JPH03288160A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To allow fixing at a low temp. and to make improvement in offset resistance by incorporating a binder resin, metal compd. and coloring agent into the toner, consisting the binder resin of a specific vinyl copolymer and polyester resin and using a metal complex for a metal compd. CONSTITUTION:This toner contains the binder resin, the metal compd. and a coloring agent. The binder resin is synthesized from a vinyl copolymer consisting of a copolymer of at least a monomer having a carboxylic acid group and other copolymerizable monomer and the polyester resin consisting of the polycondenrate of a polybasic acid component and polyhydric alcohol component. This resin contains 5 to 50 wt.% THF insoluble component and has at least one peak in the region of 2000 to 20000 mol. wt. in the mol. wt. distribution of the THF soluble component. A metal complex is used as the metal compd. The THF insoluble component refers to the weight ratio of the polymer component which is made insoluble with the THF in the resin compsn. The fixing at the low temp. is executed in this way and the improvement in the offset resistance is made.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a toner for developing electrostatic images used in electrophotography, electrostatic printing, and magnetic recording, and in particular, a toner suitable for hot roll fixing. Regarding.

[Prior Art] Conventionally, as an electrophotographic method, U.S. Patent No. 2,297°69
Although many methods are known, such as those described in Japanese Patent Publication No. 1, Japanese Patent Publication No. 42-23910, Japanese Patent Publication No. 43-24748, etc., in general, photoconductive substances are used and various means are used. An electrical latent image is formed on the photoreceptor using a method, and then the latent image is developed using toner, and if necessary, the toner image is transferred to a transfer material such as paper. It is fixed and a copy is obtained.

Various methods and apparatuses have been developed for the above-mentioned final step of fixing the toner image on a sheet such as paper, but the most common method at present is a compression heating method using a heated roller.

In the press-heating method using a heated roller, fixing is carried out by passing the toner image surface of the fixing sheet while contacting it under pressure with the surface of a heated roller, which has a surface that has releasability for the toner. In this method, the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, so the thermal efficiency when fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. I can do it,
Very effective in high-speed electrophotographic copying machines. However, in the above method, since the surface of the heat roller and the toner image contact each other under pressure in a molten state, a part of the toner image adheres to and transfers to the surface of the fixing roller, and this is transferred again to the next sheet to be fixed, resulting in so-called This may cause an offset phenomenon and stain the fixing sheet. Preventing toner from adhering to the surface of the heat fixing roller is considered to be one of the essential conditions for the heat roller fixed fixing method.

Conventionally, in order to prevent toner from adhering to the fixing roller surface, for example, the roller surface was made of a material with excellent release properties for toner, such as silicone rubber or fluorine-based resin, and the surface was further coated with offset prevention and roller surface coatings. In order to prevent fatigue, the surface of the roller is coated with a thin film of a liquid with good mold releasability, such as silicone oil.

However, although this method is extremely effective in preventing toner offset, it requires a device to supply the offset prevention liquid, resulting in problems such as the complexity of the fixing device. .

Therefore, it is not desirable to prevent offset by supplying an offset-preventing liquid, and rather the development of a toner with high offset resistance over a wide fixing temperature range is currently desired. Therefore, in order to increase the releasability of the toner, a method of adding wax such as low molecular weight polyethylene or polypropylene that melts sufficiently when heated has been used, but while it is effective in preventing offset, it reduces the cohesiveness of the toner. As a result, the charging characteristics become unstable, which tends to lead to a decrease in durability. Therefore, as other methods, various attempts have been made to improve the binder resin.

For example, the glass transition temperature (
It is also known to improve the melt viscoelasticity of toner by increasing its Tg) and molecular weight. However, in such a method, when the offset phenomenon is improved, the fixing performance becomes insufficient, and a problem arises in that the fixing performance at low temperatures required for high-speed development and energy saving, that is, the low-temperature fixing performance is poor.

Generally, in order to improve the low-temperature fixing properties of toner, it is necessary to reduce the viscosity of the toner during melting and increase the adhesion area with the fixing substrate, and for this purpose, the Tg and molecular weight of the binder resin used should be lowered. This is required.

That is, since low-temperature fixing properties and anti-offset properties have contradictory aspects, it is extremely difficult to develop a toner that satisfies both of these functions.

In order to solve this problem, for example,
Japanese Patent Publication No. 354 discloses a toner made of a vinyl polymer that is moderately crosslinked with the addition of a crosslinking agent and a molecular weight regulator, and Japanese Patent Publication No. 55-6805 discloses a toner containing an α,β unsaturated ethylenic monomer. A toner with a wide molecular weight distribution such that the ratio of the weight average molecular weight to the number average molecular weight as a constitutional unit is 3.5 to 4.0, and furthermore, in the vinyl polymer, T81
Blend toners that combine molecular weight, gel content, etc. have been proposed.

It is true that toners based on these proposals have a lower fixation limit temperature (
Although the possible fixing temperature range between the lowest fixing temperature) and the offset temperature (the temperature at which offset begins to occur) is widened, if sufficient offset prevention performance is provided, it is possible to lower the fixing temperature sufficiently. On the contrary, if emphasis is placed on low-temperature fixability, there is a problem in that offset prevention performance becomes insufficient.

In addition, instead of these vinyl resins, toners made by crosslinking polyester resins, which are said to be essentially superior to vinyl resins in terms of low-temperature fixing properties, and further adding an anti-offset agent are also available. This is proposed in the publication No.-208559. This product has excellent low-temperature fixing properties and anti-offset properties, but its productivity as a toner (
There is a problem in terms of crushability).

In order to improve this problem, it was proposed in Japanese Patent Application Laid-Open No. 6-117 to polymerize polyester in the presence of a low molecular weight polymer containing an acid component.
This is proposed in Japanese Patent No. 1-210367. However, in this case, although the crushability is improved, there is a problem in that blocking resistance and offset resistance deteriorate.

Furthermore, in JP-A-56-116043, a vinyl monomer is polymerized in the presence of a reactive polyester resin, and a resin is polymerized through a crosslinking reaction, an addition reaction, and a grafting reaction during the polymerization process. A toner using this method has been proposed, and although it has been improved in terms of crushability, it is not possible to fully utilize the functions of each resin in terms of low-temperature fixing properties and offset prevention properties.

In addition, a toner using a resin simply blended with a polyester resin and two types of vinyl resins with different gel contents (gelation degree of 80% or more and gelation degree of less than 10%) was proposed in Japanese Patent Publication No. 1-15063. Although this product has good low-temperature fixing properties, it is still unsatisfactory in terms of anti-offset properties and crushability. Even if the ratio of vinyl resin having a gelation degree of 80% or more is increased for the purpose of improving offset resistance, offset prevention will improve, but low-temperature fixability will be significantly reduced. Furthermore, sufficient crushability cannot be achieved simply by containing a vinyl resin with a degree of gelation of less than 10%.

On the other hand, in order to meet the physical properties required for toners as described above, crosslinking is performed by reacting a polymer having a carboxylic acid with a metal compound in a binder resin (Japanese Patent Application Laid-Open No. 178249/1989). 57-178250), or a binder whose essential constituent units are a vinyl resin monomer and a more specific monoester compound is reacted with a polyvalent metal compound, and crosslinked via the metal (JP-A No. 57-178250). 1981-110155, 81-110156).

