JPH01225966A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To improve the dispersibility of an electrostatic charge control agent and to obtain a fog-free image having a sufficient image density and sharp resolving power by using a resin compsn. into which the condensation product of an org. tin compd. is previously dispersed. CONSTITUTION:The vinyl polymer which is obtd. by previously dissolving or mixing the low-mol.wt. polymer formed by synthesizing a monomer by a soln. or ion polymn. in the presence of the condensation product of the org. tin compd. expressed by formula and having the main peak of the mol.wt. distribution at 1,000-25,000 together with a crosslinking agent in or with the monomer component giving middle- and high-mol.wt. regions and by further subjecting such soln. or mixture to suspension polymn. and is uniform from the low mol.wt. to the high mol.wt. and even to the crosslinking region is used as the binder component. In formula, R1, R2 denote monovalent org. groups which are the same or different; M denotes the element of group III in the periodic table; X denotes a monovalent group. The dispersibility of the charge control agent is thereby improved and the fog-free image is 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
Although many methods are known, as described in Japanese Patent Publication No. 1, Japanese Patent Publication No. 42-23910, and Japanese Patent Publication No. 43-24748, etc., they generally utilize photoconductive substances and perform various methods. forming an electrical latent image on the photoreceptor by means;
Next, the latent image is developed using toner, and if necessary, the toner image is transferred to a transfer material such as paper, and then fixed by heat, pressure, solvent vapor, or the like to obtain a copy.

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 liquid such as silicone oil that has good mold releasability. However, although this method is extremely effective in preventing toner offset, it requires a device to supply the offset prevention liquid, resulting in problems such as the complexity of the fixing device. . Therefore, it is not desirable to prevent offset by supplying an offset-preventing liquid, and rather the development of a toner with high offset resistance over a wide fixing temperature range is currently desired. Therefore, in order to increase the releasability of the toner, a method of adding wax such as low molecular weight polyethylene or polypropylene that melts sufficiently when heated has been used, but while it is effective in preventing offset, it reduces the cohesiveness of the toner. increase,
Charging characteristics become unstable and durability tends to decrease. 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 that method is followed, there is a remarkable improvement in offset resistance and sticking resistance, but on the other hand, if the degree of crosslinking is increased, the fixing point will rise, and if the fixing temperature is low enough, offset resistance and sticking resistance will be improved.
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
In order to satisfy low-temperature fixing and anti-offset properties, a toner made by blending a polymer with a low molecular weight and a cross-linked polymer was proposed, but the cross-linked polymer has poor compatibility with other polymers. A toner that satisfies the fixing properties and developability has not yet been obtained.Furthermore, in the case of crosslinked polymers, the components added to the toner, such as pigments, charge control agents, and release agents, cannot be dispersed. There is a problem that it is difficult to obtain good development characteristics as a toner.In addition, as described in Japanese Patent Publication No. 60-20411 (To improve crushability and fixability, the number average molecular weight is 100, 0
It was proposed to mix a high polymer of 00 to 500,000 and other monomer components and then mold it to obtain a uniform polymer to make a binder resin. sex.

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 can be contained, it cannot be contained uniformly due to poor compatibility between polymers, and the toner When used as a binder, the dispersibility of the additive is poor (and a toner that satisfies the development properties and fixing properties has not been obtained. Dispersion of the agent into the polymer is important.Generally, the charge control agent is added to the thermoplastic polymer, heat-melted and dispersed, and finely pulverized during the process of making toner.However, the charge control agent itself is It has a complex structure and is easily decomposed or altered by mechanical shock, friction, and changes in temperature and humidity conditions during thermal kneading, and tends to cause a phenomenon in which charge controllability is reduced.

