JPH03223761A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain superior electrostatic characteristics and mechanical strength even under severe conditions by using a binder resin comprising 2 kinds of specified resins. CONSTITUTION:The photoconductive layer to be used comprises at least an inorganic photoconductor and the binder resins containing one of the binder resins A and one of the binder resins B. The resin A has repeating units represented by formula I (R1 being a hydrocarbon group) as the polymer components, and the resin A has cross-linking structures in advance before preparing a dispersion for forming a photoconductive layer, and an acid group, such as -PO3H2, -SO3H, and the like only on one terminal of the main polymer chain. The binder resin B contains as the polymer components, mono-functional macromonomers each having only on one terminal of each main polymer chain the polymerizable double bond group repesented by formula II in which X is -COO-, -OCO-, or the like, and each of c1 and c2 is H, halogen, cyano, or the like, thus permitting stable and good electrostatic characteristics to be maintained and sharp good-quality images to be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] 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.

(Prior Art) Electrophotographic photoreceptors have various configurations in order to obtain predetermined characteristics or depending on the type of electrophotographic process to which they are applied.

As representative electrophotographic photoreceptors, there are photoreceptors having a photoconductive layer formed on a support and photoreceptors having an insulating layer on the surface, which are widely used.

Photoreceptors, consisting of a support and at least one photoconductive layer, are used for imaging by most common electrophotographic processes, ie, charging, imagewise exposure and development, and optionally transfer.

Furthermore, a method of using an electrophotographic photoreceptor as an offset master plate for direct plate making is widely used. Particularly in recent years, direct electrophotographic lithography has become important as a method for printing high-quality printed matter with a print count of several hundred to several dozen sheets.

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 substrate, and the photoconductive layer of the recording layer has excellent charging ability, has low dark decay, large light decay, little pre-exposure fatigue, and is resistant to changes in humidity during photography. Therefore, 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.

In order to solve these problems, a copolymer component containing an acidic group in the side chain of the polymer was used as a binder resin in an amount of 0.05 to 1.
A low molecular weight resin containing 0% by weight or a low molecular weight resin that binds an acidic group to the end of the polymer main chain (Mw 10' to 1
04), the smoothness and electrostatic properties of the photoconductive layer are improved, and image quality without background smear is obtained, as disclosed in JP-A-63-217354 and JP-A-64-1, respectively.
No. 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 crosslinked network, as disclosed in JP-A No. 1-102573 and Japanese Patent Application No. 3969-1989.
1, and a technique using a low molecular weight resin (weight average molecular weight 103 to 104) in combination with a high molecular weight resin (weight average molecular weight 10' or more) is disclosed in JP-A-64-564 and JP-A-64-564. No. 63-220149, No. 63-2
No. 20140, Japanese Patent Application No. 1982-273547, Japanese Patent Application No. 1999
JP-A-116643 and JP-A-1469455 disclose a technique for using such low molecular weight substances in combination with heat and/or photo-curable resins.
No. 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.

(Intelligence B that the invention attempts to solve) However, even if 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 for light.

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. In particular, if the difference between E+zz and E171° is large, the gradation of the copied image will be soft, and furthermore, it will be difficult to reduce the residual potential after exposure, resulting in noticeable fogging of the copied image. Even when printed, serious problems such as pasting marks of the printed original appear on the 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 fluctuates, such as low temperature and low humidity, or high temperature and high first base. The goal is to provide the following.

Another object of the present invention is to provide a CPC electrophotographic 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 reproducing 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 printing durability, and does not produce imprint marks.

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

Binder resin [A]: Contains at least a repeating unit represented by the binding margin (I) below 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. At least one acidic group selected from -PO3l (showing a z group or -○R' group (I?' indicates a hydrocarbon group)) and a cyclic acid anhydride-containing group only at one end of the combined main chain. A resin having a weight average molecular weight of 1X10'' to 1XIO'.

General formula (I) % Formula % [In formula (1), R1 represents a hydrocarbon group] Binder resin [B]: Polymer component shown by the binding margin (IVa) and (■b) below. selected from at least one of these groups, -C00)l group, r1 hydrocarbon group or -0R0' group (R0' represents a hydrocarbon group) group, -CIO group, and cyclic acid anhydride-containing group. Only at one end of the polymer main chain containing at least one polymer component containing at least one component containing at least one polar group, the following
A weight consisting of at least a monofunctional macromonomer (M) with a weight average molecular weight of 2X10' or less, which is formed by bonding a polymerizable double bond group represented by I[[), and a monomer represented by the binding margin (V) below. A copolymer with an average molecular weight of 5 x 10' to 1 x 10.

- Tsuzuriyo (II) C+ Ct CHMiC O In formula (Ill), Xa bar COO- -OCO- -CHzOCOC)IzCOO- O--SO,- -CO--CON)ICOO- -CONICONH- (Here, R31 represents a hydrogen atom or a hydrocarbon group.

) cl and C3 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -Co
o-Zl or -Coo-Z+ via a hydrocarbon (each Z represents a hydrogen atom or an optionally substituted hydrocarbon group)
represents.

General formula (IVa) d, d.

1←C) I-C→- X, -Q General formula (IVb) d, d.

1←CH-Cu-! In formula (IVa) or (lVb), Xl represents the same content as X in formula (III).

0 is an aliphatic group having 1 to 18 carbon atoms or 6 to 12 carbon atoms
represents an aromatic group.

d2, d! may be the same or different from each other, and the expression (
Represents the same content as C3 and C2 in Ill).

Y is a hydrogen atom, a halogen atom, an alkoxy group, or -CO
OZx (Zt represents an alkyl group, an aralkyl group, or an aralkyl group).

General formula (V) el el C) I=C X, 10.

In formula (V), X represents the same content as X in formula (IVa), 0□ represents the same content as 01 in (R7a), and C2 may be the same or different. often,
It represents the same content as C5 and C2 in formula (I[I).

That is, the bound iF resin used in the present invention contains a polymer component of a specific repeating unit, has a crosslinked structure in advance before preparing the dispersion for forming a photoconductive layer, and has at least one polymer main chain. A low molecular weight resin [A] which is formed by bonding an acidic group (hereinafter, in this specification, unless otherwise specified, a cyclic acid anhydride-containing group is also included in the term acidic group).
and a high-molecular-weight graft copolymer resin (B) comprising at least a functional macro-septamer (M) and a monomer represented by a binding margin (V).

Furthermore, as the low molecular weight resin [A], the following - Tsuzuriyo (
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 Ia) and (Ib). A resin containing a methacrylate component and an acidic group component [
AI (this low molecular weight substance is particularly referred to as resin [A']) is preferable.

general formula () ( general formula (r　b) CH.

[In formula (Ia) or (Ib), AI and A t are each a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, a -COR3 group, or a -CO
ORi group (gs indicates a hydrocarbon group having 1 to 10 carbon atoms)
represents. However, both A and A2 do not represent hydrogen atoms.

B1 and B2 each represent a single bond or a linking group having 1 to 4 linking atoms, which connects -000- to the benzene ring. Furthermore, the resin (B) is specified only at one end of the polymer main chain. A resin formed by bonding polar groups (hereinafter particularly referred to as resin [B']) is preferable.

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 in advance 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.

This is achieved by specifying the weight average molecular weight of resin [A] and resin [B] as the binder resin of the inorganic photoconductor, as well as the content and bonding position of acidic groups in the resin. This is presumed to be due to the ability to appropriately change the strength of the interaction between the photoconductor and the resin. That is, the resin [A] with stronger interaction selectively and appropriately adsorbs to the inorganic photoconductor, while the resin [A] with weaker interaction than resin [A].
In B], it is presumed that by interacting gently with the inorganic photoconductor to the extent that the electrophotographic properties are not inhibited, both the electrophotographic properties and the mechanical strength could be significantly improved as described above.

In particular, in the case of resin [B'], since the interaction is weaker than that of resin [A], the polar group bonded to the terminal position of the polymer main chain in the resin is inorganic to the extent that it does not impede the electrophotographic properties. It is more preferable because it interacts gently with the photoconductor.

Using resin [B'] improves electrostatic properties, especially 11. R
and E17. . The properties are better, and the excellent properties achieved by using resin [A] are not hindered at all, and the effect is preferable because it hardly changes even under environmental changes such as high temperature/high temperature, low temperature/low humidity, etc.

Furthermore, when resin (A') is used, electrophotographic properties (especially vl., D, R, Ji
, E I/I. ) can be achieved.

The reason for this is unknown, but one reason is that the effect of the planar Hensen 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.

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 inorganic particles that are the photoconductor and the binder resin is not appropriate, resulting in the presence of aggregates. Because a photoconductive layer is formed in the photoconductive layer, the non-image area cannot be made uniformly and sufficiently hydrophilic even if it is desensitized using a desensitizing treatment liquid, causing printing ink to adhere during printing, and as a result, the printed matter deteriorates. Background smudges occur in non-image areas.

When the resin of the present invention is used, the adsorption/covering interaction between the photoconductor and the binder resin is properly performed, and the film strength of the photoconductive layer is maintained.

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 staining, and has sufficient film strength to be used 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 strength is also sufficient, making it possible to print more than 10,000 sheets even under harsh 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 before preparing the dispersion for forming the photoconductive layer.

The partially crosslinked structure in the resin [A] includes a monomer corresponding to the copolymerization 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 adjusting the polymerization reaction conditions appropriately so as to form a crosslinked structure by using 1.0 to 10% of polymerization.

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, as the polymerizable functional group, CHx・C)IOCL 1 CTo・CH-CHz-, CHzH(H-C-0-CH
i=C-C-O12 CH=CH-CON)l-, C1+, =f;+1-u-
-LJ=L-Ll-Ll-, CI(t=CH-CHz
-0-C-CHz=CH-NHCOCHt=CH-CI
(t-NHCO-1CFI!, Cff-5O□-1CI
(f=CFI-CO-C)It-CH-0-, CHz・
CB-5-, etc., but monomers having two or more of the above polymerizable functional groups include monomers having two or more of the same or different polymerizable functional groups. That's fine.

