JPH01225964A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To allow sufficient fixing at a low temp. and to prevent offsetting and winding round as well as to widen a fixable temp. region by using a resin compsn. in which a high crosslinking component and low mol.wt. component are uniformly mixed and dispersed. CONSTITUTION:The vinyl compd. which contains 0.1-60wt.% gel component, has a main peak in the region of 1,000-25,000mol.wt. and has at least one sub-peak or sub-shoulder in the region of 3,000-150,000 region mol.wt. in the chromatogram by GPC of the tetrahydrofuran soluble component is used as the binder resin. This polymer is the polymer synthesized from raw materials contg. alkenyl succicinic anhydride or alkenyl succinate as the monomer component. The toner which is sufficiently fixed at the low temp., prevents the offsetting and the winding round and has the wide fixable temp. region is thereby obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc., and particularly to a toner suitable for constant fixation on a heated roller.

[Conventional technology]

Conventionally, as an electrophotographic method, U.S. Patent No. 2,297,69
1 Specification, Japanese Patent Publication No. 42-23910, Japanese Patent Publication No. 43-24748, etc. (Although many methods are known, in general, photoconductive substances are used and various methods are used. An electrical latent image is formed on the photoreceptor by the means described above, and then the latent image is developed using toner, and if necessary, the toner image is transferred to a transfer material such as paper, and then heat, pressure, or solvent vapor is applied. It is used to fix images and obtain copies.

Various methods and devices have been developed for the above-mentioned final step, which is the step of fixing the toner image on a sheet such as paper. The most common method at present is the 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. A so-called offset phenomenon may occur, and the sheet to be fixed may be stained. 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 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, resulting in problems such as the complexity of the fixing device. . Therefore, it is not preferable to prevent offset by supplying an offset-preventing liquid (rather, the current situation is that it is desired to develop a toner with high offset resistance that has a wide fixing temperature range).

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, Japanese Patent Publication No. 51-23354 proposes a toner using a crosslinked polymer as a binder resin. If this method is followed, offset resistance and sticking resistance are significantly improved, 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.
A product with good sticking resistance and sufficient fixing properties has not been obtained. - In order to numerically improve fixing properties, it is necessary to lower the softening point of the binder resin by lowering its molecular weight.
This is contradictory to the measures taken to improve anti-offset properties, and lowering the softening point inevitably lowers the glass transition point of the resin, resulting in the undesirable phenomenon of blocking of the toner during storage. Therefore, JP-A-59-88748
As in the publication, a toner was proposed in which a polymer with a low molecular weight was blended with a polymer in which the gel component was cross-linked to 70% or more in order to satisfy low-temperature fixing and anti-offset properties.
The crosslinked polymer has poor compatibility with other polymers, and a toner that satisfies good fixing properties and developability has not been obtained. Furthermore, with crosslinked polymers, there is a problem that the components added to the toner, such as pigments, charge control agents, and release agents, are difficult to disperse, making it difficult to obtain good development characteristics as a toner. There is.

In addition, in order to improve crushability and fixing properties,
As shown in Publication No. 411, the number average molecular weight is ioo, oo.

It has been proposed to mix a high polymer of ~500,000 and other monomer components and then repeat the polymerization to obtain a uniform polymer and use it as a binder resin, but this method does not contain anti-offset properties in the resin component. It is not possible to contain enough highly cross-linked acid components to satisfy the property of non-wrapping around the fixing roller, and even if a portion of the acid component is produced, it cannot be contained uniformly due to poor compatibility between the polymers. When used as a toner binder, the dispersibility of additives is poor, and at present it is not possible to obtain a toner that satisfies development characteristics and fixing properties.

Furthermore, JP-A-56-158340 proposes a toner made of a low molecular weight polymer and a high molecular weight polymer, but it is difficult to actually incorporate a crosslinking component into this binder resin. In order to improve the offset resistance to higher performance, it is necessary to increase the molecular weight of the high molecular weight polymer or increase the ratio, and this direction will significantly reduce the crushability, which is not satisfactory for practical purposes. Things are hard to come by. Furthermore, regarding a toner blended with a low molecular weight polymer and a crosslinked polymer, Japanese Patent Application Laid-Open No. 58-8
Japanese Patent No. 6558 proposes a toner containing a low molecular weight polymer and an insoluble and infusible high molecular weight polymer as main resin components. If the method is followed, fixing properties and crushability will be improved, but the weight average molecular weight/number average molecular weight (M w / M n ) of the low molecular weight polymer is as small as 3.5 or less, and Insoluble and infusible high molecular weight polymer is 40-90w
Due to the large t%, it is difficult to achieve high performance in both offset resistance and crushability, and in reality, unless the fixing machine is equipped with an offset prevention liquid supply device, fixing performance and offset resistance can be achieved.

It is extremely difficult to produce a toner that satisfies the crushability. Furthermore, if the amount of insoluble and infusible high molecular weight polymer increases, the melt viscosity will become extremely high during heat kneading during toner production, so it is necessary to heat knead at a much higher temperature than usual or heat knead with 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.

