JPH02272560A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To improve electrostatic characteristics and printing resistance by incorporating a specific resin, thermo- and photosetting resins and a crosslining agent into a binder resin. CONSTITUTION:The binder resin contain the resin A, the thermo- and photosetting resins having a crosslinkable functional group and the crosslinking agent. The resin A in this case is the copolymer of 1.0X10<3> to 2.0X10<4> weight average mol. wt. consisting of the monofunctional macromonomers M of <=2X10<4> average mol. wt. which contains at least one kind of the polymer components by formulas IIa, IIb and at least one kind of the polymer components having the polar group selected from -COOH group, etc., and are formed by bonding the polymerizable double bonds expressed by formula I only to one terminal of the polymer main chain and the monomer which is expressed by formula III. In the formula I, X0 denotes -COO-, etc.; a1, a2 denote a halogen atom, etc.; X1, X2 denote the same contents as the contents of X0; Q1 denotes an aliphat. group or arom. group; b1, b2 denote the same contents as the contents of a1, a2; V denotes -CN, etc.; Y denotes a hydrogen atom, etc.; Q2 denotes the same contents as the content of Q1; c1, c2 denote the same contents as the contents of a1, a2. The electrostatic characteristics and the printing resistance are improved in this way.

Description

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

(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 comprising a support and at least one photoconductive layer are used for image formation by most common electrophotographic processes, ie, charging, image exposure and development, and optionally transfer.

Furthermore, a method of using an electrophotographic photoreceptor as an offset original plate for direct plate making is widely used.

The binder used to form the photoconductive layer of the electrophotographic photoreceptor has excellent film-forming properties and ability to disperse the photoconductive powder into the binder, and also has excellent properties as a base material for the formed recording layer. It has good adhesion to the material, and the photoconductive layer of the recording layer has excellent charging ability, low dark decay, large light decay, and low pre-exposure fatigue. It is necessary to have various electrostatic properties such as the need to maintain stable properties and excellent image focusing properties.

Examples of resins that have been known for a long time include silicone resin (Japanese Patent Publication No. 34-6670), styrene-butadiene resin (
(Japanese Patent Publication No. 35-1960), alkyd resin, maleic acid resin, polyamide (Japanese Patent Publication No. 11219-197), vinyl acetate resin (Japanese Patent Publication No. 2425-1977), vinyl acetate copolymer (Japanese Patent Publication No. 2426-197) ,acrylic resin(
(Japanese Patent Publication No. 35-11216), acrylic acid ester copolymers (e.g., Japanese Patent Publication No. 11219/1971, Japanese Patent Publication No. 36/1982)
No. 8510, Japanese Patent Publication No. 41-13946, etc.) are known.

However, in electrophotographic photosensitive materials using these resins, 1) the affinity with the photoconductive powder is insufficient, resulting in poor dispersibility of the coating liquid, and 2) the charging property of the photoconductive layer is poor. low, 3
) The quality of the image area of the copied image (especially halftone reproducibility and resolution) is poor; 4) The environment at which the copied image was created (e.g. high temperature,
5) The film strength and adhesion of the photosensitive layer are not sufficient, especially when used as an offset master, the photosensitive layer may come off during offset printing, making it impossible to print a large number of sheets. , etc. There was one of the problems.

Various methods have been proposed to improve the electrostatic properties of the photoconductive layer, and one such method includes the use of a compound containing a carboxyl group or a nitro group in an aromatic ring or a furan ring, or a dicarboxylic acid anhydride. further combined,
A method of coexisting in the photoconductive layer is disclosed in Japanese Patent Publication No. 42-6878,
It is disclosed in Japanese Patent Publication No. 45-3073. However, even with the photosensitive materials improved by these methods, their electrostatic properties are still insufficient, and none particularly excellent in light attenuation properties has been obtained. Therefore, in order to improve the lack of sensitivity of this photosensitive material, a method of adding a large amount of sensitizing dye to the photoconductive layer has been conventionally used, but the whiteness of the photosensitive materials produced by this method deteriorates significantly. However, the quality of the recording medium deteriorates, and in some cases, the dark decay of the photosensitive material deteriorates, resulting in the problem that a sufficient copy image cannot be obtained.

On the other hand, Japanese Patent Laid-Open No. 6010254 discloses a method of adjusting the average molecular weight of a resin used as a binder resin for a photoconductive layer. That is, an acrylic resin with an acid value of 4 to 50 and an average molecular weight of 103 to 104 and a component of 10'
A technique is described for improving electrostatic properties (particularly good repeatability as an RPC photoreceptor), moisture resistance, etc. by using together components having a distribution of ~2X10'.

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. For example, in Japanese Patent Publication No. 50-31OH, a (meth)acrylate monomer and other monomers are copolymerized in the presence of fumaric acid, Mwl, 8X10'~1
A combination of a resin with a TglO of 0x10' and 80°C and a copolymer consisting of a (meth)acrylate monomer and a monomer other than fumaric acid, and JP-A-53-5
No. 4027 uses a terpolymer containing a (meth)acrylic acid ester having a substituent having at least 7 carboxylic acid groups in order from the ester bond, and JP-A No. 54-20735, Japanese Patent Publication No. 57-202544
In JP-A-58-68046, a quaternary or penta-component copolymer containing acrylic acid and hydroxyethyl (meth)acrylate is used, and JP-A-58-68046 uses an alkyl group having 6 to 12 carbon atoms as a substituent ( It is described that a method using a terpolymer containing a meth)acrylic acid ester and a vinyl monomer containing a carboxylic acid is effective in improving the desensitization property of the photoconductive layer. However, even if the resin is said to be effective in the above-mentioned electrostatic properties, moisture resistance properties, and durability,
When actually evaluated, there were problems particularly in chargeability, dark charge retention, electrostatic properties of photosensitivity, smoothness of the photoconductive layer, etc., and the results were not satisfactory for practical use.

Furthermore, even in the case of a binder resin which is said to have been developed as an original plate for electrophotographic lithographic printing, when actually evaluated, there were problems with the above-mentioned electrostatic properties, scumming of printed matter, etc.

Furthermore, 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.
Low molecular weight resin containing 5 to 10% by weight (MwlO'~
104), the smoothness and electrostatic properties of the photoconductive layer are improved, and image quality without background smear is obtained. (More than MwlO'), the film strength of the photoconductive layer can be made sufficient and the rigidity resistance can be improved without impeding the above characteristics by using it in combination.
-49817, JP-A-63-220148 and JP-A-63-220148
No. 3-220149 (problem to be solved by the invention) However, even when these resins are used, the environment is high temperature and
It has been found that it is still insufficient to maintain stable performance when the temperature fluctuates significantly from high temperature to low temperature and low humidity. In particular, scanning exposure methods using semiconductor laser light require longer exposure times than conventional simultaneous exposure methods using visible light across the entire surface, and there are restrictions on exposure intensity. , higher performance is required in terms of photosensitivity.

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 humidity. It is to be.

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.

Another object of the present invention is to provide an original plate for electrophotographic planographic printing.
It has excellent electrostatic properties (particularly dark charge retention and photosensitivity), reproduces copied images that are faithful to the original, and does not cause not only uniform background smudges on the entire surface of printed matter but also dotted smudges. ,
Another object of the present invention is to provide a lithographic printing original plate having excellent rigidity resistance.

(Means for Solving the Problems) The above object is to provide an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor and a binder resin, wherein the binder resin is a resin [A] shown below. Heat and/or photocurable resin containing at least one type and a crosslinkable functional group [B
] and at least one crosslinking agent.

Resin (A); at least one of the polymer components represented by the following general formulas (Ila) and (I[b) and a -COOII group, -P
A polymer main chain each containing at least one kind of polymer component containing at least one polar group selected from Oslh group, -3Offl+ group, -0)1 group, and (representing H group) group. A weight average molecule consisting of a polymerizable double bond group represented by the following general formula (I) bonded to only one end of the! Monofunctional macromonomer of 2X10' or less (
M) and a monomer represented by the following general formula (Iff) having a weight average molecular weight of 1. OXIO3~2.
Copolymer of OXIO'.