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 1200, .1400. $600,],]
3-butylene glycol neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) or polyhydroquinphenol (e.g. hydroquinone, resorcinol, catechol and their derivatives) methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or huffs 1J/L
/ether H: dibasic acid (N such as malonic acid, succinic acid,
Vinyl esters, allyl esters, vinylamides or allylamides of glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.): polyamines (e.g. ethylene diamine, 1,3-pro and diamine, 1. Examples include condensates of 4-butylene diamine, etc.) and vinyl group-containing carboxylic acids (eg, 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.) 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, vinyloxycarbonylmethyloxycarbonyl ethylene ester acrylate, N-allylacrylamide, N-allylmethacrylamide, 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. .

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, it is sufficient that at least 5 parts by weight of the resin [A] can be dissolved in 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 benzene, toluene, xylene, and chlorobenzene, and these can be used alone or in combination.

The weight average molecular weight of resin [A] is 1 x 104 to 1 x 104
, preferably 3XIO' to 9X10''.

When the molecular weight of the resin [A] 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 1 x 104, it is undesirable because the electrophotographic properties (especially initial potential and dark decay retention rate) will deteriorate.The glass transition point of the resin [A] is preferably 1.
The temperature is 0°C to 100°C, more preferably 5°C to 95°C.

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

-Explain the repeating unit indicated by the binding margin (I).

In the repeating unit represented by general formula (I), the hydrocarbon group of R1 may be substituted with Wl.

R1 preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. The substituent may be any substituent other than the acidic group 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-R1 , -Coo-
R1, -0CO-Ra, (R represents an alkyl group having 1 to 22 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group,
dodecyl group, hexadecyl group, octadecyl group, etc.). Preferred hydrocarbon groups include optionally substituted alkyl groups having 1 to 1 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group). group, hexadecyl group, octadecyl group, 2-chloroethyl i, 2-7'romoethyl i, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), carbon number 4 to 1B optionally substituted alkenyl group (e.g. 2-methyl-
1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl 2-pentenyl group, 1-pentenyl Ll-
hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), 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), carbon number 5-8 An optionally substituted alicyclic group (e.g., cyclohexyl group, 2-cyclohexyl group, 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl group, naphthyl group, etc.) 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, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc.).

In the hydrocarbon group of L, when Ro is an aliphatic group, it is preferable that at least 60% by weight or more of the component represented by formula (I) contains a hydrocarbon group having 1 to 5 carbon atoms. .

Furthermore, the repeating unit represented by general formula (I) is the following -
Preferably, the binding margin (Ia) and/or (Ib) is indicated.

General formula (Ia) CH.

It General formula () [In formula (Ia) or (Ib), A1 and A are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, a -COR3 group, or - GOOR3
represents a group (R3 represents a hydrocarbon group having 1 to 10 carbon atoms), provided that ^ and 80 do not both represent a hydrogen atom.

B1 and B each represent a single bond or a linking group having 1 to 4 linking atoms, which connects -C00- to the benzene ring. 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 photoreceptor systems for semiconductor laser light scanning exposure.

In general formula (I a), preferred A1 and A2
In addition to hydrogen, chlorine, and bromine atoms, preferred hydrocarbon groups include alkyl groups having 1 to 4 carbon atoms (e.g., methyl, ethyl, propyl, butyl, etc.), and 7 to 9 carbon atoms. aralkyl groups (e.g. hennol group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group,
methylbenzyl 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.)
, and -COR4 and -COORa (preferred R4 include those described as the above-mentioned preferred hydrocarbon groups). However, A1
and A2 do not both represent hydrogen atoms.

In formula (Ia), B is a single bond connecting -C00- and a benzene ring, or (CL)r (a represents an integer of 1 to 3), -CI'1zCHzOCO-, iCH
zO) r- (b represents an integer of 1 or 2), -CL
Represents a linking group having 1 to 4 linking atoms, such as CL-0-.

Bt in formula (Ib'') represents the same content as B.

Formula (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.

1) CHl ) C, H5 =3 ) Hs C, Hff ) L -5 ) ) ) -8 ) CHl CH.

CH3 I Hs i-10) i-11) 12) CH.

CHl Hs 13) 14) 15) i-16) i-17) Hs Hs CHl C) If i-18) 19) i-20) 21) CH3 I Hs C) I3 I CH3 CH Tsu 22) 23) 24) -25) r CH.

I CH3 I CH3 i-26) -27) i-28) i-29) CH3 Hs lr r CH3 30) CHl 4-CH, -C-÷- i-31) C1(3 32) Hs -G-CH! -C-Yuichi -33) CH.

1 34) Hs −〇CHt−C−÷− i-35) CH.

36) CI (3 37) 1lff i -38) CHl i -39) Hs 40) L Furthermore, the resin [A] of the present invention further undergoes a resin curing reaction with at least one of heat and light. It is preferable that the resin [A] contains a functional group, that is, a heat-curable and/or photocurable functional group J. That is, the resin [A] contains a functional copolymer component and a functional copolymer component for forming a crosslinked structure in the resin [A]. formula(
I) In addition to the copolymer component corresponding to formulas (Ia) and (Ib), it is preferable that the copolymer component further contains a heat-curable 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
A], preferably 1 to 30% by weight. More preferably, it is 5 to 30% by weight.

When a heat- and/or photo-curable functional group is present in the binder resin, if the content is less than 1% by weight, the curing reaction is insufficient and the effect of improving the film strength of the light guide tJi due to the curable functional group is not observed. On the other hand, if the content exceeds 30% by weight, it becomes difficult for the binder resin of the present invention [A] to maintain excellent electrophotographic properties, and the properties deteriorate to the same as those of conventionally known binder resins. Put it away. 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, Gentabe Nagamatsu, "Photosensitive Polymer" (Kodansha, published in 1977), Takahiro Tsunoda, "New Photosensitive Resin" (Printing Society Publishing Department, published in 1981) ), Kiyoshi Kato, "Ultraviolet curing system" Chapters 5 to 7, General Technology Center (published in 1989), G, E, G
reen and B, P, 5trak, J.
Macro, Sci.

Reas, Macro Chew, C21(2)
1187-273 (1981-82), C, G, Ra
ttey+ 'Photopoly*1rizatj
on of Surface Cootings” (A,
Wiley InterScience Pub,
Functional groups used in conventionally known photosensitive resins and the like are used as the photocurable resins cited in reviews such as 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 C, M, C, Co., Ltd., published in 1986. ), Yuji Harasaki, "Latest Binder Technology Handbook", chapters n-r (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), The functional groups cited in the review articles such as Eizo Omori's "Functional Acrylic Resins" (Chikunon Stem, published in 1985) can be used.

For example, -〇H group, -5H group, -Nll! group, -NHII
S group (R5 represents a hydrocarbon group, for example, a carbon number of 1 to 1
0 optionally substituted alkyl groups (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., cyclohebutyl group, cyclohexyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group,
3-phenylpropyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group), optionally substituted aryl groups (e.g. phenyl group, tolyl group, xylyl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, naphthyl group) C0N) ICHzO
Rh (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.) a8 each represents 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. I can do it. Further, as the polymerizable double bond group, specifically, CH whose polymerization reactivity is lower than that of the monomer corresponding to the repeating unit of general formula (1).

polymerizable group, for example, CL=C-CONH1 C)lt-CH-CHz-0-C-1CHz=CH-C
FIzlIC0- C)lz=CH-5Ot- 1CTo.Cl-C0-1CH, = C1l-0 is formed.

An example of a repeating unit containing a "thermal/photocurable functional group" is given below.

On each side of the following? + and Tt are each −■ or CH
s and R++ is -co=cnz or -CHzC)
! =CHz, ll+i represents -c=cnz or -CH=CHCH, RI3RI& represents an alkyl group of 01 to C4,
e represents an integer from 1 to 11, f represents an integer from 1 to 1O, g4 represents an integer from 1 to 4, h represents an integer from 2 to 11, and ZIL represents S- or -0-. , z2 represents -OH or -NOx.

1i1) Tt -←CHI C-+- COOCH=C)+2 ii-2) I -←CL C-μ- COOCHzCH=C)It ii-3) Tt 1←cttz-c-hand- C00(CI(ri) --Coo-R1+ i-4) 1 +cnx-c-rise-C00(CHt)-0CO(CHz)e-Coo-Re
may be the same or different.

1i-5) Tt t 1i-6) T1 T; + CH-CD- COO(CHz)-0CO-R+x ii-7) 1 I + CH-CD- C00CHzCHCHzOOC-R+3H ii-8) 1 + CH.

C+ CON)l(CHz)r-OCO-Rlgii-9) +C)1. -C)-COO(CHz)*-CH-CHx-0-CD-R+s
0-Co-R+s I5 may be the same or different.

ii-10) T.

+ CHt -C) - CONH(CH2), C00CHffi-CI(CHf
fiOOC-RI 41l ii-11) T.

T.

+CH-C← Coo (C1ll), CHCH! \/ 1 ii-12) T.

C0N)IcH,0)I ii-14) T.

2,000 CH-C-)- CONHCH-OR+b ii-15) T+ 2 ti-19)-←CH-CH← In the present invention, when the resin [A] contains a photo- and/or thermosetting functional group, A crosslinking agent may be used in combination to promote crosslinking in the membrane. As the crosslinking agent, compounds commonly used as crosslinking agents can be used. Specifically, the compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), published by the Society of Polymer Science, "Komunshi Date Book Basic Edition", Baifukan (1986), etc. Can be used.