On the other hand, a normal copying machine is provided with a separating claw in the fixing process, especially in the paper ejecting process. This is provided as a means to facilitate separation of the roller and image fixing sheet when the toner image is fixed onto a fixing sheet such as paper by a heated roller in the fixing process and is discharged from between the fixing rollers. It is something that

When the copied image is completely solid, the separating claws may sometimes cause scratch-like white lines on the image. This phenomenon tends to occur more easily at high-speed copying speeds, and toners for high-speed copying speeds are particularly required to satisfy the above-mentioned performance in the fixing and developing areas, as well as to avoid white streaks caused by scratches. There is.

To meet this requirement, it has been proposed to use unsaturated or saturated polyester binder resins or high-density crosslinked resins, and various measures have also been taken, such as changing the shape of the claws on the machine body. However, there is currently a desire for an inexpensive styrene-acrylic binder resin that satisfies this performance even further.

[Purpose of the invention]

The present invention provides a toner that significantly improves the above-mentioned problems.

The objects of the present invention are listed below.

The purpose of the present invention is to provide a hot roll without applying oil.

The purpose of the present invention is to provide a dry toner suitable for a fixing method.

The object of the present invention is to contain a highly crosslinked component and a low molecular weight component,
By using a resin composition in which these are uniformly mixed and dispersed, the objective is to provide a toner that is sufficiently fixed at a lower temperature, sufficiently prevented from offset and wrapping, and has a wide fixable temperature range. .

It is an object of the present invention to provide a toner which has an acceptable agglomeration temperature and which does not block during storage and use.

The purpose of the present invention is to obtain fog-free images with sufficient image density and clear resolution by using a resin composition with excellent dispersibility of additives such as pigments, charge control agents, and mold release agents. The purpose of the present invention is to provide a toner with excellent development characteristics.

An object of the present invention is to provide a toner that has excellent durability against repeated repeated use and that can stably maintain the high-quality images described in the preceding section.

An object of the present invention is to provide a toner that does not generate white streaks caused by separation claws that sometimes occur when separating a fixing roller and an image fixing sheet.

[Summary of the invention]

That is, the present invention uses 0 gel components as a binder resin.
．． In the GPC chromatogram of the tetrahydrofuran-soluble component containing 1 to 60% by weight, the molecular weight i, o
It is a vinyl polymer having a main peak in the region of molecular weight of oo to 25,000 and at least one subpeak or subshoulder in the region of molecular weight of 3,000 to 150,000, and the polymer contains alkenyl as a monomer component. The present invention relates to a patented image-developing toner characterized by being a polymer synthesized from raw materials containing succinic anhydride or alkenyl succinic ester.

The configuration of the present invention will be explained.

In order to achieve the above objectives at the same time, we used various binder resins, and as a result of intensive study on their composition and performance, we developed a binder with a specific composition of the gel component ratio of the binder resin and the molecular weight distribution of the THF soluble content. It has been found that the toner can achieve the above-mentioned purpose when the resin is combined with a specific monomer component. In particular, a specific combination depending on the molecular weight distribution of gel components and THF-soluble components,
The presence of both components is essential, as they greatly affect the toner's offset resistance, crushability, coiling properties, low-temperature fixing properties, anti-blocking properties, and additive dispersibility.
It has also been found that the presence of alkenyl succinic anhydride or alkenyl succinic ester (mono- or diester), which is a specific thickener component, has the effect of suppressing the generation of white streaks due to separated nails.

In the resin composition in the toner of the present invention, it is necessary that everything from a high molecular weight polymer containing a crosslinked ring component to a low molecular weight polymer be uniformly mixed.

Since high molecular weight polymers containing crosslinked ring components are insoluble in solvents, it is difficult to form a solution-like mixture of high molecular weight polymers and low molecular weight polymers, and even if they are apparently mixed, It is not a truly homogeneous mixture. Furthermore, the method of thermally melting and mechanically mixing this high molecular weight polymer with a low molecular weight polymer cannot be said to achieve truly uniform mixing. Therefore, in order to create a uniform mixture of the low molecular weight component that is effective for low temperature fixing and additive dispersibility, and the crosslinked ring component that is effective for offset and wrapping, it is necessary to connect the low molecular weight component and the crosslinked ring component. The presence of non-crosslinked components in the high molecular weight range is effective.

Furthermore, it has been found that the molecular weight and proportion of components in the medium to high molecular weight range not only act as a binder, but also have great effects on low-temperature fixing, offset, toner crushability, and the like.

Therefore, in order to obtain a resin composition in which a high molecular weight polymer having a crosslinked ring component and a low molecular weight polymer are uniformly mixed, the low molecular weight polymer is mixed together with a crosslinking agent and a monomer that provides a medium to high molecular weight polymer. A preferred method is to dissolve or mix the polymer into a component and polymerize it again in the presence of the polymer to obtain a high molecular weight polymer having a crosslinked ring component through the second stage polymerization.

