JPH1124307A - Resin composition for toner and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain resin compsn. which shows excellent surface smoothness, transparency and resin strength without decreasing offset resistance, fixing property and stability, and which is suitable to be used as a high resolution full-color toner including a monocolor toner without causing filming. SOLUTION: This resin compsn. consists of a resin prepared by adding a crosslinking agent having >=10 carbon atoms in one molecule by 0.1 to 10 wt.% to the vinyl copolymer described below. The vinyl copolymer consists of styrene monomers and (meth)acrylate monomers and has the mol.wt. peak ranging 3×10<3> to 3×10<4> by GPC (gel permeation chromatography). In the mol.wt. distribution of the copolymer, the amt. B of a high mol.wt. component with >=5×10<4> mol.wt. based on 100 amt. of a low mol.wt. component with <5×10 mol.wt., and the value A obtd. by calculation of the mol.wt. peak in the high mol.wt. component ×10<-4> satisfy the relation of -4B+110>=A>=-4B+60.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner resin composition and a toner used in an electrophotographic copying machine for developing an electrostatic image.

[0002]

2. Description of the Related Art In a dry developing system, toner is usually charged by friction with iron, glass beads or the like called a carrier, and the toner is attached to an electrostatic latent image on a photoreceptor by electric attraction, and then the paper is charged. The image is transferred onto the upper surface and fixed by a heat roll or the like to form a permanent visible image.

As a fixing method, a surface of a heating roller having a surface formed of a material having a releasing property with respect to toner is applied to the surface of the heating roller.
A heating roller method is widely used in which a toner image on a fixing sheet is passed while being brought into pressure contact. According to this method, since the surface of the heating roller and the toner image of the sheet to be fixed come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing is quickly performed. And is very effective in high speed electrophotographic copiers.

However, when the surface of the heating roller and the toner image come into contact with each other in a molten state and under pressure, a part of the toner image adheres and transfers to the surface of the fixing roller, and the toner image re-transfers to the next sheet to be fixed. Cause the so-called offset phenomenon,
The sheet to be fixed may be stained.

JP-A-57-56850 discloses a developing toner containing a resin obtained by mixing and polymerizing a wax having a functional group, a styrene monomer and an ethylene acrylic derivative or an ethylene vinyl acetate copolymer. ,
Although a technique for improving the releasability from the heating roller is disclosed, since the wax does not affect the fixing property, an increase in the amount of wax adversely affects filming on a photoreceptor.

Further, a method of preventing the offset phenomenon by cross-linking the resin is also used. However, if the degree of cross-linking is increased, the pulverizability of the resin deteriorates, and it becomes difficult to pulverize and classify the resin as toner particles. There is a problem that dispersion of the colorant becomes worse.

JP-A-56-158340 discloses that at least one selected from the group consisting of a low molecular weight polymer and a high molecular weight polymer, and a styrene polymer, an acrylic polymer and a styrene-acrylic polymer is used. One type of technology is disclosed in which a toner made of a resin having a specified glass transition temperature range is used to prevent offset. However, when the amount of the high molecular weight polymer is increased, there is a problem that the fixing property is reduced. Was. Due to these problems, conventionally, toners have been manufactured by balancing offset resistance, fixability, and the like.

[0008] However, with the recent trend toward full color and high resolution, many problems have arisen with conventionally used toners. In full-color printing, it must be ensured that the fixed toner does not irregularly reflect light and impair color reproducibility.However, when a crosslinked resin or a high molecular weight resin is used as in the past, There is a problem that irregularities are formed on the fixing surface and irregular reflection occurs.

However, when the crosslinking of the resin, the use of the high molecular weight resin, and the like are simply stopped, the offset phenomenon occurs, which causes not only irregularities on the fixing surface but also defects such as soiling of the sheet to be fixed. Became.

Further, the full-color toner produces an intermediate color by superimposing toners of different color tones.
Transparency is required. Therefore, if a large amount of wax is added to prevent the offset phenomenon, transparency is impaired, and disadvantages such as difficulty in using as a full-color toner arise. In addition, due to the effect of the low-melting point component of the wax, storage stability is deteriorated, and problems such as blocking occur.

On the other hand, conventionally, toner particles have a particle size of about 10
Although particles having a particle diameter of about 8 μm have been used, particles having a particle diameter of about 8 μm have been required with the increase in resolution, and the strength of toner particles has been required. Crosslinking of resin,
The use of a high molecular weight resin or the like is effective in increasing the strength of the toner particles, but if sufficient strength is to be imparted, the pulverizability may deteriorate. On the other hand, if the strength is low, a large amount of fine powder is generated, which causes problems such as poor charging, fogging and the like, and fouling of the sheet to be fixed on a white background.

[0012] Furthermore, the cross-linking portion in the resin increases due to the decrease in the particle size, and the poor dispersion of the added wax results in the formation of toner particles of the cross-linking portion or only the wax, which deteriorates the quality. And other problems.

[0013]

SUMMARY OF THE INVENTION In view of the above, the present invention has been made in view of the above, without impairing the offset resistance and the fixability, and having a smooth surface.
An object of the present invention is to provide a toner resin composition and a toner which are excellent in transparency and resin strength and can be suitably used as a high-resolution full-color toner including monocolor without causing filming.

[0014]

Means for Solving the Problems The present invention provides a styrene-based resin.
Monomers and (meth) acrylate monomers
Gel permeation chromatography
3 × 10 ^Three~ 3 × 10^FourAnd the molecular weight
When the amount of the low-molecular-weight compound of less than 50,000 is 100
50,000 or more high molecular weight substances and molecular weight peaks of high molecular weight substances
-4B + 110 ≧ A ≧ −4B + 60 (1) (where A is the molecular weight peak of the high molecular weight compound × 10)^-FourThe table
You. B is 100 when the amount of the low molecular weight compound of less than 50,000 is 100
50,000 or more of the high molecular weight compound. Where B is
It is a positive number. ) Which satisfies the relationship expressed by)
Crosslinking agent having 10 or more carbon atoms in one molecule
From 0.1 to 10% by weight of cross-linked resin
Is a resin composition for a toner.

The present invention 2 relates to a styrenic monomer and
D) Gel permeates composed of acrylic ester monomers
The molecular weight peak was 3
× 10 ^Three~ 3 × 10^FourLess than 50,000 in molecular weight distribution
Of 50,000 or more when the amount of the low molecular weight compound is 100
The amount of the dimer and the molecular weight peak of the high molecular weight are represented by the following formula:
(1); −4B + 110 ≧ A ≧ −4B + 60 (1) (where A is the molecular weight peak of the high molecular weight compound × 10)^-FourThe table
You. B is 100 when the amount of the low molecular weight compound of less than 50,000 is 100
50,000 or more of the high molecular weight compound. Where B is
It is a positive number. ) Which satisfies the relationship expressed by)
The weight average molecular weight is 100 to 100 parts by weight
0.1 to 15 parts by weight of wax which is 10,000
And a resin composition for toner.

