JPH03267947A - Color toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To prevent the deterioration of a heat fixing roll by subjecting a pigment to surface treatment with a surfactant. CONSTITUTION:A pigment is subjected to surface treatment with an anionic, cationic, amphoteric or nonionic surfactant carefully selected according to a toner. The anionic surfactant has high alkalinity and is fit for the surface treatment of a negatively chargeable toner but is not proof against acids. The cationic surfactant has high acidity and is fit for the surface treatment of a positively chargeable toner but is not proof against alkalis. the amphoteric surfactant is stable because of acid and alkali resistances and has high negative or positive chargeability or electrical neutrality. The nonionic surfactant can continuously vary hydrophile-lipophile balance and easily regulates the amt. of electric charges rendered to a toner. The deterioration of a fixing roll can be prevented and the electrostatic charging of a developer can be stabilized.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a color toner for developing electrostatic images, and is applicable to copying machines,
It can be used for laser printers, liquid crystal printers, plain paper facsimiles, etc.

[Prior Art] Conventionally, copying machines that use electrophotography form an electrostatic image on a photoreceptor, then transfer the visualized toner image onto recording paper using a developer, and then use a pressure or heat fixing device. is fixed to obtain a visible image.

The toner used in this method is obtained by melting and kneading a pigment, a polarity control agent, etc. in a thermoplastic resin, and using a pulverizer/classifier to obtain a toner having a desired particle size.

Traditionally, the only toner used in copying machines was black toner, which uses carbon as a coloring agent, but in recent years there has been an increase in demand for monochrome toners such as red and blue, as well as for color copies with the advent of full-color copiers.

However, in a full-color copying machine, since it is necessary to stack multiple color toner layers, the amount of toner adhering to an image is greater than in a black copying machine. For this reason, toners are used that use low-temperature softening binder resins with relatively low molecular weights, such as polyester and epoxy resins, which have excellent fixing properties.

Since such toner has low releasability from the fixing roller at high temperatures, it is likely to cause the so-called hot offset phenomenon. For this reason, a fixing device is used in which a fixing roller coated with a silicone elastomer with improved release properties is coated with a release aid such as silicone oil.

However, in such a color copying machine, as the number of copies increases, the releasability of the fixing roller deteriorates, and the temperature at which hot offset occurs decreases.

When we look at the surface of the fixing roller, which has deteriorated in release properties, we find that the pigment that should have been dispersed in the toner has adhered and penetrated, causing the roller to deteriorate and the life of the roller to be shorter than that of a black copier. There was a problem.

[Problems to be Solved by the Invention] The present invention attempts to solve the above-mentioned problems of the prior art and to supply a toner that does not deteriorate the heat fixing roller.

[Means for Solving the Problem] As a result of intensive research, the present inventors have found that by surface-treating the pigment with a surfactant, the adhesion of the pigment dispersed in the toner to the fixing roller can be reduced, and the roller deterioration can be reduced. It has been found that this method is effective in preventing

The toner of the present invention is based on this knowledge.

Surfactants used for surface treatment of pigments include anionic, cationic, amphoteric and nonionic surfactants.

It is preferable to use different surfactants as follows. For example, anionic surfactants are strongly alkaline and tend to have negative polarity, so they are suitable for treating the pigment surface of negatively charged toners. However, it is sensitive to acids, so care must be taken.

Cationic surfactants are highly acidic and tend to have positive polarity, so they are suitable for treating the surface of pigments in positively charged toners. However, it is sensitive to alkalis, so care must be taken.

Amphoteric surfactants are strong and stable against acids and alkalis, and are easily charged negatively (close to anionic), easily charged positively (close to cationic), and electrically neutral. There are a wide variety of types available, making it suitable as a surface treatment agent for pigments.

Nonionic surfactants can continuously change the balance of hydrophilicity and lipophilicity, making it easy to obtain surfactants with an appropriate balance for the application. Therefore, the amount of charge on the toner can be easily adjusted.