The low molecular weight polymer in the resin composition used in the present invention can be obtained by commonly used polymerization methods such as bulk polymerization and solution polymerization.

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 that it is difficult to control the reaction. On this point, in the solution polymerization method, low molecular weight polymers can be easily obtained under mild conditions by utilizing the difference in chain transfer of radicals depending on the solvent and by adjusting the amount of initiator and reaction temperature. It is preferable to obtain a low molecular weight substance in a resin composition used in .

Note that it is difficult to synthesize a resin containing the necessary amount of gel component using only the solution polymerization method. In the presence of this low molecular weight polymer, the monomer that provides the high molecular weight polymer is polymerized together with the crosslinking agent and crosslinked ring component described below.
As a polymerization method for obtaining a gel component in the crosslinked region until it becomes an insoluble component in a solvent, an emulsion polymerization method or a suspension polymerization method is preferable.

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 crosslinked ring components can be obtained in a preferable state in which they are uniformly mixed. The thus obtained resin composition used in the toner of the present invention has a gel component of 0.1 to 60% by weight, preferably 1 to 60% by weight.
55% by weight, particularly preferably 10 to 50% by weight, in a GPC chromatogram of other solvent-soluble components,
Molecular weight is 1.000-25,000. Preferably 1.5
00-18.000. Particularly preferably 2,000 to 15
,000, and a molecular weight of 3.000 to iso, ooo, preferably 5,000.
~ioo, ooo, particularly preferably s, ooo~so,
ooo has a characteristic of having a sub-peak value (a value at which a peak having a height next to the main peak is located) or a sub-shoulder value.

The resin composition is contained as a main component in the toner of the present invention, and is preferably 60% by weight or more, preferably 80% by weight, particularly preferably 90% by weight or more based on the total amount of the binder resin.

Furthermore, in the molecular weight distribution of the GPC, the molecular weight is 3.
Divide the chromatogram into three parts with the boundary between 10,000 and 500,000, and from the high molecular weight side, component A (area of 500,000 or more),
The B component (area of 30,000 to 500,000) and the C component (area of 30,000 or less) are determined, and the composition ratio of each of them to the entire chromatogram is determined by the integral value of the chromatogram or by cutting out the chromatogram and dividing it into thirds. When determined by the gravimetric method in which the proportion is calculated based on the weight of each component, the constituent proportions are 0 to 20%, preferably 0 to 15%, more preferably 0 to 10% for component A; 10 to 60% for component B, preferably is 1
5-55%, more preferably 20-50%; C component 2
It is preferably 0 to 90%, preferably 35 to 80%, and more preferably 40 to 70%.

These reasons are because if the gel component in the resin composition exceeds 60%, the fixing temperature will increase when used in a toner due to the melting characteristics of the crosslinked component, and furthermore, the dispersion of additives will become poor. In addition, the highly cross-linked acid component is likely to be cut when resin is mixed, causing problems in toner design.If the gel component is less than 0.1%, offset and wrapping around the roller are likely to occur (furthermore, the gel component When the content is 0.1% or less and there are many high molecular weight regions, the grindability deteriorates significantly.

If the molecular weight of the solvent-soluble component is 1,000 to 25,000, there is no main peak value, and if the main peak value is 25,000 or more, the fixing temperature of the prepared toner will rise, the fixing temperature range will become narrower, and pulverization will occur. This also leads to a decline in production efficiency. Toner prepared with a molecular weight of 1.000 or less at the main peak value has extremely poor offset resistance, poor wrapping around the roller, and may cause problems with blocking. 3,000 to 150,000, and if the value is 150,000 or more, the dispersibility of the additive will be poor and the fixing temperature will rise significantly, and furthermore, the crushability will also be markedly deteriorated. ,000
In the following, the produced toner has poor offset resistance and roller wrapping (which may cause blocking problems. In the toner of the present invention, the above problems are significantly improved, and the offset resistance and roller wrapping resistance are poor. It is possible to obtain a toner with excellent pulverizability, a wide fixing temperature range, and excellent development properties.

The reason for this is that in a resin composition in which the high molecular weight polymer component and the low molecular weight polymer component including the crosslinked region are uniformly mixed, the high molecular weight and low molecular weight segments are mixedly integrated in the crosslinked region. It is thought that the high molecular weight component containing crosslinks acts as a matrix to prevent a decrease in cohesive force and excessive fluidity during thermal melting, while the low molecular weight component exhibits thermal meltability and is therefore thermally melted at a low temperature. However, it is thought that it exhibits excellent thermal melting properties, such as reducing cohesive force and suppressing excessive flow even at high temperatures. In the present invention, a polymer in which everything from low molecular weight components to highly crosslinked components are uniformly mixed means that when a toner is made using the polymer, the image density due to repeated use that occurs when a polymer is mixed non-uniformly. This means that no fogging actually occurs.

In addition, regarding crushability, the high molecular weight components other than the crosslinked region give the composition toughness, while the crosslinked region components give it brittleness, and the low molecular weight components make it easier to crush, making it easier to crush the entire composition. It is thought that the grinding properties necessary for improving production efficiency are produced.

