JP3111815B2 - Pre-crosslinked fine particle aqueous dispersion and production method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-resolution, high-sensitivity resist material useful in the manufacture of printed circuit boards, printing plates, semiconductor elements, etc., or as a flow control agent or binder for paints and printing inks, or as an adhesive. Alternatively, the present invention relates to a crosslinked fine particle aqueous dispersion which can be used as a cement admixture and further as an organic filler, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, an aqueous dispersion of crosslinked fine particles is produced by an emulsion polymerization method or a suspension polymerization method, and the use of an emulsifier and a dispersion stabilizer is essential. However, the emulsifier and dispersion stabilizer used are water-resistant of the film after drying,
There is a tendency for adverse effects such as a decrease in adhesion and adhesion. Further, in the conventional method, the particle size of the crosslinked fine particles is mainly controlled by the emulsifier and the dispersion stabilizer, and disadvantages such as the amount and type of the emulsifier and the dispersion stabilizer to be used differ depending on the target particle size. Has occurred. In addition, in controlling the particle size by suspension polymerization, there is a problem that the operation becomes complicated due to large mechanical elements.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aqueous dispersion of crosslinked fine particles which does not use an emulsifier or a dispersion stabilizer which lowers the water resistance, adhesion and adhesion of a dried film, and a process for producing the same. Is to provide.

[0004]

That is, the present invention provides:
0.1 to 90% by weight of a monomer (A) having two or more α, β-ethylenically unsaturated double bonds, and N- (3-sulfopropyl) -N-methacrylyloxyethyl-N, N-
At least one selected from the group consisting of dimethylammonium betaine, N- (3-sulfopropyl) -N-methacrylylamidopropyl-N, N-dimethylammonium betaine, and 1- (3-sulfopropyl) -2-vinylpyridinium betaine One amphoteric monomer, α, β
-Ethylenically unsaturated carboxylic acids and salts thereof, unsaturated sulfonic acids and salts thereof, unsaturated phosphoric acid monomers, monovinylpyridines, styrenes having dialkylamino groups, esters having dialkylamino groups of (meth) acrylic acid, 99.9 to 10% by weight of at least one other aqueous monomer (b) selected from the group consisting of vinyl ethers having a dialkylamino group, (meth) acrylamides having a dialkylamino group, and quaternized products thereof % In a solvent in which the monomer is homogeneously dissolved and the crosslinked fine particles obtained by polymerizing the monomer become insoluble in the absence of a dispersion stabilizer. Is obtained by inverting phase into an aqueous system, the particle size is 0.01 μm to 30 μm.
To provide an aqueous dispersion of crosslinked fine particles.

Aqueous monomers (a) having two or more α, β-ethylenically unsaturated double bonds include ethylene oxide (hereinafter referred to as EO) -modified di (meth) acrylate phosphate and EO-modified tri (phosphate) Anionic polyfunctional monomers such as (meth) acrylates, polyethylene glycol di (meth) acrylate, tri (meth) acrylate,
A nonionic polyfunctional monomer such as tetra (meth) acrylate may be mentioned, but it may be basically an aqueous polyfunctional monomer, and is not particularly limited thereto.
These may be used alone or in combination of two or more.

As the monomer (A) having two or more α, β-ethylenically unsaturated double bonds, in addition to the aqueous polyfunctional monomer exemplified as the aqueous monomer (a),
Trimethylolpropane tri (meth) acrylate, di (meth) acrylate of glycols, di (meth) acrylate of polyol, tri (meth) acrylate, tetra (meth) acrylate, polyurethane Di (meth) acrylate, tri (meth) acrylate, tetra (meth)
Acrylic esters, polyester di (meth) acrylates, tri (meth) acrylates, tetra (meth) acrylates, butadiene, isoprene, chloroprene, divinylbenzene and the like can be mentioned.
These monomers can be used alone or in combination of two or more.

Other aqueous monomers (b) copolymerizable with the monomer (A) having two or more α, β-ethylenically unsaturated double bonds include N- (3-sulfopropyl) -N
-Methacrylyloxyethyl-N, N-dimethylammonium betaine, N- (3-sulfopropyl) -N-methacrylamidopropyl-N, N-dimethylammonium betaine, 1- (3-sulfopropyl) -2-vinyl Amphoteric monomers such as pyridinium betaine; α, β-ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, maleic anhydride and itaconic anhydride And salts thereof; styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3
Unsaturated sulfonates such as -sulfopropyl (meth) acrylic acid ester and bis- (3-sulfopropyl) -itaconic acid ester and salts thereof; 2-hydroxyethyl (meth) acrylic acid monoester sulfate and salts thereof Vinyl sulfonic acid, vinyl phosphate, acid phosphoxyethyl (meth) acrylate, 3-chloro-2-acid phosphooxypropyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, bis (methacryloxyethyl) Unsaturated phosphate monomers such as phosphate, diphenyl-2-acryloyloxyethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate, dioctyl-2- (meth) acryloyloxyethyl phosphate; Jin, 2-methyl-5-vinylpyridine, mono vinylpyridine such as 2-ethyl-5-vinylpyridine; N, N-dimethylamino styrene,
Styrenes having a dialkylamino group such as N, N-dimethylaminoaminomethylstyrene; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl ( Esters having a dialkylamino group of (meth) acrylic acid such as meth) acrylate and N, N-diethylaminopropyl (meth) acrylate; 2
Vinyl ethers having a dialkylamino group such as -dimethylaminoethyl vinyl ether; N- (N ', N'
-Dimethylaminoethyl) methacrylamide, N-
(N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N′-diethylaminoethyl) methacrylamide, N- (N ′, N′-diethylaminoethyl) acrylamide, N- (N ′, N ′) -Dimethylaminopropyl) methacrylamide, N- (N ', N'-dimethylaminopropyl) acrylamide, (N', N '
-Diethylaminopropyl) methacrylamide,
(Meth) acrylamides having a dialkylamino group such as (N ′, N′-diethylaminopropyl) acrylamide or the like, or an alkyl halide (having 1 to 18 carbon atoms in the alkyl group, chlorine, bromine as halogen,
Iodine), benzyl halide, for example, benzyl chloride or benzyl bromide, alkyl or aryl sulfonic acid, for example, alkyl ester of methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid (alkyl group having 1 to 18 carbon atoms), dialkyl sulfate ( Those quaternized with a known quaternizing agent such as an alkyl group having 1 to 4 carbon atoms can be used. These can be used alone or in combination of two or more.

When polymerizing the aqueous monomer (a) having two or more α, β-ethylenically unsaturated double bonds, another monomer (B) copolymerizable with the aqueous monomer (a) is used in combination. be able to. As the other monomer (B), in addition to the aqueous monomer (b), methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylic N-butyl acid, isobutyl (meth) acrylate,
N-Amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, (meth)
2-ethylhexyl acrylate, (meth) acrylic acid n
Acrylates such as octyl, decyl (meth) acrylate, dodecyl (meth) acrylate; styrene,
Styrene-based monomers such as vinyl toluene, 2-methylstyrene, 1-butylstyrene and chlorostyrene; hydroxy-containing monomers such as hydroxyethyl acrylate and hydroxypropyl acrylate; N-methylol (meth) acrylamide, N-butoxymethyl ( N-substituted (meth) acrylic monomers such as (meth) acrylamide;
Epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, CH ₂ ＣＨCHCOOC ₂ H ₄ C
_{6 F 13, CH 2 = CHCOOC} 2 H 4 C 8 F 17, CH 2
ＣＨCHCOOC ₂ H ₄ C ₁₀ F ₂₁ , CH ₂ ＣＨCHCOOC
_{2 H 4 C 12 F 25,} 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, C
_{H 2 = C (CH 3)} COOC 2 H 4 C 12 F 25, CH 2 =
CHCOOC ₂ H ₄ (CF ₂ ) ₆ H, CH ₂ ＣＨCHCO
OC ₂ H ₄ (CF ₂ ) ₈ H, CH ₂ ＣC (CH ₃ ) CO
OC ₂ H ₄ (CF ₂ ) ₆ H, CH ₂ ＣC (CH ₃ ) CO
Examples thereof include (meth) acrylic acid esters having a fluorinated alkyl group represented by OC ₂ H ₄ (CF ₂ ) ₈ H and acrylonitrile. These are one or two
More than one species can be used in combination.

Solvents used in the present invention include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and t-butanol; ethyl acetate and butyl acetate. Esters such as acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, and methyl amyl ketone; and organic solvents such as saturated hydrocarbons such as n-hexane and n-octane. However, water-soluble organic solvents such as water-soluble alcohols such as methanol, ethanol, n-propanol and isopropanol, and water-soluble ketones such as acetone and methyl ethyl ketone are preferable, and ethanol, isopropanol and acetone are more preferable. . These solvents can be used alone or as a mixture of two or more kinds. Further, a water-soluble organic solvent can be used as a mixed solvent with water.

[0010]

The homogeneous and stable crosslinked fine particle dispersion is prepared by dissolving 0.1 to 90% by weight of a monomer (A) and 99.9 to 10% by weight of another aqueous monomer (b). In the solvent in which the crosslinked fine particles obtained by polymerizing the monomer become insoluble, a radical initiator of 0.05 to 10% by weight based on the total amount of the monomer and, if necessary, substantially in the absence of a dispersion stabilizer, and By radical copolymerization using a chain transfer agent. The amount of the monomer (A) in all the monomers is preferably in the range of 0.1 to 50% by weight. Thereafter, if necessary, water is added to the crosslinked fine particle dispersion, and then a part or all of the organic solvent is distilled off and the phase is changed to an aqueous phase to obtain a particle size of 0.01 μm to 30 μm.
A crosslinked fine particle dispersion of μm is obtained.

Examples of the radical initiator include hydroperoxides represented by t-butylhydroxyperoxide; dialkyl peroxides represented by di-t-butyl peroxide; and diacyls represented by acetyl peroxide. Peresters represented by t-butyl peracetate; ketone peroxides represented by methyl ethyl ketone peroxide; 2,2′-azobis (isobutyronitrile);
2′-azobis (2,4-dimethylvaleronitrile),
An azo polymerization initiator represented by 1,1′-azobis (cyclohexane-1-carbonitrile) and the like are exemplified.

Before inverting the crosslinked fine particle dispersion into an aqueous system, it is preferable to neutralize the aqueous monomer with a neutralizing agent in an amount of 0 to 1.5 equivalents, more preferably 0.05 to 1 equivalent, based on the aqueous monomer. it can. Depending on the amount of the neutralizing agent used, the particle size of the obtained crosslinked fine particle aqueous dispersion can be adjusted between 0.01 μm and 30 μm.

When the aqueous monomer has an acidic group,
Examples of the neutralizing agent include metal hydroxides such as sodium hydroxide and potassium hydroxide, methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine and laurylamine. ,
Myristylamine, cetylamine, stearylamine,
Oleylamine, cyclohexylamine, monoethanolamine, diethylamine, di- (n-propyl) amine, diamylamine, diethanolamine, triethylamine, triethanolamine, N, N-dimethylethanolamine, aniline, benzylamine, o-toluidine, 2-ethyl Aniline, 2-fluoroaniline, o
-Anisidine, m-toluidine, m-anisidine, m-
Phenetidine, p-toluidine, 2,3-dimethylaniline, 5-aminoindan, piperidine, morpholine,
Organic amines such as pyrrolidine, pyrrole, indole, indoline, imidazole, triazole, pyrimidine, pyrazine, pyridine, imidazoline laurate, imidazoline oleate, and polyoxypropyleneamine are used. Further, when the aqueous monomer has a basic group, as the neutralizing agent, hydrochloric acid, hydrobromic acid, sulfuric acid,
Inorganic acids such as phosphoric acid and boric acid, and organic acids such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid are used, but not particularly limited thereto. These neutralizers can be used alone or in combination of two or more.

[0015]

Next, the present invention will be specifically described with reference to examples. In the examples, all parts and percentages are by weight unless otherwise specified. The particle size distribution was measured using a laser diffraction light scattering particle size meter (“DLS700” manufactured by Otsuka Electronics Co., Ltd.).

(Production Example 1) In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet tube, 950 parts of isopropanol and EO-modified phosphoric diacrylate (manufactured by Daihachi Chemical Industry Co., Ltd.) AR-200 ") 50 parts,
Dissolve dissolved oxygen by flowing nitrogen gas. After heating the reactor to 80 ° C., 2 parts of azobisisobutyronitrile was added, and heating was continued for further 6 hours to obtain a crosslinked fine particle dispersion.
The dispersion had a solids content of 5%, a viscosity of 120 cps and a particle size of 0,0.
It was a 6 μm crosslinked fine particle dispersion.

(Production Example 2) In the same reactor as in Production Example 1,
900 parts of isopropanol, 50 methyl methacrylate
And 50 parts of EO-modified diphosphoric phosphate ("MR-200" manufactured by Daihachi Chemical Industry Co., Ltd.), and nitrogen gas is flowed to remove dissolved oxygen. After heating the reactor to 80 ° C., 4 parts of azobisisobutyronitrile was added, and heating was continued for further 6 hours to obtain a crosslinked fine particle dispersion. The dispersion was a crosslinked fine particle dispersion having a solid content of 10%, a viscosity of 150 cps, and a particle size of 0.8 μm.

(Production Example 3) In the same reactor as in Production Example 1,
900 parts of isopropanol, 70 parts of acrylic acid, and 30 parts of divinylbenzene are charged, and nitrogen gas is flowed to remove dissolved oxygen. After heating the reactor to 80 ° C., 4 parts of azobisisobutyronitrile was added, and heating was continued for another 6 hours.
A crosslinked fine particle dispersion was obtained. The dispersion has a solid content of 10
%, A viscosity of 100 cps, and a particle size of 0.2 μm.

(Production Example 4) In the same reactor as in Production Example 1,
700 parts of isopropanol, 150 parts of N, N-dimethylaminoethyl methacrylate, and 150 parts of ethylene glycol dimethacrylate are charged, and nitrogen gas is flowed to remove dissolved oxygen. After heating the reactor to 80 ° C., 6 parts of azobisisobutyronitrile was added, and heating was continued for further 6 hours to obtain a crosslinked fine particle dispersion. The dispersion has a solid content of 3.
It was a crosslinked fine particle dispersion having 0%, a viscosity of 120 cps and a particle size of 0.3 μm.

(Production Example 5) In the same reactor as in Production Example 1,
500 parts of ethanol, 200 parts of water, 200 parts of acid phosphoxyethyl acrylate, 100 parts of divinylbenzene
A portion is charged, and nitrogen gas is flowed to remove dissolved oxygen. After heating the reactor to 80 ° C., 6 parts of azobisisobutyronitrile was added, and heating was continued for further 6 hours to obtain a crosslinked fine particle dispersion. The dispersion has a solid content of 30% and a viscosity of 60 cp.
s, a crosslinked fine particle dispersion having a particle size of 0.3 μm.

(Production Example 6) In the same reactor as in Production Example 1,
900 parts of isopropanol, 70 parts of acrylic acid, and 30 parts of styrene are charged, and nitrogen gas is flowed to remove dissolved oxygen. After heating the reactor to 80 ° C., 4 parts of azobisisobutyronitrile was added and heating was continued for further 6 hours to obtain a resin solution having a solid content of 10% and a viscosity of 120 cps.

(Production Example 7) In the same reactor as in Production Example 1,
900 parts of isopropanol, methyl methacrylate 70
And 30 parts of divinylbenzene, and nitrogen gas is passed to remove dissolved oxygen. After heating the reactor to 80 ° C., 4 parts of azobisisobutyronitrile was added, and heating was continued for further 6 hours to obtain a crosslinked fine particle dispersion. The dispersion was a crosslinked fine particle dispersion having a solid content of 10%, a viscosity of 110 cps, and a particle size of 0.9 μm.

Table 1 summarizes the properties, solid content ratio, viscosity and particle size of the crosslinked fine particle dispersion and the resin solution obtained in the Production Examples.

[Table 1]

Comparative Example 6 To 100 parts of the crosslinked fine particle dispersion obtained in Production Example 1, 95 parts of water and 0.7 part of sodium hydroxide (1 equivalent to an aqueous monomer) were added, and an organic solvent was added. By distilling off and inverting the phase to an aqueous system, an aqueous dispersion of crosslinked fine particles was obtained. The obtained crosslinked fine particle aqueous dispersion has a particle size of 0.6 μm and a pH of 8.
0, a solid content of 5%, and a milky white aqueous dispersion having a viscosity of 100 cps.

Comparative Example 7 An aqueous dispersion of crosslinked fine particles was obtained in the same manner as in Comparative Example 6, except that the sodium hydroxide was changed to 0.4 part (0.5 equivalent to the aqueous monomer). The obtained crosslinked fine particle aqueous dispersion had a particle size of 1.3 μm, a pH of 5.4, and a solid content of 5%.
It was a milky white aqueous dispersion having a viscosity of 60 cps.

Comparative Example 8 An aqueous dispersion of crosslinked fine particles was obtained in the same manner as in Comparative Example 6, except that sodium hydroxide was changed to 0.2 part (0.25 equivalents to the aqueous monomer). The obtained crosslinked fine particle aqueous dispersion had a particle size of 2.5 μm, a pH of 4.3, and a solid content of 5 μm.
%, A milky-white aqueous dispersion having a viscosity of 30 cps.

Example 9 An aqueous dispersion of crosslinked fine particles was obtained in the same manner as in Comparative Example 6, except that sodium hydroxide was changed to 0.1 part (0.125 equivalent to the aqueous monomer). The obtained aqueous dispersion of crosslinked fine particles had a particle size of 4.2 μm, a pH of 3.9, and a solid content of 5 μm.
%, A milky-white aqueous dispersion having a viscosity of 10 cps.

Comparative Example 10 To 100 parts of the crosslinked fine particle dispersion obtained in Production Example 2, 90 parts of water and 1.4 parts of N, N, -dimethylethanolamine (1 equivalent to the aqueous monomer) were added. In addition, the organic solvent was distilled off and the phase was changed to an aqueous phase to obtain an aqueous dispersion of crosslinked fine particles. The crosslinked fine particle aqueous dispersion obtained has a particle size of 0.3.
This was a milky white aqueous dispersion having a particle size of 8 μm, a pH of 8.7, a solid content of 11%, and a viscosity of 60 cps.

Comparative Example 11 The aqueous dispersion of crosslinked fine particles was prepared in the same manner as in Comparative Example 10 except that N, N, -dimethylethanolamine was changed to 0.7 part (0.5 equivalent relative to the aqueous monomer). I got a body. The obtained crosslinked fine particle aqueous dispersion had a particle size of 1.7 μm and a pH of 1.7 μm.
It was a milky white aqueous dispersion having a particle size of 5.6, a solid content of 11% and a viscosity of 50 cps.

Comparative Example 12 The same procedure as in Comparative Example 10 was carried out except that the amount of N, N, -dimethylethanolamine was changed to 0.4 part (0.25 equivalent relative to the aqueous monomer). I got a body. The obtained crosslinked fine particle aqueous dispersion had a particle size of 2.5 μm and a pH of 2.5 μm.
It was a milky-white aqueous dispersion having a solid content of 5.0, a solid content of 10%, and a viscosity of 25 cps.

Comparative Example 13 The same procedure as in Comparative Example 10 was carried out except that the amount of N, N, -dimethylethanolamine was changed to 0.2 part (0.125 equivalent relative to the aqueous monomer). I got a body.
The aqueous dispersion of crosslinked fine particles obtained had a particle size of 4.0 μm, p
H4.1, a solid content of 10%, and a milky white aqueous dispersion having a viscosity of 20 cps.

Example 1 90 parts of water and 3.9 parts of sodium hydroxide (1 equivalent to an aqueous monomer) were added to 100 parts of the crosslinked fine particle dispersion obtained in Production Example 3, and an organic solvent was added. By distilling off and inverting the phase to an aqueous system, an aqueous dispersion of crosslinked fine particles was obtained. The obtained crosslinked fine particle aqueous dispersion has a particle size of 0.5 μm and a pH of 8.0.
2. A milky white aqueous dispersion having a solid content of 10% and a viscosity of 30 cps.

Example 2 An aqueous dispersion of crosslinked fine particles was obtained in the same manner as in Example 1 except that the amount of sodium hydroxide was changed to 1.9 parts (0.5 equivalent relative to the aqueous monomer). The obtained crosslinked fine particle aqueous dispersion had a particle size of 1.1 μm, a pH of 5.5, and a solid content of 10 μm.
%, A milky-white aqueous dispersion having a viscosity of 25 cps.

Example 3 1 part of sodium hydroxide (0.2 part based on aqueous monomer)
Except for changing to 5 equivalents, an aqueous dispersion of crosslinked fine particles was obtained in the same manner as in Example 1. The obtained crosslinked fine particle aqueous dispersion was a milky white aqueous dispersion having a particle size of 2.1 μm, a pH of 4.9, a solid content of 10%, and a viscosity of 20 cps.

Example 4 An aqueous dispersion of crosslinked fine particles was obtained in the same manner as in Example 1 except that sodium hydroxide was changed to 0.5 part (0.125 equivalents to the aqueous monomer). The crosslinked fine particle aqueous dispersion obtained had a particle size of 4.0 μm, a pH of 4.2, and a solid content of 1.
It was a milky white aqueous dispersion having a viscosity of 0% and a viscosity of 10 cps.

Example 5 70 parts of water and 7.2 parts of industrial acetic acid (80% acetic acid) (1 equivalent to an aqueous monomer) were added to 100 parts of the crosslinked fine particle dispersion obtained in Production Example 4. In addition, the organic solvent was distilled off and the phase was changed to an aqueous phase to obtain an aqueous dispersion of crosslinked fine particles.
The obtained crosslinked fine particle aqueous dispersion has a particle size of 0.4 μm, p
H3.5, milky white aqueous dispersion having a solid content of 29% and a viscosity of 30 cps.

Example 6 An aqueous dispersion of crosslinked fine particles was obtained in the same manner as in Example 5, except that the industrial acetic acid was changed to 3.6 parts (0.5 equivalent to the aqueous monomer). The resulting crosslinked fine particle aqueous dispersion had a particle size of 1.2 μm, a pH of 7.2, a solid content of 30%, and a viscosity of 2
It was a milky white aqueous dispersion of 0 cps.

Example 7 1.8 parts of industrial acetic acid (0.25 parts based on aqueous monomer)
(Equivalent weight), except that an aqueous dispersion of crosslinked fine particles was obtained in the same manner as in Example 5. The obtained crosslinked fine particle aqueous dispersion was a milky white aqueous dispersion having a particle size of 2.9 μm, a pH of 8.5, a solid content of 30%, and a viscosity of 10 cps.

Example 8 0.9 parts of industrial acetic acid (0.12 parts based on aqueous monomer)
Except for changing to 5 equivalents), an aqueous dispersion of crosslinked fine particles was obtained in the same manner as in Example 5. The obtained crosslinked fine particle aqueous dispersion was a milky white aqueous dispersion having a particle size of 6.0 μm, a pH of 9.7, a solid content of 30%, and a viscosity of 10 cps.

Example 9 To 100 parts of the crosslinked fine particle dispersion obtained in Production Example 5, 50 parts of water and 30.4 parts of triethanolamine (1 equivalent to the aqueous monomer) were added, and an organic solvent was added. By distilling off and inverting the phase to an aqueous system, an aqueous dispersion of crosslinked fine particles was obtained. The obtained crosslinked fine particle aqueous dispersion had a particle size of 1.2 μm,
It was a milky-white aqueous dispersion having a solid content of 8.5, a solid content of 35%, and a viscosity of 120 cps.

Example 10 An aqueous dispersion of crosslinked fine particles was obtained in the same manner as in Example 9 except that the amount of triethanolamine was changed to 15.2 parts (0.5 equivalents to the aqueous monomer). The obtained aqueous dispersion of crosslinked fine particles had a particle size of 2.4 μm, a pH of 5.8, and a solid content of 3.
It was a milky-white aqueous dispersion having a viscosity of 5% and a viscosity of 80 cps.

Example 11 An aqueous dispersion of crosslinked fine particles was obtained in the same manner as in Example 9 except that the amount of triethanolamine was changed to 7.6 parts (0.25 equivalent relative to the aqueous monomer). The obtained aqueous dispersion of crosslinked fine particles had a particle size of 4.8 μm, a pH of 3.1, and a solid content of 3.
It was a milky white aqueous dispersion having a viscosity of 3% and a viscosity of 50 cps.

Example 12 An aqueous dispersion of crosslinked fine particles was obtained in the same manner as in Example 9 except that only water was added without adding triethanolamine. The obtained crosslinked fine particle aqueous dispersion has a particle size of 8.8 μm.
m, pH 2.1, solid content 30%, viscosity 20 cps.

Comparative Example 1 To 100 parts of the resin solution obtained in Production Example 6, 90 parts of water and 3.9 parts of sodium hydroxide (1 equivalent to an aqueous monomer) were added, and the organic solvent was distilled off. An aqueous resin solution was obtained by phase inversion to an aqueous system. The resulting aqueous resin solution was a colorless and transparent aqueous resin solution having a pH of 8.2, a solid content of 10%, and a viscosity of 40 cps.

Comparative Example 2 The procedure of Comparative Example 1 was repeated, except that the amount of sodium hydroxide was changed to 1.9 parts (0.5 equivalents with respect to the aqueous monomer). did.

Comparative Example 3 The procedure of Comparative Example 1 was repeated except that the amount of sodium hydroxide was changed to 1 part (0.25 equivalent to the amount of the aqueous monomer).

Comparative Example 4 The same procedure as in Comparative Example 1 was carried out except that the sodium hydroxide was changed to 0.5 part (0.125 equivalent to the aqueous monomer). did.

[Comparative Example 5] 100 parts of water was added to 100 parts of the crosslinked fine particle dispersion obtained in Production Example 7, and the mixture gelled.

The properties, solid content ratio, viscosity, and the like of the crosslinked fine particle aqueous dispersions and resin solutions obtained in Examples and Comparative Examples were
The particle sizes are summarized in Table 2.

[Table 2]

[0050]

The crosslinked fine particle aqueous dispersion of the present invention can be used not only as an organic filler but also as reactive fine particles utilizing functional groups to paints, inks and plastics to impart various properties. Is possible.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 6/06 C08F 2/06

Claims (2)

(57) [Claims] (1) 0.1 to 90% by weight of a monomer (A) having two or more α, β-ethylenically unsaturated double bonds;
(3-Sulfopropyl) -N-methacrylyloxyethyl-N, N-dimethylammonium betaine, N- (3
-Sulfopropyl) -N-methacrylylamidopropyl-N, N-dimethylammonium betaine, and 1-
At least one amphoteric monomer selected from the group consisting of (3-sulfopropyl) -2-vinylpyridinium betaine, α, β-ethylenically unsaturated carboxylic acids and salts thereof, unsaturated sulfonic acids and salts thereof, Unsaturated phosphoric acid monomers, monovinylpyridines, styrenes having a dialkylamino group, esters having a dialkylamino group of (meth) acrylic acid, vinyl ethers having a dialkylamino group, and (meth) acrylamides having a dialkylamino group Alternatively, 99.9 to 10% by weight of at least one other aqueous monomer (b) selected from the group consisting of quaternized products is obtained by homogeneously dissolving the monomer and polymerizing the monomer. Polymerization is carried out in a solvent in which the crosslinked fine particles become insoluble, substantially in the absence of a dispersion stabilizer. Particle size of 0.01 μm or more obtained by inverting the crosslinked fine particle dispersion obtained by
30 μm cross-linked fine particle aqueous dispersion. 2. A monomer having two or more α, β-ethylenically unsaturated double bonds (A) in an amount of 0.1 to 90 wt.
(3-Sulfopropyl) -N-methacrylyloxyethyl-N, N-dimethylammonium betaine, N- (3
-Sulfopropyl) -N-methacrylylamidopropyl-N, N-dimethylammonium betaine, and 1-
At least one amphoteric monomer selected from the group consisting of (3-sulfopropyl) -2-vinylpyridinium betaine, α, β-ethylenically unsaturated carboxylic acids and salts thereof, unsaturated sulfonic acids and salts thereof, Unsaturated phosphoric acid monomers, monovinylpyridines, styrenes having a dialkylamino group, esters having a dialkylamino group of (meth) acrylic acid, vinyl ethers having a dialkylamino group, and (meth) acrylamides having a dialkylamino group Alternatively, 99.9 to 10% by weight of at least one other aqueous monomer (b) selected from the group consisting of quaternized products is obtained by homogeneously dissolving the monomer and polymerizing the monomer. Polymerization is carried out in a solvent in which the crosslinked fine particles become insoluble, substantially in the absence of a dispersion stabilizer. Crosslinked fine particle dispersion obtained by
It is neutralized with 0 to 1.5 equivalents of a neutralizing agent with respect to the aqueous monomer and then phase-converted to an aqueous phase.
A method for producing an aqueous dispersion of crosslinked fine particles of from 01 μm to 30 μm.