For example, organic silane compounds (e.g., silane cups such as vinyltrimethoxysilane, vinyltributoxysilane, T-glycidoxypropyltrimethoxysilane, T-mercaptopropyltriethoxysilane, T-aminopropyltriethoxysilane, etc.) ring agents, etc.), polyisocyanate compounds (e.g., toluylene diisocyanate, 〇-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisonanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymer polyisocyanate, etc.), polyol compounds (e.g. 1,4 butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,11-trimethylolpropane, etc.), polyamine compounds (e.g. , ethylenediamine/, T-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine,
(modified aliphatic polyamines, etc.), polyepoxy group-containing compounds, and epoxy resins (for example, "Epoxy Resins" edited by Hiroshi Kakiuchi, Shokodo (published in 1985), "Epoxy Resins" written by Kuniyuki Hashimoto, Nikkan Kogyo Shimbunsha (published in 1969) etc.), melamine resins (e.g., Part Miwa, Hideo Matsunaga, eds. [Uria Melamine Resin] Nikkan Kogyo Shimbunsha (19
Poly(meth)acrylate compounds (for example, Makoto Okawara, Takeo Saegusa, Toshinobu Higashimura, "Oligomer", Kodansha (1976), Eizo Omori, "Functional Acrylic Resin J") Examples include compounds described in Techno System (published in 1985), and specifically,
Polyethylene glycol diacrylate, nenobentyl glycol diacrylate, 1,6-hexanediol acrylate, trimethylolpropane triacrylate, pentaerythritol polyacrylate, bisphenol A-diglycidyl ether diacrylate, oligoester acrylate: The amount of the crosslinking agent used in the present invention is preferably 0.5 to 30% by weight, particularly 1 to 10% by weight based on the total amount of binder resin. .

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, acetic acid, benzenesulfonic acid, p-1 luenesulfonic 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.

When the binder resin of the present invention contains a photo- and/or thermosetting functional group in the resin [A], it is crosslinked or thermosetted after applying the photosensitive layer-forming material. In order to carry out crosslinking or thermal curing, for example, drying conditions may be made stricter than drying conditions used in conventional photoreceptor production.For example, drying conditions may be set at high temperature and/or for a long time. Alternatively, after drying the coating solvent, it is preferable to further heat treat 1, e.g. 60'C to 120°C.
'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 formula (1) (ra
) and/or (Ib), a polymeric component for forming the crosslinked structure, and any photo- and/or thermosetting functional group-containing polymeric component, as well as other polymeric components. The other polymerization component that may contain may be any component as long as it copolymerizes with the above polymerization component, and includes, for example, a repeating unit represented by formula (II).

- Tsuzuriyo (II) b+ bz 1 1←C)l-C-111 T-R.

[In formula (n), T is -coo-1-OCO-1n
CL) rOCO-1-(CHzh-COO-1-o--
5o! (R9 represents the same content as R8 in formula (1).) R1 is synonymous with R in formula (I).

b 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. (Re represents a hydrocarbon group having 1 to 18 carbon atoms),] more preferably bl
+ba may be the same or different, and is 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-R.

or -C)ItCOO-R (here, R 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, a butyl group, a hexyl group, an octyl group) , decyl group, dodecyl 71
4, tridecyl group, tetradecyl group, hexadecyl group,
Examples include octadecyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, etc., and these alkyl groups,
The alkenyl group may have the same substituent as shown for R1 above.

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, methacryloamid, acrolein, methacrolein, vinyl group-containing heterocyclic compounds (e.g. N-vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, etc.) , acrylamide, methacrylamide, and the like. However, other copolymerization components are not limited to these.

Further, the resin [A] used as the binder resin of the present invention has a -POsHt group or -OR' group ( R' represents a hydrocarbon group)) and a cyclic acid anhydride-containing group.

The amount of the acidic group bonded to the end of the polymer main chain 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 cannot be obtained; on the other hand, if the acidic group content is more than 15% by weight, the dispersibility will be reduced. The film smoothness and high-temperature electrophotographic properties are lowered, and when used as an offset master, background smearing is increased. In “acidic group bonded to one end” (
R' represents a hydrocarbon group), and R and R.

is preferably 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, chlorobenzyl 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,
methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.).

Furthermore, the cyclic acid anhydride-containing group is a group containing at least one d-cyclic acid anhydride, and examples of the cyclic acid anhydride include aliphatic dicarboxylic acid anhydride and aromatic dicarboxylic acid anhydride. Can be mentioned.

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

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-heteroatom bonds (heteroatoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), and heteroatoms-heteroatoms. R1 is composed of any combination of bonding atomic groups, such as 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, etc.)
, +C) I=CH→-1-x〉t4 to 8 hydrocarbon groups (e.g. methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, benzyl group, phenethyl group, phenyl group, tolyl group, etc.) or -〇R
zs (Rzs represents the same content as the hydrocarbon group of R1)], and the like.

The resin [A] of the present invention, in which a specific acidic 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. 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
uirk.

Encycle, Polym, Sci, Eng+-
7: 551 (1987), Yoshiki Chujo and Yuya Yamashita, “Dye and Medicine,” Betsu, 232 (1985), Akira Ueda, Susumu Nagai, “Science and Industry,” Deaf, 57 (1986), and other reviews and references cited therein. It can be manufactured by the method described in .

Specifically, the polymer of the resin [A] used in the present invention includes a monomer corresponding to the repeating unit represented by the general formula (I), and a polyfunctional monomer for forming the above-mentioned crosslinked structure. A method in which a mixture of a chain transfer agent containing a monomer, an optional other monomer, and an acidic group to be bonded to one end is polymerized using a polymerization initiator (for example, an azobis compound, a peroxide, etc.), or the above-mentioned chain transfer method. A method of polymerizing using a polymerization initiator containing the acidic group without using an agent, or a method using a compound containing the acidic group as both the chain transfer agent and the polymerization initiator, and furthermore, the above-mentioned 3. 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 the chain transfer agent used include mercapto compounds containing the acidic group or a substituent that can be derived from the acidic group (for example, 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-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 (for example, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-ml -)' ethanesulfonic 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.

The weight average molecular weight of the resin (B) is 5 x 10' to 1 x 10''
, better than 8 x lO'~5 x 10s.

-The proportion of the functional macromonomer in the polymer is preferably 1 to 70% by weight, and -The proportion of the monomer represented by the binding margin (II[) in the polymer is preferably 30 to 70% by weight. Preferably it is 99% by weight.

The glass transition point of the resin (B) is preferably 0"6 to 11
The temperature is more preferably 20°C to 90°C than 0°C5.

Furthermore, if the molecular weight of the binder resin (B) is smaller than 5 x 10', the membrane strength cannot be maintained sufficiently;
When it becomes larger, the dispersibility decreases and the film smoothness deteriorates.
The quality of the copied image (particularly the reproducibility of fine lines and characters deteriorates) is deteriorated, and furthermore, when used as an offset master, background stains become significant.

If the content of -functional macrocrystals in the binder resin (B) is less than 1.0% by weight, electrophotographic properties (especially dark decay rate and photosensitivity) will decrease, and electrophotographic properties will fluctuate depending on environmental conditions. becomes particularly large in combination with a near-infrared to infrared spectral sensitizing dye.

This is thought to be due to the fact that the amount of the macromonomer that becomes the graft portion is small, resulting in a composition that is almost the same as that of conventional homopolymers or random copolymers.

On the other hand, if the content of the -functional macromonomer exceeds 70%, the copolymerizability of the macromonomer according to the present invention with monomers corresponding to other copolymerization components will not be sufficient, and it will not be possible to use it as a binder resin. Also, sufficient electrophotographic characteristics cannot be obtained.

In the resin [B] of the present invention, the -functional macromonomer (M) provided as a copolymerization component of the graft type copolymer resin will be explained in more detail.

The monofunctional macromonomer (M) has a polymerizable double bond group represented by -binding margin (I[l)] and - binding margin (rVa) and (
rVb) and at least one polymer component containing a specific polar group (-C0OH group, PO3Hz group, OH or acid anhydride-containing group). It is bonded only to one end of the polymer main chain and has a weight average molecular weight of 2 x 10' or less.

In general formulas (III), (It/a) and (]Vb), each of the hydrocarbon groups contained in C3, CzbXo, d+, dz, xl, Ql and Q6 has the indicated number of carbon atoms (unsubstituted hydrocarbon ) as a group, but these hydrocarbon groups may have a substituent.

In the general formula (I[[), Xo is -COO-1-O
CO-1CLOCO-1-CHzOO--0--5O□
In addition to --CO-2, preferred hydrocarbon groups include optionally substituted alkyl groups having 1 to 18 carbon atoms (e.g., 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 group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), optionally substituted alkenyl groups having 4 to 18 carbon atoms (for example, 2-methyl -1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-
2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2hexenyl group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (
For example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromohensyl group, methylhensyl 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-cyclohexylethyl group, 2cyclopentylethyl group, etc.), or an optionally substituted aromatic group having 6 to 12 carbon atoms 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) group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobusoylamidophenyl group, etc.) can be mentioned.

It may have a group. Examples of substituents include halogen atoms (e.g., chlorine atom, bromine atom, etc.), alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), alkinoquino groups (e.g., methoxy group, ethoxy group, propioxy group, butoxy group, etc.)
etc.

C5 and ct may be the same or different from each other,
Preferably a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), -COO-Zl or one coo via hydrocarbon
-Z, (Zl is preferably a hydrogen atom or a carbon number 1
~18 alkyl group, alkenyl group, aralkyl group, alicyclic group, or aryl group, which may be substituted, and specifically, 1? represents the same content as that described for s+).

Examples of the hydrocarbon in the -C00-Z+ group via the hydrocarbon include a methylene group, an ethylene group, a propylene group, and the like.

More preferably, in the binding margin (I[l), χ. is C
OO-OCOCH20COCH2COO-0--CON
HCoo--COIJI(CONFI--CONI) (which may be the same or different from each other, each being a hydrogen atom, a methyl group, C00Zs or -CHxCOOZs (Zs is more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (
(For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.).

