JP3058476B2 - Method for producing microgel - Google Patents

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]

2. Description of the Related Art Conventionally, as the prior art of microgel,
JP-A-55-71713, JP-A-54-78791
And JP-A No. 52-117951 are known. By the way, a polyhydric alcohol diacrylate such as diethylene glycol dimethacrylate and a polymerizable monomer such as lauryl acrylate are subjected to a polymerization reaction in an aromatic hydrocarbon solvent such as toluene, benzene or xylene in the presence of a polymerization initiator to form a copolymer. Methods for producing polymer resins are known. The resin thus obtained has been widely used for paints and adhesives. However, in such a method for producing a resin (solution), since an aromatic hydrocarbon solvent is used, crosslinking of the resin is liable to proceed, and the resin is macrogelled during a polymerization reaction, and the resin is solidified during storage and the like. was there. The same applies to the case where the non-aqueous resin is used for paints and adhesives, and the solidification during storage lowers the adhesive strength. Therefore, in order to solve these problems, conventionally, it was necessary to suppress the amount of a polyfunctional acrylate such as a polyvalent glycol diacrylate to 3% by weight or less. Even if the above problem is solved in this way, the resin is soluble in an aromatic solvent and a microgel cannot be obtained, and thus can be obtained in a dissolved state. Is not desirable because it has a low adsorbing power of the resin to the pigment and an insufficient adhesive power, especially when used for an electrodeposition paint.

Further, the aromatic solvent used in this method has high toxicity and flammability, and has not only a problem in environmental health, but also a problem in that there is a great risk of fire.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to have low toxicity and flammability, low solubility in the resulting resin,
The use of a non-aqueous solvent which is photochemically inert produces excellent non-aqueous microgel resin dispersion which is excellent in preservability, does not cause a decrease in adhesive strength, and has few environmental health problems and a low fire risk. It is an object of the present invention to provide a method and a method for producing a non-aqueous microgel having a uniform particle size. Another object of the present invention is to provide:
An object of the present invention is to provide a non-aqueous microgel suitable as an electrophotographic toner.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the problem can be solved by copolymerization with a combination of specific monomers in a non-aqueous solvent, and have reached the present invention.

That is, the present invention provides at least one kind of monomer A selected from the group consisting of monomers represented by the following general formulas (1) to (3) in a non-aqueous solvent in the presence of a polymerization initiator: A method for producing a microgel, comprising polymerizing a monomer mixture containing at least a crosslinking agent B.

General formula (1) RCH ＝ CHO (where R represents H or C _n H _{2n + 1} , n = 1 to 20) General formula (2)

[0008]

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Wherein R represents H or CH ₃ , X and Y each represent a halogen or an alkyl group.

[0010]

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Wherein R represents H or CH ₃ , and X represents a halogen or an alkyl group.

Formula (1) RCH ＝ CHO (where R represents H or C _n H _{2n + 1} (n = 1 to 20)) A monomer represented by the above formula (1) used in the present invention. As A, for example, No. 1 CH ₃ CH = CHO, No. 2 CH ₂ = CHO, No. 3 C ₂ H ₅ CH = CHCHO, No. 4 C ₃ H ₇ CH = CHO CHO, No. 5 C _{5 H 11 CH = CHCHO, No.6 C} 10 H 21 CH = CHCHO, No.7 C 12 H 25 CH = CHCHO, No.8 C 16 H 33 CH = CHCHO, No.9 C 18 H 37 CH = CHCHO, No.10 C ₂₀ H ₄₁ CH = CHCHO and the like.

The monomer A represented by the general formula (2) used in the present invention includes, for example,

[0014]

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And the like.

The monomer A represented by the above general formula (3) includes, for example,

[0017]

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And the like.

The polyfunctional monomer B which is a crosslinking agent used in the present invention includes polyhydric alcohols and dimethacrylates (eg, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol). Glycol triacrylate, triethylene glycol trimethacrylate, butanediol diacrylate, butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6
-Hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylol methane triacrylate, tetramethylol methane trimethacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, dipropylene glycol diacrylate, dipropylene Glycol dimethacrylate, trimethylol hexane triacrylate, trimethylol hexane trimethacrylate,
Pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, trimethylolethane triacrylate, trimethylolethane methacrylate), divinylbenzene, and the like.