Furthermore, JP-A No. 3-214760 and JP-A No. 63-21
No. 7362, No. 63-217383, No. 83-217
No. 364 discloses that the molecular weight distribution is divided into two groups, low molecular weight and high molecular weight, and the polyvalent metal ion is reacted with the carboxylic acid group contained on the low molecular weight side to cause crosslinking (
It has been disclosed that a dispersion of a metal compound is added to a solution obtained by solution polymerization, and the mixture is heated to cause a reaction. However, in either method, the reaction between the binder and the metal compound or the introduction of the metal compound into the binder is not possible. The metal compound is not sufficiently dispersed, and the physical properties required of the toner, particularly fixing properties and anti-offset properties, are not satisfied. Furthermore, since it is necessary to blend a large amount of the metal compound with the binder resin, the blended metal compound may exhibit a catalytic effect on the binder resin depending on the conditions, making it easier for the binder and resin to gel, resulting in the metal compound being mixed with the binder resin. It is difficult to determine manufacturing conditions for blending to obtain a desired toner, and even if manufacturing conditions can be determined, there are problems such as difficulty in achieving reproducibility.

Furthermore, even if the binder resin contains a carboxylic acid group that reacts with a metal compound, if the carboxylic acid group is anhydrous, that is, in a ring-closed state, the crosslinking reactivity with the metal compound is weak, resulting in crosslinking. strength is not sufficient, and offset resistance and fixing properties cannot be satisfied.

Further, JP-A No. 63-216063 discloses a combination of ionic crosslinking of a binder resin with a metal and an offset inhibitor, or JP-A No. 62-28075
Publication No. 7 proposes that the binder be provided with a polar functional group formed by a reaction between an acid anhydride group and a cationic component to improve chargeability. It has not yet been possible to satisfy all the physical properties required of a toner, such as offset resistance, fixing properties, and developability.

As described above, it is extremely difficult to achieve high performance in both heating fixing properties, offset resistance, and crushability related to fixing. In particular, pulverization during toner production is an important factor in today's trend toward smaller toner particle sizes due to demands for high quality, high resolution, and high fine line reproducibility of copied images. Since the process requires a very large amount of energy, improving crushability is also important from the perspective of energy conservation.

In addition, toner fusion to the inner wall of the crushing device tends to occur with toner having good fixing performance, which deteriorates the crushing efficiency.

As a further aspect, in another copying process, there is a process of cleaning the toner remaining on the photoreceptor after transfer.

Today, cleaning using a plate (blade cleaning) has become popular in view of the need for smaller, lighter, and more reliable equipment. With the increase in the lifespan of photoconductors, the miniaturization of photoconductor drums, and the increase in speed of systems, the requirements for toners such as fusion resistance and filming resistance with respect to photoconductors have become stricter. In particular, amorphous silicon photoreceptors that have recently been put into practical use are extremely durable and
The lifespan of organic photoreceptors (organic photoreceptors) is also increasing, and therefore the toner performance required of toners is becoming more advanced.

In addition, miniaturization requires the ability to fit each element into a small space. As a result, there is less space for air to flow properly, and the heat sources of the fixing device and exposure system are very close to the toner hopper and cleaner, exposing the toner to a high-temperature atmosphere. Therefore, it has become impossible to put toners into practical use unless they have better anti-blocking properties.

Furthermore, the various performances required of toners as listed above are often contradictory to each other, and it has become increasingly desirable in recent years to satisfy both of them with high performance.
Furthermore, although research has been conducted on comprehensive measures that include development characteristics, there is still not enough research.

[Problems to be Solved by the Invention] An object of the present invention is to provide a toner that solves the above-mentioned problems.

The objects of the present invention are listed below.

An object of the present invention is to provide a toner suitable for a hot roll fixing method that does not apply oil.

An object of the present invention is to provide a toner that can be fixed at a low temperature and has excellent offset resistance.

The purpose of the present invention is to fix at a low temperature, fuse to a photoreceptor,
The object of the present invention is to provide a toner that does not cause filming even in high-speed systems and even after long-term use.

An object of the present invention is to provide a toner that can be fixed at a low temperature, has excellent blocking resistance, and can be used satisfactorily even in a high-temperature atmosphere, especially in a small machine.

An object of the present invention is to provide a toner that is fixed at a low temperature and that can be produced efficiently and continuously because the crushed material does not fuse to the inner wall of the device during the crushing process during toner manufacturing.

An object of the present invention is to provide a toner that has excellent anti-offset properties and excellent pulverization properties, and thus has good production efficiency.

An object of the present invention is to provide toner that has been passed through a cleaning method using a plate.

An object of the present invention is to provide a toner that has good pulverizability, generates less coarse powder, and therefore has less scattering around the image, and can form a stable and good developed image.

[Means and effects for solving the problems] The present invention provides a toner containing at least a binder resin, a colorant, and a metal compound, wherein the binder resin is copolymerizable with at least a monomer having a carboxylic acid group. It consists of a vinyl copolymer made of a copolymer with a monomer, and a polyester resin made of a condensation polymer of a polybasic acid component and a polyhydric alcohol component.
Molecular weight 2.0 in molecular weight distribution in THF soluble content
00 to 15.000, and the vinyl copolymer has a THF-insoluble content of less than 5% by weight and a THF-soluble content of molecular weight 2,000 to 20.00% by GPC. A vinyl copolymer (A) having at least one peak in the 000 region, and a THF-insoluble component of 10% by weight or more, and a THF-soluble component having a molecular weight in the region of 20.000 to 100.000 in the molecular weight distribution by GPC. and a vinyl copolymer (B) having at least one peak or shoulder, and in the binder resin, the vinyl copolymer (A), the vinyl copolymer (B) and the polyester resin (C) In weight ratio (A):
This is a toner for developing an electrostatic image, characterized in that (B):(C) is blended in a ratio of 0 to 40:20 to 80:5 to 40.

In the present invention, T)IP-insoluble matter refers to THF in the resin composition.
It can be used as a parameter indicating the degree of crosslinking of a resin composition containing a crosslinked component. The THF-insoluble content is defined by the measured value as follows.

That is, weigh out 0.5 g of resin sample (24 mesh passes, 60 mesh powder), thimble filter paper (for example, Toyo Roshi Co., Ltd. No. 86R, size 28).
x100+nm) and applied to a Soxhlet extractor.
Extract for 12 hours using 150 to 200 mf of THF as a solvent, take out the thimble (THF outflow cycle once/4 minutes), dry thoroughly, and weigh the THF-insoluble matter (
Wig). The THF-insoluble content of the resin is determined from the following formula.

2 THF insoluble content (%) = -X100 1 The THF residue in the present invention is the weight percentage of the polymer component (substantially ultra-high molecular weight polymer) that is difficult to extract or is insoluble by THF among the resin components in the toner. shows,
It can be used as a parameter indicating the degree of existence of ultra-high molecular weight components. The THF residue is defined by the value measured as follows.

That is, weigh approximately 0.5 g of a toner sample, and place it on a thimble filter paper (for example, No. 86 R size 28 x 100 mm).
(manufactured by Toyo Roshi Co., Ltd.), put it in a Soxhlet extractor, extracted using THF 150-200 mI2 as a solvent for 12 hours, (1 THF outflow cycle 74 minutes), took out the thimble filter, dried it thoroughly, and weighed the THF residue. do. T.H.
The F residue is calculated by subtracting the pigment weight from the sample toner weight for a non-magnetic toner, and subtracting the pigment and magnetic weight from the sample toner weight (Wlg) for a magnetic toner, and the pigment weight from the THF residue weight in the toner. , the weight (w, g) obtained by subtracting the magnetic weight, etc., according to the following formula.

