JPH0338651A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To provide the toner which is fixed at a low temp. and does not generate the fusing and filming to a photosensitive body even in a high-speed system and in long-time using by using a binder resin which is obtd. by polymerizing a vinyl monomer cong. >=2 kinds of polymn. initiators which are different in half-life and having specific properties. CONSTITUTION:The vinyl monomer is polymerized by incorporating the >=2 kinds of the polymn. initiators which are different in the half-like having 1.5 to 5 ratio of the half-life at 70 deg.C of the polymn. initiator having the longest half-life and the polymn. initiator having the shortest half-life therein. The reaction time is shortened by using >=2 kinds of the polymn. initiators in such a manner. Further, the THF insoluble component of the binder resin is incorporated in the toner at 10 to 60wt.% and further the THF soluble component is required to be Mw/Mn >=5. The offset resistance is degraded when Mw/Mn is below 5. The ratio of the component of <=10,000mol.wt. in the binder resin is preferably 10 to 50wt.%, more preferably 20 to 39wt.%.

Description

Detailed Description of the Invention [Field of Application in Industry A] The present invention relates to a toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. The present invention relates to a toner for developing electrostatic images suitable for fixed application on a roller.

[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. A constant electric latent image is formed on the photoreceptor by a method, and then the latent image is developed using a toner, and if necessary, the toner image is transferred to a transfer material such as paper, and then heated, pressured, heated and pressed, or Copies are obtained by fixing with solvent vapor, and the toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above-mentioned steps are repeated.

In recent years, such copying devices have begun to be used not only as office copy machines for copying original manuscripts, but also as computer output printers and personal copiers for individuals.

Therefore, smaller size, lighter weight, higher speed, and higher reliability are being strictly pursued, and machines are being constructed from simpler elements in various respects. As a result, the performance required of toner has become more advanced, and it has become impossible to create better machines unless the performance of toner can be improved.

For example, various methods and apparatuses have been developed for the process of fixing a toner image on a sheet such as paper, but the most common method at present is a compression heating method using a heated roller.

The pressure heating method using a heating roller performs fixing by passing the toner image surface of the sheet to be fixed under pressure while contacting the surface of a heating roller whose surface is made of a material that has releasability for 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. It is 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 portion 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 resin, and the surface was also coated with anti-offset and roller surface coatings. In order to prevent fatigue, the roller surface 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, so it has problems such as making the fixing device complicated. .

This is in the opposite direction to miniaturization and weight reduction, and what's more, silicone oil and other substances may evaporate due to heat and contaminate the interior of the aircraft. Therefore, instead of using a silicone oil supply device, we proposed a method of adding a release agent such as low molecular weight polyethylene or low molecular weight polypropylene to the toner, with the idea of supplying an anti-offset liquid from within the toner during heating. has been done. If a large amount of such additives is added in order to obtain a sufficient effect, it may cause filming on the photoreceptor or contaminate the surface of a toner carrier such as a carrier or sleeve, deteriorating the image and causing practical problems. Therefore, a small amount of release agent is added to the toner to the extent that the image does not deteriorate, and a device that cleans the toner by supplying a small amount of release oil or using a device such as a web to take up the offset toner. They are used together.

However, in view of recent demands for smaller size, lighter weight, and higher reliability, it is necessary and desirable to eliminate even these auxiliary devices. Therefore, it is difficult to meet the demands without further improving the performance of toner fixing, offset, etc., and it is difficult to achieve this without further improving the binder resin of the toner. As a technique for improving the binder resin of a toner, for example, Japanese Patent Publication No. 51-23354 proposes a toner using a crosslinked polymer as a binder resin. If this method is followed, it will be effective in improving offset resistance and clinging resistance, but on the other hand, if the degree of crosslinking is increased, the fixing point will rise, and the fixing temperature will be sufficiently low, resulting in good offset resistance and clinging resistance. However, no one with sufficient fixing properties has been obtained. Generally, in order to improve fixing properties, it is necessary to lower the softening point by lowering the molecular weight of the binder resin, which is contradictory to measures to improve offset resistance. Inevitably, the glass transition point of the resin decreases, and the undesirable phenomenon of blocking of the toner during storage also occurs.

In contrast, JP-A-56-158340 proposes a toner made of a low molecular weight polymer and polymer 2, but this binder resin cannot actually contain a crosslinking component. However, in order to improve offset resistance with higher performance, it is necessary to increase the molecular weight or ratio of the high molecular weight polymer. This method significantly reduces the crushability, and it is difficult to obtain a product that is practically satisfactory. Further, regarding toners containing a blend of a low molecular weight polymer and a crosslinked polymer, for example, JP-A-58-88
No. 558 proposes a toner containing a low molecular weight polymer and an infusible high molecular weight polymer as main resin components. If the method is followed, fixing properties and crushability tend to be improved, but the weight average molecular weight/number average molecular weight (Mw/Mn) of the low molecular weight polymer is as small as 3.5 or less, and the insoluble and infusible Due to the large content of high molecular weight polymer, 40 to 9 Qwt%, it is difficult to satisfy both offset resistance and crushability with high performance, and in practice, fixing devices equipped with a supply device for anti-offset liquid are difficult to achieve. Unless one is skilled, it is extremely difficult to produce a toner that fully satisfies fixing properties (especially high-speed fixing), offset resistance, and crushability.

Furthermore, if there is a large amount of insoluble, infusible high molecular weight polymer, the melt viscosity will become extremely high during heat kneading during toner production, so it must be heat kneaded at a much higher temperature than usual, or heat kneaded at a high shear. As a result, the former has the problem of deterioration of toner properties due to thermal decomposition of other additives, and the latter has the problem that the molecules of the binder resin are excessively cut, making it difficult to achieve the original offset resistance performance.

Furthermore, in JP-A-80-188958, a low molecular weight polyalpha-
A toner comprising a resin composition obtained by polymerization in the presence of methylstyrene has been proposed.

In particular, in this publication, the number average molecular weight (Mn) is from 9,000 to
It is said that a range of 30.000 is preferable, but if Mn is increased in order to further improve offset resistance, fixing performance and pulverization during toner production become a practical problem. Sexual satisfaction is difficult. In this way, a toner with poor crushability during toner production is not preferable because it reduces the production efficiency during toner production, and also because the toner has rough toner properties and tends to be easily pulverized, resulting in uneven images.