General formula (1) In formula (1), Xo is -COO-, -0CO-, -CIl
zOCO-1X+ Q+ General formula (ffb) b+ bt ←CH-C-←- In formula (■a) or (II b), X is (7) in formula (1)
) represents the same content as X. Q, has 1 to 18 carbon atoms
represents an aliphatic group or an aromatic group having 6 to 12 carbon atoms.

b3, b! may be the same or different from each other, and the expression (
Represents the same content as a8 and a in 1).

(represents a hydrogen chloride group).

ass at may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -C
oo-Z+ or -Coo-Z+ (Z
+ indicates a hydrogen atom or a hydrocarbon group that may be substituted)
represents.

General formula (I[a) Y is a hydrogen atom, a halogen atom, an alkoxy group, or -CO
OZz (L represents an alkyl group, an aralkyl group, or an aralkyl group).

In formula (III), X represents the same content as X in formula (1), Q2 represents the same content as Ql in formula (I[a), cl and Co are al, a! in formula (1) may be the same or different from each other. represents the same content as .

The binder resin used in the present invention includes a low molecular weight graft copolymer [A] containing at least a functional macromonomer (M) and a monomer represented by formula (III);
It is composed of at least one of a heat and/or photocurable resin [B] that forms a crosslinked structure between polymers and a crosslinking agent.

The graft type copolymer used in the present invention has a -POsH, group, -3o, 11 group, -COOH at one end of the polymer main chain.
group, υH, which may be a superordinating C; this resin [A] may also be particularly referred to as resin [A']).

The conventionally known acidic group-containing binder resins as mentioned above are mainly used for offset masters, and their molecular weight is large (for example, 5.
X10' or more), and these copolymers were random copolymers, and the acidic group-containing copolymer components were randomly present in the polymer main chain.

On the other hand, resin [A] used in the binder resin of the present invention
is a graft-type copolymer, and the acidic groups or hydroxyl groups contained in the resin are not randomly present in the main chain of the polymer, but are only randomly present in the graft region, or even optionally. These are copolymers in which polar groups (acidic groups or hydroxyl groups) are specifically bonded, such that they are present only at the ends of the copolymer main chain.

Therefore, the portion of the polar group present at a specific position away from the main chain of the polymer adsorbs to the stoichiometric defects of the inorganic photoconductor, and the main chain portion of the polymer covers the surface of the photoconductor. It is estimated that the coating is loose and sufficient. It has been found that by doing so, the tramp of the photoconductor is compensated for and the humidity characteristics are improved, while the photoconductor is sufficiently dispersed and agglomeration is suppressed. In other words, when the weight average molecular weight of the polymer is small, the coverage of the surface of the photoconductor is improved, and in the case of a high molecular weight polymer, the coverage of the photoconductor surface is significantly improved in the case of a random copolymer. This is thought to be due to the fact that the phenomenon of promoting aggregation among like-minded people is suppressed. Therefore, the surface of the photoconductive layer becomes smooth. On the other hand, when a photoreceptor with a rough surface of the photoconductive layer is used as an electrophotographic lithographic printing original plate, the dispersion state of the zinc oxide particles that are the photoconductor and the binder resin is not appropriate, resulting in the presence of aggregates. Since a photoconductive layer is formed in this state, even if desensitization treatment is performed using a desensitization treatment liquid, the non-image area cannot be made uniformly and sufficiently hydrophilic, causing printing ink to adhere during printing, resulting in blockage. As a result, background stains occur in non-image areas of printed matter.

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

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

Even when only the low molecular weight resin [A] in the present invention is used as the binder resin, the photoconductor and the binder resin can sufficiently adsorb and coat the particle surface, which improves the smoothness of the photoconductive layer. It has good electrostatic properties, provides image quality without background smearing, and has sufficient film strength for use as a CPC photoreceptor or as an offset original plate for printing several tens of sheets. However, as in the present invention, by coexisting a heat and/or photocurable resin (B) or a crosslinking agent, it is preferable that the resin (when using the resin [B], the resin [A] and the resin [ A bridging structure was formed between resin [A] and the mechanical film strength of the photoconductive layer, which was still insufficient with resin [A] alone, was able to be further improved without impairing the function of resin [A]. Therefore, the photoreceptor of the present invention has excellent electrostatic properties even under fluctuating environmental conditions, has sufficient film strength, and can be used under harsh printing conditions (for example, when printing pressure is strong in large printing presses). It is now possible to print 6,000 to 7,000 sheets even in cases such as

A catalyst may be added to promote the above-mentioned crosslinking reaction, or both the heat and/or photocurable resin [B] and the crosslinking side may be used together with the resin [A].

In resin [A], the weight average molecular weight of the grafted gold polymer is 1X10' to 2X10', preferably 3X10'
~I
, when a polar group is bonded to the end of the copolymer main chain, the proportion of the polar group in the copolymer is 0.5 to 15
% by weight, preferably from 1 to 10% by weight. Further, the glass transition point of the resin [A] is preferably -20"0 to 120"
The temperature is preferably between -10°C and 90°C.

Furthermore, if the molecular weight of the resin [A] is smaller than 1X10', the film forming ability will decrease and sufficient film strength cannot be maintained, and if the molecular weight is larger than 2X10', even the resin of the present invention has electrophotographic properties (especially This is not preferable because the initial potential and dark decay retention rate deteriorate. Particularly in the case of such a polymer, if the content of polar groups exceeds 3% by weight, the electrophotographic properties deteriorate significantly, and when used as an offset master, background smudge becomes noticeable.

If the content of polar groups (polar groups in the graft and any polar groups at the end of the main chain) in the binder resin [A] is less than 0.5% by weight, the initial potential will be low and sufficient image density will not be obtained. . On the other hand, if the content of the polar group is more than 15% by weight, the dispersibility will be lowered, the film smoothness and the high-temperature electrophotographic properties will be lowered, and furthermore, background smear will increase when used as an offset master.

The -functional macromonomer (M) provided as a copolymerization component of the graft type copolymer resin [A] of the present invention will be explained in more detail. -Functional macromonomer (M)
- A polymerizable double bond group represented by the formula (1) is combined with at least one of the polymer components represented by the general formulas (IIa) and (IIb) and a specific polar group (-COOH5,
-P(hH, group, -5Q,)I group, -OH group OH, which is bonded only to one end of the polymer main chain, and has a weight average molecule of I2 x 104 or less It is.

In general formulas (1), (■a) and (Il b), a
, , a2, Xo, b+, bz, ×1, rho, and v each have the indicated number of carbon atoms (as an unsubstituted hydrocarbon group); It may have.

In general formula (1), xo is -COO-1-OCO
-1c++, oco-1-CHzOO-, -0-, -3
(h-, -CO-1R11 is a hydrogen atom, and preferable hydrocarbon groups include an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, heptyl group) 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-2-hexenyl group groups), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group,
(2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic group having 5 to 8 carbon atoms Group (
For example, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group) or carbon number 6-1
2 optionally substituted aromatic groups (e.g. phenyl group,
Naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group,
butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc.).

Examples of the substituent which may have a substituent include a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a chloromethyl group, a methoxymethyl group, etc.) ), alkoxy groups (eg, methoxy group, ethoxy group, propioxy group, butoxy group, etc.).

al and a2 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-z , or C00Z via hydrocarbon
+ (Z+ is preferably a hydrogen atom or a carbon number of 1 to 18
represents an alkyl group, alkenyl group, aralkyl group, alicyclic group, or aryl group, which may be substituted, and specifically represents the same content as described for R8 above.

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

More preferably, for general formula (1). is Coo
OCOCHzOCOCHzCOO-I, al
+ at may be the same or different, and each represents a hydrogen atom, a methyl group, -C00Zl or -C)I, C00Z
l iz+ is more preferably a hydrogen atom or a carbon number of 1 to
6 alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.). ).

Even more preferably, either one of al and am represents a hydrogen atom.

That is, specifically, as the polymerizable double bond group represented by the general formula (1), CHzCOOCRl CIl□C00HCHz
=CS Cl1z=C, CHt=CI-CONI+-2
o=c −o −o=c −o − and the like.

In the general formula (Ua) or (Ilb), X is the formula (1
) represents the same content as xo in formula (I), b,, b, may be the same or different from each other;
za represents the same content.

