JPH04356512A - Production of microgel - Google Patents

Abstract

PURPOSE:To obtain a microgel which has a uniform particle diameter and excellent shelf stability, is free from a decrease in bondability, and is less apt to cause environmental or hygienic problems by polymerizing a monomer mixture with a specific composition in a nonaqueous medium in the presence of a polymerization initiator. CONSTITUTION:At least one monomer (A) selected from those represented by formula I (wherein R is a 1-20C alkyl), formula II (wherein R is H or a 1-20C alkyl), formula III (wherein R1 is H or a 1-20C alkyl and R2 is CnH2n(OH), wherein(n) is 1 to 20), and formula IV (wherein R is H or CH3 and X is a halogen) is mixed with at least one monomer (B) selected from polyfunctional monomers (e.g. ethylene glycol diacrylate) and monomers capable of solvating in a nonaqueous medium before and after polymerization (e.g. lauryl methacrylate). This monomer mixture is polymerized in a nonaqueous medium in the presence of a polymerization initiator to obtain a microgel. When the polymerization is conducted in the presence of a pigment, the obtained microgel is useful as a toner for electrophotography.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing microgels useful for printing inks, paints, adhesives, toners for electrophotographic liquid developers, and the like.

0002

[Prior Art] Conventionally, the prior art of microgels is as follows:
JP-A-55-71713, JP-A-54-78791, JP-A-52-117951, etc. are known. By the way, polyhydric alcohol diacrylate such as diethylene glycol dimethacrylate and a polymerizable monomer such as lauryl acrylate are co-polymerized in the presence of a polymerization initiator in an aromatic hydrocarbon solvent such as toluene, benzene, or xylene. Methods of producing polymeric resins are known. The resins obtained in this way have been widely used for paints and adhesives. However, since aromatic hydrocarbon solvents are used in these resin (solution) manufacturing methods, crosslinking of the resin tends to proceed, leading to problems such as macrogelation of the resin during the polymerization reaction and solidification of the resin during storage. was there. The same applies when this non-aqueous resin is used for paints or adhesives, and the adhesive strength decreases due to solidification during storage. In order to solve these problems, it has conventionally been necessary to suppress the amount of polyfunctional acrylic ester such as polyvalent glycol diacrylate to 3% by weight or less. Moreover, even if the above problems were solved in this way, the resin is soluble in aromatic solvents, and it is not possible to obtain a microgel, so it is obtained in a dissolved state, so if it is used as it is in a paint. Since the adsorption power of the resin to the pigment is low and the adhesive strength is insufficient, it is undesirable especially when used in electrodeposition paints.

Furthermore, the aromatic solvent used in this method is highly toxic and flammable, which not only poses problems in terms of environmental hygiene, but also poses a risk of fire.

[0004] In general, microgels are produced using the conventional emulsion polymerization method.
A production method using a suspension polymerization method is known. For example, there are Shinsuke Yamazaki et al. Surface, 25, 86 (1987) and Takeyasu Yamamoto et al. 5th Polymer Microsphere Symposium (1988) P56. Although this method yields a polymer with a fine particle size, the emulsifier and dispersant remain in the coating film, causing problems in moisture absorption resistance and the like. On the other hand, little is known about the method for producing non-aqueous microgels. Tsubuko et al. Polymer Paper Collection vol. 46, No. 11, P7
23-731 (Nov. 1989), but it had the drawback of a wide particle size distribution.

[0005]

[Problems to be Solved by the Invention] The objects of the present invention are to have low toxicity and flammability, and low solubility in the resulting resin.
In addition, by using a photochemically inert non-aqueous solvent, we can produce a non-aqueous microgel resin dispersion that has excellent storage stability, does not reduce adhesive strength, has fewer problems in terms of environmental hygiene, and has less risk of fire. is to provide a method,
Another object of the present invention is to provide a method for producing a non-aqueous microgel having a uniform particle size. Another object of the present invention is to provide a method for producing a microgel useful as an electrostatographic toner.

[0006]

[Means for Solving the Problems] As a result of extensive studies, the present inventors found that the problem could be solved by copolymerization using a specific combination of monomers in a non-aqueous solvent, leading to the present invention.

That is, the present invention provides at least one monomer A represented by the following general formulas (1) to (4), a polyfunctional monomer, and the solvent in the presence of a polymerization initiator in a nonaqueous solvent. This is a method for producing a microgel, characterized by polymerizing a monomer mixture containing at least one monomer B consisting of monomers that are solvated before and after polymerization.

General formula (1) RCH=CHCOOCH=CH2 (wherein R represents CnH2n+1 (n=1 to 20)) General formula (2) (CH2=CRCOO)2O (wherein R represents CnH2n+1(n = 1 to 20) or H) General formula (3) R1CH=CHCOOR2 (wherein, R1 is H or CnH2n+1 (n = 1 to 20)
, R2 represents CnH2n(OH)) General formula (4) CH2=C(R)COO(CH2)nX (wherein, R is H
or CH3, n is 1 to 20, and X represents a halogen) Examples of the monomer A represented by the above general formula (1) used in the present invention include No. 1 CH3-CH=CH-COOCH=CH2
, No. 2 C2H5-CH=CH-COOCH=C
H2, No. 3 C3H7-CH=CH-COOCH
=CH2, No. 4 C4H9-CH=CH-COO
CH=CH2, No. 5 C5H11-CH=CH-
COOCH=CH2, No. 6 C8H17-CH=
CH-COOCH=CH2, No. 7 C10H
21-CH=CH-COOCH=CH2, No. 8
C15H31-CH=CH-COOCH=CH2,
No. 9 C20H41-CH=CH-COOC
Examples include H=CH2.

Further, as the monomer A represented by the above general formula (2), for example, No. 1 (CH2=CH-COO)2O, No. 2
[CH2=C(CH3)-COO]2O, No. 3
[CH2=C(C2H5)-COO]2O, No.
4 [CH2=C(C5H11)-COO]2O, N
o. 5 [CH2=C(C12H25)-COO]2
O, No. 6 [CH2=C(C18H37)-CO
O]2O, No. 7 [CH2=C(C20H41)
-COO]2O and the like.

These monomers A are crosslinking components that form a microgel, and the solvating monomer B described below polymerizes on the surface of the microgel to improve dispersion, adhesion, and the like. It also functions as a control agent for creating uniform microgel particles.

