JPH05241374A - Production of electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To improve dispersibility and to eliminate the fogging of a picture and the contamination of machines by suspension-polymerizing a mixture consisting of an addition-polymerizable monomer, a high molecular substance having an oxazoline(OXZ) ring in the molecule and a colorant in the presence of a polymerization initiator. CONSTITUTION:A polyester A having an OXZ ring in the molecule, a polyurethane B having an OXZ ring in the molecule and a styrenic copolymerizable resin C having an OXZ ring in the molecule are exemplifed as the high molecular substance having an OXZ ring in the molecule. The polyester A is synthesized by thermally polymerizing a polybasic acid (a), a polyhydric alcohol (b) and an oxazoline compd. (c) having a hydroxyl group in the molecule having a structure shown by the formula or by heating the lower ester of a polybasic carboxylic acid, the polyhydric alcohol (b) and the oxazoline compd. (c) to cause transesterification. In the formula, R1 is alkylene or arylene groups, R2 is alkylene groups, and R3, R4 and R5 are hydrogen or alkyl groups.

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 a toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, etc. The toner obtained has good pigment dispersibility. The feature is that a clear image can be obtained.

[0002]

2. Description of the Related Art Conventionally, toners for developing electrostatic images have been prepared by mixing pigments such as carbon black, phthalocyanine blue, carmine 6B, benzidine yellow and magnetite with a binder resin, melt-kneading them, and cooling and pulverizing them with a jet mill. It is manufactured through a process of pulverizing with a machine and classifying particles of 5 to 25 μm.

However, since the pigment such as carbon black has a poor affinity with the binder resin, it has to be dispersed for a long time with a powerful kneader such as a ball mill. Insufficient dispersion of the pigment causes the pigment to aggregate and become inhomogeneous in the toner particles, or separate from the resin, which hinders the dispersion stability of suspension polymerization and reduces the particle size. The particles have a wide distribution, which is not preferable as a toner. That is, such toner causes inconveniences such as image fogging, insufficient resolution, and machine contamination.

Further, since such a method requires a great deal of labor and energy for melt-kneading and pulverizing, the advent of a more streamlined manufacturing method is desired. As an attempt to do so, a pigment such as carbon black and other additives are dispersed or dissolved in an addition polymerizable monomer, suspended in an aqueous medium as fine particles of about 5 μm, and heated in the presence of a polymerization initiator. Various methods have been proposed for producing fine particle toner by stirring.

The method for producing a toner by the suspension polymerization method has an economical advantage that the production process is labor-saving and, in addition, a toner having a finer particle diameter can be obtained as compared with a toner obtained by conventional kneading and pulverization. There is also a feature that the resolution of the image is high.

Specifically, for example, a method of heating a monomer in the presence of carbon black and graft-polymerizing it on carbon black (Japanese Patent Laid-Open No. 58-116944) has been disclosed. Although excellent dispersibility in the polymerizable monomer can be obtained, during the graft polymerization,
It requires a long reaction time at a high temperature, which is disadvantageous in the manufacturing process. Other methods have been disclosed in which carbon black is dispersed in a monomer in the presence of a polymerization initiator (JP-A-57-181553 and JP-A-61-23533). Dispersion is not satisfactory.

[0007]

The present invention is excellent in the dispersibility of the pigment by the suspension polymerization method similar to the above, and it is
An object of the present invention is to provide a method for producing a toner for developing an electrostatic charge image, which does not cause insufficient resolution and mechanical contamination.

[0008]

Means for Solving the Problems The present inventors have found that when a pigment is mixed with an addition polymerizable monomer, a small amount of a polymer substance having an oxazoline (hereinafter abbreviated as OXZ) ring in the molecule is used. It was found that the addition of the pigment markedly improved the dispersibility of the pigment, and the present invention was completed.

That is, the present invention is characterized in that a mixture of at least an addition-polymerizable monomer, a polymer having an OXZ ring in the molecule, and a colorant is subjected to suspension polymerization in the presence of a polymerization initiator. And a method for producing a toner for developing an electrostatic image.