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 (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, an octyl group, a decyl group,
Dodecyl group, tridecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2
-hydroxylethyl group, 2-methoxyethyl group, 2-
Ethoxyethyl group, 2-cyanoethyl group, 3-chloropropyl L2-(trimethoxysilyl)ethyl group, 2-tetrahydrofuryl group, 2-thienylethyl group, 2-N,
N-dimethylamineethyl group, 2-N,N-diethylaminoethyl group, etc.), cycloalkyl group having 5 to 8 carbon atoms (
For example, cycloheptyl group, cyclohexyl group, cyclooctyl group), optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group) group, chlorobenzyl group, bromobenzyl group, dichlorobenzyl group, methylbenzyl group, chloro-methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group,
aliphatic groups such as methoxyhensyl groups, etc., and furthermore, carbon atoms of 6 to
12 optionally substituted aryl groups (e.g., phenyl group, tolyl group, xylyl group, chlorophenyl group, bromophenyl group, dichlorophenyl group, chloro-methyl-phenyl group, methoxyphenyl group, methoxycarbonylphenyl group, naphthyl group, Examples include aromatic groups such as chloronaphthyl group, etc.).

In formula (I[a), preferably xl is -C00OC
Represents 00 CIh0C00 in OClft.

Preferred examples of bl and b2 represent the same contents as a5 and a2 described above.

In the general formula (n b), ■ is -CN, -CONH2
Also, carbon atoms (e.g. chlorine atom, bromine atom, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, propioxy group,
butoxy group, etc.) or -COOZ2 (Z preferably represents an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryl group).

The macromonomer (M) has the formula (lla) and/or (I
It may contain two or more kinds of polymer components represented by Ib). In the case of 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 component in the macromonomer (M).

Furthermore, ζ, xl in the -formula (ffa) is -COO-
In this case, it is preferable that the polymer component represented by formula (I[a) is contained in an amount of at least 30% by weight of all the polymer components in the macromonomer (M).

Furthermore, in the macromonomer (M), formula (Ila)
and/or a polar group (-COOI+) copolymerized as a further component with the copolymer component represented by (IIb)
1□ Any vinyl compound containing the polar group that can be copolymerized with the macromonomer (M) can be used. For example, see "Polymer Data Handbook [Basic Edition]" edited by the Society of Polymer Science and Technology, Baifukan (1
986), etc. Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-7toxymethyl form, α(2-aminomethyl form, α-chloro form, α-bromo form, α- Fluorobody, α
-tributylsilyl form, α-cyano form, β-chloro form,
β-bromo form, α-chloro form, β-medixy form, α, β
-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid semi-esters, itaconic acid semi-amides, crotonic acid, 2-alkenylcarboxylic acids (e.g. 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2- octenoic acid,
4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphoric acid Examples include half-ester derivatives of vinyl or allyl groups of acids, dicarboxylic acids, and alcohols, and compounds containing the polar group in the W substituent of these carboxylic or sulfonic acid ester derivatives and amide derivatives.

Examples of OH include the same hydrocarbon groups as mentioned above for ``in'' in formula (Ila). Examples of the OH group include vinyl group- or allyl group-containing alcohols (for example, allyl alcohol, ester substituents such as methacrylic acid ester, acrylamide, etc., compounds containing 100 groups in the N-substituent, etc.), hydroxyphenol, or Examples include methacrylic acid esters or amides containing a hydroxyphenyl group as a substituent.

For example, the following monomers are shown as examples,
The scope of the present invention is not limited thereto.

Here, on each side below, a is one ■, -CL, Ct
, -Br, -CN, -CLCOOCL or -CIl
, C0OH, b represents one or -Cll, j
represents an integer from 2 to 18, k represents an integer from 2 to 5, and 2
represents an integer of 1 to 4, and m represents an integer of 1 to 12.

(A-1) (A-2) CH, 2C 0OH CH.

CH= CH 0OH (A-5) CI(, -C C0NH(CH, 1COOH (A-6) (A-7) (A-8) (A-9) (A-10) Coo(CHz)- NHCO(CHz)-Cool(A
-17) b (A-18) (A-19) (A-20) (^-21) (A-30) CHz C00 (CHz) -5O3H (^-31) (A-38) (A-39 ) (＾-40) (A-36) CH,=c C0N(Ct(zcIItcOo)l) z(A-37
) (A-41) co, =c COO(CHz)4CON(CHtGHz(:0OH)
t(A-42) (＾-47) (A-43) C11゜(A-48) (A-44) (A-49) (A-46) (A-51) (A-53) b ( A-56) The amount contained as a copolymer component containing a nuclide group in all polymer components in the macromonomer (M) is preferably 0.5 to 50 parts by weight per 1 part of all polymer components 1001ii. , more preferably 1 to 40 parts by weight.

When the monofunctional macromonomer composed of these polar group-containing random copolymers is contained in the resin [A] as a copolymerization component, the polar groups contained in all the graft parts in the resin [A] are The total amount of the components is preferably 0.1 to 10 parts by weight per 10 parts of all polymer components in the resin [A]. More preferably, -COOH group, -SO
3H group and -POJt group.

When containing an acidic group selected from the following, the total amount present in the graft portion in resin [A] 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 vinyl vI4
(For example, 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 consisting of at least a repeating unit represented by the formula (I[a) and/or (I[b)] and a repeating unit containing a specific polar group, as described above. Formula 0, which has a chemical structure in which the polymerizable double bond group represented by formula (1) is bonded directly to only one end of the combined main chain, or is bonded by an arbitrary linking group. (1) Components and formula (I[a)
The linking group that connects the component (II b) or the polar group-containing component is a carbon-carbon bond (-double bond or double bond), a carbon-heteroatom bond (heteroatoms include, for example, an oxygen atom, sulfur atoms, nitrogen atoms, silicon atoms, etc.), heteroatom-heteroatom bond groups.

x More specific linking groups include +C→-l3 (R+!, RI3 is a hydrogen atom, a halogen atom (e.g.
fluorine atom, chlorine atom, bromine atom, etc.), cyano group, hydroxy, alkyl group (e.g. methyl group, ethyl group, propyl group, etc.)], Root -CON-l4 SO□N IICOO R eyes (I[ represents a single linking group or two or more linking groups composed of any combination selected from the atomic groups such as [indicates a hydrocarbon group etc. expressing the same contents as Q+ in a)].

If the weight average molecular weight of the macromonomer (M) exceeds 2X10', the copolymerizability with the monomer [A] will decrease, which is undesirable.On the other hand, if the weight average molecular weight is too small,
Since the effect of improving the electrophotographic properties of the photosensitive layer is reduced, l
It is preferable that it is not less than Xl0''.

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

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

Polym, Sci, Eng,, 551 (1
987), P, F, Rempps E, Franta,
Adu, Polym, Scf, 58.1 (19
84), Yuji Yogami, Chemical Industry, Sara, 56 (1987),
Yuya Yamashita, Polymer, 4.988 (1982), Shibe Kobayashi, Polymer, Dish, Hiroshi Ito-1 Polymer processing, Stripping, 262
(1986), Raiku Shibu, Takashi Tsuda, Functional Materials, 198
7 No., 10.5, etc., and references cited therein.
It can be synthesized according to methods described in patents and the like.

However, since the macromonomer (M) 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.

One method is, for example, as shown in reaction formula (1), using a monomer containing the acidic group in the form of a protected functional group, and carrying out radical polymerization and terminal reactive group formation using the above method. This is to be introduced.

Reaction formula (1) Protecting group for C0OH; for example, -C(C, H mountain,
Polymerizable group introduction reaction deprotection group reaction CH.

The polar groups (-SO3H group, -P(hHz group, H etc.) can be carried out by conventionally known methods.Specifically, J, F.

W. McOmie, “Protective
Gvoups in Organic Chem
istry”, Plenum Press (
1973), 7j1. Greene.

Protective Gvoups in Orga
nic 5ynthesis"John Wiley
& 5ous (1981), Ryohei Oda r Polymer Fine Chemicals” Kodansha (1976), Yoshiyu Iwakura, Keisuke Kurita “Reactive Polymers” Kodansha (1977), G, B
erner et al., J., Radiation C.
urjng, 1986, No. 10, PIO, JP 62-212669, JP 62286064, JP 62-210475, JP 62-1956
No. 84, JP-A-62-258476, JP-A-63-2
No. 60439, patent application No. 1983-220510, patent application No. 1983
It can be synthesized using the method described in No. 2-226692 and the like.