As the monomer A represented by the above general formula (3) used in the present invention, for example, No. 1C
H3-CH=CHCOOCH3, No. 2 CH3-
CH=CHCOOC2H5, No. 3CH3-CH
=CHCOOC4H9, No. 4 CH3-CH=C
HCOOC10H21, No. 5 CH3-CH=C
HCOOC12H25, No. 6 CH3-CH=C
HCOOC16H33, No. 7 CH2=CHCO
OCH3, No. 8 CH2=CHCOOC5H11
, No. 9 CH2=CHCOOC2H5OH, No
．． 10 CH2=CHCOOC20H41No. 11
C12H25CH=CHCOOCH3, No. 12
C18H37CH=CHCOOC2H5, No. 1
3 C3H7CH=CHCOOC12H25, and the like.

As the monomer A represented by the above general formula (4) used in the present invention, for example, No. 1C
H2=CHCOOCH2CH2Br, No. 2CH
2=CHCOOCH2CH2I, No. 3 CH2=
CHCOOCH2CH2Cl, No. 4 CH2=C
HCOOCH2CH2CH2Br, No. 5 CH2
=C(CH3)COOCH2CH2I, No. 6C
H2=C(CH3)COOCH2Br, No. 7C
H2=C(CH3)COO(CH2)5Br, No
．． 8 CH2=C(CH3)COO(CH2)12C
l, No. 9 CH2=CHCOO(CH2)18B
r, No. 10 CH2=CHCOO(CH2)20
I, etc. can be mentioned.

[0013] Monomer B used in the present invention to be solvated with the solvent before and after polymerization includes:
Those represented by the general formula CH2=CRCOOCnH2n+1 (R is H or a methyl group) are preferred, such as lauryl methacrylate, lauryl acrylate, stearyl methacrylate, stearyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, dodecyl methacrylate, dodecyl acrylate, hexyl Examples include methacrylate, hexyl acrylate, cetyl methacrylate, cetyl acrylate, vinyl laurate, and vinyl stearate. In addition, in monomer B, "solvated after polymerization" means that the monomer B unit of the copolymer is solvated with a solvent.

[0014] Also, polyfunctional monomer B used in the present invention
Examples include polyhydric alcohols, dimethacrylates (e.g. ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol methacrylate, triethylene glycol triacrylate, triethylene glycol trimethacrylate, butanediol diacrylate, butanediol dimethacrylate) , 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethanetetraacrylate, tetra Methylolmethanetetramethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate,
Trimethylolhexane triacrylate, trimethylolhexane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, trimethylrollethane triacrylate, trimethylol (ethane methacrylate), divinylbenzene, etc.

In the present invention, the above general formula (1), (
In 2), monomer A can be copolymerized in an amount of 0.1 to 50% by weight and solvating monomer B can be copolymerized in an amount of 50 to 90% by weight based on the total monomers.

When the monomer A component of general formulas (1) and (2) is less than 0.1% by weight, the formation of microgels is reduced. Moreover, if it exceeds 50% by weight, the particle size becomes large and the particle size distribution becomes wide.

On the other hand, if the solvating monomer B is less than 50 wt %, the particle size of the microgel tends to increase and the adhesive strength also decreases. If it exceeds 90%, there are manufacturing problems such as the microgel particles becoming too small.

When monomer A of general formula (3) is used, it is 30 to 95% by weight of the total monomers, and when monomer A of general formula (4) is used, it is 50 to 90% by weight. Polyfunctional monomer B can be copolymerized in an amount of 0.1 to 30% by weight. The monomer A components of general formulas (3) and (4) contribute to the charging, dispersion, and adhesive properties of the microgel, and their effects are reduced if their amounts are less than 30% by weight and 50% by weight, respectively. Moreover, if the content exceeds 95% by weight and 90% by weight, respectively, it becomes difficult to form microgels. When these monomers are used, it is easier to produce microgels than when conventional (meth)acrylic acid ester monomers are used, and the microgel particles are uniform and small in size.

On the other hand, if the polyfunctional monomer is less than 0.1% by weight, it becomes difficult to form microgels. If it exceeds 30% by weight, macrogelation occurs.

In addition, in the present invention, especially the monomer A
When general formulas (1) and (2) are used as monomer B, and a solvating monomer is used as monomer B, Ca(OH)2, CaC
metal salts such as l2, ZnCl2, NaCl, MgCO3,
It is also possible to add small amounts of basic substances such as triethylamine, diethylamine, pyridine, ammonia, and morpholine. The amount added is preferably 1% by weight or less, if necessary.

In the present invention, the pigments present in the polymerization system include carbon black, oil blue, alkali blue, phthalocyanine blue, phthalocyanine green,
Examples include dyes or pigments such as spirit black, aniline black, oil violet, benzidine yellow, methyl orange, brilliant carmine, fast red, crystal violet, triiron tetroxide, nigrosine, titanium oxide, and zinc oxide. These pigments are preferably present in an amount of 5 to 50% by weight based on the monomer mixture.

Further, in the present invention, other polymerizable monomer C or silica fine particles or silica particles with a softening point of 60 to 1 are added to the resin manufacturing process.
Wax or polyolefin at about 30°C can be added. When fine silica particles are used, the resin is considered to be obtained with the fine silica particles incorporated into its network structure. In this case, the silica itself does not undergo physical changes such as dissolution during the reaction. In any case, in the case of silica, the specific gravity is similar to that of the dispersion medium;
By preventing gelation of the resin, dispersion stability can be further improved. On the other hand, when wax or polyolefin is used, these are dissolved in the reaction system by heating during the polymerization reaction, but after the reaction, they are precipitated into fine particles by cooling, and the resin is obtained in a state that is adsorbed to these fine particles. considered to be a thing. Here, wax or polyethylene has a specific gravity similar to that of the dispersion medium, prevents the resin from gelling, and has a molecular structure similar to that of the dispersion medium.
It not only helps improve dispersion stability, but also helps improve adhesiveness because it has a low softening point. The appropriate amount of silica, wax or polyolefin to be added is about 1 to 50 parts by weight per 100 parts by weight of the resin.

Next, the materials used in the present invention will be explained.

