JPH0444047A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain the electrophotographic sensitive body having an excellent electrostatic characteristic, moisture resistance and durability by incorporating at least one kind of resins [A] and at least one of any of thermo- and/or photosetting resins [B] and crosslinking agent into a binder resin. CONSTITUTION:At least one kind of the resins [A] and at least one of any of the thermo- and/or photosetting resins [B] and the crosslinking agent are incorporated into the binder resin. The resins [A] contain at least one kind of monofunctional macromonomers (M) as a copolymer component in the terminal of the main chain of the B block polymer of the A B block copolymer constituted of the A block contg. at least one kind of a -PO3H2 group, -COOH group, etc., and the polymer components and the B block expressed by formula I. In the formula I, a1 and a2 respectively denote a hydrogen atom, halogen atom, etc.; V1 denote -COO-, -OCO-, etc.; R1 denotes a hydrocarbon group. The electrophotographic sensitive material having the excellent electrostatic characteristic and the sharp and good quality images is obtd. 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. A photoreceptor composed of a support and at least one photoconductive layer is most preferably -Il
It is used for image formation by electrophotographic process such as charging, image exposure and development, and further, if necessary, transfer.

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

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, and also has excellent film-forming properties and excellent dispersion ability of the photoconductive powder into the binder resin. The photoconductive layer of the recording layer has good adhesion to the substrate, and the photoconductive layer of the recording layer has excellent charging ability, has low dark decay, large light decay, and low pre-exposure fatigue, and is easily resistant to changes in humidity during imaging. 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 resins have many problems, particularly in chargeability, dark charge retention, electrostatic properties of photosensitivity, smoothness of photoconductive layer, etc., and are 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 (interval 10" to 1
04) or a low molecular weight resin (intervals 103 to 104) in which an acidic group is bonded only to one end of the polymer main chain, the smoothness and electrostatic properties of the photoconductive layer are improved; Moreover, it was possible to obtain flawless image quality.
3-217354, JP-A No. 6470761, and JP-A No. 2-67563, respectively.

Also, as a binder resin, a resin containing an acidic group in the side chain of the copolymer or a polymeric component bonded to the end of the main chain of the polymer and containing a heat- and/or photo-curable 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 fIi in which a resin containing an acidic group in the side chain of the copolymer or bonded to the end of the main chain of the polymer is used in combination with a crosslinking agent. JP-A-102573 and No. 2-874, respectively, and a technique of using the low molecular weight resin (weight average molecular weight 103 to 104) in combination with a high molecular weight resin (weight average molecular weight 104 or more) was disclosed in JP-A-64.
-564, 63-220149, 63-220
No. 148, JP-A No. 1-280761, JP-A No. 1-1166
43 and 1-169455, and JP-A-1-211766 and JP-A-2-34859 disclose a technique for using such a low molecular weight material in combination with a heat and/or photocurable resin. Techniques using ζ in combination with polymers are disclosed in JP-A-2-53064, JP-A-2-56558, and JP-A-63-254,786, respectively. It is stated that by these techniques, the film strength of the photoconductive layer can be made sufficient and the mechanical strength can be increased without impeding the above-mentioned properties due to the use of a resin containing an acidic group at the side chain or terminal end. has been done.

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

The present invention is intended to improve the following problems with conventional electrophotographic photoreceptors.

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

Another object of the present invention is to provide a 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 Problem) 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 at least one of the following resins [A]. It has been found that this can be achieved by an electrophotographic photoreceptor characterized by containing at least one of a heat and/or photocurable resin [B], and a crosslinking agent.

Resin (A); has a weight average molecular weight of 1XIO3 to 2X1.O', and P
A polymer component containing at least one acidic group selected from O, lh group, -COOI+ group, -3O3I+ group, phenolic group (R' represents a hydrocarbon group), and cyclic acid anhydride-containing group. At the end of the polymer main chain of the B block of an A-B block copolymer consisting of a Δ bronc containing at least one kind and a B bronc containing at least a polymer component shown in the following - ritual (1), A graft type copolymer containing at least one monofunctional macromonomer (M) formed by bonding a polymerizable double bond group as a copolymerization component.

-Ritual (I) ~←C11-C→-- ν -R [In (1), al and a2 each do not represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group.

v, is -C00-1-oco-1→-C112f, OC
O represents), -〇--8O□----C (1--CON
When R1 represents a hydrogen atom or a hydrocarbon group. ] That is, the binder resin used in the present invention has a specific acidic group as shown in "2" (hereinafter, unless otherwise specified, the acidic group includes a cyclic acid anhydride-containing group) in the graft portion. At least one of a graft copolymer resin (A) comprising a component containing a methacrylate component and a component containing a methacrylate component as block components, a heat and/or photocurable resin [B], and a crosslinking agent. It has been found that the electrophotographic properties and mechanical strength (printing durability when used as a printing plate) of the resulting photoreceptor are improved when the photoreceptor contains the following. Here, both the heat and/or photocurable resin CB) and the crosslinking agent may be used at the same time, or only one of them may be used.

The resin used in the present invention [Al is a graft copolymer, and the A block of the graft part is made of at least one polymeric component containing at least one type selected from the above-mentioned specific acidic groups at the end of the graft part. The B block contains a polymer component containing at least one methacrylate component represented by formula (1).

Among the acidic group-containing binder resins known to improve the smoothness and electrostatic properties of the photoconductive layer, those using low molecular weight polymers have acidic group-containing polymeric components randomly present in the polymer main chain. or resins with an acidic group bonded only to one end of the polymer main chain.

On the other hand, the resin (A) used in the binder resin of the present invention
The acidic groups contained in the resin are not present randomly in the polymer main chain nor are they bonded only to the ends of the polymer main chain, but are present in the graft portion and are present in the polymer main chain. The chemical structure of the polymer molecular chain is significantly specified so that it exists as a block (ie, A block) at a location apart from the A block.

In the resin of the present invention (Al), the acidic groups unevenly distributed in the terminal region of the graft portion in the polymer sufficiently adsorb to the stoichiometric defects of the inorganic photoconductor, and the other blocks constituting the main chain of the polymer It is estimated that the part covers the surface of the inorganic photoconductor gently and sufficiently.The effect of sufficient adsorption to the surface of the inorganic photoconductor and coating near the surface is greater than that of known resins. By being more effective, there is a sufficient adsorption area even if the stoichiometric defect area of the inorganic photoconductor changes slightly, so the inorganic photoconductor and resin (A) are always stable. It is inferred that the interaction is maintained, and the present invention can sufficiently compensate for the tramp of the photoconductor and improve the humidity characteristics, while improving the humidity characteristics of the photoconductor, compared to conventionally known acidic group-containing resins. It was found that by sufficiently dispersing and suppressing agglomeration, stable and high-performance electrophotographic properties were maintained even when the environment varied significantly from high temperature and high temperature to low temperature and low humidity. Or photocurable resin [
B] and/or the crosslinking agent, the resin (
In A), the mechanical strength of the photoconductive layer, which is insufficient in the case of A), is made sufficient. This is particularly effective when using a scanning exposure method using a semiconductor laser. Moreover, the smoothness of the surface of the photoconductive layer is further improved. When a photoreceptor with a rough photoconductive layer surface 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, and aggregates may be present. Because a photoconductive layer is formed, 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, resulting in damage to printed matter. Background stains occur in non-image areas.

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

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

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

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 be sufficiently adsorbed and coat the particle surface, which improves the smoothness of the photoconductive layer. It has good electrostatic properties, provides image quality without blurring, 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 the resin (B) and/or the crosslinking agent as in the present invention, the function of the resin [A] is not impaired in any way, and the mechanical properties of the photoconductive layer are still insufficient with the resin (A) alone. We were able to further improve the target strength. Therefore, the photoreceptor of the present invention has excellent electrostatic properties even under fluctuating environmental conditions, and has sufficient film strength. etc.), it is now possible to print at least 6,000 sheets.

The polymer component in the macromonomer (M) in the resin [A] of the present invention is composed of A-blocks and B-blocks as described above, and the abundance ratio of A-blocks/B-blocks is , preferably 1-70/99-30 (weight ratio), more preferably 3-50/97-50 (weight ratio)
weight ratio).

In the graft copolymer [A] of the present invention, the macromonomer (M) and other monomers (for example, the monomer of formula (TI))
The existence ratio of is 1 to 60/99 to 40 (weight ratio), preferably 5 to 40/95 to 60 (weight ratio).

In the resin [A] of the present invention, the amount of the acidic group-containing component contained in the macromonomer (M) is 1
00 parts by weight, preferably 3 to 30 parts by weight, preferably 3 to 30 parts by weight.
It is 20 parts by weight. That is, the proportion of acidic groups present in the resin [A] is determined by the preferred ratio depending on the composition ratio of the A-block in the macromonomer (M) and the copolymerization ratio of the macromonomer (M) in the resin (A). It can be adjusted to

Further, in this resin (A), as a component copolymerizable with the macromonomer (M), monomers shown in the following -ritual (II) are preferable, particularly selected from the following -ritual (lla) and/or (Tub). Monomers are preferred.

Formula (■) CI+3 CI□=Coo-RZ [In formula (n), R2 represents a hydrocarbon group. ] (In the formula,
X and x2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, -CO
Zi or -COOZ3 (Z3 each represents a hydrocarbon group having 1 to 10 carbon atoms). However, X + h
Both 2 do not represent a hydrogen atom.

Ll and I7° each represent a single bond or a linking group having 1 to 4 linking atoms that connects -C00- to the Hensen ring. ] The monomers copolymerized with the macromonomer (M) in the resin (A) include the above general formula (IIa) and/or the general formula (
IIb) A resin containing at least a copolymer with a substituent-containing methacrylate monomer containing a substituted Hensen ring or a naphthalene ring (hereinafter this resin [A] will be referred to as resin (A')). In some cases, even better electrophotographic properties (especially V+o, Il, R, R, El/, O)
Nomukai'2 is 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 meccrylate, 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.

If the molecular weight of the binder resin (A) is smaller than 1Xl0', the film forming ability will be reduced and sufficient film strength will not be maintained.On the other hand, if the molecular weight is larger than 2 x 104, even the resin of the present invention can be used at high temperatures. - Fluctuations in electrophotographic characteristics (especially initial potential and dark decay retention rate) become large under harsh conditions of low temperature and low humidity, and the effect of the present invention in obtaining stable copied images is diminished.

The glass transition point of the resin (A) is preferably -40°C to 1
It is 10°C.

The macromonomer content in the binder resin (A, ) is 1
．． If it is less than 0% by weight, electrophotographic properties (especially dark decay rate,
In addition, fluctuations in electrophotographic properties due to environmental conditions become large, especially in combination with near-infrared to infrared spectral sensitizing dyes. This is thought to be due to the fact that the amount of the macromonomer that forms part I of the t:J graph is small, resulting in a composition that is almost the same as that of conventional pomopolymers or random copolymers.

On the other hand, if the content of macro-1 monomer exceeds 60%, the copolymerizability of monomers corresponding to other copolymerization components with the macro-1 monomer according to the present invention will not be sufficient, and even when used as a binder resin. It becomes impossible to obtain sufficient electrophotographic characteristics.

The details of the binder resin (A) used in the present invention will be explained.

First, the monofunctional macromonomer (M) used in the graft copolymer of the present invention will be explained in more detail.

The acidic groups contained in the components constituting the A-block of the macromonomer (M) include -PO311□ group, -C
ool group, -3O311 group, phenolic group, hydrocarbon group) and/or cyclic acid anhydride-containing group, preferably -COOIl group, -5O3++ (R'
represents a hydrocarbon group), and R and R' preferably represent an aliphatic group having 1 to 22 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, Dodecyl group, octadecyl group, 2-chloroethyl group, 2-methoxypropyl group, 3-ethoxypropyl group, crotonyl group, butenyl group, cyclohexyl group, hensyl group, phenethyl group, 3-phenylpropyl group, methylhensyl group, chlorohensyl group, fluorohensyl group, methoxyhensyl group, etc.), or optionally substituted aryl groups (for example, phenyl group, tolyl group, ethylphenyl group (, p[]pylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group) group, chloro-
methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butquinphenyl group, etc.).

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

Examples of aliphatic dicarboxylic anhydrides include succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclobencune, 2-dicarboxylic anhydride ring, cyclo to 4-→non-1,2 -Dicarboxylic acid anhydride ring, cyclohexene ring, 2-dicarboxylic acid anhydride ring, 2,3-bicyclo[2,2,2)octane dicarboxylic acid anhydride ring, etc., and these rings are, for example, chlorine atom , a halogen atom such as a bromine atom, an alkyl group such as a methyl group, an ethyl group, a butyl group, a 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,
Alkyl groups such as propyl group and butyl group, human t-coxyl group, cyano group, 21,4 group, alkoxycarbonyl group (
The alkoxy group may be substituted with, for example, a nodoxy group, an oxy group, etc.