Examples of the binder resin for the toner used in the present invention include polystyrene, poly p-chlorostyrene, polyvinyltoluene, styrene-p-chlorostyrene copolymer, and styrene-p-chlorostyrene copolymer.
Homopolymers of styrene and its substituted products, such as propylene copolymers, styrene vinyl toluene copolymers, and copolymers thereof; styrene-methyl acrylate copolymers, styrene-ethyl acrylate copolymers, styrene-acrylic Copolymers of styrene and acrylic esters such as butyl methacrylate copolymers; styrene-methyl methacrylate copolymers,
Copolymers of styrene and methacrylic esters such as styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-methyl chloromethacrylate copolymer; styrene and acrylic ester and Multi-component copolymers with methacrylic acid esters: Others: styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-butashune copolymer, styrene-vinyl methyl ketone copolymer, styrene-
Styrenic copolymers of styrene and other vinyl monomers such as acrylonitrile-indene copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, Polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin Wax etc. can be used alone or in combination.

Further, the toner of the present invention may contain a small amount of a charge imparting agent, such as a dye or pigment, a charge control agent, etc., in order to provide more efficient charge imparting, but the amount may be considerably less than conventional toners. Examples of charge-imparting agents include metal complexes of monoazo dyes, nitrohumic acid and its salts, salicylic acid, naphthoic acid, metal complexes of dicarboxylic acids such as Co, Cr, and Fe, sulfonated copper phthalocyanine pigments, nitro groups, and halogens. Examples include chlorinated paraffins of styrene oligomers, melamine resins, organic acid salts of metals such as zinc salicylate, chromium salicylate, chromium tert-butylsalicylate, and aluminum tert-butylsalicylate, and organometallic complexes such as zinc α-naphthoate complexes.

As a method for surface treating the pigment in the present invention, a known method can be used. For example, pigments may be dispersed in a solvent, a surfactant solution may be added little by little to the solution while stirring, and then heated or vacuum dried, or the pigment may be placed in a cylinder and blown up with air. There are methods such as spraying a solution and drying it, and using a wet dispersion device such as a ball mill or vibration mill to disperse pigments and surfactants in a solvent, then taking them out and drying them.