In addition, JP-A-56-16144 discloses that a binder resin component having at least one maximum value in each region of molecular weight 103 to 8 x 10' and molecular weight 105 to 2 x 10' in the molecular weight distribution by GPC is disclosed. toner is suggested. In this case, the toner has excellent crushability, anti-offset properties, fixing properties, buoy 2 lemming and fusion 1 image properties on the photoreceptor, but there is a demand for further improvements in the anti-offset properties and fixing properties of the toner. In particular, it is difficult for such resins to meet today's strict demands while maintaining or improving various other properties by further improving fixing properties.

Further, as a problem in the production of the binder, if a large amount of unreacted J# total polymer remains in the binder even after the polymerization is completed, blocking properties and offset properties, which are characteristics of the toner, may be adversely affected. In order to solve this problem of workability during binder production, Japanese Patent Application Laid-Open No. 58-37651 discloses that among polymerization initiators with different half-lives of 2 fffi or more, polymerization initiator A has the longest half-life and polymerization initiator A has the shortest half-life. The half-life τA/τB ratio of initiator B at 70°C is lO~t
A proposal has been made for a vinyl resin for toners obtained by polymerization in which a polymerization initiator, i.e., o', is present from the initial stage of polymerization.

This method attempts to produce a resin having good toner properties by controlling the concentration of active species in the reaction initiator during the polymerization process. however,
Depending on the polymerization salinity, a polymerization initiator with a long half-life tends to remain, which is unfavorable in terms of toner properties. Furthermore, it takes a long time to decompose the material to a level that poses no practical problems, resulting in poor production efficiency.

Another drawback is that at polymerization temperatures suitable for decomposing polymerization initiators with long half-lives, polymerization initiators with short half-lives decompose too quickly, making it difficult to obtain the desired molecular weight distribution.

As described above, it is extremely difficult to achieve high performance in terms of fixing performance, crushability, and workability during manufacturing. Grindability during toner production is an important factor as toner particle sizes are becoming smaller today due to the demand for higher quality, higher resolution, and fine line reproducibility of copied images. Since grinding 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 is more likely to occur with toner having good fixing performance, which impairs 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. Nowadays, cleaning using a blade (blade cleaning) has become common in view of the miniaturization, weight reduction, and reliability of devices. 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 adhesion resistance and filming resistance for 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 the various performances required of toners are therefore becoming more sophisticated.

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.

As shown in the attached Figure 7, the various performances required of toner are often contradictory, and although it is increasingly desired and researched to satisfy both of them with high performance, there is still insufficient performance. There's nothing.

[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.

It is an object of the present invention to provide a toner suitable for a hot roll fixing method without applying oil.

An object of the present invention is to provide a toner suitable for a cleaning method using a blade.

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,
It is an object of the present invention to provide a toner that does not cause filming even in high-speed systems and even after long-term use.

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner that can be fixed at low temperatures, has excellent anti-blocking properties, and can be used satisfactorily even in high-temperature atmospheres, especially in small machines.

An object of the present invention is to provide a toner that can be efficiently and continuously produced because it is fixed at a low temperature and the pulverized material does not fuse to the inner wall of an apparatus during the pulverization process during toner production.

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

An object of the present invention is to provide a toner that has excellent anti-offset properties, does not contain an unnecessarily large amount of tetrahydrofuran (Tl(F) insoluble matter), and does not undergo alteration or deterioration during the toner heat kneading process.

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 for developing electrostatic images having at least a binder resin and a colorant, in which the binder resin contains: i) 2 fffi or more polymerization initiators having different half-lives; ii) The binder resin contains 10 to 80% by weight (based on the binder resin) of THF-insoluble content, and the TI (F-soluble content) of the binder resin. In the molecular weight distribution by GPC, weight average molecular weight/number average molecular weight (Mw/Mn)≧
5, has at least one peak in the molecular weight region of 2,000 to 10,000, and has a molecular fi of 15,000
At least 1 peak or shoulder in the region of ~100.000
The toner for developing an electrostatic image is characterized in that the binder resin contains 10 to 50% by weight of a component having a molecular weight of 10,000 or less.

The present invention will be explained in detail below.

When the binder resin is dissolved in a solvent such as TIIF, 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. T) Focusing on the position of the peak of the molecular weight distribution of the IF-insoluble matter and the THF-soluble matter, the relationship between the position and the crushability is as shown in FIG. From now on T)
A system with no or a small amount of IF-insoluble matter is very disadvantageous in terms of grindability, and as mentioned above, in order to improve the grindability, T) simply change the peak position of the molecular weight distribution of the IF-soluble matter to the low molecular weight position. This proves that the direction in which the particles are shifted to 100% decreases the offset resistance, and it is difficult to satisfy both the offset resistance and the crushability.

From this study, it has been found that it is very effective to include a specific amount of T)IF insoluble matter not only for the purpose of anti-offset properties, as is generally 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, for example, as shown in FIG. 9, it was found that components having a molecular weight of about io, ooo or less and a component having a molecular weight of about 10,000 or more have different functions in the GPC molecular weight distribution.

That is, the molecular weight of the entire binder resin is 10,00
The content ratio of components with a molecular weight of 0 or less does not strongly affect fixing properties or anti-offset properties as is usually said, but rather has little to do with it within a certain range, and instead affects crushability. It turned out that they are strongly related.

Furthermore, other studies have shown that the THF-insoluble content of binder resins mainly affects offset resistance, clinging properties, and crushability, and that the THF-soluble content has a molecular weight of 10.0%.
The components below 00 mainly affect the crushing property, blocking property, adhesion to the photoreceptor, filming property, and adhesion to the inner wall of the grinding device, and the molecular weight of the THF-soluble component to,
It has been found that components of ooo or higher mainly affect fixing properties. The proportion of components with a molecular weight of 10,000 or less is preferably 10 to 50 wt%, preferably 20 to 39 wt%.
%. In order to achieve sufficient performance, the molecule 51
10.000 or less and 2.000 or more (preferably 2.000 or more
,000 to 8,000''), and a peak or shoulder in the region of molecule ff115,000 to 100,000 (preferably 20,000 to T0,000).2,000 to There is no peak at 10.000 and a peak at molecular weight 2.000 or less, but the molecule f
If the proportion of components having an i of 10.000 or less exceeds 50 vt%, problems such as blocking resistance, adhesion to the photoreceptor, filming, and adhesion to the inner wall of the grinding device will arise. There is no peak at molecular weights below 10,000, and there are peaks at molecular weights above 10,000. However, if the proportion of components with molecular weights below 10,000 is less than 10 wt%, grindability becomes a problem, and the formation of coarse particles also becomes a problem. Become.