In addition, general formula (4) RCH = CHCOOCH = CH ₂ [wherein R represents C _n H _{2n + 1} (n = 1 to 20)] general formula (5) (CH ₂ = CRCOO) ₂ A monomer represented by O [where R represents C _n H _{2n + 1} (n = 1 to 20) or H] can be used as the crosslinking agent monomer B.

Examples of the monomer B represented by the general formula (4) used in the present invention include: No. 1 CH ₃ —CHＣＨCH—COOCH ＝ CH ₂ , No. 2 C ₂ H ₅ —CH ＝ CH -COOCH = CH ₂ , No. 3 C ₃ H ₇ -CH = CH-COOCH = CH ₂ , No. 4 C ₄ H ₉ -CH = CH-COOCH = CH ₂ , No. 5 C ₅ H ₁₁ -CH = CH-COOCH = CH ₂ , No. 6 C ₈ H ₁₇ -CH = CH-COOCH = CH ₂ , No. 7 C ₁₀ H ₂₁ -CH = CH-COOCH = CH ₂ , No. 8 C ₁₅ H ₃₁ -CH = CH-COOCH = CH _2, can be cited _{No.9 C 20 H 41 -CH = CH} -COOCH = CH 2 and the like.

Examples of the monomer B represented by the above general formula (5) include No. 1 (CH ₂ ＣＨCH—COO) ₂ O and No. 2 [CH ₂ ＣC (CH ₃ ) —COO] _2. O, No. 3 [CH ₂ ＣC (C ₂ H ₅ ) -COO] ₂ O, No. 4 [CH ₂ ＣC (C ₅ H ₁₁ ) -COO] ₂ O, No. 5 [CH ₂ ＣC _{(C 12 H 25) -COO]} 2 O, No.6 [CH 2 = C (C 18 H 37) -COO] 2 O, No.7 [CH 2 = C (C 20 H 41) -COO] 2 O 2 and the like can be mentioned.

In the present invention, when the monomer A is a monomer represented by the general formula (1) with respect to all monomers, 30
90 to 90% by weight, 1 to 50% by weight in the case of the general formulas (2) and (3), and 0.1 to 15% by weight when the monomer B is used with the monomer of the general formula (1) %, And when used with the general formulas (2) and (3), can be copolymerized at 0.01 to 30% by weight.

The monomer A component contributes to the formation, dispersion and adhesion of the microgel, and the effect is reduced when the monomer A component of the general formula (1) is less than 30% by weight. Also 90
Exceeding the weight percentage produces a macrogel.

On the other hand, when the amount of the monomer B is less than 0.1% by weight,
Microgels are less likely to form. On the other hand, if it exceeds 15%, it becomes easy to form a macrogel.

When the amount of the monomer A component represented by the general formulas (2) and (3) is less than 1% by weight, the effect is not obtained.
If it exceeds, the particle size becomes too large. When combined with the general formulas (2) and (3), the monomer B is 0.01%
%, The effect is not obtained, and if it exceeds 30% by weight, macrogelation is not preferred.

In the present invention, another polymerizable monomer C or fine silica particles or a softening point of 60 to 1 is added to the resin production process.
A wax or polyolefin at about 30 ° C. can be added. When silica fine particles are used, it is considered that the resin is obtained in a state where the silica fine particles are incorporated in the network structure. In this case, the silica itself, of course, does not undergo physical changes such as dissolution during the reaction. In any case, in the case of silica, the specific gravity is close to the dispersion medium,
Further, by preventing gelation of the resin, the 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, as a result of precipitation into fine particles by cooling, the resin is obtained in a state adsorbed by these fine particles. It is considered something. Here, wax or polyethylene has a specific gravity close to that of the dispersion medium and prevents gelling of the resin, and also has a molecular structure similar to that of the dispersion medium.
Not only does it help to improve dispersion stability, it also helps to improve adhesion because of its low softening point. The addition amount of silica, wax or polyolefin is suitably about 1 to 50 parts by weight based on 100 parts by weight of the resin.

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

In the present invention, other monomers can be copolymerized if necessary. Such other polymerizable monomers C include polar monomers and other reactive monomers, and as the polar monomers, unsaturated carboxylic acids, unsaturated carboxylic anhydrides, unsaturated nitrogen-containing compounds,
Examples include glycidyl group-containing unsaturated compounds, alkyl acrylate (1 to 5 carbon atoms) esters and / or alkyl methacrylate (1 to 5 carbon atoms) esters. Here, examples of the unsaturated carboxylic acid and its anhydride include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, aconitic acid, cinnamic acid and anhydrides thereof. Examples of the unsaturated nitrogen-containing compound include vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine, N-vinylpyridine, N-vinylimidazole,
Examples thereof include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and the like. Further, as the alkyl (C1-5) ester of acrylic acid or methacrylic acid, methyl acrylate, methyl methacrylate,
Examples thereof include ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, and butyl methacrylate. Further, typical examples of the glycidyl group-containing unsaturated compound include glycidyl acrylate and glycidyl methacrylate.