It has been found that the specific monomer component in the present invention is effective against white streaks caused by separation claws that sometimes occur when the heat roller and image fixing sheet are separated in the fixing process.

The specific monomer component is a long chain alkenylsuccinic anhydride having an alkenyl group having 8 to 20 carbon atoms and its mono- and diesters represented by the following formula.

[In the formula, R and R' represent a hydrogen atom or an alkyl group. However, the sum of the carbon numbers of R and R' is a positive integer of 8 to 20. ] This long-chain alkenylsuccinic anhydride can be used as the specific monomer of the present invention in the form of a monoester by a non-catalytic reaction or a diester by an acidic catalytic reaction, by reacting it with an alcohol if necessary.

White lines caused by the separation claw are likely to occur during continuous copying at high speeds. This is because high-speed copying machines must use a fixing roller with a large heat capacity and generally a large curvature in order to instantly and continuously fix the toner on the image fixing sheet in the toner fixing process, and the low speed As with separation in high-speed copying machines, it is not always possible to rely on the difference between the inherent stiffness of the image fixing sheet and the curvature of the fixing roller, so the cause is that the separation depends on that proportion of the separation claw. .

The separation claw physically scrapes off the toner layer on the surface of the image fixing sheet, so toner with poor fixing properties tends to cause white streaks and is brittle. Toner also has a similar tendency. On the other hand, if the toner has surface smoothness, even if the toner layer is scraped off, the marks of the separation nails will not remain as white streaks. This is very advantageous for countermeasures.

One possible method for imparting surface smoothness is to add various waxes or low-molecular-weight polyolefins during toner preparation, but these blending methods leave problems with dispersion and crosstalk and are insufficient in terms of toner stability. The fundamental problem has not been solved yet, and further improvements are awaited.

Long-chain alkenylsuccinic anhydride or its ester derivative, which is an essential monomer component in the present invention, has a copolymer composition that combines the gel component with excellent surface smoothness and fixing properties with the peak and shoulder or subpeak of the THF-soluble component. It can be incorporated into the resin itself, and it also has the characteristic of exhibiting excellent surface smoothness without being affected by dispersion or crosstalk during toner production.

The reason for this is that when a long-chain alkenylsuccinic anhydride or ester derivative is introduced into a resin as a comonomer component, the resin structurally becomes a cross-linked styrene-acrylic polymer with a low-molecular-weight olefin grafted onto it. Therefore, it can be assumed that excellent surface smoothness is imparted to the resin itself and the toner. Further, depending on the purpose of the toner, this long-chain alkenylsuccinic anhydride can be used to design resins and toners by reacting it with alcohol as an ester derivative as a comonomer component as described above. For example, when considering the high humidity resistance or environmental characteristics of the toner, it is possible to use the anhydride portion of alkenylsuccinic acid as a mono- or diester as a comonomer component, and when it is desired to impart a negative charge to the toner as a resin. Or, if you are conscious of crosslinking the charge control agent and metal during toner cross-contamination, suspension polymerization of long-chain alkenyl succinic anhydride as a comonomer component is carried out, and the anhydride is hydrolyzed to introduce succinic acid into the resin. It is conceivable to use

The long-chain alkenylsuccinic anhydride and its ester derivative in the present invention can be used as a comonomer component of the low molecular weight polymer described in the specification of the present invention, or as a comonomer component in which the low molecular weight polymer is dissolved and polymerized together with a crosslinking agent. Contains.

The content is preferably 1 to 25% by weight as a comonomer component (preferably 1 to 15% by weight, more preferably 1 to 25% by weight).
It is 10% by weight.

If the content is less than 1% by weight, when used as a toner, white streaks may sometimes occur due to separation claws in high-speed copying machines, and if it exceeds 25% by weight, the Tg of the binder resin itself or the toner decreases. Blocking is likely to occur.

In the present invention, the gel component refers to the weight proportion of a polymer component that has been crosslinked and becomes insoluble in a solvent in a resin composition, and is used as a parameter indicating the degree of crosslinking of a resin composition containing a highly crosslinked component. be able to. What is the gel component?
It is defined by the values measured as follows.

In other words, if the sample is only resin, 0.5 to 1.0 g
Weigh out a certain amount of resin (W+g), put it in a thimble filter paper (Toyo Roshi Model Nα86R), apply it to a Soxhlet extractor, and use 100 to 200 ml of chloroform as a solvent. using 6
After time extraction and evaporation of the extracted soluble components with a solvent, vacuum drying was performed at 100° C. for several hours, the amount of the soluble resin component was weighed (W2g), and calculated according to the following formula.

Gel component content = (W, -W2)/W, X100 (%)
If the sample is toner, the series of extraction operations is the same as for resin, but for non-magnetic toner, the pigment weight is extracted from the sample toner weight, and for magnetic toner, the pigment and magnetic weight are extracted from the sample toner weight. It can be calculated from the subtracted weight (W3g) and the weight of the solvent-soluble component in the toner (W4g) according to the following formula.