The present invention 3 relates to a styrenic monomer and
D) Gel permeates composed of acrylic ester monomers
The molecular weight peak was 3
× 10 ^Three~ 3 × 10^FourLess than 50,000 in molecular weight distribution
Of 50,000 or more when the amount of the low molecular weight compound is 100
The amount of the dimer and the molecular weight peak of the high molecular weight are represented by the following formula:
(1); −4B + 110 ≧ A ≧ −4B + 60 (1) (where A is the molecular weight peak of the high molecular weight compound × 10)^-FourThe table
You. B is 100 when the amount of the low molecular weight compound of less than 50,000 is 100
50,000 or more of the high molecular weight compound. Where B is
It is a positive number. ) Which satisfies the relationship expressed by)
A resin composition for a toner comprising:
Copolymer is a vinyl copolymerizable monomer containing a polar group.
It is obtained by copolymerizing the body at 0.01 to 10% by weight
It is a resin composition for toner.

Hereinafter, the present invention 1 will be described in detail. The resin composition for a toner according to the first aspect of the present invention is obtained by adding a crosslinker having 10 or more carbon atoms in one molecule to a vinyl copolymer comprising a styrene monomer and a (meth) acrylate monomer. It is made of a resin that is crosslinked by containing 0.1 to 10% by weight.

The vinyl copolymer used in the present invention 1 comprises a styrene monomer and a (meth) acrylate monomer. The styrene monomer is not particularly limited, for example, styrene, o-methylstyrene,
m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, pt-butylstyrene, pn-hexylstyrene, p- n-octylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,
4-dichlorostyrene and the like.

The (meth) acrylate monomer is not particularly restricted but includes, for example, methyl acrylate,
Ethyl acrylate, propyl acrylate, n-acrylate
-Butyl, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacryl Alkyl esters of acrylic acid or methacrylic acid such as n-octyl acid, dodecyl methacrylate, stearyl methacrylate; 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, Diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, bisglycidyl methacrylate, polyethylene glycol dimethacrylate, methacryloxy Chiruhosufeto, and the like. Among them, ethyl acrylate, propyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate and the like are preferable.

The vinyl copolymer may be obtained by copolymerizing another vinyl monomer. The other vinyl monomer is not particularly limited, for example, acrylic acid, methacrylic acid, α-ethylacrylic acid, acrylic acid such as crotonic acid or α-alkyl derivative or β
-Alkyl derivatives; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid or monoester derivatives or diester derivatives thereof; monoacryloyloxyethyl succinate, monomethacryloyloxyethyl succinate, acrylonitrile,
Examples include methacrylonitrile and acrylamide.

The vinyl copolymer has a molecular weight peak of 3 × 10 ^{3 to} 3 × 10 ^{4 as} determined by gel permeation chromatography (GPC). If it is less than 3 × 10 ³ , a problem may occur in storage stability, and
^When it exceeds ⁴ , not only the fixing property may be deteriorated but also the fixing surface smoothness after the fixing may be deteriorated. Preferably, 5 × 10 ³
1.5 × 10 ⁴ .

In the molecular weight distribution measured by GPC, the amount of the high molecular weight polymer of 50,000 or more when the amount of the low molecular weight material of less than 50,000 is set to 100, The molecular weight peak satisfies the relationship of the following formulas (a) and (b). A ≦ −4B + 110 (a) A ≧ −4B + 60 (b) In the formula, A represents a molecular weight peak of a high molecular weight compound × 10 ⁻⁴ . B represents the amount of the high molecular weight substance of 50,000 or more when the amount of the low molecular weight substance of less than 50,000 is set to 100. Where B is
It is a positive number.

If the above A is outside the range of the above formula (a), the surface smoothness (gloss) is determined from the difference in the melt viscosity of the high molecular weight substance.
Is impaired, and there is a possibility that the desired coloring property cannot be obtained in full color. Further, if the value is outside the range of the above formula (b), the durability of the resin is weak, and fog or the like is likely to occur due to deterioration of the resin during long-term evaluation, so that the range is limited to the above range. Preferably, it is a range represented by the following formula (2). -4B + 100≥A≥-4B + 70 (2)

The above vinyl copolymer preferably has a glass transition point (Tg) of 50 ° C. or higher. When the temperature is lower than 50 ° C., the cohesiveness may be deteriorated. In the molecular weight distribution of the vinyl copolymer measured by GPC,
There may be multiple peaks and shoulders.

The synthesis of the above vinyl copolymer is carried out by, for example,
Although suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization and the like can be used, it is preferable to perform solution polymerization in order to improve the dispersibility of polyolefin and the like. When two or more peaks are present in the molecular weight distribution of the vinyl copolymer, the low-molecular-weight polymer component and the high-molecular-weight polymer component may be hot-melt blended. It is preferable to remove the solvent after dispersing in a solvent. Further, it is preferable to polymerize the low molecular weight polymer component in the presence of the high molecular weight polymer component.

In the resin composition for a toner of the present invention 1, the vinyl copolymer is crosslinked by containing a crosslinking agent in an amount of 0.1 to 10% by weight. When the content of the crosslinking agent is 0.
When the amount is less than 1% by weight, the resin strength of the obtained resin composition for toner becomes weak, and when the amount exceeds 10% by weight, the resin composition is excessively crosslinked, so that a gel component is easily generated and the pulverizability as a toner deteriorates. Since the dispersibility of carbon, carbon and the like also deteriorates, it is limited to the above range. Preferably, it is 1 to 7% by weight.

The crosslinking agent has 10 or more carbon atoms in one molecule. If it is less than 10, the resin strength is slightly weak, and it becomes difficult to use the toner as a small particle size toner for full-color, high-resolution. Preferably, it is 12 to 30.

As the cross-linking agent, structurally, general cross-linking agents such as aromatic and aliphatic ones can be used, but those having a straight chain structure and two aromatic rings in one molecule can be used. Those having the above are preferable.

The crosslinking agent is preferably a compound containing two or more polymerizable double bonds, for example, aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene and derivatives thereof; ethylene glycol dimethacrylate, trimethylol Di (meth) acrylate or tri (meth) acrylate such as propane triacrylate;
And diethylenic carboxylic acid esters.

In the toner resin composition of the present invention 1, vinyl acetate, vinyl chloride, ethylene and the like may be copolymerized with the styrene copolymer as long as the object of the present invention can be achieved. Alternatively, a polymer of these monomers may be blended.

The resin composition for toner of the present invention 1 may be mixed with a polyester resin, an epoxy resin, an aliphatic amide, a bisaliphatic amide, a metal soap, paraffin and the like.
The resin composition for a toner of the present invention 1 includes, as a charge control agent,
Dyes such as nigrosine and spiron black (manufactured by Hodogaya Chemical Co., Ltd.); and other phthalocyanine-based pigments may be added.