Even more preferably, one of C8 and C2 represents a hydrogen atom.

That is, the polymerizable double bond represented by - Tsuzuri margin (I[[)■ Specifically, as a combining group, CM, ・CH-C-0-■ 0=C-O- O++C-O- COOCHz 0 It will be done.

In the general formula (TVa) or (IVb), X is the formula (
Represents the same content as X in III).

dl, d, may be the same or different from each other, and have the formula (I[
[) Represents the same content as C3 and C2 in parentheses.

Q is an aliphatic group having 1 to 18 carbon atoms or an aliphatic group having 6 to 12 carbon atoms
represents an aromatic group, specifically an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group) , dodecyl group, tridecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2
-bromoethyl group, 2-hydroxylethyl group, 2-methquinethyl group, 2-ethoxyethyl group, 2-cyanoethyl group, 3-chloropropyl group, 2-(trimethoxysilyl)ethyl group, 2-tetrahydrofuryl group, 2- thienylethyl group, 2-N,N-dimethylaminoethyl group,
2-N, N-diethylaminoethyl group], carbon number 5-
8 cycloalkyl group (e.g. cyclohebutyl group, cyclohexyl group, cyclooctyl group, etc.), carbon number 7-12
optionally substituted aralkyl groups (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, dichlorobenzyl group, methylbenzyl group, chloro -methyl-benzyl group, dimethylbenzyl group,
aliphatic groups such as trimethylbenzyl group, methoxybenzyl group, etc.), and optionally substituted aryl groups having 6 to 12 carbon atoms (e.g., phenyl group, tolyl group, xylyl group, chlorophenyl group, bromophenyl group, dichlorophenyl group) , chloro-methyl-phenyl group, methoxyphenyl group, methoxycarbonylphenyl group, naphthyl group, chloronaphthyl group, etc.).

In formula (rVa), preferably X is -COO--
OCO--CH, COO--CH□oco-o-CO-
-COIIHCOO--CONHCONH--CONI
(Preferred examples of -dl and d2 represent the same contents as cl and C8 described above.

In general formula (IVb), Qo is -CN, C0NH
z or an atom (for example, a chlorine atom, a bromine atom, etc.), an alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.) or -COOZZ (Z! is preferably an alkyl group having 1 to 8 carbon atoms, carbon represents an aralkyl group or an aryl group of numbers 7 to 12).

The macromonomer (M) has the formula (IVa) and/or (I
It may contain two or more kinds of polymer components represented by Vb).

When Ql is an aliphatic group, the aliphatic group having 6 to 12 carbon atoms is preferably used in an amount not exceeding 20% by weight of the total polymer components in the macromonomer (M).

Furthermore, when xl in the binding margin (IVa) is -COO-, at least 3 of the polymer components represented by the formula (IVa) are present in all the polymer components in the macromonomer (M).
It is preferable that the content is 0% by weight or more.

Furthermore, in the macromonomer (M), a polar group (-(:00)1■ OH Cl0 group, As the component containing a cyclic acid anhydride-containing group, a vinyl-based component containing the above polar group that can be copolymerized with a monomer corresponding to the copolymer component represented by formula (IVa) and/or (IVb) is used. Any compound can be used. For example, as described in F Polymer Data Handbook [Basic Edition] J Baifukan (published in 2986), edited by the Society of Polymer Engineers, acrylic acid, α- and/or β
-Substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2-amino)methyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α- Cyano form, β-chloro form, β-bromo form, β-fluoro form, β-medixy form, α.

β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acid 1! (e.g. 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octinoic 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, dicarboxylic acid, half-ester derivatives of vinyl or allyl groups of alcohols, and ester derivatives of these carboxylic acids or sulfonic acids. , a compound containing the polar group in a substituent of an amide derivative, and the like.

1 In the PR group, Ro represents the same content as the above R in resin [A], and the acid anhydride-containing group is also as described above.

-OH group is vinyl group- or allyl group-containing alcohol 11! (For example, allyl alcohol, methacrylic acid ester, ester substituent such as acrylamide, compound containing -OR group in N-substituent, etc.), methacrylic acid ester or amide containing hydroxyphenol or hydroxyphenyl group as a substituent I can list several types.

The third component, formula (IVa) and/or (lVb)
Examples of the vinyl compound containing the above-mentioned polar group that can be copolymerized with the monomer corresponding to the copolymer component represented by include the following monomers, but the scope of the present invention is It is not limited to these.

Here, on each side below, Q+ is -H1-CH3,
CI, -Br, -CN, -CHzCOOCH3
Or -CB, C0OH, Q! is -H or -CH,
, j represents an integer of 2 to 18, k represents an integer of 2 to 5, i represents an integer of 1 to 4, and ■ represents an integer of 1 to 12.

(DJ) Ql CH1=C 0OH (D-2) L CH= CH 0OH (D-3) t (D-4) 2 CHz Coo(C)l, C00H (D-5) Ql ([1-6 ) t (D-7) z (D-8) z cuz=c ■ C0NH (CHz) 1lOCO (CHz) , C00
)I(D-91 z Clh"'C C0NHCOO(Ctl z), 1COOH(D-1
0) Q CH2H2 CONHCONH (CHz) 1lCOOH (D-11
') Q.

CH3 C)It CHxCOOH CONHC)I CH2COOH (D 13) 0□ (D-14) t CH2=C FistCoo(CHz)-NHCO(CHz)-Goon(D
-15) CHz”CHCHzOCO(CHz)-COOH(D-
16) CH1=CH+CH2-+7j-C00H (D-17) 2 (D-18) Q! (D-19) Q.

([1-20) Q small (D-21) t llz O I C0O(CHtyT-0-P-OH H (D-22) (D-23) Qtomi H (D-24) Q.

0) (D-25) t H (D-26) (D-27) (D-29) (D-30) 2 CH2 Coo (CHri, 5OJ (D-31) 2 (D-32) (D-36) (D-37) (D-38) Q.

g-wealth 2 so, n (D-40) ff1 (D-41) Q.

(D-42) 1 ■ cuz=c Coo(CHri　;0H (D-43) Hff CH= CI Coo(CHI)jOR (El-44) Q small (D-45) t (D-46) t (D-47) t (D-48) Q mushroom CH2=C CH, 0) 1 CON)Ic)l C11,0)l (D-49) CL=Cto1CHt-+7i0H (D-50) ill.

(D-51) (D-52) CH! "" CH+CHt -+1-(00(CH!
) TOH (D-53) 0° (D-54) 0 Q chamber C)2=C Coo(C)It)-COO(CHz) JOH Among all the polymer components in the macromonomer (M), the polar group The amount contained as a copolymer component containing 10
It is preferably 0.5 to 50 parts by weight, more preferably 1 to 40 parts by weight per 0 parts by weight.

When the monofunctional macro-septumer composed of these polar group-containing random copolymers is contained in the resin (B) as a copolymerization component, the polar group contained in all the graft parts in the resin (B) The total amount of the group-containing components is preferably 0.1 to 10 parts by weight per 100 parts by weight of all polymer components in the resin (B).

More preferably -C0011 group, -5OJ group and -P
o, 81 groups, the total amount present in the graft portion in the resin (B) is 0.1 to 5% by weight.

The macromonomer (M) may contain other polymer components other than these. For example, monomers corresponding to other polymerizable repeating units include acrylonitrile, methacrylonitrile, acrylamide, etc. methacrylamides, styrene and its derivatives (e.g. vinyltoluene, chlorostyrene, dichlorostyrene, bromostyrene, hydroxymethylstyrene, N,N-dimethylaminomethylstyrene, etc.), heterocyclic vinyls (e.g. vinylpyridine, vinylimidazole) , vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.).

When these other monomers are contained, it is preferably 1 to 20 parts by weight per 100 parts by weight of the total polymer components of the macromonomer (M).

The macromonomer provided in the present invention is a random polymer main chain consisting of at least a repeating unit represented by - binding margin (IVa) and/or (IVb) and a repeating unit containing a specific polar group, as described above. has a chemical structure in which a polymerizable double bond group represented by - binding margin (II) is directly bonded to only one end of the bonding group or bonded by an arbitrary linking group.

The linking group that connects the formula (I [l) component and the formula (IVa) or (IVb) component or the polar group-containing component includes a carbon-carbon bond (-poly bond or double bond), a carbon-hetero atom Bonds (heteroatoms include, for example, oxygen atoms,
sulfur atoms, nitrogen atoms, silicon atoms, etc.), heteroatoms -
It is composed of any combination of atomic groups of heteroatom bonds.

at h2 R23 is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxy group,
represents an alkyl group (e.g. methyl group, ethyl group, propyl group, etc.), -(CH=CH)-1xa CRsa, Rss is a hydrogen atom, a hydrocarbon having the same content as Ω1 in the above formula (IVa) (indicates the group, etc.)
It represents a single linking group selected from the atomic groups such as, or two or more linking groups composed of any combination.

If the weight average molecular weight of the macromonomer (M) exceeds 2X10', copolymerizability with the monomer represented by formula (V) will decrease, which is undesirable.On the other hand, if the weight average molecular weight is too small, electrons in the photosensitive layer Since the effect of improving photographic properties becomes small, it is preferable that it is 1×10 4 or more.

The macromonomer (M) used in the present invention can be produced by a conventionally known synthesis method. Specifically, radical polymerization is carried out using a polymerization initiator and/or chain transfer agent containing a reactive group such as a carboxyl group, a carboxyhalide group, a hydroxyl group, an amino group, a halogen atom, or an epoxy group in the molecule. A macromer is synthesized by a method such as a radical polymerization method by reacting the obtained oligomer with a terminal reactive group bond with various reagents.

Specifically, P, Dreyfuss & R, P, Qu
irk, Encycl.