As another method, for example, as shown in reaction formula (■), after synthesizing an oligomer as described above, a "specific reactive group" bonded to one end of the oligomer and a This is a synthesis method that takes advantage of the difference in reactivity with the polar group and reacts it with a reagent containing a polymerizable double bonding group that reacts only with "specific reactivity."

Reaction formula (II) CH.

As shown in reaction formula (U), specific examples of combinations of specific functional groups are shown in Table 8 as follows. However, the present invention is not limited thereto, and the important thing is that macromonomerization can be achieved without protecting the nuclide groups in the oligomer by utilizing the reaction selectivity in ordinary organic chemical reactions. It would be good if it were done.

Examples of chain transfer agents that can be used include mercapto compounds containing the polar group or a substituent that can later be induced into the polar 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)amino)propionic acid, N(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptobutanesulfonic acid, 4-mercaptobutanesulfonic acid , 2-mercaptoethanol, 3-
mercap)-1,2-propanediol, 1-mercapto-2-propanediol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercapto-3, 2-mercapto-3
-pyridinol, etc.) or disulfide compounds which are oxidized products of these mercapto compounds, or alkyl compounds encoding the above polar groups or substituent groups (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-cyanopropanol), 2,2'-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'-azobis(2-(2
-imidapurin-2-yl)propane], 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane], 2,2'-azobis(2[
1-(2-hydroxyethyl)-2-imidacillin-2
-yl]propane), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], and 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 1 OH part of the total monomers.

Specific examples of the macromonomer (M) of the present invention include the following compounds. However, the scope of the present invention is not limited to these. In each case below, b represents -■ or CHI, and d represents -H
1-CH2 or -CHzCOOCHs, R is -C
nLa-+ (n represents an integer from 1 to 1 day), -Br,
-CHx, -COC1+3 or -COOCHs)
, -1 is -CN, -0COCHx, -CONHz
or -Chis, -2 is -CI, -Br, -
CN or -QC)I! , r represents an integer of 2 to I8, S represents an integer of 2 to 12, and t represents an integer of 2 to 4.

(M-1) (G5) (G2) (M-6) H (G3) (G4) (M-8) (G9) (M-10) (M-16) (M-17 ) (M-18) H (M-12) (M-15) (M-19) 00 (CIri) toco (CHz) tcOOHC
H,Ol((M-22)(M-25)(M-23)(M-26) Hon-Coo(CH,OH(M-24) On the other hand, the monomer copolymerized with the above-mentioned macromonomer CM) The mer is represented by the general formula (Ill). In the formula (III), C1 and C2 may be the same or different from each other, and the formula (
1) al and mu represent the same content. X, is the formula (I[
X and 6 in a) each represent the same content as Ql in formula (na).

In the resin of the present invention, the composition ratio of the copolymerization component having the macromer (M) as a repeating unit and the copolymerization component having the monomer represented by formula -a (Ill) as a repeating unit is preferably 1 to 1. The weight composition ratio is 90/99 to 10 (weight composition ratio), more preferably 5 to 60/95 to 40.

In addition, in the polymer main chain, -PO3H oligogroup, -3O3H group,
Those containing no copolymer component containing polar groups such as -Cool group and -PO3R+ group are preferred.

Further, the resin [A] of the present invention preferably contains a functional group that enhances the crosslinking effect between the resin [A] and the crosslinking agent and/or the resin (B), and these functional groups include -OH group, -3H group, -NH, group, NHRI6 group (R1, is an alkyl group having 1 to 8 carbon atoms (e.g. methyl group, ethyl group,
a functional group having at least one dissociable hydrogen atom, such as a propyl group, a butyl group, a hexyl group, etc.) or an aryl group (e.g., a phenyl group, a tolyl group, a methoxyphenyl group, a butylphenyl group, etc.); -CONHGHZOR+y (R1? represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group)), cinnamoyl group, 3,4-disubstituted maleimide ring Groups (for example, 3.4-dimethyl substituted product, 3-methyl-4-ethyl substituted product, 3.4-dichloro substituted product, 3.4-dibromo substituted product, etc.), and the like.

The copolymer component containing these functional groups may be any vinyl compound containing such functional groups that can be copolymerized with the macromonomer (M> and the monomer of formula (III)), For example, see the Polymer Data edited by the Polymer Science Society of Japan.
It is described in "Handbook [Basic Edition]" Baifukan (1986), etc. Specifically, 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, α,-chloro-β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (e.g. 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-
hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acids. Half ester derivatives of vinyl or allyl groups, and ester derivatives of these carboxylic acids or sulfonic acids,
Examples include compounds containing the functional group in a substituent of an amide derivative.

The proportion of copolymer components containing these functional groups is
1 to 40% by weight of resin [A], preferably 5 to 2%
It is 0% by weight.

In addition, the resin [A] of the present invention includes the above-mentioned macromonomer (M), the monomer of formula (Ill), and any monomer containing a functional group that enhances the crosslinking effect, as well as monomers other than these. may be contained as a further copolymerization component.

For example, α-olefins, vinyl alkanoates or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides, nuccrylamides, styrenes, heterocyclic vinyl 1! (e.g. vinylpyrrolidone, vinylpyridine, vinylimidazole,
vinylthiophene, vinylimidacilline, vinylpyrazole, vinyldioxane, vinylquinoline, vinylthiazole, vinyloxazine, etc.).

However, these other monomers other than the macromonomer (M), the monomer of formula (I[l), and any functional group-containing monomer that enhances the crosslinking effect may exceed 20% by weight in the copolymer. Never.

In the graft copolymer of the present invention, the macromonomer (
When the copolymerization component corresponding to M) is 30% by weight or less,
If the amount exceeds 97% by weight, the copolymerization with the monomer of the formula (Ill) will not proceed sufficiently, resulting in the desired graft copolymerization. This is not preferable because a polymer consisting only of the monomer of the general formula (I [ Agglomeration will occur.

Furthermore, the resin [A] contains a -PO3H2 group only at one end of the polymer main chain containing at least one repeating unit represented by formula (II[) and at least L repeating units represented by a macromonomer. , -3o, has a chemical structure bonded via an If group.

Bonding groups include carbon-carbon bonds (-double bonds or double bonds), carbon-hetero atom bonds (hetero atoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), and hetero atoms-hetero atoms. A copolymer consisting of at least one type of acid polar group composed of any combination of atomic groups of atomic bonds (
resin (A')), or a copolymer [A] and (A') may be used together, where the polar group represents the content of 11°R2°, and the polar group directly attached to one end of the main chain, or any linkage (R1, ~R
2゜indicates the same contents as R1t to R+a above respectively)
It is a linking group composed of a single atomic group or a combination of two or more atomic groups selected from the following.

In the resin [A] used in the present invention, in order to synthesize the resin [A'] in which the polar group is bonded to the terminal of the main chain of the polymer, at least the macromonomer (M) described above and the formula ( , 111) by using in combination a polymerization initiator or chain transfer agent containing the polar group or a specific reactive group that can be derived therefrom in the molecule.

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.

The binder resin of the present invention is the resin [A] (resin [A]) as described above.
′] may contain two or more types.

The resin (B) is a heat and/or photocurable resin containing a crosslinkable functional group, that is, a functional group that generates a crosslinking reaction by at least one of heat and light to form a bridge between polymers. Preferably, it reacts with the functional group that may be contained in the resin [A] to form a crosslinked structure.

That is, it utilizes a reaction mode in which bonding between molecules by condensation reaction, addition reaction, etc., or crosslinking by polymerization reaction is caused by heat and/or light.

Specifically, the thermosetting functional group includes a functional group having a dissociable hydrogen atom (for example, -OF+ group, -5R group, NHR
z+ group (Rz+ represents a hydrogen atom, an optionally substituted aliphatic group having 1 to 12 carbon atoms, or an optionally substituted aryl group)), NC3, and a cyclic dicarboxylic acid anhydride. -CONHCHzORzt (Rzz represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, hexyl group) or polymerizable Examples include double bond groups.

Preferable examples of the functional group having a dissociable hydrogen atom include 10H group, -5H group, and -NHR*+ group.