In the resin composition for toner of the present invention 1, carbon black, chrome yellow, aniline blue or the like can be used as a coloring material. To the resin composition for toner of the present invention 1, a low molecular weight polyethylene wax, a polypropylene wax or the like may be added as a release agent, and hydrophobic silica or the like may be added to improve fluidity. Further, the resin composition for toner of the present invention 1 may be used as a magnetic toner by mixing magnetic powder.

The resin composition for a toner of the present invention 2 is prepared by adding a vinyl copolymer comprising a styrene monomer and a (meth) acrylate monomer to 100 parts by weight of the vinyl copolymer. And a resin obtained by adding 0.1 to 15 parts by weight of a wax having a weight average molecular weight of 100 to 10000.

The styrene monomer is not particularly restricted but includes, for example, those exemplified in the description of the present invention 1. The (meth) acrylic ester monomer is not particularly limited, and examples thereof include those exemplified in the description of the present invention 1. The vinyl copolymer,
Other vinyl monomers may be copolymerized, and examples thereof include those exemplified in the description of the present invention 1. .

The above-mentioned vinyl copolymer is subjected to gel permeation chromatography (GPC) in the same manner as in the present invention 1.
Is 3 × 10 ^{3 to} 3 × 10 ⁴ .
If it is less than 3 × 10 ³ , a problem may occur in storage stability, and if it exceeds 3 × 10 ⁴ , not only the fixability may deteriorate, but also the fixing surface smoothness after fixing may deteriorate. Is limited to the above range. Preferably, it is 5 × 10 ^{3 to} 1.5 × 10 ⁴ .

In the molecular weight distribution measured by GPC in the same manner as in the present invention 1, the amount of the high molecular weight polymer of 50,000 or more, where the amount of the low molecular weight less than 50,000 is 100, And the molecular weight peak of the high molecular weight compound have the relationship of the following formulas (a) and (b). A ≦ −4B + 110 (a) A ≧ −4B + 60 (b) In the formula, A represents a molecular weight peak of a high molecular weight compound × 10 ⁻⁴ . B represents the amount of the high molecular weight substance of 50,000 or more when the amount of the low molecular weight substance of less than 50,000 is set to 100. Where B is
It is a positive number.

If the above A is out of the range of the above formula (a), the surface smoothness (gloss) is determined from the difference in the melt viscosity of the high molecular weight substance.
Is impaired, and there is a possibility that the desired coloring property cannot be obtained in full color. Further, if the value is outside the range of the above formula (b), the durability of the resin is weak, and fog or the like is likely to occur due to deterioration of the resin during long-term evaluation, so that the range is limited to the above range. Preferably, it is a range represented by the following formula (2). -4B + 100≥A≥-4B + 70 (2)

It is preferable that the above-mentioned vinyl copolymer has a Tg of 50 ° C. or higher as in the case of the present invention 1. When the temperature is lower than 50 ° C., the cohesiveness may be deteriorated. The vinyl-based copolymer may have a plurality of peaks or shoulders in the molecular weight distribution measured by GPC as in the first invention.

The synthesis of the vinyl copolymer is carried out by, for example,
It can be carried out by the method exemplified in the description of the present invention 1.

The resin composition for a toner of the present invention 2 is prepared by adding a wax having a weight average molecular weight of 100 to 10000 to 100 parts by weight of the same vinyl copolymer as described in the present invention 1. -15 parts by weight. The wax is a gloss auxiliary mainly for giving gloss. The wax has a weight average molecular weight of 100 to 10,000. If it is less than 100, a problem occurs in storage stability, and 100
If it exceeds 00, the releasability from the fixing roll is poor and an offset is likely to occur, so that it is limited to the above range.
Preferably, it is 200-6000. More preferably, it is 400 to 1,000.

The molecular weight distribution of the above wax is preferably narrow, and the degree of dispersion is preferably 10 or less, more preferably
It is less than 3. This is effective for maintaining the transparency and preservability of the resin, and the higher the weight average molecular weight distribution of the wax, the more the transparency of the resin is impaired. Further, as the molecular weight distribution increases, components having a weight average molecular weight of less than 100 increase, which may adversely affect the storage stability.

If the amount of the wax is less than 0.1 part by weight, the effect of the addition of the wax does not appear, the gloss of the fixing surface cannot be maintained, and offset tends to occur.
If the amount exceeds 15 parts by weight, filming on the photoreceptor is likely to occur, and the transparency of the resin deteriorates, so that the resin may not be used as a full-color toner.
It is limited to the above range. Preferably, it is 0.2 to 10 parts by weight.

The wax is not particularly restricted but includes, for example, synthetic waxes such as polyethylene wax and polypropylene wax; and natural waxes such as paraffin wax and animal and plant waxes. Paraffin wax, polyethylene wax, polypropylene wax, etc., which are easy to remove, are preferably used.

The synthesis of the resin composition for toner of the present invention 2 is as follows:
For example, after the above-mentioned vinyl copolymer is synthesized, wax may be added and synthesized, or the above-mentioned vinyl copolymer may be copolymerized while the wax is dispersed. In this case, it is more preferable to carry out polymerization after dispersing the polyolefin or the like in advance, since the dispersion of the polyolefin or the like becomes very good and the physical properties of the toner become very good.

In the resin composition for a toner of the present invention 2, vinyl acetate, vinyl chloride, ethylene or the like may be copolymerized with the styrene copolymer as long as the object of the present invention can be achieved. Further, a polymer of these monomers may be blended.

Further, the resin composition for toner of the present invention 2 comprises:
Polyester resin, epoxy resin, aliphatic amide, bisaliphatic amide, metal soap, paraffin, etc. may be mixed in the same manner as in the toner resin composition of the present invention 1. Nigrosine, spiron black are used as charge control agents. Dyes such as;
Other phthalocyanine-based pigments and the like may be added, and as a coloring material, carbon black, chrome yellow, aniline blue, and the like may be added, and as a release agent, a low-molecular-weight polyethylene wax, a polypropylene wax, or the like is added. Alternatively, hydrophobic silica or the like may be added to enhance fluidity. Further, the resin composition for a toner of the present invention 2 may be mixed with a magnetic powder and used as a magnetic toner similarly to the resin composition for a toner of the present invention 1.

The resin composition for toner of the present invention 3 further comprises a polar group-containing vinyl copolymerizable monomer in addition to a styrene monomer and a (meth) acrylate monomer. It is obtained by copolymerizing from 01 to 10% by weight.

The styrenic monomer is not particularly limited, and examples thereof include those exemplified in the description of the present invention 1. The (meth) acrylic ester monomer is not particularly limited, and examples thereof include those exemplified in the description of the present invention 1.

The vinyl-based copolymerizable monomer containing a polar group is used in order to favorably disperse additives such as CCA when the resin composition for toner of the present invention 3 is formed into a toner. Is done. The content of the polar group-containing vinyl copolymerizable monomer is 0.01 to 1 in the vinyl copolymer.
0% by weight. When the content is less than 0.01% by weight, the above C
The effect of improving the dispersibility of additives such as CA cannot be obtained. If the content exceeds 10% by weight, the hygroscopicity increases, the environmental stability deteriorates, and poor charging may occur. You. Preferably, it is 0.1 to 5% by weight.

