JPH03219254A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To maintain good electrostatic characteristics even if the environment at the time of formation of copied images fluctuates by incorporating specific binder resins into a binder resin. CONSTITUTION:At least one kind of the resin A and at least one kind of the resin B are incorporated into the binder resin. The resin A contains the repeating unit expressed by formula I as a polymer component, previously has a crosslinked structure prior to the prepn. of the dispersion for forming the photoconductive layer and is the resin of 1X10<3> to 1X10<4> weight average mol. wt. which is formed by bonding the acidic group selected from a -PO3H2 group, etc., only to one terminal of the polymer main chain. The binder resin B is the resin which has 5X10<4> to 5X10<4> weight average mol. wt., contains the repeating unit expressed by formula II as a polymer component and previously has a crosslinked structure prior to the prepn. of the dispersion for forming the photoconductive layer. In the formula II, X3 denotes -COO-, -OCO-, -SO2, etc.; Q3 denotes 1 to 22C hydrocarbon group; d1 and d2 respectively denote a hydrogen atom, halogen atom, cyano group, etc. The excellent electrostatic characteristics are maintained in this way even under severe conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having excellent electrostatic properties and moisture resistance.

In particular, it relates to a CPC photoreceptor with excellent performance.

[Conventional technology]

Electrophotographic photoreceptors take various configurations in order to obtain predetermined characteristics or depending on the type of electrophotographic process to which they are applied.

Typical electrophotographic photoreceptors include photoreceptors with a photoconductive layer formed on a support and photoreceptors with an insulating layer on the surface.
A photoreceptor consisting of two photoconductive layers can be produced by the most common electrophotographic processes, namely charging, image exposure and development.
Furthermore, it is used for image formation by transfer, if necessary.

Furthermore, the method of using an electrophotographic photoreceptor as an offset master plate for direct plate making has become widespread (in practical use).In recent years, direct electrophotographic lithography has been used to produce high-quality printed matter with a number of prints ranging from several hundred to several dozen sheets. This is becoming an important printing method.

The binder resin used to form the photoconductive layer of the electrophotographic photoreceptor has excellent film-forming properties itself and ability to disperse photoconductive powder into the binder resin. The photoconductive layer of the recording layer has excellent adhesion to the base material, and the photoconductive layer of the recording layer has excellent charging ability, has low dark decay, large light decay, and low pre-exposure fatigue, and is highly resistant to changes in humidity during photographing. It is necessary to have various electrostatic properties such as the need to stably maintain these properties and excellent imaging performance.

Furthermore, research is being carried out on lithographic printing original plates using electrophotographic photoreceptors, and a binder resin for the photoconductive layer that has both the electrostatic properties of an electrophotographic photoreceptor and the printing properties of a printing original plate has been developed. is necessary.

However, conventionally known binder resins have many problems, particularly in electrostatic properties such as chargeability, dark charge retention, photosensitivity, and smoothness of the photoconductive layer.

To solve these problems, we used a polymer with acidic groups as a binder resin! ! The copolymer component contained in the chain is 0.05~
A low molecular weight resin containing 10% by weight or a low molecular weight resin that binds an acidic group to the end of the polymer main chain (ffw 10”
- 104) to improve the smoothness and electrostatic properties of the photoconductive layer, and to obtain image quality free from background smear, as disclosed in JP-A-63-217354 and JP-A-6, respectively.
No. 4-70761.

In addition, as a binder resin, a resin containing a polymeric component containing an acidic group in the side chain of the copolymer, or bonded to the end of the main chain of the polymer, and containing a thermally and/or photocurable functional group. The technique using this is disclosed in Japanese Patent Application Laid-open No. 1-100554 and Japanese Patent Application No. 1983-3.
No. 9690 discloses a technique in which a resin containing an acidic group in the side chain of the copolymer or bonded to the end of the main chain of the polymer is used in combination with a crosslinking agent, as disclosed in JP-A No. 1-102573 and Japanese Patent Application No. 1983-3969.
1, and a technique using a low molecular weight resin (weight average molecular weight 10' to 104) in combination with a high molecular weight resin (weight average molecular weight 104 or more) is disclosed in JP-A No. 64-564, No. 63-220149, No. 63-2
No. 20140, Japanese Patent Application No. 1982-273547, Japanese Patent Application No. 1999
-116643 and JP-A-1-169455 disclose a technique for using such a low molecular weight material in combination with a heat and/or photo-curable resin.
-26561, respectively. It is stated that by these techniques, the film strength of the photoconductive layer can be made sufficient and the mechanical strength can be increased without impeding the above-mentioned properties due to the use of a resin containing an acidic group at the side chain or terminal end. has been done.

(Problem to be solved by the invention) However, even when these resins are used, the environment is high temperature and
It has been found that it is still insufficient to maintain stable performance when the temperature fluctuates significantly from high temperature to low temperature and low humidity. In particular, scanning exposure methods using semiconductor laser light require longer exposure times than conventional simultaneous exposure methods using visible light across the entire surface, and there are restrictions on exposure intensity. , higher performance is required in terms of photosensitivity.

Furthermore, when a scanning exposure method using semiconductor laser light is adopted in an electrophotographic lithographic printing original plate, actual tests using a conventional photoreceptor show that the electrostatic properties described above are unsatisfactory. Especially E+zt and E l/I
. The large difference between the gradation and the gradation of the copied image becomes soft, and furthermore, it becomes difficult to reduce the residual potential after exposure, resulting in noticeable fogging of the copied image.Also, even when printed as an offset master, This has resulted in serious problems such as the appearance of pasted marks from printed manuscripts on printed matter.

The present invention is intended to improve the problems of conventional electrophotographic photoreceptors as described above.

An object of the present invention is to provide an electrophotographic photoreceptor that stably maintains good electrostatic properties and produces clear, high-quality images even when the environment during copy image formation changes such as low temperature and low humidity or high temperature and high humidity. It is to provide.

Another object of the present invention is to provide a cpci H photosensitive photoreceptor with excellent electrostatic properties and low environmental dependence.

Another object of the present invention is to provide an electrophotographic photoreceptor that is effective in a scanning exposure method using semiconductor laser light.

A further object of the present invention is to use an electrophotographic lithographic printing original plate that has excellent electrostatic properties (particularly dark charge retention and photosensitivity), reproduces a copy image that is faithful to the original image, and is capable of covering the entire surface of a printed matter. To provide a lithographic printing original plate which does not generate not only such background stains but also dotted background stains, has excellent rigidity resistance, and does not cause pasting marks.

(Means for Solving the Problems) The above object is to provide an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor and a binder resin, wherein the binder resin is a resin [A] represented by the following. at least one of
It has been found that this can be achieved by an electrophotographic photoreceptor characterized by containing at least one of a seed and a resin [B].

Resin (A): contains at least a repeating unit represented by the following formula (r) as a polymer component, has a crosslinked structure in advance before preparing the dispersion for forming a photoconductive layer, and has at least one polymer main chain -POsHz group or -OR'i only at one end of
(R' represents a hydrocarbon group)) and a cyclic acid anhydride-containing group, the resin has a weight average molecular weight of 1XIO3 to 1X10'.

General formula (1) % formula % [In formula (1), R2 represents a hydrocarbon group. ] Resin [B
]: has a weight average molecular weight of 5X10' or more and has the following formula (
A resin containing at least a repeating unit represented by I[[) as a polymer component and having a crosslinked structure before preparing a dispersion for forming a photoconductive layer.

-Final formula (Ill) d+ dz HX3-Q3 [In the formula, ×3 is -COOOCOCHzOco=-C)I
ZCOO--represents -0- or -5Ox-.

Q3 represents a hydrocarbon group having 1 to 22 carbon atoms.

d and d may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -Coo-23, or a hydrocarbon group having 1 to 8 carbon atoms. (Zs represents a hydrocarbon group having 1 to 18 carbon atoms). ] That is, the binder resin used in the present invention has a terminal acidic group having a crosslinked structure in advance (hereinafter, unless otherwise specified, the term "acidic group" includes a cyclic acid anhydride-containing group). ) is composed of at least a bonded low molecular weight resin [A] and a high molecular weight resin [B) having a crosslinked structure in advance.

Furthermore, as the low molecular weight resin [A], the following formula (
Ia) and - having a specific substituent containing a benzene ring or an unsubstituted naphthalene ring having a specific substituent at the 2-position and/or the 2-position and the 6-position, as shown in formula (Ib) Resin containing a methacrylate component and an acidic group component [
A] (hereinafter, this low-molecular-weight substance is particularly referred to as resin [A']).

General formula (Ia) General formula (Ib) OH1 [In formula (Ia) or (Ib), A1 and A2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom , -COR3 group or -COOR3
represents a group (Ri represents a hydrocarbon group having 1 to 10 carbon atoms). However, A1 and A do not both represent hydrogen atoms.

B1 and B2 each represent a single bond or a linking group having 1 to 4 linking atoms that connects -000- to the benzene ring. ] Furthermore, the high molecular weight resin [B] further has a -POalh group, -5O3H group, -Cool group, -OH group, -3H group,
Ii R.

At least one scratching group selected from OH group (Re represents the same content as R), cyclic acid anhydride-containing group, -CHO group, CONHZ group, 5OJHz group, and hydrogen atom or hydrocarbon group) (hereinafter, this resin may be particularly referred to as resin [B']), and furthermore, resin [B] is a resin formed by bonding the acidic group or cyclic acid shown in resin [A). More preferably, the resin does not contain a repeating unit containing an anhydride-containing group as a polymer component.

The first feature of the electrophotographic photoreceptor of the present invention is that the resin [A] contained in the binder resin has a crosslinked structure before preparing the dispersion for forming a photoconductive layer. That is, the binder resin [
This means that a part of the polymer is crosslinked as a characteristic of the resin [A] itself used in A], and is formed within the binder resin during the coating on a support, drying process, etc. after preparing the dispersion. It is distinguished from a crosslinked structure that can be

According to the present invention, by using a low-molecular-weight resin with a terminal acidic group bond that has a cross-linked structure in advance as a binder resin, electrostatic It was found that there were significant improvements in properties (especially electrostatic properties under harsh conditions) and water retention. This difference in performance is believed to occur when the photoconductor is dispersed in the binder resin, that is, when the binder resin is allowed to interact with the photoconductor. That is, it is very effective to control the interaction of the binder resin with the photoconductor during dispersion according to the present invention, and it is presumed that this greatly influences the electrophotographic performance obtained after film formation.

Resin [B] does not impede the high performance electrophotographic properties obtained by using resin [A], and provides sufficient mechanical strength to the photoconductive layer, which is insufficient with resin [A] alone. It has been found that sufficiently good damage resistance can be obtained even when the environment changes as described above or when a low-output laser beam is used.