4 THF residue = -X100 3 In the present invention, the molecular weight of the peak and/or shoulder of a chromatogram by GPC (gel permeation chromatography) is measured under the following conditions.

The sample is prepared as follows.

Place the sample in THF and leave it for about 12 hours, then shake thoroughly and mix with THF.
For example, Ekiklodisc 25CR manufactured by Gelman Science Japan Co., Ltd. can be used. ) are used as G and PC samples.

Also, the sample concentration is 0.5 to 5 mg/ml of resin component!
Adjust so that

In the present invention, the molecular weight of the peak and/or shoulder of a chromatogram of a THF-soluble component by GPC (gel permeation chromatography) is measured under the following conditions.

That is, the column was stabilized in a heat chamber at 40°C, and THF was added to the column at this temperature as a solvent.
(Tetrahydrofuran) is flowed at a flow rate of 1 mR/min, and approximately 100 kl of THF sample solution is injected for measurement.

In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithm value and the count number of a calibration curve prepared using several types of monodisperse polystyrene standard samples. Standard polystyrene samples for creating a calibration curve include, for example, polystyrene samples manufactured by Pressure Chemical Co., Ltd., Toyo Tsudani Gyosha Co., Ltd., and Showa Denko Co., Ltd. with a molecular weight of 1.
It is appropriate to use at least 10 standard polystyrene samples of about 02 to 10'. Further, an RI (refractive index) detector is used as a detector.

In addition, in order to measure the molecular weight range of 102 to 3 x 10', it is recommended to combine multiple commercially available polystyrene gel columns (for example, 5h column manufactured by Showa Denko Co., Ltd.).
odex GPCKF-801, 802, 803゜80
4, 805.806. combination of goop, Wa
Ultra Styla Gel 500A-TH manufactured by TERS
F, 10"A-THF, 10'A-THF, 10
Examples include combinations of 11A-THE, 10'A-THF, and A-Toluene series.

Furthermore, 5hodex GPCKF-801, 802, 80 was used to measure the molecular weight range of 102 to 2
Examples include the combination of 3,804,805°806, 807.800P.

The present invention will be explained in detail below.

In order to achieve the above objectives at the same time, various binder resins were used, and their composition and performance were carefully studied from various angles. As a result, it has been found that this can be achieved when the ratio of the THF-insoluble portion of the binder resin and the molecular weight distribution of the THF-soluble portion are in a specific configuration. When the binder resin is dissolved in a solvent such as THF, it can be separated into an insoluble component and a soluble component, and the molecular weight distribution of the soluble component can be measured by GPC. Focusing on the peak positions of the molecular weight distribution of THF-insoluble and THF-soluble components, systems with no or a small amount of THF-insoluble matter are extremely disadvantageous in terms of crushability, and as mentioned above, it is important to improve crushability. This proves that simply shifting the peak position of the molecular weight distribution of THF-soluble components to a lower molecular weight position deteriorates offset resistance, making it difficult to satisfy both offset resistance and crushability. There is.

From this study, it has been found that it is very effective to contain a specific amount of THF-insoluble matter not only for the purpose of anti-offset properties, as is usually thought, but also for the purpose of improving crushability.

Furthermore, the molecular weight distribution of the THF-soluble content, the property of whether the fixable temperature is high or low (hereinafter simply referred to as fixability), offset resistance, crushability, and blocking resistance were investigated. As a result, the molecular weight in GPC molecular weight distribution was 10.0.
It has been found that components having a molecular weight of less than 0.00 and a component having a molecular weight of about 10,000 or more have different functions. In other words, the content ratio of components having a molecular weight of 10,000 or less to the entire binder resin does not strongly affect fixing properties or anti-offset properties, as is usually said. It was found that there was no relationship between the two, but instead it was strongly related to the crushability.

Furthermore, based on other studies, the binder resin is basically T.
The HF-insoluble content mainly affects offset resistance, wrapping properties, and crushability, and the THF-soluble content has a molecular weight of 10.00.
0 or less components mainly affect the crushing property, blocking property, adhesion to the photoreceptor, filming property, and adhesion to the inner wall of the grinding device, and furthermore, the molecular weight of the THF soluble component io, oo
It was discovered that the above components affect offset resistance and fixing properties, and that among various binder resins, polynisder resin, which is made of a condensate of a polybasic acid component and a polyhydric alcohol component, exhibits the best fixing properties. Ta.

The reason for this is that the critical surface tension of polyester resin is lower than that of paper (in addition, the ester group, which is the main polar group, and the carboxyl group and hydroxyl group coexisting in the molecule have affinity with the hydroxyl group of paper through hydrogen bonding). This is because it is thought to have a fixation effect.

Furthermore, when a resin binder having a wide molecular weight distribution ranging from low molecular weight to high molecular weight is used, contamination of the fixing roller may occur even if no offset occurs when copying is continued. This occurs because the affinity of the toner for the fixing roller is stronger than the affinity for the paper, and it is known that this is particularly caused by the composition on the low molecular weight side. As a result, the releasability of the roller becomes poor (the toner that has adhered to the roller may adhere to the transfer paper again, or the transfer paper may wrap around the fixing roller).
Such disadvantages occur. Even if a roller whose surface layer is coated with a fluororesin having low surface tension is used, it will be contaminated if a binder resin without polar groups such as a vinyl copolymer is used. Therefore, we introduced a carboxylic acid group into a vinyl copolymer as in the present invention,
Furthermore, it has been found that it is very effective to include a polyester resin containing acid groups in the binder composition to impart polarity.

To explain the present invention more specifically, the binder resin composition used in the toner of the present invention contains a THF-insoluble content (gel content) of 5 to 50% by weight (based on the binder resin), preferably 10 to 45% by weight. has been done. The reason for this is that if the THF-insoluble content in the resin composition exceeds 50% by weight, its melting properties will lead to an increase in fixing temperature when used in a toner, and furthermore, the dispersion of additives will deteriorate. Furthermore, the highly crosslinked region component is likely to be cut when the resin is cross-wired, causing problems in toner design. On the other hand, if the gel content is less than 5% by weight, offset and wrapping around the roller tend to occur, and if the gel content is less than 5% by weight and there is a large amount of high molecular weight, the crushability will be significantly deteriorated.

The binder resin is a vinyl copolymer made of a polyester resin made of a condensate of a polybasic acid component and a polyhydric alcohol component, a monomer containing a carboxylic acid group, and another copolymerizable monomer. It is composed of

The vinyl copolymer of the binder resin contains a THE-insoluble component of less than 5% by weight, preferably less than 3% by weight, and has a molecular weight of 2.000 to 10.000 in the GPC chromatogram of the THF-soluble component. , preferably 2.0
The vinyl copolymer (A) has at least one peak in the range of 00 to 00 g, ooo, and the THF-insoluble component is contained in an amount of 10% by weight or more, preferably 20 to 90% by weight, and the THF-insoluble component is contained in the copolymer (A). 15 in the GPC chromatogram
,000-100,000, preferably 20,000
a vinyl copolymer (B) having at least one peak in the region of ~70,000, the vinyl copolymers (A) and (B), and the polyester resin (
C) and the weight ratio (A) : (B) : (C)
= 0-40:20-80:5-40 preferably (
A) : (B) : (C) = 0~35:25~
The ratio is 75:5 to 35.

