JPS61124961A - Electrophotographic developing composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition capable of fixing at a low temp. by incorporating to said composition, a polyester resin obtd. by copolycondensating a specific diol component, a carboxylic acid component, 5-30mol% of a specific two or more valence alcohol and/or epoxy resin contg. a tertiary amino group on the basis of the total components as a main component of a binding agent. CONSTITUTION:The main component of the binding agent comprises the polyester resin obtd. by copolymerizing the diol component shown by formula I, the carboxylic acid component composed of a tetra carboxylic acid or its acid anhydride or its lower alkyl ester shown by formula II and 5-30mol% either the two or more valence alcohol or the carboxylic acid shown by formulas III-V or the two or more valence alcohol and/or the epoxy compd. contg. the tertiary amino group shown by formula VI. The above described polyester resin has 80-180 deg.C softening point.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a developer composition for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, and the like. More specifically, the present invention relates to a positively chargeable developer composition.

[Conventional technology and problems]

As a conventional electrophotographic method, as described in U.S. Patent Nos. 2,297,691 and 2,357,809, etc.
Uniformly charge the photoconductive insulating layer.

The layer is then exposed to light, the charge on the exposed areas dissipates to form an electrical latent image, and a colored electrically charged fine powder called toner is deposited on the latent image. visualized by (development process),
After transferring the obtained visible image to a transfer material such as transfer paper (
(transfer step), and permanent fixation (fixing step) by heating, pressure or other suitable fixing methods.

In this way, toner is used not only in the development process but also in the transfer process.
It must have the functions required in each step of the fixing process.

Generally, toner is subjected to mechanical frictional force due to shearing force and impact force during mechanical operation in a developing device, and deteriorates during copying of tens to tens of thousands of sheets. To prevent such toner deterioration, it is best to use a strong resin with a large molecular weight that can withstand mechanical friction, but these resins generally have a high softening point and are suitable for non-contact fixing methods such as oven fixing and infrared fixing. With radiant fixing, the thermal efficiency is poor, so fixing is not sufficient.Also, since the contact fixing method has good thermal efficiency, even in the widely used heat roller constant fixing method, it is necessary to use the heat roller in order to achieve sufficient fixation. It becomes necessary to raise the temperature, which not only causes adverse effects such as deterioration of the fixing device, curling of paper, and increased energy consumption, but also causes a significant drop in production efficiency when producing toner by pulverizing such resins. descend. Therefore, it is not possible to use a binder resin that has a high degree of polymerization and also has a high softening point.

On the other hand, in the heat roller fixed fixing method, the heating roller surface and the toner image surface of the fixing sheet come into pressure contact, so the thermal efficiency is extremely high, and it is widely used from low speeds to high speeds.
When the heating roller surface and the toner image surface come into contact, the toner adheres to the heating roller surface and is transferred to a subsequent transfer paper or the like. A so-called offset phenomenon is likely to occur. In order to prevent this phenomenon, the surface of the heated CI-9 is treated with a material with excellent mold release properties such as fluorine-based resin, but a mold release agent such as silicone oil is also applied to the surface of the heating roller to prevent the offset phenomenon. Completely prevented.

However, the method of applying silicone oil etc.
This is not preferable because the fixing device is not only bulky but also complicated, resulting in large costs and is likely to cause trouble.

Also, as described in Japanese Patent Publication No. 55-6895 and Japanese Patent Application Laid-open No. 56-98202, there is a method of improving the offset phenomenon by widening the molecular weight distribution width of the binder resin, but this method does not require a high degree of polymerization of the resin. It is also necessary to increase the fixing temperature.

As a further improved method, as described in Japanese Patent Publication No. 57-493, Japanese Patent Application Laid-open No. 50-441336, and Japanese Patent Application Publication No. 57-57553, there is a method of improving the offset phenomenon by making the resin asymmetrical and crosslinking it. However, the retention point has not improved.

Generally, the minimum fusing temperature is between cold offset and hot offset, so the usable temperature range is between the minimum fusing temperature and hot offset. By raising the hot offset temperature as much as possible, the fixing temperature used can be lowered and the usable temperature range can be expanded, resulting in energy savings, high-speed fixing, and prevention of paper curl. In addition, since double-sided copying can be performed without trouble, there are many advantages such as making the copying machine more intelligent, controlling the temperature of the fixing device more accurately, and relaxing the tolerance range.

Therefore, resins and toners with good fixing properties and offset resistance are always desired.

Furthermore, when using a styrene-based binder resin to meet such requirements, Japanese Patent Application Laid-Open No. 49-65232, 4i! As described in Japanese Patent Application Laid-open No. 50-28840 and Japanese Patent Application Laid-open No. 50-81542, methods of adding paraffin wax, low molecular weight polyolefin, etc. as anti-offset agents are known, but they are ineffective if the amount added is small. It has been confirmed that if the amount is too large, the developer deteriorates quickly, and in the case of polyester resin, even if the anti-offset agent mentioned above is applied, it has little effect, and if the amount used is too large, the developer deteriorates quickly.

Polyester resin inherently has good fixing properties.

As described in US Pat. No. 3,590,000.

The non-contact fixing method can also fix the image satisfactorily, but the offset phenomenon tends to occur, making it difficult to use the fixed fixing method using a heat roller. JP-A-50-44856, JP-A-57
As described in JP-A-57555 and JP-A-57-109875, polyester resins with improved anti-offset properties using polyhydric carboxylic acids do not have sufficient anti-offset properties to be used, or do not have sufficient anti-offset properties to be used. This does not sacrifice the low-temperature fixability inherent to polyester resins, but also has extremely poor crushability in the toner production process, which also poses problems in developer production.

Further, toner is generally composed of a binder resin, a colorant, and other additives, and the binder resin is the main component.

As toner binder resins, coumaron indene resins, terpene resins, styrene resins or their copolymer resins, polyester resins, epoxy resins, etc. are generally used, but there are few binder resins that are strongly positively charged by friction. . To make toner positive polarity, it is generally known to add additives such as nigrosine dye as a charge control agent, but this method has poor compatibility with the binder resin that constitutes the main component of toner, and If the particles are mixed for a long time in the developing device, the particles will be destroyed, and if nigrosine etc. is simply dispersed, particles with the opposite (negative) polarity that do not contain nigrosine etc. will be generated, which will interfere with the image signal. A so-called soil pressure phenomenon occurs in which toner adheres to areas where there is no toner. Furthermore, when nigrosine dye or the like is used, since it has hydrophilic properties, the amount of charge changes depending on the humidity of the environment, resulting in a decrease in image quality. In addition, nigrosine dyes generally have strong coloring and have drawbacks such as incompatibility with color toners and dusting. In view of the above, it is desired to develop toner binder resins and toners that are strongly positively charged, unaffected by environmental humidity, and have excellent durability.

Fixed images are often stored in files, but depending on the material of the file, problems such as fusing of the copy to the file and transfer of the image often occur.

The present invention was made to meet these demands, and its purpose is to provide a developing device that can prevent offset without applying an anti-offset liquid in a heat roller fixed fixing method, and that can fix at a lower fixing temperature. The goal is to provide medicine.

Another object of the present invention is to provide a developer which can prevent offset without adding an offset preventing agent in a heat roller constant fixing method and which can be fixed at a lower fixing temperature.

Another object of the present invention is to provide a developer that has good fluidity, does not cause blockiness, and has a long life (hard to deteriorate).

Another object of the present invention is to improve kneading properties during developer production.

The objective is to provide a developer with good pulverizability.

Another object of the present invention is to provide a dry developer for electrophotography,
It is an object of the present invention to provide a toner that forms sharp, capri-free images using a toner binder resin that is strongly positively charged in nature, and more particularly to improve the above-mentioned drawbacks due to the influence of environmental humidity. It is an object of the present invention to provide a toner in which the binder resin essentially has positive triboelectric charging properties, which is extremely small and has excellent durability.

Another object of the present invention is to provide a clear color developer with good transparency.

Another object of the present invention is to provide a developer that does not cause fusion with files or transfer of images to files even when stored in files.

[Means for solving problems]

The present inventors have achieved the present invention as a result of extensive research to achieve the above object.

That is, the present invention provides an electrophotographic developer composition comprising a binder resin and a colorant, in which the main component of the binder resin is (a) represented by the following formula (wherein R represents ethylene or propylene group, x+y
each represents an integer greater than or equal to 1, and! The average value of +7 is 2-7. ) and (b) (a) a divalent carboxylic acid containing alkyl or alkenylsuccinic acid, its acid anhydride, or its alkyl ester (t)) and! 7 Mellitic acid or its acid anhydride or its lower alkyl ester and (C) the following formula % formula % (or an alkenylene group or alkylene group having 5 to 50 carbon atoms having one or more side chains having 3 or more carbon atoms) A carboxylic acid component consisting of a tetracarboxylic acid represented by, its acid anhydride, or its lower alkyl ester, in which (b) is 0 to 30 mol% of the total carboxylic acid component, and (C) is the total carboxylic acid component 0 to 20 mol% of the carboxylic acid component; Divalent or higher alcohols or carboxylic acids, or divalent or higher alcohols represented by the following general formula (R1, R2, only 51"71RII in formulas (B) to (4))
IR91R1゜, R1□.

R1□l "i31"i41 R16 has 1 carbon atom
-15 alkylene group, It6 represents an alkyl group or alkylene group having 1 to 10 carbon atoms, and X represents hydrogen or a hydroxyl group. R1□ and RlB represent an alkyl group having 1 to 4 carbon atoms, and R1□ and RlB may form a heterocyclic ring of the same nitrogen atom. R5 and R11 represent an alkyl group having 1 to 10 carbon atoms. Moreover, R15 represents charcoal. ) and/or (1)) An electrophotographic developer, which is a polyester resin completely cocondensed with an epoxy compound having a tertiary amino group, and the softening point of the polyester resin is 80 to 180°C. This relates to a composition.

The diol component (a) in the present invention includes polyoxypropylene (2゜2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (
3,3) -2,2-bis(4-hydroxyphenyl)
Globan, polyoxyethylene (2°a) -2,2
-bis(4-hydroxyphenyl)furopane, polyoxypropylene(2,0)-polyoxyethylene(2,0
) -2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (6) -2,2-bis(4
-hydroxyphenyl)propane, and optionally other polyols, such as polyoxypropylene (12) -2,2-bis(4-hydroxyphenyl)propane, polyoxyphenylethylene (3
) -2,2-bis(4-hydroxyphenyl)propane, ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol, nonamethylene Glycol, Decametine/Glycol, Neopentylene Gelicol, p-
Xylylene glycol.

m-xylylene glycol, 1,4-cyclohexane dimetatool, 1,4-cyclohexane jetanol, 1
, 4-cyclohexanediol, 1°5-cyclohexane dimetatool, glycerin.

Polyoxyethylene (6) glycerin, polyoxypropylene (12)-pentaerythritol, etc. can be added to the polyol component in an amount of about 10 mol% or less, but polyoxyphenylethylene <S>-2,2-bis(4-hydroxy) With highly sterically hindered substances such as phenyl)furopane, the reaction proceeds, m<, glycerin, polyoxyethylene (
6) Care must be taken when using a resin containing a highly hydrophilic polyol such as pentaerythritol, as the image quality of the developer tends to deteriorate.

In addition, among the carboxylic acid components of (1) in the present invention, the alkyl or alkenyl succinic acids include n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, indodecyl succinic acid, n-octylsuccinic acid, n-
-octenysuccinic acid, n-butylsuccinic acid, etc.

By using alkyl or alkenyl succinic acid, it is possible to lower the minimum fixing temperature without lowering the offset generation temperature, but if it is too little, the effect will be weak, and if it is too much, the Tg will decrease and toner caking will easily occur. It's not stupid, and it becomes difficult to control the reaction. Therefore, its content is preferably 0.5 to 50 mol% in the carboxylic acid component. In addition, divalent carboxylic acids other than alkyl or alkenylsuccinic acids that can be used in the present invention include fumaric acid,
Maleic acid, succinic acid, adipic acid, speric acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid,
Examples include 2,6-su7thalenedicarboxylic acid.

(1)) Trimellitic acid is a preferable acid component that improves the offset phenomenon, but if it is present in large amounts, it is difficult to control the reaction, and it is difficult to obtain polyester resin with stable performance, and the resin becomes hard and pulverized. (difficult), undesirable phenomena such as a significant decrease in toner conversion efficiency and an increase in the minimum fixing temperature occur. Therefore, the content of trimellitic acid is 0 to 30 mol% in the carboxylic acid component. Furthermore, as the tetracarboxylic acid (0) used in the present invention, (1) 4-neopentylizonyl-1,2, 6,7-hebutanetetracarboxylic acid (2) 4-neopentyl-1,2,6,7-hebutene (
4)-Tetracarboxylic acid (3) 3-methyl-4-hebetenyl-1,2,5,6-
Hexanetetracarboxylic acid (4) 3-methyl-3-hebutyl-5-methyl-1,2
,6,7-heptene(4)-tetracarboxylic acid(5)5
-nonyl-4-methylisonyl-1,2,5,6-hexanetetracarboxylic acid (6) 3-desylizonyl-1,2,5,6-hexanetetracarboxylic acid (7) 3-nonyl-1,2, 6,7-heptene(4)-
Tetracarboxylic acid (8) 3-decenyl-1,2,5,6-hexanetetracarboxylic acid (9) 3-butyl-5-ethylenyl-1,2,5,6-
Hexanetetracarboxylic acid (1o) s-methyl-4-butyrisonyl-1,2,
S, 7-hebutanetetracarboxylic acid (11) 5-methyl-4-butyl-1,2,6,7-heptene (4)-tetracarboxylic acid (12) s-methyl-5-octyl-1,2 ,6,
Examples include 7-heptene(4)-tetracarboxylic acid. The structural formulas of these compounds are shown below. 1. For convenience, all are shown in the form of acid anhydrides.

By using these tetracarboxylic acids, the minimum fixing temperature can be lowered considerably in the fixing process, and offset resistance can be improved, but a small amount will have little effect; If used, not only will the fixing properties deteriorate, but it will also be difficult to control the degree of resin polymerization during manufacturing.
Therefore, its content is 0 to 20 mol% in the carboxylic acid component.
It is more preferably 1 to 10 mol%. Similar tetracarboxylic acids include aliphatic tetracarboxylic acids without side chains or aliphatic tetracarboxylic acids with very short side chains, such as 1°2.7.8-octanetetracarboxylic acid, 1,2,5. 6-hexanetetracarboxylic acid, 1
, 2,11.12-dodecanetetracarboxylic acid, 3-methyl-1,2,10゜11-wandecanetetracarboxylic acid, 4-ethyl-1,2,7,8-octene(4)-tetracarboxylic acid However, tetracarboxylic acids having 11 or more side chains with 3 or more carbon atoms have no effect on low-temperature fixing properties or anti-offset properties, and increasing the amount used tends to cause toner caking, making it difficult to manufacture. It is also difficult to control the reaction time, which is undesirable.

Also, alicyclic polycarboxylic acids, aromatic tetracarboxylic acids, such as 5-methyl-5-succinyl-4-cyclohexene-1,2-dicarboxylic acid, pyromellitic anhydride, benzophenonetetracarboxylic acid, fuculobentene Tetracarboxylic acid, melfanic acid, and the like often cause decomposition, sublimation, coloring, etc. during resin production, and are less effective in low-temperature fixing properties and offset resistance.

Further, as the (c)(a) dihydric or higher alcohol or carboxylic acid having a tertiary amino group in the present invention, the following can be mentioned.

(1) Glycol N, M'-bis(hydroxymethyl)piperazine, having the chemical structure shown by the general formula
N,N'-bis(hydroxymethyl)methylbiperazine, N,N'-bis(2-hydroxypropyl)piperazine, N,N'-bis(2-hydroxypropyl)
-2,5-dimethylpiperazine, N, M'-bis(
2-hydroxyethyl)-2,5-dimethylpiperazi 7
, N,N'-bis(2-hydroxy-2-methylglobil)piperazine, N,N'-bis(2-methyl-2-
hydroxynonyl)piperazine, N,N'-bis(
2-hydroxy-5-methoxylglobil)piperazine, N,N'-bis(3-phenyl-2-hydroxypropyl)piperazine, and the like.

(2) dicarboxylic acid or its lower ester N,N'-bis(carboxymethyl)piperazine having the chemical structure represented by general formula (2),
N,N'-bis(carboxyethyl)piperazine, H
, M'-bis(carboxymethyl) -2゜6-dimethylpiperazine, N, N'-bis(5-carboxypropyl)piperazine, N-(2-carboxyethyl) -N
'-(carboxylic methyl)piperazine, etc.

(3) alcohol N, N-bis(2-hydroxyethyl)methylamine having a chemical structure represented by general formula (g);
N,N-bis(2-hydroxyethyl)cyclohexylamine, N,N-bis(2-hydroxypropyl)methylamine% N,N-bis(2-hydroxypropyl)inglovirine, triethanolamine, etc.

(4) Carboxylic acid or its lower ester M having the chemical structure represented by general formula (g), N-bis(carboxymethyl)methylamine, N
, N-bis(2-carboxycmethyl)methylamine,
N,N-bis(2-carboxyethyl/I/)-inglobylamine, N-carboxymethyl-11-(2-carboxyethyl)methylamine, nitrilotriacetic acid, and the like.

(5) Glycol 2-methyl-2-N,N-dimethylaminemethyl-1, having a chemical structure represented by general formula (V),
3-Globanediol, 2-methyl-2-N, N-diethylaminomethyl-1,3-propanediol, 2-ethyl-2-N, N-di-n-propylaminomethyl-
1,3-propanediol, 2-methyl-2-N,N-
Di-n-butylaminomethyl-1,3-gulonokundiol, 2-methyl-2-N,N-dimethylaminoethyl-1,5-propanediol, Z-methyl-2-piperidinomethyl-1,3-propane Diol, bis(2-N
, N-dimethylaminomethyl)-1,5-propanediol, bis(2-M, 11-diisoglobylaminemethyl)-1,5-jropanediol, 3-methyl-3
-N,N-dimethylaminomethyl-1,5-bentanediol, 3-methyl-5-N,N-diethylaminomethyl-1,5-bentanediol, 4-ethyl-4-N
, N-di-isopropylaminomethyl-1,6-hexanediol and the like.

(6) dicarboxylic acid 4-methyl-4-N,N-dimethylaminomethyl-azelaic acid, 5-methyl-5-N,N-diethylaminoethyl-undecanedioic acid having a chemical structure represented by the general formula ff), 6-Nichiru 6- N, N
-di-n-propylaminomethyl-brassillic acid, 9-
Methyl-9-N,N-dimethylaminomethyl-nonadecanedionic acid, etc. 0 (7) Alcohol N, N' represented by general formula (4)
-dimethyl-M, N'-bis(2-and droxyethyl)ethylenediamine, N,N'-dicyclohexyl-
N,N'-bis(2-hydroxyethyl)hexamethylenediamine% N,N'-diethyl-N,N'-bis(2-hydroxypropyl)ethylenediamine, N
, N'-diptyl-N.

N'-bis(2-hydroxypropyl)pentamethylenediamine, etc.

Examples of the epoxy compound having a tertiary amine group (1) in the present invention include the following.

The above components having tertiary amino groups positively charge the triboelectrically negatively charged polyester, but if it is less than 5 mol% of the total components, it has no effect, and if it exceeds 3σ mol%, the moisture resistance of the toner increases. becomes worse. In addition, components having primary and secondary amino groups are preceded by amidation and are less effective in making the charging characteristics positive. Particularly preferably, piperazine derivatives, triethanolamine or tt nitrilotriacetic acid are used.

Further, the softening point (A8TM l!128-31TI?: equivalent ring and ball softening point) of the polyester resin used in the developer composition of the present invention is preferably 80 to 180°C, and if it is too low, the offset resistance will be insufficient. However, if it is too high, the fixing properties will be insufficient.

The polyester resin used in the present invention is prepared by combining a polyhydric carboxylic acid component and a polyol component in an inert gas atmosphere.
It can be produced by condensation polymerization at a temperature of ~250°C. At this time, commonly used esterification catalysts such as zinc oxide, stannous oxide, diptyltin oxide, dibutyl are used to accelerate the reaction. Tin silacrate etc. can be used. It can also be produced under reduced pressure for the same purpose.

Colorants used in the present invention include carbon black, acetylene black, and phthalocyanine 7'A/-.
, Permanent Brown FG, 7'lJ Leanto First Scarlet, Pigment Green B10-Damine-B Base, Tsurpen Trend 49, Solpen Torez)
146.Solvent Blue 35 and mixtures thereof, and are usually used in an amount of about 1 to 15 parts by weight per 100 parts by weight of the binder resin.

When making a magnetic toner using the binder resin according to the present invention,
Examples of magnetic materials include alloys or compounds containing ferromagnetic elements such as ferrite and magnetite.
The magnetic material can be used in the form of a fine powder with an average particle size of 0.1 to 1 μm and dispersed in a binder resin in an amount of 40 to 70% by weight.

Known property improving agents contained in toner include charge control agents, anti-offset agents, fluidizing agents, etc., but since the resin of the present invention has good properties by itself,
There is no need to add these property improvers during toner preparation.
Alternatively, even if it is added, it may be added in a small amount.

〔Example〕

Examples of the present invention will be described below, but the BA of the present invention is not limited to these examples.

Example 1 Polyoxypropylene (2,2) -2,2-bis(4
-Hydroxyphenyl)propane 1440F.

Indodecenyl succinic acid 305f1 Fumaric acid 310
F, 5-isodecenyl-1,,2,5,6-hexanetetracarboxylic acid 5f1 trimellitic acid 201 and 3t
Hydroquinone made of glass 3! Put them in a 200℃ flask, attach a thermometer, a stainless steel stirring rod, a dehydration tube with a reflux condenser, and a nitrogen introduction tube, and stir at 200℃ under a nitrogen stream in an electric heating mantle. React,
When the hydroxyl value reached 5 (myKOTi/l) or less, 100f of triethanolamine was added and the reaction was continued at 200°C. The degree of polymerization is AsTMI! The softening point was tracked in accordance with Z8-51T, and the reaction was terminated when the softening point reached 125°C. The resulting resin was a pale yellow solid, and the glass transition temperature measured by DSO (differential calorimeter) was 59°C. 95 parts of the resin and 5 parts of carbon black (Su-Gal 400R, manufactured by Cabot) were milled in a ball mill. After mixing, the mixture was kneaded, pulverized, and classified to obtain a toner having an average particle size of 13.2 μm.

The obtained toner was mixed with carrier iron powder (manufactured by Nippon Tetsuko Co., Ltd.; F
iFV200/30G) and measured the amount of charge using a blow-off type charge amount measuring device, it was +13μC/
It was written as l.

The toner 91f was mixed with carrier iron powder (manufactured by Nippon Tetsuko Co., Ltd.; 1
CFv 200 /s o o ) 1209 t.

Prepare the developer and use a commercially available electrophotographic copying machine (the photoconductor is an organic photoconductor, the roller rotation speed is 255 mm, the temperature of the heat roller in the fixing device is variable for 7 seconds, and the oil coating device is removed). When the image was produced using the , a clear image was obtained with no background smudges, smearing, or missing solid black areas. When the fixing temperature of the fixing device was controlled at 140° C. to 220° C. and the image fixability and offset property were evaluated, the image was sufficiently fixed at 142° C. and no hot offset occurred. After printing up to 50,000 images,
Clear images were obtained with no missing parts of the ground turnip or black peta.

The minimum fixing temperature here means placing a load of 500 tons on a sand eraser with a 150 x 7.5 size bottom and rubbing it back and forth 5 times over the fixed image through the fixing device.

The optical reflection density is measured before and after rubbing with a Macbeth reflection densitometer, and the temperature of the fixing roller is defined as the temperature of the fixing roller when the fixing rate exceeds 70% according to the following definition.Example 2 Polyoxypropylene (2,2) -2,2-bis(4
-Hydroxyphenyl)furopane 140021 octylsuccinic acid 1801t terephthalic acid 660t, and the following epoxy compound 80f % 5F titanium tetrabutoxide were used to produce a resin using the same equipment and procedure as in Example 1 until the softening point reached 125°C. When this occurred, the reaction was terminated. The resulting resin is a pale yellow solid with a glass transition point of 60.5°C.
Met.

After mixing TS resin qs part and 5 parts of carbon black (SU-GA/I/400R manufactured by Cabot Corporation) in a ball mill,
After cross-mixing, pulverization, and classification, a toner with an average particle size of 13.2 μm was obtained. The charge amount of the obtained toner was +14 μc/f.

The toner 91F was mixed with carrier iron powder (manufactured by Nippon Tetsuko Co., Ltd.; K
F"7200/300) 1209 f to prepare a developer, and when an image was produced using the same evaluation machine as in Example 1, a clear image was obtained with no background smudges, bleeding, or missing solid black areas. The fixing temperature of the fixing device was set to 140°C to 220°C.
When the fixing and offset properties of the image were evaluated by controlling the temperature at 145° C., the image was sufficiently fixed at 145° C. and no hot offset occurred. When images were printed up to 30,000 sheets, clear images were obtained with no missing ground or solid black areas.

Example 5 Polyoxypropylene (2,2) -2,2-bis(4
-Hydroxyphenyl)propane 1400F.

N,N'-bis(2-hydroxypropyl)piperazine 202f, dimethyl terephthalate 796F.

Using isododecenyl succinic acid 51F,) trioctyl limellitate 160f and 5t diptyltin oxide,
A resin was produced using the same apparatus 1 procedure as in Example 1, and the reaction was terminated when the softening point reached 125°C. The obtained resin was a pale yellow solid with a glass transition point of 61°C.

95 parts of the resin and s part of carbon black (SU-GAL 400 R, manufactured by Cabot Corporation) were mixed in a ball mill, mixed, crushed, and classified to obtain a toner having an average particle size of 13.3 μm.

The amount of charge of the obtained toner was +15 μc/f.

Station toner 91F with carrier iron powder (made by Nippon Iron Powder Co., Ltd. i1)
When a developer was prepared by mixing it with flFV 200/300) 1209 F and an image was produced using the same evaluation machine as in Example 1, a clear image was obtained with no background smudges, K bleeds, or missing black solid areas. Ta. Set the fixing temperature of the fixing device to 140℃
The temperature was controlled at ~220°C and the fixing and offset properties of the image were evaluated, and the image was sufficiently fixed at 141°C, with no hot offset occurring. When images were printed up to 30,000 sheets, clear images were obtained with no background or black areas missing.

Comparative Example 1 Polyoxyethylene (2,2) -2,2-bis(4-
Hydroxyphenyl)propane 52st.

Polyoxyethylene (z) -2,2-bis(4-hydroxyphenyl)furopane 4881% Fumaric acid 13
9f,) Limellitic acid 126f15-・indecenyl-
1,2,5,6-hexanetetracarboxylic acid 60f1 Isododecenyl succinic acid 170f and 1.5r hydroquinone were placed in a glass 2.04 flask and dehydrated using a thermometer, a stainless steel stirring bar, and a reflux condenser. A tube and a nitrogen introduction tube were attached, and the reaction was carried out in an electric heating mantle at 200° C. with stirring under a nitrogen stream. The reaction was terminated when the softening point reached 122°C. The glass transition temperature by D80 was 62°C.

Claims (1)

[Claims] 1. In an electrophotographic developer composition comprising a binder resin and a colorant, the main component of the binder resin is (a) represented by the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) ( In the formula, R represents ethylene or propylene group, x, y
each represents an integer of 1 or more, and the average value of x+y is 2 to 7. ); and (b) (a) a divalent carboxylic acid containing alkyl or alkenylsuccinic acid, or an acid anhydride thereof, or an alkyl ester thereof; (b) trimellitic acid, an acid anhydride thereof, or a lower thereof; Alkyl ester and (c) the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (X is an alkenylene group or alkylene group with 5 to 30 carbon atoms having one or more side chains with 3 or more carbon atoms) A carboxylic acid component consisting of a tetracarboxylic acid represented by, its acid anhydride, or its lower alkyl ester, in which (b) is 0 to 30 mol% of the total carboxylic acid component, and (c) is 0 to 30 mol% of the total carboxylic acid component. 0 to 20 mol% of a carboxylic acid component and (c) an amount of 5 to 30 mol% of all components (a) having a chemical structure represented by the following general formulas (I) to (V) in the molecule. Divalent or higher alcohols or carboxylic acids, or divalent or higher alcohols represented by the following general formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VI) (R_1, R_2, R_5, R_ in formulas (III) to (VI)
7, R_8, R_9, R_1_0R_1_1, R_1_
2, R_1_3, R_1_4, R_1_6 are alkylene groups having 1 to 15 carbon atoms, and R_6 is an alkylene group having 1 to 10 carbon atoms.
is an alkyl group or an alkylene group, and X represents hydrogen or a hydroxyl group. R_1_7 and R_1_8 represent an alkyl group having 1 to 4 carbon atoms, and R_1_7 and R_1_8
may form a heteroartic ring of the same nitrogen atom. R
_3 and R_4 represent an alkyl group having 1 to 10 carbon atoms. Further, R_1_5 represents an alkyl group having 1 to 3 carbon atoms or ▲a numerical formula, chemical formula, table, etc. are available. )as well as/
or (b) an electrophotographic developer composition, which is a polyester resin obtained by cocondensation polymerization with an epoxy compound having a tertiary amino group, the polyester resin having a softening point of 80 to 180°C. 2. The electrophotographic developer composition according to claim 1, wherein component (c) contains a piperazine derivative, triethanolamine, or nitrilotriacetic acid.