Other polymerizable monomers C include styrene, vinyl toluene, vinyl acetate and the like.

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

The non-aqueous solvents used in the present invention include aliphatic hydrocarbons, various silicone oils, fluorine oils, mineral oils, vegetable oils and the like. As the aliphatic hydrocarbon, ligroin, n-hexane, n-pentane, n-heptane, n
-Octane, i-octane, 1-dodecane, i-nonane (as the above commercially available products, Expar Isopar H,
G, L, K: Naphtha No. 6 and Shell Sole manufactured by Ciel Oil Co., Ltd.), carbon tetrachloride, perfluoroethylene and the like. These aliphatic hydrocarbons have higher flash points and lower toxicity than aromatic solvents such as benzene and toluene. Since the solubility of the resin of the present invention is lower than that of the aromatic solvent, the resin is less likely to gel or solidify during the polymerization reaction or storage. These petroleum aliphatic hydrocarbons are solvents having a high insulating property (electric resistance of 10 ¹⁰ Ω · cm or more) and a low dielectric constant (dielectric constant of 3 or less). In addition, an aromatic solvent such as benzene or toluene may be added to these aliphatic solvents as long as the amount is small.

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

[0034] Pigments include carbon black, oil blue, alkali blue, phthalocyanine blue, phthalocyanine green, spirit black, aniline black, oil violet, benzine yellow, methyl orange, brilliant carmine, fast red, crystal violet, ferric oxide, nigrosine, and oxide. Dyes or pigments such as titanium and zinc oxide are exemplified.

The microgel containing the pigment obtained according to the present invention is useful as an electrophotographic toner.

An embodiment of the present invention will be described below.

[0037]

【Example】

Example 1 In a 2.0-liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 300 g of isooctane was placed, and 95 g
Heated to ° C. A solution consisting of 190 g of the monomer A of the general formula (1) No. 6, 10 g of methacrylic acid, 10 g of divinylbenzene and 6 g of azobisisobutyronitrile was added dropwise thereto over 3 hours, and then at the above temperature for another 4 hours. The polymerization reaction was carried out by stirring, and the polymerization rate was 93% and the viscosity was 260
A cp resin dispersion was obtained. The particle size of the resin was 2-3 μm. When dodecyl methacrylate was used in place of the No. 6 monomer, there was a particle size distribution of 0.3-4 .mu.m.

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 heated at 100 ° C.
, And then cooled to a viscosity of 250 cp and a particle size of 3
~ 4μ of colloidal silica-containing microgel resin dispersion was obtained.

Example 3 In the same flask as in Example 1, silicone oil, KF58
300 g (manufactured by Shin-Etsu Silicone Co., Ltd.) was taken and heated to 90 ° C. 300 g of a monomer A represented by the general formula (1) No. 7 and N
A solution consisting of 5 g of vinylpyridine, 25 g of ethylene glycol dimethacrylate and 3 g of benzoyl peroxide was added dropwise over 1.5 hours, followed by stirring at the above temperature for 4 hours to carry out a polymerization reaction, a polymerization rate of 96% and a viscosity of 720 cp, A microgel resin dispersion having a particle size of 2 to 3 μ was obtained. When lauryl methacrylate is used in place of the monomer of No. 7, 3
There was a particle size distribution of ９9μ.

Example 4 In a flask, 300 g of the microgel resin dispersion obtained in Example 3 was mixed with 20 g of bleached beeswax, and mixed at 95 ° C. for 2 hours.
After stirring for 2 hours, cool to a viscosity of 510 cp and a particle size of 5 to 6μ.
A microgel resin dispersion containing bleached beeswax was obtained.