In this blending ratio of each component, the vinyl copolymer (A)
When the ratio exceeds 40, offset resistance and blocking resistance are insufficient. In addition, if the ratio of the vinyl copolymer CB) is less than 20, it will have an adverse effect on offset or blocking, and if it exceeds 80, the grindability will be poor (which will cause problems in production such as generation of coarse powder. When the proportion of resin (C) is less than 5, the effect of adding the polyester resin is not sufficiently exhibited, resulting in poor fixing and developing properties, and when it is more than 40% by weight, the crushability is poor (and production This will cause problems on the surface.

In the vinyl copolymer which is one of the constituent components of the binder resin of the present invention, as the monomer containing a carboxylic acid group therein, a dicarboxylic acid half ester monomer is particularly preferably used.

Examples of dicarboxylic acid half ester monomers that can be used in the present invention include monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate, monophenyl maleate, monomethyl fumarate, and fumaric acid. Half esters of α,β-unsaturated dicarboxylic acids such as monoethyl, monobutyl fumarate, monophenyl fumarate, etc.; n-
Half esters of alkenyldicarboxylic acids such as monobutyl butenylsuccinate, monomethyl n-octenylsuccinate, monoethyl n-butenylmalonate, monomethyl n-dodecenylglutarate, monobutyl n-butenyladipate; monomethyl phthalate, phthalic acid Half esters of aromatic dicarboxylic acids such as monoethyl ester and phthalic acid monobutyl ester; and the like.

The dicarboxylic acid half ester described above may be added in an amount of 1 to 30% by weight, preferably 3 to 20% by weight, based on the total monomers constituting the binder resin.

The reason why the above dicarboxylic acid half ester monomer is selected is that suspension polymerization is preferred as a method for producing the resin, as will be described in detail later. In the suspension polymerization, it is not appropriate to use an acid monomer with high solubility in an aqueous suspension (because it is preferable to use an ester with low solubility).

Examples of comonomers that can be copolymerized with the carboxylic acid-containing monomer to obtain the vinyl copolymer of the present invention include the following.

For example, styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p
-Phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-
Butylstyrene, pn-hexylstyrene, pn-
Octylstyrene, pn-nonylstyrene, pn-
Styrene and its derivatives such as decylstyrene and p-n-dodecylstyrene; Ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; Unsaturated polyenes such as butadiene; Vinyl chloride, vinylidene chloride, vinyl bromide , vinyl halides such as vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylate α-methylene aliphatic monocarboxylic acid esters such as n-octyl acid, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate , ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-acrylate
Acrylic acid esters such as octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate; vinyl methyl ether, vinyl ethyl ether,
Vinyl ethers such as vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone. Vinyl naphthalenes: Acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; Vinyl monomers are used alone or in combination of two or more. However, monomers are selected and used so that at least one vinyl monomer is included.

Among these, combinations of monomers that result in styrene copolymers and styrene-acrylic copolymers are preferred.

In order to achieve the object of the present invention, the binder resin used in the present invention needs to be a polymer crosslinked with a crosslinkable monomer as exemplified below.

Aromatic divinyl compounds, such as divinylbenzene, divinylnaphthalene, etc.; diacrylate compounds linked with an alkyl chain, such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1
．． 4-butanediol diacrylate, 1.5-bentanediol diacrylate, 1.6-hexanediol diacrylate, neopentyl glycol diacrylate, and the above compounds in which the acrylate is replaced with methacrylate; alkyl containing an ether bond Chained diacrylate compounds, such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate,
Polyethylene glycol #400 diacrylate, polyethylene glycol #600 diacrylate, dipropylene glycol diacrylate, and the above compounds in which the acrylate is replaced with methacrylate; diacrylate compounds connected by a chain containing an aromatic group and an ether linkage such as polyoxyethylene (2)-2,2-
Bis(4-hydroxyphenyl)propane diacrylate, polyoxyethylene (4)-2,2-bis(4-hydroxyphenyl)propane diacrylate, and the above compounds in which the acrylate is replaced with methacrylate; , polyester type diacrylate compounds, for example, the trade name MANDA (Nippon Kayaku). Examples of polyfunctional crosslinking agents include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and compounds in which the acrylate of the above compounds is replaced with methacrylate; Examples include allyl cyanurate and triallyl trimellitate.

These crosslinking agents are preferably used in an amount of about 0.01 to 5% by weight (more preferably about 0.03 to 3% by weight) based on 100% by weight of other monomer components.

Among these crosslinking monomers, aromatic divinyl compounds (particularly divinylbenzene),
Mention may be made of chain diacrylate compounds containing aromatic groups and ether linkages.

Furthermore, the composition of the polyester resin used in the present invention is as follows.

Dihydric alcohol components include ethylene glycol,
Propylene glycol, 1,3-butanediol, 1.
4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-bentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or bisphenol and its derivatives represented by the formula (A); (wherein R is ethylene or propylene group, X + 5'
are each an integer greater than or equal to 0, and the average value of x+y is 0 to 10.

Also, diols represented by the formula (B); Diols such as can be mentioned.

Divalent acid components include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or their anhydrides, and lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid. or its anhydride, lower alkyl ester;
Alkenylsuccinic acids or alkylsuccinic acids such as n-dodecenylsuccinic acid and n-dodecylsuccinic acid, or anhydrides thereof, lower alkyl esters, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid, or anhydrides thereof , dicarboxylic acids such as lower alkyl esters, and derivatives thereof.

In addition, trivalent or higher alcohol components that also act as crosslinking components and 3
An acid component having a value higher than the value can be used in combination.

In the present invention, the trihydric or higher polyhydric alcohol component includes sorbitol, 1,2,3.6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2
．． 4-Butanetriol, 1, 2.5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3.5
Examples include polyhydric alcohols having a valence of 3 or more, such as 4-lyhydroxybenzene.

In addition, as the trivalent or higher polyhydric carboxylic acid component in the present invention, trimellitic acid, pyromellitic acid, 1,2.4-
Benzenetricarboxylic acid, 1,2.5-benzenetricarboxylic acid, 2.5.7-naphthalenetricarboxylic acid, 1
, 2.4-naphthalenetricarboxylic acid, 1.2.4-butanetricarboxylic acid, l, 2.5-hexanetricarboxylic acid, ■, 3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra(methylenecarboxylic acid) ) Methane, 1,2,7.8-octane tetracarboxylic acid, Empol trimer acid, and their anhydrides, lower alkyl esters, the following formula (where X represents one or more side chains having 3 or more carbon atoms) Polyhydric carboxylic acids such as tetracarboxylic acids represented by (alkylene group or alkenylene group having 5 to 30 carbon atoms), anhydrides thereof, lower alkyl esters, and derivatives thereof.

The alcohol component used in the present invention is 35 to 65
ffloρ%, preferably 40 to 60 mon)%, and 65 to 35 m0I as the acid component! %, preferably 60~
Desirably, it is 40 mojl'%.

In addition, polyvalent components of trivalent or higher valence account for 5 to 60 m of the total components.
o1% is desirable.

In the present invention, the preferred alcohol component of the polyester resin is a bisphenol derivative represented by the above formula (A), and the acid component includes phthalic acid, terephthalic acid, isophthalic acid or anhydride thereof; succinic acid, n- Examples include dodecenylsuccinic acid or its anhydride; dicarboxylic acids such as fumaric acid, maleic acid, and maleic anhydride; tricarboxylic acids such as trimellitic acid or its anhydride; and the like.

This is because polyester resins obtained with these acids and alcohols exhibit sharp melting characteristics, have good fixing properties as toners that are constantly worn on a hot roller, and are excellent in offset resistance.

Furthermore, the glass transition temperature of the polyester resin obtained here is 50 to 70°C, preferably 55 to 65°C, and the number average molecular weight is 11vin 1,500 to 10,000, preferably 2.000 to 7,000. Molecular weight MW
6,000-952 200,000 preferably 10,000-150,00
It is desirable that it be 0.

Further, it is desirable that the acid value is 100 or less, preferably 50 or less, and the hydroxyl value is 60 or less, preferably 30 or less. This is because as the number of terminal groups in the molecular chain increases, when the toner is made into a toner, the charging characteristics of the toner become more dependent on the environment.

In the present invention, a binder resin composed of a polyester resin, a vinyl copolymer (A) (low molecular weight type), and a vinyl copolymer (B) (high molecular weight type) is used using the above components. It is preferable that the acid value of the binder resin as a whole is 50 or less. If the acid value is larger than these values, the environmental dependence of charging upon forming a toner will increase, or the molecular weight will decrease, resulting in problems such as a narrow fixing temperature range.

Here, the acid value and hydroxyl value of the resin were measured by the following method.

Sample 2 to 10 g was weighed into a 200 to 300 mN Erlenmeyer flask, and 50 mp of a mixed solvent of methanol:toluene = 30 ml was added to dissolve the resin. If the solubility seems poor, a small amount of acetone may be added.

Pre-standardized N/10 K using a mixed indicator of 0.1% bromothymol blue and phenol red.
Titration was carried out with an OH to alcohol solution, and the acid value was determined from the consumption amount of alcohol potassium solution using the following formula (3).

Acid value = KOH (mp number) XNX56.1/sample weight - (
3) (N is the factor of N/10 KOH) Also,
The hydroxyl value is calculated according to the following formula (4) after acetylating the sample by heating it with an excess acetylating agent, such as acetic anhydride, and measuring the saponification value of the acetylated product produced.

(However, A represents the saponification value after acetylation, and B represents the saponification value before acetylation.) The method for synthesizing the binder resin related to the present invention is basically a method of synthesizing two or more types of polymers. is preferred.

That is, a first polymer (vinyl copolymer (A)) that has a small amount of THF-insoluble content and is soluble in a polymerization monomer is dissolved in a polyester resin (C) and a polymerization monomer, and the monomers are polymerized to form a resin composition. This is the way to obtain. In this case, a composition is formed in which the former and latter polymers are uniformly mixed.

The low molecular weight polymer (vinyl copolymer (A)) in the binder resin composition used in the present invention can be obtained by a commonly used polymerization method such as a bulk polymerization method or a solution polymerization method.

In the bulk polymerization method, low molecular weight polymers can be obtained by polymerizing at high temperatures to slow down the termination reaction rate.
There is a problem in controlling the reaction. On the other hand, in the solution polymerization method, low molecular weight polymers can be mildly produced by making use of differences in chain transfer of radicals depending on the solvent and by adjusting the amount of initiator and reaction temperature. It can be easily obtained under the following conditions, and is preferable for obtaining the low molecular weight substance in the resin composition used in the present invention.

Solvents used in solution polymerization include xylene, toluene,
Cumene, cellosolve acetate, isopropyl alcohol, benzene, etc. are used. In the case of styrene monomers, xylene, toluene or cumene are preferred. It is appropriately selected depending on the polymer to be polymerized. In addition, the initiator is
rt, butyl peroxide, tert-butyl peroxybenzoate, benzoyl peroxide, 2.2
'-azobisisobutyronitrile, 2,2'-azobis(2,4 dimethylvaleronitrile), etc. are monomers of 100
0.1 parts by weight or more (preferably 0.4 to 0.4 parts by weight)
15 parts by weight). The reaction temperature is
Although it varies depending on the solvent, initiator, and polymer to be polymerized, it is preferable to carry out the reaction at a temperature of 70°C to 180°C. In solution polymerization, 30 parts by weight of monomer per 100 parts by weight of solvent
Preferably, the amount is 400 parts by weight.

This low molecular weight polymer is polymerized again together with the polyester resin and the monomer that gives the medium/high molecular weight polymer (vinyl copolymer (B)), but the gel in the crosslinked region remains until it becomes a solvent-insoluble component. Preferred polymerization methods for obtaining the components include emulsion polymerization and suspension polymerization.

Among these, the emulsion polymerization method uses monomers that are almost insoluble in water (
In this method, monomers are dispersed as small particles in an aqueous phase using an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. In this method, the heat of reaction can be easily controlled, and since the polymerization phase (oil phase consisting of polymer and monomer) is separate from the aqueous phase, the termination reaction rate is low, and as a result, the polymerization rate is fast. Furthermore, since the polymerization process is relatively simple and the polymerization product is fine particles, it is difficult to add colorants, charge control agents, and other additives during toner production. This method is advantageous compared to other methods as a method for producing a binder resin for toner because it is easy to mix with other materials.

However, the added emulsifier tends to make the resulting polymer impure, and operations such as salting out are required to extract the polymer.
To avoid this inconvenience, suspension polymerization is advantageous.

Taking the suspension polymerization method as an example, monomers containing a suspended low molecular weight polymer are polymerized together with a crosslinking agent, so that the resin composition is formed into a pearl shape, and the low molecular weight polymer is formed into a resin composition. to medium to high molecular weight polymers containing crosslinking region components can be obtained in a preferable state in which they are uniformly mixed.

In suspension polymerization, for 100 parts by weight of an aqueous solvent,
It is preferable to use the polyester resin and the monomer in an amount of 100 parts by weight or less (preferably 10 to 90 parts by weight).

Usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate, etc., and there are appropriate amounts depending on the amount of monomer relative to the aqueous solvent, but generally from 0.05 to 100 parts by weight of the aqueous solvent.
1 part by weight is used.

The polymerization temperature is suitably 50 to 95°C, but should be appropriately selected depending on the initiator used and the intended polymer. As for the type of initiator, any one that is insoluble or poorly soluble in water can be used; for example, benzoyl peroxide, tert-butyl peroxyhexanoate, etc. It is used in an amount of .5 to 10 parts by weight.

In addition, in the present invention, a desired binder resin can be obtained without adding the low-molecular-weight premium vinyl copolymer (A) during suspension polymerization. In this case, suspension polymerization may be carried out using the above polyester resin and a compound other than (A).

As the reactive metal compound used in the present invention, those containing the following metal ions can be used. Suitable monovalent metal ions include Na'', Li''''+ Cs'', Ag''+8
g", Cu", etc., and divalent metal ions include 1
3eil+, 14g24. Ca24. Hg2+″
, Sn"", Pb", Co24Ni2+, Zn2
+ etc. In addition, as trivalent ions, l"", 8
0M*, Co3+″ N i3+, r3+″ r
There are 3+ etc. Among the compounds containing metal ions as mentioned above, the more decomposable the compound, the better the results.

This is presumed to be because metal ions in the decomposable compounds more easily bond to carboxyl groups in the polymer through thermal decomposition.

Among the reactive metal compounds, organometallic compounds have excellent compatibility and dispersibility with the polymer, and crosslinking by reaction with the metal compound proceeds more uniformly in the polymer, giving better results.

Among the above-mentioned reactive organometallic compounds, those containing organic compounds with high vaporizability and sublimation properties as ligands and counterions are particularly useful.Metal ions, ligands, and counterions Examples of organic compounds having the above-mentioned properties include salicylic acid, salicylic acid, salicylamide, salicylamine, salicylaldehyde, salicyrosalicylic acid, di-tert-butylsalicylic acid, and derivatives thereof; , acetylacetone, propionacetone, and other β-diketones, and low-molecular-weight carboxylic acid salts such as acetate and propionic acid.

It is also possible to impart charge controllability to the toner particles to the metal complex. Examples of such metal complexes include azo metal complexes represented by the following general formula [I].

[T] In the formula, M represents a coordination center metal, and Cr C with a coordination number of 6
o, Ni, Mn, Fe, etc. Ar is an aryl group, such as a phenyl group or a naphthyl group, which may have a substituent. Examples of the substituent in this case include a nitro group, a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group. X, X', Y, Y' are -O-, -CO
-, -NH-, -NR- (R is an alkyl group having 1 to 4 carbon atoms). KfB represents hydrogen, sodium, potassium, ammonium, and aliphatic ammonium.

Next, a specific example of the mirror will be shown.

(Margin below) During the ceremony, M represents a coordination center metal; Coordination number 6 Cr.

Co.

Ni.

Examples include Mn.

A is (X is hydrogen atom, halogen atom, di Toro group) Ba (kyl or alkenyl group) represents.

ys is hydrogen, Na or a basic organic acid metal complex represented by the following general formula [IT] which imparts negative chargeability, and examples thereof include thorium, potassium, ammonium, and aliphatic ammonium. 2 is 10- or -C-O-
It can be used clearly.

It is.

Next, specific examples of the complex will be shown.

Complex [n]-1 Complex [JT]-2 Complex [11]-6 Complex group] Complex [11] Complex [11]-4 Complex [11]-8 Complex [II]-5 Complex [11]-9 These These metal complexes can be used alone or in combination of two or more.

The amount of the metal complex added to the toner particles varies depending on the type of toner binder, whether a carrier is used in combination, the pigment that colors the toner, and the reactivity of the metal complex with the binder. It is 0.01 to 20% by weight, preferably 0.1 to 10% by weight, based on 100% by weight of the binder.

In addition, by reacting with the binder during melt mixing, the metal complex has higher decomposition and reactivity than when added during binder synthesis, and has excellent compatibility with the binder or dispersibility in the binder, and can be used in toner. It has the advantage of providing stable charging properties.

In the present invention, it is possible to impart charge control properties to the metal compound as a crosslinking component as a toner, but if necessary, a charge control agent can also be used separately from this, and conventionally known charge control agents can be used. A negative or positive charge control agent is used.

Charge control agents known in the art today include:

The following substances are used to control the negative chargeability of toner.

For example, organometallic complexes and chelate compounds are effective, including the aforementioned monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid-based metal complexes. Others include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

The following substances are used to control the toner to be positively charged.

For example, modified products with nigrosine and fatty acid metal salts; tributylbenzylammonium-1-hydroxy-4-
Onium salts such as naphthosulfonates, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, and phosphonium salts that are analogs thereof, and lake pigments thereof. Triphenylmethane dyes and their lake pigments. (Lake forming agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.) Metal salts of higher fatty acids,
Acetylacetone metal complex. dibutyltin oxide,
diorganotin oxides such as dioctyltin oxide and dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate, dicyclohexyltin borate, etc.
These can be used alone or in combination of two or more. Among these, charge control agents such as nigrosine and quaternary ammonium salts are particularly preferably used.

In the toner of the present invention, it is preferable to add fine silica powder to improve charging stability, developability, fluidity, and durability.

The silica fine powder used in the present invention has a specific surface area of 30 m2/g or more (especially 5
0 to 400 m2/g) gives good results. 0.0% of fine silica powder per 100 parts by weight of toner.
0.01 to 8 parts by weight, preferably 0.1 to 5 parts by weight.

In addition, the fine silica powder used in the present invention may include, if necessary,
Silicone oil, various modified silicone oils, silicone oil, various modified silicone oils, silane coupling agents, etc. for the purpose of hydrophobization, chargeability control, etc.
It is also preferable that the material be treated with a treatment agent such as a silane coupling agent having a functional group or another organosilicon compound, or with a combination of various treatment agents.

Other additives include lubricants such as Teflon, zinc stearate, and polyvinylidene fluoride, with polyvinylidene fluoride being preferred. Alternatively, abrasives such as cerium oxide, silicon carbide, and strontium titanate are preferred, with strontium titanate being preferred. Or, for example, titanium oxide,
Fluidity imparting agents such as aluminum oxide, especially hydrophobic ones, are preferred. A small amount of an anti-caking agent, a conductivity imparting agent such as carbon black, zinc oxide, antimony oxide, tin oxide, or a white fine particle and a black fine particle of opposite polarity can be used as a developability improving agent.

In addition, in order to improve mold releasability during hot roll fixing, waxy substances such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, carnauba wax, Sasol wax, paraffin wax, etc. are added to 100% by weight of the binder resin. It is also one of the preferred embodiments of the present invention to add about 0.5 to 10% by weight to the toner.

Furthermore, when the toner of the present invention is used as a two-component developer, it is used in combination with carrier powder. In this case, the mixing ratio of toner and carrier powder is 0 as toner concentration.
．． 1 to 50% by weight, preferably 0.5 to 10% by weight, more preferably 3 to 5% by weight.

As the vine carrier used in the present invention, all known carriers can be used, such as iron powder, ferrite powder, magnetic powder such as nickel powder, glass beads, etc., and their surfaces are coated with fluorine resin, vinyl Examples include those treated with a silicone resin or a silicone resin.

Furthermore, the toner of the present invention can further contain a magnetic material and be used as a magnetic toner. In this case, the magnetic material also serves as a coloring agent. The magnetic materials contained in the magnetic toner of the present invention include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and aluminum, cobalt, copper, lead, and metals of these metals.
Magnesium, tin, zinc, antimony, beryllium,
Examples include alloys of metals such as bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

The average particle size of these ferromagnetic substances is preferably about 0.1 to 2 pm, preferably about 0.1 to 0.5 pm, and the amount contained in the toner is about 20 to 200 parts by weight per 100 parts by weight of the resin component. parts, particularly preferably resin component 100
It is preferably 40 to 150 parts by weight.

In addition, the magnetic properties when IOK Oe is applied are coercive force 20 to 15.
00e Saturation magnetization 5 (1 to 200 emu/g, residual magnetization 2
~20 emu/g is desirable.

Colorants that can be used in the toners of the present invention include any suitable pigments or dyes. Toner colorants are well known and include pigments such as carbon black, aniline black, acetylene black, and naphthol yellow.
Hansa Yellow Rhodamine Lake, Alizarin Lake,
Examples include red iron, phthalocyanine blue, and indanthremble. These are used in necessary and sufficient amounts to maintain the optical density of the fixed image, and are
．． The amount added is 1 to 20 parts by weight, preferably 2 to 10 parts by weight. Further, dyes are also used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthine dyes, methine dyes, etc.
．． The amount added is preferably 1 to 20 parts by weight, preferably 0.3 to 3 parts by weight.

To prepare the toner for developing electrostatic images according to the present invention, a binder resin, a metal compound, a pigment such as a coloring agent, or a dye, a magnetic material, a charge control agent as necessary, other additives, etc. are added to Henschel. Mixer Mix thoroughly with a mixer such as a ball mill, then melt, knead, and knead using a heat kneader such as a heated roll, kneader, or extruder to make the resins compatible with each other. The toner according to the present invention can be obtained by dispersing or dissolving pigments, dyes, and magnetic substances, cooling and solidifying them, and then crushing and classifying them.

Further, if necessary, desired additives are sufficiently mixed using a mixer such as a Henschel mixer to obtain the toner for developing electrostatic images according to the present invention.

[Examples] The present invention will be described below with reference to specific examples, but the present invention is not limited to these in any way. In addition, “department”
all mean "parts by weight".

Synthesis Example 1 The above components were added dropwise over 4 hours to 200 parts of cumene heated to reflux temperature. Furthermore, under cumene reflux (146~
Solution polymerization was completed at 156° C.) and cumene was removed. The obtained copolymer has a molecular weight of 4000. Tg=60°C.

30 parts of the copolymer was dissolved in the following monomer mixture to prepare a mixed solution.

170 parts of water in which 0.1 part of the compound was dissolved was added to form a suspension and dispersion. The suspension dispersion was added to a reactor containing 15 parts of water and purged with nitrogen, and after the reaction was completed, the reactor was dehydrated and dried to obtain a binder resin composition. In this composition, the THF-insoluble components and the THF-soluble components were uniformly mixed, and the vinyl copolymer and the polyester resin were uniformly mixed. The THF-insoluble content of the resulting resin composition was 35 parts. In addition, when we measured the molecular weight distribution of THF-soluble components, we found that GPC
In the chart, there was a peak at about 15,000, and the Tg of the resin was 57°C. Tg is the resin at 50℃,
It was annealed for 48 hours and then determined by differential scanning calorimetry. Moreover, the acid value as a binder resin is 17.
It was 5.

Synthesis Example 2 To the above mixed solution, the polyvinyl alcohol portion and each of the above components were added dropwise over 4 hours into 200 parts of xylene heated to reflux temperature. Furthermore, under reflux of xylene (138-14
Solution polymerization was completed at 4° C.) and xylene was removed. The obtained copolymer has a molecular weight of 6000. Tg=61°C.

10 parts of the copolymer was dissolved in the following monomer mixture to prepare a mixture.

The above dispersion was added to a reactor containing 15 parts of water and purged with nitrogen, and the reaction was carried out at a reaction temperature of 70 to 95° (T-6 hours. After the reaction was completed, separation, dehydration, and drying were performed to obtain a resin composition. Ta.

The THF-insoluble content of the resulting resin composition was 40% by weight. In addition, when we measured the molecular weight distribution of THF-soluble components,
In the GPC chart, there was a peak at about 10,000, and debris at about 53,000. Also, the Tg of the resin is 5
The temperature was 9°C. The acid value was 28.5.

Synthesis Example 3 170 parts of water in which 1 part of partially saponified polyvinyl alcohol was dissolved was added to the above mixture to prepare a suspension and dispersion.

150 parts of cumene was placed in a reactor, and the temperature was raised to reflux temperature. Further, the above mixture was added dropwise to the cumene over 4 hours under reflux. Then, the polymerization was completed under cumene reflux (146 to 156°C), and cumene was removed. The obtained polystyrene has a main peak at molecule [17000, Tg = 72
It was ℃. 35 parts of the above polystyrene was dissolved in the following monomer mixture to form a mixture.

Synthesis Example 4 Adding 0.1% polyvinyl alcohol partially saponified product to the above mixture
170 parts of water was added to form a suspension and dispersion. The above dispersion was added to a reactor containing 15 parts of water and purged with nitrogen, and reacted for 6 hours at a reaction temperature of 70 to 95°C. After the reaction was completed, the mixture was separated, dehydrated, and dried to obtain a copolymer composition of polystyrene, styrene-n-butyl acrylate, and polyester. The obtained resin showed 0 on the GPC chart.
, 90,000 and a shoulder at 6,60,000, and the THF-insoluble content was 43% by weight. Further, Tg was 58.7°C and acid value was 17.5.

Add 0% of the partially saponified polyvinyl alcohol to the above mixed solution.
A dispersion was prepared by adding 170 parts of water in which 1 part was dissolved. water 15
The above dispersion was added to a reactor which had been replaced with nitrogen and reacted for 6 hours at a reaction temperature of 70 to 95°C. After the reaction is complete,
A resin composition was obtained by dehydration and drying. The molecular weight distribution of the obtained resin had a peak at 50,000, a shoulder at 60,000, a THF insoluble content of 45% by weight, a Tg of 59°C,
The acid value was 20.4.

Comparative Synthesis Example 1 In Synthesis Example 1, 60 parts of the low molecular weight type vinyl copolymer (A) obtained by solution polymerization, 16 parts of styrene monomer, 15 parts of n-butyl acrylate, 4 parts of monobutyl maleate, A resin composition was obtained by suspension polymerization using the same formulation as in Synthesis Example 1 except that 5 parts of polyester resin was used. The obtained resin had a peak at the 04,000 position and a shoulder at the 10,000 position in the GPC chart of the THF soluble content, and the THF insoluble content was 3% by weight.

Further, the Tg was 48°C and the acid value was 13.2.

Comparative Synthesis Example 2 A resin composition was obtained using the same recipe as in Synthesis Example 1 except that the polyester resin was not added during suspension polymerization. The obtained resin has peaks at approximately 6,000 and 52,000 positions in the GPC chart of the THF-soluble content, the THF-insoluble content is 15% by weight, and the Tg of the resin is 57°C.
, the acid value was 1015.

Comparative Synthesis Example 3 In Synthesis Example 1, 5 parts of the low molecular weight type vinyl copolymer (A) obtained by solution polymerization, 59 parts of styrene monomer, 28 parts of n-butyl acrylate, 3 parts of monobutyl maleate, A resin composition was obtained by suspension polymerization using the same formulation as in Synthesis Example 1 except that 5 parts of polyester resin was used. The obtained resin has a peak at a position of approximately 60,000 in the GPC chart of T) IF soluble content, and 12.
His shoulders were at the 00,000 position. Also, the THF-insoluble content is 55
% by weight. Tg is 60℃, acid value is 13. It was l.

Example 1 After premixing the above materials in a Henschel mixer, 130
Melt kneading was carried out using a twin-screw kneading extruder at .degree. After cooling the mixed material, it was roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet stream, and then classified using an air classifier to obtain a black material with a volume average particle size of 8.5 parts m. A fine powder (toner) was obtained. The melt index value of this toner was determined using an apparatus described in JISK 7210 at 125°C.
The value was 2.8 when carried out under the condition of 1.0 kg, and this value suggests that metal crosslinking has progressed sufficiently.

0 parts of hydrophobic colloidal silica per 100 parts of the above toner
．． Four parts were dry mixed to form a developer.

The image properties, fixing properties, offset properties, etc. of this developer were evaluated using a Canon copier NP-8580 using an α-5L photoreceptor. The resulting copied image had a high reflection image density of 1.40, and a good image with high resolution and no fogging (no toner scattering around the image) was obtained.

In addition, in terms of durability, the image after 200,000 copies is completely unchanged compared to the initial image, has almost no environmental dependence, and is free from filming and fusion on the photoreceptor. (The fixing roller was not contaminated by copying.

The blocking property was measured by the change in the degree of aggregation when about 10 g of toner was placed in a 100 cc poly cup and left at 50° C. for one day. The degree of aggregation was measured using a powder tester manufactured by Line Micron Co., Ltd. The index of blocking property was the difference in degree of aggregation between the product left at room temperature and the product left at 50° C. for 1 day.

In addition, depending on how dirty the cleaning wave is during continuous copying, toner that has been picked up by the cleaning wave may transfer to the upper roller and contaminate the copied material. After returning the cleaning mechanism of the fixing roller to its normal state and taking 200 copies continuously, take copies one copy at 30 second intervals for up to 3 minutes to check whether image contamination occurs, and then fix the fixing roller. The state of dirt on the cleaning wave of the roller was evaluated.

The wrapping property was determined by continuously copying 30 completely black images, and if the copied images that passed through the fixing roller were sometimes curled, the number of sheets that curled was used as an index for evaluating the wrapping property. .

The results of the image evaluation are shown in the table below.

Evaluation of fixing properties, offset properties, wrapping properties, image properties, and durability was performed according to the following procedures.

The fixing performance was determined by leaving the evaluation machine overnight in a low temperature, low humidity environment (15°C, 10%), and then continuously printing 200 sheets after the evaluation machine and its internal fixing device had completely adapted to the low temperature and low humidity environment. A copy image was taken, and the 200th copy image was used for evaluation of fixability. To evaluate the fixability, the image was rubbed with Silbon paper back and forth 10 times under a load of about 100 g, and peeling of the image was evaluated by the rate of decrease in reflection density (%).

In particular, the offset property was evaluated by removing the cleaning mechanism of the fixing roller and determining the number of copies it took to stain the image or stain the roller based on the number of copies that could be made.

Example 2 The above materials were made into toner by the same method as Example 1,
A developer was obtained. Image evaluation was also performed in the same manner as in Example 1. The results are shown in the table below.

Example 3 The above materials were made into a toner in the same manner as in Example 1 to obtain a developer. Image evaluation was also performed in the same manner as in Example 1. The results are shown in the table below.

Example 4 In Example 1, a toner was produced and produced using the same recipe as in Example 1 except for using the resin binder obtained in Synthesis Example 4.
evaluated. The results are shown in the table below.

Example 5 A toner was prepared in the same manner as in Example 1 except that 5 parts of carbon black was added instead of magtite.

To 8 parts of this toner, 100 parts of a ferrite carrier (particle size: 80 gm) whose surface was coated with a fluororesin was mixed to prepare a developer. Also, only toner was used as a replenisher. When this developer was subjected to image evaluation using a Canon copier NP-6650, the image quality was good, and a stable image was obtained after 200,000 copies. Furthermore, no filming or fusion of toner on the photosensitive drum was observed.

Example 6 A toner was prepared in the same manner as in Example 1 except that 5 parts of acetylacetone cobalt [III] and 7 parts of nigrosine were added instead of complex [I]-2. For image evaluation, the NP8580 was modified and evaluated using a machine equipped with a reversal development structure, and a good image could be obtained. The detailed results are shown in the table.

Comparative Example 1 Example 1 except that the resin obtained in Comparative Synthesis Example 1 was used.
A toner was produced and evaluated in the same manner as described above.

As shown in the table, the obtained toner had poor anti-blocking properties and anti-offset properties, and when we looked at the fixing roller after copying 200,000 copies, we found that it was black (contaminated). Even during copying, paper jams occurred frequently due to toner being fused to the fixing/separating claw.

Comparative Example 2 Example 1 except that the resin obtained in Comparative Synthesis Example 2 was used.
A toner was produced and evaluated in the same manner as described above.

The results showed that the toner was slightly inferior to the toner produced in Example 1, with an image density of 1.28 to 1.33 and a density reduction rate of 20% in the fixability test.

Comparative Example 3 Example 1 except that the resin obtained in Comparative Synthesis Example 3 was used.
A toner was produced in the same manner. At this time, during kneading, the dispersibility of each component was poor, and the discharge speed of the mixed material was about 40% of that in the example. Furthermore, a large amount of coarse powder was generated after crushing. When the same evaluation as in Example 1 was carried out, results were obtained that particularly the developability and fixability were extremely poor.

[Effects of the Invention] The toner of the present invention has significantly improved the problems associated with conventional toners, has excellent offset resistance and roller wrapping resistance, has a wide fixing temperature range, and has excellent crushability with excellent development properties. You can get a good toner.

The cause of this is that in a resin composition consisting of polyester and a vinyl copolymer that is uniformly mixed from a high molecular weight polymer component containing a crosslinked region to a low molecular weight polymer component, there is a high molecular weight and low molecular weight polymer component in the crosslinked region. It is thought that the molecular weight segments are mixed and integrated, and the high molecular weight components including crosslinks are
During heat melting, it acts as a matrix to prevent a decrease in cohesive force and excessive fluidity.On the other hand, as a result of low molecular weight components exhibiting heat meltability, they are heat melted at low temperatures, but even at high temperatures they prevent a decrease in cohesive force and excessive fluidity. It is thought that it exhibits excellent thermal melting properties that suppress flow. In the present invention, a polymer in which low molecular weight components to highly crosslinked components are uniformly mixed is:
This means that when a toner is prepared using it, there is virtually no reduction in image density or fog due to repeated use, which occurs when a non-uniformly mixed polymer is used.

Regarding pulverization, the polymer region components other than the crosslinked region give the composition toughness, while the crosslinked region components give it brittleness, and the low molecular weight region components make it easier to crush, thereby improving the overall strength of the composition. It is thought that the grinding characteristics necessary to improve production efficiency are generated.

Furthermore, the binder resin contains a polyester resin consisting of a condensate of a polybasic acid component and a polyhydric alcohol component, and the vinyl copolymer contains a carboxylic acid group that can be anhydrated in the molecule. By reacting the toner with a metal compound and crosslinking it, a toner with excellent anti-offset properties, anti-blocking properties, and fixing properties can be obtained.

In particular, when used as a negatively charged toner, acid anhydration (
(not involved in crosslinking), it is possible to obtain sufficient charging ability as a toner, less environmental dependence, and good development characteristics.

Claims (3)

[Claims] (1) A toner containing at least a binder resin, a colorant, and a metal compound, wherein the binder resin is a vinyl copolymer made of a copolymer of a monomer having at least a carboxylic acid group and another copolymerizable monomer. Consisting of a polyester resin consisting of a polymer, a condensation polymer of a polybasic acid component and a polyhydric alcohol component, the THF-insoluble content is 5 to 50% by weight, and the molecular weight distribution in the THF-soluble content is 2,000 to 20,000.
The vinyl copolymer has a peak in the molecular weight region of 2,000 to 15,000 in the GPC molecular weight distribution of the THF-soluble portion with a THF-insoluble content of less than 5% by weight. A vinyl copolymer (A) having at least one of and a vinyl copolymer (B) having at least one vinyl copolymer (A) in the binder resin.
, vinyl copolymer (B) and polyester resin (C)
The weight ratio is (A):(B):(C)=0~40:20~
A toner for developing electrostatic images characterized by having a ratio of 80:5 to 40. (2) The binder resin is mixed with vinyl copolymer (B) in the presence of vinyl copolymer (A) and polyester resin (C).
2. The toner for developing an electrostatic image according to claim 1, wherein the toner is synthesized by polymerizing a monomer forming a monomer. (3) The toner for developing an electrostatic image according to claim (1), wherein a metal complex is used as the metal compound.