The polar group is not particularly restricted but includes, for example, halogens, hydroxyl, amino, nitro, carboxyl, formyl, alkoxy, nitrile,
Examples thereof include ester groups excluding those of (meth) acrylic acid esters, and are preferably acid groups from the viewpoint of odor and polarity. The acid component containing an acid group is not particularly limited, and examples thereof include those containing a carboxyl group such as benzoic acid; and those containing a sulfonic acid group such as benzenesulfonic acid. Among them, those containing a carboxyl group are preferred.

The above-mentioned carboxyl group-containing vinyl copolymerizable monomer is not particularly restricted but includes, for example, acrylic acid such as acrylic acid, methacrylic acid and crotonic acid or α-alkyl or β-alkyl derivatives thereof; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and monoester derivatives thereof, and the like. These may be used alone or in combination of two or more.

The vinyl copolymer was subjected to gel permeation chromatography (GPC) in the same manner as in the present invention 1.
Is 3 × 10 ^{3 to} 3 × 10 ⁴ .
If it is less than 3 × 10 ³ , a problem may occur in storage stability, and if it exceeds 3 × 10 ⁴ , not only the fixability may deteriorate, but also the fixing surface smoothness after fixing may deteriorate. Is limited to the above range. Preferably, it is 5 × 10 ^{3 to} 1.5 × 10 ⁴ .

In the molecular weight distribution measured by GPC in the same manner as in the present invention 1, the amount of the high molecular weight polymer of 50,000 or more, where the amount of the low molecular weight less than 50,000 is 100, And the molecular weight peak of the high molecular weight compound satisfy the relationship of the following formulas (a) and (b). A ≦ −4B + 110 (a) A ≧ −4B + 60 (b)

If the above A is out of the range of the above formula (a), the surface smoothness (gloss) is determined from the difference in the melt viscosity of the high molecular weight substance.
Is impaired, and there is a possibility that the desired coloring property cannot be obtained in full color. Further, if the value is outside the range of the above formula (b), the durability of the resin is weak, and fog or the like is likely to occur due to deterioration of the resin during long-term evaluation, so that the range is limited to the above range. Preferably, it is a range represented by the following formula (2). -4B + 100≥A≥-4B + 70 (2)

The above vinyl copolymer may be copolymerized with other vinyl monomers. The other vinyl monomer is not particularly limited, for example, fumaric acid,
Diester derivatives such as maleic acid, citraconic acid and itaconic acid; monoacryloyloxyethyl succinate, monomethacryloyloxyethyl succinate, acrylonitrile, methacrylonitrile, acrylamide, vinyl acetate, vinyl chloride, ethylene and the like.

The above-mentioned vinyl copolymer preferably has a Tg of 50 ° C. or higher, as in the first invention. When the temperature is lower than 50 ° C., the cohesiveness may be deteriorated. The vinyl-based copolymer may have a plurality of peaks or shoulders in the molecular weight distribution measured by GPC as in the first invention.

The synthesis of the above vinyl copolymer is carried out by, for example,
It can be carried out by the method exemplified in the description of the present invention 1.

Further, the resin composition for toner of the present invention 3 comprises:
Polyester resin, epoxy resin, aliphatic amide, bisaliphatic amide, metal soap, paraffin, etc. may be mixed in the same manner as in the toner resin composition of the present invention 1. Nigrosine, spiron black are used as charge control agents. Dyes such as;
Other phthalocyanine-based pigments and the like may be added, and as a coloring material, carbon black, chrome yellow, aniline blue, and the like may be added, and as a release agent, a low-molecular-weight polyethylene wax, a polypropylene wax, or the like is added. Alternatively, hydrophobic silica or the like may be added to enhance fluidity. Further, the resin composition for a toner of the present invention 3 may be mixed with a magnetic powder and used as a magnetic toner similarly to the resin composition for a toner of the present invention 1.

The resin composition for a toner of the present invention 3 uses a vinyl copolymer containing a vinyl copolymerizable monomer having a polar group, so that the dispersibility of a carrier, CCA and the like can be improved. It is possible to improve the color development as a full color.

The resin compositions for toners of the present invention 1, 2 and 3 are preferably used for toners, and particularly suitable for full color toners.
Such a toner is also one of the present invention.

The toner of the present invention contains a coloring material, a charge control agent, and the like in the above resin composition for a toner, and further, if necessary, disperses and mixes magnetic powder and the like, and then heat-melts, kneads, and pulverizes the mixture. Manufactured.

The resin compositions for toners of the present invention 1, 2 and 3 have a molecular weight peak of 3 × 10 3 by GPC.
^{3 to} 3 × 10 ⁴ , and in the molecular weight distribution, the amount of the high molecular weight compound of 50,000 or more when the amount of the low molecular weight substance of less than 50,000 is set to 100, and the molecular weight peak of the high molecular weight substance are as follows: Formula (1): -4B + 110 ≧ A ≧ −4B + 60 (1) (where A represents the molecular weight peak of the high molecular weight compound × 10 ⁻⁴ . B represents the amount of the low molecular weight compound of less than 50,000 as 100 and Represents the amount of the high molecular weight body of 50,000 or more when
It is a positive number. The use of a vinyl copolymer satisfying the relationship represented by the formula (1) prevents the offset without impairing the transparency and enables the production of a resin that does not deteriorate even in long-term evaluation.

The resin composition for toner of the present invention 1
Since the crosslinked resin is used in this vinyl copolymer containing 0.1 to 10% by weight of a crosslinking agent having 10 or more carbon atoms in one molecule, the gloss of the fixed surface after fixing is impaired. Without this, the resin strength could be improved.

The resin composition for a toner of the present invention 2 contains 0.1 to 15 parts by weight of a wax having a weight average molecular weight of 100 to 10,000 based on 100 parts by weight of the vinyl copolymer. It was possible to prevent offset and improve the surface smoothness (gloss) of the fixing surface without impairing the transparency and storage stability of the resin for full-color toner.

The resin composition for a toner of the present invention 3 is obtained by copolymerizing a styrene-based monomer and a (meth) acrylate-based monomer with a vinyl-based copolymerizable monomer having a polar group. As a result, the durability and fixing strength of the resin were enhanced without impairing the transparency of the resin and the surface smoothness (gloss) of the fixing surface, and it was possible to produce a resin that did not deteriorate even in long-term evaluation.