In addition, since it is difficult to uniformly disperse these charge control agents in thermoplastic polymers, differences in triboelectric charge may occur between toner particles obtained by pulverization, resulting in fogging during development, toner scattering, and developing sleeves. Problems such as image unevenness occur due to contamination. This problem becomes noticeable when copies are made many times (overlapping), and the result is that the toner is practically unsuitable for copying machines.Furthermore, under high humidity conditions, the transfer efficiency of toner images decreases, causing a practical problem. In some cases,

Therefore, various methods have been conventionally used to improve the dispersibility of the charge control agent, which is an additive, and to satisfy the development characteristics. For example, basic nigrosine dyes are used by forming salts with higher fatty acids in order to improve the compatibility with thermoplastic resins.

However, in this method, unreacted fatty acids or salt dispersion products are often exposed on the toner surface and contaminate the carrier or toner carrier, causing a decrease in toner fluidity, fog, and a decrease in image density. It is the cause.

Furthermore, a method of mechanically pulverizing and mixing the charge control agent powder and resin powder in advance and then hot-melting and kneading them has been used, but the inherent poor dispersion cannot be avoided and it is still insufficient for practical use. Uniformity of charge was not obtained.

Furthermore, Japanese Patent Application Laid-Open No. 192958/1983 proposes a toner containing a polymer obtained by suspension polymerization in the presence of a fatty acid and a carboxy group-modified nigrosine dye. However, nigrosine dyes generally have a polymerization inhibiting effect, making it difficult to obtain a desired polymer, and even if a polymer with improved dispersibility is obtained, the above-mentioned fixing properties, offset resistance, and resistance to fixing rollers may be affected. It is extremely difficult to arbitrarily design a polymer that satisfies the wrapping properties. Furthermore, regarding the dispersibility of additives, a toner containing a dye composition obtained by polymerizing an unsaturated monomer in the presence of a quinone imine dye was proposed in JP-A-60-67563; Sometimes, the mechanical hot melt kneading process with the resin cannot be avoided, and the dispersion of the charge control agent itself and its inherent poor dispersion cannot be completely avoided (
There are still points to be improved.

In addition, even if the toner is apparently dispersed by a mechanical method, the transfer efficiency of the toner image decreases especially under high temperature conditions, and many of them are unusable, even at room temperature. When this toner is stored for a long period of time, it tends to deteriorate due to the instability of the charge control agent (in many cases, it cannot be used as a toner).

Furthermore, when conventional charge control agents are used in toner, long-term use may cause the charge control agents to adhere to the surface of the photoreceptor or promote toner adhesion, adversely affecting latent image formation (
There are many things that have a negative effect on the cleaning process of a copying machine, such as the filming phenomenon), those that cause scratches on the surface of the photoreceptor or cleaning members such as cleaning blades, and those that promote friction of the members.

Furthermore, when conventional charge control agents are used in toner, there are few that significantly affect the thermal melting properties of the toner and reduce fixing performance. There are some that increase the tendency of paper to cling to the roller and reduce the durability of the roller.

In this way, it is necessary to improve the shortcomings of charge control agents, and also to respond to the recent technological trends of personalization and speeding up of copying machines (when considering improvements in fixing properties and developability, it is necessary to further improve low-temperature fixing properties). It is desired to develop a polymer for toner that can practically satisfy all of the following requirements: offset resistance, non-wrapping property to a fixing roller, and excellent developability.

[Purpose of the invention]

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

The objects of the present invention are listed below.

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

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 purpose is to provide a toner that can be sufficiently fixed at a lower temperature, can sufficiently prevent 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 object of the present invention is to use a resin composition in which a charge control agent, that is, a condensate of an organic tin compound, is predispersed, so that the dispersibility of the charge control agent is excellent, the image density is sufficient, and the image density is clear and there is no fog. The purpose of the present invention is to provide a toner with excellent development characteristics that allows images to be obtained.

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.

[Summary of the invention]

That is, the present invention contains a gel component of 0.1 to 60% by weight, and has a molecular weight of 1.000 to 25.0% in a GPC chromatogram of a tetrahydrofuran soluble component.
It has a main peak value at 00 and a molecular weight of 3,000.
~150,000 (in polymers with both one subpeak value or subshoulder value, molecular weight 1,
A toner characterized by containing a vinyl polymer produced by polymerizing a low molecular weight polymer giving a main peak between 000 and 25,000 in the presence of a condensate of an organotin compound represented by the following formula. Our goal is to provide the following.