Further, in the present invention, the surface of the photoconductive layer has smoothness. On the other hand, when a photoreceptor with a rough surface of the photoconductive layer is used as an electrophotographic lithographic printing original plate, the dispersion state of the zinc oxide particles that are the photoconductor and the binder resin is not appropriate, resulting in the presence of aggregates. Since a photoconductive layer is formed in the dry state, even if desensitization treatment is performed using a desensitization treatment liquid, the non-image areas cannot be made uniformly and sufficiently hydrophilic, causing printing ink to adhere during printing, resulting in Background stains occur in non-image areas of printed matter.

Furthermore, it was found that the photosensitivity was better than that of a random copolymer resin containing a polar group in the side chain connecting to the main chain of the polymer.

The spectral sensitizing dye, which is normally used to maintain photosensitivity in the visible to infrared light range, fully functions its spectral sensitizing action when adsorbed to the photoconductor. It is assumed that the polymer-containing binder resin interacts appropriately with the photoconductor without inhibiting adsorption of the spectral sensitizing dye. This effect was particularly remarkable with cyanine dyes or phthalocyanine pigments, which are particularly effective as dyes for spectral sensitization of near-infrared to infrared light.

According to the present invention, resin [A] and resin [B] are used as a binder resin for an inorganic photoconductor by specifying the weight average molecular weight of each resin, the content of acidic groups in the resin, and the bonding position. This is presumed to be due to the ability to appropriately change the strength of the interaction between the inorganic photoconductor and the resin. That is, the resin [A] with stronger interaction is selectively and appropriately adsorbed to the inorganic photoconductor, while the resin [B] of the present invention is moderately crosslinked, and furthermore, the resin [B'] is mainly Since it is a copolymer with a polar group bonded only to one end of the chain, the interaction between the polymer chains and the weak interaction between the polar group and the photoconductive particles work synergistically, resulting in electrophotography. It is thought that this material has both extremely excellent performance in terms of properties and film strength.

Also, when resin [A'] is used, electrophotographic properties (especially ■1°, D, R, RE) are better than those of resin [A].
1yIo) can be achieved.

The reason for this is unknown, but one reason is that the effect of the planar benzene ring or naphthalene ring with a substituent at the ortho position, which is the ester component of methacrylate, is due to the effect of the zinc oxide interface in the film. This is thought to be due to proper arrangement of these polymer molecular chains.

In addition, if the polymer component of resin [B] contains a polar group similar to that optionally contained at the end of the main chain of resin [A], the dispersion of the photoconductor will be destroyed, resulting in aggregates or precipitates. or even if a coating film is formed, the electrostatic properties of the resulting photoconductor may be significantly reduced, the smoothness of the photoconductor surface may become rough, and its strength against mechanical abrasion may deteriorate. This is not desirable because it causes

Even when only the low molecular weight resin [A] in the present invention is used as the binder resin, the photoconductor and the binder resin can sufficiently adsorb and coat the particle surface, which improves the smoothness of the photoconductive layer. It has good electrostatic properties, provides image quality without background smearing, and has sufficient film strength for use as a CPC photoreceptor or as an offset original plate for printing several tens of sheets. However, by coexisting resin [B] as in the present invention, the mechanical strength of the photoconductive layer, which is still insufficient with resin [A] alone, can be further improved without alienating the function of resin [A]. I was able to do it. Therefore, the photoreceptor of the present invention has excellent electrostatic properties even when environmental conditions vary, and
The film has sufficient strength, making it possible to print more than 8,000 sheets even under severe printing conditions (for example, when printing pressure is high with a large printing press).

The binder resin [A) of the present invention will be explained below.

As mentioned above, the first characteristic of the resin [A] is that it has a crosslinked structure in advance before the photoconductive layer-forming dispersion@5 adjustment.

The partially crosslinked structure in resin [A] includes a monomer corresponding to the copolymerizable component represented by the general formula (I) and two polymerizable functional groups copolymerizable with the monomer. Polyfunctional monomers containing 20% by weight or less of the total monomers,
Preferably, it can be formed by using 1.0 to 10% by weight and polymerizing by appropriately adjusting the polymerization reaction conditions so as to form a crosslinked structure.

When the polyfunctional monomer exceeds 20% by weight of the total monomers, the solubility of the resulting resin in organic solvents decreases, which is not preferable.

In addition, the formation of a crosslinked structure by intermolecular bonds through condensation reactions, addition reactions, etc. causes some deterioration in the electrostatic properties of the resulting electrophotographic photoreceptor, whereas when a crosslinked structure is obtained by the above polymerization, is preferable since no deterioration of electrostatic properties is observed.

Specifically, the polymerizable functional group is CH, .CuO CHz OCL 1 CH=C)l-C-0-1CHz=CH-CONH-,
CJ=C-CONH1 CL=CH-CHi-0-C-CHrCH-NHCOC
Hz engineering C) I-CHl-NHCO-1CHz=CH-5
(h-, CHz; C) I-COCHg=CI(-0-,
CHt=CH-5-, etc., but monomers having two or more of the above polymerizable functional groups are monomers having two or more of the same or different polymerizable functional groups. Specific examples of monomers having two or more polymerizable functional groups include styrene derivatives such as divinylbenzene and trivinylbenzene as monomers having the same polymerizable functional group. : Polyhydric alcohol (e.g. ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol 11200, 400.1600.1,3-
butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) or polyhydroxyphenols (such as hydroquinone, resorcinol, catechol and their derivatives) methacrylic acid, acrylic acid or crotone Acid esters, vinyl ethers or esters dibasic acids (e.g. malonic acid, succinic acid, glutaric acid,
Vinyl esters, allyl esters, vinylamides or allylamides of adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.): polyamines (e.g. ethylene diamine, 1,3-propylene diamine, 1.
4-butylene diamine, etc.) and a vinyl group-containing carboxylic acid (for example, methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

In addition, monomers having different polymerizable functional groups include, for example, carboxylic acids containing vinyl groups [e.g., methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpropionic acid, acryloylpropionic acid, itaconyloyl acetic acid, itaco Niloylpropionic acid, reactants of carboxylic acid anhydride and alcohol or amine (e.g. allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.)) Containing ester derivatives or amide derivatives (e.g. vinyl methacrylate, vinyl acrylate,
Vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate,
Vinyl methacryloylpropionate, allyl methacryloylpropionate, vinyloxycarbonylmethyl methacrylate, vinyloxycarbonylmethyloxycarponyl ethylene ester acrylate, N-allylacrylamide, N-allylmethacrylamide, N-allylitaconamide, methacryloylpropionic acid allylamide, etc.) or amino alcohols (e.g., aminoethanol, 1-aminopropanol, ■-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and a condensate of a vinyl group-containing carboxylic acid. .

As described above, the resin [A] of the present invention is characterized by having a crosslinked structure in at least a part of the polymer, and further contains an inorganic photoconductor and the binder resin for forming a photoconductive layer. It needs to be soluble in the organic solvent used to prepare the dispersion. Specifically, any solvent may be used as long as it dissolves at least 5 parts by weight of the resin [A] in 100 parts by weight of the toluene solvent at a temperature of 25°C.Solvents for these applications include dichloromethane, dichloroethane, Halogenated hydrocarbons such as chloroform, methylchloroform, trichlene, alcohols such as methanol, ethanol, propatool, butanol, acetone,
Ketones such as methyl ethyl ketone and cyclohexanone,
Ethers such as tetrahydrofuran and dioxane, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, glycol ethers such as ethylene glycol monomethyl ether and 2-methoxyethyl acetate, benzene, toluene, xylene, Examples include aromatic hydrocarbons such as chlorobenzene,
These can be used alone or in combination.

The weight average molecular weight of resin [A] is lXl0' to 1x104
, preferably 3X10'' to 9X103.

When the molecular weight of the resin CA) is smaller than 1X10'', film formation is reduced and sufficient film strength cannot be maintained.

On the other hand, if the molecular weight is greater than 1X10', it is undesirable because the electrophotographic properties (especially initial potential and dark decay retention) will deteriorate.The glass transition point of the resin [A] is preferably 11
The temperature is preferably 5°C to 95°C, more preferably 0°C to 100°C.

The proportion of the copolymerized component corresponding to the repeating unit of the general formula [the same formula] in the polymer is preferably 30% by weight or more, more preferably 50 to 99% by weight.

The repeating unit represented by general formula (I) will be explained.

-i In the repeating unit represented by formula (1), the hydrocarbon group of R1 may be substituted.

R preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and the substituent may be any substituent other than the acidic group bonded to one end of the main chain of the polymer. Often, for example, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), -0-Rz--COO
-Rz, -0CO-Ri, (R1 represents an alkyl group having 1 to 22 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group , octadecyl group, etc.). Preferred hydrocarbon groups include optionally substituted alkyl groups having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group,
dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl L2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), substitution with 4 to 18 carbon atoms an optionally substituted alkenyl group (for example, 2-methyl-1
-propenyl group, 2-butenyl group, 2-pentenyl group,
3-methyl 2-pentenyl group, l-pentenyl group, ■-
hexenyl group, 2-hexenyl group, 4-methyl-2hexenyl group), optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group,
(dimethylbenzyl group, dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexyl group, 2-cyclopentylethyl group, etc.) or having 6 to 12 carbon atoms. Aromatic groups that may be substituted (for example, phenyl group, naphthyl group, tolyl group, bovine silyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxy Phenyl group, decyloxydiphenyl group, riphenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group,
acetylphenyl group, methoxycarbonylphenyl group,
(ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc.).

In the hydrocarbon group of R1, when R is an aliphatic group, preferably the hydrocarbon group having 1 to 5 carbon atoms is at least
It is preferable that the content is 60% by weight or more in the component represented by formula (1).

Furthermore, the repeating unit represented by general formula (I) is the following -
Preferably, it is represented by formula (Ia) and/or (1b).

General formula (Ia) H3 2 General formula (Ib) [In formula (Ia) or (Ib), ^ and A2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, atom, -COII, group or -COOR
represents an s group (Rs represents a hydrocarbon group having 1 to 10 carbon atoms), provided that both A and At do not represent a hydrogen atom.

B1 and B! each represents a single bond or a linking group having 1 to 4 linking atoms, which connects -C00- to a benzene ring.] Resin [A] has the above formula (Ia) and/or (Ib)
It has been found that when a methacrylate component having a specific substituent as shown in the formula is contained, the electrostatic properties are further improved, and this is particularly effective for a photoreceptor system using a semiconductor laser beam scanning exposure method.

In general formula (Ia), preferable A1 and A2 are hydrogen, chlorine and bromine atoms, respectively, and preferable hydrocarbon groups include alkyl groups having I to 4 carbon atoms (e.g. methyl group, ethyl group, propyl group). , butyl group, etc.), aralkyl group having 7 to 9 carbon atoms (e.g. benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylhensyl group, methoxybenzyl group, chloro-methyl −
benzyl group, etc.) and aryl groups (e.g. phenyl group, tolyl group, silyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group, etc.), -COR4 and -COOR4 (preferred R4 is the above-mentioned preferred hydrocarbon group) ) can be mentioned. However, A, and A
Both 2 do not represent a hydrogen atom.