Polym, Sci, Eng,, 7.551 (1
987), P., F., Rempp, &E., Franta.
, Adv, Po1y*, Sci,, 58.1 (
1984), Yuji Yogami [Chemical Industry J 38.56 (1
9B? ), Yuya Yamashita r Polymer” ■, 98B (198
2), Shibe Kobayashi, “Polymer” Tetsu, 625 (1981),
Hiroshi Ito - "Polymer Processing" Jin 262 (1986), Kishibe Higashi, Takashi Tsuda F Functional Materials ■Nugi No. 10.5, etc. Synthesis according to the method described in the review and the literature/patent calculation cited therein. I can do it.

However, since the macromonomer (?I) of the present invention contains the polar group as a constituent of its repeating unit, it is synthesized with the following considerations in mind, for example.

As one method, for example, as shown in the following reaction formula (1), a monomer containing the polar group in the form of a protected functional group is used, and the above method is used to carry out radical polymerization and a terminal reactive group. This will introduce the following.

Reaction formula N) Polymerizable group introduction reaction L *Protecting group of C00N, for example, -C(C6HJ
3. The polar groups (-5O3H group, -PO3
The protective group introduction reaction and deprotection reaction (for example, hydrolysis reaction, hydrogenolysis reaction, oxidative decomposition reaction, etc.) of H2 group, H hydrate-containing group can be carried out by conventionally known methods. Specifically, J, F, W, McOa+ie+”Prot
active Gvoups in Organjc
Chemistry''.

PIenu* Press (1973), T, W
, Greene, “Protective Gvou
ps in Organic 5ynthesis'+
John Wtley & 5ons (1981)
, Ryohei Oda “Polymer Fine Chemicals” Kodansha (197
6th year), Giyu Iwakura, Keisuke Kurita “Reactive Polymer” Kodansha (
(1977), G., Berneret al+ J.
, Radiation Cuying+ 1986+
No. IO, plO1 JP-A-62-212669,
JP-A-62-286064, JP-A-62-21047
No. 5, JP-A-62-195684, JP-A-62258
No. 476, JP-A No. 63-260439, Patent Application No. 62-
It can be synthesized using the methods described in Japanese Patent Application No. 220510, Japanese Patent Application No. 62-226692, and the like.

Another method is to synthesize an oligomer as described above, for example, as shown in reaction formula (n) below, and then
Polymerization double bonding that reacts only with the "specific reactivity" by utilizing the difference in reactivity between the "specific reactive group" bonded to one end of the oligomer and the polar group contained in the oligomer. This is a method of synthesis by reacting with a group-containing reagent.

Reaction formula (It) 0 copies C1l.

Table A shows specific examples of combinations of specific functional groups in the rod shown in reaction formula (I[). However, the present invention is not limited thereto, and the important thing is that macromonomerization can be achieved without protecting the acidic groups in the oligomer by utilizing the reaction selectivity in ordinary organic chemical reactions. It would be good if it were done.

Table A Table (continued) Chain transfer agents that can be used include, for example, mercapto compounds containing the polar group or a substituent that can later be induced into the polar group (e.g., thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-Mercaptopropionic acid, 3
-Mercaptopropionic acid, 3-mercaptoacetic acid, N-
(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-CN-(2-mercaptoethyl)carbamoyl]propionic acid, 3-(N-(2-mercaptoethyl)aminocopropionic acid, N-(3- Mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptoethanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercaptoethanol)-1,2-propanediol, 1-mercapto-2propanediol tool, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercapto-2-butanol, 2-mercapto-3-viridinol, etc.) or disulfide compounds that are oxidized products of these mercapto compounds, or the above polar groups or Iodized alkyl compounds containing substituents (e.g. iodoacetic acid, iodopropionic acid, 2-iodoethanol,
2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferred are mercapto compounds.

Specific reactive group-containing polymerization initiators that can be used include, for example, 2,2'-azobis(2-cyatuburobanol L2,2'-azobis(2-cyanopentanol), 4,4'- Azobis (4-cyanovaleric acid),
4.4°-Azobis(4-cyanovaleric acid chloride)
, 2.2'-azobis(2-(5-methyl-2-imidacillin-2-yl)propane), 2.2'-azobisC2-(2-imidacillin-2-yl)propane], 2
．． 2'-azobis(2-(3,4,5,6-tetrahydrobyrimidin-2-yl)propane), 2,2'-azobis(2-[1-(2-hydroxyethyl)-2-imidapurine- 2-yl]propane), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], or derivatives thereof.

The amount of these chain transfer agents or polymerization initiators is 0.1 to 15% by weight, preferably 0.5 to 10% by weight, based on 100 parts by weight of the total monomers.

Specific examples of the macromonomer buffer of the present invention include the following compounds. However, the scope of the present invention is not limited to these.

In addition, on each side below, Q2 represents -H or -CHl, and Ω8 represents -B, -C)13 or -CO□C00CI
Ix, R41 is -CaHz++-+ (n is 1 to
(indicates an integer of 18), Br, -CH3, -COCHs
or -COOCHs)CN, -0COCI+
, , -CONH, or -CbHs, -2 is CI
, -Br, -CN or -0CL, r is 2 to 18
, S represents an integer from 2 to 12, and t represents an integer from 2 to 4.
indicates an integer.

(M-1) C+t (T2) Q mushroom (T3) Q! (G4) (G5) (1'l-6) C00CLCHCHJH H (M-7) (M-8) 0G9) 01( (M-10) 2 (M-11) (M-12) ( M-13) CHx=CH-CTo-COOCHzCHzS(Li2
) (M-15) 0°cozo.

(L16) 0to17) (M-18) z (M-19) 0g (M-20) Shiu (Hshith)zU-t’-υ■ 1 (M-22) (M-23) z (M-24) z il Shiri υ -1 (M-25) Q friend CH1=C COOCHzCtlCLOOC-CLCLS-Umbrella H (1'l-26) Ω.

CI(!=C CM.

C0CI(fc)lyo0COCHtCHzC-NingN ShiUUka+ ShiuUshit1glLn! ! ”! SILIUr+other,
The monomer copolymerized with the macromonomer (M) described above is represented by general formula (V).

In formula (V), C9 and C2 may be the same or different from each other, and C3 and C! of formula (III)! represents the same content as .

X and 0□ respectively represent the same contents as X in formula (IVa) and OI in 2 (IVa).

In the resin of the present invention, the composition ratio of the copolymer component having macromonomer (11) as a repeating unit and the copolymer component having a repeating unit of the monomer represented by - binding margin (V) is as follows:
Preferably it is 1-90/99-10 (weight composition ratio), more preferably 5-60/95-40 (weight composition ratio).

Furthermore, for the purpose of improving mechanical strength, the same heat-curable and/or photo-curable functional group-containing component as described above for resin CA) may be contained as a copolymer component.

In the resin (B) of the present invention, the polymer main chain contains POs
Hz group, -5Q, )I group, -COOI+ group, -OI group,
Those containing no co-1 H polymerization component containing a cyclic acid anhydride-containing group and a polar group of -P-[1, group are preferred.

Further, the resin (B) of the present invention can be prepared using the above-mentioned macromonomer.
Along with the monomers (M) and -Funenin (V), monomers other than these may be contained as further copolymerization components.

For example, α-olefins, vinyl alkanoates or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, heterocyclic vinyls (e.g., vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidapurine, vinylpyrazole, vinyldioxane, vinylquinoline, vinylthiazole, vinyloxazine, etc.).

However, the amount of these other monomers other than the macromonomer (M) and the monomer of formula (V) does not exceed 20% by weight in the copolymer.

Furthermore, the resin (B) contains at least one type of repeating unit represented by -boatman (V) and at least one type of repeating unit represented by the macromonomer (M), only at one end of the polymer main chain. It may be a copolymer (resin (B')) formed by bonding at least one of the polar groups,
Further, copolymers [B] and [B'] may be used in combination.

Here, the polar group has a chemical structure in which it is 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. It is composed of any combination of atomic groups of atomic bonds, and is selected from NCO0-SO, -CON-1za14Rgo4 (Rff!-Rxa each indicates the same content as R1-11xn above), etc. A linking group composed of a single atomic group or a combination of two or more.

In the resin (B) used in the present invention, in order to synthesize the resin [B'] in which the polar group is bonded to the terminal of the polymer main chain, at least the above-mentioned macromonomer (M) and - This can be achieved by concurrently using a polymerization initiator or chain transfer agent containing the polar group or a specific reactive group that can be derived therefrom in the molecule during the polymerization reaction with the monomer represented by (V).

Specifically, it can be obtained in the same manner as the method for oligomers bonded with a reactive group at one end as described above in the synthesis of macromonomers.

In the present invention, resin [A] and resin [B] (
In addition to [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.

When 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) are lost.

In addition, when the resin [A) and/or [B] of the present invention contains the thermosetting functional group, a reaction accelerator may be added as necessary to promote the crosslinking reaction in the photosensitive layer film. In the case of a reaction mode that forms a chemical bond between functional groups, for example, an organic acid (acetic acid, propionic acid, acetic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), a crosslinking agent, etc. may be added. Can be mentioned.

As a crosslinking agent, specifically, Shinzo Yamashita and Tosuke Kaneko ed.
Compounds described in "Crosslinking Agent Handbook" published by Taiseisha (1981) etc. can be used. For example, commonly used crosslinking agents such as organic silane, polyurethane, polyisocyanate, epoxy resin, melamine resin, etc. A curing agent or the like can be used.

In the case of a polymerizable reaction mode, a polymerization initiator (peroxide, azobis-based compound, etc., preferably an azobis-based polymerization initiator), a monomer containing a polyfunctional polymerizable group (for example, vinyl Methacrylate, allyl methacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, divinyl succinate, divinyl adipate, diallyl succinate,
2-methylvinyl methacrylate, divinylbenzene, etc.).

Further, in the present invention, when using a binder resin containing such a thermosetting functional group, a thermosetting treatment is performed. This heat curing treatment can be carried out by tightening the drying conditions during conventional photoreceptor production. For example, from 60°C to
The treatment may be carried out at 120° C. for 5 to 120 minutes, and when the above-mentioned reaction accelerator is used in combination, the treatment can be carried out under milder conditions.

The ratio of the amount of resin [A] (including (A')) and resin (B) (including (B')) used in the present invention depends on the type, particle size, and surface condition of the inorganic photoconductive material used. Although it varies depending on the situation, the ratio of resin [A] and resin (B) used is generally 5 to 6.
0:95-40 (weight ratio), preferably 10-4
The ratio is 0:90 to 60 (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.

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, per 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 LILI ((Na8) p. 12, Cj.
Young et al., RCA Revieldj, 469
(1954).

Wataru Kiyota, Journal of the Institute of Electrical Communication Engineers J 63 C (No.
, 2).

97 (1980), Yuji Harasaki et al., Industrial Chemistry Magazine,
Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthine dyes, phthalein dyes, polymethine dyes (e.g., oxonol dye, merocyanine dye,
cyanine dyes, logcyanine dyes, styryl dyes, etc.),
Examples include phthalocyanine dyes (which may contain metal).

More specifically, examples using mainly carbonium dyes, triphenylmethane dyes, xanthine dyes, and phthalein dyes include Japanese Patent Publication No. 51452 and Japanese Patent Publication No. 5
0-90334, JP 50-114227, JP 53-39130, JP 53-82353, U.S. Patent No. 3,052,540, U.S. Patent No. 4,054
, No. 450, and JP-A-5716456.

oxonol dye, merocyanine dye, cyanine dye,
Polymethine dyes such as rhodacyanine dyes include F,
M, Harmmar rThe Cyanine
Dyes andRelated Co5pounds
J. et al., and more specifically, U.S. Pat. No. 3,047,384, U.S. Pat.
No. 110,591, U.S. Patent No. 3,121.008;
U.S. Patent No. 3.125.447, U.S. Patent No. 3,12
No. 8.179, U.S. Patent No. 3,132,942, U.S. Patent No. 3.622.317, British Patent No. 1,226,
892, British Patent No. 1,309.274, British Patent No. 1,405,898, Japanese Patent Publication No. 48-7814, Japanese Patent Publication No. 55-188.92, and the like.

Furthermore, as a polymethine dye that spectrally sensitizes in the near-infrared to infrared light region with a long wavelength of 700 n- 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. 3.
No. 619.154, U.S. Patent No. 4,175,956;
'Re5earch Disclosure J 19
B2 year, 216. Examples include those described on pages 117 to 118.

The photoreceptor of the present invention is excellent in that its performance does not easily vary depending on the sensitizing dye, even when various sensitizing dyes are used together. Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers such as chemical sensitizers can be used in combination.
a 8''), p. 12 of the review, etc., of electron-accepting compounds (e.g., halogens, benzoquinone, chloranil, acid anhydrides, organic carboxylic acids, etc.), Hiroshi Komon et al., ``Recent photoconductive materials and photoreceptors. "Development and Practical Application" Chapters 4 to 6 2 Nippon Kagaku Information Co., Ltd. Publishing Department (1986), cited in the review of polyaryl alkane compounds, hindered phenol compounds,
Examples include p-phenylenediamine compounds.

The amount of these various additives added is not particularly limited, but
Usually 0.0001 to 2.0 parts per 100 parts by weight of photoconductor.
It is 0 parts by weight.

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

In addition, when a photoconductive layer is used as a charge generation layer in a laminated photoreceptor consisting of a charge generation layer and a charge transport layer, the thickness of the charge generation layer is 0.01 to 1μ, particularly 0.05 to 0.5μ. suitable.

In some cases, an insulating layer is added mainly for the purpose of protecting the photoreceptor, improving its durability, dark decay characteristics, etc.

At this time, the insulating layer is set to be relatively thin, and when the photoreceptor is used for a specific electrophotographic process, the insulating layer provided is set to be relatively thick.

In the latter case, the thickness of the insulating layer is between 5 and 70μ, in particular 1
It is set to 0 to 50μ.

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 for the electrophotographic photosensitive layer is preferably electrically conductive.As the electrically conductive support, for example, a base material such as metal, paper, or plastic sheet impregnated with a low-resistance substance is used in the same manner as in the past. those that have been subjected to conductive treatment, such as 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 also to prevent curling, and those that have been coated with at least one layer for the purpose of preventing curling, etc. Those with a water-resistant adhesive layer on the surface of the body, those with at least one pre-coated layer provided on the surface layer of the support as required, and those with a conductive plastic base coated with A1 or the like and laminated with paper. You can use the ones that have been prepared.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto “Electronic Photography J 14. (No. 1), p.
2-11 (1975), Hiroyuki Moriga “Introductory Chemistry of Special Paper” Kobunshi Publishing (1975), Mon, F. Hoov
er, J. Macromol.

Sci, Chew, A-4(6)+ No. 1327
-1417 pages (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 of A, , A- ethyl methacrylate 95g, 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.

Azobisisobutyronitrile (A, 1.B, N
,) was added and reacted for 4 hours. B, N
Add 0.8g of A, 1. for 3 hours. B, N, 0.
5g was added and reacted for 3 hours. The weight average molecular weight (Frw) of the obtained copolymer was 8.3 x 10'.

A of A: A A mixed solution of 95 g of benzyl methacrylate, 1.5 g of ethylene glycol dimethacrylate, 1.0 g of n-dodecyl mercaptan, 150 g of toluene and 50 g of isopropyl methacrylate was heated to a temperature of 85° under a nitrogen stream.
It was heated to C. While stirring, 5.0 g of 4,4'-azobis(4cyanovaleric acid) (A, C, V,) was added and reacted for 5 hours. 1 g of was added and reacted for 4 hours.

What is the η- of the obtained copolymer? , 5X10'.

A-8 ~ 2: A-~ A- In Synthesis Example 1 of Resin [A], instead of ethyl methacrylate, thioglycolic acid, and divinylbenzene, the compounds in Table 1 below were added in the amounts listed in Table 1. Each copolymer was synthesized repeatedly under the same conditions as in Synthesis Example 1 except that each copolymer was used. The π- of each copolymer obtained ranged from 5X10' to 9X10''.

(The following is a blank space) Part A: A-23 A mixed solution of 95 g of 2-chlorophenyl methacrylate, 5 g of 2-mercaptoethanol, 2.3 g of divinylbenzene, and 200 g of toluene was heated at a temperature of 75°C under a nitrogen stream.
It was heated to Under stirring, azobis(isohalene o 2)
') 2 g of (A, IJ, N,) was added and reacted for 4 hours, 0.8 g of Sarani A, r, V, N, was added for 3 hours, and 0.8 g of Sarani A, IV, N, was added. 8g was 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 20
It was reprecipitated into a methanol solution containing 12% and the precipitate was collected. The yield after drying under reduced pressure is 65g and the nail size is 7.5X10
It was Ko.

80m 24: A-24 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. 2g of B and N were added and reacted for 4 hours, and then A, 1. 0.5g of B and N were added and reacted for 3 hours.

The nail of the obtained copolymer was 8.5 x 10'.

Monomer [A] L 2-chloro-6-methylphenyl methacrylate 66.
5g, monomer (B) below 30g thioglycolic acid 3
．． A mixed solution of 5 g of divinylbenzene, 3 g of divinylbenzene, and 200 g of toluene was used, and the following reaction was carried out in the same manner as in Synthesis Example 24.

The resulting copolymer had a 1- size of 9 x 10''.

Monomer (B) CO.

A mixed solution of 90 g of ethyl methacrylate, 10 g of 2-hydroxyethyl methacrylate, 5 g of thioglycolic acid, and 200 g of toluene was heated to a temperature of 75° C. while stirring under a nitrogen stream. 1.0 g of 2,2"-azobisisobutyronitrile (abbreviated as A, 1.B, N,) was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate), N, N- Add 1.0 g of dimethyldodecylamine and 0.5 g of t-butylhydroquinone, and reduce the temperature to 10
The mixture was stirred at 0°C for 12 hours. After cooling, this reaction solution was
- The weight average molecular weight of the 0 polymer, which was reprecipitated in hexane 21 to obtain 82 g of white powder, was 3.8 x 10'.

(MM-1) Butyl methacrylate 90g, methacrylic acid 10g,
2-mercaptoethanol 4g, tetrahydrofuran 2
00. The mixed solution was heated to a temperature of 70'C under a nitrogen stream. ^, 1. 1.2g of B and N were added and reacted for 8 hours.

The reaction solution was then cooled in a water bath to a temperature of 20°C,
10.2 g of triethylamine was added, and 14.5 g of methacrylic acid chloride was added dropwise at a temperature of 25° C. or less to remove the supernatant, followed by further stirring for 1 hour. Thereafter, 0.5 g of t-butylhydroquinone was added and the mixture was heated to 60°C and stirred for 4 hours. After cooling, the mixture was added dropwise to 1N water with stirring for about 10 minutes), stirred as it was for 1 hour and allowed to stand, and then the water was removed by decantation. After two more washes with water, it was dissolved in 1001d of tetrahydrofuran and reprecipitated in 2iV of petroleum ether. The precipitate was collected by decantation and dried under reduced pressure. The yield of the viscous material obtained was 65 g, and the weight average molecular weight was 5.6×10 3 .

(MM-2) Hensyl methacrylate) 95 g.

A mixture of 5 g of 2-phosphonoethyl methacrylate, 4 g of 12-aminoethyl mercaptan and 200 g of tetrahydrofuran,
The mixture was heated to 70° C. with stirring under a nitrogen stream.

^, 1. 1.5g of B and N were added and reacted for 4 hours, and then A, 1Bj1. Next, this reaction solution was cooled to a temperature of 20°C, 10g of acrylic anhydride was added, and the mixture was stirred at a temperature of 20 to 25°C for 1 hour.

Next, add 1.0 g of L-butylhydroquinone and bring the temperature to 50.
Stirred at ~60°C for 4 hours. After cooling, the reaction mixture was clarified in 1 liter of water while stirring for about 10 minutes, and after stirring for 1 hour, it was allowed to stand, and the water was removed in a 5-liter decant. After repeating the washing with water two more times, it was dissolved in tetrahydrofuran 100H1 and petroleum ether 2I!
, re-sinked inside. Collect the precipitate by decantation,
Dry under reduced pressure.

The yield of the obtained viscous material was 70 g, and the weight average molecular weight was 7.
It was 4 x 10'.

(MM 3) 2-chlorophenyl methacrylate 95g1 The following structure (
A mixed solution of 5 g of the monomer 1), 4 g of thioglycolic acid, and 200 g of toluene was heated to 70° C. under a nitrogen stream. A.1. Add 1.5g of B and N and react for 5 hours,
Furthermore, A.1. 0.5g of B and N were added and reacted for 4 hours.

Next, 2.4 g of glycidyl methacrylate-H, 1. N,N-dimethyldodecylamine. 1.5 g of h- and t-butylhydroquinone were added and reacted at a temperature of 110°C for 8 hours.

After cooling, the reaction mixture was mixed with 3 g of p-)luenesulfonic acid,
The solution was added to 100 ml of a 90 vol 1% aqueous solution of tetrahydrofuran, and stirred at a temperature of 30 to 35°C for 1 hour.

The above mixture was reprecipitated in a mixed solution 21 of water/ethanol ((1/3) volume ratio), and the precipitate was collected by decantation.The precipitate was dissolved in 200% of tetrahydrofuran and n-hexane. It was reprecipitated in 2N to obtain 58 g of powder with a zero weight average molecular weight of 7.6 x 10''.

Monomer (1) CH.

L (MM-4) C1l.

2.6-cyclophenyl methacrylate 95g, 3=
A mixed solution of 5 g of (2° nitrohensyloxysulfonyl)propyl methacrylate, 150 g of toluene and 50 g of isopropyl alcohol was heated to 80° C. under a nitrogen stream. 2. 5.0 g of 2'-azobis(2-cyanovaleric acid) (abbreviation: A, CJ,) was added and reacted for 5 hours, and then A, C, ■, and 1. Og was added and the mixture was reacted for 4 hours. After cooling, the reaction product was reprecipitated into methanol 21, filtered, and dried under reduced pressure.

50g of the above powder, 14g of glycidyl methacrylate, N
A mixture of 0.6 g of N-dimethyltosylamine, 1.0 g of t-butylhydroquinone, and 100 g of toluene was stirred at a temperature of 110°C for 10 hours. After cooling to room temperature 8
The mixture was irradiated with light for 1 hour under stirring using a 0W high-pressure mercury lamp. Thereafter, the reaction mixture was reprecipitated into 1 liter of methanol, and the powder was dried under reduced pressure using a filter. Yield 34g and weight average molecular weight? , 3X10'.

(MM-5) CI(ff Coo(CBa)isOJ B: B 80 g of benzyl methacrylate, 20 g of the compound (MM-2) of macromonomer synthesis example 2, and 100 g of toluene
The mixed solution of g was heated to a temperature of 75° C. under a nitrogen stream.

1. 0.8 g of 1'-azobis(cyclohexane-1-carbocyanide) (abbreviation A, B, C, C,) was added and reacted for 4 hours, and then A, 1. 0.5g of B and N were added and reacted for 3 hours.

The weight average molecular weight (fl) of the obtained copolymer was 1, OX
It was 10'.

CB-1) A mixed solution of 70 g of 2-chlorophenyl methacrylate, 30 g of the compound (MM-1) of macromonomer synthesis example 1, 0.7 g of thioglycolic acid, and 150 g of toluene was heated to a temperature of 80°C under a nitrogen stream. did. ^, B, C, C
, was added and reacted for 5 hours, and then A, B, C, C,
Added 0.3g of A, B, C, C and reacted for 3 hours.
, and reacted for 3 hours.

The resulting copolymer 6 was 9.2X10'.

CB-2) ethyl methacrylate 60g, compound of macromonomer synthesis example 4: MM-425g, methyl acrylate 1
A mixed solution of 5 g and 150 g of toluene was heated to 75°C under a nitrogen stream. Add 0.5g of A, C, V and 5
After reacting for an hour, 0.3 g of ^, C, V was added and reacted for 4 hours.

The sum of the obtained copolymers is 1. It was IX 10'.

(B-3) In the same manner as in the production example of resin (B-1), each resin [B] was synthesized using methacrylate and macromonomer corresponding to Table 2 below.

6 of each resin [B] is 9.5 x 10' to 1.2 x 10
' range.

(Margins below) B 12-1: B-12-B-19 Resin CB-
Resin (B) shown in Table 3 below was synthesized in the same manner as in Production Example 2) by changing the methacrylate and the macromonomer mercapto compound.

6 of each resin [B] is 9X10'~1. It was in the range of 1×10′.

(The following is a blank space) B-21: B-0 to B-27 In the same manner as in Production Example 3 of resin (B), methacrylate,
The resins [B] shown in Table 4 below were synthesized by changing the macrochemicals and the azobis-based compounds.

6 for each resin (B) ranged from 9.5XIO' to 1.5XIO'.

(Left below) Actual JF Example 1 - A-C Resin (A-9) 6g (as solid content), Resin CB-1
) 34g (as solid content), cyanine dye with the following structure (r) 0.018g, maleic anhydride 0.13g
A mixture of 300 g of toluene and 300 g of toluene was dispersed in a ball mill for 4 hours to prepare a photosensitive layer-forming product, and this was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 22 g/rrf. An electrophotographic light-sensitive material was prepared by drying at 20° C. for 30 seconds and then leaving it in the dark at 20° C. and 65% RH for 24 hours.

Cyanine dye (I) (CHz) asOse (CHz)asOsK Kita tdlN: Instead of the binder resin used in Example 1, 6 g of resin (R-1) with the following structure and poly(ethyl methacrylate HMw 2.4X10') :An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that 34 g of resin CR-2) was used.

(R-1) ■ cooc, )I, C0OH &6.5X10' This ldl ratio: Instead of the binder resin used in Example 1, 6 g of resin (R-3) with the following structure 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) H3 HOOC-CHz-5ncHz-C'F-OOCJs Yw 6.5xlO" This l■1q' Instead of the binder resin used in Example 1, resin (R
-3) An electrophotographic photoluminescent material was produced in the same manner as in Example 1, except that 6 g of resin [R-4] having the following structure was used.

(R-4) C.B.

(Weight ratio) &8.0X10' Film properties (surface smoothness), electrostatic properties, image capture properties, and image capture properties of these photosensitive materials were investigated under environmental conditions of 30°C and 8o% R)I. . Furthermore, when these photosensitive materials are used as original plates for offset masters, the desensitization property of the photoconductivity (represented by the contact angle with water of the photoconductive layer after desensitization treatment) and printability (resistance to background smearing) are evaluated. Printability, etc.) were investigated.

The above results are summarized in Table-5.

(The following is a blank space) Table 5 The implementation aspects of the evaluation items shown in Table 5 are as follows.

Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was tested using a Beck smoothness tester (Kumagai Riko ■
The smoothness (
see/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 Shinrai Kagaku ■) under a load of 60 g/cd, and was repeatedly probed with emery paper (11000) 1000 times to remove abrasion powder and determine the remaining film rate (%) as the weight of the photosensitive layer decreased and was taken as mechanical strength.

Note 3) Electrostatic properties: In a dark room at a temperature of 20°C and 165% RH, each photosensitive material was subjected to corona discharge for 20 seconds using a paper analyzer (Paper Analyzer 5P-428 manufactured by Kawaguchi Denki ■) at -6 kV. Leave it for 10 seconds, and at this time the surface potential ν
1° was measured. Then, the potential Vll+ after being allowed to stand still in the dark for 180 seconds. The retention of the potential after dark decaying for 180 seconds, that is, the dark decay retention rate (DPI)
? (χ)) was calculated as (shi+go/shi16)×100(%).

After the surface of the photoconductive layer is charged to -500 μm by corona discharge, it is irradiated with monochromatic light with a wavelength of 785 nm to increase the surface potential (
The time required for V+o) to attenuate to 1/10 is determined, and the exposure amount E+7+o(erg/cd) is calculated from this.

Furthermore, as in the El/10 measurement, -500
After charging to v, irradiation with monochromatic light of wavelength 785n-,
Determine the time required for the surface potential (v1.) to attenuate to force/month/100, and then calculate the exposure amount E1/. . (Bg/cj) is calculated.

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

Next, it was charged with ν to -5, and using a 2.81 output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 785nv) as a light source, 50srg was applied on the surface of the photosensitive material.
As a liquid developer after exposure at a pitch of 25 μ and a scanning speed of 330 s/sec under an irradiation dose of /cd,
The resulting copy image (fog, image quality) was visually evaluated by developing and fixing using ELP-T (manufactured by Fuji Photo Film ■).

Environmental conditions during imaging were 20'C65%RH and 30'C80
%RH' was carried out.

Note 5) Contact angle with water: Desensitizing treatment liquid EPL-EX for each photosensitive material (Fujisha)
After the 171 side of the film was diluted twice with distilled water (by passing it through an etching processor once) to make the surface fat-free, water droplets of 2.1 of distilled water were placed on it to form the film. The contact angle with water is measured using 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 then used as an offset master. The number of sheets that can be printed using an off-cent printing machine (Oliver 55 type manufactured by Sakurai Seisakusho) without causing stains in the non-image areas or problems with the image quality of the image areas is shown (the higher the number of prints, the higher the rigidity resistance. It means something good.

As shown in Tables 5 to 5, 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 blur and the quality of the copied images was clear. 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.

Moreover, the electrostatic properties of Comparative Examples A to C were lower than those of the photosensitive materials of the present invention. In Comparative Example C, the film strength was improved and the electrostatic properties were also V. ,[1,R,R,,El
/I. The values obtained were quite satisfactory.

However, when looking at the El/10° value, the value was higher than that of the light-sensitive material of the present invention.* El/l.

. In actual imaging performance, the value indicates how much potential remains in the non-image area (already exposed area) after exposure. Indicates that stains will no longer occur.

Specifically, it is necessary to make the residual potential below -10V, that is, to actually keep it below VmIOV,
Regarding the amount of exposure required, in the scanning exposure method using semiconductor laser light, it is important to keep the exposure amount below V,1~IOV with a small exposure amount due to the design of the optical system of the copying machine (equipment cost). , accuracy of the optical system optical path, etc.) is very important.

From the above, when an image was actually captured using an apparatus with a slightly lower exposure dose, Comparative Example A could not obtain a satisfactory copy image because DJ, R, was extremely low.

In Comparative Example B, the image deteriorated significantly under high temperature and high humidity conditions, resulting in a decrease in density in the image area, fading of thin lines and letters, and blurring in the non-image area. In Comparative Example C, the image was quite satisfactory under room temperature and room temperature conditions, but under high temperature and high temperature conditions, ground blurring, fading of fine lines in the image area, etc. occurred. In addition, even when used as an offset master original plate, under printing conditions that allow the photosensitive material of the present invention to print 10,000 sheets or more, in all of Comparative Examples A to C, background stains occurred in the non-image areas of the printed matter at the beginning of printing. have done. This means that a clear copy image cannot be obtained.
The ground yellowtail was unable to be removed even with desensitization treatment.

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.

In Example 1, resin (A-9:l and resin (B-1)
) in place of each resin (Al and each resin (B
), 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 -
6.

(Margin below) Table 6 Electrostatic properties were measured under (30'C 180% RH) conditions (direct and offset master plates were used and printed in the same manner as in Example 1. I was able to print more than one page.

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'].

In the back application binary measurement example 1, the resin shown in Table 7 below [A] was used as the binder resin.
] 7.6 g and resin [B] 34 g, and in place of 0.02 g of cyanine dye CI), a dye with the following structure (
II) An electrophotographic light-sensitive material was produced under the same conditions as in Example 1 except that 0.019 g was used.

Dye (n) (CL) asOze (C) 12) 4SO3 Table 7 The photosensitive materials of the present invention all have chargeability, dark charge retention,
It has excellent light intensity, and the actual copied image can be used even under high temperature and high humidity conditions (30°).
Even under severe conditions (C, 80% RH), it provided clear images without any 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.

34 and 35 and D Resin [A-2) (Example 34) or Resin (A-13) (
6.5 g of any of Example 35), resin CB-2333
, 5g, zinc oxide 200g, uranine 0.02g, rose bengal 0.04g, bromophenol blue 0.03g, phthalic anhydride 0.20g and toluene 30g.
0g of the mixture was dispersed in a ball mill for 4 hours to prepare an angry light layer-forming product, and this was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 20g/nf.
Dry for 1 minute at 0°C then 20°C in the dark.
Each electrophotographic photoreceptor was prepared by leaving it for 24 hours under conditions of %I'lH.

In Comparative Example 34, 6.5 g of resin (A-2), resin (
B-2) Instead of 33.5g, resin [R-3]6
．． 5g and resin (R-4) 33.5g were used.
A photosensitive material was produced in the same manner as in Example 34.

In the same manner as in Example 1, the characteristics of each photosensitive material were investigated. The results are summarized in Table 8 below.

(Margin below) Table In the above measurements, the electrostatic properties and imaging properties were performed in the same manner as in Example 1, except that the following procedures were followed.

Note 7) Electrostatic characteristics El/I11 and El/l. . 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 (Vie) is 1/10 or E17.
．． . . Find the time it takes for the exposure to decay to
El/l. Or calculate El/10° (runx seconds).

Note 8) Imaging properties After leaving each photosensitive material for one day and night under the following environmental conditions, use a fully automatic plate making machine EPL-404V (manufactured by Fuji Photo Film ■).
A copy image (fogging, image quality) obtained by plate making using EPL-T as a toner was visually evaluated. The environmental conditions at the time of lift injury were 20°C 65%R) I (1) and 30°C8
Performed at 0% RH(II). However, the manuscript for copying (ie, the draft 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 a photosensitivity E of 171°. The electrostatic properties of the photosensitive material of the present invention are good;
Furthermore, Example 35, which used the resin [A] having a specific substituent, had very good results, especially the value of El/10° was small.

When examining the actual imaging performance, it was found that in the comparative example, in addition to the original, the frame of the cut out and pasted portion (i.e. 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.

In Example 34, instead of 6.5 g of resin (A-2) and 33.5 g of resin (B-2), 6.5 g of resin [A] and resin CB of Table 9 below were used. ) Each photosensitive material was produced in the same manner as in Example 34, except that 33.5 g was used.

Table 9 Table (Continued) All of the photosensitive materials of the present invention have excellent chargeability, dark charge retention, and photosensitivity, and the actual reproduced images are also produced at high temperatures (30°C, 18°C).
Even under the harsh conditions of 0%R1(), clear images were produced without any occurrence of ground force 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.

Back coating charcoal and resin (/l-14) (Example 50) or resin [A-
15] (Example 51), 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 50) was added to this dispersion.
or 0.5 g of 1.6 hexanediol (Example 51)
was added and further dispersed in a ball mill for 10 minutes.

The dry adhesion amount is 20g/nf on conductive treated paper.
It was coated with a wire bar so that Then in the dark at 20°C 165% I? ) Each electrophotographic photoreceptor was produced by leaving it for 24 hours under the conditions of I.

When these photosensitive materials were examined for electrostatic properties and imaging properties in the same manner as in Example 34, they showed good performance.

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

(Effect of the invention)

Claims (4)

[Claims] (1) In an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor and a binder resin, the binder resin includes at least one binder resin [A] represented below and a binder resin. An electrophotographic photoreceptor characterized by containing at least one kind of [B]. Binder resin [A]: contains at least a repeating unit represented by the following general formula (I) as a polymer component, has a crosslinked structure in advance before preparing the dispersion for forming a photoconductive layer, and contains at least one polymer -PO_3H_2 groups, -SO_3H only at one end of the main chain
at least one acidic group selected from group, -COOH group, -P-OH group {R represents a hydrocarbon group or -OR' group (R' represents a hydrocarbon group)}, and a cyclic acid anhydride-containing group Weight average molecular weight formed by bonding groups 1×10^3 to 1×
10^4 resin. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In formula (I), R_1 represents a hydrocarbon group. [Binder resin [B]; At least one of the polymer components represented by the following general formulas (IVa) and (IVb), -COOH group, -PO_3
There are H_2 groups, -SO_3H groups, -OH groups, ▲mathematical formulas, chemical formulas, tables, etc.▼{R_0 is a hydrocarbon group or -OR_
0' group (R_0' represents a hydrocarbon group)} group,
Only one end of the polymer main chain contains at least one polymer component containing at least one component containing at least one polar group selected from -CHO group and cyclic acid anhydride-containing group. Weight average molecular weight 2 x 10 formed by bonding polymerizable double bond groups represented by general formula (III)
A copolymer having a weight average molecular weight of 5 x 10^4 to 1 x 10^6 and comprising at least a monofunctional macromonomer (M) of ^4 or less and a monomer represented by the following general formula (V). General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (III), X_0 is -COO-, -OCO-, -C
H_2OCO-, -CH_2COO-, -O-, -SO
_2-, -CO-, -CONHCOO-, -CONHC
ONH-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. (Here, R_3_1 represents a hydrogen atom or a hydrocarbon group.) c_1 and c_2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -
COO_-Z_1 or -COO_-Z via hydrocarbon
_1 (Z_1 each represents a hydrogen atom or a hydrocarbon group that may be substituted). General formula (IVa) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IVb) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In formula (IVa) or (IVb), X_1 is X in formula (III)
Represents the same content as _0. Q_1 is an aliphatic group having 1 to 18 carbon atoms or 6 to 1 carbon atoms
2 represents an aromatic group. d_1 and d_2 may be the same or different from each other,
It represents the same content as c_1 and c_2 in formula (III). Q_0 is -CN, -CONH_2 or ▲ mathematical formula, chemical formula,
▼ represents a hydrogen atom, a halogen atom, an alkoxy group, or -COOZ_2 (Z_2 represents an alkyl group, an aralkyl group, or an aryl group). General formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (V), X_2 represents the same content as X_1 in formula (IVa), and Q_2 represents the same content as Q_1 in (IVa). represents. e_1 and e_2 may be the same or different, and represent the same contents as c_1 and c_2 in formula (III). (2) The resin [A] contains repeating units represented by the following general formula (I a) and general formula (I b) as a polymer component corresponding to the repeating unit represented by the general formula (I) above. The electrophotographic photoreceptor according to claim 1, which contains at least 30% by weight of at least one of the following. 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, A_1 and A_2 do not both 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) The resin [B] has -PO_3H_2 groups, -SO_
3H group, -COOH group, -OH group, ▲Mathematical formula, chemical formula, table, etc.▼Group {R_0 is a hydrocarbon group or -OR_0
' group (R_0' represents a hydrocarbon group)} and a cyclic acid anhydride-containing group is bonded to the end of the polymer main chain of the copolymer. The electrophotographic photoreceptor according to any one of claims (1) to (3), which is a resin comprising: