JPH05188639A - Resin composition for toner and toner - Google Patents

Abstract

PURPOSE:To obtain a resin composition for toner and the toner excellent in offsetting resistance in a wide fixation temp. range, excellent in fixation and anti-blocking property and drastically improved in the soiling of a roll. CONSTITUTION:1 pt.wt. p-toluene sulfonic acid and 5 pts.wt. carbon black are mixed to 100 pts.wt. copolymer made from 75 pts.wt. styrene, 5 pts.wt. methyl metacrylate, 15 pts.wt. n-butylacrylate and 5 pts.wt. acrylic acid and having 61 deg.C glass transition temp. and 245000 weight av. molecular weight and are roll kneaded at 160 deg.C for 5min and are finely pulverized. 0.5 pts.wt. hydrophobic silica particulate is added herein to obtain the desired toner. In this case, though the copolymer is not substantially reformed by the actuation of p-toluenesulfonic acid, when heated by the heating roll for fixation in the using process of an electronic coping machine, the copolymer is substantially reformed by the actuation of p-toluenesulfonic acid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to electrophotography and the like.
The present invention relates to a resin composition for a toner used for developing an electrostatic image and a toner using the resin composition.

[0002]

2. Description of the Related Art In electrophotography and the like, a dry developing system is often used as a system for developing an electrostatic charge image. In this dry developing method, a triboelectric chargeable fine powder developer called a toner in which a colorant such as carbon black is dispersedly contained in a resin is used.

Usually, toner charged by friction adheres to an electrostatic latent image on a photoconductor by an electric attraction to form a toner image, and then this toner image is transferred onto a sheet,
The toner is fixed with a heating roller having a releasing property.

Such toner has anti-offset property (no toner adheres to the heating roller), fixability (toner adheres firmly to the paper), anti-blocking property (no toner particles aggregate), etc. Various performances are required. In particular, a toner having excellent offset resistance over a wide fixing temperature range is required.

As this kind of toner, Japanese Patent Application Laid-Open No. 3-817 is known.
No. 79 discloses styrene monomer and / or (meth)
It has been proposed to use a resin obtained by modifying a copolymer of an acrylic acid ester monomer and a vinyl monomer having an acid group by the action of an organic sulfonic acid compound.

The toner obtained by the technique described in the above publication is excellent in offset resistance in a wide fixing temperature range, has good fixing property and blocking resistance, and is used for a heating roller fixing type electrophotographic copying machine. It is useful as a toner.

[0007]

However, although the above toner is excellent in offset resistance in a wide fixing temperature range, it is not yet sufficiently satisfactory and there is room for improvement. In particular, in order to prevent offset more effectively,
There is a case where a cleaning roller is attached to the heating roller for fixing, but in this case, the toner is accumulated on the cleaning roller, and a so-called roller stain phenomenon occurs.
Further, it is advantageous that the fixing temperature is as low as possible.

The present invention is intended to solve the above problems, and an object of the present invention is to have excellent offset resistance in a wide fixing temperature range, good fixing property and blocking resistance. It is an object of the present invention to provide a resin composition for a toner and a toner in which the roller stain phenomenon is significantly improved.

[0009]

The toner resin composition of the present invention comprises a styrene monomer and / or a (meth) acrylic acid ester monomer and an acid group-containing vinyl monomer. It is characterized in that the polymer contains a resin obtained by mixing an organic sulfonic acid compound. Further, the toner of the present invention is characterized by containing the above resin composition for toner.

In the present invention, examples of the styrene-based monomer serving as a constitutional unit of the copolymer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and α.
-Methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene , Pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene and the like. Of these, styrene is preferred.

Further, it becomes a constitutional unit of the copolymer (meta)
Examples of the acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylate. N-octyl acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylic acid Examples thereof include diethylaminoethyl and α-methyl chloroacrylate. Among these, methyl methacrylate, (meth)
N-butyl acrylate and 2-ethylhexyl acrylate are preferred.

Further, as the acid group of the vinyl-based monomer having an acid group serving as a constitutional unit of the copolymer, one of acid groups such as carboxylic acid, sulfonic acid, sulfinic acid, phosphonic acid, boric acid or the like is used. Among these, a carboxyl group is preferable from the viewpoints of acid strength and ease of copolymerization.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid such as (meth) acrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid and β-methylcrotonic acid, and alkyl derivatives thereof. ;
Unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid; unsaturated carboxylic acid monoester derivatives such as succinic acid mono (meth) acryloyloxyethyl ester and phthalic acid mono (meth) acryloyloxyethyl ester Be done.

The above-mentioned copolymers of styrene-based monomers and / or (meth) acrylic acid ester-based monomers and vinyl monomers having an acid group can be used for solution polymerization, suspension polymerization, emulsion polymerization and It can be obtained by a conventionally known polymerization method such as bulk polymerization. The solution polymerization method is particularly preferable.

The copolymer obtained is a copolymer of a styrene monomer and a vinyl monomer having an acid group, a (meth) acrylic acid ester monomer and a vinyl monomer having an acid group. There are three types of copolymers, a copolymer with a polymer and a copolymer of a styrene monomer, a (meth) acrylic acid ester monomer, and a vinyl monomer having an acid group.

In the present invention, the content of the styrene monomer component is 40 to 95% by weight, more preferably 60 to 9%.
0% by weight, the content of the (meth) acrylic acid ester-based monomer component is 4 to 40% by weight, more preferably 10 to 40% by weight, and the content of the vinyl-based monomer having an acid group is 0.5 to
It is preferred to use 20% by weight, more preferably 1-10% by weight of the copolymer.

If the content of the styrenic monomer component is less than 40% by weight, the pulverizability of the toner may deteriorate. Further, if the content of the (meth) acrylic acid ester-based monomer component is less than 4% by weight, the fixability of the toner may deteriorate. Further, when the content of the vinyl-based monomer component having an acid group is less than 0.5% by weight, the modification with the organic sulfonic acid compound is not sufficient and the effect of improving the offset resistance of the toner is not exhibited. Or
Roller stain phenomenon often occurs. On the other hand, if the content of the vinyl-based monomer component having an acid group exceeds 20% by weight, the blocking resistance and fluidity of the toner may deteriorate.

A metal ion-crosslinked copolymer obtained by reacting the above copolymer with a polyvalent metal compound may be used. If such a copolymer of metal ion cross-linking is used, the fixing temperature range becomes wider. Further, the charged state of the toner particles is also stabilized. In this case, as the metal of the polyvalent metal compound to be reacted with the above-mentioned copolymer, Cu, Ag,
Be, Mg, Ca, Sr, Ba, Zn, Cd, Al, T
Examples thereof include i, Ge, Sn, V, Cr, Mo, Mn, Fe, Co and Ni. Among these metals, alkaline earth metals and zinc group metals are preferable, and Mg and Zn are particularly preferable.

Examples of these polyvalent metal compounds include fluoride, chloride, chlorate, bromide, iodide, oxide, hydroxide, sulfide, sulfite, sulfate, selenide, telluride, Examples thereof include nitrides, nitrates, phosphides, phosphinates, phosphates, carbonates, orthosilicates, acetates, oxalates, and lower alkyl metal compounds such as methylated and ethylated compounds. Of these, acetates and oxides are preferable.

These polyvalent metal compounds are preferably used in an amount such that the molar ratio to the vinyl monomer component having an acid group is 0.05 to 1. If the molar ratio is less than 0.05, there is no effect, and conversely, if the molar ratio is greater than 1, the fixability of the toner may deteriorate.

In order to react the above-mentioned copolymer with a polyvalent metal compound, the copolymer is obtained by solution polymerization, and then the polyvalent metal compound dispersed in a solvent is charged into the polymerization system, if necessary. ,
A method in which the reaction is carried out by heating at an appropriate temperature and then the solvent is removed to obtain a metal ion-crosslinked copolymer is preferably adopted. In some cases, the polyvalent metal compound may be dispersed in the polymerization system together with the solvent before the solution polymerization. In addition, a method in which a polyvalent metal compound is mixed with the copolymer and the mixture is subjected to melt kneading at an appropriate temperature using a roll mill, a kneader, an extruder or the like to cause a reaction can also be employed.

As the polyvalent metal compound, it is possible to use a compound previously reacted with the copolymer as described above, or to use a mixture of the copolymer with the polyvalent metal compound. In this case, the toner is converted into a metal ion-crosslinked copolymer by heating in the course of use, and the fixing temperature range is further widened. Further, the charged state of the toner particles is also stabilized.

The glass transition temperature of the copolymer used in the present invention is preferably 40 ° C. or higher. If the glass transition temperature is lower than 40 ° C., the blocking resistance and fluidity of the toner may deteriorate. The number average molecular weight of the copolymer is preferably in the range of 30,000 to 300,000.

Examples of the organic sulfonic acid compound mixed with the above copolymer include methanesulfonic acid, ethanesulfonic acid,
Alkylsulfonic acids such as n-butanesulfonic acid, isobutanesulfonic acid and octanesulfonic acid and their metal salt compounds; aromatic sulfonic acids such as benzenesulfonic acid, toluenesulfonic acid and naphthalenesulfonic acid and their metal salt compounds; naphtholsulfonic acid , Taurine, sulfanilic acid, naphthylamine sulfonic acid, sulfobenzoic acid, and the like. Among these, the melting point is 4
An organic sulfonic acid compound having a temperature of 0 ° C. or higher is preferable.

These organic sulfonic acid compounds are added to 1 mol of the vinyl-based monomer component having an acid group in the copolymer,
It is preferably mixed with the copolymer in a proportion of 0.001 to 10 mol. If the mixing amount is less than 0.001 mol, the reaction with the acid group portion of the copolymer cannot be sufficiently caused, the effect of improving the offset resistance of the toner does not appear, and the roller stain phenomenon occurs. I have something to do. On the contrary, if the mixing amount exceeds 10 moles, the blocking resistance and fluidity of the toner may deteriorate.

As a specific method for mixing the organic sulfonic acid compound with the above copolymer, (1) the resinous copolymer is pulverized, and an appropriate amount of the organic sulfonic acid compound is added thereto,
Method of mixing with a ribbon blender, Henschel mixer, etc. (2) A method in which an appropriate amount of an organic sulfonic acid compound is added to a resinous copolymer and the mixture is kneaded with a roll mill, a kneader, an extruder or the like. (3) A method in which a resinous copolymer, an appropriate amount of an organic sulfonic acid compound, and an organic solvent are dissolved and mixed, and then the organic solvent is removed and finely pulverized. (4) A method of copolymerizing the above monomers, adding an appropriate amount of an organic sulfonic acid compound to this system, and stirring. The above four methods are mainly adopted.

However, in this case, the above-mentioned mixing operation is carried out at a temperature as low as possible so that the copolymer is not modified by the action of the organic sulfonic acid compound. Thus, the toner resin composition of the present invention is obtained. In this toner composition, the fact that the copolymer is not uniformly modified by the action of the organic sulfonic acid compound and is simply uniformly mixed means that the melt flow and melting of the copolymer before and after the above mixing operation are performed. It can be determined by measuring the viscosity and the average molecular weight and confirming that there is substantially no change in the melt viscosity and the average molecular weight before and after the measurement.

The toner resin composition of the present invention contains
Within the scope capable of achieving the object of the present invention, polystyrene, polyvinyl acetate, polyvinyl chloride, polyamide resin, polyethylene, polypropylene, polyester resin, acrylic resin, styrene-acrylic acid ester copolymer resin,
A known toner resin such as a styrene-butadiene copolymer resin or an epoxy resin, or a known resin composition for a toner produced by using these resins, and other toner additives may be mixed. Further, the resin composition for toner of the present invention can be used as an additive for toner for improving offset resistance and roller stain.

To produce a toner using such a toner resin composition of the present invention, for example, a coloring agent such as carbon black and other conventionally known toner additives are added to the toner resin composition. Agent, ribbon blender,
A method in which a Henschel mixer or the like is mixed, the mixture is kneaded using a roll mill, a kneader, an extruder or the like, and then cooled and finely pulverized is mainly adopted. Thus, the toner of the present invention is obtained. Also in this case, kneading and pulverization are performed at a temperature as low as possible so that the copolymer is not modified by the action of the organic sulfonic acid compound.

[0030]

[Function] A resin obtained by mixing an organic sulfonic acid compound with a copolymer of a styrene monomer and / or a (meth) acrylic acid ester monomer and a vinyl monomer having an acid group is contained. In the process of using this toner, the above-mentioned copolymer is modified by the action of organic sulfonic acid, and the molecular weight and melt viscosity of the toner are increased as compared with the unmodified copolymer.