In formula ([a), B is a direct bond or -+C1(z)i (a is 1
represents an integer of ~3) , -CHzCToOCO-, -
(CH20h-(b represents an integer of 1 or 2),-
Represents a linking group having 1 to 4 linking atoms, such as CHzCL-0-.

Bz in formula (lb) represents the same content as B1.

2 (Ia) preferably used in the resin [A] of the present invention
Specific examples of the repeating unit represented by (Ib) are listed below. However, the scope of the present invention is not limited thereto.

i　　　　　　　　CL ) CH3 =7 ) CH3 8 ) CH3 r ) CH3 ) Shigo -11) -12) i-13) CH.

CH.

CH.

Hs CH3 CH3 CH3 Hs l -14) CH3 -15) Hs ! 16) Hz 17)゛ Hs -22) C) 13 -23) CH3 24) CH3 125) CH.

lIr 18) CH.

i-19) CHl -20) CH3 21) CH3 26) CH.

-27) C) 13 28) CHl 29) CH3 lr r i-30) CH.

÷CH2−C−+− i-34) CH.

Thousand CH1-C-÷- 31) Hx 32) CI+3 1+CH1-C-10- i-36) Hs i-37) HI 33] CH.

3 days) HI i -39) CH3 1-40) Furthermore, the resin [A] of the present invention further contains a functional group that performs a curing reaction of the resin by at least one of heat and light, that is, "heat and/or light". or a photocurable functional group. That is, the resin [A] contains a functional copolymer component and the formula (
I) In addition to the copolymer component corresponding to formulas (Ia) and (Ib), it is preferable to further contain a copolymer component containing a heat- and/or photo-curable functional group. This improves the film strength and increases the mechanical strength of the electrophotographic photoreceptor.

The proportion of the above-mentioned [copolymer component containing a thermally and/or photocurable functional group] in the resin [A] of the present invention is as follows:
A], preferably 1 to 30% by weight. More preferably, it is 5 to 30% by weight.

When a thermally and/or photocurable functional group is present in the binder resin, if its content is less than 1% by weight, the curing reaction will be insufficient and the effect of improving the film strength of the photoconductive layer due to the curable functional group will be reduced. can not see. On the other hand, if the content exceeds 30% by weight,
The binder resin [A] of the present invention also has difficulty maintaining excellent electrophotographic properties, and the properties deteriorate to the same as those of conventionally known binder resins. Furthermore, when used as an offset master, background stains occur in non-image areas of printed matter.

Specific examples of photocurable functional groups include Hideo Inui, Gentabu Nagamatsu, "Photosensitive Polymer" (Kodansha, published in 1977), Takahiro Tsunoda, "New Photoresin J (Printing Society Publishing Department, published in 1981) ), Kiyoshi Kato, [Ultraviolet curing system Chapters 5 to 7,
General Technology Center (published in 1989), G, E, Gr.
een and B, P, 5trak, J.
Macro, Sci.

Reas, Macro Chew, C21(2)
, 187-273 (1981-82), C,G,
Rattey, 'Phomuopolymir
Ization of SurfaceCooti
ngs” (^, Wiley InterScien
Functional groups used in conventionally known photosensitive resins and the like are used as photocurable resins cited in reviews such as CE Pub, 1982).

Furthermore, the "thermosetting functional group" in the present invention refers to a functional group other than the above-mentioned acidic group, and includes, for example, Tsuyoshi Endo, "Refinement of Thermosetting Polymers, published by C, M, C Co., Ltd., 1986. , Yuji Harasaki "Latest Binder Technology Handbook" Chapter ■-I (General Technology Center, published in 1985), Takayuki Otsu "Synthesis, design and development of new applications of acrylic resin" (Chubu Business Development Center Publishing Department, published in 1985), Omori The functional groups cited in the review articles such as Eizo's "Functional Acrylic Resins" (Technosystem, 1985) can be used.

For example, -〇)1 group, -5H group, -NH, group, -NtlR
s group [R3 represents a hydrocarbon group, for example, a carbon number of 1 to 1
O optionally substituted alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, 2-chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, etc.), An optionally substituted cycloalkyl group having 4 to 8 carbon atoms (e.g. cycloheptyl group, cyclohexyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g. hensyl group, phenethyl group, 3-phenylpropyl group) chlorohensyl group, methylhensyl group, methoxybenzyl group, etc.), optionally substituted aryl groups (for example, phenyl group, tolyl group, xylyl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, naphthyl group, etc.). raC0NHCHiO
R6 (R6 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (
For example, methyl group, ethyl group, propyl group, butyl group,
(hexyl group, octyl group, etc.)], -N-C・0
group and -C-CI group (at and a2 each represent a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, etc.) or an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, etc.)), etc. can be mentioned. In addition, the polymerizable double bond group is specifically a polymerizable group having a lower polymerizability (C)13 than the polymerizability of the monomer corresponding to the repeating unit of general formula (I), for example, CH2=C -C0NH1 C1h=CH-CHz-0-C-1CHz=CH-CH
z-NHCOCH2=CH-5o□-, C1h=CH-
CO-1CHt=CH-0 is formed.

“An example of a repeating unit containing a heat/photocurable functional group J is given below.

On each side below, T1 and T2 are respectively −■ or CH
3, R1+ is -CH=CH2 or -CHzCt
l=CHz, R+2 indicates -c=coz or -CH=CHCH3, R1ffl3 co=cnz, -C=CH2 or -CH=C)lcH3
, RI5R16 represents an alkyl group of CI"Ca, e represents an integer of 1 to 11, f represents an integer of 1 to 10, g represents an integer of 1 to 4, and h represents an integer of 2 to 11. An integer is shown, Zl shows S- or -0-, Z2 shows -OH or -N11.

ii -1) I -←CH, -C-masu- cooco=coz 1i-2) T -4C11□ C,4- COoC)IZcH・C11z ii-3) -G-CI+□ C-rise- Coo(CHz )a-Coo-R 11-4) T+ 1←CHz C-→-- C00(CHI)-0CO(CHI)--Coo-Rl
e may be the same or different.

1i-5) 1 2 +CH-C→- COO-R.

ii -10) +CH, -CtoC0NH(CHz)ecOOcHz-CHCHzOOC
-RH ii -13) t 1,000C1(C→- C0N)ICLOH ii-6) 2 + CH C→- COO(CHz)llOCO-R ii-7) 1 2 +CH-C→- COOCJIzCHCHzooC-R+yH ii-8 ) +CH2-C)-CONH(CHz)v-OCO-R ii-9)T.

0-CO-R+s Ls may be the same or different.

ii -14) 2 +CII-C→- CONHCHzOR+b ii -15) 1 2 ii -18) T1 T2 1,000CH-C-)- COO(CHz)h-Zz ii -19) -←CH-C)lMoCoo (CH
g) z-NGO In the present invention, when the resin [A] contains a photo- and/or thermosetting functional group, a cross-linking agent may be used in combination to promote cross-linking in the film. As the crosslinking agent used, compounds commonly used as crosslinking agents can be used. Specifically, Shinzo Yamashita and Tosuke Kaneko (ed.) [Crosslinking Agent Handbook] published by Taiseisha (1981), The Society of Polymer Science and Technology (ed.) "Polymer Data Handpunk Basic Edition" Baifukan (1986)
Compounds described in et al. can be used.

For example, silane cambling agents such as organic silane compounds (e.g., vinyltrimethoxysilane, vinyltriptoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropinitriethoxysilane, γaminopropyltriethoxysilane) etc.), polyisocyanate compounds (e.g., toluylene diisocyanate, 0-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymeric polyisocyanate, etc.), polyol compounds (e.g., 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1
11-trimethylolpropane, etc.), polyamine compounds (e.g., ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds, and Epoxy resins (for example, "Epoxy Resin" edited by Hiroshi Kakiuchi, published by Shokodo (1985), "Epoxy Resin" edited by Kuniyuki Hashimoto
Compounds described in Nikkan Kogyo Shimbun (published in 1969), etc.), melamine resins (for example, compounds described in "Uria Melamine Resin" edited by Kazuhiro Miwa and Hideo Matsunaga, Nikkan Kogyo Shimbun (published in 1969), etc.) etc.) Poly(meth)acrylate compounds (for example, Makoto Okawara, Takeo Saegusa, Toshinobu Higashimura (eds.), Oligomer J Kodansha (1976), Eizo Omori, "Functional Acrylic Resins" Technosystem (1985)
Specific examples include polyethylene glycol diacrylate, nenopentyl glycol diacrylate, l6-hexanediol acrylate, trimethylolpropane triacrylate,
Pentaerythritol polyacrylate, bisphenol A-diglycidyl ether diacrylate, oligoester acrylate: these include methacrylates. ) etc. The amount of the crosslinking agent used in the present invention is 0.5 to 30% by weight based on the total amount of binder resin,
In particular, it is preferably 1 to IO% by weight.

In the present invention, a reaction accelerator may be added to the binder resin as necessary in order to promote the crosslinking reaction in the photosensitive layer.

When the crosslinking reaction is a reaction mode in which a chemical bond is formed between functional groups, examples thereof include organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.).

When the crosslinking reaction is a polymerizable reaction mode, a polymerization initiator (peroxide, azobis compound, etc.) may be used, and preferably,
azobis polymerization initiator), polyfunctional polymerizable monomers (e.g. vinyl methacrylate, allyl methacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, divinyl succinate, divinyl adipate, diallyl succinate) , 2-methylvinyl methacrylate, divinylbenzene, etc.).

Furthermore, in the present invention, resins other than the resin of the present invention can also be used in combination. Examples of these resins include:
Examples include alkyd resins, polybutyral resins, polyolefins, ethylene-vinyl acetate copolymers, styrene resins, styrene-butadiene resins, acrylate-butadiene resins, vinyl alkanoate resins, and the like.

If the above-mentioned other resin exceeds 30% (weight ratio) of the total binder resin amount using the resin of the present invention, the effects of the present invention (especially improvement in electrostatic properties) will be lost.

In the case where the resin [A] contains a photo- and/or thermosetting functional group, the binder resin of the present invention is crosslinked or heat-cured after the photosensitive layer-forming material is applied. In order to carry out crosslinking or thermosetting, for example, the drying conditions are made stricter than those used in the production of conventional photoresists. For example, the drying conditions are high temperature and/or long time. Alternatively, after drying the coating solvent, it is preferable to further perform a heat treatment. For example, 60℃~120'
C for 5-120 minutes. When the above-mentioned reaction accelerator is used in combination, the treatment can be carried out under milder conditions.