Example 5 300 g of Isopar C and 30 g of colloidal silica were placed in the same flask as in Example 1, and heated to 90 ° C. Among them, 150 g of the monomer A represented by the general formula (1) No. 8, 15 g of glycidyl methacrylate, 20 g of trimethylolpropane triacrylate, and 40 g of methyl methacrylate
g of lauroyl peroxide and 6.3 g of lauroyl peroxide were added dropwise, and the mixture was further stirred at the above temperature for 4 hours to carry out a polymerization reaction, a polymerization rate of 95%, a viscosity of 230 cp and a particle size of 2.5.
~ 3 microgel resin dispersions were obtained.

Example 6 The same flask as in Example 1 was charged with 300 g of Isopar L and 60 g of polyethylene (AC-6 manufactured by Allied Chemical Co.) and heated to 95 ° C. Next, the above-mentioned general formula (1)
A solution consisting of 180 g of No. 9 monomer A, 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 mixture was stirred at the above temperature for 3 hours to carry out a polymerization reaction. At a rate of 96%, the viscosity is 240 cp, and the particle size is 0.5 to 1.
A microgel resin dispersion of 0μ was obtained.

Example 7 In the same flask as in Example 1, 300 g of Isopar H, 180 g of No. 10 monomer A of the general formula (1), 40 g of dodecyl acrylate, 15 g of diethylene glycol dimethacrylate, 5 g of acrylic acid and 3 g of benzoyl peroxide were placed in the same flask.
The polymerization reaction was carried out by stirring at 90 ° C. for 6 hours to obtain a microgel resin dispersion having a polymerization rate of 98.3%, a viscosity of 160 cp and a particle size of 1 to 2 μm.

Example 8 300 g of isooctane was placed in a 2.0-liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser.
Heated to ° C. In this, dodecyl methacrylate 190
g, a solution comprising 10 g of the monomer A of the formula (2) No. 1, 10 g of divinylbenzene and 6 g of azobisisobutyronitrile was added dropwise over 3 hours, followed by stirring at the above temperature for another 4 hours to carry out the polymerization reaction. This was performed to obtain a resin dispersion having a polymerization rate of 92% and a viscosity of 260 cp. The particle size of the resin is 1.
5μ.

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 the mixture was heated at 100 ° C.
After heating for 3 hours, the mixture was cooled and had a viscosity of 320 cp and a particle size of 2.
μ of colloidal silica-containing microgel resin dispersion was obtained.

Example 10 Silicone oil and KF58 were placed in the same flask as in Example 8.
300 g (manufactured by Shin-Etsu Silicone Co., Ltd.) was taken and heated to 90 ° C. Next, the monomer A300 of the formula (2) No. 2 was added thereto.
g, 15 g of N-vinylpyridine, 25 g of ethylene glycol dimethacrylate and 3 g of benzoyl peroxide were added dropwise over 1.5 hours, followed by stirring at the above temperature for 4 hours to carry out a polymerization reaction. Viscosity 160c
p, a microgel resin dispersion having a particle size of 2 to 3 μ was obtained.

Example 11 In a flask, 300 g of the microgel resin dispersion obtained in Example 3 was mixed with 20 g of bleached beeswax, and mixed at 95 ° C. for 2 hours.
After stirring for 2 hours, cool to a viscosity of 200 cp and a particle size of 3-4 μm.
A microgel resin dispersion containing bleached beeswax was obtained.

Example 12 The same flask as in Example 8 was charged with 300 g of tap water and 30 g of colloidal silica, and heated to 90 ° C. 2 in this
A solution consisting of 150 g of ethylhexyl methacrylate, 15 g of glycidyl methacrylate, 20 g of the monomer A of the formula (2) No. (3), 40 g of methyl methacrylate, 15 g of trimethylolpropane trimethacrylate and 6.3 g of lauroyl peroxide was added dropwise.
Further, the polymerization reaction was carried out by stirring at the above temperature for 4 hours to obtain a microgel resin dispersion having a conversion of 96%, a viscosity of 280 cp and a particle size of 1.8 to 2.

Example 13 The same flask as in Example 8 was charged with 300 g of Isopar L and 60 g of polyethylene (AC-6 manufactured by Allied Chemical Co.), and heated to 95 ° C. Next, 180 g of stearyl methacrylate and the monomer A4 of the formula (2) No. 4 were added thereto.
0 g, 3 g of fumaric acid, 20 g of divinylbenzene and 4 g of lauryl peroxide were added dropwise over 3 hours, and the mixture was further stirred at the above temperature for 3 hours to carry out a polymerization reaction. The polymerization rate was 98%, the viscosity was 290 cp, and the particle size was 290 cp. 0.8-1μ
Was obtained.