The mechanism of action of modifying the copolymer in this manner is that the toner is heated by a heating roller for fixing in the course of use, so that a large amount of heat history is finally given to the organic sulfonic acid compound. It acts as a catalyst and crosslinks at the acid group part of the copolymer or at the acid group part and the ester bond part to increase its molecular weight and melt viscosity, thereby exhibiting good offset resistance and roller fouling. It is presumed that this does not occur and the fixing temperature is prevented from rising.

[0032]

EXAMPLES Examples and comparative examples of the present invention will be shown below. Example 1 75 parts by weight of styrene, 5 parts by weight of methyl methacrylate, 15 parts by weight of n-butyl acrylate and 5 parts by weight of acrylic acid were copolymerized to obtain a glass transition temperature of 61 ° C. and a weight average molecular weight of 2
45,000 copolymers were obtained. The glass transition temperature was measured by a differential scanning calorimeter (DSC). The weight average molecular weight was measured by gel permeation chromatography (GPC).

To 100 parts by weight of this copolymer, 1 part by weight of p-toluenesulfonic acid and 5 parts by weight of carbon black (Dia Black SH: Mitsubishi Kasei Co., Ltd.) were mixed, roll-kneaded at 160 ° C. for 5 minutes, and after cooling. The toner was manufactured by coarsely pulverizing and further finely pulverizing with a jet mill to an average particle size of 11 μm, and mixing with 0.5 part by weight of hydrophobic silica fine powder. In this case, the toner before roll kneading and the toner after roll kneading have substantially the same glass transition temperature and average molecular weight, and there is no significant difference. At a kneading temperature of 160 ° C., the copolymer is practically treated by the action of p-toluenesulfonic acid. It was confirmed that it was not modified to.

10 g of this toner was placed in a 100 cc beaker and allowed to stand in a constant temperature bath at 50 ° C. for 16 hours, and then blocking resistance was evaluated by the presence or absence of coalescence of particles. As a result, the blocking resistance was good.

4 parts by weight of this toner is added to an average particle size of 50-80.
A fine powder developer is prepared by mixing with 96 parts by weight of an iron powder carrier of μm, and the fine powder developer is mounted on a modified machine of an electrophotographic copying machine (U-Bix 2500 manufactured by Konica Corporation) to fix the fixing temperature range. It was measured. This fixing temperature range is indicated by changing the setting temperature of the heating roller for fixing so that the fixing can be performed well without causing offset. As a result, the fixing temperature range is 1
Good fixing was possible in a wide temperature range of 65 to 205 ° C.

Further, after copying 20,000 sheets continuously,
Visually check the dirt on the cleaning roller 1 (no dirt) ~
When the evaluation was made on a scale of 5 (few stains), the evaluation result was 2, which was good.

Example 2 80 parts by weight of styrene, 2-ethylhexyl acrylate 1
8 parts by weight and 2 parts by weight of monoacryloyloxyethyl succinate were copolymerized to obtain a copolymer having a glass transition temperature of 60 ° C. and a weight average molecular weight of 175,000.

To 100 parts by weight of this copolymer, 8 parts by weight of p-toluenesulfonic acid and 5 parts by weight of carbon black (Dia Black SH: Mitsubishi Kasei Co.) were mixed, and the mixture was roll-kneaded at 160 ° C. for 5 minutes and cooled. The toner was manufactured by coarsely pulverizing and further finely pulverizing with a jet mill to an average particle size of 11 μm, and mixing with 0.5 part by weight of hydrophobic silica fine powder. Thereafter, the same procedure as in Example 1 was performed.

As a result, the blocking resistance was good. The fixing temperature range was 160 to 205 ° C., and good fixing was possible in a wide temperature range. The stain on the cleaning roller was rated 2.

Example 3 75 parts by weight of styrene, 16 parts by weight of n-butyl acrylate and 9 parts by weight of methacrylic acid were copolymerized to obtain a copolymer having a glass transition temperature of 65 ° C. and a weight average molecular weight of 75,000. ..

To 100 parts by weight of this copolymer, 5 parts by weight of carbon black (Dia Black SH: manufactured by Mitsubishi Kasei Co., Ltd.) was mixed, roll-kneaded at 160 ° C. for 5 minutes, cooled and coarsely crushed, and further, average particle size was 11 μm with a jet mill. It was finely pulverized to obtain a toner. Further, to 100 parts by weight of this toner, 0.1 part by weight of naphthalene sulfonic acid and 0.
Toner was manufactured by mixing 5 parts by weight. Hereinafter, Example 1
I went the same way.

As a result, the blocking resistance was good. Further, the fixing temperature range was 155 to 200 ° C., and good fixing was possible in a wide temperature range. In addition, the dirt of the cleaning roller was good in the evaluation 2.

Example 4 80 parts by weight of styrene, 10 parts by weight of n-butyl acrylate, and 10 parts by weight of monomethacryloyloxyethyl succinate were copolymerized to obtain a glass transition temperature of 63 ° C. and a weight average molecular weight of 15,000. A coalesced (A) was obtained.

Separately, 80 parts by weight of styrene and 20 parts by weight of n-butyl methacrylate were copolymerized to give a glass transition temperature of 5
A copolymer having a weight average molecular weight of 65,000 at 8 ° C. was obtained. 100 parts by weight of this copolymer was mixed with 3 parts by weight of p-toluenesulfonic acid and roll-kneaded at 160 ° C. for 5 minutes to obtain a copolymer (B) of p-toluenesulfonic acid mixture.

To 70 parts by weight of the above copolymer (A) and 30 parts by weight of a copolymer (B) of p-toluenesulfonic acid mixture, 5 parts of carbon black (Dia Black SH: manufactured by Mitsubishi Kasei Co., Ltd.)
1 part by weight, roll kneading at 160 ° C. for 5 minutes, cooling, coarse pulverization, fine pulverization with a jet mill to an average particle size of 11 μm, and mixing with 0.5 parts by weight of hydrophobic silica fine powder to produce a toner. did. Thereafter, the same procedure as in Example 1 was performed.

As a result, the blocking resistance was good. Further, the fixing temperature range was 160 to 205 ° C., and good fixing was possible in a wide temperature range. In addition, the dirt of the cleaning roller was good in the evaluation 2.

Example 5 70 parts by weight of styrene, 15 parts by weight of methyl methacrylate,
15 parts by weight of n-butyl acrylate was copolymerized to obtain a copolymer having a glass transition temperature of 61 ° C. and a weight average molecular weight of 130000.

To 100 parts by weight of this copolymer, 5 parts by weight of carbon black (Dia Black SH: manufactured by Mitsubishi Kasei Co.) and 30 parts by weight of the toner prepared in Example 1 were mixed, roll-kneaded at 160 ° C. for 5 minutes and cooled. The toner was manufactured by coarsely pulverizing and further finely pulverizing with a jet mill to an average particle size of 11 μm, and mixing with 0.5 part by weight of hydrophobic silica fine powder. Thereafter, the same procedure as in Example 1 was performed.

As a result, the blocking resistance was good. Further, the fixing temperature range was 160 to 205 ° C., and good fixing was possible in a wide temperature range. In addition, the dirt of the cleaning roller was good in the evaluation 2.

Example 6 75 parts by weight of styrene, 10 parts by weight of methyl methacrylate,
A copolymer was obtained by copolymerizing 10 parts by weight of n-butyl acrylate and 5 parts by weight of monoacryloyloxyethyl succinate. 100 parts by weight of this copolymer and magnesium oxide of 0.
After stirring 5 parts by weight of toluene under reflux for 2 hours to cause a reaction, the toluene was removed to obtain a metal ion-crosslinked copolymer having a glass transition temperature of 63 ° C. and a weight average molecular weight of 210000.

To 100 parts by weight of this metal ion-crosslinked copolymer, 2 parts by weight of p-toluenesulfonic acid and 5 parts by weight of carbon black (Diablack SH: Mitsubishi Kasei Co., Ltd.) were mixed and rolled at 160 ° C. for 5 minutes. After kneading and cooling, coarse crushing,
Further, it was finely pulverized by a jet mill to have an average particle size of 11 μm, and 0.5 part by weight of hydrophobic silica fine powder was mixed to produce a toner. Thereafter, the same procedure as in Example 1 was performed.

As a result, the blocking resistance was good. The fixing temperature range was 160 to 215 ° C., and good fixing was possible in a wide temperature range. The stain on the cleaning roller was rated 2.

Example 7 76 parts by weight of styrene, 2-ethylhexyl acrylate 1
A copolymer was obtained by copolymerizing 5 parts by weight and 9 parts by weight of acrylic acid. 100 parts by weight of this copolymer and 0.
After stirring 8 parts by weight of toluene under reflux for 2 hours to cause a reaction, toluene was removed to obtain a metal ion-crosslinked copolymer having a glass transition temperature of 64 ° C. and a weight average molecular weight of 185,000.

To 100 parts by weight of this metal ion-crosslinked copolymer, 5 parts by weight of carbon black (Dia Black SH: manufactured by Mitsubishi Kasei Co., Ltd.) was mixed, roll-kneaded at 160 ° C. for 5 minutes, cooled, coarsely crushed, and further jetted. Average particle size of 11μ
Finely pulverized to m to obtain a toner. Further, this toner 10
Toner was manufactured by mixing 0 part by weight of naphthalene sulfonic acid 0.2 part by weight and hydrophobic silica fine powder 0.5 part by weight. Thereafter, the same procedure as in Example 1 was performed.

As a result, the blocking resistance was good. The fixing temperature range was 165 to 210 ° C., and good fixing was possible in a wide temperature range. In addition, the dirt of the cleaning roller was good in the evaluation 2.

Example 8 80 parts by weight of styrene, 18 parts by weight of n-butyl acrylate and 2 parts by weight of monomethacryloyloxyethyl succinate were copolymerized to obtain a copolymer. 100 parts by weight of this copolymer and 1 part by weight of magnesium acetate are reacted under stirring under reflux of toluene for 2 hours, and then toluene is removed to obtain a glass transition temperature of 62 ° C. and a weight average molecular weight of 80,000 metal ion crosslinking. A copolymer of

100 parts by weight of this metal ion-crosslinked copolymer were mixed with 8 parts by weight of p-toluenesulfonic acid and 5 parts by weight of carbon black (Dia Black SH: manufactured by Mitsubishi Kasei Co.) and rolled at 160 ° C. for 5 minutes. After kneading and cooling, coarse crushing,
Further, it was finely pulverized by a jet mill to have an average particle size of 11 μm, and 0.5 part by weight of hydrophobic silica fine powder was mixed to produce a toner. Thereafter, the same procedure as in Example 1 was performed.

As a result, the blocking resistance was good. The fixing temperature range was 160 to 210 ° C., and good fixing was possible in a wide temperature range. The stain on the cleaning roller was rated 2.

Example 9 80 parts by weight of styrene, 16 parts by weight of n-butyl acrylate and 4 parts by weight of methacrylic acid were copolymerized to obtain a copolymer. 100 parts by weight of this copolymer and 0.6 parts by weight of zinc oxide were reacted under stirring under reflux of toluene for 2 hours, and then the toluene was removed to obtain a metal having a glass transition temperature of 63 ° C. and a weight average molecular weight of 130000. An ionically crosslinked copolymer (C) was obtained.

Separately, 75 parts by weight of styrene and n of acrylic acid
-Copolymerizing 25 parts by weight of butyl to give a glass transition temperature of 5
A copolymer having a weight average molecular weight of 60,000 at 8 ° C. was obtained. 100 parts by weight of this copolymer was mixed with 5 parts by weight of p-toluenesulfonic acid and roll-kneaded at 160 ° C. for 5 minutes to obtain a copolymer (D) of p-toluenesulfonic acid mixture.

To 80 parts by weight of the above-mentioned copolymer (C) and 20 parts by weight of a copolymer (D) of p-toluenesulfonic acid mixture, carbon black (Dia Black SH: manufactured by Mitsubishi Kasei) 5
1 part by weight, roll kneading at 160 ° C. for 5 minutes, cooling, coarse pulverization, fine pulverization with a jet mill to an average particle size of 11 μm, and mixing with 0.5 parts by weight of hydrophobic silica fine powder to produce a toner. did. Thereafter, the same procedure as in Example 1 was performed.

As a result, the blocking resistance was good. Further, the fixing temperature range was 160 to 210 ° C., and good fixing was possible in a wide temperature range. In addition, the dirt of the cleaning roller was good in the evaluation 2.

Example 10 Copolymer having 70 parts by weight of styrene, 10 parts by weight of n-butyl methacrylate and 20 parts by weight of n-butyl acrylate, a glass transition temperature of 61 ° C. and a weight average molecular weight of 145,000. Got

To 100 parts by weight of this copolymer, 5 parts by weight of carbon black (Dia Black SH: manufactured by Mitsubishi Kasei) and 20 parts by weight of the toner prepared in Example 6 were mixed, and the mixture was heated to 160 ° C.
Roll kneading for 5 minutes, cooling, coarse pulverization, fine pulverization with a jet mill to an average particle size of 11 μm, and mixing with 0.5 part by weight of hydrophobic silica fine powder to produce a toner. Thereafter, the same procedure as in Example 1 was performed.

As a result, the blocking resistance was good. Further, the fixing temperature range was 160 to 210 ° C., and good fixing was possible in a wide temperature range. In addition, the dirt of the cleaning roller was good in the evaluation 2.

Comparative Example 1 Example 5 was repeated except that 30 parts by weight of the toner prepared in Example 1 was not mixed.

In this case, the blocking resistance was good. However, the fixing temperature range is 160 to 185 ° C., which is narrower than that of Example 5, and the cleaning roller stain is rated 5, which is inferior to the toner of Example 5.

Comparative Example 2 Example 1 was repeated except that 1 part by weight of p-toluenesulfonic acid was not mixed.

In this case, the blocking resistance was good. However, the fixing temperature range is 165 to 190 ° C., which is narrower than that of Example 1, and the cleaning roller stain is rated 5, which is inferior to the toner of Example 1.

Comparative Example 3 The procedure of Example 2 was repeated, except that the roll kneading condition of 160 ° C. for 5 minutes was changed to 180 for 15 minutes. The toner after roll kneading has a glass transition temperature of 68 ° C. and a weight average molecular weight of 335,000, which is considerably higher than that before roll kneading.
It was confirmed that it was substantially modified by the action of toluenesulfonic acid.

In this case, the blocking resistance was good, and the dirt on the cleaning roller was good (Evaluation 2). However, the fixing temperature range is 175 to 215 ° C., which is narrower than that of Example 2, and the fixing temperature is high, which is inferior to the toner of Example 2.

Comparative Example 4 Example 10 was repeated except that 20 parts by weight of the toner prepared in Example 6 was not mixed.

In this case, the blocking resistance was good. However, the fixing temperature range is 160 to 185 [deg.] C., which is narrower than that of Example 10, and the cleaning roller stain is rated 5, which is inferior to the toner of Example 10.

Comparative Example 5 Example 6 was repeated except that 2 parts by weight of p-toluenesulfonic acid was not mixed.

In this case, the blocking resistance was good. However, the fixing temperature range is 170 to 200 ° C., which is narrower than that of Example 6, and the cleaning roller stain is rated 5, which is inferior to the toner of Example 6.

Comparative Example 6 The procedure of Example 8 was repeated, except that the roll kneading condition of 160 ° C. for 5 minutes was changed to 180 for 15 minutes. The toner after roll kneading has a glass transition temperature of 68 ° C. and a weight average molecular weight of 305,000, which is considerably higher than that before roll kneading.
It was confirmed that it was substantially modified by the action of toluenesulfonic acid.

In this case, the blocking resistance was good, and the dirt on the cleaning roller was good (Evaluation 2). However, the fixing temperature range is 180 to 225 ° C., which is narrower than that of Example 8, and the fixing temperature is high, which is inferior to the toner of Example 8.

[0078]

As described above, the resin composition for a toner and the toner of the present invention contain the styrenic monomer and / or (meth).
Contains a resin prepared by mixing an organic sulfonic acid compound with a copolymer of an acrylic ester monomer and a vinyl monomer having an acid group, which allows offset resistance in a wide fixing temperature range. It has excellent cleaning properties, greatly reduces dirt on the cleaning roller, and has good fixing properties and blocking resistance. Also, the fixing temperature can be set to a relatively low temperature.

Therefore, the resin composition for a toner and the toner of the present invention can be suitably used for a heating roller fixing type electrophotographic copying machine from low speed to high speed. It can also be used as an additive for toner.

Claims (2)

[Claims] 1. A resin obtained by mixing an organic sulfonic acid compound with a copolymer of a styrene monomer and / or a (meth) acrylic acid ester monomer and a vinyl monomer having an acid group. A resin composition for a toner, which is contained. 2. A toner containing the resin composition for a toner according to claim 1.