Specifically, the polymerizable double bond group is CH! =
CH-1CHz -CHCHz-OCHs CH,=CH-C-0-1CH,=C-C-0-CHt
O CH=CH-C-0-1CH,=CH-C0NHOCR
, O II I IICH, =CH-
0-C-1CH,=C-0-C-CHz = CH-C
H! OC-1CH,=CH-NHCO-1CH! =
CH-C)! , -NHCO-CHz -CHSO-
1CH, -CH-3O-CH, -CH-0-1CH, -
CH-3- etc. can be mentioned.

Examples of photocurable functional groups include Takahiro Tsunoda, "Photosensitive Resin", Printing Society Publishing Department (1972), Motobe Nagamatsu, Hideo Inui, "Photosensitive Polymer", Kodansha (1977) G, A
, Delgenne, “Encyclopedia o
f PoyerserScience and T
technology, 5upple*ant,”
Vol 1 (1976) etc. can be used. Specific examples thereof include addition polymer groups such as allyl ester groups and vinyl ester groups, cinnamoyl groups, and dimerization groups such as optionally substituted maleimide ring groups.

Examples of the resin (B) of the present invention include polymers or copolymers containing the above functional groups.

Specifically, Tsuyoshi Endo's "Refinement of Thermosetting Polymers" (C,
M, C■, 1986), Yuji Harasaki, "Latest Binder Technology Handbook", Chapter 11-1 (General Technology Center, 19
(published in 1985), Takayuki Otsu, “Synthesis, design and development of new uses for acrylic resins” (Chubu Business Development Center Publishing Department, published in 1985), Eizo Omori, “Functional acrylic resins” (Technosystem, published in 1985), etc. For example, polyester resin, unmodified epoxy resin, polycarbonate resin, vinyl alkanoate resin, modified polyamide resin, phenol resin, modified alkyd resin, melamine resin, acrylic resin, styrene resin, etc. It is sufficient that these resins contain the above-mentioned functional group for forming a crosslinking reaction.Preferably, these resins do not contain the polar group represented by resin [A] or are modified. can be used as the resin of the present invention.

Specific examples of monomers corresponding to the coelectric component containing these functional groups include vinyl compounds containing these functional groups.

For example, see the Polymer Data Handbook [Polymer Data Handbook]
Basic Edition] Baifukan (published in 1986), etc.

Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2-aminomethyl form, α-chloro form, α-bromo form, α- Fluoro form, α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α-chloro-β
-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (
For example, 2-pentenoic acid, 2-methyl-2-hexenoic acid,
2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, In the substituents of vinyl sulfonic acid, vinylphosphonic acid, half-ester derivatives of vinyl or allyl groups of dicarboxylic acids, and the ester derivatives and amide derivatives of these carboxylic acids or sulfonic acids, or in the substituents of styrene derivatives, the above-mentioned Examples include vinyl compounds containing functional groups.

More specifically, a (meth)acrylic copolymer containing a total amount of 30% by weight or more of a monomer represented by the following general formula (IV) as a copolymerization component is cited as an example of resin [B]. be able to.

General formula (■) T CH, -C Coo R*s In the general formula (rV), T represents a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom), a cyano group, or an alkyl group having 1 to 4 carbon atoms. represent.

Ro is an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group,
dodecyl group, tridecyl group, tetradecyl group, 2-methoxyethyl group, 2-ethoxyethyl group, etc.), carbon number 2~
18 optionally substituted alkenyl groups (e.g. vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.), carbon number 7
~12 optionally substituted aralkyl groups (e.g. benzyl group, phenethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), optionally substituted cycloalkyl groups having 5 to 8 carbon atoms (e.g. cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.)
, aryl group (eg, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group, chlorophenyl group, dichlorophenyl group, etc.).

In the resin (B), the "copolymer component containing a crosslinkable (crosslinkable) functional group" is preferably 0.5 to 40 mol%.

The weight average molecular weight of the resin (B) is preferably 1 x 101 ~
lXl0', more preferably 5X103 to 5X1
0'.

The ratio of resin [A] and resin [B] used in the present invention varies depending on the type, particle size, and surface condition of the inorganic photoconductive material used, but in general, the ratio of resin [A] and resin [B] used is is 5 to 80 to 95 to 20 (weight ratio), preferably 10 to 50 to 90 to 50 (weight ratio).

On the other hand, as the crosslinking agent used in the present invention, 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 (19'81), "Polymer Data Handbook Basic Edition" published by the Society of Polymer Science, Baifukan (1986), etc. can be used.

For example, silane coupling agents such as organic silane compounds (e.g., vinyltrimethoxysilane, vinyltributoxysilane, T-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, T-aminopropyltriethoxysilane) etc.), polyisocyanate compounds (e.g. Eva, toluylene diisocyanate, 0-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, isophorone) diisocyanate, polymeric polyisocyanate, etc.), polyol compounds (e.g., 14-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol,
1.1゜1-trimethylolpropane, etc.), polyamine compounds (e.g., ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-amine ethylpiperazine,
modified aliphatic polyamines, etc.), polyepoxy group-containing compounds, and epoxy resins (for example, "New Epoxy Resins" edited by Hiroshi Kakiuchi, published by Shokodo (1985), "Epoxy Resins" edited by Kuniyuki Hashimoto, published by Nikkan Kogyo Shimbunsha (published in 1969) etc.), melamine resins (e.g., "Uria Melamine Resin" edited by Kazuhiro Miwa and Hideo Matsunaga, Nikkan Kogyo Shimbunsha (1)
969), etc.) poly(meth)
Acrylate compounds (e.g. Shin Okawara, Takeo Saegusa,
Toshinobu Higashimura (ed.) “Oligomer” Kodansha (1976) Eizo Omori “Functional Acrylic Resin” Technosystem (198)
Specific examples include polyethylene glycol diacrylate, neopentyl glycol cyacrylate, 1,6-hexanediol acrylate, trimethylolpropane triacrylate, and pentaerythritol polyacrylate. acrylate, bisphenol A-diglycidyl ether diacrylate,
Oligoester acrylates: These include methacrylates. ) etc.

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 the 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, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.).

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

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

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

The binder resin of the present invention is crosslinked or thermally cured after applying the photosensitive layer forming material. To perform crosslinking or thermosetting,
For example, the drying conditions are made stricter than those used in conventional photoreceptor production. For example, the drying conditions are high temperature and/or long time. Alternatively, after drying the coating solvent, it is preferable to further heat treat 1, for example at 60'C to 120°C for 5 to
Process for 120 minutes. When used together with the reaction accelerators mentioned above,
Can be processed under milder conditions.

Further, crosslinking should be carried out at least between the resins of the present invention, but it may also be carried out between the resins of the present invention and other resins. Preferably.

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

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

In the present invention, various dyes can be used in combination as spectral sensitizers if necessary.
Young et al., RCA Review L2. ,． 4
69 (1954), Wataru Kiyota, Journal of the Institute of Electrical Communication J63-C (8112), 97 (1980), Yuji Harasaki et al., Industrial Chemistry Journal ■, 78 and 188 (1963),
Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthine dyes, phthalein dyes, polymethine dyes (e.g. oxonol,
merocyanine pigment, cyanine pigment, logocyanine pigment,
Styryl dyes), phthalocyanine dyes (which may contain metals), and the like.

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

oxonol dye, merocyanine dye, cyanine dye,
Polymethine dyes such as logcyanine dyes include F, M
, Ha+u+er, rThe Cyanine
Dyes and Related Compound
ds" etc. can be used, and more specifically, pigments described in U.S. Pat. No. 3,047,384 and U.S. Pat. No. 311 can be used.
No. 0591, US Pat. No. 3,121,008, US Pat. No. 3,125,447, US Pat. No. 3,128,179, US Pat. No. 3,132,942, US Pat.
No. 74, British Patent No. 1405898, Special Publication No. 4B-7
Examples include dyes described in Japanese Patent Publication No. 814 and Japanese Patent Publication No. 55-18892.

Furthermore, as a polymethine dye that spectrally sensitizes in the near-infrared to infrared light region with a long wavelength of 100 nm or more, JP-A-47-84
No. 0, JP-A No. 47-44180, JP-A No. 51-410
No. 61, JP-A-49-5034, JP-A-49-451
No. 22, JP-A-5746245, JP-A-56-351
No. 41, JP-A-57-157254, JP-A-61-2
No. 6044, JP-A No. 61-27551, U.S. Patent No. 3
619154, U.S. Patent No. 4175956, rRe
search I)isclosure J 1982
216, pages 117 to 11B.