Further, if there is no peak or shoulder in the region where the molecular fi is 15,000 or more, and there is a peak only in the region where the molecular weight is 15,000 or less, offset resistance becomes a problem. Molecular weight 1
If there is no peak or shoulder in the region of 5,000 to too, ooo, and there is a main peak above too, ooo, the crushability becomes a problem.

Furthermore, it is necessary that the TIIF soluble content satisfies Mw/Mn≧5, and when Mw/Mn is less than 5, the offset resistance tends to decrease, which becomes a problem.

Preferably, Mw/Mn is 80 or less, and more preferably 10≦My/Mn≦80.

In particular, when Mw/Mn satisfies lO≦Mw/Mn≦80, the crushability is improved.

It exhibits particularly excellent performance in various properties such as fixing properties, offset resistance, and image quality.

Note that here, Mw is a weight average molecular weight measured by GPC described below, and Mn is a number average molecular weight measured by a similar measurement.

Further, the THF-insoluble content of the binder resin of the toner is required to be 10 to 80 wt%. THF insoluble content is 10
If it is less than wt%, offset resistance becomes a problem, and 80wt
If it exceeds %, problems of deterioration such as molecular chain scission due to thermal kneading during toner production may occur. Preferably, the content of the THF-insoluble matter is 15 to 49 wt%, which is good in terms of crushability and offset resistance.

Also, when comparing the glass transition point Tgl of the resin with a molecular weight of 10,000 or less in the molecular weight distribution of the TIIF soluble component and the glass transition point Tgt of the entire toner, if the relationship of Tg+≧Tgt is 5, the fixing property, crushability, photosensitivity The adhesion to the body, the filming property, the adhesion to the inner wall of the crushing device, the blocking resistance, etc. are improved.

In order to solve the problem of workability during production, we investigated the half-life at 70°C of two or more polymerization initiators with different half-lives, the one with the longest half-life (■) and the one with the shortest half-life (■).
, τ■ A polymerization initiator having a ratio τ■/T■ of 1.5 to 5 is contained to polymerize the vinyl monomer. Here, by setting an appropriate polymerization temperature for the polymerization initiator with the shortest half-life, it is possible to control the amount of polymerization initiator during the polymerization process, especially after the middle stage of polymerization, and a toner with good properties can be obtained. can get.

It is also good to slightly increase the polymerization temperature at the final stage of polymerization.

On the other hand, if it is larger than 5, the polymerization initiator with the longest half-life tends to remain, and not only is there no effect when used in combination, but the remaining polymerization initiator may cause adverse effects on toner properties, which is not preferable. Moreover, if it is less than 1.5, the combined effect will be small. The ratio of the amount of the polymerization initiator ■ with the longest half-life to the polymerization initiator ■ with the shortest half-life, ■/■, is 0.1-
1.0 is preferred.

Furthermore, it has been found that the reaction time can be shortened by using two or more types of polymerization initiators according to the present invention. This makes effective use of the reaction vessel, is very effective in production, and is advantageous in terms of cost.

Here, as the polymerization initiator used, a normal oil-soluble initiator is used in combination, for example,
Butyl peroxide, tert-butyl peroxybenzoate, benzoyl peroxide, 2.27-azobisisobutyronitrile, 2.2'-azobis(2,
(4dimethylvaleronitrile), tert-butylperoxyisobutyrate, and the like.

Tg+ here is measured by the following method. THF was flowed at a flow rate of 7 mN per minute at a temperature of 25°C, and the concentration of THF-soluble components in the toner was approximately 3 mg/ml.
About 3 ml of THF sample solution is injected into a molecular weight distribution measuring device, and components with a molecular weight of 10,000 or less are fractionated. After separation,
The solvent is distilled off under reduced pressure, and the mixture is further dried at 90° C. under reduced pressure for 24 hours. The above operation is repeated until about 20B of components with a molecular weight of 10,000 or less are obtained, and annealing is performed at 50° C. for 48 hours. Thereafter, Tg is measured by differential scanning calorimetry, and this value is defined as Tg+.

TSKgel G20001 (,
TSKgelG2500)1. TSKgel G30
00H, TSKgel G4000H (both manufactured by Toyo Soda Kogyo ■), etc., but in the present invention, TSKgel G
2000H and TSKgel G3000H were used in combination.

Also, the value of Tgt, which is the Tg of the toner, is when the toner is heated at 50°C.
Annealed for 48 hours and then determined by differential scanning calorimetry.

The most preferred embodiment of the present invention is as shown in FIG.
In the GPC molecular weight distribution of the HF soluble fraction, the molecular weight was 15,
If the height of the highest peak in the region of 000 to ioo, ooo is 65, and the height of the highest peak in the region of molecular weight 2,000 to 10,000 is hl, then the ratio of h+/h2 is 0.4/ 1-4. This is a toner containing a binder resin having a ratio of Q/1. In addition, TI (for the number average molecular weight of the F soluble fraction, 2,000≦Mn≦9,000
is preferred. When Mn<2,000, offset properties become a problem, and when 9,000<Mn, pulverization properties and fixing properties become problems.

The TIIF-insoluble content in the present invention refers to the weight percentage of the polymer component (substantially crosslinked polymer) that has become insoluble in the T)IF solvent in the resin composition in the toner, and refers to the weight percentage of the polymer component (substantially crosslinked polymer) in the resin composition in the toner. It can be used as a parameter to indicate the degree of crosslinking of a substance. The THF-insoluble content is defined by the value measured as follows.

That is, a toner sample of 0.5 to 1.0 g with a molecular weight of Lg) and a thimble filter paper (for example, Toyo Roshi No. 86R)
) in a Soxhlet extractor and TH as a solvent.
After extracting for 6 hours using F 100-200mj+ and evaporating the soluble components extracted with the solvent, 1
Vacuum dry at 00°C for several hours and weigh the amount of TI (F soluble resin component (Lg). Let the weight of components other than the resin component such as magnetic material or pigment in the toner be (Lg).THF
The insoluble content is calculated from the following formula.

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.

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 rnR per minute, and 50 to 200 μg of a THF sample solution of the resin adjusted to a sample concentration of 0.05 to 0.6% by weight is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithm of a calibration curve prepared using several types of monodisperse boristyrene standard samples and the number of counts. Standard polystyrene samples for creating a calibration curve include, for example, Pressure Chemical Co.
manufactured by Toyo Sodani Gyo Co., Ltd. with a molecular weight of 6 x 102
．． 2. IX 10', 4 X 10', 1.75
X 10'.

5, I X 10' 1. IX 10' 3.9X
10' 8.8X 10'2 X 10', 4.
It is appropriate to use a standard polystyrene sample of 48 x 10' and at least the IO point. Further, an R1 (refractive index) detector is used as a detector.

In addition, as a column, in order to accurately measure the molecular weight region of 103 to 2 x 10', it is recommended to combine a plurality of commercially available polystyrene gel columns, such as Waters
μm Styragal 500.10', 10
', 10' combination, 5hod manufactured by Showa Denko
ex KF-80M, KF-802, 803, 804
, 805 combination, or TSKgel manufactured by Toyo Soda
G100OH, G2000H, G2500H.

G3000H, G4000H, G5000H, G800
A combination of 0H, G700OH, GM)I is preferred.

The weight percent of the binder resin of the present invention having a molecular weight of 10,000 or less is the molecular weight to
.

The resin composition in the toner of the present invention is preferably one obtained by polymerizing one or more monomers selected from styrenes, acrylic acids, methacrylic acids, and derivatives thereof from the viewpoint of development characteristics, charging characteristics, and the like. Examples of monomers that can be used include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, and the like.

Acrylic acids, methacrylic acids and their derivatives include acrylic acid, methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, n acrylate
- Acrylic acid esters such as -tetradecyl, n-hexadecyl acrylate, lauryl acrylate, cyclohexyl acrylate, diethylaminoethyl acrylate, and dimethylaminoethyl acrylate, as well as methacrylic acid, methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-methacrylate
Ethylhexyl, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-methacrylate
Examples include methacrylic acid esters such as -hydroxypropyl, dimethylaminoethyl methacrylate, glycidyl methacrylate, and stearyl methacrylate. In addition to the above-mentioned monomers, small amounts of other monomers can be used to achieve the objectives of the invention, such as acrylonitrile, 2-vinylpyridine, 4-vinylpyridine, vinyl carbazole, vinyl methyl ether, butadiene, isoprene, maleic anhydride.

Maleic acid, maleic monoesters, maleic diesters, vinyl acetate, etc. may also be used.

Examples of crosslinking agents used in the toner of the present invention include divinylbenzene, bis(4-acryloxypolyethoxyphenyl)propane, ethylene glycol diacrylate, and 1.3-butylene glycol diacrylate as bifunctional crosslinking agents. -butanediol diacrylate,
1.5-bentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol #20G, #400. #800 each diacrylate.

Examples include dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester diacrylate (MANDA Nippon Kayaku), and methacrylates obtained by replacing the above acrylates with methacrylates.

As polyfunctional crosslinking agents, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis(4-methacryloxy, polyethoxyphenyl) Propane, diallyl phthalate, triallyl cyanurate, triallyl asocyanurate, triallyl isocyanurate.

Examples include triallyl trimellitate and diarylchlorendate.

The method for synthesizing the binder resin according to the present invention basically consists of two steps.
f! A method of synthesizing a polymer of II or higher is preferred.

That is, T) A first polymer that is soluble in IF and soluble in a polymerization monomer is dissolved in a polymerization monomer, and the monomer is polymerized to obtain a resin composition.

In this case, a composition is formed in which the former and latter polymers are uniformly mixed.

T) The first polymer soluble in IF is preferably subjected to solution polymerization or ionic polymerization, and the second polymer for producing a component insoluble in THF is obtained by dissolving the first polymer. It is synthesized by suspension polymerization or bulk polymerization in the presence of two or more types of crosslinking monomers and polymerization initiators under the following conditions. The amount of the first polymer is 10 to 120 (preferably 2
It is preferable to use 0 to 100 parts by weight.

FIG. 2 of the accompanying drawings shows a GPC chart of the THF-soluble content of the resin composition obtained in Synthesis Example 1, which will be described later.

FIG. 3 shows a GPC chart of polystyrene prepared by solution polymerization, which is the first polymerization. The polystyrene was soluble in T)IP, soluble in styrene monomer and n-butyl acrylate monomer as polymerization monomers, and had a main peak at a molecular weight of 3,500.

Figure 4 shows the styrene-acrylic acid n-
This figure shows a GPC chart of the THF-soluble portion of a butyl copolymer produced by suspension polymerization. The styrene-n-butyl acrylate copolymer had a main peak at molecule i40,000.

FIG. 5 is a combination of the chart in FIG. 3 and the chart in FIG. 4.

FIG. 6 shows a combination of the chart in FIG. 2 and the chart in FIG. 5 (where solid lines are indicated by broken lines).As is clear from FIG. The resin composition obtained had a GPC chart different from that of a mixture of separately polymerized polystyrene and styrene-n-butyl acrylate copolymer.In particular, on the high molecular weight side, styrene- It is found that a high molecular weight component, which was not formed when the n-butyl acrylate copolymer was used alone, is produced.This high molecular weight component is added to the first stage during suspension polymerization, which is the second stage of polymerization. Since the polystyrene prepared by the solution polymerization in the step is present, the polystyrene acts like a polymerization regulator, and as a result, the THF-insoluble portion of the styrene-n-butyl acrylate copolymer and the TIIF-soluble portion are separated. The resin composition of the present invention has a uniform composition in which THF-insoluble components, TIIF-soluble high-molecular-weight components, THF-soluble intermediate-molecular-weight components, and TI(F-soluble low-molecular-weight components) are uniformly adjusted. Further, the resin composition according to the present invention generates a new peak in the region of molecular weight of 300,000 or more (preferably 500,000 or more) due to molecular chain scission during the melt-kneading process during toner production. Therefore, it has the ability to adjust the fixing properties and anti-offset properties of the toner.

Furthermore, in the present invention, GPC of the THF soluble portion of the toner
The component having a molecular weight of 300,000 or more is 5 to 30% by weight (preferably 10 to 30% by weight) based on the binder resin.
) is better. Further, in the GPC of the T)IF soluble toner, those having a clear peak at a molecular weight of 300,000 or more (preferably 500,000 or more) are preferred from the standpoint of improving offset resistance and wrapping resistance.

As the charge control agent used in the toner of the present invention, a conventionally known positive or negative charge control agent can be used. Charge control agents known in the art today include the following:

(1) The following substances can be used to control positively charged C of toner.

Nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), basic dyes (e.g. C,1, Ba5ic Yellow 2 (C,1,
41000), C, 1, Ba5ic Yellow 3
,C,1,Ba5ic Red 1 (C,I.

4516G), C,1,Ba5ic Red 9 (C
, 1,42500), C,I.

Ba5ic Violet 1 (C, 1, 42S35)
,C,1,Ba5ic Violet3 (C,1,4
2555), C,i Ba5ic Violet 1
0 (C, I.

45170), C, 1, Ba5ic Violet 1
4 (C,1,42510) ・C,1,Ba5ic
Blue 1 (C, 1, 42025), C, 1, Ba
5icBlue 3 (C, 1, 51005), C,
1, Ba5ic Blue 5 (C, 1°42140
), C,1,Ba5ic Blue 7 (C,1,4
2595), c, r.

Ba5ic Blue 9 (C, 1, 52015),
C, 1, Ba5ic Blue 24 (C, r, 520
30), 1. Ba5ic Blue25 (C,
1,52025), [:, 1. Ba5ic Blue
28 (C,1,44025), C,1,Ba5ic
Green 1 (C, 1, 42040), C, 1, B
a5ic Green 4 (C, I.

42,000), these basic dye lake pigments (
Phosphortungstic acid is used as a lake agent.

Phosphormolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide,
ferrocyanide, etc.), C, I.

5ovent Black 3 (C, 1, 26150
), Hansa Yellow G (C, 1, 11680), C,
1, Mordlant Black 11. C,I,
Pigment Black 1st prize.

Or, for example, pencil methyl-hexadecyl ammonium chloride, decyl-trimethyl ammonium chloride, dialkyltin compounds such as dibutyl and dioctyl, metal salts of higher fatty acids, inorganic fine powders such as glass, mica, and zinc oxide, EDT^, and acetylacetone. Polyamine resins such as metal complex rings, vinyl polymers containing amine groups, and condensation polymers containing amino groups.

In particular, from the viewpoint of dispersibility, nigrosine, metal salts of higher fatty acids, vinyl polymers having amino groups, and the like are preferred.

(2) The following substances can be used to control the negative chargeability of toner. Special Publication No. 41-20153, No. 42-2759
Examples include metal complex salts of monoazo dyes described in No. 6, No. 44-6397, and No. 45-26478.

Dyes and pigments such as nitrofumic acid and its salts or C,1,14645 described in JP-A No. 50-133338, JP-B No. 55-42752, JP-B No. 58-4150
No. 8, Special Publication No. 58-7384, Special Publication No. 59-7311
Zn, Aj), Go, Cr, F of salicylic acid, naphthoic acid, dicarboxylic acid described in No. 4 etc.
metal complexes such as e, sulfonated copper phthalocyanine pigments, nitrile groups, halogen-introduced styrene oligomers, chlorinated paraffins, etc. In particular, from the viewpoint of dispersibility, metal complexes of monoazo dyes, metal complexes of salicylic acid, alkylsalicylic acid, naphthoic acid, and guicarboxylic acid are preferred.

Good results can be obtained with the toner of the present invention even when additives are mixed therein as required. Examples of 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, among which strontium titanate is preferred. Alternatively, fluidity imparting agents such as colloidal silica and aluminum oxide are particularly preferred, especially hydrophobic colloidal silica. Examples include anti-caking agents, conductivity imparting agents such as carbon black, zinc oxide, antimony oxide and tin oxide, fixing aids such as low molecular weight polyethylene, low molecular weight polypropylene and various waxes, and anti-offset agents. Further, a small amount of white fine particles and black fine particles of opposite polarity can be used as a developing property improving agent.

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

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

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 oxide such as magnetite, hematite, and ferrite, or a compound of divalent metal and iron oxide: iron;
cobalt.

Metals like nickel or these metals aluminum, cobalt, lead, magnesium, tin, zinc, antimony, beryllium, bismuth.

cadmium, calcium, manganese, selenium, titanium,
Examples include alloys of metals such as tungsten and vanadium, and mixtures thereof.

These ferromagnetic materials preferably have an average particle size of about 0.1 to 2 μm, preferably about 0.1 to 0.5 μm, and are particularly preferably spherical. The amount to be contained in the toner is approximately 20 to 200 parts by weight per 100 parts by weight of the resin component, particularly preferably 40 to 180 parts by weight per 100 parts by weight of the resin component.
Good weight section.

Furthermore, a coloring agent may be added to the toner of the present invention if necessary.

Any suitable pigment or dye can be used as the colorant used in the toner of the present invention. Toner colorants are well known and include pigments such as carbon black, aniline black, acetylene black, naphthol yellow,
Hansa yellow.

Examples include rhodamine lake, alizarin lake, red iron, phthalocyanine blue, and indan strenblue.

These are used in an amount necessary and sufficient to maintain the optical density of the fixed image, and should be added in an amount of 0.1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 10 parts by weight of the resin. Further, dyes are also used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthine dyes, methine dyes, etc. 0.1 to 20% per 100 parts by weight of resin.
The addition amount is preferably 0.3 to affi parts by weight.

To prepare the toner for developing an electrostatic image according to the present invention, the resin composition and charge control agent according to the present invention, if necessary, a magnetic material, a pigment or dye as a coloring agent, additives, etc. are mixed in a ball mill or other machine. Pigments or dyes are dispersed or dissolved in the mixture, which is thoroughly mixed with a mixer and then melted, kneaded, and kneaded using a heat kneader such as a heated roll, kneader, or extruder to make the resins compatible with each other. After cooling and solidifying, the toner is crushed and classified to obtain a toner having an average particle size of 3 to 20 μm.

The present invention will be specifically explained below with reference to Examples, but this is not intended to limit the present invention in any way, and the numbers in the following formulations are parts by weight.

(Left below) [Example] 200 parts of cumene was placed in a 1-skin reactor, and the temperature was raised to reflux temperature. To this was added 100 parts of styrene monomer and
A mixture of 8 parts of butyl peroxide was added to 4 parts of cumene under reflux.
It dripped over time. Furthermore, under reflux of cumene (146°C
The polymerization was completed overnight at ~156°C) and the cumene was removed. The obtained polystyrene is soluble in THF and has a Mw
= 3.700, Mw/Mn = 2.64° The molecular weight where the main beak of GPC is located is 3.500° Tg = 57
It was ℃. A GPC chart of the polystyrene is shown in FIG.

Dissolve 30 parts of the above polystyrene in the following monomer mixture,
A combined solution was obtained. te■/τ■ is approximately 1.8.

Add 0% of the partially saponified polyvinyl alcohol to the above mixed solution.
170 parts of water in which 1 part was dissolved was added to form a suspension dispersion. The above is in a reactor filled with 15 parts of water and replaced with nitrogen! ! ! ! A turbid dispersion was prepared, and a suspension polymerization reaction was carried out at a reaction temperature of 70 to 95°C for 5 hours. After the reaction was completed, the mixture was separated, dehydrated, and dried to obtain a composition of polystyrene and styrene-n-butyl acrylate copolymer. In the composition, THF-insoluble and THF-soluble components were uniformly mixed, and polystyrene and styrene-n-butyl acrylate copolymer were uniformly mixed. THF-insoluble portion of the obtained resin composition (24 mesh passes).

Y measured with 80 mesh powder was 40 wt%. Furthermore, when we measured the molecular weight distribution of THF-soluble components, G
In the PC chart, peaks are at approximately 4,000 and 3,500,000, Mn = 0,560,000, Mw = 140,000 M
w/Mn = 25 + molecular weight of 10,000 or less was 21 wt%.

Furthermore, the Tg of the resin is 59°C, and the glass transition point Tg1 of the components of 10,000 or less separated by GPC is 57°.
It was C.

A GPC chromatogram of the THF-soluble fraction is shown in FIG.

In addition, the characteristics related to the molecular weight of each resin and resin composition were measured by the following method.

5hodex KF-80M as a column for GPC measurement
using a GPC measuring device (150c manufactured by Waters)
ALC/GPC) was installed in a 40°C heat chamber with a THF flow rate of 1 mJ/min and a detector under RI conditions.
GPC was measured by injecting p#. The calibration curve for molecular weight measurement is molecular weight 0.5 XIO3,2,35XIO
', 10.2 XIO3゜35x103.110x1
03.200xlO", 470xlO", 1200x
10”, 2700 xlO”, 8420 xlO3
A THF solution of 10 monodispersed polystyrene reference materials (manufactured by Waters) was used.

30 parts of polystyrene obtained in Synthesis Example 1 was dissolved in the following monomer mixture to prepare a mixed solution.

The above mixture was subjected to suspension polymerization in the same manner as in Synthesis Example 1 to obtain a composition of polystyrene and styrene-n-butyl acrylate copolymer. The THF-insoluble content of this resin composition is 75
% by weight, and contained a large amount of THF-insoluble matter.

Ecology J-L Salmon 1 30 parts of polystyrene obtained in Synthesis Example 1 was dissolved in the following monomer mixture to prepare a mixed solution. τ■/te■ is approximately 1.
It is 8.

The above mixture was subjected to suspension polymerization in the same manner as in Synthesis Example 1 to obtain a composition of polystyrene and styrene-n-butyl acrylate copolymer. GPC of THF soluble components of this composition
There were peaks at molecular weights of approximately 4,000 and 150,000.

150 parts of xylene was placed in a soybean paste reactor and the temperature was raised to reflux temperature. A mixture of 100 parts of styrene monomer, 2 parts of tert-butyl peroxybenzoate, and 1 part of di-tert-butyl peroxide was added dropwise to the mixture over 4 hours under reflux of xylene. Furthermore, under reflux of xylene (138-1
Solution polymerization was completed at 44°C) and xylene was removed.

The obtained polystyrene is soluble in THF and Mw=
10.000, Mw/Mn = 3.22. Molecular weight 11
There was a main peak at the position of ,000, and Tg=82°C.

Dissolve 30 parts of the above polystyrene in the following monomer mixture,
A mixed solution was prepared. τ■/τ■ is approximately 1.8.

The above mixture was subjected to suspension polymerization in the same manner as in Synthesis Example 1 to obtain a composition of polystyrene and styrene-n-butyl acrylate copolymer. GP of the TIIF soluble component of this composition
In C, there was substantially no peak at a molecular weight of about 10.000 or less.

L Kozu Onitate A 170 parts of water in which 0.1 part of partially saponified polyvinyl alcohol was dissolved was added to the following monomer mixture to prepare a suspension dispersion. τ■/τ■ is approximately 1.8.

(Left below) The above dispersion was added to a reactor containing 15 parts of water and purged with nitrogen, and a suspension polymerization reaction was carried out at a reaction temperature of 70 to 95°C for 5 hours. After the reaction was completed, the mixture was dehydrated and dried to obtain a styrene-n-butyl acrylate copolymer.

This copolymer has a main peak with a molecular weight of approximately 17.000.
There was virtually no peak at a molecular weight of 10,000 or less.

150 parts of cumene was placed in a reactor and heated to reflux temperature. The following mixture was added dropwise to the cumene over 4 hours under reflux.

Furthermore, polymerization was completed under cumene reflux (146 to 156°C), and cumene was removed. The obtained styrene-n-butyl acrylate copolymer had Mw=6,900, Mw/M
It had a main peak at n = 2.3, molecular weight 7.100, and Tg = 80°C.

40 parts of the above styrene-n-butyl acrylate copolymer was dissolved in the following monomer mixture to form a mixture. τ■／τ■
is approximately 1.8.

Add 0.1% of partially saponified polyvinyl alcohol to the above mixture.
170 parts of water was added to prepare a suspension and dispersion.

The above dispersion was added to a reactor containing 15 parts of water and purged with nitrogen, and reacted at a reaction temperature of 70 to 95°C for 5 hours. After the reaction is completed, it is separated in a furnace, dehydrated and dried, and the styrene-acrylic acid n-
A composition of a butyl copolymer and a styrene-n-butyl methacrylate copolymer was obtained.

200 parts of cumene was placed in the main reactor and heated to reflux temperature. The following mixture was evaporated under cumene reflux for 4 hours.

Polymerization was completed under roughly cumene reflux (146-156°C) and cumene was removed. The obtained polystyrene has Mw
=3,700, Mw/Mn=2.64, molecular weight 3.5
It had a main peak at 00, and Tg=57°C. 30 parts of the above polystyrene was dissolved in the following monomer mixture to form a mixture. te■/te■ is approximately 1.8.

Add 0.1% of partially saponified polyvinyl alcohol to the above mixture.
170 parts of water was added to prepare a suspension and dispersion.

The above dispersion was added to a reactor containing 15 parts of water and purged with nitrogen, and reacted at a reaction temperature of 70 to 95°C for 5 hours. After the reaction is completed, it is separated in a furnace, dehydrated, dried, and separated into polystyrene and styrene.
A composition of 2-ethylhexyl acrylate copolymer was obtained.

150 parts of cumene was placed in a reactor and heated to reflux temperature. The following mixture was added dropwise to the cumene over 4 hours under reflux.

Furthermore, polymerization was completed under cumene reflux (146 to 156°C), and cumene was removed. The obtained polystyrene has Mw=
5,200, Mw/Mn= 2.74, molecular weight 5.30
The main beak was at 0, and Tg = 75°C. 50 parts of the above polystyrene was dissolved in the following monomer mixture to form a mixture. τ■/τ■ is approximately 1.8.

Add 0.1% of partially saponified polyvinyl alcohol to the above mixture.
170 parts of water was added to prepare a suspension and dispersion. water 1
The above dispersion was added to a reactor containing 5 parts and purged with nitrogen,
The reaction was carried out at a reaction temperature of 70 to 95°C for 5 hours. After the reaction was completed, the mixture was separated in a furnace, dehydrated, and dried to obtain a composition of polystyrene and styrene-n-butyl acrylate copolymer.

200 parts of cumene was placed in a Dopi-Satama reactor and the temperature was raised to reflux temperature. The following mixture was added dropwise to the cumene over 4 hours under reflux.

Polymerization was completed under roughly cumene reflux (146-156°C) and cumene was removed. The obtained styrene-methyl methacrylate copolymer has a Mw of 3,900°Mw/
Mn = 2.8, molecular weight 4,100, had a main peak at position (7), and Tg = 80°C. 30 parts of the above styrene-methyl methacrylate copolymer was dissolved in the following monomer mixture to form a mixture. te■/τ■ is approximately 1.8.

Add 0.1% of partially saponified polyvinyl alcohol to the above mixture.
170 parts of water was added to prepare a dispersion. The above dispersion was added to a reactor containing 15 parts of water and purged with nitrogen, and reacted at a reaction temperature of 70 to 95°C for 5 hours. After the reaction is complete, i
The mixture was dehydrated and dried from door to door to obtain a composition of styrene-methyl methacrylate copolymer and styrene-n-butyl acrylate copolymer.

4 Blood plate 1 200 parts of cumene was placed in a reactor and heated to reflux temperature. The following mixture was added dropwise to the cumene over 4 hours under reflux.

Furthermore, polymerization was completed under cumene reflux (146 to 156°C), and cumene was removed. The obtained styrene-α-methylstyrene had Mw = 4.500 and Mw/Mn = 2.
8, has a main peak at a molecular weight of 4.400, and has a T
g=63°C.

30 parts of the above styrene-〇-methylstyrene copolymer was dissolved in the following monomer mixture to form a mixture. L■/-c■
was about 1.8.

Add 0.1% of partially saponified polyvinyl alcohol to the above mixture.
170 parts of water was added to prepare a suspension and dispersion. water 1
The above dispersion was added to a reactor containing 5 parts and purged with nitrogen,
The reaction was carried out at a reaction temperature of 70 to 95°C for 5 hours. After the reaction was completed, the mixture was separated in a furnace, dehydrated, and dried to obtain a composition of styrene-α-methylstyrene copolymer and styrene-n-butyl acrylate copolymer.

Comparative Synthesis Example 5 200 parts of cumene was placed in a reactor and heated to reflux temperature. The following mixture was added dropwise under reflux over 4 hours.

Polymerization was completed under roughly cumene reflux (146-156°C) and cumene was removed. The obtained polystyrene has Mw
= 3,700, Mw/Mn = 2.84, molecular weight 3
, 500, and Tg=57°C.

Dissolve 30 parts of the above polystyrene in the following monomer mixture,
It was made into a mixture. τ■/te■ was approximately 1.8.

Add 0.1% of partially saponified polyvinyl alcohol to the above mixture.
170 parts of water was added to prepare a dispersion. The above dispersion was added to a reactor containing 15 parts of water and purged with nitrogen, and reacted at a reaction temperature of 70 to 95°C for 5 hours. After the reaction is complete,
The mixture was separated in a furnace, dehydrated, and dried to obtain a composition of polystyrene and styrene-n-butyl acrylate copolymer. The THF-insoluble content of this composition was approximately 3% by weight, and contained only a small amount of THF-insoluble content.

10 nuts 1 After pre-mixing the above materials with a Henschel mixer, 150
The mixture was kneaded for 15 minutes in a two-roll mill heated to .degree. After cooling the slurry, it was roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain a black fine powder with a volume average particle size of 12.0 μm. I got it. A GPC chart of the TI (F soluble content) of the black fine powder is shown in FIG.

0.4 parts of colloidal silica fine powder was dry mixed with 100 parts of the black fine powder to obtain a developer (toner).

The crushability of the toner can be expressed as the amount of toner that can be crushed per unit time, and in the case of this toner, the crushability was 15kg/hr at an air pressure of 5.5kg/cm2, which was very good. Furthermore, no fusion occurred inside the crusher.

In addition, the blocking property is as follows: Approximately 10g of toner is
The samples were placed in a plastic top (c) and left at 50 tons for one day, and the change in agglomeration degree was examined. The degree of aggregation was measured using a wire micron powder tester. The product left at room temperature and the product left for 5011 days showed almost the same values at 10% by weight and 12% by weight, and the difference (ΔG) was 2%, so it was confirmed that there was no substantial blocking.

Regarding fixing properties, offset properties, single wrap properties, image quality, and durability, Canon high-speed copying machines were used.

The test was conducted using NP-8570 (70 sheets per minute, 100V).

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.

A test was conducted by lowering the set temperature of the fixing device by 5°C. The fixability was determined by rubbing the image with Silvon C paper back and forth with a load of about 100 g, and the peeling of the image was expressed as a percentage decrease in reflection density (%).

The evaluation image was viewed at the 200th image out of 200 consecutive images.

The wrapping property was determined by printing three completely black images and checking the appearance of the claw marks of the peeling angle of the fixing roller on the images, and how much the film relied on the claws.

As a result, the fixing performance was very good with a decrease rate of 3%, the offset performance was good with no roller stains on the image even after printing 40,000 sheets, and the wrapping performance was also good with only slight marks from the claws on the image. However, it was very good.

Also, using an image with an image area ratio of approximately 5%, approximately 40,000
A durability test was conducted on the sheet, and the image was good, with no fusion to the photoreceptor or filming.

A toner was prepared in the same manner as in Example 1 using the resin compositions prepared in Comparative Synthesis Examples 1 to 5 instead of the resin composition in Example 1, and the toner was used in Comparative Example 1. I gave it a rating of ~5.

The toners of Comparative Examples were evaluated in the same manner as in Example 1 and were listed in Group 1.

Example 2 A toner was prepared using the above mixture in the same manner as in Example 1.

The volume average particle size was 12.2 μm.

The colloidal silica fine powder treated with amino-modified silicone oil was used.

The crushability of the toner was very good at a throughput of 16 kg/hr. There was also no fusion within the crusher. The blocking property was ΔG=3%, with no problem at all.

Further, image quality and fixing were evaluated using a personal copying machine FC-5 manufactured by Canon.

As a result, the image was good and continued to appear until the toner ran out, and there was no filming or fusion on the photoreceptor.

In addition, the set temperature of the fuser was lowered by 10°C, the cleaning mechanism of the fuser was removed, and the above image was produced, but the fixing performance was very good with a decrease rate of about 0%, and the offset and wrapping properties were also improved. There was no problem.

A toner was prepared in the same manner except that the resin composition of Example 2 was changed to the resin composition of Synthesis Example 3.

The volume average particle size of the toner was 11.7 μm.

The crushability of the toner was very good at a throughput of 15.5 kg/hr. There was also no fusion within the crusher.

The blocking property was ΔG=2%, and there was no problem at all.

Further, image quality and fixing were evaluated using a Canon NP-5540 copying machine (OPC photoreceptor, 40 sheets per minute).

As a result, the image was good and stable even after 40,000 sheets of durability. Further, there was no filming or fusion on the photoreceptor.

We also lowered the set temperature of the fuser by 10 degrees Celsius and removed the fuser's cleaning mechanism to achieve the durability described above, but the fixing performance was very good with a decrease rate of about 3%, and there were also problems with offset and wrapping properties. There wasn't.

Oori 1 A toner was prepared in the same manner except that the resin composition of Example 2 was changed to the resin composition of Synthesis Example 4. The volume average particle size of the toner was 12.0 μm.

The crushability of the toner was very good with a throughput of 16.2 kg/hr. There was also no fusion within the crusher. The blocking property was ΔG=3%, and there was no problem at all.

In addition, image quality and fixing were evaluated using digital copying mNP-9030 using Canon's amorphous S1 photoreceptor. As a result, the image was good, and a stable image was obtained after 40,000 sheets of durability. Further, there was no filming or fusion on the photoreceptor.

We also lowered the set temperature of the fuser by 10 degrees Celsius and removed the fuser's cleaning mechanism to achieve the durability described above, but the fixing performance was very good with a decrease rate of about 2%, and there were also problems with offset and wrapping properties. There wasn't.

Higashi Toyosato j A toner was prepared in the same manner except that the resin composition of Example 1 was changed to the resin composition of Synthesis Example 5. The volume average particle size of the toner was 11.7 μm.

The crushability of the toner was very good with a throughput of 17.1 kg/hr. There was also no fusion within the crusher. The blocking property was ΔG=3%, and there was no problem at all.

Further, image quality and fixing were evaluated using a Canon NP-400RE copying machine.

As a result, the image was good and stable even after 40,000 sheets of durability. Further, there was no filming or fusion on the photoreceptor.

We also lowered the temperature setting of the fuser by 10 degrees Celsius and removed the fuser's cleaning mechanism to achieve the durability described above, but the fixing performance was very good with a decrease rate of about 4%, and there were also problems with offset and wrapping properties. There wasn't.

3 parts of low molecular weight polypropylene A toner was prepared using the above-mentioned base material in the manner of Example 1, and the toner was mixed with 20 parts of
Approximately 10% by weight of iron powder having a particle size of 0 mesh to 300 mesh was mixed to prepare a developer. Further, only toner was used as a replenisher.

The crushability of this toner was very good at a throughput of 15.2 kg/hr. Furthermore, there was no fusion within the crusher. The blocking property was ΔG=4%, and there was no problem at all.

Further, the image quality and fixing properties were evaluated using a Canon High Speed Copy i NP-8500 super machine. As a result, the image was good and stable even after 90,000 sheets of durability. Also, there was no filler for the drums.

Further, the set temperature of the fixing device was lowered by 10° C., and the cleaning mechanism of the fixing device was removed to carry out the above durability, but the fixing performance was good with a decrease rate of about 5%. In addition, the offset property and wrapping property were also good.

Table 2 shows the characteristics of the toner.

[Effects of the Invention] The toner of the present invention has good pulverization properties, no fusion within the pulverizer, and no problem with blocking properties.

Further, it shows stable image quality and fixing property, and also has good offset property and wrapping property.

[Brief explanation of drawings]

In the accompanying drawings, FIG. 1 shows the T of the toner prepared in Example 1.
A GPC chart of HF soluble content is shown. FIG. 2 shows a GPC chart of the THF-soluble portion of the resin composition prepared in Synthesis Example 1. Figure 3 shows the GPC chart of the polystyrene used in Synthesis Example 1, and Figure 4 shows the T of the polystyrene obtained by suspension polymerization of the styrene-n-butyl acrylate copolymer used in Synthesis Example 1. ) Shows a GPC chart of IF soluble content. FIG. 5 is a combination of the charts in FIGS. 3 and 4, and FIG. 6 shows a chart for comparing and explaining FIGS. 2 and 5. FIG. 7 is a graph showing the correlation between each characteristic required of a toner, FIG. 8 is a graph showing the relationship between the content of THF-insoluble matter and the crushability, and FIG. FIG. 3 is a diagram showing a graph relating to the correlation between the content of components below OQQ and toner characteristics.

Claims (1)

[Scope of Claims] An electrostatic image developing toner comprising at least a binder resin and a colorant, wherein the binder resin comprises: i) polymerizing vinyl monomers containing two or more types of polymerization initiators with different half-lives; ii) The binder resin contains 10 to 80% by weight of the THF-insoluble portion (based on the binder resin), and the weight average molecular weight is determined by GPC molecular weight distribution of the THF-soluble portion of the binder resin. / number average molecular weight (Mw/Mn)≧5, has at least one peak in the molecular weight region of 2,000 to 10,000, and has a molecular weight of 15,000 to 10
The binder resin contains at least one peak or shoulder in the region of 0,000 and a component with a molecular weight of 10,000 or less.
A toner for developing an electrostatic image, characterized in that the content is 0 to 50% by weight.