[0066]

BEST MODE FOR CARRYING OUT THE INVENTION

(Examples) Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 A 3-L separable flask was charged with 900 g of toluene, 130 g of a polymer having a molecular weight of 300,000 having a molecular weight of 300,000 with 85% styrene and 15% n-butyl acrylate, and stirred, and the gas phase was replaced with nitrogen gas. Thereafter, the system was warmed to the boiling point of toluene. While stirring with refluxing toluene, 810 g of styrene, 130 g of n-butyl acrylate, 35 g of methyl methacrylate, polyethylene glycol dimethacrylate as a crosslinking agent (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester 9G, carbon number 26, 25 g of a straight-chain carbon number 24) and azobisisobutyronitrile (AIB) as a polymerization initiator
N) A solution in which 50 g of a mixture was dissolved was dropped over 3 hours to perform solution polymerization. After completion of the dropwise addition, the mixture was aged for 1 hour while stirring at a temperature at which toluene was boiling. Thereafter, while gradually raising the temperature of the system to 200 ° C., the solvent was removed from the toluene under reduced pressure to obtain a resin. The resin was cooled and pulverized to obtain a resin composition A for toner. The resin composition A for toner has a maximum value of 10,000 in the molecular weight distribution,
g was 58 ° C. In the molecular weight distribution, when the amount of the low molecular weight compound of less than 50,000 is set to 100, the amount of the high molecular weight compound of 50,000 or more is 13, and the molecular weight peak of the high molecular weight compound is 2
It was 80,000.

6 parts by weight of carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation) and wax (Viscol 660, manufactured by Sanyo Chemical Industries, Ltd.) were added to 100 parts by weight of the resin composition A for toner.
P) 4 parts by weight, charge control agent (manufactured by Hodogaya Chemical Industry Co., Ltd., TP
-302) 3 parts by weight are melt-blended by a continuous kneader (manufactured by Kurimoto Iron & Steel Co., Ltd.), and after cooling, a coffee mill (manufactured by Matsushita Electric Industrial Co., Ltd., CARIOCA-MIL)
L), and further finely pulverized with a jet mill (manufactured by Nippon Pneumatic Industries, Ltd., Labjet), and a 50% average particle size of about 8 microns with a classifier (manufactured by Nippon Pneumatics, MDS-2). Was prepared.

0.5 parts by weight of silica (Aerosil R972D, manufactured by Nippon Aerosil Co., Ltd.) was added as an external additive, and the mixture was sufficiently stirred to obtain a toner. For color toners, disazo yellow for yellow and carmine 6 for magenta
B and cyan were prepared similarly using copper phthalocyanine instead of carbon black.

A developer was prepared by mixing 6 parts by weight of the toner with 94 parts by weight of a ferrite carrier having an average particle diameter of 50 to 80 μm, and a copy was obtained using the developer. The electrophotographic copying machine used was a modified version of Ricoh's Pretail 550.

Evaluation Method Regarding offset and fixing surface smoothness (gloss), the set temperature of the heating roller of the electrophotographic copying machine was set at 180 ° C., and the offset and fixing surface smoothness (gloss) at that time were observed.
も の indicates that no offset occurred, Δ indicates that some offset occurred, and x indicates that offset occurred. For the fixing surface smoothness (gloss), a gloss meter (Gross Gardner, USA, gloss guard, incident angle 60 degrees)
, A gloss of 50 or more is good (）), a gloss of 45 to 5
0 was slightly defective (不良), and gloss less than 45 was defective (x).

The resin strength was determined by the amount of fine powder generated when pulverized by a pulverizer. ◎: very good without generating fine powder, を: good, fine: slightly generated and slightly weak, and ×: fine powder generated and weak: x. As for the running, a running test of 10,000 sheets was performed in a room at a temperature of 30 ° C. and a humidity of 50%, and deterioration of an image at that time was observed. When the image was clear, the result was ○, when the image was slightly disturbed, the result was Δ, and when the image was disturbed, the result was ×.

Results As a result of evaluating the toner using the resin composition A for toner, no offset was generated, the gloss was good at 50 or more for all the colors, and the resin strength was very good. Was. Using this developer, temperature 30 ° C, humidity 50%
When a running test of 10,000 sheets was performed in the room, the image was clear, and almost no image deterioration occurred.

Example 2 A 3-L separable flask was charged with 900 g of xylene, 75 g of styrene, and 30 g of a high-molecular-weight substance having a molecular weight of 800,000 and 25% of n-butyl acrylate, and stirred, and the gas phase was replaced with nitrogen gas. Thereafter, the system was warmed to the boiling point of xylene.
With the xylene refluxed, 780 g of styrene, 140 g of n-butyl acrylate, 30 g of methyl methacrylate, and 2,2-bis [4-
A mixture prepared by dissolving 15 g of (acryloxydiethoxy) phenyl] propane (NK ester A-BPE-4, containing two aromatic rings, manufactured by Shin-Nakamura Chemical Co., Ltd.) and 50 g of benzoyl peroxide (BPO) as a polymerization initiator was mixed with 4
The solution polymerization was performed while dropping over time. After the completion of the dropwise addition, while stirring at the temperature at which xylene boils,
Aged for 1 hour. Thereafter, while gradually raising the temperature of the system to 200 ° C., xylene was desolvated under reduced pressure to obtain a resin. The resin was cooled and pulverized to obtain a resin composition B for toner. This toner resin composition B had a maximum value at 12,000 in the molecular weight distribution, and Tg was 57 ° C. In the molecular weight distribution, the amount of the high molecular weight substance of 50,000 or more when the amount of the low molecular weight substance of less than 50,000 is 100 is 0.03,
The molecular weight peak of the high molecular weight product was 630,000.

A developer was prepared and tested in the same manner as in Example 1 except that the resin composition for toner B was used instead of the resin composition for toner A, and as a result, no offset was found. The gloss was good for all colors with a gloss of 50 or more, and the resin strength was very good. When a running test of 10,000 sheets was performed in a room at a temperature of 30 ° C. and a humidity of 50% using this developer, the image was clear.
Almost no toner deterioration occurred.

Example 3 Instead of polyethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester 9G, carbon number 26, straight-chain carbon number 24), diethylene glycol dimethacrylate (manufactured by Kyoeisha Yushi Kagaku Kogyo KK, light ester 2EG) ,
A developer was prepared and tested in the same manner as in Example 1 except that the number of carbon atoms was 14, and the number of straight-chain carbon atoms was 10). It was as good as 50 or more, and the resin strength was good.
A running test of 10,000 sheets was performed in a room at a temperature of 30 ° C. and a humidity of 50% using this developer. As a result, the image was clear and almost no image deterioration occurred.

COMPARATIVE EXAMPLE 1 When the amount of the high molecular weight substance was 250 g and the amount of the low molecular weight substance less than 50,000 in the molecular weight distribution was 100, the amount of the high molecular weight substance of 50,000 or more was 25. A developer was prepared and tested in the same manner as in Example 1 except that a resin composition for toner having a molecular weight peak of 280,000 was used.
No offset has occurred, and gloss is 3 for all colors.
It was worse than 0. The resin strength was good. A running test of 10,000 sheets was performed in a room at a temperature of 30 ° C. and a humidity of 50% using this developer. As a result, the image was clear and almost no image deterioration occurred.

Comparative Example 2 When the amount of the high molecular weight compound was 60 g and the amount of the low molecular weight compound having a molecular weight distribution of less than 50,000 was 100, the amount of the high molecular weight compound of 50,000 or more was 6, and the amount of the high molecular weight compound was 6. Has a molecular weight peak of 28
A developer was prepared and tested in the same manner as in Example 1 except that a thousand resin compositions for toner were used, and as a result, offset was generated. The glossiness of all colors was good with a gloss of 50 or more. The resin strength was slightly weak, and some fine powder was generated. When a running test of 10,000 sheets was performed in a room at a temperature of 30 ° C. and a humidity of 50% using this developer, the image was slightly disturbed, and the image was deteriorated.

Comparative Example 3 In place of polyethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester 9G, carbon number 26, linear carbon number 24), ethylene glycol diacrylate (manufactured by Kyoeisha Yushi Kagaku Kogyo KK, EG- A, a developer was prepared in the same manner as in Example 1 except for using C8),
As a result of the test, no offset was generated, and the glossiness of all colors was as good as 50 or more in gloss. The resin strength was slightly weak, and some fine powder was generated. When a running test of 10,000 sheets was performed in a room at a temperature of 30 ° C. and a humidity of 50% using this developer, the image was slightly disturbed, and the image was deteriorated.

Comparative Example 4 A developer was prepared and tested in the same manner as in Example 1 except that no cross-linking agent was used. As a result, an offset was generated, and the glossiness of all the colors was 50 or more. Met.
The resin strength was weak, and fine powder was generated. Further, when a running test of 10,000 sheets was performed in a room at a temperature of 30 ° C. and a humidity of 50% using this developer, the image was disturbed and the image was deteriorated.

Comparative Example 5 A developer was prepared and tested in the same manner as in Example 2 except that the amount of the crosslinking agent was changed to 110 g. As a result, the resin gelled and could not be evaluated.

The results of Examples 1 to 3 and Comparative Examples 1 to 5 are summarized in Table 1. In addition,-in a table | surface means that evaluation was not able to be performed.

[0083]

[Table 1]

Example 4 900 g of toluene, 60% of styrene, 17% of n-butyl acrylate, 23% of methyl methacrylate, and a high molecular weight compound having a molecular weight peak of 400,000 and 1 were placed in a 3 L separable flask.
00g and THERMOLETS SF made by China Essential Oil Co., Ltd.
After 33 g of 6099 (weight average molecular weight 848) was added and stirred, the gas phase was replaced with nitrogen gas, and the system was heated to the boiling point of toluene. 870 g of styrene and n-acrylic acid were stirred while toluene was refluxed.
Solution polymerization was carried out while dropping a mixture of 130 g of butyl and 50 g of AIBN as a polymerization initiator dropwise over 4 hours. After completion of the dropwise addition, the mixture was aged for 1 hour while stirring at a temperature at which toluene was boiling. Thereafter, while gradually raising the temperature of the system to 180 ° C., toluene was removed under reduced pressure to obtain a resin. The resin was cooled and pulverized to obtain a resin composition C for toner. Resin composition C for toner is
There is a maximum plant at 6 × 10 ³ in the molecular weight distribution, and Tg is 58 ° C.
Met. In the molecular weight distribution, when the amount of the low molecular weight substance of less than 50,000 is set to 100, the amount of the high molecular weight substance of 50,000 or more is 10
And the molecular weight peak of the high molecular weight product was 370,000.

Carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation) was added to 100 parts by weight of the resin composition C for toner.
6 parts by weight and 3 parts by weight of a charge control agent (Orient Chemical Industries, Bontron S-34) are melt-blended by a continuous kneader (manufactured by Kurimoto Steel Works), cooled, and then coffee mill (manufactured by Matsushita Electric Industrial Co., Ltd., CARIOCA-). MIL
L), coarsely pulverized with a jet mill (Labjet, manufactured by Nippon Pneumatic Industries, Ltd.), and a classifier (MDS-2, manufactured by Nippon Pneumatics, Inc.) with a 50% average of about 9.3 microns. A toner powder having a particle size was prepared.
0.5 parts by weight of silica (Aerosil R972D, manufactured by Nippon Aerosil Co., Ltd.) was added as an external additive, and the mixture was sufficiently stirred to obtain a toner.

The color toner was prepared in the same manner using disazo yellow for yellow, carmine 6B for magenta, and copper phthalocyanine for cyan instead of carbon black. 6 to 5 parts by weight of the toner
Ferrite carrier 9 having an average particle size of 0 micron
4 parts by weight to prepare a developer, and a copy was obtained using the developer. The electrophotographic copying machine used was a modified version of Acolor 636 manufactured by Fuji Xerox.
The fixing temperature was set at a value at which the density of a copy image changed when the copy was rubbed with a sand eraser for a typewriter while variously changing the set temperature of a heating roller of an electrophotographic copying machine.

Evaluation Method Offset and fixing surface smoothness (gloss) were evaluated in the same manner as in Example 1 except that the set temperature of the heating roller of the electrophotographic copying machine was 190 ° C.

The filming and durability were evaluated by performing a running test of 10,000 sheets in a room at a temperature of 30 ° C. and a humidity of 50%, and by attaching wax to the photoreceptor and deteriorating the image at that time. If filming did not occur, ○
What happened was marked X. In addition, ○ indicates that the image was clear, Δ indicates that the image was slightly unclear, and X indicates that the image was unclear. Regarding the transparency, the hue of the halftone portion after fixing was visually evaluated, and the case where the halftone was able to be reproduced was evaluated as ○, and the case where the halftone was not reproduced was evaluated as ×.

As a result of evaluating the toner using the resin composition C for toner, no offset was generated, and the glossiness of all the colors was good, that is, the gloss was 50 or more. As a result of a running test using this developer, there was no filming, the image was clear, and no filming on the photoreceptor was observed. Also, halftones could be reproduced beautifully.

Example 5 In a 3 L separable flask, 900 g of xylene, 85 g of styrene, 40 g of a high molecular weight substance having a molecular weight peak of 800,000 and 15% of n-butyl acrylate, and 40 g of NO.
After 90 g of PALETS MP-85 (weight average molecular weight 608) was added and stirred, the gas phase was replaced with nitrogen gas, and the system was heated to the boiling point of xylene. While the xylene is refluxing, styrene 740
g, 160 g of n-butyl acrylate, 100 g of methyl methacrylate, and a mixture in which 60 g of BPO and a polymerization initiator were dissolved were dropped over 2 hours to perform solution polymerization. After completion of the dropwise addition, the mixture was further aged for 2 hours while stirring at a temperature at which xylene boils. Thereafter, the temperature of the system is set to 200
The xylene was desolvated under reduced pressure while gradually increasing the temperature to ℃, to obtain a resin. The resin was cooled and pulverized to obtain a resin composition D for toner. The resin composition D for toner had a maximum value at 8 × 10 ³ in the molecular weight distribution, and Tg was 59 ° C. In the molecular weight distribution, the amount of the low molecular weight compound of less than 50,000
And the amount of the high molecular weight body of 50,000 or more is 4,
The molecular weight peak of the high molecular weight product was 600,000.

A developer was prepared and tested in the same manner as in Example 4 except that the resin composition D for toner was used instead of the resin composition C for toner. As a result, no offset was found. The glossiness of all colors was good with a gloss of 50 or more. As a result of a running test using this developer, there was no filming and the image was clear. Also, halftones could be reproduced beautifully.

Comparative Example 6 When the amount of the high molecular weight substance was 140 g and the amount of the low molecular weight substance less than 50,000 in the molecular weight distribution was 100, the amount of the high molecular weight substance of 50,000 or more was 14, and the amount of the high molecular weight substance was 14. A developer was prepared and tested in the same manner as in Example 5, except that a resin composition for toner having a molecular weight peak of 600,000 was used.
Although no offset occurred, the glossiness of all colors deteriorated to a gloss of 30 or less. As a result of a running test using this developer, no filming on the photoreceptor was observed, and the image was clear. Also, halftones could be reproduced beautifully.

Comparative Example 7 When the amount of the high molecular weight compound was 10 g, and the amount of the low molecular weight compound less than 50,000 in the molecular weight distribution was 100, the amount of the high molecular weight compound of 50,000 or more was 1, and the amount of the high molecular weight compound was 1. Has a molecular weight peak of 37
A developer was prepared and tested in the same manner as in Example 4 except that a thousand toner resin compositions were used. As a result, offset was generated. However, the gloss was as good as 50 or more for all colors. As a result of a running test using this developer, no filming on the photoreceptor was observed, but the image was slightly unclear. However, the halftone was reproduced beautifully.

Comparative Example 8 The addition amount of THERMOLETS SF6099 was 200
A developer was prepared and tested in the same manner as in Example 4 except that the amount was changed to g. As a result, no offset was generated, and the glossiness of all colors was as good as 50 or more in gloss. As a result of a running test using this developer, filming was severe and the image was slightly unclear. Also, halftones could not be reproduced clearly.

Comparative Example 9 A developer was prepared and tested in the same manner as in Example 5 except that the amount of NOPALETS MP-85 was changed to 10 g. As a result, an offset was generated. But,
The glossiness of all colors was good with a gloss of 50 or more. As a result of a running test using this developer, there was no filming and the image was clear. Also, halftones could be reproduced beautifully.

Comparative Example 10 A developer was prepared and tested in the same manner as in Example 5, except that VISCOL 330P (number average molecular weight: 15,000) manufactured by Sanyo Chemical Industries, Ltd. was used instead of NOPALETS MP-85. , The offset was slightly generated. However, the gloss was as good as 50 or more for all colors. Using this developer, a running test was performed on 10,000 sheets in a room at a temperature of 30 ° C. and a humidity of 50%. As a result, no filming was observed and the image was clear. Also, halftones could be reproduced beautifully.

The results of Examples 4 to 5 and Comparative Examples 6 to 10 are summarized in Table 2.

[0098]

[Table 2]

Example 6 A 3-L separable flask was charged with 900 g of xylene, 150 g of a high-molecular-weight substance having a molecular weight peak of 400,000 and containing 80% of styrene and 20% of n-butyl acrylate and stirred, and the gas phase was replaced with nitrogen gas. After that, the system was warmed to the boiling point of xylene. While stirring with the xylene refluxing,
Solution polymerization was performed while dropping a mixture of 800 g of styrene, 150 g of n-butyl acrylate, 50 g of acrylic acid and 50 g of BPO as a polymerization initiator dropwise over 3 hours. After completion of the dropwise addition, the mixture was aged for 1 hour while stirring at a temperature at which xylene boils. Thereafter, while gradually raising the temperature of the system to 200 ° C., xylene was desolvated under reduced pressure to obtain a resin. The resin was cooled and pulverized to obtain a resin composition E for toner. The resin composition E for toner is
The molecular weight distribution had a maximum value at 10,000, and the Tg was 58 ° C. In the molecular weight distribution, the amount of the low-molecular
The amount of the high molecular weight compound of 50,000 or more when it was set to 0 was 15, and the molecular weight peak of the high molecular weight product was 340,000.

Carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation) was added to 100 parts by weight of the obtained resin composition E for toner.
6 parts by weight, wax (Viscol 5 manufactured by Sanyo Chemical Industries, Ltd.)
50P) 4 parts by weight, charge control agent (manufactured by Hodogaya Chemical Co., Ltd.
3 parts by weight of TP-302) were melt-blended by a continuous kneader (manufactured by Kurimoto Iron and Steel Works), cooled, and then coffee mill (manufactured by Matsushita Electric Industrial Co., Ltd., CARIOCA-MI).
LL), and further finely pulverized by a jet mill (manufactured by Nippon Pneumatic Industries, Ltd., Lab Jet), and a 50% average particle size of about 9 μm is classified with a classifier (MDS-2, manufactured by Nippon Pneumatics). To prepare toner powder.

As an external additive, 0.5 parts by weight of silica (Aerosil R972D, manufactured by Nippon Aerosil Co., Ltd.) was added and sufficiently stirred to obtain a toner. For color toners, disazo yellow for yellow and carmine 6 for magenta
B and cyan were prepared similarly using copper phthalocyanine instead of carbon black. The toner 6
A part by weight was mixed with 94 parts by weight of a ferrite carrier having an average particle diameter of 50 to 80 microns to prepare a developer, and a copy was obtained using the developer. The electrophotographic copying machine used was a modified version of Ricoh's Pretail 550.

Evaluation Method Offset and fixing surface smoothness (gloss) were evaluated in the same manner as in Example 4. The resin strength and the environmental stability were evaluated by performing a running test of 10,000 sheets in a room at a temperature of 30 ° C. and a humidity of 50%, and based on deterioration of an image at that time and a decrease in a charge amount due to moisture absorption.も の indicates that the toner did not deteriorate, △ indicates that the toner slightly deteriorated, and x indicates that the toner deteriorated slightly.

Regarding environmental stability, the change in concentration was 20%.
The sample was evaluated as good when the density was less than 0, and evaluated as poor when the change in density was 20% or more. Regarding the dispersibility of pigments and CCA, the degree of dispersion was confirmed by observing TEM photographs.
も の indicates that the degree of dispersion was good, Δ indicates that the degree of dispersion was good, and x indicates that the degree of dispersion was poor.

As a result of evaluating the toner using the resin composition E for toner, no offset was generated, and the glossiness of all the colors was good, that is, the gloss was 50 or more. A running test of 10,000 sheets was performed using the developer in a room at a temperature of 30 ° C. and a humidity of 50%. As a result, the image was clear and the toner hardly deteriorated. Environmental stability was good and dispersibility was also very good.