Furthermore, the resin [A] of the present invention has the above-mentioned formula (1), (I
In addition to a polymer component selected from the repeating units represented by a) and/or (Ib), the polymer component for forming the crosslinked structure, and any photo- and/or thermosetting functional group-containing polymer component, other polymer components It may contain ingredients. The other polymerization component may be any component that copolymerizes with the above-mentioned polymerization component, and includes, for example, a repeating unit represented by formula (n).

- Formula (II) T-R.

[In (I[), T is -COO-1-OCO-1
-CC1+,)-OCO-1-(CHz)r-COO-
1-O--SO.

R7 represents the same content as R1 in formula (I). ) R has the same meaning as R8 in formula (1).

bl and bt may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -Coo-Rs, or a hydrocarbon group having 1 to 8 carbon atoms. -COO-R++ (Re is 1 to 18 carbon atoms
represents a hydrocarbon group). ] More preferably, , b, which may be the same or different, are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), -COO-R1, or -CL
COO-Rs (here R8 is more preferably carbon number 1
~18 alkyl or alkenyl groups, such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, pentenyl group, hexenyl group, octenyl group, decenyl group, etc., and these alkyl groups and alkenyl groups may have the same substituents as shown in R5 above)
represents.

Further, other monomers constituting repeating units other than these include, for example, styrenes (e.g. styrene, vinyltoluene, chlorostyrene, bromostyrene, dichlorostyrene, vinylphenol, methoxystyrene, chloromethylstyrene, methoxymethyl styrene, acetoxystyrene, methoxycarbonylstyrene, methylcarbamoylstyrene, etc.), acrylonitrile, methacrylaterile, acrolein, methacrolein, vinyl group-containing heterocyclic compounds (e.g. N-vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, etc.), Examples include acrylamide and methacrylamide. However, other copolymerization components are not limited to these.

Furthermore, the resin used as the binder resin of the present invention (Al is a -PO:+Hz group, or -OR'
(R' represents a hydrocarbon group)) and a cyclic acid anhydride-containing group.

The amount of the acidic group bonded to the end of the main chain of the polymer in the resin (A) is preferably 0.000 parts per 100 parts by weight.
It is 5 to 15% by weight, more preferably 2 to 10% by weight.

If the acidic group content in the resin [A] is less than 0.5% by weight, the initial potential will be low and sufficient image density will not be obtained. On the other hand, if the acidic group content is more than 15% by weight, the dispersibility decreases, film smoothness and high-temperature electrophotographic properties decrease, and furthermore, background smudge increases when used as an offset master. In the 1 P-OH group in the "acidic group bonded to one end of the polymer main chain" contained in the resin [A], R is a hydrocarbon group or -OR' group (R' is a hydrocarbon group R and R preferably represent an aliphatic group having 1 to 22 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 2-
Chloroethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, allyl group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group , methoxybenzyl group, etc.), or an optionally substituted aryl group (e.g., phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, (dichlorophenyl group, metquinphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.)
etc.

In addition, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride include aliphatic dicarboxylic acid anhydride and aromatic dicarboxylic acid anhydride. It will be done.

Examples of aliphatic dicarboxylic anhydrides include succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclobencune-1,2-dicarboxylic anhydride ring, and cyclohexane-1,2-dicarboxylic anhydride ring. cyclohexene-1,2-dicarboxylic acid anhydride ring, 2,3-bicyclo(2,2,2)octane dicarboxylic acid anhydride ring, and the like. may be substituted with a halogen atom, an alkyl group such as a methyl group, an ethyl group, a butyl group, or a hexyl group.

Examples of aromatic dicarboxylic anhydrides include phthalic anhydride rings, naphthalene-dicarboxylic anhydride rings, pyridine-dicarboxylic anhydride rings, thiophene-dicarboxylic anhydride rings, etc. For example, halogen atoms such as chlorine atom and bromine atom, methyl group, ethyl group,
It may be substituted with an alkyl group such as a propyl group or a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (for example, a methoxy group, an ethoxy group, etc.).

The specific acidic group bonded to only one end of the polymer main chain has a chemical structure in which it is bonded directly to one end of the polymer main chain or via an arbitrary linking group.

Bonding groups include carbon-carbon bonds (-double bonds or double bonds), carbon-hetero atom bonds (hetero atoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), and hetero atoms-hetero atoms. A halogen atom, (e.g., fluorine atom, chlorine atom, bromine atom, etc.), cyano group, hydroxyl group, alkyl group (e.g., methyl group, ethyl group, Propyl L3
)1z* SO□--CON--3O□N--NHCOO-1~N
1(CON)l-124 to 8 hydrocarbon groups (e.g. methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, hensyl group, phenethyl group, phenyl group, tolyl group, etc.) or -0R
zs (Rgs represents the same content as the hydrocarbon group of Ls)], etc.

The resin [A] of the present invention, which has a specific acidic group bonded only to at least one end of the polymer main chain, can be obtained by attaching various reagents to the ends of living polymers obtained by conventionally known anionic or cationic polymerization. Reaction method (ionic polymerization method) Radical polymerization method using a polymerization initiator and/or chain transfer agent containing a specific acidic group in the molecule (radical polymerization method), or the above-mentioned ionic polymerization method It can be easily produced by a synthetic method such as a method in which a polymer containing a reactive group at the end obtained by a legal or radical polymerization method is converted into the specific acidic group of the present invention by a polymer reaction.

Specifically, P, Dreyfuss, R, P, Q
uirkEncycl, Polym, Sci, E
ng, 1: 55H1987), Yoshiki Nakajo, Yuya Yamashita "Dye and Medicine", So, 232 (1985), Akira Ueda,
It can be produced by the method described in the review articles such as Susumu Nagai's "Science and Industry" Competition, 57 (1986) and the literature cited therein.

Specifically, the polymer of the resin [A] used in the present invention includes a monomer corresponding to the repeating unit represented by formula CI), and a polyfunctional monomer for forming the above-mentioned crosslinked structure. A method of polymerizing a mixture of other monomers and a chain transfer agent having an acidic group to be bonded to one end using a polymerization initiator (for example, an azobis compound, a peroxide, etc.), or the above chain transfer agent. A method of polymerizing using a polymerization initiator containing the acidic group without using the acidic group, or a method using a compound containing the acidic group as both the chain transfer agent and the polymerization initiator. In one way,
By using a compound containing an amino group, a halogen atom, an epoxy group, an acid halide group, etc. as a chain transfer agent or a substituent of a polymerization initiator, and then reacting with these functional groups in a polymer reaction after a polymerization reaction. It can be produced using a method of introducing the acidic group. Examples of chain transfer agents used include mercapto compounds containing the acidic group or a substituent that can be introduced into the acidic group (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid). , 3-
Mercaptoacetic acid, N-(2-mercaptopropionyl)
Glycine, 2-mercaptonicotinic acid, 3-(N-(
2-mercaptoethyl)carbamoyl]propionic acid,
3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine,
2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2
-Mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanediol, 3
-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-viridinol, etc.), or iodized alkyl compounds containing the above acidic groups or substituents (e.g. iodoacetic acid, iodopropion) acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferred are mercapto compounds.

These chain transfer agents or polymerization initiators are each used in an amount of 0.5 to 15 parts by weight based on 100 parts by weight of the total monomers,
Preferably it is 1 to 10 parts by weight.

Next, the resin [B] used in the present invention will be explained.

On the other hand, the resin [B] is a polymer containing at least one type of repeating unit represented by the formula (III), and a resin having a weight average molecular weight of 5×10' or more with a part of the polymer crosslinked, and more Preferably weight average molecular weight 8XIO
'~6X10'.

The glass transition point of the resin [B] is preferably 0°C to 120"
C range, more preferably 10°C to 95°C.

When the weight average molecular weight of the resin [B] is less than 5×10′, the film strength becomes insufficient. Furthermore, if the weight average molecular weight of the resin [B] exceeds the above-mentioned preferred upper limit, it is not preferable because the solubility in organic solvents will be almost eliminated and it will become practically unusable.

The resin (B) of the present invention satisfies the above-mentioned physical properties, has a part of the polymer crosslinked, and further contains a polymer component selected from repeating units represented by the general formula (I) as a homopolymer component. It is a polymer or copolymer that is contained as a copolymer component or as a copolymer component with another monomer that can be copolymerized with a monomer corresponding to the repeating unit represented by the general formula (DI).

In the repeating unit represented by general formula (III), the hydrocarbon group may be substituted.

- In the formula (I[[), X is preferably -COO
OCOCH20COCHzCOO- or -0-, more preferably -COOCHzCOo- or 0-.

Q preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. The substituent may be any substituent other than a polar group that can be bonded to one end of the main chain of the polymer, such as halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), 0-V+ -Coo-V
z, -0CO-V3, (v1 to v3 are carbon numbers 6 to 22
represents an alkyl group, such as a hexyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, an octadecyl group, and the like. Preferred hydrocarbon groups include optionally substituted alkyl groups having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group,
Butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group,
2-chloroethyl 7k, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), carbon number 4
~18 optionally substituted alkenyl/14 (e.g., 2-methyl-1-probeny/L4, 2-butenyl group,
2-pentenyl group, 3methyl-2-pentenyl group, 1-
ben-5-= group, l-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), carbon number 7-12
optionally substituted aralkyl groups (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorohensyl group, bromohensyl group, methylbenzyl group, ethylhensyl group, methoxybenzyl group, (dimethylhensyl group, dimethoxyhensyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or 6 carbon atoms ~12 optionally substituted aromatic groups (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group,
Dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxy carbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc.).

dl and d may be the same or different, and are preferably a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms, -Coo-Zs or -CHtCOO-Zs (L preferably represents an aliphatic group having 1 to 22 carbon atoms). More preferably, dl and d2 may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (
For example, methyl group, ethyl group, propyl group, etc.), -C
OO-Z+ or -CHICoO-Z3 (Z3 more preferably represents an alkyl group or alkenyl group having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, a propyl group,
Examples include butyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, etc. These alkyl groups and alkenyl groups Said 0. may have the same substituents as shown in ).

In resin [B], a commonly known method can be used to introduce a crosslinked structure into the polymer. That is, there are two methods: a method in which a polyfunctional monomer is coexisting in the polymerization reaction of monomers, and a method in which a functional group that promotes a crosslinking reaction is contained in the polymer and crosslinked by a polymer reaction.

The resin [B] of the present invention has a simple manufacturing method (for example, it requires a long reaction time, the reaction is not quantitative, and there are few problems such as contamination of impurities due to the use of reaction accelerators, etc.). , a functional group that undergoes a self-crosslinking reaction: C0NH
A cross-linking reaction using CHzOI+++ (R:++ represents a hydrogen atom or an alkyl group) or polymerization is effective.

In the case of a polymerization-reactive group, the polymerizable functional group is preferably 2
A method in which polymer chains are bridged by polymerizing a monomer having at least 1 or more monomers with a monomer of the formula (I [[)] is preferred.