The photoreceptor of the present invention is also 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.
) Electron-accepting compounds (e.g., halogens, benzoquinone, cranyl, acid anhydrides, organic carboxylic acids, etc.) in the review cited on page 12, Hiroshi Komon et al., "Recent Development and Practical Application of Photoconductive Materials and Photoreceptors" ” Chapters 4 to 6: Polyarylalkane compounds, hindered phenol (1,1, p-phenylenediamine compounds, etc.) cited in the review published by Nihon Kagaku Information Co., Ltd. Publishing Department (1986).

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

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 preferably 0.01 to 1μ, particularly 0.05 to 0.5μ. suitable.

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 resin. Thermoplastic resins and curable resins such as acrylic resins, polyolefin resins, urethane resins, epoxy resins, melamine resins, and silicone resins are used as appropriate.

The photoconductive layer according to the invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably electrically conductive.As the electrically conductive support, for example, a substrate such as metal, paper, plastic sheet, etc. with low resistance can be used. The back side of the substrate (the side opposite to the side on which the photosensitive layer is provided) is coated with a small amount (one or more layers) for the purpose of preventing curling, etc. A water-resistant adhesive layer is provided on the surface of the support, at least one pre-coat layer is provided as necessary on the surface layer of the support, and a conductive plastic base is vapor-deposited with A1, etc. You can also use paper laminated with paper.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, Electrophotography, 14, (Nal), pp. 2-11 (1975), Hiroyuki Moriga, "Introductory Chemistry of Special Papers", Kobunshi Publishing (1975), M, F.

Hoover+J, Macro+wo1. Sci
, Chem, A-4(6) + No. 1327-14
17 (1970) etc. is used.

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

Macromonomer Production Example 1: MM-1 A mixed solution of 90 g of ethyl methacrylate, 2-hydroxyethyl methacrylate Log, 5 g of thioglycolic acid, and 200 g of toluene was heated to a temperature of 75° C. while stirring under a nitrogen stream. 2. Add 1.0 g of 2'-azobisisobutyronitrile (abbreviation A, 1.B, N,),
It reacted for 8 hours. Next, 8 g of glycidyl methacrylate and 1.0 g of N,N-dimethyldodecylamine were added to this reaction solution.
g and 0.5 g of t-butylhydroquinone were added, and the mixture was stirred at a temperature of 100° C. for 12 hours. After cooling, this reaction solution was reprecipitated into n-hexane 22 to obtain 82 g of white powder.

The weight average molecular weight of the polymer was 3.8XIO'.

(MM-1) Macromonomer production example 2: MM-2 Butyl methacrylate) 90g, methacrylic acid 10g12
- 4 g of mercaptoethanol and 2 g of tetrahydrofuran
00 g of the mixed solution was heated to a temperature of 70°C under a nitrogen stream. A.1. 1.2 g of B and N were added and reacted for 8 hours.

Next, this reaction solution was 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 with stirring at a temperature of 25°C or less. After the dropwise addition, the mixture was further stirred for 1 hour.

Thereafter, 0.5 g of L-butylhydroquinone was added, heated to a temperature of 60"C, and stirred for 4 hours. After cooling, it was added dropwise to water with stirring for about 10 minutes), then stirred for 1 hour and left to stand. After that, the water was removed by decantation. After washing with water twice more, 1 ml of tetrahydrofuran was added.
00 and reprecipitated in petroleum ether 22. The precipitate was collected by decantation and dried under reduced pressure. The yield of the viscous material obtained was 65g, and the weight average molecular weight was 5.6X.
It was 103.

(MM-2) Production example 3 of Hff Macro-Natsumer: MM-3 95 g of benzyl methacrylate, 5 g of 2-phosphonoethyl methacrylate, 4 g of 2-aminoethyl mercaptan
A mixture of 200 g of tetrahydrofuran and 200 g of tetrahydrofuran was heated to 70° C. with stirring under a nitrogen stream.

A.1. B, N, 1.5g were added and reacted for 4 hours, and A, 1. 0.5 g of B and N were added and reacted for 4 hours. Next, this reaction solution was cooled to a temperature of 20°C, log 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 t-butylhydroquinone and bring the temperature to 50.
Stir at ~60°C for 4 hours. After cooling, the reaction mixture was added dropwise to water 11 while stirring over about 10 minutes, stirred as it was for 1 hour, and left to stand, and the water was removed by decantation. After repeating the washing with water two more times, it was dissolved in 100 d of tetrahydrofuran and reprecipitated in 21 d of petroleum ether. The precipitate was collected by decantation and dried under reduced pressure.

The yield of the viscous material obtained was 70g, and the weight average molecular weight was 7.4.
It was XIO'.

(MM-3) Manufacture example 4 of macro-natsummer: MM-4 90 g of 2-chlorophenyl methacrylate, the following structure (
A mixed solution of 10 g of the monomer of 1), 4 g of thioglycolic acid, and 200 g of toluene was heated to a temperature of 70° C. under a nitrogen stream. A.1. 1.5 g of B and N were added and reacted for 5 hours, and then A, 1. B, N, 12.4 g of 6th glycidyl methacrylate, which was reacted for 4 hours by adding 0.5 g of N.
, 1.0 g of N-dimethyldodecylamine, and 1.5 g of t-butylhydroquinone were added, and the reaction was carried out at a temperature of 110"C for 8 hours. After cooling, the reaction mixture was mixed with 3 g of P-) toluenesulfonic acid, 90 vol.
d to the solution and stirred for 1 hour at a temperature of 30 to 35°C. 2N mixed solution of water/ethanol ((1/3) volume ratio)
The above mixture was reprecipitated in the container, and the precipitate was collected by decantation. This precipitate was dissolved in 200 parts of tetrahydrofuran and diluted with n-hexane. , re-sedimented into powder 58g
The zero weight average molecular weight obtained was 7.6 x 10'.

Monomer (1) Hs C■.

(MM-4) Manufacture example 5 of macro-natsummer: MM-5 95 g of 2,6-cyclophenyl methacrylate, 3-
A mixed solution of 5 g of (2'-nitrobenzyloxysulfonyl)propyl methacrylate, 150 g of toluene, and 50 g of isopropyl alcohol was heated under a nitrogen stream at a temperature of 8.
Warmed to 0°C. 2. Add 5.0 g of 2'-azobis(2-cyanovaleric acid) (abbreviation: ^, C, V,) and react for 5 hours, then add 1.0 g of A, C, ν,
Time reacted. 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. 80W after cooling to room temperature
The mixture was irradiated with light for 1 hour under stirring using a high-pressure mercury lamp. The reaction mixture was then reprecipitated into methanol 12,
The powder was filter dried under reduced pressure. The yield was 34 g and the weight average molecular weight was 17.3XI03.

(MM-5) The molecular weight was 8y6X10'.

(A-1) *Coo(Cut)isOJ Production example 1 of resin [A]: A-1 Benzyl methacrylate 65g 1 Methyl acrylate) 1
5g, compound of macromonomer synthesis example 2 (MM-2)
A mixed solution of 20 g and 100 g of toluene was heated to a temperature of 100° C. under a nitrogen stream. A.1. ,B,N,,
6g was added and reacted for 4 hours, and then A, 1. B.N.
3 g was added and reacted for 3 hours. Weight average of the obtained copolymer Resin [A] Production example IA = 2 2-chlorophenyl methacrylate 70 g 1 Macromonomer synthesis example 1 compound (MM-1) 30 g, β-
Mercaptopropionic acid 3.0g and toluene 150g
The mixed solution was heated to a temperature of 80°C under a nitrogen stream. A
, 1. B.N.

Add 1.0g and react for 4 hours, then add A, 1B, N, 0.
Add 5g and wait for 2 hours, then add A, 1. 0.3 g of B and N were added and reacted for 3 hours.

The weight average molecular weight of the obtained copolymer was 8.5×103.

(A-2) (A-3) Production example IA-3 of resin [A] 60 g of 2-chloro-6-methylphenyl methacrylate
, Compound of macromonomer synthesis example 4: MM-425
A mixed solution of 15 g of 61 methyl acrylate, 100 g of toluene, and 50 g of isopropyl alcohol was heated to a temperature of 80° C. under a nitrogen stream. 5 g of A, C, V, etc. were added and reacted for 5 hours, and then 1 g of A, C, V, etc. was added and reacted for 4 hours. The weight average molecular weight of the obtained copolymer was 8.
It was 5×10”.

Production Examples 4 to 13 of Resin [A]: A-4 to A-13 Each resin [A] shown in Table 1 below was produced in the same manner as Production Example 1 (A-1) of Resin [A]. did. The weight average molecular weight of each resin [A] is 6. The range was from OXIO'' to 9XLO'.

Production examples 14 to 27 of resin [A]: A-14 to A-2
7 Production Example 2 of Resin [A] Each resin [A] shown in Table 2 below was produced in the same manner as in (A-2). The weight average molecular weight of each type [A] was in the range of 5X10' to 9X10'.

Production examples 28 to 33 of resin [A]: A-28 to A-3
3 Each resin having the structure shown in Table 3 below was manufactured by the same method as above.

Each resin 6 was 6X103 to 9X103.

Example 1 Resin (A-20) 3 produced in Production Example 20 of Resin [A]
8 g (as solid content), 200 g of zinc oxide, 0.02 heptamethine cyanine dye (1) represented by the following structural formula
After dispersing a mixture of g, 0.30 g of phthalic anhydride, and 300 B of toluene in a ball mill for 3 hours, 2 g of 1,3-xylylene diisocyanate was added, and the mixture was further dispersed in a ball mill for 10 minutes.

This was applied to electrically conductive treated paper using a wire bar so that the dry adhesion amount was 22 g/bore, heated at 100°C for 15 seconds, then heated at 120°C for 2 hours. An electrophotographic light-sensitive material was prepared by leaving it for 24 hours under conditions of C165%RH.

cyanine dye (1)), zinc oxide 200g, cyanine dye (1) 0.
02 g, phthalic anhydride 0.30 g and toluene 30
0 g of the mixture was dispersed in a ball mill for 2 hours.

This was applied to electrically conductive treated paper using a wire bar so that the dry adhesion amount was 22 g/po, and heated at 100°C for 15 seconds. Then, in the dark (20'C, 65% I?)
) An electrophotographic light-sensitive material was produced by leaving it for 4 hours under the following conditions.

Comparative Example B In Example 1, instead of 38 g of resin (A-20), resin (R-1) having the following structure (weight average molecular weight 7.5
An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that 38 g of X103) was used.

Resin (R-1) Comparative Example A 40 g of the resin (A-20) used in Example 1 (solid content Comparative Example C In Comparative Example A, instead of 40 g of the copolymer (a-20), the following structure was used. An electrophotographic light-sensitive material was prepared in the same manner as in Comparative Example A except that 40 g of copolymer (R-2) was used.

Resin (R-2) Table 4 Weight average molecular weight: 34,000 When the film properties (surface smoothness), electrostatic properties, imaging properties, and environmental conditions of these photosensitive materials are set to 30'C80%11)1 We investigated the imaging performance of Furthermore, when these photosensitive materials are used as original plates for offset masters, the photoconductive properties (represented by the contact angle with water of the photoconductive layer after non-fat processing) and printability (background stains, The printing durability, etc.) were investigated.

The above results are summarized in Table 4.

The implementation aspects of the evaluation items shown in Table 4 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 under the condition of an air volume of 1 cc.

Note 2) Mechanical strength of the photoconductive layer: The surface of the obtained photosensitive material was measured using Hayton-14 type surface test material (manufactured by Shinrai Kagaku ■) with a load of 50 g/c + Il and emery paper (JIlooO) with a strength of 1000. Remaining film rate (χ) from the weight reduction of the photosensitive layer by repeatedly searching and removing abrasion powder
The mechanical strength was determined by determining the 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 at -6 kV for 20 seconds using a paper analyzer (Paper Analyzer 5P-428 model manufactured by Kawaguchi Electric). After that, leave it for 10 seconds, and at this time the surface potential v
1° was measured at 0, then the potential v1° after being left undisturbed for 90 seconds in the dark. The retention of potential after 90 seconds of dark decay, that is, the dark decay retention rate (D).

R, R(χ) (V+oo/V+o) X100(X)
I asked for it. In addition, the surface of the photoconductive layer is heated by corona discharge.
Shun charged to 00V, the surface of the photoconductive layer was heated with a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780n).
) irradiation with light, find the time until the surface potential (vl.) attenuates to 1710, and from this, the exposure I E + y +
. (erg/c4) is calculated. .

The environmental conditions during the measurement were 20°C, 65% RH ([) and 30°C, 180% R) I (II).

Note 4) Imaging performance: After leaving each photosensitive material for one day and night under the following environmental conditions, each photosensitive material was charged at -6KV and used as a light source with a 2.8d output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780nm) on the surface of the photosensitive material.
After exposure at a pitch of 25 and a scanning speed of 30 (1 m/sec) under an irradiation dose of rg/c4, the image was developed and fixed using ELF-T (manufactured by Fuji Photo Film) as a liquid developer. The obtained copied images (fogging, image quality) were visually evaluated.The environmental conditions at the time of image capture were as follows:
20”C65%RH (1) and 30°C80%RH (■)
It was carried out in

Note 5) Contact angle with water: After each photosensitive material was passed once through an etching process sensor using a desensitizing liquid aLp-E (manufactured by Fuji Photo Film) to make the surface of the photoconductive layer desensitized. , add distilled water 2 to this
A μl water droplet is placed on the plate, and the contact angle with the water formed is measured using a goniometer.

Note 6) Rigidity Resistance After making the plate in the same manner as for imaging performance in Note 3) above, it was treated to make it fatless under the same conditions as Note 4) above, and this was used as an offset master for offset printing I! (Oliver Model 52, manufactured by Sakurai Seisakusho ■), and indicates the number of sheets that can be printed using high-quality paper as printing paper without causing problems with background stains in the non-image areas of the printed matter and image quality in the image areas (the higher the number of sheets printed, the more (indicates good rigidity resistance).

As shown in Table 4, the photosensitive material of the present invention had good strength and electrostatic properties of the smooth film of the photoconductive layer, and the actual copied images had no blurring (the quality of the copied images was also clear). This is presumed to be because the photoconductor and the binder resin are sufficiently adsorbed and coat the particle surface.For the same reason, even when used as an offset master original, desensitization treatment is required. It can be seen that the desensitization treatment with the liquid has progressed sufficiently, and the contact angle with water in the non-image area is as small as 10 degrees or less, indicating that it has become sufficiently hydrophilic.In fact, Comparative Example A deteriorates after 1000 sheets. Even if printing under the printing conditions, in the case of the present invention, 7000
Even after printing a sheet, no background staining was observed when observing the background smearing of the printed matter.

Comparative Example A, which used only the resin [A] of the present invention without using a crosslinking agent, had extremely good electrostatic properties, but when printed using it as an offset master original, the image quality of the printed matter deteriorated after 1000 sheets. Deteriorated.

In addition, Comparative Example B, which used a resin having carboxyl groups directly in the straight chain without having a graft portion, adhered for 90 seconds and had l? ,R
, decreased, and El/+6 also increased.

Furthermore, in Comparative Example C, in which the weight average molecular weight was increased with a copolymer having a chemical structure having a carboxyl group directly in a linear chain, similar to the resin of Comparative Example B, without using a crosslinking agent, the electrostatic properties has deteriorated significantly.

This is presumed to be due to an increase in the molecular weight of the binder resin, which causes adsorption to the photoconductor particles and aggregation between the particles, resulting in an adverse effect.

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

Example 2 8 g of the above resin (A-29), the following resin (B-1)
32g, zinc oxide 200g, cyanine dye (1) used in Example 1 0.02g, phthalic anhydride 0.40g
A mixture of 300 g of toluene and 300 g of toluene was dispersed in a ball mill for 3 hours.

This was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 20 g/I, heated at 100"C for 15 seconds, and then heated at 120"C for 1 hour.
An electrophotographic light-sensitive material was prepared by leaving it for 24 hours under C565%RH conditions.

Resin (B-1) CH, CHff Each characteristic was measured in the same manner as in Example 1, and the following results were obtained.

Smoothness of photoconductive layer: 135 (cc/5ec) Strength of photoconductive layer: 90% Electrostatic properties V+o(V) [1,I? , R(χ
) E+y+. Cerg/cd)■ (20℃, 65χ
R)I)-5658628■(30°C280χR1(
)-5508032 Side view: (20°C965χRH
) and (30°C, 80χRH), good copied images were obtained.

Printing durability: Good printed images were obtained up to 6000 sheets.

As described above, the photosensitive material of the present invention was able to obtain excellent electrophotographic properties and high printing durability.

Examples 3 to 10 6.5 g of resin [A] in Table 5 below, 533.5 g of resin CB in Table 5 below, 200 g of zinc oxide, 0.018 g of cyanine dye (U) below, 0.30 g of maleic anhydride
g and 300 g of toluene were dispersed in a ball mill for 3 hours.

A predetermined amount of the crosslinking agent shown in Table 5 below was added to this, and the mixture was further dispersed in a ball mill for 10 minutes. This was applied to conductive-treated paper with a wire bar to a dry adhesion of 20 g/rrr, heated at 100°C for 15 seconds, and then further heated at 120°C for 2 hours. An electrophotographic light-sensitive material was prepared by leaving it for 24 hours under conditions of %RH.

Cyanine Dye (II) Dye [B] The electrostatic properties of these photosensitive materials were measured using a paper analyzer in the same manner as in Example 1.

Each of the photosensitive materials of the present invention has chargeability, dark charge retention,
It has excellent light sensitivity, and the actual copied images can be produced even under high temperature and high humidity (30°C1).
Even under the harsh conditions of 80%R)I), a clear image was obtained without any occurrence of ground force blur or thin line skipping.

When each photosensitive material is used as an offset master original plate, the desensitization treatment with the desensitization treatment liquid progresses sufficiently, and the contact angle with water in the non-image area of each master original plate is as small as 15 degrees or less, which is sufficient. It had become hydrophilic. 60 prints with clear images without blurring when actually printed.
I was able to print between 00 and 7000 sheets.

Examples 11 to 16 7 g of resin (A) shown in Table 6 below, resin (B) shown in Table 6 below
(7) Group X resin 20g, zinc oxide 200g, rose bengal 0.50g, bromophenol blue 0.2
A mixture of 5 g of uranine, 0.30 g of uranine, 0.30 g of phthalic anhydride, and 240 g of toluene was dispersed in a ball mill for 3 hours.

Next, resin 13 of group Y of resin (B) in Table 6 below is added to this.
Add a solution of 10 g dissolved in 80 g of toluene, and add 10 g of
Dispersed in a ball mill for minutes. This was applied to conductive treated paper with a wire bar so that the dry adhesion amount was 18g/rrf, heated at 110'C for 30 seconds, and then further heated at 120°C for 2 hours. IIH
An electrophotographic window light material was produced by leaving it for 24 hours under the following conditions.

The photosensitive material of the present invention has chargeability, dark charge retention,
It has excellent photosensitivity, and the actual copied images can be used even at high temperatures (30°).
Even under the harsh conditions of (C-80% RH), clear images were produced with no soil blurring.

Furthermore, using this as the original version of the offset master,
Even when printing 6,000 to 7,000 sheets, the printed matter had clear image quality.

However, the plate making of photosensitive materials is done using a fully automatic plate making machine ELP404V.
(manufactured by Fuji Photo Film ■) using ELP-T as a toner to form a toner image.

Examples 17-18 8 g each of resins (A-32) and (A-33) shown in Table 7 below, 32 g each of resin (B) shown in Table 7 below, 20 g of zinc oxide
0g, uranine 0.02g, rose bengal 0.0
By leaving a mixture of 4 g, 0.03 g of bromophenol blue, 0.20 g of phthalic anhydride and 300 g of toluene in a ball mill at 2 hours in the dark under the conditions of 20"C and 65% RH for 24 hours. Each electrophotographic photoreceptor was produced. The characteristics of the obtained photoreceptor are shown in Table 7.

Table 7 A photosensitive material was prepared by dispersing the material, and it was coated on a paper treated with a wire using a wire bar so that the dry adhesion amount was 20 g/I, and dried at 110 DEG C. for 1 minute.

Next, after exposing the entire surface to a high-pressure mercury lamp for 3 minutes, each photosensitive material was exposed to a paper analyzer (Paper Analyzer 5P-428 model manufactured by Kawaguchi Electric) in a dark room at a temperature of 20°C and 165% RH. After corona discharge for 20 seconds at 6kV using
゜ was measured at 0, and then the potential V after being left undisturbed for 60 seconds in the dark. The retention of the potential after dark decaying for 60 seconds, that is, the dark decay retention rate (DRR (2)), is
(V)・/L. ) x 100 (χ). or,
After the surface of the photoconductive layer is charged to -400V by corona discharge, the surface of the photoconductive layer is irradiated with visible light at an illuminance of 2.0 lux, and the time required for the surface potential (vie) to attenuate to 1710V is determined. From now on, the exposure amount E171° (looks
seconds).

Regarding electrostatic properties, Ueki's photosensitive material under conditions of (30°C, 280% RH) has excellent chargeability, dark charge retention, and photosensitivity.
Even in the harsh conditions of high temperature (30° C., 180% RH), the actual copied images produced clear images without any occurrence of ground force blur or skipped fine lines.

Furthermore, when printed as an offset master master plate, the prints have a clear image with no blurring in the non-image area.
I was able to print ~6500 sheets.

(Effects of the Invention) According to the present invention, an electrophotographic photoreceptor having excellent electrostatic properties and mechanical strength can be obtained.

Claims (2)

[Claims] (1) In an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material and a binder resin, the binder resin includes at least one resin [A] shown below;
Heat and/or photocurable resin containing a crosslinkable functional group [B
] and at least one crosslinking agent. Resin [A]; at least one of the polymer components represented by the following general formulas (IIa) and (IIb), -COOH group, -PO_3
There are H_2 groups, -SO_3H groups, -OH groups, and ▲mathematical formulas, chemical formulas, tables, etc.▼(R_1 is a hydrocarbon group or -OR
Only at one end of the polymer main chain containing at least one kind of polymer component containing at least one polar group selected from the group _2 (R_2 represents a hydrocarbon group), the following general A monofunctional macromonomer (M) having a weight average molecular weight of 2 x 10^4 or less formed by bonding a polymerizable double bond group represented by the formula (I) and the following general formula (III
) A copolymer having a weight average molecular weight of 1.0 x 10^3 to 2.0 x 10^4 and consisting of at least the monomers represented by: General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (I), X_o is -COO-, -OCO-, -C
H_2OCO-, -CH_2COO-, -O-, -SO
＿２-CO-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ mathematical formulas, chemical formulas,
There are tables, etc., which represent ▼ (here, R_1_1 represents a hydrogen atom or a hydrocarbon group). a_1 and a_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_1 via hydrocarbon
(Z_1 represents a hydrogen atom or a hydrocarbon group that may be substituted). General formula (IIa) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIb) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ In formula (IIa) or (IIb), X_1 is X in formula (I)
Represents the same content as _0. Q_1 is carbon number 1-18
represents an aliphatic group or an aromatic group having 6 to 12 carbon atoms. b_1 and b_2 may be the same or different from each other,
Represents the same content as a_1 and a_2 in formula (I). V represents -CN, -CONH_2 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and Y is a hydrogen atom, a halogen atom,
It represents an alkoxy group or -COOZ_2 (Z_2 represents an alkyl group, an aralkyl group, or an aryl group). General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (III), X_2 represents the same content as X_0 in formula (I), and Q_2 represents the same content as Q_1 in formula (IIa). represents the content. c_1 and c_2 may be the same or different, and represent the same contents as a_1 and a_2 in formula (I). (2) The resin [A] further includes -PO_3H_2 groups, -S
There are O_3H groups, -COOH groups, OH groups, and ▲mathematical formulas, chemical formulas, tables, etc.▼(R_3 is a hydrocarbon group or -OR_
4 (R_4 represents a hydrocarbon group)} group is bonded to the end of the main chain of the graft copolymer.
) The electrophotographic photoreceptor described above.