Example 7 A 3-L separable flask was charged with 900 g of xylene, 80 g of a high molecular weight substance having a molecular weight peak of 700,000 with 75% styrene and 25% n-butyl acrylate, and stirred, and the gas phase was replaced with nitrogen gas. After that, the system was warmed to the boiling point of xylene. With the xylene refluxing, while stirring,
Solution polymerization was carried out while dropping a mixture of 760 g of styrene, 130 g of n-butyl acrylate, 100 g of methyl methacrylate, 10 g of methacrylic acid and 40 g of BPO as a polymerization initiator dropwise over 4 hours. After completion of the dropwise addition, the mixture is further stirred at a temperature at which xylene boils for 1 hour.
Aged for hours. Thereafter, while gradually raising the temperature of the system to 200 ° C., xylene was desolvated under reduced pressure to obtain a resin. The resin was cooled and pulverized to obtain a resin composition F for toner. The resin composition F for toner has a molecular weight distribution of 1.
50,000 had a maximum value, and Tg was 63 ° C. In the molecular weight distribution, when the amount of the low molecular weight compound having a molecular weight of less than 50,000 was taken as 100, the amount of the high molecular weight compound of 50,000 or more was 8, and the molecular weight peak of the high molecular weight compound was 560,000.

A developer was prepared and tested in the same manner as in Example 6 except that the resin composition F for toner was used instead of the resin composition E for toner. As a result, no offset was found. Also, the glossiness of all colors was as good as 50 or more. Using this developer, the temperature is 30 ° C. and the humidity is 5
A running test of 10,000 sheets was performed in a 0% room. As a result, the image was clear and toner deterioration hardly occurred. In addition, environmental stability was good, and dispersibility was also very good.

Comparative Example 11 A developer was prepared and tested in the same manner as in Example 6 except that 130 g of acrylic acid was used. As a result, no offset was generated and the glossiness was as good as 50 or more. there were. Using this developer, the temperature is 30 ° C. and the humidity is 50%.
When a running test was performed on 10,000 sheets in the room, the toner was hardly deteriorated. However, the environmental stability was very poor and fogging had occurred. But,
Dispersibility was very good.

Comparative Example 12 A developer was prepared and tested in the same manner as in Example 7 except that methacrylic acid was not used. As a result, no offset was generated and the glossiness was as good as 50 or more. there were. Using this developer, the temperature is 30 ° C. and the humidity is 50%.
When a running test was performed on 10,000 sheets in the room, the toner was hardly deteriorated. The environmental stability was also very good. However, dispersibility worsens,
Color development was poor.

Comparative Example 13 When the amount of the high molecular weight compound was 200 g, and the amount of the low molecular weight compound less than 50,000 in the molecular weight distribution was 100, the amount of the high molecular weight compound of 50,000 or more was 20, and the amount of the high molecular weight compound was 20. A developer was prepared and tested in the same manner as in Example 6, except that a resin composition for toner having a molecular weight peak of 340,000 was used.
No offset has occurred, and gloss is 3 for all colors.
It was worse than 0. Also, using this developer at a temperature of 3
When a running test was performed on 10,000 sheets in a room at 0 ° C. and 50% humidity, toner deterioration hardly occurred. The environmental stability was also very good, and the dispersibility was also very good.

Comparative Example 14 A developer was prepared and tested in the same manner as in Example 7 except that no high molecular weight compound was used. As a result, an offset was generated. However, the gloss was as good as 50 or more for all colors. Also, using this developer, the temperature is 30 ° C.
When a running test was performed on 10,000 sheets in a room with a humidity of 50%, a slight deterioration of the toner occurred. But,
The environmental stability was always good and the dispersibility was also good.

The results of Examples 6 to 7 and Comparative Examples 11 to 14 are summarized in Table 3.

[0112]

[Table 3]

[0113]

Since the resin composition for toner and the toner of the present invention have the above-mentioned constitutions, it is possible to improve the fixability and the surface smoothness after fixing. Also, without impairing the surface smoothness after fixing, increase the resin rigidity, and
Carrier and CCA can be dispersed well,
Since it has good color developability and can be reduced in particle size, it can be suitably used as a high-resolution full-color toner.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 220: 12 220: 04) (C08L 25/14 91:06)

Claims (4)

[Claims] 1. A styrene monomer and a (meth) acrylate monomer having a molecular weight peak of 3 × 10 ³ to 3 by gel permeation chromatography.
× 10 ⁴ , and in the molecular weight distribution, when the amount of the low molecular weight compound of less than 50,000 is 100, the amount of the high molecular weight compound of 50,000 or more and the molecular weight peak of the high molecular weight compound are represented by the following formula (1). -4B + 110 ≧ A ≧ −4B + 60 (1) (where A represents the molecular weight peak of the high molecular weight compound × 10 ⁻⁴ . B represents 5 when the amount of the low molecular weight compound of less than 50,000 is defined as 100). Represents the amount of a high molecular weight substance of 10,000 or more, where B is
It is a positive number. A) a resin obtained by crosslinking a vinyl copolymer satisfying the relationship represented by the formula (1) with 0.1 to 10% by weight of a crosslinking agent having 10 or more carbon atoms in one molecule. Resin composition for toner. 2. A styrene monomer and a (meth) acrylate monomer having a molecular weight peak of 3 × 10 ³ to 3 by gel permeation chromatography.
× 10 ⁴ , and in the molecular weight distribution, when the amount of the low molecular weight compound of less than 50,000 is 100, the amount of the high molecular weight compound of 50,000 or more and the molecular weight peak of the high molecular weight compound are represented by the following formula (1). -4B + 110 ≧ A ≧ −4B + 60 (1) (where A represents the molecular weight peak of the high molecular weight compound × 10 ⁻⁴ . B represents 5 when the amount of the low molecular weight compound of less than 50,000 is defined as 100). Represents the amount of a high molecular weight substance of 10,000 or more, where B is
It is a positive number. ) Is 100 to 100 parts by weight of the vinyl copolymer satisfying the relationship represented by the weight average molecular weight of 100 to
A resin composition for a toner, comprising 0.1 to 15 parts by weight of a wax of 10,000. 3. A styrene monomer and a (meth) acrylate monomer having a molecular weight peak of 3 × 10 ³ to 3 by gel permeation chromatography.
× 10 ⁴ , and in the molecular weight distribution, when the amount of the low molecular weight compound of less than 50,000 is 100, the amount of the high molecular weight compound of 50,000 or more and the molecular weight peak of the high molecular weight compound are represented by the following formula (1). -4B + 110 ≧ A ≧ −4B + 60 (1) (where A represents the molecular weight peak of the high molecular weight compound × 10 ⁻⁴ . B represents 5 when the amount of the low molecular weight compound of less than 50,000 is defined as 100). Represents the amount of a high molecular weight substance of 10,000 or more, where B is
It is a positive number. A) a resin composition for a toner comprising a vinyl copolymer satisfying the relationship represented by the formula (1), wherein the vinyl copolymer has a vinyl group copolymerizable monomer having a polar group of 0.01 to A resin composition for a toner, which is obtained by copolymerizing 10% by weight. 4. A toner comprising the resin composition for toner according to claim 1, 2 or 3.