Gel component content = (W3-W4) /W3X 100
(%) The evaporated dry product of the solvent-soluble component obtained in the above operation is dissolved in THF (tetrahydrofuran), passed through a sample processing filter, and then used as a sample for GPC.

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 mj7 per minute, and 50 to 200 μl of a THF sample solution of the resin adjusted to a sample concentration of 0.05 to 0.1% by weight 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. As a standard polystyrene sample for creating a calibration curve,
For example, Pressure Chemical C
o, or manufactured by Toyo Tsudani Gyosha with a molecular weight of 6X1.
0”, 2.lX10”.

4X10'', 1.75X10', 5.1X10', 1.
lX10'.

3.9X10', 8.6X10', 2X10',
It is appropriate to use at least 10 standard polystyrene samples of 4.48 x 10' (7).

Further, an R1 (refractive index) detector is used as a detector.

In addition, as a column, in order to accurately measure the molecular weight range of 10' to 2X10', it is recommended to combine multiple commercially available polystyrene gel columns (for example, water column).
μmstyragej' 500 manufactured by R.S. 1
0", 10'.

10' combination, 5hodex manufactured by Showa Denko
KF-80M, KF-802, 803, 804, 80
5 combination, KA-802, 803, 804, 805 (
7) Combination or TSKgef G1 manufactured by Toyo Soda
00OH, G2000H.

G2500H, G3000H, G4000H, G500
0H, G6000H.

Any combination of G700OH and GMH is desirable.

The resin composition in the toner of the present invention contains a high molecular weight polymer component containing a crosslinking component and a low molecular weight polymer component, both of which contain one or more types selected from styrenes, acrylic acids, methacrylic acids, and derivatives thereof. Monomers obtained by copolymerizing with the above-mentioned specific monomers are preferred from the viewpoint of development characteristics and charging characteristics. Examples of monomers that can be used include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, etc. Examples of acrylic acids, methacrylic acids, and their derivatives include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl allylate, n-tetradecyl acrylate, and acrylic acid. Examples include acrylic acid esters such as n-hexadecyl acid, lauryl acrylate, cyclohexyl acrylate, diethylaminoethyl acrylate, and dimethylaminoethyl acrylate; similarly, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, Butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, methacrylate Examples include methacrylic acid esters such as 2-hydroxypropyl acid, dimethylaminoethyl methacrylate, glycidyl methacrylate, and stearyl methacrylate. Furthermore, in addition to the above-mentioned monomers, a small amount of other monomers such as acrylonitrile may be added to the high molecular weight polymer component containing a crosslinked region and the low molecular weight polymer component in the resin component of the present invention. , 2-vinylpyridine, 4-vinylpyridine, vinylcarbazole, vinyl methyl ether, butadiene, imprene, maleic anhydride.

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

Examples of the crosslinking agent used to form the crosslinking component of the resin component of the toner of the present invention include divinylbenzene, bis(4-acryloxypolyethoxyphenyl)propane, and ethylene glycol diacrylate). ,
1.3-butylene glycol diacrylate, 1,
4-butanediol diacrylate, 1,5-pentanediol diacrylate), 1,6-hexane glycol diacrylate.

Neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol #200° #400. #60
0 each diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester diacrylate (MANDA Nippon Kayaku) and all of the above acrylates replaced with methacrylates, pentaerythritol triacrylate as a multi-functional crosslinking agent, Trimethylolethane triacrylate, trimethylolpropane triacrylate.

Tetramethylolmethane tetraacrylate, oligoester acrylate and its methacrylate, 2.2
-bis(4-methacryloxy, polyethoxyphenyl)
Examples include propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate, and the like.

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 the toner to be positively charged.

Nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 1627/1983), basic dyes (e.g. C, 1, Ba5ic Yellow 2 (C,
1,41000), C,1,Ba5ic Yellow
w 3, C, 1, Ba5ic Red 1 (C, 1
, 45160), C,1,Ba5icRed 9 (
C,1,42500), C,1,Ba5ic Vio
letl (C0I, 42535), C, 1, Ba5i
c Violet 3 (C0I, 42555),
C, I, Ba5ic Violet 10 (C, 1
, 45170), C, 1, Ba5ic Violet
14 (C, 1, 42510), C, 1, Ba5ic
Blue 1 (C,!

42025), C, 1, Ba5ic Blue 3
(C, 1, 51005), C91, Ba5ic B
lue 5 (C, 1, 42140), C, I.

Ba5ic Blue 7 (C, 1,42595
), C01, Ba5icBlue 9 (C,1,5
2015), C0I, Ba5ic Blue24
(C, 1, 52030), C, 1, Ba5ic Bl
ue 25 (C, 1, 52025), C, 1, Ba5
ic Blue 26 (C.

1.44045), C, 1, Ba5ic Green
1 (C, I.