Examples of anionic surfactants that treat the pigment surface include fatty acid salts, alkyl sulfates, ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl diallyl ether sulfonates, and alkyl phosphates. The above fatty acid salts include laurate, myristate, valmitate, stearate, oleate, propionate,
caproate, enanthate, caprylate, pelargonate, caprate, undecylate, tridecylate, pentadecylate, fatty acid soaps, organic base soaps, metal soaps, rosin acid soaps, Tall oil soaps, naphthenic acid soaps, bile acid soaps, paraffin oxidized carboxylic acids, oxyfatty acids, paraffin electrolyzed oxidized fatty acids, alkyl side chain fatty acids, polychlorinated fatty acids, maleic acid-bonded carboxylic acids, alkylaryl Carboxylic acid, acid amide bonded fatty acids, acid amide ether bonded carboxylic acid, m-acylaminobenzoic acid,
Urea-bonded carboxylic acid, urethane-bonded carboxylic acid, ester-bonded carboxylic acid, complex ester-bonded carboxylic acid, ether-bonded carboxylic acid, hydrogenated alkylphenoxyacetic acid, polyether-bonded carboxylic acid, modified ether-bonded carboxylic acid, thioether-bonded carboxylic acid, sulfone Bound carboxylic acids, modified sulfone-bonded carboxylic acids, amides, thioether-bonded carboxylic acids, sulfated oils, highly sulfated oils, higher alcohol sulfates, petroleum olefin sulfates, sulfated monoglycerides, lysonoleic acid monoglyceride sulfates, Formaldehyde condensed ester-bonded sulfate ester, fatty acid amide sulfate ester, fatty acid anilide sulfate ester, fatty acid ethanolamide sulfate ester, acylaminocyclohexanol sulfate ester,
Polymerized castor oil ethanolamide sulfate, fatty acid allylamide sulfate, malic acid amide sulfate, urethane-bonded sulfate, amide, sulfonamide-bonded sulfate, polyethylene glycol ether sulfate, alkanesulfonic acid, petroleum sulfonic acid, hydroxyalkyl sulfonic acid , α-sulfo fatty acids, ketosulfonic acids, fatty acid alkyl ester tertiary sulfonic acids,
Fatty alcohol nasulfoacetic acid ester, α-sulfolauric acid ester, dialkyl sulfosuccinic acid, monoalkyl sulfosuccinic acid, modified sulfosuccinic acid ester, taurine-derived amide-bonded sulfonic acid, aminomethane sulfonic acid type amide-bonded sulfonic acid, mercaptoethane sulfonic acid derivative , urethane-linked sulfonic acids, urea-linked sulfonic acids, amides, urethane-linked sulfonic acids, mixed amide ester sulfonic acids, sulfosuccinimides, sulfomalonate dialkylamides, aliphatic ether-linked sulfonic acids, aromatic ether-linked sulfonic acids, sulfoxide-linked sulfones Acid, thioether-bonded sulfonic acid, amidothioether-bonded sulfonic acid, sulfonamide-bonded sulfonic acid, thioamide-bonded sulfonic acid, lower alkylnaphthalene sulfonic acid, lower dialkylnaphthalene sulfonic acid, benzylnaphthalene sulfonic acid, dinaphthylmethane sulfonic acid, alpha-naphthalene sulfonic acid acid, 1.3.8-naphthalenetrisulfonic acid, tetralinsulfonic acid, octahydroanthracenesulfonic acid, benzylsulfanilic acid,
dimethylmethanilic acid, alkylphenol sulfonic acid,
Alkylnaphthol sulfonic acid, cyclohexylnaphthalene sulfonic acid, naphthalene condensate sulfonic acid, rosin sulfonic acid, terpineol sulfonic acid, lignin sulfonic acid, alkylbenzene sulfonic acid, alkylnaphthalene sulfonic acid, alkylphenol sulfonic acid, oleic acid-bonded arylsulfonic acid, alkenylphenol Sulfonic acid, terpenephenol sulfonic acid, dilaurylnaphthalene sulfonic acid, alkyldesoxybenzoin sulfonic acid, acylbenzene sulfonic acid, alkylrosine sulfonic acid, sulfophthalic acid ester, substituted sulfophthalic acid ester, sulfobenzoic acid ester, sulfosalicylic acid ester, sulfonate Phenoxyacetic acid ester, phenol ester sulfonic acid, complex ester-bonded sulfonic acid, arylamide sulfonic acid, acylmethanilic acid,
0-toluidite sulfonic acid, naphthenic acid anilide sulfonic acid, acylaminoarylsulfonic acid, acylanisidine sulfonic acid, acyl toluidine sulfonic acid, phenoxyacetic acid octylcyclohexylamide sulfonic acid,
Hexadecylamine-4-sulfophthalamide, 4-sulfophthalic acid acylaminoanilide, acylaminomethylphenol sulfonic acid, acylaminoethylphenol sulfonic acid, acylaminoethyl phenyl ether sulfonic acid, phenylhydrazito sulfonic acid among fatty acids,
Phenol ether sulfonic acid, cresol ether sulfonic acid, resorcin ether sulfonic acid, phenoxyethyl alkyl ether sulfonic acid, phenoxyethyl alkyl phenol ether sulfonic acid, benzyl ether sulfonic acid, phenylbenzyl ether sulfonic acid, thiothioether bonded alkylaryl sulfonic acid, sulfone bond Alkylaryl sulfonic acid, acetal-bonded alkylanyl sulfonic acid, sulfonic acid ester-bonded alkylaryl sulfonic acid, heterocyclic-bonded alkylaryl sulfonic acid, indole sulfonic acid, lecithin, alkyl phosphate ester, unsaturated acid phosphate ester,
Fatty alcohol polyoxyalkyl ether phosphates, alkylphenol phosphates, polyhydric alcohol fatty acid phosphates, oxyacid ester phosphates, alkyl superphosphates, alkyl phosphites, alkylphosphonic acids, alkylaryls Phosphonic acid, phosphinate amine salt, acyloxyphosphonic acid, oxyphosphonic acid, ketophosphonic acid, sulfonic acid sulfate, alkylsulfinic acid, alkylthiosulfate, alkylhydrosulfite, alkylpersulfate, alkylsulfamic acid, amide-linked sulfamic acid , alkylsulfonamide, alkylacylsulfonamide, alkyldisulfonimide, alkylsulfonylurea, alkyldithiocarbamic acid, and the like.

Examples of cationic surfactants for surface treating pigments include long-chain primary amine salts, higher alkyltrimethylammonium salts, higher alkyldimethylethylammonium salts, higher alkyldimethylbenzylammonium chlorides, higher alkylpyridinium halides, and higher alkylquinolinium. Halide, higher alkylpyridinium sulfate, higher alkylpyridinium sulfonate, triamylbutylammonium cymenesulfonate, dimethylphenylbenzylammonium dibutylnaphthalene sulfonate, trimethylheptylammonium sulfated butyl oleate, dodecylpyridinium abietate,
Alkylaminoethanol, polyhydroxyamine, higher alkylethylenediamine, α-alkylbenzyldiamine, p-alkylcyclohexylamine, N-alkylmorpholine, alkylglucamine, alkylmethoxyaniline, dimethylacylanilium salts, alkylquinoline, alkylaminopyridine, Sulfonamide-linked pyridinium salts, sulfonamide-linked amines, fatty acid hydroxyethylethyleneamide, fatty acid polyethylene polyamide, diacylpolyethylene polyamine, acylaminoethylmorpholine, long-chain aminoethyl acetate amide, long-chain amino acid ethanolamide, acylamino aromatic amine, acylamino fat group amines, nicotinic acid amide, triethanolamine ester, N-alkylethanolamine ester, polyoxyethanolamine fatty acid ester, long-chain amino alcohol ester, ester-bonded pyridinium salts, aminoethylethanolamine ester, amino acid ester, N-alkylglycine ester , betaine ester, diester pyridinium salt, hydroxyethyl aspartate, dimethylaminobenzoic acid ester, hydroxyethyl aromatic amine ester, aminoethylthioether, aminoethylthioalkyl ether, aminophenylsulfone, 2-
Methylbenzimidazole, bisimidacillin, dihydroindole, tetrazolium salts, aminodioxane, 1,2-oxazine derivatives, alkylguanidine, acylaminoguanidine, alkyl biguanide, alkylguanamine, long chain amine oxide, phosphonium salts,
Arsonium salts, chelylamine, higher alkylbenzyldimethylbenzyl chlorides, alkyldimethylmethallylammonium halides, cholanylamine, α-amino fatty acid derivatives, α-aminoketone derivatives, alkylaminoethanol, polyhydroxyamine, bisammonium compounds, ρ-alkylcyclohexylamine , N
- Higher alkylcyclohexylamines, bismorpholinomethyl polyhydric alcohols, glucose Schiff base, higher alkyldimethylanilium salts, ρ-alkylaminodimethylaniline, dimethylacylanilium salt, alkylnicotinium halide salt, alkylpyridine,
Alkylaminopyridine, alkylaminoquinoline, acylaminoethylpyridinium salts, long-chain aminoethylpropionic acid amide, long-chain aminoacetic acid ethanolamide, acylaminoaromatic amine, nicotinic acid amide, N-
dialkylglycine long chain amide, alanine amide derivative, urea-conjugated aromatic amine, urea-conjugated ethylenediamine,
Amide-bonded amino alcohol fatty acid ester, lauryl alcohol/glycine ester, ether ester-bonded pyridinium salts, hydroxyethylpyridine ester, alkylphenol/aminosulfonic acid ester,
Ethanolamine higher alcohol enals, alkoxyethylmorpholine, ether-linked primary amine, dihydric phenol/aminoethyl ether, alkylphenol/aminoethyl ether, alkoxyquinoline, aminoethylthioether, aminoethylthioalkyl ether, ester/thio/ether Bound amine, aminophenylsulfone, 2-methylbenzimidazole, 2-alkylbenzimidazole, higher alkylimidacillins, aminoethylimidacillin, dihydroindole,
Higher alkylaminotriazole, triazolium salts, mercaptobenzothiazole, higher alkyloxazoline, dialkylguanidine, acylaminoguanidine, alkyl biguanide, alkylacyl biguanide, alkylguanamine, isothiourea, thiourea-bonded amide, amide-bound isothiourea, 0-alkylurea , higher alkylamidines, bisamidines, alkylamidines, modified amine oxides, sulfonium halides, sulfonium sulfates, etc., but other cationic surfactants may also be used.

Examples of amphoteric surfactants for treating the pigment surface include N-alkylglycine, N-alkyldiglycine, N-alkyltriglycine, amide-bonded betaine, quaternary aspartic acid derivatives, amino acids, amide-ester-bonded betaine,
B-aminopropionic acid, polyethylene polyamine derivatives, salicylic acid derivatives, sulfonamide-linked amino acids, hydroxyethylamine sulfate, glycerinamine sulfate, hydroxyethylimidacillin sulfate, alkyl taurine, aminoalkanesulfonic acid, aniline sulfonic acid derivatives , alkylbenzyl taurine, taurine-bonded succinate ester, alkylsulfobenzyl dimethyl ammonium salt, α-alkylsulfobenzylamine, imidacillin sulfonic acid, aminoethylimidacillin benzaldehyde sulfonic acid condensed Schiff base, benzimidazole sulfonic acid derivatives, Examples include triazine derivatives.

Examples of nonionic surfactants for treating the surface of pigments include the following. Fatty alcohol/polyoxyethylene ether, alkylphenol/polyoxyethylene ether, oxo alcohol/polyoxyethylene ether, ether alcohol/polyoxyethylene ether, bisphenol/polyoxyethylene ether,
Secondary alcohol/polyoxyethylene ether, polyalkylcyclohexanol polyoxyethylene ether, alkyl mercaptan/polyoxyethylene ether, glycerin monoether, ether-linked cyclohexanol/polyoxyethylene succinate, polyethylene glycol fatty acid ester, fat Alcohol, glycerin monofatty acid nystel, oxyacid lower ester, acylmalic acid hydroxyester, higher alkyl urethane, fatty acid monoethanolamide, sulfonamide, fatty acid acylmethylglucamine, fatty acid polyoxyethyleneamide, fatty acid hydrazide derivative, disulfonamide polyoxy Ethylated products, fatty acid ethanolamide derivatives, polyoxyethylene methylene ether,
Fatty acid acyl polyester, alkylphenol glucoside, higher alcohol glucoside, β-aminoethyl glucoside, polyhydric alcohol glucoside, hydroxysulfone, alkyl jetanolamide, hydroxyamide,
Examples include oxymethyl methanolamide, methylol fatty acid amide, hydroxyethyl urea, and the like.

As the colorant and pigment used in the present invention, all known colorants for toners can be used.

As the black coloring agent, for example, carbon black, aniline black, furnace black, lamp black, etc. can be used.

Examples of pigments include the following.

yellowish> [Example code] Hereinafter, the present invention will be specifically explained with reference to Examples.

The amounts (parts) of each component described in each example are parts by weight.

Pigment Surface Treatment I Pigments were surface treated using each of the above formulations. The following method was used for surface treatment. The mixture was placed in a ball mill together with a solvent (water), and after being dispersed for 24 hours, it was taken out and dried to obtain a treated pigment.

Example I-1 Resin: Styrene-2-ethylhexyl acrylate copolymer 100 parts Polar control agent: Salicylic acid zinc salt 1 part Treated pigment 1-15 parts A mixture of the above composition was thoroughly stirred and mixed in a Henschel mixer, and then heated in a hot roll mill. The mixture is melt-kneaded, cooled to room temperature, coarsely ground using a hammer mill, and then finely ground using an air jet mill. Classify the fine powder to have a particle size of 5 to 2.
A toner of 5 μm was obtained.

5 parts of the above toner and iron powder carrier (TEFV 150/
250 mesh, made by Nippon Steel Powder) were mixed in a ball mill to prepare a two-component developer. Even after copying 100,000 copies using a color copying machine, Cocolor 5000 [manufactured by Ricoh], no hot offset occurred and the images were good.

When the surface of the fixing roller was observed, it was found to be in the same state as the initial state, and there was no pigment penetration.

Example! -2 Resin: 100 parts of styrene-2-ethylhexyl acrylate copolymer Polar control agent: 1 part of zinc salicylate salt 35 parts of treated pigment I A mixture having the above composition was made into a toner in the same manner as in Example 1-1,
Upon evaluation, even after copying 100,000 copies, there was no hot offset and no pigment penetration into the roller.

Comparative Example I-1 Resin: Styrene-2-ethylhexyl acrylate copolymer 100 parts Polar control agent: Salicylic acid zinc salt 1 part Pigment: Disazo Yellow 8G (untreated) 5 parts A mixture of the above composition was prepared in the same manner as in Example 1-1. into toner,
Upon evaluation, hot offset occurred after 30,000 copies were made, and the roller surface turned yellow, indicating penetration of the pigment.

Pigment surface treatment■ Pigments were surface treated using each of the above formulations. The surface treatment was carried out in the same manner as in pigment surface treatment I.

Example 11-1 Resin: Styrene-methyl acrylate copolymer 100 parts Polarity control agent: Zinc salicylate 1 part Treated pigment - 15 parts Using the above mixture, a toner was prepared in the same process as in Example 1-1. The toner was prepared and tested under the same conditions as in Example 1-1.

As a result, the condition of the surface of the fixing roller was similar to the initial condition, and there was no penetration of pigment.

Example n-2 Resin: styrene-butadiene copolymer 100 parts Polar control agent: 1 part zinc salicylate salt - 24 parts Treated pigment - 24 parts A mixture of the above composition was made into a toner in the same manner as in Example I-1,
Upon evaluation, even after copying 100,000 copies, there was no hot offset and no pigment penetration into the roller.

Example 11-3 Resin: Polymethyl methacrylate 100 parts Polar control agent: Salicylic acid zinc salt 1 part Treated pigment - 32 parts A mixture having the above composition was made into a toner in the same manner as in Example 1-1,
Upon evaluation, even after copying 100,000 copies, there was no hot offset and no pigment penetration into the roller.

Example 11-4 Resin: Polyvinyl acetate Polarity control agent = Quaternary ammonium salt treated pigment 11-3 A mixture having the above composition was made into a toner in the same manner as in Example I-1.

5 parts of the above toner and iron powder carrier (TEFV-150/
95 parts of 250 mesh Nippon Iron Powder) were mixed in a ball mill to prepare a positively charged two-component developer.

Using the positively charged two-component developer, a positively charged toner was obtained in which hot offset did not occur even after copying 100,000 copies using a copying machine, Recopy FT4820 [manufactured by Kansuko Co., Ltd.], and the pigment did not penetrate into the roller.

Comparative Example 11-1 Resin: 100 parts of styrene-methyl acrylate copolymer Polar control agent: 1 part of zinc salicylate salt Pigment: Disazo Yellow 8G (
(untreated) 5 parts The mixture having the above composition was made into a toner in the same manner as in Example 1-1,
Upon evaluation, hot offset occurred after 30,000 copies were made, the roller surface turned yellow, and pigment penetration was observed.

Comparative Example I>2 Resin: Polymethyl methacrylate 100 parts Polar control agent: Salicylic acid zinc salt 1 part Pigment Nidiane Blue FB
2 parts of K (untreated) A mixture of the above composition was made into a toner in the same manner as in Example 1-1, and when evaluated, hot offset occurred after copying 55,000 copies, and the roller surface turned blue. Pigment penetration was observed.

Pigment surface treatment■ Pigments were surface treated using each of the above formulations. The surface treatment was performed in the same manner as in pigment surface treatment I.

Example m-1 Resin: Polyethylene 100 parts Polarity control agent Open-side lytic acid zinc salt 1 part Treated pigment - 15 parts The mixture having the above composition was thoroughly stirred and mixed in a Henschel mixer, then melt-kneaded in a hot roll mill, Cool to room temperature, coarsely pulverize with a hammer mill, finely pulverize with an air jet mill, and classify with a zigzag classifier, average particle size 11.0 μm.
I got the toner.

A test was conducted using the above toner under the same conditions as in Example 1-1.

As a result, the condition of the surface of the fixing roller was similar to the initial condition, and there was no penetration of pigment.

Example lll-2 Resin: Styrene-methyl acrylate copolymer 100 parts Polar control agent: Salicylic acid zinc salt 1 part Treated pigment --
24 parts The mixture having the above composition was made into a toner in the same manner as in Example m-1,
Upon evaluation, even after copying 100,000 copies, there was no hot offset and no pigment penetration into the roller.

Example m-3 Resin: Polystyrene 100 parts Polar control agent: Salicylic acid zinc salt 1 part Treated pigment - 32 parts A mixture having the above composition was made into a toner in the same manner as in Example m-1,
Upon evaluation, even after copying 100,000 copies, there was no hot offset and no pigment penetration into the roller.

Comparative Example m-1 Resin: Polyester 100 parts Polar control agent: Salicylic acid zinc salt 1 part Pigment: Disazo Yellow 8
G (untreated) 5 parts The mixture having the above composition was made into a toner in the same manner as in Example m-1,
Upon evaluation, hot offset occurred after 30,000 copies were made, the roller surface turned yellow, and pigment penetration was observed.

Pigment surface treatment■ Pigments were surface treated using each of the above formulations. The surface treatment was carried out in the same manner as in pigment surface treatment I.

Example IV-1 Resin: polyethylene 100 parts Polarity control agent: 1 part zinc salicylate salt Treated pigment - 15 parts A mixture of the above composition was finely pulverized in the same process as in Example I-1, and then classified using a zigzag classifier. A toner having an average particle size of 11.0 parts was obtained.

A two-component developer was prepared using the above toner in the same manner as in Example I-1, and tested in the same manner.

As a result, the condition of the surface of the fixing roller was similar to the initial condition, and the pigment did not penetrate into the roller.

Example IV-2 Resin: Styrene-methyl acrylate copolymer 100 parts Polar control agent: Zinc salicylate 1 part Treated pigment - 24 parts A mixture of the above composition was made into a toner in the same manner as in Example IV-1 and evaluated. As a result, even after copying 100,000 copies, there was no hot offset, and no pigment penetrated into the roller.

Example IV-3 Resin: Polystyrene 100 parts Polar control agent: Zinc salicylate 1 part Treated pigment - 32 parts A mixture of the above composition was made into a toner in the same manner as in Example IV-1, and when evaluated, 100,000 copies were obtained. Even after, there was no hot offset and no pigment penetration into the roller.

Preparation of surface treatment agent V Put 50 g of the above combination of nonionic surfactant and anionic surfactant in a ratio of 50:50 into a single Erlenmeyer flask, add 151 ml of solvent (water), and mix with a stirrer for 3 ml.
The mixture was stirred for 0 minutes to prepare a surface treatment agent.

Pigment surface treatment■ Pigments were surface treated using each of the above formulations. The surface treatment was carried out in the same manner as in pigment surface treatment I.

Example V-1 Resin: Polyethylene 100 parts Polarity control agent: 1 part zinc salicylate salt Treated pigment - 15 parts A mixture of the above composition was pulverized in the same process as in Example 1-1, and then classified using a zigzag classifier. A toner having an average particle size of 11.0 μm was obtained.

A two-component developer was prepared using the above toner in the same manner as in Example 1-1, and tested in the same manner.

As a result, the condition of the surface of the fixing roller was similar to the initial condition, and the pigment did not penetrate into the roller.

In addition, the toner charge was always stable, with an initial charge of 117 μc/g, while the developer charge after 10,000,000 copies was 114 μc/g, with little environmental fluctuation. .

Example V-2 Resin: 100 parts of styrene-methyl acrylate copolymer Polar control agent: 1 part of zinc salicylate salt V-24 parts of treated pigment A mixture having the above composition was made into a toner in the same manner as in Example V-1,
As a result of evaluation, there was no hot offset even after copying 100,000 copies, there was no pigment penetration into the roller, and the amount of charge was stable, with an initial charge of -16 μc/g and a charge of -13 μc/g after copying 100,000 copies. Met.

Example V-3 Resin: Polystyrene 100 parts Polarity control agent:
Salicylic acid zinc salt 1 part Treated pigment - 32 parts The mixture having the above composition was made into a toner in the same manner as in Example V-1,
When evaluated, there was no pigment penetration into the hot offset roller even after 100,000 sheets had been copied, and the charge amount was stable, with an initial charge of -18μc/g and a charge after 100,000 copies of 1.4μc/g. there were.

Comparative Example V-1 Resin: Polyester 100 parts Polar control agent: Salicylic acid zinc salt 1 part Pigment: Disazo Yellow 8
G (untreated) 5 parts The mixture having the above composition was made into a toner in the same manner as in Example V-1,
Upon evaluation, hot offset occurred after 30,000 copies were made, the roller surface turned yellow, and pigment penetration was observed.

In addition, the amount of charge varies greatly, with initial charging of -18μc/
By the end of copying 30,000 copies, the amount of charge had decreased to 18 μc/g, and toner was scattering inside the copying machine.

Preparation of surface treatment agent■ Put 50g each of the above combination of nonionic surfactant and cationic surfactant in a ratio of 50+50 into a 19-inch Erlenmeyer flask, add one drop of solvent (water), and mix with a stirrer for 30g.
The mixture was stirred for several minutes to prepare a surface treatment agent.

Pigment surface treatment■ Pigments were surface treated using each of the above formulations. The surface treatment was carried out in the same manner as in the pigment surface treatment I.

Example Vl-1 Resin: Polyethylene 100 parts Polarity control agent Open side lytic acid zinc salt 1 part Treated pigment - 15 parts A mixture of the above composition was pulverized in the same process as in Example 1-1, and then pulverized using a zigzag classifier. It was classified to obtain a toner with an average particle size of 11.0 μl.

A two-component developer was prepared using the above toner in the same manner as in Example 1-1, and tested in the same manner.

As a result, the condition of the surface of the fixing roller was similar to the initial condition, and the pigment did not penetrate into the roller.

Further, the charge of the toner was always stable, and while the initial charge amount was 116 μc/g, the charge amount of the developer after copying 100,000 sheets was 113 μc/g, and environmental fluctuations were small.

Example VI-2 Resin: Styrene-methyl acrylate copolymer 100 parts Polar control agent: Zinc salicylate 1 part Treated pigment --
24 parts The mixture having the above composition was made into a toner in the same manner as in Example Vl-1 and evaluated. Even after copying 100,000 copies, there was no penetration of the pigment into the hot offset roller, the amount of charge was stable, and the initial charge was - The charge after copying 100,000 sheets was -14 μc/g.

Example VI-3 Resin: Polystyrene 100 parts Polar control agent: Salicylic acid zinc salt 1 part Treated pigment -- 32 parts A mixture of the above composition was made into a toner in the same manner as in Example VI-1, and when evaluated, 100,000 copies were obtained. There was no pigment permeation into the hot offset roller even after printing, and the charge amount was stable, with an initial charge of -18 μc/g and a charge after copying 100,000 copies of -14 μc/g.

Put 50g of the above combination of nonionic surfactant and amphoteric surfactant in a ratio of 50:50 into a 151 Erlenmeyer flask, add 151 of a solvent (water) and stir with a stirrer for 30 minutes to remove the surface treatment agent. Created.

Pigments were surface treated using each of the above formulations. The surface treatment was carried out in the same manner as in pigment surface treatment I.

Example ■-1 Resin: Polyethylene 100 parts Polarity control agent: Salicylic acid zinc salt 1 part Treated pigment--15 A mixture of the above composition was pulverized in the same process as in Example I-1, and then classified with a zigzag classifier, A toner with an average particle size of 11.0 μm was obtained.

A two-component developer was prepared using the above toner in the same manner as in Example I-1, and tested in the same manner.

As a result, the condition of the surface of the fixing roller was similar to the initial condition, and the pigment did not penetrate into the roller.

In addition, the charge of the toner was always stable, and while the initial charge amount was 116 μc/g, the charge amount of the developer after 100,000 copies was 14 μc/g, and environmental fluctuations were small.

Example ■-2 Resin: 100 parts of styrene-methyl acrylate copolymer Polarity control agent: 1 part of zinc salicylate salt Treated pigment - 24 parts A mixture having the above composition was made into a toner in the same manner as in Example ■-1,
When evaluated, there was no pigment penetration into the hot offset roller even after 100,000 sheets had been copied, and the charge amount was stable, with an initial charge of -18 μc/g and a charge after 100,000 sheets of copying of -15 μc/g. Ta.

Example ■-3 Resin: Polystyrene 100 parts Polar control agent: Salicylic acid zinc salt 1 part Treated pigment--32 A mixture with the above composition was made into a toner in the same manner as in Example ■-1,
When evaluated, there was no pigment penetration into the hot offset roller even after 100,000 copies had been copied, and the charge amount was stable, with an initial charge of -17 μc/g and a charge after 100,000 copies of -16 μc/g. Ta.

[Effects of the Invention] As described above, by using the toner of the present invention, the pigment of the toner is less likely to adhere to the fixing roller, and as a result, the life of the fixing roller is extended. Further, the charging of the developer is also stabilized.

Claims (2)

[Claims] (1) A color toner for developing electrostatic images, characterized in that the pigment is surface-treated with any one of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. (2) The static pigment according to claim (1), wherein the pigment is surface-treated with a mixture of a nonionic surfactant and one of anionic surfactants, cationic surfactants, and amphoteric surfactants. Color toner for developing charge images.