(In the formula, R1 and R2 are -valent organic groups and represent the same or different groups, M represents an element of group II in the periodic table, and X represents a monovalent group.) [Details of the invention [Explanation] The above purpose is to synthesize a low molecular weight polymer having a main peak of molecular weight distribution in the range of 1,000 to 25,000, synthesized by solution or ionic polymerization of monomers in the presence of a condensate of an organic tin compound, by pretreatment with a crosslinking agent. It can be obtained by dissolving or mixing it with a monomer component that gives a medium to high molecular weight range, and then subjecting it to suspension polymerization. This can be achieved by containing in the toner a vinyl polymer that is uniform from a low molecular weight region to a high molecular weight and crosslinked region.

In the present invention, the gel component refers to the weight percentage of a polymer component in a resin composition that has been crosslinked and becomes insoluble in a solvent, and is used as a parameter to indicate the degree of crosslinking of a resin composition containing a highly crosslinked component. Can be done. The gel component is defined by the value measured as follows.

That is, if the sample is only resin, weigh out a certain amount of resin (0.5 to 1.0 g).
α86R) and subjected to a Ntuxle extractor, using 100 to 200 m of chloroform or THF as a solvent.
After extracting with It for 6 hours and evaporating the extracted soluble components with a solvent, vacuum drying at 100° C. for several hours, the amount of soluble resin components was weighed (W2g) and calculated according to the following formula.

Gel component content” (W 1W 2) / W,
X 100 (%) When the sample is toner, the series of extraction operations is the same as for resin, but for non-magnetic toner, the pigment weight is calculated from the sample toner weight, and for magnetic toner, the pigment and magnetic material are calculated from the sample toner weight. The weight after subtracting the weight (Wsg) and the weight of the solvent-soluble components in the toner (W4g)
) can be calculated 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) at 1 mi per minute! Measurement is performed by injecting 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. 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
Co, or manufactured by Toyo Tsudani Gyo Co., Ltd. with a molecular weight of 6X10
”, 2.lX10”, 4X10”.

1.75X10', 5. lX10', 1. lX1
0', 3.9X10''.

It is appropriate to use a standard polystyrene sample of 8.6 x 10', 2 x 10', or 4.48 x 10', and use a small number (at least 10 points) of standard polystyrene. Also, use an RI (refractive index) detector as the detector. .

In addition, in order to accurately measure the molecular weight range of 10'' to 2X10', it is recommended to use a combination of multiple commercially available polystyrene gel columns (for example, water column).
μmstyrage I! manufactured by R.S. 500.
10", 10', 10' combination, 5hodex KF-80M manufactured by Showa Denko, KF-802
,803,804,805 combination, KA-802,8
03, 804, 805 combination, or TSKge 12 G100OH, G2000 manufactured by Toyo Tsudani Industry
H.

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

Any combination of G700OH and GMH is desirable.

The resin composition containing a condensate of an organic tin compound 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 styrenes, acrylic acids, methacrylic acids and Those obtained by polymerizing one or more monomers selected from the derivatives are preferable from the viewpoint of development characteristics and charging characteristics. Examples of monomers that can be used include styrene, α-methylstyrene, vinyltoluene, and chlorostyrene. Acrylic acids, methacrylic acids, and their derivatives include acrylic acid, methyl acrylate, ethyl acrylate, and propyl acrylate.

Butyl acrylate, octyl acrylate, allyl acid 2
- Acrylic acid esters such as ethylhexyl, n-tetradedyl acrylate, n-hexadecyl acrylate, lauryl acrylate, cyclohexyl acrylate, diethylaminoethyl acrylate, and dimethylaminoethyl acrylate, as well as methacrylic acid and methacrylic acid. Methyl.

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, methacrylic acid 2
Examples include methacrylic acid esters such as -hydroxyethyl, 2-hydroxypropyl methacrylate, 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, isoprene, maleic anhydride, maleic acid, maleic acid monoesters, maleic diesters, vinyl acetate, etc. may 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, l
, 4-butanediol diacrylate), 1.5-bentanediol diacrylate, 1.6-hexane glycol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate,
Triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol #200. #400゜#600 Each diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate (all the acrylates listed in MANDA Nippon Kayaku Nipponka quantity are replaced with methacrylates, as multi-functional crosslinking agents) Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis(4-methacryloxypolyethoxyphenyl)propane, diallyl phthalate ,
Examples include triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diarylchlorendate, and the like.

In the resin composition containing the condensate of an organic tin compound in the toner of the present invention, it is necessary that everything from the high molecular weight polymer to the low molecular weight polymer containing the crosslinking region component be uniformly mixed. Since the high molecular weight polymer containing the crosslinking region component is insoluble in the solvent, it is difficult to mix the high molecular weight polymer and the low molecular weight polymer in a solution state, and even if they are mixed apparently, 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 achieve a uniform mixture of low molecular weight components that are effective for low temperature fixing and additive dispersibility, and crosslinking region components that are effective for offset and wrapping, it is necessary to connect the low molecular weight components and crosslinking region components. The presence of non-crosslinked components in the high molecular weight range is effective. moreover,
It has been found that the molecular weight and ratio 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, and toner pulverization properties. Therefore, in order to obtain a resin composition in which a high molecular weight material having a crosslinking region component and a low molecular weight polymer are uniformly mixed, the low molecular weight polymer must be mixed in advance with a crosslinking agent and a monomer component that provides a medium to high molecular weight polymer. A preferred method is to dissolve or mix the polymer into a polymer, polymerize it again, and obtain a high molecular weight polymer having a crosslinking region 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 in controlling the reaction. On the other hand, the solution polymerization method makes use of differences in radical chain transfer depending on the solvent, and by adjusting the amount of initiator and reaction temperature, it is possible to make low molecular weight polymers milder. It can be easily obtained under the following conditions, and is preferable for obtaining the low molecular weight substance in the resin composition used in the present invention.

Note that it is difficult to synthesize a resin containing the necessary amount of gel component using only the solution polymerization method. Further, in order to obtain a low molecular weight polymer, it is also possible to obtain a preferable low molecular weight polymer by using anionic, cationic or other ionic polymerization methods.

The low molecular weight polymer synthesized in the presence of the condensate of the organotin compound mentioned above is polymerized again together with the monomer that gives the high molecular weight polymer while containing the crosslinking agent and crosslinking region component mentioned above. As a polymerization method for obtaining a gel component in the crosslinked region until it becomes a component, an emulsion polymerization method or a suspension polymerization method is preferable. The addition ratio of the low molecular weight polymer is preferably 10 to 50% by weight based on the vinyl polymer obtained by polymerization again.

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. It is possible to obtain a preferable state in which the components from 1 to 1, including crosslinking region components, to high molecular weight polymers 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 5% by weight.
5% by weight, particularly preferably 10 to 50% by weight, and other solvent-soluble components have a molecular weight of 1.000 to 25,000, preferably 1.50 in a GPC chromatogram.
0-18,000.

Particularly preferably, the main peak value (the value at which the highest peak is located in the GPC chromatogram) is between 2,000 and 15,000, and the molecular weight is between 3,000 and 150.
,000°, preferably 5,000 to 100,000. Particularly preferably, s, ooo to so, and ooo have 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 above 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 9% 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%.

The reason for these is that if the gel component in the resin composition is 60% or more, the melting characteristics of the crosslinked component will cause an increase in fixing temperature when used in a toner, and furthermore, the dispersion of additives will be poor. , The highly cross-linked acid component is likely to be cut off during resin kneading (which can cause problems in toner design. If the gel component is less than 0.1%, offset and wrapping around the roller are likely to occur; If the content is less than .1% and there are many high molecular weight regions, the grindability will be significantly deteriorated.

If the molecular weight of the solvent-soluble component is 1,000 to 25,000, there is no main peak value (If the main peak value is 25,000 or more, the fixing temperature of the prepared toner will increase and the fixing temperature range will be narrowed. If the molecular weight of the main peak value is less than 1,000, the produced toner will have significantly poor offset resistance, poor wrapping around the roller, and problems with blocking. may occur.

The molecular weight of the sub-peak or sub-shoulder value is 3,000
If the value is not 150,000 or more than 150,000, the dispersibility of the additive will be poor, the fixing temperature will rise significantly, and the grindability will also deteriorate significantly. If the molecular weight of the sub-peak or sub-shoulder value is 3,000 or less, the produced toner will have poor offset resistance and poor wrapping around a roller, which may cause problems in blocking. In the toner of the present invention, the above-mentioned problems are significantly improved, and a toner with excellent pulverizability, excellent offset resistance and roller wrapping resistance, wide fixing temperature range, and excellent development properties can be obtained.

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.

Furthermore, in the present invention, a polymer in which a condensate of an organic tin compound is uniformly dispersed means that when a toner is made using the polymer, nigrosine is dispersed unevenly or in a state where nigrosine is decomposed. This means that fog during development, toner scattering, image unevenness due to current sleeve contamination, etc. do not actually occur.

Specific examples of condensates of organotin compounds according to the present invention are illustrated below.

(11) (CH= C-CH2)2SnO(A
A'-0H) 0 In the present invention, since the charge control agent is already uniformly dispersed in the toner polymer, there is no need to add any more charge control agent during heating and melting in terms of charging properties. If necessary, they can be added in an appropriate proportion within a range that does not cause any adverse effects.

In this case, the following charge control agent is used. Nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 1627/1983), basic dyes (for example, C,1, Ba5ic Yellow 2 (C,1
, 41000), C, 1, Ba5ic Yellow
3, C01, Ba5ic Red 1 (C,
1,45160), C01, Ba5icRed 9
(C,1,42500), C,1,Ba5ic Vi
oletl (C, 1, 42535), C, 1, Ba5
ic Violet 3 (C.

1.42555), C, 1, Ba5ic Violet
10 (C,1,45170), C,1,Ba5ic
Violet 14 (C, 1, 42510),
C01, Ba5ic Blue 1 (C, 1, 4
2025), C,1,Ba5icBlue 3 (C
, 1, 51005), C, 1, Ba5ic Blue
5 (C,1,42140), C,1,Ba5ic
Blue 7 (C, 1° 42595), C, 1, B
a5ic Blue 9 (C, 1, 52015), C
,1,Ba5ic Blue 24 (C,1,
52030), C, I.

Ba5ic Blue 25 (C, 1,520
25), C,1, Ba5icBlue 26 (C,
1,44045), C,1,Ba5ic Green
l (C, 1, 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, ferrocyanide) compound, etc.), C, 1,5 oventBlack
3 (C, 1, 26150), Hansa Yellow G
(C.

1.11680), C, 1, Mordlant Bl
ack 11, C01, P i g m e n t
B 1 a c k 1, gilt night, asphalt, etc.

Or, for example, benzylmethyl-hexadecyl ammonium chloride, decyl-trimethyl ammonium chloride, dialkyltin compounds such as dibutyl and dioctyl, metal salt glasses of higher fatty acids, inorganic fine powders such as mica and zinc oxide, metal complexes of EDTA and acetylacetone, etc. , polyamine resins such as vinyl polymers containing amino groups and condensation polymers containing amino groups.

Good results can also 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 preferably 0.1 to 50% by weight, preferably 0.5 to 10% by weight, and more preferably 3 to 5% by weight in terms of toner concentration.

All known carriers can be used in the present invention, such as magnetic powders such as iron powder, ferrite powder, and nickel powder, glass beads, etc., and carriers whose surfaces have been 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, lead, magnesium, tin, and other metals such as iron, cobalt, and nickel. Examples include alloys of metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

These ferromagnetic materials have an average particle size of 011 to 2 μm, preferably 0.1 to 1 μm, particularly preferably 001 to 0.5 μm.
m is preferred, and the amount 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 150 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, 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 are preferably 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. 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 5 to 20 pm.

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 to obtain a toner, a method of forming a capsule toner consisting of a core and a shell, etc. 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 heated to reflux temperature. To this, 90 parts of styrene, 1 part of α-methylstyrene
A mixture of 0 parts, 10 parts of organic tin compound condensate (1), and di-tert-butyl peroxide parts was added dropwise over 4 hours, and further under cumene reflux (146 to 156°C).
Solution polymerization was completed over 4 hours, and cumene was removed to obtain low molecular weight polymer-1.

Next, low molecular weight polymer - 130 parts, styrene 54 parts, n
-Butyl acrylate 16 parts, divinylbenzene 0
．． A homogeneous mixture of 3 parts of benzoyl peroxide and 0.8 parts of partially saponified polyvinyl alcohol 0.1% aqueous solution 5
00 parts, and polymerized for 15 hours at a polymerization temperature of 80°C to uniformly mix from a high molecular weight polymer containing a gel component to a low molecular weight polymer, and furthermore, a condensate of an organic tin compound (1) was obtained. A pearl-like resin composition that was evenly dispersed was obtained and dried under reduced pressure to obtain a resin composition-1.

Approximately 0.5 g of resin composition = 1 was accurately weighed, placed in a thimble filter paper (Toyo Roshi Model No. 86R), and Soxhlet extracted for 6 hours using 180 ml of chloroform as a solvent.
After evaporating the medium in the extracted soluble components, vacuum drying was performed at 100°C for 12 hours, and the amount of soluble resin components was weighed. From the sample weight and this value, gel components were determined according to the above formula. The weight (degree of crosslinking) was determined.Furthermore, this soluble resin component was dissolved in THF to prepare a sample with a concentration of 0.1% by weight, which was passed through a sample pretreatment filter for non-aqueous systems and used as a sample for GPC.GPC measurement 5h as a column for
Using odex KF-80M, it was installed in a 40°C heat chamber of a GPC measuring device (150CALC/GPC manufactured by Waters) at a THF flow rate of 1 ml/min.
The detector is under R1 condition and the sample is 200μ! GPC was measured by injection. The calibration curve for molecular weight measurement is 0.5×10” molecular weight.

2.35X10", IO, 2Xlo3, 35X10",
ll0XIO3゜200X10', 470X103.
1200X10", 2700X10".

A THF solution of a 10-point monodisperse polystyrene reference material (manufactured by Waters Inc.) of 8420 x 10" was used. The weight of the gel component of resin composition-1 was 28% by weight, and the molecular weight main peak value of the eluted component was 4500. Subpeak value was 36. .00
It was 0. A chromatogram obtained by GPC is shown in FIG.

[Synthesis Example 2] Except for using 0.4 parts of divinylbenzene and 0.9 parts of benzoyl peroxide as an initiator in suspension polymerization,
Pearl-shaped resin composition-2 was obtained in the same manner as in Synthesis Example-1. The gel component of the resin composition is 45%, the molecular weight of the eluted component is 4,500, the main peak value is 4,500, and the shoulder value is 28,0.
It was 00.

[Synthesis Example 3] Pearl-shaped resin composition-3 was prepared in the same manner as Synthesis Example-1 except that 0.4 parts of triethylene gelcol diacrylate was used instead of divinylbenzene as a crosslinking agent in the suspension polymerization. Obtained. Gel component of the resin composition: 30%
The main peak value of the molecular weight of the eluted component was 4,500, and the sub-peak value was 42,000.

[Synthesis Example 4] In the synthesis of a low molecular weight polymer, carbon tetrachloride was added to the solvent, and 90 parts of styrene, 10 parts of α-methylstyrene, and di-
Low molecular weight polymer-2 was synthesized in the same manner as low molecular weight polymer-1 except that 4 parts of t-butyl peroxide was used.
I got it. Next, a pearl-shaped resin composition-4 was obtained in the same manner as in Synthesis Example 1 except that 30 parts of low molecular weight polymer-2, 4 parts of α-methylstyrene, and 1.3 parts of benzoyl peroxide were used. Ta. 20% gel component of the resin composition
, the molecular weight main peak value of the eluted component was 1,300. The shoulder value was 12,000.

[Synthesis Example 5] Low molecular weight polymerization-1 except that in the synthesis of a low molecular weight polymer, α-methylstyrene was not used, the amount of styrene was increased by that amount, and 2.2 parts of di-t-butyl peroxide was used.
Low molecular weight polymer-3 was obtained in the same manner as in the synthesis. Next, a pearl-shaped resin composition-5 was obtained in the same manner as in Synthesis Example 1 except that 310 parts of a low molecular weight polymer and 0.5 parts of t-butylperoxy 2-ethylhexanoate were used as an initiator. . The gel component of the resin composition was 41%, and the main peak value of the molecular weight of the eluted component was 110,000. The sub-peak value was 25,800.

[Synthesis Example 6] In the synthesis of a low molecular weight polymer, α-methylstyrene was not used, the amount of styrene was increased by that amount, and the sheet tert
Low molecular weight polymer-4 was obtained in the same manner as the synthesis of low molecular weight polymer-1 except that 2.5 parts of -butyl peroxide was used. Next, a pearl-shaped resin composition was prepared in the same manner as in Synthesis Example 1 except that 430 parts of a low molecular weight polymer and 0.2 parts of t-butylperoxy 2-ethylhexanoate were added as an initiator. Product-6 was obtained. The gel component of the resin composition was 42%, the main peak value of the molecular weight of the eluted component was 28,000, and the sub-peak value was 181,000.

[Synthesis Example 7] In the synthesis of a low molecular weight polymer, 90 parts of styrene, 10 parts of α-methylstyrene, and 8 parts of di-t-butyl peroxide were used instead of using the condensate (1) of an organic tin compound. Low molecular weight polymer-5 was obtained in the same manner as low molecular weight polymer-1. Next, add 3 parts of low molecular weight polymer-5.
0 parts, 54 parts of styrene.

A pearl-shaped resin composition was prepared in the same manner as in Synthesis Example 1 except that 16 parts of n-butyl acrylate, 1.2 parts of divinylbenzene, and 0.8 parts of t-butylperoxy-2-ethylhexanoate were used. I got a 7.

The gel component of the resin composition is 78%, the main peak value of the molecular weight of the eluted component is 3,800, and the sub-peak value is 86.0.
It was 00.

Table 1 [Example 1] The above materials were thoroughly mixed using a blender, and then kneaded using two rolls heated to 150°C. After the kneaded material was left to cool naturally, it was 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 11 to 12 μm. I got it. Silica produced by a wet method was mixed with this in a Henschel mixer to form a toner. This toner was continuously coated at 3,00% using a Canon NP-3525 copier using an OPC photoreceptor.
After 00 sheets of durability, the image density was 1.2 to 1.3.
Clear images with high resolution and no fog were obtained. Furthermore, when we examined the offset, fixing properties, and wrapping by changing the fixing roller temperature using the NP-3525 fuser, as shown in Table 2, no offset occurred from 140°C to 230°C, and fixing at 150°C It also had good properties and did not get wrapped around the rollers. It was also found that this toner has excellent crushability and blocking resistance at 50° C. for one day.

[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 NP-3525 manufactured by Canon was used.
After 3,000 consecutive copies were made using a copier,
A clear image with high resolution and no fog was obtained with an image density of 1.25 to 1.35. Furthermore, when we examined the offset, fixing test, and wrapping by changing the fixing roller temperature using the NP-7550 fuser, as shown in Table 2, no offset occurred from 140°C to 230°C.
The fixability at 50° C. was good, and no wrapping around the roller occurred. It was also found that there was no problem with the blocking properties of the toner at 50°C for one day, and that this toner also had excellent crushability.

[Example 3] Example 1 except that resin composition-3 was used.
When a toner was prepared in the same manner as above and subjected to 3,000 continuous copies using a Canon NP-3525 copier, clear images with an image density of 1.15 to 1.3 and no fog and high resolution were obtained. . In addition, when we investigated the offset, fixing performance, and wrapping by changing the temperature of the fixing roller using the NP-3525 fuser, we found that the results are shown in Table 2 (offset does not occur between 140°C and 230°C, but does not occur at 150°C). The fixing properties were relatively good, and no wrapping around the roller occurred.Furthermore, the blocking properties of this toner at 50° C. for one day were problematic (although it was found that the toner's pulverization properties were also excellent).

[Example 4] A toner was prepared in the same manner as in Example 1 except that 4100 parts of the resin composition was used, and a toner was prepared using Canon NP-3.
After 3,000 continuous sheets of durability with a 525 copier,
A clear image with high resolution and no fog was obtained with an image density of 1.2 to 1.3. Using the NP-3525 fuser, we investigated offset, fixing performance, and wrapping by changing the temperature of the fixing roller. As shown in Table 2, offset did not occur between 140°C and 230°C, and the fixing performance at 150°C was comparable. The results were good, and no wrapping around the roller occurred. Further, the blocking property at 50° C. for one day was completely satisfactory, and the toner pulverization property was almost satisfactory.

[Comparative Example 1] Example 1 except that 5100 parts of the resin composition was used.
Create toner in the same manner as Canon NP-352.
When I ran 3,000 continuous sheets with 5, the image density was 1.
．． 1 to 1.2, a slightly foggy image is obtained, NP-
Offset and fixability with 3525 fixing device.

In the winding evaluation, there was no offset at 230°C, no blocking at 50°C for one day, and no winding on the roller, but offset at 140°C, and 150°C.
The fixing properties were poor (and the crushability was extremely poor).

[Comparative Example 2] Example 1 except that 6100 parts of the resin composition was used.
and all (make toner in the same way, Canon type NP-3
525 for 3,000 continuous sheets, the images obtained had no fog, but the image density was 1.05 to 1.1.
It was as low as 5. In addition, in the evaluation of offset and fixing properties of 9 wraps using the NP-3525 fuser, no offset at 230°C, no blocking at 50°C for one day, and no wrapping around the roller occurred, but offset at 140°C and 140 Both the fixing properties at ℃ were poor (and the toner pulverization properties were extremely poor).

[Comparative Example 3] A toner was prepared in the same manner as in Example 1 except that 7100 parts of the resin composition and 2 parts of Nigrosine were used, and the toner was subjected to continuous 3,000-sheet durability using Canon NP-3525. The image density was as low as 0.90 to 1.08, and only images with a slight fog were obtained.

Offset and fixing performance with NP-3525 fixing device.

In the evaluation of wrapping, there were no problems with offset at 230°C, wrapping, and blocking property at 50°C for one day, but the fixing performance at 150°C and offset at 140°C were poor (and the crushability was also satisfactory). It wasn't.

Table-2

[Brief explanation of the drawing]

FIG. 1 shows a chromatogram for Example 1, and FIG. 2 shows a chromatogram for Comparative Example 1.

Claims (1)

[Claims] (1) Contains a gel component of 0.1 to 60% by weight, has a main peak value in the molecular weight region of 1,000 to 25,000, and has a molecular weight of 3,000 in a GPC chromatogram of a tetrahydrofuran soluble component. ~150,00
It is a polymer having at least one subpeak or subshoulder in the region of 0, and has a molecular weight of 1,000 to 25,
A low molecular weight polymer that gives a main peak at 000 has the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 and R_2 are monovalent organic groups and represent the same or different groups, and M 1. A toner for developing an electrostatic image, characterized in that it is polymerized in the presence of a condensate of an organic tin compound represented by a group III element in the table, and X represents a monovalent group.