42040), C, 1, Ba5ic Green
4 (C, 1,42000), lake pigments of these basic dyes, (lake-forming agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide). compound, ferrocyanide, etc.), C,1,5ovent
Black 3 (C, 1, 26150), Hansa Yellow G (C, 1, 11680), C, 1, Mordl
ant Black 11, C, 1, Pigmen
t Black 1, Gilt Night, Asphalt, etc.

Or, for example, benzylmethyl-hexadecyl ammonium chloride, decyl-trimethyl ammonium chloride, or dibutyl.

Dialkyltin compounds such as dioctyl, metal salts of higher fatty acids, inorganic fine powders such as zinc oxide, metal complexes such as EDTA and acetylacetone, polyamine resins such as vinyl polymers containing amino groups, condensation polymers containing amino groups, etc. .

(2) The following substances can be used to control the negative chargeability of toner. Special Publication No. 41-20153, No. 43-27
No. 596, No. 44-6397, No. 45-26
Metal complex salts of monoazo dyes, such as those described in Publication No. 478.

Dyes and pigments such as nitrofumic acid and its salts or C,1,14645 described in JP-A-50-133338, JP-B No. 55-42752, JP-B-Sho 58
Co, Cr, and Fe of salicylic acid, naphthoic acid, and dicarboxylic acid described in Japanese Patent Publication No. 41508, Japanese Patent Publication No. 58-7384, Japanese Patent Publication No. 59-7385, etc.
metal complexes such as sulfonated copper phthalocyanine pigments,
Styrene oligomers with nitro groups and halogens introduced, chlorinated paraffins, etc.

Further, good results can be obtained with the toner of the present invention when additives are mixed therein as required. Examples of additives include lubricants such as Teflon and zinc stearate, abrasives such as cerium oxide, silicon carbide, and strontium titanate, flow agents such as colloidal silica and aluminum oxide, anti-caking agents, and carbon. Conductivity imparting agents such as black, zinc oxide, antimony oxide, tin oxide, or low molecular weight polyethylene.

Examples include fixing aids such as 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 developability improver.

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 0.1 to 50% by weight, preferably 0.5 to 50% by weight in terms of toner concentration.
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 magnetic powders such as iron powder, ferrite powder, nickel powder, glass beads, etc., and those whose surfaces are treated with resin etc. Things can be given.

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, and metals of these metals;
,lead.

Magnesium, tin, zinc, antimony, beryllium,
Examples include alloys of metals such as bismuth, cadmium, calcium, manganese, selenium, titanium, 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 1 μm, and are contained in the toner in an amount of about 2 to 100 parts by weight of the resin component.
0 to 200 parts by weight, particularly preferably 40 to 150 parts by weight per 100 parts by weight of the resin component.

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, such as pigments such as carbon black, alinine black, and acetylene black.

These include naphthol yellow, Hansa yellow, 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, per 100 parts by weight of the resin. Further, dyes are also used for the same purpose. For example, azo dyes and anthraquinone dyes.

There are xanthine dyes, methine dyes, etc. Resin 100
0.1 to 20 parts by weight, preferably 0.3 to 20 parts by weight
A good addition amount is 3 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. Mix thoroughly with a mixer, then heat roll and negoo.

Pigments or dyes are dispersed or dissolved in the resin by melting, kneading, and kneading using a heat kneader such as an extruder to make the resins compatible with each other. After cooling and solidifying, the pigment or dye is crushed and classified to obtain an average particle size of 5. A toner of ~20 μm can be obtained.

Alternatively, the material can be obtained by dispersing the material in a binder resin solution and then spray-drying it, or by mixing the specified material with the monomers that should constitute the binder resin, emulsifying it to form a suspension, and then polymerizing it. A polymerization method for obtaining a toner or a method for forming a capsule toner consisting of a core and a shell can be applied.

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

[Synthesis Example 1] 200 parts by weight of cumene was placed in a reactor, and the temperature was raised to reflux temperature. To this, 100 parts by weight of styrene monomer and
A mixture of 8 parts by weight of ert-butyl peroxide was added dropwise over 4 hours, and then cumene was added under reflux (146 to 156 parts by weight).
The solution polymerization was completed at 10°C (°C), and cumene was removed to obtain low molecular weight polymer-1. The main peak value of the obtained polymer by GPC was 4,500.

Next, 150 parts of low molecular weight polymer and 75 parts of styrene.

A homogeneous mixture of 19 parts of n-butyl acrylate, 5 parts of dodecenylsuccinic anhydride, 1 part of divinylbenzene and 4 parts of benzoyl peroxide was suspended and dispersed in 300 parts of water in which 0.8 parts of partially saponified polyvinyl alcohol was dissolved. The resin composition was polymerized for 15 hours at a polymerization temperature of 80°C to obtain a burl-shaped resin composition in which a high molecular weight polymer including a gel component to a low molecular weight polymer were uniformly mixed, and dried under reduced pressure to obtain a resin composition. It was set to 1.