The polymer substance having an OXZ ring in the molecule used in the present invention includes a polyester (A) having OXZ in the molecule, a polyurethane (B) having OXZ in the molecule, and an OXZ ring in the molecule. Examples thereof include styrene-based copolymer resin (C).

The polyester (A) undergoes a heat polymerization reaction of a polybasic acid (a), a polyhydric alcohol (b) and an oxazoline compound (c) having a hydroxy group in the molecule having the following structure, or It is synthesized by heating a lower ester of a carboxylic acid, a polyhydric alcohol (b) and an oxazoline compound (c) to carry out a transesterification reaction.

[0012]

[Chemical 1]

In the formula, R ₁ is an alkylene group, a cycloalkylene group or an arylene group, R ₂ is an alkylene group, R ₃ , R
₄ , R ₅ represents hydrogen or an alkyl group.

[0014]

[Chemical 2]

In the formula, R ₁ is an alkyl group, a cycloalkyl group or an aryl group, R ₂ and R ₃ are alkyl groups, and R ₄ and R ₅ are hydrogen or an alkyl group.

[0016]

[Chemical 3]

In the formula, R ₁ represents an alkyl group, a cycloalkyl group or an aryl group, R ₂ represents an alkyl group R ₃ , R ₄ or R ₅ represents hydrogen or an alkyl group. OXZ represented by formula (III)
Since the compound is monofunctional, it functions as a molecular weight regulator.

Various methods for producing these OXZ compounds have been disclosed (Chemical Review, Vol. 71, p. 483, 19).
71), but the most typical method is a method of heating amino alcohols and carboxylic acids to perform dehydration ring closure.

Examples of amino alcohols include 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol and 2-amino-2-hydroxymethyl-1,3-propanediol, and carboxylic acid. As, lower fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, higher fatty acids such as stearic acid, palmitic acid, oleic acid, benzoic acid, succinic acid, adipic acid, sebacic acid, dibasic acids such as terephthalic acid, etc. It is illustrated.

Examples of the polybasic acid constituting the polyester in the present invention include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecenyl succinic acid, n-dodecyl succinic acid, malonic acid, maleic acid, fumaric acid, citracone. Examples thereof include dibasic acids such as acid, itaconic acid, glutaconic acid, cyclohexane-dicarboxylic acid, orthophthalic acid, isophthalic acid and terephthalic acid.

As the polyhydric alcohol constituting the polyester in the present invention, ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,
3-propylene glycol, 1,4-butanediol,
1,3-butanediol, 1,4-butenediol,
Examples of dihydric alcohols include 1,5-pentanediol, 1,6-hexanediol, hydrogenated bisphenol A, hydrogenated bisphenol A alkylene oxide adduct, and bisphenol A alkylene oxide adduct.

Polyurethane (B) is synthesized by synthesizing a polyester polyol having OXZ in the molecule according to the above method, and then adding polyisocyanate to carry out a urethanization reaction.

The styrene-based copolymer resin (C) is styrene, vinyltoluene, α-methylstyrene, methylmethacrylate, ethylmethacrylate, propylmethacrylate, n-butylmethacrylate, t-butylmethacrylate, 2-ethylhexylmethacrylate. One or more addition-polymerizable monomers such as acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, acrylic acid and methacrylic acid, and 2-vinyl-2- OXZ, 5-methyl-2-vinyl-2-OXZ, 4,4-dimethyl-2-vinyl-2-OXZ, 4,4-dimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazine, 4,4,6-trimethyl-2-vinyl- , 6 Jihidoro 4H over 1,3 Okisajin, 2-isopropenyl Lu 2-0XZ, 4, 4
-Dimethyl-2-isopropenyl-2-OXZ, 4-acryloylurooxymethyl-2,4-dimethyl-2-O
XZ, 4-methacryloyloxymethyl-2-phenyl-4-methyl-2-OXZ, 2- (4-vinylphenyl) -4,4-dimethyl-2-OXZ, 4-ethyl-4
-Hydroxymethyl-2-isopropyl-2-OXZ,
It is obtained by copolymerizing with vinyl OXZs such as 4-ethyl-4-carbethoxymethyl-2-isopropenyl OXZ.

