resin dispersion. There is also an example in which a colored aqueous resin dispersion colored by this method is actually applied (JP-A-58-55356). However, since the colored resin obtained by such a method has a structure in which a coarse pigment is dispersed inside the particles, there are problems in color density, sharpness, particle size, shape uniformity, and the like. was there.

As a method for solving these problems, there is a method in which a functional group is previously introduced into the resin particle surface, and a dye is reacted with the functional group to dye the resin (Japanese Patent Laid-Open No. 62-184072). The obtained colored resin was colored only on its surface, and had a drawback that the color density after drying or after welding was low.

In addition, homopolymerization of a dye having a polymerizable double bond,
Alternatively, a method of obtaining a colored resin by copolymerizing the dye with a monomer having a polymerizable double bond copolymerizable therewith is also known (JP-A-62-36403). In this method, when a multicolor resin is produced, it is complicated to prepare a dye having a double bond as a raw material for each color, which is a problem in industrial production.

Furthermore, there is a method in which a methanol solution of the dye is added to the latex to absorb or adsorb the dye to the latex particles (Japanese Patent Application Laid-Open No. 63-170470). In addition, dyes that are soluble in methanol are limited, and the absorption / adsorption process has a long time, and in that method, it is difficult to contain a high concentration of dye in latex particles. there were.

Accordingly, it has been desired to develop a method for producing a colored aqueous resin dispersion which has good dispersion stability and can satisfy all of the color density and sharpness, and the particle size and shape uniformity.

[Means for solving the problem]

Under such circumstances, the present inventors have conducted intensive studies, and as a result, when producing a colored aqueous resin dispersion using a copolymer, using a hydrophilic organic solvent as a solvent for the copolymerization reaction,
Before or after the copolymerization reaction, a coloring dye capable of being uniformly dispersed in the resin particles was added, and then water was added to carry out phase inversion to solve the above-mentioned problems, and completed the present invention.

That is, the present invention reacts a monomer having a salt-forming group and a polymerizable double bond with a monomer having a polymerizable double bond copolymerizable therewith in a hydrophilic organic solvent solution. It is intended to provide a method for producing a colored aqueous resin dispersion, characterized in that a color dye is added before or after the polymerization reaction when water is added to the reaction solution to invert the phase.

Examples of the monomer having a salt-forming group and a polymerizable double bond used in the production method of the present invention include an anionic monomer such as an unsaturated carboxylic acid monomer, an unsaturated sulfonic acid monomer, and an unsaturated phosphoric acid monomer; Cationic monomers such as unsaturated tertiary amine-containing monomers and unsaturated ammonium salt-containing monomers; N- (3-sulfopropyl) -N-methacrylyloxyethyl-N, N-dimethylammonium betaine, N- (3 And amphoteric monomers such as-(sulfopropyl) -N-methacrylylamidopropyl-N, N-dimethylammonium betaine and 1- (3-sulfopropyl) -2-vinylpyridinium betaine.

Specific examples of these monomers include, among the anionic monomers, unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid or anhydrides thereof. Objects and the like.

Examples of the unsaturated sulfonic acid monomer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 3-sulfopropyl (meth) acrylate, bis- (3-sulfopropyl) -itaconate and salts thereof. And 2-hydroxyethyl (meth) acrylic acid sulfuric acid monoester and salts thereof.

As unsaturated phosphoric acid monomers, vinyl phosphonic acid,
Vinyl phosphate, acid phosphoxyethyl (meth) acrylate, 3-chloro-2-acid phosphooxypropyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, bis (methacryloxyethyl) phosphate, diphenyl-2- Methacryloyloxyethyl phosphate, diphenyl-2-acryloyloxyethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate, dibutyl-2
-Acryloyloxyethyl phosphate, dioctyl-2- (meth) acryloyloxyethyl phosphate, and the like.

