JPH1039543A - Resin composition for toner and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin compsn. for a toner excellent in surface smoothness, transparency and resin strength without deteriorating anti-offsetting property, fixability, and stability and suitable for use as a high resolution full-color toner as well as a monocolor toner and a toner. SOLUTION: This resin compsn. for a toner contains a resin obtd. by incorporating 0.1-10wt.% crosslinking agent having >=10 carbon atoms in one molecule into a vinyl copolymer and crosslinking the copolymer. The copolymer consists of a styrene monomer and a (meth)acrylic ester monomer and has the peak of mol.wt. by gel permeation chromatography in the range of 3×10<3> -3×10<4> . In the mol.wt. distribution of the copolymer, a part whose mol.wt. is <=100,000 accounts for >=70wt.%.

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 an electric attractive force. 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.

Japanese Patent Application Laid-Open No. 57-56850 discloses a developing device 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 by using a toner 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-57-178251 and JP-A-6-175395 disclose methods of increasing resin strength by metal cross-linking to prevent offset. Depending on conditions such as storage temperature and storage period, the degree of metal crosslinking changes.
There is a problem that it is difficult to manufacture products of a certain quality, and it is susceptible to seasonal fluctuations.

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-acryl 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 resin is increased, there is a problem that the fixing property is reduced. . Due to these problems, conventionally, toners have been manufactured by balancing offset resistance, fixability, and the like.

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 or the use of the high molecular weight resin is simply stopped, the offset phenomenon occurs, which causes not only irregularities on the fixing surface but also defects such as staining 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.

[0013] Furthermore, the cross-linked portion in the resin is increased due to the decrease in the particle size, and the poor dispersion of the added wax causes the formation of toner particles of the cross-linked portion or only the wax, resulting in deterioration of quality. And other problems.

[0014]

SUMMARY OF THE INVENTION In view of the above, it is an object of the present invention to provide a high-resolution image including monocolor without impairing the offset resistance, fixing property and stability, having excellent surface smoothness, transparency and resin strength. An object of the present invention is to provide a toner resin composition and a toner that can be suitably used as a full-color toner.

[0015]

The present invention comprises a styrene-based monomer and a (meth) acrylate-based monomer, and has a molecular weight peak of 3 × 10 ³ to 3 × by gel permeation chromatography. A vinyl copolymer having a molecular weight distribution of 10 ⁴ or less and a molecular weight distribution of 100,000 or less containing 70% by weight or more contains a crosslinking agent having 10 or more carbon atoms in one molecule in an amount of 0.1 to 10% by weight. And a resin composition for toner comprising a crosslinked resin.

The present invention 2 relates to a vinyl copolymer comprising a styrene monomer and a (meth) acrylate monomer, wherein a crosslinking agent having 10 or more carbon atoms in one molecule is added to a vinyl copolymer. 10% by weight and crosslinked resin 10
The weight average molecular weight is 300 to 1000 based on 0 parts by weight.
0 and a wax having a dispersity of 1.5 or less
A resin composition for toner containing up to 15 parts by weight.

The present invention relates to a styrene monomer, (meth)
Acrylic ester monomers, and a polar group-containing vinyl copolymerizable monomer, the content of the polar group-containing vinyl copolymerizable monomer is 0.01 to 10% by weight % Of a vinyl copolymer containing 0.1 to 10% by weight of a crosslinking agent having 10 or more carbon atoms in one molecule.

Hereinafter, the present invention 1 will be described in detail. 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, pn-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, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and the like are preferable.

The above vinyl copolymer may contain other vinyl monomers. The other vinyl monomer is not particularly limited, for example, acrylic acid,
Acrylic acid such as methacrylic acid, α-ethylacrylic acid, crotonic acid or an α-alkyl derivative or β-alkyl derivative thereof; fumaric acid, maleic acid, citraconic acid,
Unsaturated dicarboxylic acids such as itaconic acid or monoester derivatives or diester derivatives thereof; monoacryloyloxyethyl succinate, monomethacryloyloxyethyl succinate, acrylonitrile, methacrylonitrile, acrylamide and the like.

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 3 × 1 3
0 ⁴ When more than, fixability not only be exacerbated, since the fixing surface smoothness after fixing may be deteriorated, the above range is critical. Preferably, 5 × 10
^{It is 3 to} 1.5 × 10 ⁴ .

In the above-mentioned vinyl copolymer, a portion having a molecular weight of 100,000 or less in the molecular weight distribution measured by GPC is 70% by weight or more. When the content is less than 70% by weight, the fixing surface smoothness (gloss) after fixing may be deteriorated, so that the content is limited to the above range. Preferably, it is at least 80% by weight.

The above-mentioned 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. More preferably, it is 50 to 100 ° C. More preferably, 55 to
80 ° C.

In the molecular weight distribution of the vinyl copolymer measured by GPC, a plurality of peaks and shoulders may exist. 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.

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. 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.

The resin composition for toner of the present invention 1 comprises a resin obtained by crosslinking a vinyl copolymer containing 0.1 to 10% by weight of a crosslinking agent. When the content of the cross-linking agent is less than 0.1% by weight, the resin strength of the obtained resin composition for toner becomes weak, and when it exceeds 10% by weight, the resin composition is excessively cross-linked, so that a gel component is easily generated. Since the pulverizability of the toner deteriorates and the dispersibility of carbon and the like also deteriorates, the above range is limited. Preferably, 1 to 7% by weight
It is.

The above 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 is difficult to use the toner as a small particle size toner for full-color, high-resolution. Preferably, it is 12 to 50.

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. When the cross-linking agent is a linear one, the main chain preferably has 12 or more carbon atoms.

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.
In order to enhance fluidity, hydrophobic silica or the like may be added. Further, the resin composition for toner of the present invention 1 may be used as a magnetic toner by mixing magnetic powder.

The present invention 2 relates to a vinyl copolymer comprising a styrene monomer and a (meth) acrylate monomer, wherein a crosslinking agent having 10 or more carbon atoms in one molecule is added to a vinyl copolymer. 10% by weight and crosslinked resin 10
The weight average molecular weight is 300 to 1000 based on 0 parts by weight.
0 and a wax having a dispersity of 1.5 or less
A resin composition for toner containing up to 15 parts by weight.

In the present invention 2, the vinyl copolymer comprises a styrene monomer and a (meth) acrylate monomer. The styrene monomer is not particularly limited, and 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.

In the present invention 2, the vinyl copolymer is crosslinked by containing a crosslinking agent having 10 or more carbon atoms in one molecule in an amount of 0.1 to 10% by weight. The crosslinking agent is not particularly limited, and includes, for example, those exemplified in the description of the present invention 1. Among them, straight-chain ones and those containing two or more polymerizable double bonds are preferable.

The vinyl copolymer has a Tg of 50 to 1
Preferably it is 00 ° C. More preferably, 55 to
80 ° C. The vinyl copolymer may have a plurality of peaks and shoulders in the molecular weight distribution measured by GPC.

In the synthesis of the vinyl copolymer, 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 characterized in that a wax is added to 100 parts by weight of a resin obtained by crosslinking the above-mentioned vinyl copolymer by adding the above-mentioned crosslinking agent in an amount of 0.1 to 10% by weight. 0.1 to 15 parts by weight. If the content of the wax is less than 0.1 part by weight, the gloss of the fixing surface cannot be maintained, and offset tends to occur.
When the amount exceeds the weight part, adverse effects such as filming on the photoreceptor occur. More preferably, it is 0.5 to 10 parts by weight.

The above-mentioned wax is a gloss auxiliary mainly for giving gloss. The wax has a weight average molecular weight of 30.
0 to 10,000. If it is less than 300, there is a problem in storage stability, and if it exceeds 10,000, the gloss of the fixing surface cannot be maintained, so that it is limited to the above range. Preferably, it is 350-3000. More preferably, 400
~ 1000.

The wax has a degree of dispersion of 1.5 or less. When it exceeds 1.5, the low molecular weight component increases,
Since there is a problem in storage stability, it is limited to the above range. Preferably, it is 1.2 or less.

The above wax has a softening point of 60 to 150 ° C.
It is preferred that If the temperature is lower than 60 ° C., blocking may occur during storage at room temperature. If the temperature is higher than 150 ° C., melting becomes difficult at the time of fixing, and surface smoothness at the time of fixing, that is, gloss may be impaired. More preferably, it is 70 to 100 ° C.

The wax preferably has a peak temperature by DSC of 60 to 100 ° C. If the temperature is lower than 60 ° C., blocking may occur during storage at room temperature,
If the temperature exceeds 100 ° C., it becomes difficult to melt at the time of fixing, and the surface smoothness (gloss) at the time of fixing may be impaired. More preferably, it is 65 to 90 ° C.

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.

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 present invention 3 comprises a styrene monomer, (meth)
Acrylic ester monomers, and a polar group-containing vinyl copolymerizable monomer, the content of the polar group-containing vinyl copolymerizable monomer is 0.01 to 10% by weight % Of a vinyl copolymer containing 0.1 to 10% by weight of a crosslinking agent having 10 or more carbon atoms in one molecule. Hereinafter, the present invention 3 will be described in detail.

In the present invention 3, the vinyl copolymer is composed of a styrene monomer, a (meth) acrylate monomer, and a vinyl copolymerizable monomer having a polar group. .

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 added to make the resin composition for toner of the present invention 3 into a toner in order to disperse additives such as CCA well. You. The content of the polar group-containing vinyl copolymerizable monomer is 0.01 to 10 in the vinyl copolymer.
% By weight. If the amount is less than 0.01% by weight, the effect of the addition of the polar group-containing vinyl copolymer cannot be obtained. If the amount is more than 10% by weight, poor charging may occur. Is done. Preferably, 0.1
~ 5% by weight.

The polar group is preferably an acid component from the viewpoint of odor and polarity. The acid component 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.

In the present invention 3, the vinyl copolymer is crosslinked by containing a crosslinking agent having 10 or more carbon atoms in one molecule in an amount of 0.1 to 10% by weight. The crosslinking agent is not particularly limited, and includes, for example, those exemplified in the description of the present invention 1. Among them, a straight-chain compound having two or more aromatic rings in one molecule is preferable.

The above vinyl copolymer preferably has a molecular weight peak by GPC of 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. There is. More preferably, 5 × 10
^{It is 3 to} 1.5 × 10 ⁴ .

In the above-mentioned vinyl copolymer, a portion having a molecular weight of 100,000 or less in a molecular weight distribution measured by GPC is preferably 70% by weight or more. If the amount is less than 70% by weight, the fixing surface smoothness (gloss) after fixing may be deteriorated. More preferably, it is 80% by weight or more.

The above-mentioned vinyl copolymer preferably has a Tg of 50 ° C. or higher. More preferably, 50 to 10
0 ° C. More preferably, it is 55 to 80 ° C. The vinyl copolymer may have a plurality of peaks and shoulders in the molecular weight distribution measured by GPC.

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

The content of the crosslinking agent is 0.1 to 10% by weight in the vinyl copolymer. When the amount is less than 0.1% by weight, the resin strength of the obtained resin composition for a toner is weakened. The content is limited to the above range, because it deteriorates and the dispersibility of carbon and the like also deteriorates. Preferably, it is 1 to 7% by weight.

In the toner resin composition of the present invention 3, 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. Further, a polymer of these monomers may be blended.

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 toner of the present invention 1, 2, or 3 is preferably used for a toner, and can be particularly preferably used for a full-color toner. 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 composition for a toner of the present invention 1 comprises a GPC
The polymer has a peak of molecular weight of 3 × 10 ^{3 to} 3 × 10 ⁴ and a vinyl copolymer having a molecular weight distribution of 100,000 or less and 70% by weight or more. In addition, the surface smoothness after fixing can be improved. The resin composition for toner of the present invention 1 uses a crosslinked resin containing 0.1 to 10% by weight of a crosslinking agent having 10 or more carbon atoms in one molecule in the vinyl copolymer. Therefore, the resin rigidity can be improved without impairing the gloss of the fixing surface after fixing, and the particle size can be reduced ideally as a high-resolution full-color toner.

The resin composition for toner of the present invention 2 contains 0.1 to 10 crosslinkers having 10 or more carbon atoms in one molecule.
% By weight and cross-linked to improve the resin rigidity without impairing the gloss of the fixing surface after fixing, and to reduce the particle size ideal as a high-resolution full-color toner. Wax having a molecular weight of 300 to 10,000 and a dispersity of 1.5 or less is 0.1 to 15;
Since it is contained by weight%, the surface smoothness (gloss) of the fixing surface can be obtained without impairing the transparency and storage stability of the resin for full-color toner.

The resin composition for a toner of the present invention 2 has an improved anti-offset property and a good dispersion of carbon, pigment and the like by the combination of these, and the resin composition for a toner of the present invention 2 can be used in a monocolor only. It is possible to produce from a toner to a high-resolution full-color toner.

The resin composition for toner of the present invention 3 uses a vinyl copolymer containing a vinyl copolymerizable monomer having a polar group, so that the dispersion of the carrier and CCA is improved. As a result, the color development as a full color can be improved. In addition, by using a cross-linked resin containing 0.1 to 10% by weight of a cross-linking agent having 10 or more carbon atoms in one molecule, the resin rigidity can be improved without impairing the gloss of the fixing surface after fixing. It is possible to reduce the particle diameter as a high-resolution full-color toner.

[0066]

The present invention will be described in more detail with reference to the following 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, the gas phase was replaced with nitrogen gas, and the system was heated to the boiling point of toluene. While stirring while refluxing toluene occurred, 740 g of styrene and 130 g of n-butyl acrylate were used.
g, methyl methacrylate 60 g, ethylene glycol dimethacrylate as a cross-linking agent (manufactured by Kyoeisha Yushi Kagaku Kogyo KK, light ester EG, carbon number 12, straight-chain carbon number 8)
Solution polymerization was performed while dropping a mixture in which 30 g of azobisisobutyronitrile (AIBN) as a polymerization initiator was dissolved over 30 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 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.
Resin composition A for toner had a maximum value of 15,000 in the molecular weight distribution, and Tg was 60 ° C.

6 parts by weight of carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation) and 100 parts by weight of wax (Viscol 550, manufactured by Sanyo Chemical Industries, Ltd.) are 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 Works Co., Ltd.), and after cooling, a coffee mill (manufactured by Matsushita Electric Industrial Co., Ltd., CARIOCA-MIL)
L), coarsely pulverized with a jet mill (Nippon Pneumatic Industries, Ltd., Lab Jet), and a classifier (Nippon Pneumatics, MDS-2) with a 50% average particle size of about 9 microns. To prepare toner powder.

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 size of 50 to 80 microns, and a copy was obtained using the developer. The electrophotographic copying machine used was a modification of Acolor 930 manufactured by Fuji Xerox.

Evaluation Method Regarding offset and fixing surface smoothness (gloss), the set temperature of the heating roller of the electrophotographic copying machine was set at 190 ° C., and the offset and fixing surface smoothness (gloss) at that time were observed.
も の indicates that no offset occurred, and X indicates that an offset occurred. For the fixing surface smoothness (gloss), a gloss meter (Gross Guard, manufactured by Gardner, USA)
(Incident angle of 60 degrees), and a gloss of 50 or more is good (○),
The gloss 45 to 50 was slightly defective (不良), and the gloss less than 45 was defective (x).

The resin strength was 1 in a room at 30 ° C. and 50% humidity.
A running test was performed on 10,000 and 30,000 sheets, and the deterioration of the toner at that time was observed.も の indicates that the toner did not deteriorate even after 30,000 sheets, ○ indicates that the toner did not deteriorate after 10,000 sheets, and X indicates that the toner deteriorated after less than 10,000 sheets. Further, regarding the storage stability, the degree of blocking of the resin after standing at 50 ° C. for 24 hours was checked.も の indicates that no blocking was observed, and X indicates that blocking was observed.

As a result of evaluating the toner using the resin composition A 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. However, when 30,000 sheets of running were performed, the image was clear, but the toner was slightly deteriorated. As for the storage stability, no blocking or the like was observed, and there was no problem at all.

Example 2 900 g of xylene was placed in a 3 L separable flask, the gas phase was replaced with nitrogen gas, and the system was heated to the boiling point of xylene. 820 g of styrene and n-butyl acrylate 13 were stirred with xylene refluxing.
0 g, methyl methacrylate 30 g, polyethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester 14G, carbon number 36, straight-chain carbon number 3) as a crosslinking agent
4) Solution polymerization was carried out while dropping a mixture of 20 g and 24 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 xylene boils. Then, the temperature of the system is reduced to 2
While gradually raising the temperature to 00 ° C., xylene was removed under reduced pressure to obtain a resin. The resin was cooled and pulverized to obtain a resin composition B for toner. This resin composition B for toner
Has a maximum value at 20,000 in the molecular weight distribution, and Tg is 63 ° C.
Met.

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. 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. No deterioration of the toner occurred in the running test of 30,000 sheets. As for the storage stability, no blocking or the like was observed, and there was no problem at all.

Example 3 900 g of xylene was placed in a 3 L separable flask, the gas phase was replaced with nitrogen gas, and the system was heated to the boiling point of xylene. In a state where xylene is refluxed, 820 g of styrene and n-butyl acrylate 12 are stirred.
0 g, methyl methacrylate 40 g, 2,2 as a crosslinking agent
-Bis [4- (methacryloxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester BPE-100,
20 g of BPO4 as a polymerization initiator
While dropping the mixture in which 2 g was dissolved over 4 hours,
Solution polymerization was performed. 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 C for toner. This resin composition C for toner has a maximum value of 13,000 in the molecular weight distribution,
g was 60 ° C.

A developer was prepared and tested in the same manner as in Example 1 except that the resin composition C for toner was used instead of the resin composition A 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. No deterioration of the toner occurred in the running test of 30,000 sheets. As for the storage stability, no blocking or the like was observed, and there was no problem at all.

Comparative Example 1 Instead of ethylene glycol dimethacrylate (Kyoeisha Yushi Kagaku Kogyo Co., Ltd., light ester EG, carbon number 12), ethylene glycol diacrylate (Kyoeisha Yushi Kagaku Kogyo Co., Ltd., EG-A, carbon number 8) A developer was prepared and tested in the same manner as in Example 1 except that No. was used. As a result, no offset was generated and the glossiness was as good as 50 or more. Further, using this developer, a temperature of 30
When a running test was performed on 10,000 sheets in a room with a humidity of 50% and a humidity of 50%, the image was slightly disturbed, and the toner was slightly deteriorated. Further, in the running of 30,000 sheets, toner deterioration was observed. As for the storage stability, no blocking or the like was observed, and there was no problem at all.

Comparative Example 2 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, it was found that the gloss was the same as that of the resin composition A for toner. Although it was as good as 50 or more, offset occurred. 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 toner was deteriorated. As for the storage stability, no blocking or the like was observed, and there was no problem at all.

Comparative Example 3 The same operation as in Example 1 was carried out except that the amount of the crosslinking agent was changed to 110 g. As a result, the entire resin gelled, and the resin could not be produced.

Comparative Example 4 The weight of AIBN was 80 g, and the peak of the molecular weight distribution was 3000.
A developer was prepared and tested in the same manner as in Example 1 except that the value was less than 1. As a result, offset occurred, and the glossiness was offset. When a running test was performed on 10,000 sheets in a room at a temperature of 30 ° C. and a humidity of 50% using this developer, the image was disturbed and the toner was deteriorated. The storage stability was also very poor.

Comparative Example 5 A polymer having the same composition as the resin of Example 2 and having a molecular weight peak of 500,000 (65% by weight of a component having a molecular weight of 100,000 or less) was prepared, and 450 g of the polymer was melt-blended. A developer was prepared and tested in the same manner as in Example 2. As a result, no offset occurred, but the glossiness of all colors was 30 or less. However, when a running test was performed on 10,000 sheets in a room at a temperature of 30 ° C. and a humidity of 50% using this developer, there was almost no deterioration of the toner, and there was no problem at all. Examples 1 to 3 and Comparative Example 1
Table 1 summarizes the results of Nos. To 5.

[0083]

[Table 1]

Example 4 A 3-L separable flask was charged with 900 g of toluene and
Polyethylene wax (manufactured by China Essential Oil Co., Ltd.)
Noparets MP-85, softening point 89 ° C, DSC peak 8
4.8 ° C, weight average molecular weight 608, dispersity 1.04) 3
After adding 0 g and stirring, and replacing the gas phase with nitrogen gas,
The system was warmed to the boiling point of toluene. 800 g of styrene, 140 g of n-butyl acrylate and polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.
30 g of K ester A-200, 14 carbon atoms and azobisisobutyronitrile (AIBN) 3 as a polymerization initiator
While dropping the mixture in which 0 g was dissolved over 4 hours,
Solution polymerization was performed. 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 D for toner. The resin composition D for a toner had a maximum plant at a molecular weight distribution of 15,000 and a Tg of 58 ° C.

Carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation) was added to 100 parts by weight of the resin composition D for toner.
6 parts by weight, wax (Viscol 6 manufactured by Sanyo Chemical Industries, Ltd.)
60P) 1 part by weight and 3 parts by weight of a charge control agent (manufactured by Hodogaya Chemical Co., Ltd., TP-302) are melt-blended by a continuous kneader (manufactured by Kurimoto Steel Works), cooled, and then cooled, and a coffee mill (Matsushita Electric Industrial Co., Ltd.) Manufactured by CARIOCA
-MILL), and further finely pulverized by a jet mill (manufactured by Nippon Pneumatic Industries, Ltd., Lab Jet), and a classifier (MDS-2, manufactured by Nippon Pneumatic Industries, Ltd.) is used to obtain a 50% average particle size of about 9 microns. To prepare toner powder. 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.
A toner was obtained.

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 94 having an average particle size of 0 microns
The developer was mixed with parts by weight to prepare a developer, and a copy was obtained using the developer. The electrophotographic copying machine used was a modification of Acolor 686 manufactured by Fuji Xerox Co., Ltd.

Evaluation Method For the offset and the fixing surface smoothness (gloss), the offset and the fixing surface smoothness (gloss) at the set temperature of the heating roller of the electrophotographic copying machine were set at 190 ° C.も の indicates that no offset occurred, △ indicates that an offset occurred slightly, and X indicates that an offset occurred.
The fixing surface smoothness (gloss) was measured using a gloss meter (Gardner Co., USA, gloss guard, incident angle 60 degrees), and a gloss of 5
0 or more was evaluated as good (良好), gloss 45 to 50 was slightly poor (５０), and gloss less than 45 was evaluated as poor (x).

The resin strength and filming on the photoreceptor were tested by running 10,000 sheets in a room at a temperature of 30 ° C. and a humidity of 50%, and the deterioration of toner and the degree of adhesion to the photoreceptor at that time were examined. The resin strength was evaluated as ○ when toner deterioration did not occur, and as X when toner deterioration occurred. Filming was evaluated as ○ when it did not occur, and as X when it occurred. 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 D for toner, no offset occurred, 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, the image was clear and toner deterioration hardly occurred. No filming on the photoreceptor was observed. Halftones could be reproduced beautifully.

Example 5 In a 3 L separable flask, 900 g of xylene and
Polyethylene wax (manufactured by China Essential Oil Co., Ltd.)
Noparets MP-70, softening point 75 ° C, DSC peak 7
0.7 ° C, weight average molecular weight 428, dispersity 1.2) 50
g was stirred and the gas phase was replaced with nitrogen gas, and then the system was heated to the boiling point of xylene. 800 g of styrene, 130 g of n-butyl acrylate and 50 g of methyl methacrylate were stirred with xylene refluxing.
g, a solution obtained by dissolving 20 g of polyethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester 14G, carbon number 36) as a crosslinking agent and 24 g of AIBN as a polymerization initiator was dropped over 3 hours, and solution polymerization was carried out. Was. 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 180 ° C., xylene was desolvated under reduced pressure to obtain a resin. This resin is cooled, crushed,
A resin composition E for toner was obtained. Resin composition E for toner
Has a maximum value at 20,000 in the molecular weight distribution, and Tg is 63 ° C.

A developer was prepared and tested in the same manner as in Example 4 except that the resin composition E for toner was used in place of the resin composition D for toner. As a result, no offset was found. Although the glossiness was slightly inferior to that of the resin composition D for toner, all the colors were good with a gloss of 50 or more. As a result of a running test using this developer, the image was clear,
Deterioration of the toner hardly occurred. No filming on the photoreceptor was observed. Halftones could be reproduced beautifully.

Comparative Example 6 As a crosslinking agent, polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-200, carbon number 1)
A developer was prepared and tested in the same manner as in Example 4 except that ethylene glycol diacrylate (manufactured by Kyoeisha Yushi Kagaku Kogyo KK, EG-A, carbon number 8) was used instead of 4). No offset has occurred,
The glossiness was somewhat inferior to 45 to 50, and the grindability was somewhat inferior. As a result of a running test using this developer, the image was clear and toner deterioration hardly occurred. No filming on the photoreceptor was observed. Halftones could be reproduced beautifully.

Comparative Example 7 A developer was prepared and tested in the same manner as in Example 4 except that no cross-linking agent was used. As a result, the gloss was 50% for all colors in the same manner as the toner resin composition D. Although the above was good, an offset occurred. As a result of a running test using this developer, no filming on the photoreceptor was observed. The halftone could be reproduced finely, but the image was disturbed and the toner was deteriorated.

Comparative Example 8 A developer was prepared and tested in the same manner as in Example 4 except that no wax was used. As a result, a slight offset was generated, and the glossiness of all the colors was 30 or less in gloss. Worsened. As a result of a running test using the developer, toner deterioration hardly occurred. No filming on the photoreceptor was observed. Halftones could be reproduced beautifully.

Comparative Example 9 Example 4 except that the amount of wax added was 200 g.
As a result of preparing a developer in the same manner as described above and performing a test, no offset was generated, and the gloss was 50% for all colors.
Above was good. As a result of a running test using this developer, toner deterioration hardly occurred, but the image was disturbed and filming on the photoconductor was severe,
The test was interrupted at 3000 sheets. Halftone could not be reproduced.

Comparative Example 10 A developer was prepared in the same manner as in Example 4, except that the wax was polypropylene wax (Hymer 330P, weight average molecular weight 15000, manufactured by Sanyo Chemical Industries, Ltd.).
As a result of the test, no offset occurred, but the glossiness was inferior to 40 or less. As a result of a running test using this developer, the image was clear and toner deterioration hardly occurred. No filming on the photoreceptor was observed. Halftones could be reproduced beautifully.

The results of Examples 4 to 5 and Comparative Examples 6 to 10 are summarized in Table 2. In the table, “−−” indicates that evaluation could not be performed.

[0098]

[Table 2]

Example 6 900 g of toluene was placed in a 3 L separable flask, the gas phase was replaced with nitrogen gas, and the system was heated to the boiling point of toluene. 780 g of styrene and 135 g of n-butyl acrylate were stirred while toluene was refluxed.
g, acrylic acid 55 g, diethylene glycol dimethacrylate as a cross-linking agent (light ester 2EG, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd., carbon number 12, straight-chain carbon number 10) 30
g and a mixture in which 42 g of BPO was dissolved as a polymerization initiator was dropped over 4 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 F for toner. In the resin composition F for toner, the molecular weight distribution had a maximum value of 12,000, and the Tg was 61 ° C.

Carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation) was added to 100 parts by weight of the obtained resin composition F for toner.
6 parts by weight, wax (Viscol 6 manufactured by Sanyo Chemical Industries, Ltd.)
60P) 4 parts by weight, charge control agent (Hodogaya Chemical Industry Co., Ltd.
3 parts by weight of TP-302) were melt-blended by a continuous kneader (manufactured by Kurimoto Iron 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
Parts by weight were 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 Regarding offset and fixing surface smoothness (gloss), the offset and fixing surface smoothness (gloss) at that time were set at 190 ° C. with the set temperature of the heating roller of the electrophotographic copying machine.
も の indicates that no offset occurred, and X indicates that an offset occurred. For the fixation surface smoothness (gloss), use a gloss meter (Gardner Co.,
(Incident angle of 60 degrees), and a gloss of 50 or more is good (○),
The gloss 45 to 50 was slightly defective (不良), and the gloss less than 45 was defective (x). Resin strength and environmental stability are temperature 3
A running test was performed on 10,000 and 30,000 sheets in a room at 0 degrees and a humidity of 50%, and the deterioration of toner and the change in image density at that time were observed.

A toner that did not deteriorate even on 30,000 sheets was evaluated as ◎, a toner that did not deteriorate on 10,000 sheets was evaluated as ○, and a toner that deteriorated on less than 10,000 sheets was evaluated as x. Regarding the environmental stability, ○ indicates that the concentration change was less than 20%, and X indicates that the change was 20% or more. Further, regarding the storage stability, 50
The degree of blocking of the resin after standing at 24 ° C. for 24 hours was checked.も の indicates that no blocking was observed, and X indicates that blocking was observed. Regarding the dispersion of the pigment and CCA, the degree of dispersion was confirmed by observing a TEM photograph.分散 indicates that the dispersion was good, △ indicates that the dispersion was fairly good, and x indicates that the dispersion was poor.

As a result of evaluating the toner using the resin composition F for toner, no offset occurred, 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. However, when 30,000 sheets of running were performed, the image was clear, but the toner was slightly deteriorated. However, the environmental stability was good. As for the storage stability, no blocking or the like was observed, and there was no problem at all. Also, the dispersion was very good.

Example 7 A 3-L separable flask was charged with 900 g of xylene, the gas phase was replaced with nitrogen gas, and the system was heated to the boiling point of xylene. 800 g of styrene and n-butyl acrylate 14 were stirred with xylene refluxing.
0 g, methyl methacrylate 30 g, methacrylic acid 10
g, polyethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-400,
Solution polymerization was carried out while dropping a mixture of 20 g of 24 carbon atoms, 24 g of linear carbon atoms) and 32 g of BPO 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 xylene boils. Thereafter, while gradually raising the temperature of the system to 200 ° C., xylene was desolvated under reduced pressure to obtain a resin. This resin was cooled and pulverized to obtain a resin composition G for toner.
In the resin composition G for toner, the molecular weight distribution had a maximum value of 20,000, and the Tg was 63 ° C.

A developer was prepared and tested in the same manner as in Example 6 except that the resin composition G for toner was used instead of the resin composition F 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. Even in the running test of 30,000 sheets, no deterioration of the toner occurred. The environmental stability was also good. As for the storage stability, no blocking or the like was observed, and there was no problem at all. Also, the dispersion was very good.

Example 8 900 g of xylene was placed in a 3 L separable flask, the gas phase was replaced with nitrogen gas, and the system was heated to the boiling point of xylene. With the xylene refluxed, 800 g of styrene and 15 g of n-butyl acrylate were stirred while stirring.
A mixture obtained by dissolving 0 g, 30 g of methacrylic acid, 20 g of EO-modified bisphenol A diacrylate (manufactured by Kyoeisha Yushi Kagaku Kogyo KK, BP-4EA, containing two aromatic rings) as a crosslinking agent and 32 g of AIBN as a polymerization initiator was taken over 4 hours. While dropping, solution polymerization was performed. After dropping,
Further, the mixture was aged for 1 hour with 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 H for toner. The resin composition H for toner had a maximum value at 14,000 in the molecular weight distribution, and Tg was 60 ° C.

A developer was prepared and tested in the same manner as in Example 6 except that the resin composition H for toner was used instead of the resin composition F 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. Even in the 30,000-sheet running test, the deterioration of the toner hardly occurred. The environmental stability was also good. As for the storage stability, no blocking or the like was observed, and there was no problem at all. Also, the dispersion was very good.

Comparative Example 11 Instead of diethylene glycol dimethacrylate (Kyoeisha Yushi Kagaku Kogyo Co., Ltd., light ester 2EG, carbon number 12, straight-chain carbon number 10), ethylene glycol diacrylate (Kyoeisha Yushi Kagaku Kogyo Co., Ltd., EG-A) A developer was prepared and tested in the same manner as in Example 6, except that C8 was used, and as a result, no offset occurred and the glossiness was as good as 50 or more. When a running test was performed on 10,000 sheets in a room at a temperature of 30 ° C. and a humidity of 50% using this developer, the image was slightly disturbed, and the toner was slightly deteriorated. In addition, toner deterioration was observed in 30,000 sheets of running. However, the environmental stability was good. As for the storage stability, no blocking or the like was observed, and there was no problem at all. Also, the dispersion was very good.

Comparative Example 12 A developer was prepared and tested in the same manner as in Example 6 except that no cross-linking agent was used. Although the gloss was good at 50 or more, an offset occurred. 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 toner was deteriorated. However, the environmental stability was good. As for the storage stability, no blocking or the like was observed, and there was no problem at all. However, some dispersion failure was observed.

Comparative Example 13 The operation was carried out in the same manner as in Example 6 except that the amount of the crosslinking agent was changed to 120 g. As a result, the entire resin gelled, and the resin could not be produced.

Comparative Example 14 The weight of AIBN was 80 g, and the peak of the molecular weight distribution was 3000.
A developer was prepared and tested in the same manner as in Example 6 except that the amount was set to less than 3. As a result, offset occurred, and the glossiness was offset. When a running test was performed on 10,000 sheets in a room at a temperature of 30 ° C. and a humidity of 50% using this developer, the image was disturbed and the toner was deteriorated. The storage stability was also very poor. However, environmental stability and dispersion were good.

Comparative Example 15 A developer (molecular weight: 100,000) was prepared in the same manner as in Example 7 except that a polymer having the same composition as in Example 7 and a molecular weight peak of 500,000 was prepared, and 450 g of the polymer was melt-blended. The following components (65% by weight) were prepared and tested. As a result, no offset was generated, but the gloss was 3% for all colors.
0 or less. However, when using this developer,
When a running test was performed on 10,000 sheets in a room at 0 ° C. and a humidity of 50%, toner deterioration hardly occurred and the image was clear. Even in the 30,000-sheet running test, no deterioration of the toner was observed, and the environmental stability was good. As for the storage stability, no blocking or the like was observed, and there was no problem at all. The dispersion was also good.

Comparative Example 16 A developer was prepared and tested in the same manner as in Example 6 except that acrylic acid was not used. As a result, the gloss was as good as 50 or more, and the offset was not generated. Did not. Using this developer, the temperature is 30 ° C. and the humidity is 50.
% Of the rooms were tested in a running test.
Deterioration of the toner hardly occurred. In the 30,000-sheet running test, the toner was slightly deteriorated. However, the environmental stability was good. As for the storage stability, no blocking or the like was observed, and there was no problem at all. However, poor dispersion was observed.

Comparative Example 17 A developer was prepared and tested in the same manner as in Example 6 except that the amount of acrylic acid was changed to 130 g. As a result, the glossiness was good with a gloss of 50 or more, and no offset occurred. Was. Using this developer, the temperature is 30 ° C. and the humidity is 50.
% Of the rooms were tested in a running test.
Deterioration of the toner hardly occurred. In the 30,000-sheet running test, the toner was slightly deteriorated. However, environmental stability had deteriorated. As for the storage stability, no blocking or the like was observed, and there was no problem at all. The dispersion was also good. Table 3 summarizes the results of Examples 6 to 8 and Comparative Examples 11 to 17.

[0116]

[Table 3]

[0117]

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. Further, the resin rigidity can be increased and the carrier and CCA can be dispersed well without impairing the gloss of the fixing surface after the fixing, and the color development is good, and the particle size can be reduced. So
It can be suitably used as a high-resolution full-color toner.

Claims (4)

[Claims] 1. A styrene monomer and a (meth) acrylate monomer having a molecular weight peak of 3 × 10 ³ or more as determined by gel permeation chromatography.
3 × 10 ⁴ , and 7 or less in the molecular weight distribution
0% by weight or more of vinyl copolymer
0.1 to 10% by weight of a crosslinking agent having 0 or more carbon atoms
A resin composition for a toner, comprising a resin which is contained and crosslinked. 2. A vinyl-based copolymer comprising a styrene-based monomer and a (meth) acrylate-based monomer, wherein a crosslinking agent having 10 or more carbon atoms in one molecule is used in an amount of 0.1 to 1%.
0.1 to 15 parts by weight of a wax having a weight average molecular weight of 300 to 10000 and a dispersity of 1.5 or less with respect to 100 parts by weight of a crosslinked resin containing 0% by weight. A resin composition for a toner, comprising: 3. A polar copolymer containing a styrene monomer, a (meth) acrylate monomer and a polar group-containing vinyl copolymerizable monomer. The vinyl copolymer having a content of a hydrophilic monomer of 0.01 to 10% by weight is crosslinked by containing 0.1 to 10% by weight of a crosslinking agent having 10 or more carbon atoms in one molecule. A resin composition for a toner, comprising: 4. A toner comprising the resin composition for toner according to claim 1, 2 or 3.