The content of the OXZ ring in the present invention is not specified, but the addition polymerizable monomer and OXZ in the molecule are not specified.
With respect to the total amount of polymer substances containing OXZ skeleton (C ₃ N
O) is preferably 0.001 to 5%. 0.001%
If it is less than 5%, the effect of dispersing the pigment is small, and if it exceeds 5%, the resin may be colored or the hygroscopicity may increase.

The addition-polymerizable monomer of the present invention includes the following. Styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene Styrene such as p-tert-butylstyrene, pn-hexylstyrene, pn-dodecylstyrene and its derivatives: Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride: vinyl acetate, propion Vinyl esters such as vinyl acrylate and vinyl benzoate: methyl methacrylate, ethyl methacrylate, propyl methacrylate, -n-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate,
Α-methylene aliphatic monocarboxylic acid esters such as n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate: methyl acrylate, ethyl acrylate, acrylic Propyl acid, n-butyl acrylate, teracrylate
Acrylic esters such as t-butyl, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate: vinyl methyl ether, vinyl ethyl ether, Vinyl ethers such as vinyl isobutyl ether: Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone: N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole,
N-vinyl compounds such as N-vinylpyrrolidone: vinylnaphthalenes: acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

Further, a crosslinking agent may be present to polymerize the addition-polymerizable monomer to obtain a crosslinkable polymer. As the cross-linking agent, divinylbenzene, divinylnaphthalene, divinyl ether, divinyl sulfone, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, 1, 3-butylene glycol dimethacrylate,
1,6-hexane glycol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4-acryloxydiethoxyphenyl) propane, trimethylolpropane trimethacrylate, trimethylol Examples thereof include propane triacrylate, tetramethylolmethane tetraacrylate, dibromoneopentyl glycol dimethacrylate, diallyl phthalate and the like.

The above-mentioned cross-linking agent has fixing property and offset resistance,
From the viewpoint of durability and the like, the amount used is preferably 0.2 to 2.0% by weight based on the polymerizable mixture. As the polymerization initiator, known polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, isopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide. Etc.

The amount of these polymerization initiators used is generally 0.1 to 10%, preferably 0.5 to 5%, based on the weight of the polymerizable mixture. Known pigments and dyes can be used as the colorant of the present invention. For example, among the pigments, black pigments include channel black, furnace black, thermal black, acetylene black, and the like, and color pigments include cadmium yellow, Hansa yellow G, naphthol yellow S, pyrazolone red, permanent red 4R, molybdenum. Orange,
Asto violet red B, phthalocyanine blue B, fast sky blue, phthalocyanine green, malachite green, naphthol green B and the like can be mentioned.
Examples of the dye include C.I. I. Assid blue 9, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I.
I Modern Blue 7, C.I. I Direct Green 6,
C. I Basic Green 4, CI Basic Green 6
Etc.

To use the toner of the present invention as a magnetic toner, magnetic powder may be contained. As such magnetic powder, for example, powder of ferromagnetic metal such as iron, cobalt, nickel or powder of alloy or compound such as magnetite, hematite or ferrite is used. The content of these magnetic powders is 15 with respect to the toner weight.
~ 70% is preferred.

Further, among the toner raw material components, a charge control agent, a fluidity modifier, a cleaning agent, and
You may add additives, such as a filler. As the charge control agent, nigrosine dyes, alkoxylated amines, quaternary ammonium salts, alkylamides, phosphorus and tungsten simple substances and compounds, molybdic acid chelate pigments, fluorinated activators, hydrophobic agents are used as charge control agents. And the like. In addition, those that give negative charge include metal salts of monoazo dyes, electron-accepting organic complexes, chlorinated polyolefins, chlorinated polyesters, sulfonylamines of copper phthalocyanine, oil black, metal salts of naphthenic acid, metal salts of fatty acids, resins. Acid soap etc. are mentioned.

As the fluidity modifier, colloidal silica, silicon varnish, metal soap, nonionic surfactant,
There are fine particles of polyvinyl fluoride. Examples of the cleaning agent include aluminum stearate, calcium stearate, zinc stearate, and zinc laurate as metal salts of fatty acids. Other examples include colloidal silica and powder of tetrafluoroethylene resin.

Examples of the filler include calcium carbonate, clay, talc, soft pigment, kaolin, silica and the like. In addition, low molecular weight polyethylene, low molecular weight polypropylene, for the purpose of improving releasability at the time of heat roll fixing,
It is also possible to add a wax-like substance such as microcrystalline wax, carnauba wax, and sol wax in an amount of about 0.5 to 15% by weight.

The charge control agent and the fluidity modifier may be mixed with the resulting toner particles. Examples of the suspension stabilizer used in the present invention include polyvinyl alcohol, gelatin, methylhydropropyl cellulose, ethyl cellulose, hydroxyethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and salts thereof, starch, gum alginate. , Organic suspension stabilizers such as casein, tricalcium phosphate, talc, barium sulfate, bentonite, aluminum hydroxide, ferrous hydroxide, calcium hydroxide, alumina,
Colloidal silica etc. are mentioned. These suspension stabilizers are preferably used in the range of 0.1 to 10% by weight.

As an auxiliary dispersant for the stabilizer, 0.00
1 to 0.1% by weight of surfactant may be used. This promotes the action of the above dispersion stabilizer, and specific examples include sodium dodecylbenzenesulfonate,
Sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium allylalkyl polyethersulfonate, sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, sodium stearate, calcium oleate,
3.3-disulfone diphenylurea, 4,4-diazobisamino-8 naphthol-6-sodium sulfonate, orthocarboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4, 4 diazobis β-naphthol disulfonic acid sodium salt and the like can be mentioned.

Further, the water-soluble monomer is liable to undergo emulsion polymerization in water, and the emulsion-polymerized fine particles stain the suspension-polymerized product. To prevent this, a water-soluble polymerization inhibitor such as a metal salt is added to add water. It is also possible to prevent emulsion polymerization in the phase.
In order to reduce the solubility of monomers in water, NaCl, KC
1, salts such as Na ₂ SO ₃ can also be added.

Next, the method for producing the toner for developing an electrostatic charge image of the present invention will be specifically described. Addition polymerizable monomer and OX in the molecule
A polymeric substance containing Z, a pigment, and if necessary, a charge control agent and other additives are thoroughly mixed with a mixer such as a ball mill or an ultrasonic homogenizer. When the polymer substance containing the OXZ group of the present invention is present, the pigment is not easily separated even if left dispersed for several hours. On the other hand, when the OXZ group is not present, it takes a long time to disperse the pigment, and the pigment is easily separated when left standing.

Next, a polymerization initiator was dissolved in this mixture, and 1
After pouring into an aqueous medium containing 10 times the amount of a dispersant and dispersing the particles into 5 to 25μ fine particles with a powerful disperser such as a homomixer, a homogenizer, or an ultrasonic homogenizer, a comparison is made to the extent that the particles do not coalesce. Polymerization is carried out while circulating nitrogen while gently stirring. Although the polymerization temperature is set by the activation temperature of the initiator, it is usually 50 ° C to 10 ° C.
It is 0 ° C.

After completion of the polymerization, water is separated, washed, dried, and if necessary, classified to obtain a toner. The toner of the present invention thus produced has a uniform particle size of 5 to 5 as compared with the toner obtained by the prior art in which the conventional OXZ group is not present.
Particles of 25μ were obtained in high yield, and the image quality developed using this was high in resolution and good without image fog.

[0039]

EXAMPLES Examples of the present invention will be specifically shown below, but the present invention is not limited to these examples. "Parts" means parts by weight unless otherwise specified.

[Synthesis Example] Synthesis of OXZ compound 2-amino-2-ethyl-1.3-propanediol 2
38 g (2 mol) and 146 g (1 mol) of adipic acid were placed in a flask equipped with a stirrer and reacted at 170 to 190 ° C. for 10 hours while flowing nitrogen to obtain a light brown reaction product. The water effluent was 72 grams. When analyzed by infrared absorption spectrum and C ¹³ NMR, it was confirmed to be an oxazoline compound shown below.

[0041]

[Chemical 4]

Example 1 (Synthesis of Polyester Containing OXZ Group) 31.2 g of the OXZ compound obtained in the synthesis example, 318.7 g of 2.2 mol of bisphenol A ethylene oxide adduct, 166 g of terephthalic acid, And 0.048 g of dibutyltin oxide were placed in a flask equipped with a stirrer,
The mixture was allowed to react at 9 ° C. for 9 hours to give an OXZ skeleton (C ₃ NO) of 2.7.
% Polyester was synthesized. This resin has a softening temperature of 120 ° C., an acid value of 4 mg / g, and a hydroxyl value of 23 mg / g.
Met.

(Synthesis of Toner by Suspension Polymerization) Polyester containing the above OXZ group 5 parts styrene 75 parts n-butyl acrylate 20 parts divinylbenzene 1 part carbon black (MT100 manufactured by Mitsubishi Kasei) 5 parts VISCOL 550P (Sanyo Chemical Co., Ltd.) Polypropylene wax) 4 parts Bontron S-34 (charge control agent manufactured by Orient Chemical Co.) 2 parts The above raw materials were kneaded with a roll mill for 10 hours. During this period, a sample was taken and the dispersed state of carbon black was observed. As a result, the carbon black was dispersed as fine particles at the third hour and was not separated even if left alone.

Next, 2 parts of azobisisobutyronitrile were dissolved in the above-mentioned raw material mixed solution, and 5% by weight of polyacrylic acid (Nippon Pure Chemical, Julimer AC10H) and hydroxyethyl cellulose (Fuji Chemical AG15F). ) 0.0
Add 500 parts by weight of ion-exchanged water in which 2% by weight was dissolved, and use a TK homogenizer manufactured by Tokushu Kikai Kogyo
The mixture was stirred at 000 rpm for 30 minutes to obtain a dispersion of fine particles having a particle size of about 5μ. Next, the mixture was transferred to a flask equipped with a paddle type stirrer, and stirring was continued at 70 ° C. at a stirring rate of 200 rpm for 10 hours while flowing nitrogen to complete the reaction. After cooling to room temperature, strain with a 200 Messi filter cloth, filter, wash,
It was dried to obtain a toner. The yield was 72%. When the particle size distribution was measured with a Leather Micron Sizer manufactured by Seishin Enterprise, the average particle size D ₅₀ corresponding to a cumulative distribution of 50% was 7.
5μ, particle diameter D ₁₀ corresponding to 10% cumulative distribution is 4.2μ
The particle diameter D ₉₀ corresponding to 90% was 10 μ.

30 parts of this toner is used as a carrier E of Nippon Iron Powder.
When mixed with 1000 parts of FV200 / 300 to adjust the developer and subjected to a development test using a TOSHIBA copying machine Rheodry 3504, the resolution, gradation and denseness of the solid part were good, and there was no blurring or fog. Good quality images were obtained.

Comparative Example 1 A polyester containing no OXZ was synthesized from 116 g of terephthalic acid, 351.2 g of 2.2 mol of bisphenol A ethylene oxide adduct, and 0.048 g of dibutyltin oxide.

When the experiment of Example 1 was conducted using the above polyester instead of the polyester containing OXZ, the pigment dispersibility was difficult when kneading with a roll mill, and even when kneading for 10 hours, carbon black aggregates were formed. Seen and separated on standing. In the suspension polymerization step, the dispersion became unstable 5 minutes after the initiation of the polymerization, so the initial charge and the equivalent amount of the dispersant were added. When the slurry after completion of the polymerization was filtered with a 200-mesh filter cloth, the yield of particles passing through the filter cloth was only 10%, which was not suitable for toner.

Example 2 (Synthesis of Polyurethane Containing OXZ Group) 31 g of the OXZ compound obtained in the synthesis example, 423 g of 2.2 mol of bisphenol A ethylene oxide adduct, 166 g of terephthalic acid, 0 of dibutyltin oxide. 0.06 g was placed in a flask equipped with a stirrer, and dehydration condensation reaction was carried out at 240 ° C. to obtain a polyester polyol containing an OXZ group. Acid value 0.5mgKOH / g, hydroxyl value 77mgKO
It was H / g. Then, at 150 ° C., 47 grams of diphenylmethane diisocyanate was gradually added to give a softening temperature of 110.
The reaction is carried out until the temperature reaches ℃ and the OXZ skeleton (C ₃ NO) is added to 2.
A polyurethane containing 4% was synthesized. (Production of Toner by Suspension Polymerization) The experiment of Example 1 was conducted using the above-mentioned polyurethane containing OXZ group instead of polyurethane containing OXZ group. The dispersibility of carbon black is good, the yield of particles that have passed through a 200 mesh filter cloth is 70%, D ₅₀ is 8.3μ, and D ₁₀ is 5.1.
The μD ₉₀ was 11.7μ. Using this toner, a toner test was conducted in the same manner as in Example 1. As a result, the resolving power, gradation, and denseness of the solid portion were good, and there was no blurring or fog.
Good quality images were obtained.

[Comparative Example 2] 422.8 g of ethylene oxide 2.2 mol adduct of bisphenol A, 166 g of terephthalic acid and 0.06 g of dibutyltin oxide were charged in a flask equipped with a stirrer, and dehydration condensation reaction was carried out at 240 ° C. , Acid value 0.5mg KOH / g hydroxyl value 77mg
A KOH / g polyester polyol was obtained.

Then, 47 g of diphenylmethane diisocyanate was gradually added at 150 ° C. and reacted until the softening temperature reached 110 ° C. to obtain polyurethane. When the experiment of Example 2 was conducted using the above polyurethane instead of the polyurethane containing OXZ, it was difficult to disperse the pigment by kneading with a roll mill, and agglomerates of carbon black were observed even after kneading for 10 hours. Then it separated. In the suspension polymerization step, the dispersion became unstable 5 minutes after the initiation of the polymerization, so the initial charge and the equivalent amount of the dispersant were added. When the slurry after the completion of polymerization was filtered with a 200-mesh filter cloth, the yield of particles passing through the filter cloth was only 8%, which was not suitable for toner. [Example 3] In Example 1 A reactive polystyrene XUS made by Dow Chemical Co., which is a copolymer of styrene and vinyl oxazoline, instead of the polyester containing OXZ.
The raw material mixture was kneaded by a roll mill using 5 weight parts of -40056.01 (oxazoline content rate 1%). The carbon black was uniformly dispersed within 3 hours.

To this mixture, 2 parts by weight of azoisobutyronitrile as an initiator was added and dissolved. Next, 100 parts of calcium phosphate 10% slurry manufactured by Taihei Chemical Industry, 1 part of Shin-Etsu Chemical Poval PA05, and 500 parts of ion-exchanged water were added, and 1 using a TK homogenizer manufactured by Special Machine Industry Co., Ltd.
The mixture was stirred at 0000 rpm DE for 5 minutes to obtain a fine particle dispersion having a particle size of 5 μm.

Then, the mixture was transferred to a flask equipped with a paddle type stirrer, and stirring was continued at 70 ° C. at a stirring rate of 200 rpm for 10 hours while flowing nitrogen to complete the reaction. After cooling to room temperature, strain with a 200 Messi filter cloth, filter, wash,
It was dried to obtain a toner. The yield was 90%. When the particle size distribution was measured with a Leather Micron Sizer manufactured by Seishin Enterprise, D ₅₀ was 5.5 μ, D ₁₀ was 2.8 μ, and D ₉₀ was 8.
It was 6μ.

30 parts of this toner is used as a carrier E made of Nippon Iron Powder.
When mixed with 1000 parts of FV200 / 300 to adjust the developer and subjected to a development test using a TOSHIBA copying machine Rheodry 3504, the resolution, gradation and denseness of the solid part were good, and there was no blurring or fog. Good quality images were obtained.

Comparative Example 3 The experiment of Example 3 was repeated using 5 parts of polystyrene (Dick Styrene CR2500) manufactured by Dainippon Ink and Chemicals instead of styrene-vinyl oxazoline. Dispersion of carbon black is difficult 10
Aggregates of carbon black were observed even after kneading for a while, and carbon black separated when left standing. 70% of the particles obtained by suspension polymerization passed through a 200-mesh filter cloth.
Thus, D ₅₀ is 14.5μ, D ₁₀ is 3.1μ, and D ₉₀ is 21.
The particle size distribution was broad at 2μ.

When an image test was carried out using this toner, blurring and fog occurred and the image was unclear. [Comparative Example 4] Styrene 80 parts n-Butyl acrylate 20 parts Divinylbenzene 1 part Carbon black 5 parts Viscole 550P 4 parts Bontron S-34 2 parts The experiment of Example 3 was carried out using the above raw materials containing no polymer substance. I repeated.

It is difficult to disperse carbon black, and agglomerates of carbon black were observed even after kneading for 10 hours, and carbon black was separated when left standing. 60% of the particles obtained by suspension polymerization passed through a 200 mesh filter cloth,
D ₅₀ is 14.2μ, D ₁₀ is 3.0μ, D ₉₀ is 20, 5μ
The particle size distribution was broad.

When an image test was carried out using this toner, blurring and fog occurred and the image was not clear. [Example 4] Fastogen Super Red 7 manufactured by Dainippon Ink and Chemicals, which is a red pigment instead of carbon black
The experiment of Example 3 was repeated using 5 parts of 100Y, replacing Bontron S-34 with Bontron E-84. The dispersibility of the pigment was good. The yield of particles passing through a 200 mesh filter cloth is 75%, D ₅₀ is 14.2μ,
D ₁₀ was 3.0 μ and D ₉₀ was 20.5 μ. When a development test was conducted, a clear red image free from fogging and blurring was obtained.

Comparative Example 5 The experiment of Example 4 was repeated without adding the polymer substance containing oxazoline. Two
Only 15% yield of particles passed through 00 Messi filter cloth
The D ₅₀ was 30 μ, the D ₁₀ was 20 μ, and the D ₉₀ was 40 μ, and the particle size was too large to be suitable as a toner.

Comparative Example 6 Instead of the OXZ group-containing polyester, 2-m-phenylene bis (2-oxazoline) and 2-p-phenylene bis (2) manufactured by Showa Denko KK were used.
-Oxazoline) was used to knead the raw material mixture in Example 1 with a roll mill and the dispersibility of carbon black was examined. The effect of improving the was not found.

[0060]

According to the method of the present invention, it is possible to produce a toner for developing electrostatic images in which the pigment is uniformly dispersed and the particle size distribution is sharp by suspension polymerization. This toner enables clear image copying.

[Procedure amendment]

[Submission date] February 23, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Further, a crosslinking agent may be present to polymerize the addition-polymerizable monomer to obtain a crosslinkable polymer. As the cross-linking agent, divinylbenzene, divinylnaphthalene, divinyl ether, divinyl sulfone, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, 1,3 -Butylene glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4-acryloxydiethoxyphenyl) Propane, trimethylolpropane trimethacrylate, trimethylolpropane triac Rate, tetramethylolmethane tetraacrylate, dibromo neopentyl glycol dimethacrylate, and diallyl phthalate and the like.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

To this mixture, 2 parts by weight of azoisobutyronitrile as an initiator was added and dissolved. Next, 100 parts of 10% calcium phosphate slurry manufactured by Taihei Chemical Industry, 1 part of Poval PA05 manufactured by Shin-Etsu Chemical, and 500 parts of ion-exchanged water were added, and the mixture was stirred at 10,000 rpm for 5 minutes using a TK homogenizer manufactured by Special Machine Industry, A fine particle dispersion having a particle size of 5 μm was obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08F 283/00 MQW 7142-4J 283/02 MQS 7142-4J

Claims (3)

[Claims] 1. A mixture of at least (A) an addition-polymerizable monomer, (B) a polymeric substance having an oxazoline ring in the molecule, and (C) a colorant is suspended in the presence of a polymerization initiator. A method for producing a toner for developing an electrostatic image, which comprises polymerizing. 2. A polymer having an oxazoline ring in the molecule (B), a polyester having an oxazoline ring in the molecule, a polyurethane having an oxazoline ring in the molecule,
The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the toner is one type or two or more types of a styrene-based copolymer resin having an oxazoline ring in the molecule. 3. The oxazoline ring is 0.001 to 5% by weight, based on the total amount of the (A) addition-polymerizable monomer and the (B) polymer substance. Method for producing toner for developing electrostatic image of.