Examples of the cationic monomer include monovinylpyridines such as vinylpyridine, 2-methyl-5-vinylpyridine and 2-ethyl-5-vinylpyridine; N, N-dimethylaminostyrene, N, N-dimethylaminostyrene and the like. Styrenes having a dialkylamino group of: N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminopropyl Methacrylate, N, N-dimethylaminopropyl acrylate, N, N-diethylaminopropyl methacrylate, N, N-diethylaminopropyl acrylate and other esters having a dialkylamino group of acrylic acid or methacrylic acid; 2-dimethylaminoethyl vinyl ether and the like Dialkylamino Vinyl ethers having a group: N- (N ', N'-dimethylaminoethyl) methacrylamide, N- (N', N'-dimethylaminoethyl) acrylamide, N- (N ', N'-diethylaminoethyl) methacryl Amide, N- (N ', N'-diethylaminoethyl) acrylamide, N- (N', N '
-Dimethylaminopropyl) methacrylamide, N-
Acrylamide having a dialkylamino group such as (N ', N'-dimethylaminopropyl) acrylamide, N- (N', N'-diethylaminopropyl) methacrylamide, N- (N ', N'-diethylaminopropyl) acrylamide or Methacrylamides or an alkyl halide thereof (having an alkyl group having 1 to 18 carbon atoms;
Chlorine, bromine, iodine as a halogen, benzyl halide such as benzyl chloride or benzyl bromide, alkyl ester of alkyl or aryl sulfonic acid such as methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid (alkyl group having 1 to 1 carbon atoms) 18) and quaternized with a known quaternizing agent such as dialkyl sulfate (alkyl group having 1 to 4 carbon atoms).

Further, the monomer having a double bond copolymerizable with the monomer having a salt-forming group and a polymerizable double bond used in the production method of the present invention is not particularly limited. For example, methyl acrylate, acrylic acid Ethyl, isopropyl acrylate, n-butyl acrylate, ibutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, acrylic acid Acrylic esters such as dodecyl; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, methacrylic acid n-octyl, 2-ethylhexyl methacrylate Methacrylates such as styrene, decyl methacrylate and dodecyl methacrylate; styrene-based monomers such as styrene, vinyl toluene, 2-methylstyrene, 1-butylstyrene and chlorostyrene; hydroxyethyl acrylate and hydroxypropyl acrylate A hydroxy group-containing monomer; N-substituted (meth) acrylic monomers such as N-methylol (meth) acrylamide and N-butoxymethyl (meth) acrylamide;
Epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; or the following formula: CH ₂ CHCHCOOC ₂ H ₄ C ₆ F ₁₃ , CH ₂ CHCHCOOC ₂ H ₄ C ₈ F ₁₇ , CH ₂ CHCHCOOC ₂ H ₄ C _{10 F 21, CH 2 = CHCOOC} 2 H 4 C 12 F 23, CH 2 = C (CH 3) COOC 2 H 4 C 6 F 13, CH 2 = C (CH 3) COOC 2 H 4 C 8 F 17, _{CH 2 = C (CH 3)} COOC 2 H 4 C 10 F 21, CH 2 = C (CH 3) COOC 2 H 4 C 12 F 23, CH 2 = CHCOOC 2 H 4 CF 2 6 H, CH 2 = CHCOOC _{2 H 4 CF 2 8 H,} CH 2 = C (CH 3) COOC 2 H 4 CF 2 6 H, CH 2 = C (CH 3) COOC 2 H 4 fluorinated alkyl group represented by CF _{2 8} H, etc. And (meth) acrylic acid esters containing them, and acrylonitrile and the like.

As the solvent for the copolymerization reaction in the present invention, a hydrophilic organic solvent is used, which preferably has a boiling point or an azeotropic point lower than the boiling point of water, for example, methanol, ethanol, n-propanol, isopropanol, n- Alcoholic solvents such as butanol, secondary butanol, tertiary butanol, isobutanol, diacetone alcohol and 2-iminoethanol; ketones such as acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, methyl isobutyl ketone and methyl isopropyl ketone Ester solvents such as ethyl acetate and propyl acetate; ether solvents such as dioxane and tetrahydrofuran, and isopropanol, acetone and methyl ethyl ketone are particularly preferable.

These hydrophilic organic solvents can be used alone or in appropriate combination of two or more kinds, and if necessary, a high boiling point hydrophilic organic solvent can be used in combination. Such high-boiling hydrophilic organic solvents include phenoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether,
Examples thereof include diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, and 3-methyl-3-methoxybutanol.

In order to copolymerize the above-mentioned monomer (A) having a salt-forming group and a polymerizable double bond with the monomer (B) having a polymerizable double bond copolymerizable therewith, The reaction is preferably performed at a weight ratio of (A) :( B) = 1: 49 to 1: 3. When the ratio of the monomer having a salt-forming group and having a polymerizable double bond is smaller than the above range, a colored aqueous resin having a small particle size and uniform and stable dispersion cannot be obtained. In such a case, a practically durable colored aqueous resin cannot be obtained, which is not preferable.

Further, in the production method of the present invention, the copolymerization reaction may be performed by a known polymerization method such as a solution polymerization method, a bulk polymerization method, and a precipitation polymerization method using a known radical initiator. For this reason, it is preferable to use a solution polymerization method and immediately proceed to the next step after polymerization. After the polymerization, the copolymer obtained before the phase inversion to the aqueous phase can be purified by a known method. The weight average molecular weight of the obtained copolymer is preferably 10,000 to 500,000, and 50,000
0 to 200,000 is more preferred. If the weight average molecular weight is less than 10,000, the physical properties of the coating film are inferior, and if it exceeds 500,000, phase inversion to an aqueous phase becomes difficult, and a colored aqueous resin dispersion cannot be obtained.

In the production method of the present invention, a colored aqueous resin dispersion having excellent dyeing properties and dispersion stability can be obtained by adding a coloring dye to the reaction solution before or after the copolymerization reaction. The coloring dye used here is not particularly limited as long as it is soluble in a hydrophilic organic solvent used as a solvent for the copolymerization reaction, for example, CI-10355, CI-110
00, CI-11005, CI-11020, CI-11160, CI-11350, CI
-11360, CI-11380, CI-11385, CI-11390, CI-1180
0, CI-11810, CI-11840, CI-11920, CI-12000, CI
-12005, CI-1255, CI-12100, CI-12150, CI-1217
0, CI-2620, CI-47000, CI-60505, CI-60725, CI
−61100, CI−61105, CI−61110, CI−61565, CI−6157
Colored dyes such as red, blue, and yellow, such as 0, CI-64500, and CI-52015, various colors obtained by mixing these, or black are used.

It is preferable to add these coloring dyes in such an amount as to contain about 0.01 to 20% by weight, especially 0.1 to 10% by weight in the intended colored aqueous resin dispersion.

Further, when the salt-forming group of the obtained copolymer is not ionized, ionization is carried out with a neutralizing agent as necessary. When a monomer that is already a salt is used as the monomer having a polymerizable double bond having a salt-forming group, ionization with a neutralizing agent is not necessary. It is preferable to use in a makeup cosmetic such as nail enamel, eyeshadow and the like because the colorized aqueous resin dispersion is less irritating to nails and skin because the resulting aqueous dispersion becomes less irritating to nails and skin.

As the neutralizer, a known acid or base may be used depending on the type of the salt-forming group. Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid; and organic acids such as acetic acid, propionic acid, lactic acid, succinic acid, and glycolic acid. Examples of the base include tertiary amines such as trimethylamine and triethylamine; ammonia, sodium hydroxide and the like. The degree of neutralization is not particularly limited, but it is preferable to neutralize the obtained colored aqueous resin dispersion so that the pH of the dispersion is near neutrality.

If water is added to the reaction solution and the phase is inverted, a colored aqueous resin dispersion is obtained. It is preferred that the hydrophilic organic solvent is removed from the phase-shifted colored aqueous resin dispersion by distillation, and the colored aqueous resin can be obtained as a powder by removing water by freeze-drying or the like. In this case, the copolymer is preferably one having a relatively high Tg, for example, one having a room temperature or higher.

[Action and effect of the invention]

The colored aqueous resin dispersion obtained by the production method of the present invention has good dyeing properties and dispersion stability, and also has excellent color density and sharpness. Paper, wood, leather, rubber, plastic, metal, glass, concrete, plaster, ceramic siding, AL
By impregnating it into a C plate or applying it to the surface, it can be colored and at the same time improve the performance such as surface coating, adhesion, and texture improvement. It can be used in fields where rubber latex and resin emulsions are generally applied. In addition to the immunological measurement utilizing the agglutination reaction of particles, the present invention can be applied to various sensors.

Furthermore, since the colored aqueous resin dispersion obtained by the production method of the present invention has a polymer surface-active action even in structural terms, it can be used as a binder and has a wide range of uses as a general surfactant. For example, protective colloids for emulsion polymerization,
It can be used as a dispersant, coagulant, binder, surface modifier and the like for various particles.

Further, the colored aqueous resin dispersion obtained by the production method of the present invention has excellent dispersibility when added to other systems, and can be used as a coloring material such as various liquids, paste-like dispersions and solutions. It can be formed into a solid colored product by adding it to a resin or the like and then molding it. In addition, since the resin particles themselves are colored with a coloring dye component capable of molecular dispersion, the dried product has excellent transparency, and can be applied to a color image forming colorant of a color copier, various terminal devices, and the like. is there.

Furthermore, since various functional groups derived from monomers having a salt-forming group and a polymerizable double bond are present on the surface of the colored aqueous resin dispersion obtained by the production method of the present invention, various functional substances By introducing the above, various other applications can be applied.

〔Example〕

Next, the present invention will be described specifically with reference to examples.
The present invention is not limited by this.

All parts and percentages in the examples are by weight unless otherwise specified.

Example 1 A reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet tube was charged with 100 parts of methyl ethyl ketone, and heated to 80 ° C. under a nitrogen gas stream.

Subsequently, 47 parts of methyl methacrylate from which dissolved oxygen had been removed in advance, 49 parts of n-butyl acrylate, 4 parts of acrylic acid and 0.2 part of 2,2′-azobisisobutyronitrile were charged into the dropping funnel, and a nitrogen gas stream was supplied. It is added dropwise over 2 hours.
After the completion of the dropwise addition, the mixture was further heated for 2 hours, a solution prepared by dissolving 0.2 part of 2,2'-azobisisobutyronitrile in 5 parts of methyl ethyl ketone was added, and the mixture was further heated for 5 hours to remove the acrylic copolymer solution. Obtained.

The copolymer solution was neutralized by adding 4 parts of 2-amino-2-methyl-1-propanol, and furthermore, CI-11350 (CI So
lvent Yellow 4) 0.5 part and 200 parts of methyl ethyl ketone were added and stirred. After adding 500 parts of ion-exchanged water and inverting the phase, methyl ethyl ketone was distilled off at 40 ° C. under reduced pressure to give an orange transparent colored aqueous resin dispersion (solid content: 30%, colored dye content: 0.15 %).

Example 2 The same reactor as in Example 1 was charged with 80 parts of isopropanol and heated to 80 ° C. under a stream of nitrogen gas.

Subsequently, 30 parts of t-butyl methacrylate from which dissolved oxygen was previously removed from the dropping funnel, 62 parts of ethyl acrylate, N, N-
Dimethylaminoethyl methacrylate 4 parts and 2,2'-
Azobis (2,4-dimethylvaleronitrile) (0.1 part) is charged and added dropwise over 3 hours under a nitrogen gas stream. After the completion of the dropwise addition, the mixture was further heated for 3 hours, a solution prepared by dissolving 0.2 part of 2,2'-azobis (2,4-dimethylvaleronitrile) in 5 parts of isopropanol was added, and the mixture was further heated for 8 hours to continue the acrylic copolymer. A polymer solution was obtained.

The copolymer solution was neutralized by adding 3 parts of acetic acid.
One part of -12510 (CI Solvent Red 1) and 150 parts of isopropanol were added and stirred. Here, 400 parts of ion-exchanged water was added, and after phase inversion, isopropanol was distilled off at 40 ° C. under reduced pressure to give a red translucent colored aqueous resin dispersion (solid content: 3
2%, coloring dye content: 0.35%).

Example 3 The same reactor as in Example 1 was charged with 100 parts of acetone,
The mixture was heated to 70 ° C. under a stream of nitrogen gas.

Subsequently, 20 parts of styrene in which dissolved oxygen was previously removed from the dropping funnel, 30 parts of acrylonitrile, 100 parts of 2-ethylhexyl methacrylate, 50 parts of dimethylacrylamide and 2,2 parts
1 part of 2'-azobisisobutyronitrile is charged and added dropwise over 2 hours under a stream of nitrogen gas. After completion of the dropwise addition, the mixture was further heated for 3 hours, a solution prepared by dissolving 1 part of 2,2'-azobisisobutyronitrile in 10 parts of acetone was added, and the mixture was further heated for 5 hours to obtain a copolymer solution. .

CI-11360 (CI Solvent Brown) was added to this copolymer solution.
3) 1 part and 200 parts of acetone were added and stirred. here,
After adding 800 parts of ion-exchanged water and inverting the phase, acetone is distilled off at 40 ° C. under reduced pressure, and a brown translucent colored aqueous resin dispersion (solid content: 28%, colored dye content: 0.30%) I got

Example 4 97 parts of methyl methacrylate was placed in a reactor similar to that of Example 1,
80 parts of n-butyl acrylate, 23 parts of acrylic acid and 2 parts of benzoyl peroxide were added, stirred, and heated to 90 ° C. under a nitrogen gas stream. The polymerization is continued for about 1 hour, and the viscosity becomes 1 poise (90
℃), quenched to room temperature with ice water, solid content about
A 25% syrup is obtained.

110 g of this syrup is put on two tempered glass plates (200 × 200 ×
5 mm) was framed with a soft vinyl chloride resin tube, injected into a reactor fixed with a metal plate to a thickness of 4 mm, heated at 50 ° C. for 6 hours, and further heated at 100 ° C. for 2 hours. After cooling,
100 parts of the bulk polymer was taken out and dissolved in 150 parts of methyl ethyl ketone to obtain a copolymer solution.

The copolymer solution was neutralized by adding 10 parts of 2-amino-2-methyl-1-propanol, and furthermore, CI-11350 (IC So
lvent Yellow 4) 3 parts and methyl ethyl ketone 200 parts were added and stirred. After adding 500 parts of ion-exchanged water and inverting the phase, methyl ethyl ketone was distilled off at 40 ° C. under reduced pressure to give an orange translucent colored aqueous resin dispersion (solid content: 29%,
(Colored dye content: 1.0%).

Comparative Example 1 100 parts of methyl ethyl ketone was charged into a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet tube, and heated to 80 ° C. under a nitrogen gas stream.

Subsequently, 47 parts of methyl methacrylate from which dissolved oxygen had been removed in advance, 49 parts of n-butyl acrylate, 4 parts of acrylic acid and 0.2 part of 2,2′-azobisisobutyronitrile were charged into the dropping funnel, and a nitrogen gas stream was supplied. It is added dropwise over 2 hours.
After the completion of the dropwise addition, the mixture was further heated for 2 hours, a solution prepared by dissolving 0.2 part of 2,2'-azobisisobutyronitrile in 5 parts of methyl ethyl ketone was added, and the mixture was further heated for 5 hours to remove the acrylic copolymer solution. Obtained.

The copolymer solution was neutralized by adding 4 parts of 2-amino-2-methyl-1-propanol, and 200 parts of methyl ethyl ketone was further added and stirred. After adding 500 parts of ion-exchanged water thereto and inverting the phase, methyl ethyl ketone was distilled off at 40 ° C. under reduced pressure to obtain a transparent aqueous resin dispersion. This is CI-
Add 0.5 part of 11350 (CI Solvent Yellow 4) and stir,
An orange translucent colored aqueous resin dispersion (solid content: 30%, coloring dye content: 0.15%) was obtained.

Comparative Example 2 The same reactor as in Comparative Example 1 was charged with 100 parts of toluene.
The mixture was heated to 80 ° C. under a nitrogen gas stream.

Subsequently, 47 parts of methyl methacrylate from which dissolved oxygen had been removed in advance, 49 parts of n-butyl acrylate, 4 parts of acrylic acid and 0.2 part of 2,2′-azobisisobutyronitrile were charged into the dropping funnel, and a nitrogen gas stream was supplied. It is added dropwise over 2 hours.
After completion of the dropwise addition, the mixture was further heated for 2 hours, a solution prepared by dissolving 0.2 part of 2,2'-azobisisobutyronitrile in 5 parts of toluene was added, and the mixture was further heated for 5 hours to remove the acrylic copolymer solution. Obtained.

The copolymer solution was neutralized by adding 4 parts of 2-amino-2-methyl-1-propanol, and furthermore, CI-11350 (CI So
lvent Yellow 4) 0.5 part and toluene 200 parts were added and stirred. Here, 500 parts of ion-exchanged water was added, and after phase inversion, toluene was distilled off at 40 ° C. under reduced pressure to give a yellow-white colored aqueous resin dispersion (solid content: 28%, colored dye content: 0.15 %).

Test Example 1 Stationary stability test: After the colored aqueous resin dispersions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were allowed to stand at room temperature for one month, respectively, the state of the appearance was observed. In Examples 1 to 4, there was no change, but Comparative Example 1 showed a small amount of precipitate, and Comparative Example 2 showed separation and a large amount of precipitate.

Test Example 2 Dilution stability test: The colored aqueous resin dispersions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each diluted so that the solid content was 1%,
This was placed in a glass tube having an inner diameter of 7 mm and a length of 30 cm and sealed. After standing at room temperature for 24 hours, the appearance was observed. Examples 1 to 4 showed no change, but Comparative Example 1 showed a small amount of precipitate, and Comparative Example 2 showed separation and large amount. Precipitate was seen.

Test Example 3 Judgment test for gloss: The colored aqueous resin dispersions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each applied to a glass plate using a 0.254 mm applicator. The gloss after drying at room temperature for 3 hours was measured using a gloss meter manufactured by Murakami Color Materials Co., Ltd., and it was found that Examples 1-4 had better gloss than the uncoated glass plate. Examples 1 and 2 were less glossy than the uncoated glass plate.

Test Example 4 Transparency Judgment Test: The colored aqueous resin dispersions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were each applied to a glass plate using a 0.254 mm applicator. Observation of the transparency after drying at room temperature for 3 hours showed that Examples 1 to 4 had good transparency, but Comparative Examples 1 and 2 had very poor transparency.

Claims (3)

(57) [Claims] 1. A monomer having a salt-forming group and a polymerizable double bond in a hydrophilic organic solvent solution of a coloring dye, and a monomer having a polymerizable double bond copolymerizable therewith. And adding water to the reaction solution to cause phase inversion, thereby producing a colored aqueous resin dispersion. 2. A reaction between a monomer having a salt-forming group and a polymerizable double bond and a monomer having a polymerizable double bond copolymerizable therewith in a hydrophilic organic solvent solution. And dissolving the coloring dye in the reaction solution, and then adding water to invert the phase to produce a colored aqueous resin dispersion. 3. The method according to claim 1, wherein a neutralizing agent is added to the reaction solution.
A method for producing the colored aqueous resin dispersion according to the above.