Approximately 0.5 g of resin composition-1 was accurately weighed, placed in a thimble filter paper (Toyo Roshi &86R), and chloroform 1 was added as a solvent.
80mj! Soxhlet extraction was carried out for 6 hours using Soxhlet, followed by evaporation to remove the medium in the extracted soluble components, followed by vacuum drying at 100° C. for 12 hours, and the amount of soluble resin components was weighed. From the sample weight and this value, the gel component weight (degree of crosslinking) was determined according to the above-mentioned formula. Furthermore, this soluble resin component was dissolved in THF to prepare a sample with a concentration of 0.1% by weight, and passed through a sample pretreatment filter for non-aqueous systems.
This was used as sample C. As a column for GPC measurement, Shod
Using exKF-80M double columns, 40
Built into a heat chamber at ℃, THF flow rate 1mf/m
in.

The detector measured GPC by injecting 200 μl of the sample under RI conditions. Calibration curves for molecular weight measurement include molecular weights of 0.5 x 10", 2.35 x 10", and 10.
2X10”.

35X103. ll0XIO", 200X10', 47
0X10”.

1200XIO", 2700X10", 8420X
10” (7) A THF solution of 10 points of monodispersed polystyrene reference material (manufactured by Waters) was used.

The gel component weight of resin composition-1 was 30% by weight, the molecular weight of the eluted component had a main peak value of 4,500, and a sub-peak value of 4.
It was 0,000. A chromatogram obtained by GPC is shown in FIG.

[Synthesis Example 2] Burl-shaped resin composition-2 was obtained in the same manner as Synthesis Example 1, except that 0.5 parts of triethylene glycol diacrylate was used instead of divinylbenzene as a crosslinking agent in the suspension polymerization. . The gel component of the resin composition was 22% by weight, and the main peak value of the molecular weight of the eluted component was 4.
500, and the sub-peak value was 52,000.

[Synthesis example 3] In suspension polymerization - 170 parts of low molecular weight polymer.

A burl-shaped resin composition was prepared in the same manner as in Synthesis Example 1 using 85 parts of styrene, 10 parts of dimethyldodecenyl succinate, 4 parts of n-butyl acrylate, 0.7 parts of divinylbenzene, and 3.5 parts of benzoyl peroxide. Product-3 was obtained.

The gel component of the resin composition was 25% by weight, the molecular weight main peak value of the eluted component was 4.500, and the sub-peak value was 47,000.

[Synthesis Example 4] In the synthesis of a low molecular weight polymer, 3 parts of benzoyl peroxide was used as an initiator, and a low molecular weight polymer-2 was obtained in the same manner as in the synthesis example of low molecular weight polymer-1. Next, 70 parts of the obtained low molecular weight polymer-2 was added.

75 parts of styrene, 24 parts of n-butyl acrylate.

1 part of divinylbenzene and 0.8 part of t-butylperoxy-2-ethylhexanoate were added to obtain a burl-shaped resin composition-4 in the same manner as in Synthesis Example-1.

The gel component of the resin composition was 36% by weight, the molecular weight main peak value of the eluted component was 28,000, and the sub-peak value was 98,000.

[Synthesis example 5 In suspension polymerization, 15 parts of low molecular weight polymer-1.

A burl-shaped resin composition was prepared in the same manner as in Synthesis Example 1, except that 2.2 parts of divinylbenzene, 75 parts of styrene, 24 parts of n-butyl acrylate, and 2 parts of t-butyl-peroxy-2-functional tylhexanoate were added. -5 was obtained. The gel component of the resin composition is 76% by weight, the main peak of the molecular weight of the eluted component is 6,000, and the sub-peak value is 86.
,000.

[Synthesis Example 6] Styrene monomer 100 in the synthesis of low molecular weight polymer
Low molecular weight polymer-3 was obtained in the same manner as the synthesis of low molecular weight polymer-1, except that 2.4 parts of benzoyl peroxide was used. Next, 70 parts of low molecular weight polymer-3,
A burl-shaped resin composition was prepared in the same manner as in Synthesis Example 1, except that 0.5 parts of t-butylperoxy-2-ethylhexanoate, 75 parts of styrene, 24 parts of n-butyl acrylate, and 1 part of divinylbenzene were used as initiators. Product-6 was obtained. The gel component of the resin composition was 32% by weight, the main peak value of the molecular weight of the eluted component was 124,000, and the sub-peak value was 30.000.

Component A of the vinyl polymer obtained in each synthesis example.

The proportions of component B and component C are shown in Table 1 below.

Table-1 [Example 1] After premixing the above materials with a Henschel mixer,
The kneaded material was kneaded for 20 minutes in a two-roll mill heated to ℃, then allowed to cool, and then pulverized with a cutter mill, further pulverized using a pulverizer using a jet stream, and then further pulverized using a wind classifier. It was classified to obtain a black fine powder with a volume average particle size of 11 μm. A toner was prepared by dry mixing 0.4 parts of colloidal silica fine powder to 100 parts of the black fine powder.

When this toner was used for continuous printing of 5,000 copies using a Canon NP-8570 copier that uses an amorphous silicon photoreceptor, clear images with high resolution and no fog were obtained with an image density of 1.3 to 1.35. It was done. Furthermore, NP-
Offset and fixability test 2 using 8570 fuser with different fixing roller temperature Wrapping and blocking,
Furthermore, after careful consideration of the crushability of the toner, we found that
As shown in Table 2, no offset occurred in a wide temperature range from 140 to 230°C, the fixing performance at 150°C was good, and no wrapping around the roller occurred.
This toner was also excellent in crushability and blocking resistance at 50° C./day.

The evaluation of white streaks caused by the separation claw in the present invention was carried out using a high-speed copying machine manufactured by Canon NP-8570.

In other words, when 10 sheets of A-3 size copy paper are taken in succession with all-black images so that the amount of toner on the paper is constant per unit area, the white stripes at the leading edge of the images (scuff marks due to scratches) and its length). As shown in Table 2 (this toner had no problem with white streaks).

[Example 2] A toner was prepared in the same manner as in Example 1 except that 2100 parts of the resin composition was used, and Canon NP-8570 was used.
When I ran a continuous s, oooo number of copies on a copying machine,
A clear image with high resolution and no fog was obtained with an image density of 1.3 to 1.35. Using NP-8570 fuser,
By changing the temperature of the fixing roller, we investigated the offset, fixing performance, 9 wrapping, blocking, and toner crushability, and as shown in Table 2, the offset was 1.
This did not occur up to 40 to 230°C, and the fixing performance at 150°C was relatively good, and no wrapping around the roller occurred. Further, no blocking occurred during one day at 50° C., and the crushability was also good. There was also no problem with white streaks caused by the separation nails.

[Example 3] Example 1 except that 100 parts of resin composition-3 was used.
When a toner was prepared in the same manner as above and subjected to 5,000 continuous copies using a Canon NP-8570 copier, clear images with an image density of 1.25 to 1.3 and no fog and high resolution were obtained. . Using the NP-8570 fuser, we investigated the offset, fixing properties, wrapping properties, blocking, and toner crushability by changing the fixing roller temperature, and as shown in Table 2, the offset was 140°C to 2.
It did not occur up to 30°C, the fixing property at 1500C was good, and no wrapping around the roller occurred.

Furthermore, the blocking property and toner pulverization property at 50'C/1 day were excellent, and no white streaks due to separation nails were generated.

[Comparative Example 1] Example 1 except that 100 parts of resin composition-4 was used.
A toner was prepared in the same manner. When this toner was used in a Canon NP-8570 copying machine for 5,000 continuous copies, it produced clear images with an image density of 1.1-1.2 and no fog, and the offset by the NP-8570 fuser. In the evaluation of fixing properties with 2 wraps, no offset or wrapping occurred at 230°C, and no blocking occurred at 50°C for one day, but as shown in Table 3, offset occurred at 140°C, and fixing at 150°C did not occur. It was found that the properties of the powder were poor and the crushability was extremely poor.

In addition, white streaks caused by the separation nail occurred from the beginning of continuous copying of an entirely black image.

[Comparative Example 2] Example 1 except that 100 parts of resin composition-5 was used.
Create toner in the same manner as Canon NP-857.
When I ran 5,000 continuous sheets at 0, the image density was 0.
．． It was low at 95 to 1.15, and only slightly foggy images were obtained. In addition, in the evaluation of offset and fixing properties with 2 wraps using the NP-8570 fuser, there were no problems with offset, wraps, and blocking resistance at 230°C for one day at 50°C, but fixing properties at 150°C and fixing properties at 140°C were The offset was poor and the crushability was also unsatisfactory. In addition, white streaks caused by the separation nail occurred from the beginning of continuous copying of an entirely black image.

[Comparative Example 3] Example 1 except that 6100 parts of the resin composition was used.
Create toner in the same manner as Canon NP-857.
When I ran 5,000 continuous sheets at 0, the image density was 1.
．． 1 to 1.2, a slightly foggy image is obtained, NP-
In the evaluation of offset and fixing properties with 8570 fuser with 2 wraps, there was no offset at 230°C, and no blocking or wrapping around the roller after 1 day at 50°C, but offset at 140°C and fixing properties at 150°C. Both were poor, and the crushability was extremely poor. Furthermore, white streaks caused by the separation nail occurred from the initial stage of the all-black image to the top to bottom of the image.

Table-2 Table-3

[Brief explanation of the drawing]

In the accompanying drawings, FIG. 1 shows a chromatogram for the resin of Example 1, and FIG. 2 shows a chromatogram for the resin of Comparative Example 3.

Claims (1)

[Claims] Contains 0.1 to 60% by weight of a gel component as a binder resin, and has a molecular weight of 1,000 to 25,000 in a GPC chromatogram of a tetrahydrofuran soluble component.
has a main peak in the region of 3,000 to 150
A vinyl polymer having at least one subpeak or subshoulder in the region of ,000, and the polymer is a polymer synthesized from raw materials containing alkenylsuccinic anhydride or alkenylsuccinic ester as a monomer component. A toner for developing electrostatic images characterized by: