JPH1124309A - 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 vinyl copolymer consisting of styrene monomers, (meth)acrylate monomers and vinyl copolymerizable monomers containing polar groups. The copolymn. degree of the vinyl copolymerizable monomers having polar groups is 0.01 to 10 wt.%. The vinyl copolymer has the mol.wt. peak ranging from 3×10<3> to 3×10<4> by gel permeation chromatography and contains >=70 wt.% of a component having <=10×10<4> mol.wt. in the mol.wt. distribution.

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 powder, glass beads or the like called a carrier, and the toner adheres to an electrostatic latent image on a photoreceptor by electric attraction. The image is transferred onto a sheet 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. Discloses a technique for improving the releasability from a heating roller. However, since 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 the dispersion of the colorant becomes worse.

JP-A-57-178251 and JP-A-6-175395 disclose methods of increasing the resin strength by metal cross-linking and preventing the offset phenomenon. And storage temperature,
Since the degree of metal cross-linking changes depending on conditions such as the storage period, there is a problem that it is difficult to manufacture a product having a constant quality and is easily affected by seasonal fluctuations.

JP-A-56-158340 discloses that at least one selected from the group consisting of a styrene polymer, an acrylic polymer and a styrene-acryl polymer, comprising a low molecular weight polymer and a high molecular weight polymer. A technique for preventing the offset phenomenon by using one kind of resin made of a resin having a specified glass transition temperature range has been disclosed. However, when the amount of the high molecular weight polymer is increased, there is a problem that the fixing property is reduced. there were. 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, a conventional resin cross-linked resin or high molecular weight polymer is used. As a result, 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.

Further, when the particle size is reduced, if the crosslinked portion in the resin is large or the dispersion of the added wax is poor, toner particles of only the crosslinked portion or the wax are formed, and the quality is deteriorated. There are problems.

[0014]

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

[0015]

The present invention comprises a styrene monomer, a (meth) acrylate monomer, and a vinyl copolymerizable monomer containing a polar group. A resin composition for a toner comprising a vinyl copolymer having a copolymerization ratio of a vinyl copolymerizable monomer having a group of 0.01 to 10% by weight, wherein the vinyl copolymer is The resin composition for toner has a molecular weight peak of 3 × 10 ^{3 to} 3 × 10 ^{4 as} determined by gel permeation chromatography, and a portion of 100,000 or less in the molecular weight distribution is 70% by weight or more. Hereinafter, the present invention will be described in detail.

The resin composition for a toner according to the present invention comprises a vinyl copolymer. The vinyl copolymer is obtained by copolymerizing a styrene monomer, a (meth) acrylate ester monomer, and a vinyl copolymerizable monomer having a polar group as constituent components. .

The styrene monomer is not particularly restricted but includes, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethyl styrene,
pn-butylstyrene, pt-butylstyrene, p
-N-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. Of these, ethyl acrylate, propyl acrylate, acryl n-butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate and the like are preferred.

The above-mentioned polar group-containing vinyl copolymerizable monomer is added in order to favorably disperse additives such as CCA when the resin composition for toner of the present invention is formed into a toner. . The copolymerization ratio of the polar group-containing vinyl copolymerizable monomer is 0.01 to 10 in the vinyl copolymer.
% By weight. When the content is less than 0.01% by weight, the above CC
If the dispersing effect of the additive such as A is reduced, and if the content exceeds 10% by weight, charging failure may occur, so the content is limited to the above range. Preferably, it is 0.1 to 5% by weight.

Examples of the polar group include halogens, hydroxyl groups, amino groups, nitro groups, carboxyl groups, formyl groups, alkoxyl groups, nitrile groups, and ester groups excluding those of (meth) acrylate. Can be Among them, a carboxyl group is preferable in terms of odor and polarity.

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 above-mentioned vinyl copolymer has a molecular weight peak of 3 × 10 ^{3 to} 3 × 10 ⁴ 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, 4 × 10 ³
８8 × 10 ³ .

In the above-mentioned vinyl copolymer, a portion having a molecular weight of 100,000 or less is 70% by weight or more in a molecular weight distribution measured by GPC. When the content is less than 70% by weight, the fixing surface smoothness (gloss) after fixing deteriorates, and it becomes difficult to use the toner as a full-color toner. Preferably, it is at least 80% by weight. In the molecular weight distribution of the vinyl copolymer measured by GPC,
There may be multiple peaks and shoulders.

The weight average molecular weight (Mw) of the vinyl copolymer is preferably 15 × 10 ⁴ or less. 15x
When more than 10 ^4, there is a risk the surface smoothness is not sufficient. More preferably, it is 10 × 10 ⁴ or less.

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.

The vinyl copolymer may be obtained by copolymerizing 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.

In the synthesis of the vinyl copolymer, for example,
A suspension polymerization method, an emulsion polymerization method, a solution polymerization method, a bulk polymerization method and the like can be used. Among them, a solution polymerization method is preferably used.

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, but more homogeneously. For dispersion, 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 toner resin composition of the present invention has a weight average molecular weight of 10 per 100 parts by weight of the vinyl copolymer.
0.1 to 15 parts by weight of a wax of 0 to 10000 can be contained.

If the weight average molecular weight of the wax is less than 100, there is a problem in storage stability. If the weight average molecular weight exceeds 10,000, the gloss of the fixing surface cannot be maintained, so that the above range is limited. Preferably, it is 200-6000. More preferably, it is 300 to 1,000. If the amount of the wax is less than 0.1 part by weight, it is difficult to maintain the gloss of the fixing surface, and an offset phenomenon is likely to occur. If the amount exceeds 15 parts by weight, filming and transparency to the photoreceptor are caused. This is not preferable because adverse effects such as deterioration of the image may occur. More preferably, it is 0.2 to 10 parts by weight.

The above-mentioned wax is used mainly as a gloss auxiliary for giving gloss, and preferably has a softening point of 60 to 150 ° C. If the temperature is lower than 60 ° C, blocking may occur during storage at room temperature.
It becomes difficult to melt at the time of fixing, and the surface smoothness at the time of fixing, that is, gloss may be impaired. More preferably,
65-120 ° 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. Preferred are paraffin wax, polyethylene wax, polypropylene wax and the like, which are easy to carry out.

In the resin composition for a toner of the present invention,
As long as the object of the present invention can be achieved, a polymer such as vinyl acetate, vinyl chloride, or ethylene may be blended with the vinyl copolymer. The resin composition for a toner of the present invention includes a polyester resin, an epoxy resin, an aliphatic amide,
Bis aliphatic amides, metal soaps and the like may be mixed. Dyes such as nigrosine and spiron black (manufactured by Hodogaya Chemical Co., Ltd.); and other phthalocyanine pigments may be added to the resin composition for a toner of the present invention as a charge control agent.

In the resin composition for toner of the present invention, carbon black, chrome yellow, aniline blue or the like can be used as a colorant. To the resin composition for a toner of the present invention, 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 enhance fluidity. Further, a magnetic powder may be mixed with the resin composition for a toner of the present invention to be used as a magnetic toner.

The resin composition for toner may be synthesized, for example, by synthesizing the vinyl copolymer and then adding a wax thereto, or dispersing the wax and dispersing the vinyl copolymer. May be copolymerized. 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 a toner of the present invention can be suitably used for a toner such as a full-color toner. Such a toner is also one of the present invention.

The toner of the present invention contains a coloring agent, 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 has a molecular weight peak by GPC of 3 × 10 ^{3 to} 3 × 10 ⁴ , and a portion having a molecular weight distribution of 100,000 or less has a vinyl copolymer content of 70% by weight or more. , The fixing property is good, and the surface smoothness (gloss) after fixing can be improved. Further, the resin composition for a toner of the present invention is obtained by copolymerizing a vinyl-based copolymerizable monomer having a polar group with the vinyl-based copolymer in an amount of 0.01 to 10% by weight.
It becomes possible to improve the dispersibility of additives such as A.
Further, a wax having a weight average molecular weight of 100 to 10000 is added in an amount of 0.1 to 100 parts by weight of the vinyl copolymer.
By adding 15 to 15 parts by weight, the glossiness of the fixed surface after fixing, which is important as a high-resolution full-color toner, can be improved.

[0039]

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, the gas phase was replaced with nitrogen gas, and the system was heated to the boiling point of toluene. 780 g of styrene and 180 g of n-butyl acrylate were stirred while toluene was refluxed.
g, 40 g of methacrylic acid and a mixture in which 50 g of benzoyl peroxide (BPO) as a polymerization initiator were dissolved were dropped over 5 hours to perform solution polymerization. After completion of the dropwise addition, the mixture was aged for 2 hours 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. In the resin composition A for toner, the molecular weight distribution had a maximum value of 11,000, and the Tg was 60 ° C. The portion having a molecular weight distribution of 100,000 or less was 95% or more.

To 100 parts by weight of the resin composition A for toner, 6 parts by weight of carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation) and wax (Viscol 550, manufactured by Sanyo Chemical Industries, Ltd.)
P) 4 parts by weight, a charge control agent (manufactured by Orient Chemical Industries,
3 parts by weight of Bontron S-44) 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)
-MILL), further finely pulverized by a jet mill (manufactured by Nippon Pneumatic Industries, Ltd., Labjet), and a 50% average of about 9 microns by a classifier (MDS-2, manufactured by Nippon Pneumatics). A toner powder having a particle size was prepared.

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.

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 microns, and a copy was obtained using the developer. The electrophotographic copying machine used was a modified version of Acolor 636 manufactured by Fuji Xerox Co., Ltd.

Evaluation Method Regarding the fixability and the surface smoothness (gloss) of the fixed surface, the set temperature of the heating roller of the electrophotographic copying machine was set at 180 ° C., and the fixability and the surface smoothness (gloss) of the fixed surface at that time. I saw
The fixability was evaluated by observing the degree of density reduction when the fixing surface was rubbed with an eraser.
% Or more and less than 30% was defined as (△). The surface smoothness (gloss) of the fixing surface was determined by using a gloss meter (Gardner Co., USA, gloss guard, incident angle: 60 degrees), and a gloss of 50 or more was good (○), and a gloss of 45 to 50 was slightly poor (△). , Gross 4
Less than 5 was regarded as defective (x).

Regarding environmental stability, 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. The case where the image was clear was evaluated as ○, and the case where the image deteriorated was evaluated as ×. Regarding storage stability, 50 ° C, 24
The degree of blocking of the resin after standing for a time was checked.も の indicates that no blocking was observed, and X indicates that blocking was observed. Regarding dispersibility, pigments and CCA
And the like, the degree of dispersion was confirmed by observing a TEM photograph.も の indicates that the dispersibility was good, △ indicates that the dispersibility was slightly degraded, and X indicates that the dispersibility was degraded.

As a result of evaluating the toner using the resin composition A for toner, the fixability was good and the glossiness was 50% for all colors.
Above was good. Using this developer, a running test of 10,000 sheets was performed in a room at a temperature of 30 ° C. and a humidity of 50%, and the image was clear. As for the storage stability, no blocking or the like was observed, and there was no problem at all. The dispersibility was also very good.

Example 2 900 g of xylene was placed in a 3 L separable flask, 50 g of a high molecular weight substance having a molecular weight peak of 500,000 containing 75% of styrene and 25% of n-butyl acrylate was placed, and the gas phase was replaced with nitrogen gas. Thereafter, the system was warmed to the boiling point of xylene. In a state where xylene is refluxed, 700 g of styrene, 120 g of n-butyl acrylate, 100 g of methyl methacrylate, 80 g of acrylic acid, and azobisisobutyronitrile (AIBN) 3 as a polymerization initiator are stirred while stirring.
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 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 B for toner. This resin composition B for toner has a maximum value of 14,000 in the molecular weight distribution,
g was 60 ° C. The portion having a molecular weight distribution of 100,000 or less was 90% or more.

A developer was prepared and evaluated in the same manner as in Example 1 except that the resin composition B for toner was used instead of the resin composition A for toner. As a result, the fixing property was good. The gloss was good for all colors with a gloss of 50 or more. 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. As for the storage stability, no blocking or the like was observed, and there was no problem at all. The dispersibility was also very good.

Comparative Example 1 A developer was prepared in the same manner as in Example 2, except that the amount of AIBN was 82 g and the molecular weight peak was 2500.
As a result of the test, the fixing property was good and the glossiness was 5
It was as good as 0 or more. 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. As for the storage stability, blocking and the like were considerably observed. However, the dispersibility was good.

Comparative Example 2 A developer was prepared and tested in the same manner as in Example 1 except that the amount of BPO was changed to 15 g and the molecular weight peak was set to 40,000. As a result, the fixing property was deteriorated. However, the glossiness is 5
It was as good as 0 or more. 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, images were good. As for the storage stability, no blocking or the like was observed, and there was no problem at all. The dispersibility was also good.

Comparative Example 3 A developer was prepared and tested in the same manner as in Example 2 except that the amount of the high molecular weight material was changed to 500 g. As a result, the fixing property was slightly deteriorated. Further, the glossiness also deteriorated to 30 or less. However, using this developer, the temperature is 30 ° C. and the humidity is 50.
% Of the rooms were tested in a running test.
The image was good. As for the storage stability, no blocking or the like was observed, and there was no problem at all. The dispersibility was also good.

Comparative Example 4 A developer was prepared and tested in the same manner as in Example 1 except that methacrylic acid was not used. As a result, the fixability was good and the glossiness was 50 or more. It was good. Using this developer, the temperature is 30 ° C. and the humidity is 50%.
When a running test of 10,000 sheets was performed in the room, the image was good. As for the storage stability, no blocking or the like was observed, and there was no problem at all. However, the dispersibility slightly deteriorated.

Comparative Example 5 A developer was prepared and tested in the same manner as in Example 2 except that 200 g of acrylic acid was used. As a result, the fixability was good and the glossiness was good at 50 or more. Met. However, using this developer, the temperature is 30 ° C. and the humidity is 50.
% Of the rooms were tested in a running test.
The image was very bad. As for the storage stability, no blocking or the like was observed, and there was no problem at all. Also,
Dispersibility was good. Examples 1-2 and Comparative Examples 1-5
Table 1 summarizes the results.

[0054]

[Table 1]

Example 3 In a 3 L separable flask, 900 g of toluene and 28 g of polyethylene wax (Thermolets SF4690, manufactured by Chugoku Seiyaku Co., Ltd., weight average molecular weight 710) were used as the wax.
After stirring, and replacing the gas phase with nitrogen gas, the system was heated to the boiling point of toluene. In a state where the reflux of toluene occurred, solution polymerization was performed while stirring and dropping a mixture in which 760 g of styrene, 180 g of n-butyl acrylate, 60 g of acrylic acid, and 45 g of AIBN as a polymerization initiator were dropped over 4 hours with stirring. Was. After dropping,
Further, the mixture was aged for 2 hours while stirring at the boiling temperature of toluene. 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. The resin composition C for toner has a molecular weight distribution of 7 × 10 ³
Has a maximum plant, Tg is 58 ° C., and Mw is 1.4 × 10 ⁴
Met. The portion having a molecular weight distribution of 100,000 or less was 95% or more.

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, 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 Orient Chemical Co., Ltd., Bontron S-44) are melt-blended by a continuous kneader (manufactured by Kurimoto Iron and Steel Works), cooled, and then cooled to a small crusher (Shibata). Made by Scientific Instruments, S
CM-40), and further finely pulverized by a jet mill (manufactured by Nippon Pneumatic Industries Co., Ltd., Labjet), and then classified by a classifier (Nippon Pneumatic Industries Co., Ltd., MDS-2) to about 9.3 μm. A toner powder having a 50% average particle size was prepared. Silica (Nippon Aerosil Co., Ltd.,
Aerosil R972D) was added in an amount of 0.5 part by weight and 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.

Evaluation Method The offset and the surface smoothness (gloss) of the fixing surface were determined by examining the offset and the surface smoothness (gloss) of the fixing surface when the set temperature of the heating roller of the electrophotographic copying machine was 190 ° C. Was.も の indicates that no offset occurred, △ indicates that an offset occurred slightly, and X indicates that an offset occurred. The surface smoothness (gloss) of the fixing surface is measured with a gloss meter (Gardner, USA, gloss guard, incident angle 60 °).
, 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).

Regarding filming on the photoreceptor and environmental stability, a running test of 10,000 sheets was performed in a room at a temperature of 30 ° C. and a humidity of 50%, and adhesion to the photoreceptor and a change in image density were observed. The environmental stability is good when there is no adhesion to the photoreceptor and when the change in image density is less than 10%.
% Or more was evaluated as x. Regarding filming, those that did not occur were evaluated as ○, those that slightly occurred were evaluated as Δ, and those that occurred occurred were evaluated as ×. Transparency was evaluated by visually evaluating the hue of the halftone portion after fixing, and those that could reproduce the halftone were evaluated as ○,
Those that could not be reproduced were marked as x. For dispersibility,
The degree of dispersion was confirmed by observing a TEM photograph of the pigment and CCA.も の indicates that the dispersibility was good, △ indicates that the dispersibility was slightly degraded, and X indicates that the dispersibility was degraded.

As a result of evaluating the toner using the resin composition C for toner, no offset occurred, and the glossiness of all the colors was good, that is, the gloss was 50 or more. Using this developer, a running test of 10,000 sheets was conducted in a room at a temperature of 30 ° C. and a humidity of 50%. As a result, no filming on the photoreceptor was observed and the environment stability was good. Regarding transparency, halftones could be reproduced clearly. The dispersibility was also very good.

Example 4 A 3-L separable flask was charged with 900 g of xylene, 40 g of a high molecular weight substance having 80% styrene and 20% n-butyl acrylate and having a molecular weight peak of 300,000, and polyethylene wax as a wax (Noparets, manufactured by China Essential Oil Co., Ltd.). MP-8
0, and 50 g of a weight average molecular weight 542) was added thereto, followed by stirring. After the gas phase was replaced with nitrogen gas, the system was heated to the boiling point of xylene. With the xylene refluxed, 650 g of styrene and n-butyl acrylate 2 were stirred while stirring.
00 g, methyl methacrylate 100 g, methacrylic acid 5
Solution polymerization was performed while dropping 0 g and a mixture in which 50 g of BPO was dissolved as a polymerization initiator over 3.5 hours. After completion of the dropwise addition, the mixture was further aged for 1 hour while stirring at a temperature at which xylene boils. Thereafter, the temperature of the system is set to 20
While gradually raising the temperature to 0 ° C., the solvent was removed from xylene 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 toner had a maximum value at 9 × 10 ³ in the molecular weight distribution, and Tg was 58 ° C. The portion having a molecular weight distribution of 100,000 or less was 90% or more.

A developer was prepared and evaluated in the same manner as in Example 3 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. Using this developer, a running test of 10,000 sheets was performed in a room at a temperature of 30 ° C. and a humidity of 50%. As a result, no filming on the photoreceptor was observed and the environment stability was good. Regarding transparency, halftones could be reproduced clearly. The dispersibility was also good.

Comparative Example 6 A developer was prepared and tested in the same manner as in Example 3 except that acrylic acid was not used. As a result, no offset was generated, and the gloss was determined to be glossy for all colors. It was as good as 50 or more. Using this developer, a running test of 10,000 sheets was performed in a room at a temperature of 30 ° C. and a humidity of 50%. As a result, no filming on the photoreceptor was observed and the environment stability was good. Regarding transparency, halftones could be reproduced clearly. However, the dispersibility was slightly inferior.

Comparative Example 7 A developer was prepared and tested in the same manner as in Example 4 except that the amount of methacrylic acid was changed to 140 g. As a result, no offset was generated and the gloss was 50% for all colors. Above was good. Using this developer, a running test of 10,000 sheets was performed in a room at a temperature of 30 ° C. and a humidity of 50%. No filming on the photoreceptor was observed, but the environmental stability was very poor. . However, regarding the transparency, the halftone was reproduced clearly and the dispersibility was good.

Comparative Example 8 A developer was prepared and tested in the same manner as in Example 4 except that the amount of the high molecular weight material was changed to 500 g. As a result, no offset occurred, but the glossiness was all. The color deteriorated to a gloss of 40 or less. However, 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, no filming on the photoconductor was observed.
Environmental stability was also good. Regarding transparency,
The halftone was reproduced clearly and the dispersibility was good.

Comparative Example 9 Polyethylene wax (manufactured by China Essential Oil Co., Ltd., Thermolets)
SF4690), the molecular weight peak was 1.5 × 10
^A developer was prepared and tested in the same manner as in Example 3 except that the polypropylene wax of No. ⁴ (Hymer 330P, manufactured by Sanyo Chemical Industry Co., Ltd.) was used. As a result, a slight offset was found. Was good with all colors having a gloss of 50 or more. However, when using this developer,
When a running test was performed on 10,000 sheets in a room at 0 ° C. and 50% humidity, no filming was observed on the photoreceptor, and environmental stability was good. As for transparency, halftone was reproduced clearly and dispersibility was good.

Comparative Example 10 Polyethylene wax (manufactured by Chugoku Essential Oil Co., Ltd., Nopalets MP)
A developer was prepared and tested in the same manner as in Example 4 except that the weight-average molecular weight 542) was -210 g, and no offset occurred. Above was good. However, when a running test of 10,000 sheets was conducted in a room at a temperature of 30 ° C. and a humidity of 50% using this developer, filming on the photoreceptor was slightly observed. Although the environmental stability was good, regarding the transparency, halftone could not be reproduced clearly. However, the dispersibility was good.

Table 2 summarizes the results of Examples 3-4 and Comparative Examples 6-10.

[0069]

[Table 2]

[0070]

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. In addition, the dispersibility of additives such as CCA can be improved without impairing the gloss of the fixing surface after fixing, and the coloring property is good, so that it can be suitably used as a high-resolution full-color toner. .

Claims (5)

[Claims] 1. A polar copolymer containing a styrene monomer, a (meth) acrylate monomer, and a polar group-containing vinyl copolymerizable monomer. A resin composition for a toner comprising a vinyl copolymer having a copolymerization ratio of a hydrophilic monomer of 0.01 to 10% by weight, wherein the vinyl copolymer has a molecular weight peak determined by gel permeation chromatography. Is 3 × 10 ^{3 to} 3
× 10 ⁴ , and 70,000 or less in the molecular weight distribution.
% By weight or more. 2. A toner according to claim 1, wherein 0.1 to 15 parts by weight of a wax having a weight average molecular weight of 100 to 10,000 is added to 100 parts by weight of the vinyl copolymer. Resin composition. 3. The vinyl copolymer has a molecular weight distribution of 10%.
The resin composition for a toner according to claim 1, wherein the content of 10,000 or less is 80% by weight or more. 4. The polar group of the vinyl copolymerizable monomer containing a polar group is a carboxyl group, and a wax having a weight average molecular weight of 200 to 6000 is added to 100 parts by weight of the vinyl copolymer. 4. The resin composition for toner according to claim 1, wherein 0.2 to 10 parts by weight is added. 5. A toner, wherein the resin composition for toner according to claim 1, 2, 3, or 4 is used.