Specifically, as a polymerizable functional group, CI+2・C11OC1
(3 II CHz=CH-C)lx-1CH, -CH-C-0-1
CH,=C-C-01 Clh OCH.

II 1 CH=CH-C-0, C) Iz=CH-CONH-1C
Hz=C-CONH1 CHz=C)I-CHz-0-C-2CL=CH-NH
COCHz=CH-CHz-NHCO-1CHi=CH
-5Ox-1CH1=CH-COCH,=CI+-0-
1CH, =C1 (-S-, etc.), but monomers having two or more of the above polymerizable functional groups may contain two or more of the same or different polymerizable functional groups. Any monomer having the above-mentioned properties may be used.

Specific examples of monomers having two or more polymerizable functional groups include styrene derivatives such as divinylbenzene and trivinylbenzene; polyhydric alcohols (e.g. ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol #200, I400, l600.1.3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) or polyhydroxy Esters, vinyl ethers or allyl ethers of methacrylic acid, acrylic acid or crotonic acid of phenols (eg hydroquinone, resorcinol, catechol and their derivatives) 1!
dibasic acids (e.g. malonic acid, succinic acid, glutaric acid,
Adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) vinyl esters, allyl esters, vinylamides or allylamides! = Polyamine (e.g. ethylene diamine, 3-propylene diamine,
, 4-butylene diamine, etc.) and a vinyl group-containing carboxylic acid (for example, methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

In addition, monomers having different polymerizable functional groups include, for example, carboxylic acids containing vinyl groups [e.g., methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpropionic acid, acryloylpropionic acid, itaconylyl acetic acid] , itaconiloylpropionic acid, reactants of carboxylic acid anhydride and alcohol or amine (e.g. allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.)] ester derivatives or amide derivatives containing groups (e.g. vinyl methacrylate, vinyl acrylate,
Vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate,
Vinyl methacryloylpropionate, allyl methacryloylpropionate, vinyloxycarbonylmethyl methacrylate, vinyloxycarbonylmethyloxycarbonyl acrylate ethylene ester, N-allylacrylamide, N-allylacrylamide, N-allylitaconamide, methacryloylpropionic acid allylamide, etc.) or amino alcohols (e.g., aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and a condensate of a vinyl group-containing carboxylic acid. .

In the present invention, the partially crosslinked resin [B] of the present invention is obtained by polymerizing a monomer having two or more of these polymerizable functional groups in an amount of 20% by weight or less of the total monomers. can be formed. More preferably, the monomer content is 15% by weight or less in the case of a resin synthesized by the method of introducing a polar group at the terminal with a chain transfer agent described below, and 5% by weight or less in other cases. preferable.

On the other hand, if the resin [B] does not contain a terminal polar group (not the resin [B゛] described below), a resin containing a crosslinkable functional group that causes a curing reaction with heat and/or light is used. A crosslinked structure may be formed in [B].

The functional group may be any functional group as long as it can cause a chemical reaction between molecules and form a chemical bond. That is, it is possible to use a reaction mode in which bonding between molecules by condensation reaction, addition reaction, etc. or crosslinking by polymerization reaction is caused by heat and/or light.

Specifically, a functional group 1 having a dissociable hydrogen atom [e.g. -COOFI group, POJz a, -P-OR
, group (It.

OH is an alkyl group having 1 to 18 carbon atoms, preferably 1 to 18 carbon atoms.
6 alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.), aralkyl groups having 7 to 11 carbon atoms (e.g. benzyl group, phenethyl group, methylbenzyl group, chlorobenzyl group, methoxybenzyl group) base,
etc.) or an aryl group having 6 to 12 carbon atoms (e.g. phenyl group, -tolyl group, xylyl group, mesitylene group, chlorophenyl group, ethylphenyl group, methoxyphenyl group, naphthyl group, etc.) or -0R3z group (Rzz is Rffl
The same content as the hydrocarbon group shown above)
, -OH group, NH group, NH-Rzi group (R33 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, butyl group)] respectively. The combination of selected functional groups is at least IIJl
or -CONHCHzORsi(R
za is a hydrogen atom or a methyl group, an ethyl group, a propyl group,
Examples include cases in which the group contains an alkyl group having 1 to 6 carbon atoms such as a butyl group or a hexyl group, or a polymerizable double bond group.

Specific examples of the polymerizable double bond group include those mentioned above as specific examples of the polymerizable functional group.

Furthermore, for example, Tsuyoshi Endo, “Refinement of Thermosetting Polymers J.
(C, M, C, ■, published in 1986), Yuji Harasaki, “
Latest Bainggu Technology Handbook J Chapter [+-1 (General Technology Center, published in 1985), Takayuki Otsu "Synthesis, design and development of new applications of acrylic resin" (Chubu Business Development Center Publishing Department, published in 1985), Eizo Omori " Functional acrylic resin”
(Technosystem, 1985) Hideo Inui, Gentabe Nagamatsu, "Photosensitive Polymer" (Kodansha, 1977), Takahiro Tsunoda, "New Photosensitive Resin" (Printing Society Publishing Department, 1988)
1 year), G, E, Green and, B, P.

5tar R+ J, Macro, Sci Revs
Macro, Chem, C2H2L187-273
(1981-82), C.G., Roffey, rP.
photopolymerization of 5ur
face Coatings” (A, Wiley In
It is possible to use functional groups, compounds, etc. cited in reviews such as "Lerscience Pub, published in 1982".

These crosslinkable functional groups may be contained in one copolymer component, or may be contained in separate copolymer components to carry out the crosslinking reaction.

Specific examples of monomers corresponding to the copolymer component containing these crosslinkable functional groups include - formula (
Examples include vinyl compounds containing the functional group that can be copolymerized with the monomer of III).
986), etc. Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2-aminomethyl form, α-chloro form, α-bromo form, α-fluoro form) body, α−
Tributylsilyl form, α-cyano form, β-chloro form, β
-bromo form, α-chloro-β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2
-alkenylcarboxylic acids (e.g. 2-pentenoic acid, 2-alkenylcarboxylic acids)
-methyl 2-hexenoic acid, 2-octenoic acid, 4-methyl 2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid , vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, half-ester derivatives of vinyl or allyl groups of dicarboxylic acids, and ester derivatives and amide derivatives of these carboxylic acids or sulfonic acids, in which the crosslinkable functional group is present in the substituent group. Examples include compounds containing.

The proportion of the above-mentioned "copolymer component containing a crosslinkable functional group" in the resin [B] of the present invention is preferably 1 to 1.
It is 80% by weight. More preferably, it is 5 to 50% by weight.

When producing such a resin, a reaction accelerator may be added as necessary to promote the crosslinking reaction. Examples include acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, P-toluenesulfonic acid, etc.), peroxides, azobis compounds, crosslinking agents, sensitizers, photopolymerizable monomers, and the like. As the crosslinking agent, specifically, compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), etc. can be used.

For example, commonly used organic silane, polyurethane,
A crosslinking agent such as polyisocyanate, a curing agent such as epoxy resin, melamine resin, etc. can be used.

When containing a photocrosslinking-reactive functional group, the compounds cited in the above-mentioned review of photosensitive resins can be used.

In addition, the resin [B] includes a monomer corresponding to the repeating unit represented by the general formula (III) described above and the polyfunctional monomer described above, as well as other monomers other than these [for example, resin [A ) may be contained as a copolymerization component.

As described above, the resin [B] of the present invention is characterized by having a crosslinked structure in at least a part of the polymer, and further contains an inorganic photoconductor and the binder resin for forming a photoconductive layer. It needs to be soluble in the organic solvent used to prepare the dispersion. Specifically, it is sufficient that at least 5 parts by weight of the resin [B] can be dissolved in, for example, 100 parts by weight of the toluene solvent at a temperature of 25°C. Solvents for these applications include halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, methylchloroform, trichlene, methanol, ethanol,
Alcohols such as propatool and butanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethers such as tetrahydrofuran and dioxane, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and methyl propionate, ethylene glycol monomethyl Examples include ether, glycol ethers such as 2-methoxyethyl acetate, aromatic hydrocarbons such as henzene, toluene, xylene, and chlorobenzene, and these can be used alone or in combination.

Furthermore, as a preferable embodiment of the resin [B], - formula (II
A polymer containing at least one type of repeating unit represented by I), which is partially crosslinked, and only at one end of at least one main chain contains a POJz group, -3O311 group, -COON group, - 0) 1 group (specifically the same content as described above for resin [A]), cyclic acid anhydride-containing group, -C84 group, CONHz group, hydrogen atom or A weight average molecule 15X1 consisting of at least one polar group selected from (representing a hydrocarbon group)
Weight average molecular weight of 0' or more, preferably 8X10' to 6X
10' polymer (hereinafter referred to as resin [B]).

The glass transition point of the resin [B°] is preferably O'c~12
The range is 0°C, more preferably lO'c to 95°C.

Here, -0)1% is an alcohol containing a vinyl group or an allyl group (for example, an ester substituent such as allyl alcohol, methacrylic acid ester, acrylamide, etc.),
Examples include compounds containing -OH group in the N-substituent), methacrylic acid esters or amides containing hydroxyphenol or hydroxyphenyl group as a substituent.

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride include aliphatic dicarboxylic anhydrides and aromatic dicarboxylic anhydrides.

Examples of aliphatic dicarboxylic anhydrides include succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclobencune-1,2-dicarboxylic anhydride ring, and cyclohexane-1,2-dicarboxylic anhydride ring. Examples include acid anhydride ring, cyclohexene-C2-dicarboxylic acid anhydride ring, 2,3-bicyclo(2,2,2)octane dicarboxylic acid anhydride ring, etc. These rings include, for example, chlorine atom, bromine atom, etc. may be substituted with a halogen atom, an alkyl group such as a methyl group, an ethyl group, a butyl group, or a hexyl group.

Examples of aromatic dicarboxylic anhydrides include phthalic anhydride rings, naphthalene-dicarboxylic anhydride rings, pyridine-dicarboxylic anhydride rings, thiophene-dicarboxylic anhydride rings, etc. For example, halogen atoms such as chlorine atom and bromine atom, methyl group, ethyl group,
It may be substituted with an alkyl group such as a propyl group or a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (the alkoxy group is, for example, a methoxy group or an ethoxy ring).

Specific examples of el and C2 include hydrogen atoms and optionally substituted aliphatic groups having 1 to 10 carbon atoms (e.g. methyl group,
Ethyl group, propyl group, butyl group, hexyl group, octyl group, 2-cyanoethyl group, 2-chloroethyl group, 2-
(ethoxycarbonylethyl group, benzyl group, phenethyl group, chlorobenzyl group, etc.), optionally substituted aryl groups (e.g., phenyl group, tolyl group, xylyl group, chlorophenyl group, boomophenyl group, methoxycarbonylphenyl group, cyano phenyl group, etc.).

In addition, a preferable terminal polar group in resin [B] is P
The OJz group, -COOH group, SOJ group, -OH group, and polar group have a chemical structure in which they are directly bonded to one end of the polymer main chain or bonded via an arbitrary linking group.

Bonding groups include carbon-carbon bonds (-double bonds or double bonds), carbon-hetero atom bonds (hetero atoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), and hetero atoms-hetero atoms. Atom, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), cyano group, hydroxyl group, alkyl group (e.g., methyl group, ethyl group, propyl group], (CH=CH)-1OH.

The above-mentioned specific R-bot R3 that binds only to one end of the polymer main chain? [Here, Rff'l and Ihl+ are each a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, hensyl group, phenethyl group, phenyl group) , tolyl group, etc.) or -0
Rsq CRxq represents the same content as the hydrocarbon group of R34].

The resin [B] of the present invention, in which a specific polar group is bonded to at least one end of the polymer main chain, can be obtained by attaching various reagents to the ends of living polymers obtained by conventionally known anionic or cationic polymerization. A reaction method (ionic polymerization method), a radical polymerization method using a polymerization initiator and/or chain transfer agent containing a specific polar group in the molecule (radical polymerization method), or the above ion method It can be easily produced by a synthetic method such as a method in which a polymer containing a reactive group at the end obtained by a polymerization method or a radical polymerization method is converted into the specific polar group of the present invention by a polymer reaction.

Specifically, P, Dreyfuss + R, P, Qui
rk+ Encycle.

Polym, Sci, Eng, 1:55H19
87), Yoshiki Nakajo, Yuya Yamashita “Dye and Medicine”, Utsubo, 2
32 (1985), Akira Ueda and Susumu Nagai, "Science and Industry", 57 (1986), and other reviews and documents cited therein.

Specifically, the polymer of the resin [B°] used in the present invention includes: - a monomer corresponding to the repeating unit represented by the formula (I[), a polyfunctionality for forming the above-mentioned crosslinked structure; A method in which a mixture of a monomer and a chain transfer agent containing a polar group to be bonded to one end is polymerized with a polymerization initiator (for example, an azobis compound, a peroxide, etc.), or without using the above chain transfer agent, A method of polymerization using a polymerization initiator containing the polar group, or a method of using a compound containing the polar group as both the chain transfer agent and the polymerization initiator,
Furthermore, in the above three methods, as a substituent of the chain transfer agent or polymerization initiator, an amino group, a halogen atom,
It can be produced using a method in which a polar group is introduced by performing a polymerization reaction using a compound containing an epoxy group, an acid halide group, etc., and then reacting with these functional groups in a polymer reaction. Examples of the chain transfer agent used include mercapto compounds containing the polar group or a substituent that can be derived from the polar group (e.g., thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid,
3-mercaptopropionic acid, 3-mercaptobutyric acid, N
-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-(N(2-mercaptoethyl)carbamoyl]propionic acid, 3-(N-(2-
mercaptoethyl)aminocopropionic acid, N-(3-
mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid,
4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol,
1-Mercapto-2-Propertool, 3-Mercapto-
2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-viridinol, etc.), or iodized alkyl compounds containing the above polar groups or substituents (e.g., iodoacetic acid, iodopropionic acid, 2-mercapto-3-viridinol, etc.); iodoethanol,
2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferred are mercapto compounds.

These chain transfer agents or polymerization initiators are each used in an amount of 0.5 to 15 parts by weight based on 100 parts by weight of the total monomers,
Preferably it is 1 to 10 parts by weight.

In the present invention, resin [A] and resin [B] according to the present invention
(Including [B')) Other resins can also be used in combination. Examples of such resins include alkyd resins, polybutyral resins, polyolefins, ethylene-vinyl acetate copolymers, styrene resins, styrene-butadiene resins, acrylate-butadiene resins, vinyl alkanoate resins, and the like.

If the above-mentioned other resin exceeds 30% (weight ratio) of the total binder resin amount using the resin of the present invention, the effects of the present invention (especially improvement in electrostatic properties) will be lost.

The ratio of resin CA) and resin [B] used in the present invention varies depending on the type, particle size, and surface condition of the inorganic photoconductive material used, but in general, the ratio of resin [A] and resin [B] used is The ratio is 5 to 80 to 95 to 20 (weight ratio), preferably 15 to 60 to 85 to 40 (weight ratio).

Inorganic photoconductive materials used in the present invention include zinc oxide,
Examples include titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, lead sulfide, and the like.

Preferable examples include zinc oxide and titanium oxide. The total amount of binder resin used for the inorganic photoconductive material is 10 to 100 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the photoconductor.

In the present invention, various dyes can be used in combination as spectral sensitizers, if necessary. For example, Harumi Miyamoto: Hidehiko Takei: Imaging Ezuyu 3 (Na8) p. 12, C, J.
Young et al., RCA Revie, 469.
(1954), Wataru Kiyota, Transactions of the Institute of Electrical Communication Engineers J63
-C(Nα2), 97 (1980), Yuji Harasaki et al., Industrial Chemistry Journal 66.78 and 188 (1963), Tadaaki Tani, Photographic Society of Japan Bozu I, 20B (1972), etc. Carbonium-based dyes, diphenylmethane Pigments, triphenylmethane dyes, xanthine dyes, phthalein dyes, polymethine dyes (e.g. oxonol, merocyanine dyes, cyanine dyes, logocyanine dyes, styryl dyes), phthalocyanine dyes (which may contain metals), etc. Can be mentioned.

More specifically, examples using mainly carbonium dyes, triphenylmethane dyes, xanthine dyes, and phthalein dyes include Japanese Patent Publication No. 51-452, Japanese Patent Application Laid-open No. 50-90334, and Japanese Patent Application Laid-open No. 50-90334. No. 50-114227,
JP 53-39130, JP 53-82353, U.S. Patent No. 3052540, U.S. Patent No. 40544
50, JP-A-57-16456, and the like.

oxonol dye, merocyanine dye, cyanine dye,
Polymethine dyes such as logcyanine dyes include F, M
, Hammer, rThe Cyanine
Dyes and ReIated Cotspoun
dsJ, etc., and more specifically, US Pat. No. 3,047,384, US Pat. No. 311
No. 0591, US Pat. No. 3,121,008, US Pat. No. 3,125,447, US Pat. No. 3,128,179, US Pat. No. 3,132,942, US Pat.
No. 74, British Patent No. 1405898, Special Publication No. 1974-7
Examples include dyes described in Japanese Patent Publication No. 814 and Japanese Patent Publication No. 55-18892.

Furthermore, as a polymethine dye that spectrally sensitizes the near-infrared to infrared light region with a long wavelength of 700 nm or more, JP-A-47-840
No., JP-A No. 47-44180, JP-A No. 51-4106
No. 1, JP-A-49-5034, JP-A-49-4512
No. 2, JP-A-5746245, JP-A-56-3514
No. 1, JP-A-57-157254, JP-A-61-26
No. 044, JP-A No. 61-27551, U.S. Patent No. 36
No. 19154, U.S. Pat. No. 4,175,956, rRes
arch Disclosure Jl 982,
216, pp. 117-118.

The photoreceptor of the present invention is also excellent in that even when various sensitizing dyes are used in combination, its performance does not change easily due to the sensitizing dye.

Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers such as chemical sensitizers can be used in combination. For example, the review mentioned above: Imaging 1973 (Nc
L8) Electron-accepting compounds (e.g. halogens, henzoquinone, cranyl, acid anhydrides, organic carboxylic acids, etc.) cited in the review on page 12, Hiroshi Komon et al., "Recent development and practical use of photoconductive materials and photoreceptors" Examples include polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, etc. cited in the review of Nippon Kagaku Information Co., Ltd. Publishing Department (1986), Chapter 4 to Chapter 6 of Chemical J.

The amount of these various additives added is not particularly limited, but is usually 0.001 to 2.0 parts by weight per 100 parts by weight of the photoconductor. hat 1
Department.

The thickness of the photoconductive layer is preferably 1 to 100 microns, particularly 10 to 50 microns.

Further, when a photoconductive layer is used as the charge generation layer of a photoconductor with a stacked structure of a charge generation layer and a charge transport layer, the thickness of the charge generation layer is preferably 0.01 to 1μ, particularly 0.05 to 045μ. be.

Charge transport materials for the laminated photoreceptor include polyvinylcarbazole, oxazole dyes, pyrazoline dyes, triphenylmethane dyes, and the like.

The thickness of the charge transport layer is 5 to 40 μm, particularly 10 to 3 μm.
0μ is suitable.

Typical resins used to form the insulating layer or charge transport layer include polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride copolymer resin, and polyvinyl chloride copolymer resin. Thermoplastic resins and curable resins such as acrylic resins, polyolefin resins, urethane resins, epoxy resins, melamine resins, and silicone resins are used as appropriate.

The photoconductive layer according to the invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably electrically conductive.As the electrically conductive support, for example, the base material such as metal, paper, plastic sheet, etc., has a low resistance property. those that have been subjected to conductive treatment by impregnating them, those that have been coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and further preventing curling, etc. One in which a water-resistant adhesive layer is provided on the surface of the support, one in which at least one or more precoat layer is provided on the surface layer of the support as necessary, AI! , etc. can be used, such as a substrate laminated with conductive plastic on which paper is deposited.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, Electrophotography, 14, (Nα1), pp. 2-11 (1975), Hiroyuki Moriga, “Introductory special paper chemistry j polymer publication (1975), L F.

Hoover, J., Macromol, Sci.
Ches+, A-4(6) No. 1327-1417
(1970) etc. are used.

(Example) Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto.

A: A-t ethyl methacrylate 95g 1 thioglycolic acid 5g,
A mixed solution of 2 g of divinylbenzene and 200 g of toluene was heated to a temperature of 75° C. under a nitrogen stream.

Abbisisobutyronitrile (A, 1B, N,
) 1.5g was added and reacted for 4 hours, and further A, 1. B.N.
Add 0.8g of and continue for 3 hours.1. B, N, 0.5
g and reacted for 3 hours. The weight average molecular weight (Mw) of the obtained copolymer was 8.3 x 10'.

80m 2: A-2 Hensyl methacrylate) 95g, ethylene glycol dimethacrylate 1.5g% n-dodecyl mercaptan 1
．． A mixed solution of 0g of toluene, 150g of toluene, and 50g of isopropyl methacrylate was heated to 85°C under a nitrogen stream. While stirring, 5.0 g of 4.4'-azobis(4-cyanovaleric acid) (A, C, V,) was added and reacted for 5 hours.
Furthermore, A, C, and V were added and reacted for 4 hours.

The resulting copolymer kite was 7.5X103.

A of A 3 to 20: A-3 to A 1 In Synthesis Example 1 of Resin [A], the compounds in Table 1 below are listed in Table 1 instead of ethyl methacrylate, thioglycolic acid, and divinylbenzene. Each copolymer was synthesized repeatedly under the same conditions as in Synthesis Example 1, except that each copolymer was used in an amount of . The Mw of each copolymer obtained is 5XIO' to 9X
It was in the range of 103.

(Leaving space below) 8 0 people 21: A-21 A mixed solution of 95 g of 2-chlorophenyl methacrylate, 5 g of 2-melt ptoethanol, 2.3 g of divinylhenzene, and 200 g of toluene was heated at a temperature of 75°C under a nitrogen stream.
It was heated to While stirring, azobis(isohaleronite IJ)
2 g of A, 1. Add 0.8g of V and N for 3 hours,
Furthermore, A.1. 0.8 g of ν and N were added and reacted for 3 hours.

To this reaction mixture, add 8 g of succinic anhydride and 1 g of pyridine.
was added and stirred at a temperature of 100'C for 6 hours. After cooling, water 2
It was reprecipitated into 1 liter of 0% methanol solution and the precipitate was collected. The yield after drying under reduced pressure is 65g and h is 7.5X1
It was 0".

Person A 22: A- A mixed solution of 76 g of 2-bromphenyl methacrylate, 20 g of the following monomer [A], 4 g of thioglycolic acid, 4 g of divinylbenzene, and 200 g of toluene was heated to 80°C under a nitrogen stream. A.1. Add 2g of B and N, 4
time reaction, and further A, 1. 0.5g of B and N were added and reacted for 3 hours.

The resulting copolymer nail was 8.5×10 3 .

Monomer [A] H3 2-chloro-6-methylphenyl methacrylate 66.
5g, the following monomer [B] 30g thioglycol fl
i3.5g, divinylbenzene 3g and toluene 200
The following reaction was carried out in the same manner as in Synthesis Example 22 using a mixed solution of g.

The size of the resulting copolymer was 9 x 10''.

A mixed solution of 100 g of ethyl methacrylate, 1.0 g of ethylene glycol dimethacrylate) and 200 g of toluene was heated to a temperature of 75°C under a nitrogen stream, and then 1.0 g of azobisisobutyronitrile was added and heated for 10 hours. Made it react. The weight average molecular weight of the obtained copolymer (B-1) was 4.2×10'.

Person B 2-19: B-2-B-19 resin [B
Resin [B] was produced under the same polymerization conditions as in Synthesis Example 1 using monomers and the compounds shown in Table 2 below as crosslinking monomers.

(The following is a blank space) Insertion of B 20: B-20 After heating a mixed solution of 99 g of ethyl methacrylate, 1 g of ethylene glycol dimethacrylate, 150 g of toluene, and 50 g of Metazuru to a temperature of 70°C under a nitrogen stream, 4
, 4′-azobis(4-cyanopencunic acid)1. og was added and reacted for 8 hours.

The "h" of the obtained copolymer was 1.OX 10'.

Person B 21-24: B-21-B-24 In Synthesis Example 20 of the above resin [B], polymerization initiator: 4.
Resin [B] was produced under the same conditions as in Synthesis Example 20, using the compounds shown in Table 3 below in place of 4'-azobis(4-cyanobencunic acid). Each resin claw is 1.0X10
'~3X10s.

(Left below) Person B 25: B-25 99 g of ethyl methacrylate, 1.0 thioglycolic acid
A mixed solution of 2.0 g of divinylbenzene and 200 g of toluene was heated to 80° C. with stirring under a nitrogen stream. 2. Add 0.8 g of 2'-azobis(cyclohexane-1 carbonitrile) (abbreviation A, C, 11, N,) and react for 4 hours, and then add 0.4 g of A, C, H, N. After 2 hours, 0.2 g of A, C, H, and N were added and reacted for 2 hours.

The mass of the obtained copolymer was 1.2XlO'.

Person B 26-38: In Synthesis Example 25 of B-26-B-38 resin [B], divinylbenzene 2. Instead of Og, use the table below-
Resin [B] was produced in the same manner as in Synthesis Example 25, except that the polyfunctional monomer or oligomer of No. 4 was used.

(Left below) B 39 to 46: B-39 to B-46 39 g of methyl methacrylate, 60 g of ethyl methacrylate
After heating a mixed solution of 1.0 g of mercapto compound shown in Table 5 below, 2 g of ethylene glycol dimethacrylate, 150 g of toluene, and 50 g of methanol to a temperature of 70°C under a nitrogen stream, 2.2''-azobis(isobutyro Nitrile) 0.8g was added and reacted for 4 hours, and then 2.2°-
Add 0.4g of azobis(isobutyronitrile) and add 4
Time reacted.

The nail size of each polymer obtained was 9.5X10' to 2X10'.

Table-5 Table-5 (Continued) l bi'' A-C Resin (A-736g (as solid content), Resin (B-
1) A mixture of 34 g (as solid content), cyanine dye [■] 0°018 g having the following structure, 0.15 g of salicylic acid, and 300 g of toluene was dispersed in a ball mill for 3 hours to prepare a photosensitive layer forming product. It was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 25 g/rrf, dried at 110°C for 30 seconds, and then left in the dark for 2 hours.
An electrophotographic light-sensitive material was prepared by leaving it for 24 hours under conditions of 0° C. and 65% RH.

Cyanine dye (1) (CHz)asOsθ CCHt)asOsK This 1IIN: Example except that 6 g of resin (R-1) and resin (R-2334 g) shown below were used instead of the binder resin used in Example 1. An electrophotographic light-sensitive material was produced in the same manner as in Example 1.

(R-1) H3 C1l.

COOC2H5CC00 Hff 6.5X103 (R-2) Poly(ethyl methacrylate) Mw2.4X10' and 1W: Instead of the binder resin used in Example 1, 6 g of resin (R-3) and resin (R -2) An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that 34 g was used.

(R-3) CHl HOOC-CHz-S Silkworm CH2-C to OOCJs Yw 6.0X10" This fJ!z: Instead of the binder resin used in Example 1, 6 g of the resin (R-3) shown below and An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that 34 g of resin [R-4] was used.

CR-4] CH.

-(CH, -Ch completed A CH2-CHhT-■CH2
-CHhlow COOCH3C00Ctb
C00H (weight ratio) Wr 1.8xlOS The film properties (surface smoothness), electrostatic properties, imaging performance, and imaging performance of these photosensitive materials under environmental conditions of 30° C. and 280% RH were investigated. Furthermore, when these photosensitive materials are used as original plates for offset masters, the photoconductive desensitization property (represented by the contact angle with water of the photoconductive layer after desensitization treatment) and printability (background smudge, The printing durability, etc.) were investigated.

The above results are summarized in Table 6.

(The following is a blank space) Table 6 The implementation aspects of the evaluation items shown in Table 6 are as follows.

Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was tested using a Benck smoothness tester (Kumagai Riko).
The smoothness (
sec/cc) was measured.

Note 2) Mechanical strength of photoconductive layer: The surface of the photosensitive material obtained was tested using a Hayton-14 type surface test material (
(manufactured by Shinto Kagaku ■) under a load of 60 g/d, and was repeatedly probed 1000 times with emery paper (ITOO) to remove abrasion powder, and the residual film rate (%) was determined from the weight loss of the photosensitive layer, which was taken as mechanical strength.

Note 3) Electrostatic properties: In a dark room at a temperature of 20° C. and 365% R), each photosensitive material was exposed to uN7-6 kV for 20 seconds using a paper analyzer (Paper Analyzer 5P-428 model manufactured by Kawaguchi Denki ■).

After discharging, leave it for 10 seconds, and the surface potential at this time V
IO was measured. Then, the potential v1 after being allowed to stand in the dark for 180 seconds. ．． The retention of the potential after dark decaying for 180 seconds, that is, the dark decay retention rate (DRR)
χ)] was calculated as (V+so/V+o)X100(%).

After the surface of the photoconductive layer was charged to -500 μm by corona discharge, it was irradiated with monochromatic light with a wavelength of 785 nm to increase the surface potential (
Find the time it takes for V+o) to attenuate to 1/10, and then calculate the exposure amount El/l. (erg/CT1) is calculated.

Furthermore, as in the El/l measurement, -500V was generated by corona discharge.
After charging it, it is irradiated with monochromatic light with a wavelength of 785nn+,
Find the time it takes for the surface potential (V+.) to attenuate to 1/100, and then calculate the exposure amount El/l. . (Bg/cj) is calculated.

Note 4) Imaging performance: Each photosensitive material was left for one day and night under the following environmental conditions.

Next, the surface of the photosensitive material was charged at -5 kV, and a 50 e
A copy obtained by developing and fixing using ELp-r (manufactured by Fuji Photo Film ■) as a liquid developer after exposure under an irradiation dose of RG/CD at a pitch of 25 and a scanning speed of 330 m/sec. Images (fogging, image quality) were visually evaluated.

Environmental conditions during imaging were 20”C, 65% RH and 30°C, 80°C.
%R)I.

Note 5) Contact angle with water: Each photosensitive material was passed once through an etching processor using a solution prepared by diluting the desensitizing liquid EPL-EX (manufactured by Fuji Photo Film) twice with distilled water. After desensitizing the surface of the photoconductive layer, a drop of 2 μl of distilled water was placed on it.
The formed contact angle with water is measured with a goniometer.

Note 6) Printing durability: Each photosensitive material is plate-made under the same conditions as Note 4) above to form a toner image, desensitized under the same conditions as Note 5) above, and this is used as an offset master. , indicates the number of sheets that can be printed using an offset printing machine (Oliver 52 model manufactured by Sakurai Seisakusho) without causing background stains in the non-image areas of the printed matter or problems with image quality in the image areas (the higher the number of sheets printed, the better the rigidity resistance. ).

As shown in Table 6, in the photosensitive material of the present invention, the smooth film of the photoconductive layer had good strength and electrostatic properties, and the actual copied images had no ground force and had clear copied image quality. This is presumed to be due to the photoconductor and the binder resin being sufficiently adsorbed and covering the particle surface. For the same reason, even when used as an offset master original, the desensitizing treatment with the desensitizing treatment liquid progresses sufficiently, and the contact angle with water in the non-image area is as small as 10 degrees or less, making it sufficiently hydrophilic. It can be seen that When I actually examined and observed the background stains on the printed matter, no background stains were observed.

In addition, in Comparative Examples A to C, the electrostatic properties deteriorated, and the D, R, and R values further decreased especially under high temperature and high humidity.

(Although the E value is smaller, the R, R, and R values are also smaller, resulting in a smaller apparent value).

The level of electrostatic properties in Comparative Example C may be close to a practical level depending on the imaging conditions, but if the environmental conditions change or the original is of poor quality (for example, the text is thin or the background is not white), etc. In this case, the copied image deteriorates and becomes unusable.

Furthermore, the photoconductor of the present invention and the photoconductor of the comparative example had an E17
1°. The values are significantly different. The El/10° value indicates how much potential remains in the non-image area (already exposed area) after exposure in actual imaging performance.
The smaller this value is, the less background smear will occur in the non-image area after development.

Specifically, it is necessary to set the residual potential to less than -10V, that is, to actually make it less than V*IOV,
Regarding the amount of exposure required, in the scanning exposure method using semiconductor laser light, it is difficult to reduce vR to -10V or less with a small amount of exposure due to the design of the optical system of the copying machine (equipment cost, (Accuracy of optical system optical path, etc.) is very important.

Based on the above, when images were actually taken using a device with a slightly lower exposure dose, the light-sensitive materials of Comparative Examples A to C had faded areas such as thin lines in the image areas and blurred areas in the non-image areas. . Furthermore, even when used as an offset master original plate, under printing conditions where the photosensitive material of the present invention can be used to print 10,000 or more sheets, in Comparative Examples A to C, ground blurring of the copied image occurs as background smudge on the printed matter from the beginning of printing. have done.

From the above, an electrophotographic photoreceptor that satisfies electrostatic properties and printability can be obtained only when the resin of the present invention is used.

H on the contrary In Example 1, resin (A-7) and resin (B-1)
In place of, each resin [A] and each resin [B] in Table 7 below
Each electrophotographic photoreceptor was produced in the same manner as in Example 1 except that

Electrostatic properties were measured in the same manner as in Example 1. Display the results -
7.

(Margin below) Table 7 In addition, when used as an offset master original plate and printed in the same manner as in Example 1, more than 10,000 sheets could be printed in all cases.

From the above, each of the photosensitive materials of the present invention was good in all respects of the smoothness of the photoconductive layer, film strength, electrostatic properties, and printability.

Furthermore, it was found that the electrostatic properties were further improved by using resin [A'].

Point installation ■2U In Example 1, the resin (A) shown in Table 8 below was used as the binder resin.
In place of 37.6 g and 34 g of resin [B], and in place of 0.02 g of cyanine dye (1), a dye with the following structure (U
) An electrophotographic light-sensitive material was produced under the same conditions as in Example 1 except that 0.019 g was used.

Dye (II) (CHz), 5o3e The electrostatic properties are measured values under (30″c, 8o%RH) conditions Table-8 The photosensitive material of the present invention has chargeability, dark charge retention,
It has excellent light sensitivity, and the actual copied images can be used even under high temperature and high humidity conditions (30°).
Even under the harsh conditions of 180% RH), clear images were produced with no soil blurring.

Furthermore, when this was used as an original plate for an offset master, more than 10,000 copies of clear image quality prints with no background blur were printed.

28 and 29 and D 6.5 g of either resin (A-1) (Example 28) or resin (A-8) (Example 29), resin CB-2] 33.
5g, zinc oxide 200g, uranine 0.02g, rose bengal 0.04g, bromophenol blue 0
．． 03g, phthalic anhydride 0.20g and toluene 30g
A photosensitive layer-forming product was prepared by dispersing 0 g of the mixture in a ball mill for 3 hours, and this was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 20 g/rrr.
It was dried at 10°C for 1 minute. Then, in the dark at 20℃, 65%
Each electrophotographic photoreceptor was produced by leaving it under RH conditions for 24 hours.

A photosensitive material was produced in the same manner as in Example 28, except that 33.5 g of the resin (R-4) was used instead of 33.5 g of resin CB-2). .

In the same manner as in Example 1, the characteristics of each photosensitive material were investigated. The results are summarized in Table 9 below.

Table 9 In the above measurements, the electrostatic properties and imaging performance were carried out in the same manner as in Example 1, except that the following operations were followed.

Note 7) Electrostatic characteristics El/10 and El/+o. Measuring method: After the surface of the photoconductive layer is charged to -400 V by corona discharge, the surface of the photoconductive layer is irradiated with visible light at an illuminance of 2.0 lux, and the surface potential (V, .) is 1/10 or E17. ．．
. . Find the time it takes for the light to attenuate, and then calculate the exposure amount El
/l+1 or E17. . . Calculate (looks/seconds).

Note 8) Image-sensitivity After leaving each photosensitive material for one day and night under the following environmental conditions, a copy image obtained by plate-making using EPL-T as a toner using a fully automatic plate-making IIE PL-404V (manufactured by Fuji Photo Film ■). (Capri, image quality) was visually evaluated. The environmental conditions during imaging were 20″C 65%RH (1) and 30°C 8
Performed at 0% R)I(II). However, manuscripts for copying (
That is, the original manuscript was created by cutting out and pasting other manuscripts.

No difference was observed in the smoothness and strength of the photoconductive layer among the photosensitive materials. However, in terms of electrostatic properties, the comparative example has particularly high photosensitivity El/l. . The value of was large, and this was further exacerbated at high temperatures, resulting in deterioration. The electrostatic properties of the photosensitive material of the present invention are good, and furthermore, Example 29 using the resin [A] having a specific substituent has very good properties, especially the value of El/10° is small. Ta.

When examining the actual imaging performance, in Comparative Example C, in addition to the original as a copy image, the frame of the cut out and pasted portion (that is, pasting trace) was observed as background stains in the non-image area.

However, in all cases of the present invention, clear images without background stains were obtained.

Furthermore, when these were desensitized and printed as offset printing original plates, 10,000 prints with clear image quality and no background smudge were obtained for all of the products of the present invention. However, in the comparative example, the above-mentioned pasting marks were not removed even with the desensitizing treatment, and were generated from the printed matter.

From the above, only the photosensitive material of the present invention was able to provide good characteristics.

Back ship base 21 On day 2 of Example 2, instead of 6.5 g of resin (A-1) and 33.5 g of resin CB-2), 6.5 g of resin [A] and resin [B] in Table-10 below were used. ] Each photosensitive material was produced in the same manner as in Example 28, except that 33.5 g was used.

Table 10 Table 10 (Continued) All of the photosensitive materials of the present invention have excellent chargeability, dark charge retention, and photosensitivity, and the actual copied images are also produced at high temperatures (30°C 18°C).
Even under the harsh conditions of 0% RH), clear images were produced without any occurrence of ground blur or fine line skipping.

Furthermore, when printed as an offset master original plate, clear prints with no background staining were obtained even after printing 10,000 sheets.

Underlying five u anti-liquid super resin (A-14) (Example 42) or resin [A-1
53 (Example 43), resin (B-2
) 33.5g, zinc oxide 200g, uranine 0.0
A mixture of 2 g of rose bengal, 0.04 g of rose bengal, 0.03 g of bromophenol blue, 0.20 g of phthalic anhydride and 300 g of toluene was dispersed in a ball mill for 3 hours. Next, 0.6 g of glutaric acid (Example 42) was added to this dispersion.
) or 0.5 g of 1,6-hexanediol (Example 4
3) was added and further dispersed in a ball mill for 10 minutes.

The dry adhesion amount is 20g/rr on conductive treated paper.
It was coated with a wire bar so as to have the following properties, dried at 110'C for 1 minute, and further heated at 120C for 1.5 hours. Next, each electrophotographic photoreceptor was prepared by leaving it in a dark place at 20° C. and 165% RH for 24 hours.

When these photosensitive materials were examined for electrostatic properties and imaging properties in the same manner as in Example 28, they showed good performance.

Furthermore, when printed as an original plate for offset printing, resin [
B], it became possible to print more than 10,000 sheets.

This is thought to be because the curable groups in the resin [A] were crosslinked during the heat treatment after film formation, resulting in improved film strength (effect of the invention). An electrophotographic photoreceptor having excellent electrostatic properties and mechanical strength can be obtained. The photoreceptor of the present invention is also effective in scanning exposure using semiconductor laser light.

6

Claims (1)

[Scope of Claims] (1) In an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor and a binder resin, the binder resin is at least one of the following resins [A]. and resin [B]. Resin [A]: contains at least a repeating unit represented by the following general formula (I) as a polymer component, has a crosslinked structure before preparing the dispersion for forming a photoconductive layer, and has at least one polymer main chain -PO_3H_2 groups, -SO_3H only at one end of
There are groups, -COOH groups, ▲mathematical formulas, chemical formulas, tables, etc.▼
{R represents a hydrocarbon group or -OR' group (R' represents a hydrocarbon group)} and at least one acidic group selected from a cyclic acid anhydride-containing group with a weight average molecular weight of 1× 10^3 to 1 x 10^4 resin. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In formula (I), R_1 represents a hydrocarbon group. [Resin [B]: having a weight average molecular weight of 5 x 10^4 or more, containing at least a repeating unit represented by the following general formula (III) as a polymer component, and before preparing a dispersion for forming a photoconductive layer. A resin that has a crosslinked structure in advance. General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X_3 is -COO-, -OCO-, -CH_2
OCO-, -CH_2COO-, -O- or -SO_2
- represents. Q_3 represents a hydrocarbon group having 1 to 22 carbon atoms. d_1 and d_2 may be the same or different from each other,
Each hydrogen atom, halogen atom, cyano group, carbon number 1-8
hydrocarbon group, -COO-Z_3 or -COO-Z_3 via a hydrocarbon group having 1 to 8 carbon atoms (Z_3 is 1 to 8 carbon atoms)
~18 hydrocarbon groups). ] (2) The resin [A] has the following general formula (I a) as a polymer component corresponding to the repeating unit represented by the above general formula (I).
The electrophotographic photoreceptor according to claim 1, which contains at least 30% by weight of at least one of the repeating units represented by general formula (Ib). General formula ( I a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula ( I b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In formula ( I a) or ( I b), A_1 and A_2 are mutually Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, a -COR_3 group, or a -C
OOR_3 group (R_3 represents a hydrocarbon group having 1 to 10 carbon atoms). However, both A_2 and A_2 do not represent hydrogen atoms. B_1 and B_2 each represent a single bond or a linking group having 1 to 4 linking atoms that connects -COO- to the benzene ring. ] (3) The resin [A] further contains 1 to 30 repeating units containing heat and/or photocurable functional groups as a polymer component.
Claim (1) or (2) characterized in that it contains % by weight.
The electrophotographic photoreceptor described above. (4) Resin [B] further contains -PO_3H_2 group, -SO_3H group, -COOH group, -OH group, -SH group, ▲mathematical formula, chemical formula, table, etc. only at one end of at least one polymer main chain. There are ▼ groups (R_0 represents the same content as R), cyclic acid anhydride-containing groups, -CHO groups, -CONH_
2 groups, SO_2NH_2 groups, and ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups (e_1 and e_2 may be the same or different, and each represents a hydrogen atom or a hydrocarbon group). The electrophotographic photoreceptor according to claim 1 or 2, which is a resin comprising: (5) The resin [B] is a resin that does not contain, as a polymer component, a repeating unit containing an acidic group or a cyclic acid anhydride-containing group as shown in the resin [A]. The electrophotographic photoreceptor according to any one of the above.