In the present invention, other monomers may be copolymerized if necessary. Such other polymerizable monomers C include polar monomers and other reactive monomers, and the polar monomers include unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, unsaturated nitrogen-containing compounds, and glycidyl group-containing unsaturated compounds. , alkyl acrylate (having 1 to 5 carbon atoms) ester, and/or alkyl methacrylate (having 1 to 5 carbon atoms) ester. Examples of unsaturated carboxylic acids and their anhydrides include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, aconitic acid, cinnamic acid, and their anhydrides. Examples of unsaturated nitrogen-containing compounds include vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine, N-vinylpyridine, N-vinylimidazole, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and acrylic Examples of the alkyl ester (having 1 to 5 carbon atoms) of acid or methacrylic acid include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, and butyl methacrylate. Further, typical examples of the unsaturated compound containing a glycidyl group include glycidyl acrylate and glycidyl methacrylate.

Other polymerizable monomers C include styrene, vinyltoluene, vinyl acetate, polyhydric alcohol dimethacrylate (for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol methacrylate, triethylene glycol triacrylate, Triethylene glycol trimethacrylate, butanediol diacrylate, butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1
, 6-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, dipropylene glycol diacrylate, Dipropylene glycol dimethacrylate, trimethylolhexane triacrylate, trimethylolhexane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, trimethylol ethane triacrylate, trimethylolethane methacrylate), etc.

The polymerization initiators used when polymerizing these monomers A, B, and C include benzoyl peroxide, t-butyl perbenzoate, diamyl peroxide, di-t-butyl peroxide, and lauryl peroxide. , azobisisobutyronitrile can be used.

[0027] Non-aqueous solvents used in the present invention include aliphatic hydrocarbons, various silicone oils, fluorine oils, mineral oils, vegetable oils, and the like. Aliphatic hydrocarbons include ligroin, n-hexane, n-pentane, n-heptane, n
-Octane, i-octane, l-dodecane, i-nonane (commercially available products include Exxon's Isopar H, G
, L, K: Naphtha 6, Shellzol manufactured by Shell Oil Co., etc.), carbon tetrachloride, perfluoroethylene, etc. These aliphatic hydrocarbons have a higher flash point than aromatic solvents such as benzene and toluene, and are also less toxic. Since the solubility of the resin of the present invention is lower than that of aromatic solvents, it also has the advantage that the resin is unlikely to gel or solidify during the polymerization reaction or during storage. These petroleum-based aliphatic hydrocarbons have high insulation properties (electrical resistance of 1010Ω・cm).
above), it is a solvent with a low dielectric constant (dielectric constant of 3 or less). Further, aromatic solvents such as benzene and toluene may be added to these aliphatic solvents in small amounts.

Specific examples of commercially available waxes or polyolefins having a softening point of 60 to 130°C are as follows.

[0029] Examples of the present invention are shown below.

Example 1 300 g of isooctane was placed in a 2.0 liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and 95 g of isooctane was added.
heated to ℃. In this, dodecyl methacrylate 190
g, 10 g of methacrylic acid, formula (1), No. A solution consisting of 10 g of monomer A in (1) and 6 g of azobisisobutyronitrile was added dropwise over 3 hours, and the polymerization reaction was carried out by further stirring at the above temperature for 4 hours, resulting in a polymerization rate of 96.8% and a viscosity of 210 cp. A resin dispersion was obtained. Note that the particle size of the resin was 0.5 to 0.8 μ.

Example 2 300 g of the microgel resin dispersion obtained in Example 1 was mixed with 10 g of colloidal silica in a flask, and the mixture was heated at 100°C.
After heating for 3 hours, it was cooled to a viscosity of 55 cp and a particle size of 1.
A microgel resin dispersion containing colloidal silica of 0 to 1.5 microns was obtained.

Example 3 Silicone oil and KF96 were added to the same flask as in Example 1.
, 300g of 1.5 (manufactured by Shin-Etsu Silicone Co., Ltd.) was taken at 90℃.
heated to. Next, add lauryl methacrylate 300 to this
g, N-vinylpyridine 5g, formula (1), No. (2)
A solution consisting of 25 g of monomer A and 3 g of benzoyl peroxide was added dropwise over 1.5 hours, and the polymerization reaction was carried out by stirring at the above temperature for 4 hours, resulting in a polymerization rate of 97.0% and a viscosity of 150 c.
A microgel resin dispersion having a particle size of 1 to 2 μm was obtained.

Example 4 300 g of the microgel resin dispersion obtained in Example 3 was mixed with 20 g of bleached beeswax in a flask, and heated at 95°C for 2 hours.
After stirring for 2 hours, cool to a viscosity of 100 cp and a particle size of 3 to 4 μm.
A beeswax-containing microgel resin dispersion was obtained.

Example 5 In the same flask as in Example 1, 300 g of corn oil and 30 g of colloidal silica were placed and heated to 90°C. In this, 150 g of 2-ethylhexyl methacrylate, 15 g of glycidyl methacrylate, formula (1), No. After dropping a solution consisting of 20 g of monomer A in (3), 40 g of methyl methacrylate, and 6.3 g of lauroyl peroxide, the polymerization reaction was carried out by further stirring at the above temperature for 4 hours.
Polymerization rate 95.5%, viscosity 420cp, particle size 0.4-0.
A microgel resin dispersion of No. 6 was obtained.

Example 6 300 g of Isopar L and 60 g of polyethylene (AC-6 manufactured by Allied Chemical Co., Ltd.) were placed in the same flask as in Example 1 and heated to 95°C. Next, in this, 180 g of stearyl methacrylate, 40 g of lauryl methacrylate, 3 g of fumaric acid, formula (1), No. (4) Monomer A20
A solution consisting of g and 4 g of lauryl peroxide was added dropwise over 3 hours, and further stirred at the above temperature for 3 hours to perform a polymerization reaction, resulting in a polymerization rate of 94.6%, a viscosity of 85 cp, and a particle size of 0.
．． A microgel resin dispersion liquid of 4 to 0.6 μm was obtained.

Example 7 In the same flask as in Example 1, 300 liters of Isopar H, 180 g of cetyl methacrylate, 40 g of dodecyl acrylate, formula (1), No. (5) Monomer A 15g
, take 5 g of acrylic acid and 3 g of benzoyl peroxide,
The polymerization reaction was carried out by stirring at 0°C for 6 hours, and the polymerization rate was 91.8.
A microgel resin dispersion having a viscosity of 180 cp and a particle size of 0.1 to 0.3 μm was obtained.

Example 8 After stirring, 300 g of isooctane was placed in a 2.0 liter four-necked flask equipped with a thermometer and a reflux condenser.
heated to ℃. In this, dodecyl methacrylate 190
g, glycidyl methacrylate 10g, formula (2) No.
A solution consisting of 10 g of monomer A in (1) and 6 g of azobisisobutyronitrile was added dropwise over a period of 3 hours, and the polymerization reaction was carried out by further stirring at the above temperature for 4 hours, resulting in a polymerization rate of 9.
A dispersion with a viscosity of 160 cp was obtained at 5%. 0.1 g of pyridine was added to this dispersion and dispersed at 90°C for 15 hours. Note that the particle size of the resin was 0.05 to 0.10μ.

Example 9 300 g of the microgel resin dispersion obtained in Example 8 was mixed with 10 g of colloidal silica in a flask and heated at 100°C.
After heating for 3 hours at
．． A microgel resin dispersion containing colloidal silica of 1 to 0.3 μm was obtained. Example 10 Silicone oil KF96 was added to the same flask as in Example 8.
3.0, 300g was taken and heated to 90°C. Next, 300 g of lauryl methacrylate, 5 g of N-vinylpyridine, formula (2), No. (2) Monomer A 25g,
A solution consisting of 10 g of glycidyl methacrylate and 3 g of benzoyl peroxide was added dropwise over 1.5 hours, and then stirred at the above temperature for 4 hours to perform a polymerization reaction, resulting in a polymerization rate of 96%, a viscosity of 460 cp, and a particle size of 0.5 to 1. A microgel resin dispersion liquid of .0μ was obtained.

Example 11 300 g of the microgel resin dispersion obtained in Example 10 was mixed with 20 g of bleached beeswax in a flask, stirred at 95° C. for 22 hours, and then cooled to give a viscosity of 250 cp and a particle size of 1 to 3.
A beeswax-containing microgel resin dispersion was obtained.

Example 12 In the same flask as in Example 8, 300 g of salad oil and 30 g of colloidal silica were placed and heated to 90°C. In this, 150 g of 2-ethylhexyl methacrylate, 15 g of glycidyl methacrylate, formula (2), No. (3)
After dropping a solution consisting of 20 g of monomer A, 40 g of methyl methacrylate, and 6.3 g of lauroyl peroxide, the polymerization reaction was carried out by further stirring at the above temperature for 4 hours, and the polymerization rate was 97% and the viscosity was 180 cp. .4 g was added thereto and stirred at 90°C for 16 hours. Particle size 0
．． A microgel resin dispersion of 2 to 0.3 microns was obtained.

Example 13 In the same flask as in Example 8, 300 g of Isopar L and 60 g of polyethylene (AC-6 manufactured by Allied Chemical Co., Ltd.) were placed and heated to 95°C. Next, 180 g of stearyl methacrylate, 40 g of lauryl methacrylate, 3 g of fumaric acid, formula (2), No. (4) Monomer A20
A solution consisting of 4 g of lauryl peroxide and 4 g of lauryl peroxide was added dropwise over 3 hours, and the polymerization reaction was carried out by further stirring at the above temperature for 3 hours, resulting in a polymerization rate of 92%, a viscosity of 180 cp, and a particle size of 0.
A microgel resin dispersion liquid of 0.05 to 0.1 μm was obtained.

Example 14 In the same flask as in Example 8, 300 g of Isopar H, 180 g of cetyl methacrylate, and 40 g of dodecyl acrylate were added.
g, formula (2), No. 15 g of monomer A from (6), 5 g of acrylic acid, and 3 g of benzoyl peroxide were taken and stirred at 90°C for 6 hours to perform a polymerization reaction, and Ca(OH)2 was added to 0.5 g.
5g was added and further stirred at 90°C for 10 hours until the polymerization rate was 9.
A microgel resin dispersion having a viscosity of 260 cp and a particle size of 0.3 to 0.5 μm was obtained at 8%.

Example 15 300 g of isooctane was placed in a 2.0 liter four-neck flask equipped with a stirrer, a thermometer and a reflux condenser, and 95 g of isooctane was added.
heated to ℃. Among these, the general formula (3) No. A solution consisting of 190 g of monomer A of No. 5, 10 g of methacrylic acid, 10 g of divinylbenzene, and 6 g of azobisisobutyronitrile was added dropwise over 3 hours, and then further added at the same temperature for 4 hours.
The polymerization reaction was carried out by stirring for hours, and the viscosity was 12 with a polymerization rate of 95%.
A resin dispersion of 5 cp was obtained. The particle size of the resin is 0.05
It was ~0.08μ. General formula (3) No. When dodecyl methacrylate was used instead of monomer 5, the particle size was 0.3-2μ.

Example 16 300 g of the microgel resin dispersion obtained in Example 15 was mixed with 10 g of colloidal silica in a flask.
After heating at a temperature of 3 hours, the mixture was cooled to obtain a colloidal silica-containing microgel resin dispersion having a viscosity of 220 cp and a particle size of 0.1 to 0.2 μm.

Example 17 Silicone oil and KF5 were added to the same flask as in Example 15.
300 g of No. 8 (manufactured by Shin-Etsu Silicone Co., Ltd.) was taken and heated to 90°C. Next, the general formula (3) No. 6 monomer A 300g, N-vinylpyridine 5g, ethylene glycol dimethacrylate 25g and benzoyl peroxide 3g
After dropping a solution consisting of
A microgel resin dispersion liquid of 80 cp and a particle size of 0.4 to 0.15 μm was obtained. General formula (3) No. When lauryl methacrylate is used instead of monomer 6, the particle size is 3~
It was 5μ.

Example 18 300 g of the microgel resin dispersion obtained in Example 17 was mixed with 20 g of bleached beeswax in a flask, stirred at 95° C. for 22 hours, and then cooled to give a viscosity of 220 cp and a particle size of 0.6.
A bleached beeswax-containing microgel resin dispersion of ~0.7μ was obtained.

Example 19 In the same flask as in Example 15, 300 g of sesame oil and 30 g of colloidal silica were placed and heated to 90°C. Among these, general formula (3) No. After dropping a solution consisting of 150 g of monomer A of No. 7, 15 g of glycidyl methacrylate, 20 g of trimethylolpropane triacrylate, 40 g of methyl methacrylate, and 6.3 g of lauroyl peroxide, the mixture was further stirred at the above temperature for 4 hours to carry out a polymerization reaction. Viscosity 140cp at rate 98%, particle size 0.5-0
．． A microgel resin dispersion of No. 6 was obtained.

Example 20 In the same flask as in Example 15, 300 g of Isopar L and 60 g of polyethylene (AC-6 manufactured by Allied Chemical Co., Ltd.) were added.
was added and heated to 95°C. Next, the above-mentioned No. 8
Monomer A 180g, lauryl methacrylate 40g
, a solution consisting of 3 g of fumaric acid, 20 g of divinylbenzene A and 4 g of lauryl peroxide was added dropwise over 3 hours, and further stirred at the above temperature for 3 hours to perform a polymerization reaction,
Polymerization rate 96%, viscosity 210cp, particle size 0.1-0.2μ
A microgel resin dispersion was obtained.

Example 21 In the same flask as in Example 15, 300 g of Isopar H and the above general formula (3) No. 9 monomer A 180 g, dodecyl acrylate 40 g, diethylene glycol diacrylate 15 g, acrylic acid 5 g and benzoyl peroxide 3
A polymerization reaction was carried out by stirring at 90° C. for 6 hours to obtain a microgel resin dispersion having a polymerization rate of 95%, a viscosity of 280 cp, and a particle size of 0.2 to 0.3 μm.

Example 22 300 g of isooctane was placed in a 2.0 liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and 95 g of isooctane was added.
heated to ℃. Among these, general formula (4) above No. A solution consisting of 190 g of monomer A of No. 8, 10 g of methacrylic acid, 10 g of divinylbenzene and 6 g of azobisisobutyronitrile was added dropwise over 3 hours, and then further added at the same temperature for 4 hours.
The polymerization reaction was carried out by stirring for hours, and the polymerization rate was 93% and the viscosity was 42.
A resin dispersion liquid of 0 cp was obtained. The particle size of the resin is 3 to 4μ.
Met.

Example 23 300 g of the microgel resin dispersion obtained in Example 22 was mixed with 10 g of colloidal silica in a flask.
After heating at °C for 3 hours, the mixture was cooled to obtain a colloidal silica-containing microgel resin dispersion having a viscosity of 550 cp and a particle size of 5 μm.

Example 24 Silicone oil and KF9 were added to the same flask as in Example 22.
6. Take 300g of 2.0 (manufactured by Shin-Etsu Silicone Co., Ltd.) and
heated to ℃. Next, the general formula (4) No. A solution consisting of 300 g of monomer A of No. 9, 5 g of N-vinylpyridine, 25 g of ethylene glycol dimethacrylate, and 3 g of benzoyl peroxide was added dropwise over 1.5 hours, and the mixture was stirred at the above temperature for 4 hours to perform a polymerization reaction. A microgel resin dispersion with a viscosity of 580 cp and a particle size of 2 to 3 μm was obtained at 98%.

Example 25 300 g of the microgel resin dispersion obtained in Example 24 was mixed with 20 g of bleached beeswax in a flask, stirred at 95° C. for 22 hours, and then cooled to have a viscosity of 600 cp and a particle size of 3 to 4.
A beeswax-containing microgel resin dispersion was obtained.

Example 26 In the same flask as in Example 22, 300 g of corn oil and 30 g of colloidal silica were placed and heated to 90°C. Among these, the general formula (4) No. 150 g of monomer A of No. 10,
Glycidyl methacrylate 15g, diethylene glycol diacrylate 20g, methyl methacrylate 40g
After dropping a solution consisting of 6.3 g of lauroyl peroxide and stirring at the above temperature for 4 hours to perform a polymerization reaction, the polymerization rate was 96%, the viscosity was 270 cp, and the particle size was 0.05.
A microgel resin dispersion of ~0.07μ was obtained.

Example 27 In the same flask as in Example 22, 300 g of Isopar L and 60 g of polyethylene (AC-6 manufactured by Allied Chemical Co., Ltd.) were added.
and heated to 95°C. Next, in this, the general formula (4
) No. A solution consisting of 180 g of monomer A of No. 1, 40 g of lauryl methacrylate, 3 g of fumaric acid, 20 g of divinylbenzene and 4 g of lauryl peroxide was added dropwise over 3 hours, and the polymerization reaction was carried out by further stirring at the above temperature for 3 hours, resulting in a polymerization rate of 96. %, viscosity 290 cp, particle size 0.1~
A 0.3μ microgel resin dispersion was obtained.

Example 27 In the same flask as in Example 22, 300 g of Isopar H and the above general formula (4) No. 180 g of monomer A of 2, 40 g of dodecyl acrylate, 15 g of trimethylolpropane triacrylate, 5 g of acrylic acid and 3 g of benzoyl peroxide were taken and stirred at 90°C for 6 hours to perform a polymerization reaction, resulting in a polymerization rate of 97%, a viscosity of 460 cp, and a particle size. 0.05~0.
A microgel resin dispersion liquid of 0.07μ was obtained.

Example 28 300 g of isooctane was placed in a 2.0 liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and 95 g of isooctane was added.
heated to ℃. In this, dodecyl methacrylate 190
g, 10 g of methacrylic acid, 10 g of monomer A of general formula (1) No (1) and 6 g of azobisisobutyronitrile,
A solution consisting of 50 g of carbon black Mitsubishi MA100 was added dropwise over a period of 3 hours, and the polymerization reaction was carried out by stirring at the same temperature for an additional 4 hours, resulting in a polymerization rate of 96.8% and a viscosity of 3.
50 cp of microgel colorant was obtained. Note that the particle size of the microgel colorant was 0.95μ.

100 g of this microgel colorant was dispersed in 1000 ml of Isopar H, and a plain paper copying machine, Ricopy DT,
-1200, a copy with a resolution of 6.3 lines and a fixing property of 86% was obtained, and the number of sheets printed by offset printing was 32,000 sheets. Example 29 300 g of the microgel colorant obtained in Example 28 was mixed with 10 g of colloidal silica in a flask, heated at 100°C for 3 hours, cooled, and the solvent was evaporated to reduce the particle size to 1.2.
I made μ dry toner. When copied with Ricopy FT6400 (manufactured by Ricoh), the resolution was 6.3 lines/mm,
Fixing performance was 90%, no offset occurred and environmental characteristics were good.

Example 30 In the same flask as in Example 28, silicone oil (KF
96, 1.5 (manufactured by Shin-Etsu Silicone Co., Ltd.) 300g,
Heated to 0°C. Next, add this to Crystal Violet 5
0g, lauryl methacrylate 300g, N-vinylpyridine 5g, general formula (1) No. (2) Monomer A2
After dropping a solution consisting of 5 g and 3 g of benzoyl peroxide over 1.5 hours, the polymerization reaction was carried out by stirring at the above temperature for 4 hours, resulting in a polymerization rate of 97.0%, a viscosity of 180 cp, and a particle size of 1.
~2μ of microgel colorant was obtained. 100 g of this microgel colorant was dispersed in 1000 ml of yridodecane to prepare a liquid developer. When I copied it with Ricoh DT1200,
The resolution was 8.3 lines/mm and the fixability was 83%.

Example 31 In the same flask as in Example 28, 300 g of corn oil and 30 g of colloidal silica were placed and heated to 90°C. In this, 150g of styrene and 15g of glycidyl methacrylate.
, General formula (1) No. (3) Monomer A 20g, methyl methacrylate 40g and lauroyl peroxide 6.3g carbon (Degussa Special Black No.
A dispersion obtained by dispersing 100 g of 4) with a monomer using a ball mill for 42 hours was added dropwise over 1 hour, and the mixture was further stirred at the above temperature for 4 hours to carry out a polymerization reaction, resulting in a polymerization rate of 95.5% and a viscosity of 4.
A microgel colorant of 20 cp and a particle size of 0.8 μm was obtained.

[0061] When this microgel colorant 0.8 μm was evaluated as a dry toner, the resolution was 11 lines/mm with Ricopy FT6400 (manufactured by Ricoh), the fixability was 91%, and no offset occurred even at a fixing roller temperature of 100 to 200°C. . Further, no decrease in image temperature was observed even under a 30° C.-80% RH environment. (Room temperature 20-65%RH,
ID, 1.43, 30℃-80%RH, ID, 1.41
).

Example 32 In the same flask as in Example 28, 300 g of Isopar L and 60 g of polyethylene (AC-6 manufactured by Allied Chemical Co., Ltd.) were added.
was added and heated to 95°C. Next, in this, 180g of stearyl methacrylate, 40g of lauryl methacrylate
, fumaric acid 3g, general formula (1) No. Monomer A2 of 4
A reaction solution consisting of 0 g, 4 g of lauryl peroxide, 40 g of alkali blue, and 50 g of carbon (Mitsubishi MA100) was dispersed in a ball mill for 24 hours, and then added dropwise over 3 hours, followed by further stirring at the above temperature for 3 hours to carry out the polymerization reaction. A microgel colorant having a polymerization rate of 91%, a viscosity of 240 cp, and a particle size of 2.5 μm was obtained. 50g of this microgel colorant
was dispersed in 1000 ml of Isopar H to prepare a liquid developer. When I copied it with Recopy DT1200,
An image with good sharpness was obtained with an image density of 1.38 and a resolution of 8.3 lines/mm. The fixation rate was also 86%.

Example 33 300 g of isooctane was placed in a 2.0 liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and 95 g of isooctane was added.
heated to ℃. In this, dodecyl methacrylate 190
g, 10 g of methacrylic acid, 10 g of monomer A of general formula (2) No (1) and 6 g of azobisisobutyronitrile,
A solution consisting of 50 g of carbon black (Mitsubishi MA100) was added dropwise over a period of 3 hours, and the polymerization reaction was carried out by further stirring at the above temperature for 4 hours, resulting in a polymerization rate of 94.9% and a viscosity of 3.
35 cp of microgel colorant was obtained. Note that the particle size of the microgel colorant was 0.88μ.

100 g of this microgel colorant was dispersed in 1000 ml of Isopar H, and a plain paper copying machine, Ricopy DT, was used.
When copying with -1200, the resolution was 6.3 lines, the fixation was 88%, and the toner durability was 30.0.
It was 00 pieces.

Example 34 300 g of the microgel colorant obtained in Example 33 was mixed with 10 g of colloidal silica in a flask, heated at 100° C. for 3 hours, cooled, and the solvent was evaporated to give a particle size of 2.8.
I made μ dry toner. When copied with Ricopy FT6400 (manufactured by Ricoh), the resolution was 7.1 lines/mm,
Fixing performance was 89%, no offset occurred and environmental characteristics were good.

Example 35 In the same flask as in Example 33, silicone oil (KF
96, 1.5 (manufactured by Shin-Etsu Silicone Co., Ltd.) 300g,
Heated to 0°C. Next, add this to Crystal Violet 5
0g, lauryl methacrylate 300g, N-vinylpyridine 5g, general formula (2) No. (2) Monomer A2
After dropping a solution consisting of 5 g and 3 g of benzoyl peroxide over 1.5 hours, the polymerization reaction was carried out by stirring at the above temperature for 4 hours, resulting in a polymerization rate of 96.5%, a viscosity of 230 cp, and a particle size of 1.
~2μ of microgel colorant was obtained. 100 g of this microgel colorant was dispersed in 1000 ml of yridodecane to prepare a liquid developer. When I copied it with Ricoh DT1200,
The resolution was 6.3 lines/mm and the fixability was 86%.

Example 36 In the same flask as in Example 33, 300 g of corn oil and 30 g of colloidal silica were placed and heated to 90°C. In this, 150g of styrene and 15g of glycidyl methacrylate.
, General formula (2) No. (3) Monomer A 20g, methyl methacrylate 40g and lauroyl peroxide 6.3g, carbon (Degussa Special Black No.
．． A dispersion prepared by dispersing 100 g of 4) with a monomer in a ball mill for 42 hours was added dropwise over 1 hour, and then further dispersed at the same temperature for 42 hours.
A polymerization reaction was carried out by stirring for hours to obtain a microgel colorant with a polymerization rate of 95.8%, a viscosity of 390 cp, and a particle size of 0.79 μm.

[0068] When this microgel colorant 0.79 μm was evaluated as a dry toner, it was found that Ricopy FT6400 (
(manufactured by Ricoh), the resolution was 9.0 lines/mm, the fixability was 92%, and no offset occurred even at a fixing roller temperature of 100 to 200°C. Further, no decrease in image density was observed even under an environment of 30° C. and 80% RH. (room temperature 20-65%
RH, ID, 1.44, 30℃-80%RH, ID, 1
．． 43).

Example 37 In the same flask as in Example 33, 300 g of Isopar L and 60 g of polyethylene (AC-6 manufactured by Allied Chemical Co., Ltd.) were added.
was added and heated to 95°C. Next, in this, 180g of stearyl methacrylate, 40g of lauryl methacrylate
, fumaric acid 3g, general formula (2) No. A reaction solution consisting of 20 g of monomer A in (4), 4 g of lauryl peroxide, 40 g of alkali blue, and 50 g of carbon (Mitsubishi MA100) was dispersed in a ball mill for 24 hours, and then added dropwise over 3 hours, followed by further stirring at the above temperature for 3 hours. A polymerization reaction was carried out with a polymerization rate of 93.5%, a viscosity of 260 cp, and a particle size of 2.
A 5 μm microgel colorant was obtained. 50 g of this microgel colorant was dispersed in 1000 ml of Isopar H to prepare a liquid developer. When the image was copied using Recopy DT1200, an image with good sharpness was obtained with an image density of 1.41 and a resolution of 9.0 lines/mm. The fixation rate was also 86%.

Example 38 300 g of isooctane was placed in a 2.0 liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and 95 g of isooctane was added.
heated to ℃. In this, dodecyl methacrylate 190
g, 10 g of methacrylic acid, 10 g of monomer A of general formula (3) No (1) and 6 g of azobisisobutyronitrile,
A solution consisting of 50 g of carbon black (Mitsubishi MA100) was added dropwise over a period of 3 hours, and the polymerization reaction was carried out by further stirring at the above temperature for 4 hours, resulting in a polymerization rate of 96.5% and a viscosity of 3.
40 cp of microgel colorant was obtained. Note that the particle size of the microgel colorant was 0.90μ.

100 g of this microgel colorant was dispersed in 1000 ml of Isopar H, and a plain paper copying machine, Ricopy DT,
When I made a copy with -1200, I got a copy with a resolution of 7.1 lines and fixation of 85%, and the toner durability was 30.
It was 000 pieces.

Example 39 300 g of the microgel colorant obtained in Example 38 was mixed with 10 g of colloidal silica in a flask, heated at 100° C. for 3 hours, cooled, and the solvent was evaporated to give a particle size of 1.2.
I made μ dry toner. When copied with Ricopy FT6400 (manufactured by Ricoh), the resolution was 8.0 lines/mm,
Fixing performance was 91%, no offset occurred and environmental characteristics were good.

Example 40 In the same flask as in Example 38, silicone oil (KF
96, 1.5 (manufactured by Shin-Etsu Silicone Co., Ltd.) 300g,
Heated to 0°C. Next, add this to Crystal Violet 5
0g, lauryl methacrylate 300g, N-vinylpyridine 5g, general formula (3) No. (2) Monomer A2
After dropping a solution consisting of 5 g and 3 g of benzoyl peroxide over 1.5 hours, the polymerization reaction was carried out by stirring at the above temperature for 4 hours, resulting in a polymerization rate of 97.5%, a viscosity of 170 cp, and a particle size of 1.
A ~2.5μ microgel colorant was obtained.

100 g of this microgel colorant was dispersed in 1000 ml of yridodecane to prepare a liquid developer. Ricoh D
When copied with T1200, the resolution was 7.1 lines/mm.
, the fixability was 86%.

Example 41 In the same flask as in Example 38, 300 g of corn oil and 30 g of colloidal silica were placed and heated to 90°C. In this, 150g of styrene and 15g of glycidyl methacrylate.
, General formula (3) No. (3) Monomer A 20g, methyl methacrylate 40g and lauroyl peroxide 6.3g, carbon (Degussa Special Black No.
．． A dispersion prepared by dispersing 100 g of 4) with a monomer in a ball mill for 42 hours was added dropwise over 1 hour, and then further dispersed at the same temperature for 42 hours.
A polymerization reaction was carried out by stirring for hours to obtain a microgel colorant with a polymerization rate of 96.5%, a viscosity of 400 cp, and a particle size of 0.7 μm.

When this microgel colorant 0.8 μm was evaluated as a dry toner, the resolution was 8.0 lines/mm with Ricopy FT6400 (manufactured by Ricoh), the fixability was 94%, and offset occurred even at a fixing roller temperature of 100 to 200°C. I didn't. Further, no decrease in image density was observed even under an environment of 30° C. and 80% RH. (room temperature 20-65%R
H, ID, 1.43, 30°C-80%RH, ID, 1.
41).

Example 42 In the same flask as in Example 38, 300 g of Isopar L and 60 g of polyethylene (AC-6 manufactured by Allied Chemical Co., Ltd.) were added.
was added and heated to 95°C. Next, in this, 180g of stearyl methacrylate, 40g of lauryl methacrylate
, 3 g of fumaric acid, general formula (3) No. A reaction solution consisting of 20 g of monomer A in (4), 4 g of lauryl peroxide, 40 g of alkali blue, and 50 g of carbon (Mitsubishi MA100) was dispersed in a ball mill for 24 hours, and then added dropwise over 3 hours, followed by further stirring at the above temperature for 3 hours. A polymerization reaction was carried out with a polymerization rate of 92%, a viscosity of 230 cp, and a particle size of 2.0μ.
A microgel colorant of m was obtained. This microgel colorant 5
0 g was dispersed in 1000 ml of Isopar H to prepare a liquid developer. When the image was copied using Recopy DT1200, an image with good sharpness was obtained with an image density of 1.39 and a resolution of 7.1 lines/mm. The fixation rate was also 88%.

Example 43 300 g of isooctane was placed in a 2.0 liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and 95 g of isooctane was added.
heated to ℃. In this, dodecyl methacrylate 190
g, 10 g of methacrylic acid, 10 g of monomer A of general formula (4) No (1) and 6 g of azobisisobutyronitrile,
A solution consisting of 50 g of carbon black (Mitsubishi MA100) was added dropwise over a period of 3 hours, and the mixture was further stirred at the above temperature for 4 hours to carry out a polymerization reaction, resulting in a polymerization rate of 89.5% and a viscosity of 3.
00 cp of microgel colorant was obtained. The particle size of the microgel colorant was 0.8 μm on average by volume.

100 g of this microgel colorant was dispersed in 1000 ml of Isopar H, and a plain paper copier called Ricopy DT was used.
-1200, a copy with a resolution of 7.1 lines and a fixing property of 82% was obtained, and the printing life of offset printing was 26,000 sheets.

Example 44 300 g of the microgel colorant obtained in Example 43 was mixed with 10 g of colloidal silica in a flask, heated at 100° C. for 3 hours, cooled, and the solvent was evaporated to give a particle size of 1.5.
I made μ dry toner. When copied with Ricopy FT6400 (manufactured by Ricoh), the resolution was 6.3 lines/mm,
Fixing performance was 95%, no offset occurred and environmental characteristics were good.

Example 45 In the same flask as in Example 43, silicone oil (KF
96, 1.5 (manufactured by Shin-Etsu Silicone Co., Ltd.) 300g,
Heated to 0°C. Next, add this to Crystal Violet 5
0g, lauryl methacrylate 300g, N-vinylpyridine 5g, general formula (4) No. (2) Monomer A2
After dropping a solution consisting of 5 g and 3 g of benzoyl peroxide over 1.5 hours, the polymerization reaction was carried out by stirring at the above temperature for 4 hours, resulting in a polymerization rate of 94.0%, a viscosity of 350 cp, and a particle size of 1.
~2μ of microgel colorant was obtained. 100 g of this microgel colorant was dispersed in 1000 ml of yridodecane to prepare a liquid developer. When I copied it with Ricoh DT1200,
The resolution was 9.8 lines/mm and the fixability was 83%.

Example 46 In the same flask as in Example 43, 300 g of corn oil and 30 g of colloidal silica were placed and heated to 90°C. In this, 150g of styrene and 15g of glycidyl methacrylate.
, General formula (4) No. (3) Monomer A 20g, methyl methacrylate 40g and lauroyl peroxide 6.3g, carbon (Degussa Special Black No.
．． A dispersion prepared by dispersing 100 g of 4) with a monomer in a ball mill for 42 hours was added dropwise over 1 hour, and then further dispersed at the same temperature for 42 hours.
A polymerization reaction was carried out by stirring for hours to obtain a microgel colorant with a polymerization rate of 92.5%, a viscosity of 250 cp, and a particle size of 0.8 μm.

When this microgel colorant 2.2 μm was evaluated as a dry toner, the resolution was 6.3 lines/mm with Ricopy FT6400 (manufactured by Ricoh), the fixability was 98%, and offset occurred even at a fixing roller temperature of 100 to 200°C. I didn't. Further, no decrease in image density was observed even under an environment of 30° C. and 80% RH. (room temperature 20-65%R
H, ID, 1.43, 30°C-80%RH, ID, 1.
41).

Example 47 In the same flask as in Example 43, 300 g of Isopar L and 60 g of polyethylene (AC-6 manufactured by Allied Chemical Co., Ltd.) were added.
was added and heated to 95°C. Next, in this, 180g of stearyl methacrylate, 40g of lauryl methacrylate
, fumaric acid 3g, general formula (4) No. A reaction solution consisting of 20 g of monomer A in (4), 4 g of lauryl peroxide, 40 g of alkali blue, and 50 g of carbon (Mitsubishi MA100) was dispersed in a ball mill for 24 hours, and then added dropwise over 3 hours, followed by further stirring at the above temperature for 3 hours. A polymerization reaction was carried out with a polymerization rate of 91%, a viscosity of 240cp, and a particle size of 1.5μ.
A microgel colorant of m was obtained. This microgel colorant 5
0 g was dispersed in 1000 ml of Isopar H to prepare a liquid developer. When the image was copied using Recopy DT1200, an image with good sharpness was obtained with an image density of 1.41 and a resolution of 8.3 lines/mm. The fixation rate was also 90%. When the dispersant of the microgel obtained in Example 46 in Isopar H was used as a paint for wood products, wallpaper materials, etc., it could be used as a good paint with little sagging and quick drying properties. The weather resistance against light and the like was also good.

[0085]

[Effects of the Invention] As explained above, according to the present invention, a microgel having a uniform particle size can be obtained.

Microgels obtained by polymerization in the presence of pigments are also useful as toners for electrostatic photography.

Claims (7)

[Claims] [Claim 1] In the presence of a polymerization initiator in a nonaqueous solvent,
A monomer containing at least one monomer A represented by the following general formulas (1) to (4) and at least one monomer B consisting of a polyfunctional monomer and a monomer that is solvated in the solvent before and after polymerization. A method for producing a microgel, which comprises polymerizing a mixture. General formula (1) RCH=CHCOOCH=CH2 (wherein, R represents CnH2n+1 (n=1-20)) General formula (2) (CH2=CRCOO)2O (wherein, R represents CnH2n+1 (n=1-20) 20) or H) General formula (3) R1CH=CHCOOR2 (wherein, R1 is H or CnH2n+1 (n=1 to 20)
, R2 represents CnH2n(OH)) General formula (4) CH2=C(R)COO(CH2)nX (wherein, R is H
or CH3, n is 1 to 20, X represents halogen) [Claim 2] Monomer B is CH2=CRCOOCn
2. The method for producing a microgel according to claim 1, wherein the microgel is a (meth)acrylic acid ester represented by H2n+1 (R is H or CH3, n=8 to 20). 3. The method for producing a microgel according to claim 1, wherein the monomer mixture further contains another polymerizable monomer C. 4. The method for producing a microgel according to claim 1, further comprising polymerizing in the presence of a pigment. 5. The method for producing a microgel according to claim 1, further comprising polymerizing in the presence of wax or polyolefin wax. 6. The method for producing a microgel according to claim 1, wherein the polymerization is further carried out in the presence of a metal salt and/or a basic substance. 7. The method for producing a microgel according to claim 1, wherein the nonaqueous solvent contains at least a solvent selected from aliphatic hydrocarbons, fluorine oils, silicone oils, mineral oils, and vegetable oils.