Example 14 In the same flask as in Example 8, 300 g of Isopar H, 180 g of the monomer A of the formula (2) No. 5, 180 g of dodecyl acrylate, and 15 g of diethylene glycol acrylate
g, 5 g of acrylic acid and 3 g of benzoyl peroxide,
The polymerization reaction was carried out by stirring at 90 ° C. for 6 hours, and the polymerization rate was 95%.
To obtain a microgel resin dispersion having a viscosity of 150 cp and a particle size of 1 to 2 μm.

Example 15 A 2.0-liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 300 g of isooctane,
Heated to ° C. In this, dodecyl methacrylate 190
g, a solution consisting of 10 g of the monomer A of the formula (3) No. 1, 10 g of divinylbenzene and 6 g of azobisisobutyronitrile was added dropwise over 3 hours, followed by stirring at the above temperature for another 4 hours to carry out the polymerization reaction. This was performed to obtain a dispersion having a polymerization rate of 96% and a viscosity of 180 cp. The particle size of the resin is 0.1 to
0.3 μm.

Example 16 300 g of the microgel resin dispersion obtained in Example 15 was mixed with 10 g of colloidal silica in a flask, and
After heating at 3 ° C. for 3 hours, a cooled colloidal silica-containing microgel resin dispersion having a viscosity of 220 cp and a particle size of 0.5 to 0.7 μ was obtained.

Example 17 The same flask as in Example 15 was charged with silicone oil KF9.
6,1.5 (Shin-Etsu Chemical Co., Ltd.), 300g, 90 ° C
Heated. Next, 300 g of the monomer A of the formula (3) No. 2, 5 g of N-vinylpyridine, 25 g of ethylene glycol dimethacrylate, and benzoyl peroxide 3
g of the solution was dropped over 1.5 hours, and the mixture was stirred at the above temperature for 4 hours to carry out a polymerization reaction, thereby obtaining a microgel resin dispersion having a polymerization rate of 98%, a viscosity of 120 cp, and a particle size of 1 to 2 μm.

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 cooled to a viscosity of 240 cp and a particle size of 2-3.
μ of bleached beeswax-containing microgel resin dispersion was obtained.

Example 19 In the same flask as in Example 15, 300 g of tap water and 30 g of colloidal silica were placed and heated to 90 ° C. A solution composed of 150 g of the monomer A of the formula (3) No. 3, 15 g of glycidyl methacrylate, 20 g of trimethylolpropane triacrylate, 40 g of methyl methacrylate and 6.3 g of lauroyl peroxide was added dropwise thereto. The polymerization reaction was carried out by stirring for a period of time, the polymerization rate was 94%, the viscosity was 280 cp, and the particle diameter was 0.8 to 0.1.
A 9μ microgel resin dispersion 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 Company) were placed.
And heated to 95 ° C. Next, the above equation (3) N
o.4 monomer A 180 g, lauryl methacrylate 4
0 g, 3 g of fumaric acid, 20 g of divinylbenzene and 4 g of lauryl peroxide were added dropwise over 3 hours, and the mixture was stirred at the above temperature for 3 hours to carry out a polymerization reaction. The polymerization rate was 96%, the viscosity was 140 cp, and the particle size was 140%. A 0.8 micron microgel resin dispersion was obtained.

Example 21 In the same flask as in Example 15, 300 g of Isopar H, 180 g of the monomer A of the formula (3) No. 5, 180 g of dodecyl acrylate, 15 g of diethylene glycol dimethacrylate, 5 g of acrylic acid and 3 g of benzoyl peroxide were taken, and 90 ° C. And a polymerization reaction was carried out by stirring for 6 hours to obtain a microgel resin dispersion having a polymerization rate of 92%, a viscosity of 150 cp and a particle size of 0.6 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.
Heated to ° C. In this, dodecyl methacrylate 190
g, 10 g of methacrylic acid, 10 g of monomer A of the general formula (2) No. (1) and 6 g of azobisisobutyronitrile,
After a solution consisting of 15 g of ethylene glycol dimethacrylate and 50 g of carbon black (Mitsubishi MA100) was added dropwise over 3 hours, the mixture was further stirred at the above temperature for 4 hours to carry out a polymerization reaction, and a polymerization rate of 97.0% and a viscosity of 370 cp were obtained. A microgel colorant was obtained. The particle size of the microgel colorant was 0.92μ.

100 g of this microgel coloring agent was dispersed in 1000 ml of Isopar H, and a plain paper copying machine Ricopy DT was used.
As a result of copying at -1200, a copy having a resolving power of 80 and a fixability of 87% was obtained, and the number of endurable sheets for offset printing was 30,000.

Example 23 300 g of the microgel colorant obtained in Example 22 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 diameter of 1. A 2μ dry toner was made. Recopy FT640
0 (manufactured by Ricoh), the resolution was 7.1 lines /
mm, fixability 92% Offset did not occur and environmental characteristics were good.

Example 24 Silicone oil KF9 was placed in the same flask as in Example 22.
6, 1.5 Take 300 g of Shin-Etsu Silicone Co., Ltd. at 90 ° C
Heated. Next, 30 g of trimethylolpropane triacrylate, 50 g of crystal violet, 300 g of lauryl methacrylate, and N-vinylpyridine 5
g, a solution composed of 25 g of the monomer A of the general formula (2) No. (2) 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 carry out a polymerization reaction. A microgel colorant having a viscosity of 190 cp and a particle size of 1, 2, or 3 at 0.0% was obtained. 100g of this microgel colorant
Was dispersed in 1000 ml of iriddecane to obtain a liquid developer. When the image was copied by Ricoh DT1200, the resolution was 8.0 lines / mm and the fixability was 85%.

Example 25 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. In this, 150 g of styrene and 15 of glycidyl methacrylate
g, 20 g of the monomer A of the general formula (2) No. (3), 40 g of methyl methacrylate and 6.3 g of lauroyl peroxide, 10 g of divinylbenzene, carbon degussa,
A dispersion obtained by dispersing 100 g of Special Black No. 4 with the monomer in a ball mill for 42 hours was added dropwise over 1 hour, followed by stirring at the above temperature for 4 hours to carry out a polymerization reaction, a polymerization rate of 96.0% and a viscosity of 410 cp. A microgel colorant with a particle size of 0.85μ was obtained.

When 0.8 μm of the microgel colorant was evaluated as a dry toner, the resolution was 8.0 lines / mm, the fixability was 92%, and the offset occurred even at a fixing roller temperature of 100 to 200 ° C. using Ricopy FT6400 (manufactured by Ricoh). Did not. Further, no decrease in image density was observed even under a 30 ° C.-80% RH environment (normal temperature: 20-60% RH).
H, ID 1.43, 30 ° C.-80% RHID 1.4
1).

[0064]

Example 26 300 g of isooctane was placed in a 2.0-liter four-necked flask equipped with a stirrer, a thermometer and a reflux condenser.
Heated to ° C. In this, dodecyl methacrylate 190
g, 10 g of methacrylic acid, 10 g of monomer A of the 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 3 hours, followed by stirring at the above temperature for another 4 hours to carry out a polymerization reaction, a polymerization rate of 96.3% and a viscosity of 30.
An 8 cp microgel colorant was obtained. The particle size of the microgel colorant was 0.83 μm.

100 g of this microgel colorant was dispersed in 1000 ml of Isopar H, and a plain paper copier Ricopy DT was used.
When the image was copied at -1200, a copy having a resolution of 613 and a fixability of 87% was obtained, and the durability of the toner was 30,0.
It was 00 sheets.

Example 27 In a flask, 300 g of the microgel colorant obtained in Example 26 was mixed with 10 g of colloidal silica, heated at 100 ° C. for 3 hours, cooled, and the solvent was evaporated to give a particle diameter of 1. A 2μ dry toner was made. Recopy FT640
0 (manufactured by Ricoh), the resolution was 7.3 lines /
mm, fixability 92% Offset did not occur and environmental characteristics were good.

Example 28 The same flask as in Example 26 was charged with silicone oil KF9.
6, 1, 5 Take 300 g of Shin-Etsu Silicone Co., Ltd. at 90 ° C
Heated. Next, add this to Crystal Violet 50
g, 300 g of lauryl methacrylate, 5 g of N-vinylpyridine, 25 g of monomer A of the general formula (1) No. (2)
And 3 g of benzoyl peroxide were added dropwise over 1.5 hours, followed by stirring at the above temperature for 4 hours to carry out a polymerization reaction, a polymerization rate of 97.0%, a viscosity of 180 cp, and a particle size of 1 to 2 μm.
Microgel colorant was obtained.

100 g of this microgel colorant was dispersed in 1000 ml of iriddecane to obtain a liquid developer. When copied with Ricoh DT1200, the resolution is 9.0 lines / m
m, and the fixing property was 85%.

Example 29 300 g of corn oil and 30 g of colloidal silica were placed in the same flask as in Example 26, and heated to 90 ° C. In this, 150 g of styrene and 15 of glycidyl methacrylate
g, 20 g of monomer A of the general formula (1) No. (3), 40 g of methyl methacrylate and 6.3 g of lauroyl peroxide, carbon degussa, special black No. 4
Was dispersed in a ball mill for 42 hours in a ball mill for 1 hour, and the mixture was further stirred at the above temperature for 4 hours to carry out a polymerization reaction. The polymerization rate was 95.9% and the viscosity was 301.
A microgel colorant having a cp and a particle size of 0.79 μ was obtained.

When 0.8 μm of this microgel colorant was evaluated as a dry toner, no offset occurred even when the recopy FT6400 (manufactured by Ricoh) had a resolving power of 本 / mm, a fixing property of 93%, and a fixing roller temperature of 100 to 200 ° C. . Further, no decrease in image density was observed even at a temperature of 30 ° C. to 80% RH (ambient temperature: 20 to 65% RH).
H, ID 1.42, 30 ° C.-80% RH ID 1.4
0).

Example 30 In the same flask as in Example 26 , 300 g of Isopar L and 60 g of polyethylene (AC-6 manufactured by Allied Chemical Co.)
And heated to 95 ° C. Next, 10 g of stearyl methacrylate, 40 g of lauryl methacrylate, 3 g of fumaric acid, a monomer A2 of the general formula (1) and No. (4)
0 g, lauryl peroxide 4 g, alkali blue 40 g, and a liquid obtained by dispersing a reaction solution composed of 50 g of carbon-Mitsubishi MA100 for 24 hours in a ball mill over a period of 3 hours, and further stirred at the above temperature for 3 hours to carry out a polymerization reaction. Polymerization rate 91.8%, viscosity 289 cp, particle size 1.3μ
m of microgel colorant were 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 with the Recopy DT1200, an image with good image sharpness at an image density of 1.36 and a resolution of 8.3 lines / mm was obtained. The fixing rate was 88%.

[0073]

As described above, according to the present invention, a microgel having a uniform particle size can be obtained.

The microgel containing the pigment obtained according to the present invention is useful as an electrophotographic toner.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 29/00 C08L 29/00 33/00 33/00 G03G 9/13 G03G 9/12 321 (31) Priority claim number Patent application Hei 2-285936 (32) Priority date October 25, 1990 (Oct 25, 1990) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 2-285938 (32) Priority date October 25, 1990 (Oct. 25, 1990) (33) Priority claiming country Japan (JP) (72) Inventor Shin Ogawara 2-2-1-211 Ookayama, Meguro-ku, Tokyo (72) Inventor Takanashi Former Ricoh, 1-3-6 Nakamagome, Ota-ku, Tokyo (72) Inventor Tsuyoshi Asami Ricoh, 1-3-6 Nakamagome, Ota-ku, Tokyo (58) Investigated Field (Int. Cl. ⁷ , DB name) C08F 216 / 34,16 / 34 C08F 2 / 06,2 / 44 C08F 220 / 00,20 / 00 CA (STN)

Claims (5)

(57) [Claims] At least one monomer A selected from the group consisting of monomers represented by the following general formulas (1) to (3) in a non-aqueous solvent in the presence of a polymerization initiator, and a crosslinking agent B A method for producing a microgel, comprising polymerizing a monomer mixture containing at least General formula (1) RCH ＝ CHO (where R represents H or C _n H _{2n + 1} , n = 1 to 20) General formula (2) (Wherein R represents H or CH ₃ , X and Y represent a halogen or an alkyl group) General formula (3) (Wherein R represents H or CH ₃ , X represents a halogen or an alkyl group) 2. The method for producing a microgel according to claim 1, wherein the monomer mixture further contains another polymerizable monomer C. 3. The method for producing a microgel according to claim 1, wherein the polymerization system further contains a wax or a polyolefin wax. 4. The method for producing a microgel according to claim 1, wherein the polymerization system further contains a pigment. 5. The method for producing a microgel according to claim 1, wherein the non-aqueous solvent contains at least a solvent selected from aliphatic hydrocarbons, fluorine oils, silicone oils, mineral oils, and vegetable oils.