"Polymer component containing a specific acidic group" as in "-" refers to, for example, the polymer component constituting the B block component of the present invention, that is, the corresponding vinyl component such as the methacrylate component represented by formula N). Any vinyl compound containing an acidic group that copolymerizes with the vinyl compound can be used.

For example, the Polymer Science Society of Japan's ``Polymer Data Handbook [
Basic Edition] Baifukan (published in 1986), etc.

Specifically, acrylic acid, α- and/or β-substituted acrylic M (for example, α-acetoxy form, α-acetoxymethyl form, α-(2-amino)methyl form, α-chloro form, α-bromo form, α -fluoro form, α-tributylsilyl form, α-
-ano 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, vinyl hanzene carboxylic acid, vinyl hanzene sulfone Examples include half-ester derivatives of vinyl or allyl groups of acids, vinyl sulfonic acids, vinyl phosphoric acids, and dicarboxylic acids, and compounds containing the acidic group in the substituent of these carboxylic acids or sulfonic acids, ester derivatives, and amide derivatives. .

Specific examples of these compounds include the following. However, in each side below, a is heat), -C
tL+, -CI, -Br, -CN-1-(JI
zCOOCII3 or -C112C0011, b
represents -11 or -0113, n represents an integer from 2 to 18, m represents an integer from 1 to 12, and l represents an integer from ] to 4.

(Left below) (a-1) □ C00I+ C00I+ (a-3) (a-4) C00(CI(z)ncOOI+ (a-5) 〒 (a-6) b CHz C00(CC00(CHz)noco( C1lz)+(
a-7) C00 (Ctlz) ncOo (CHz) mcOOII (
a-8) (a-9) (a-10) (a-1,5) Ctl2 C)l CHzOCO(C1lz)mcOOII(a C1l□ Ctl +CIIz〒COO11 (a (a 〒 (a (a C)13 CON II CII CIl□COO11 (a 〒 (a Ctl.-C C00(C112)m118co(Ctl2)mcOO
II (m may be the same or different) (a-20) (a-21) H (a-22) (a-23) (a-24) (a-25) (a-26 ) (a-27) (a-36) (a-28) (a-29) (a-30) 〒 (a-31) (a-37) C1+□ TeC00 (CI+2), C0N (CII□C112CO
OIl) z(a-38) (a-39) (a-40) (a-41) (a-42) (a-43) (a-44) (a-45)'' Two or more types of components may be contained in the A block, and these two or more acidic group-containing components may be contained in the Δ block by either random copolymerization or block copolymerization. , a component not containing an acidic group (for example, a component represented by the formula (1) described below) may be contained in the A block together with the acidic group-containing component, but the acidic group-containing component is 30 to 100% in the A block. Preferably, it is present in % by weight.

Next, in the above macromonomer, the component constituting the B-floc, that is, the repeating unit represented by the -C formula (+) will be explained.

In general formula (1), V is -COO-2-OCO-(
-CI+・)-OCO-+CI+・)7;C0O-(f
fi represents an integer from 1 to 3), -0---SO□Z CO---CON --5O2N--CONIIC
Examples of the OO elementary group include 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, hexadecyl group) group, octadecyl group, 2-chloroethyl group, 2bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), carbon number 4 to
18 optionally substituted alkenyl groups (e.g., 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, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., hensyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorohensyl group, bromobenzyl group) group, methylhensyl group, ethylhensyl group, dimethylpencil group, dimethoxyhensyl group, etc.), optionally substituted alicyclic groups having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexylethyl group), basis,
2-cyclopentylethyl group, etc.), or carbon number 6 to 12
An optionally substituted aromatic group (for example) l-nyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group,
Butylphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, fromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group,
propioamidophenyl group, l-decoylamidophenyl group, etc.).

R1 represents a hydrocarbon group, preferably the same as those listed as preferred hydrocarbon groups for Z1 above.

represents a hydrogen atom, and the Hensen ring may have a substituent. 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.), alkoxy groups (e.g., methoxy group,
ethoxy group, propioxy group, butoxy group, etc.).

a and a2 may be the same or different from each other,
Preferably a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, a butyl group, etc.), -COOZ2 or carbonized C00Z2 via hydrogen
(Z2 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group, or an aryl group, which may be substituted, specifically, "-" Z1 represents the same content as that described for ).

- Examples of the hydrocarbon in the COO-Zz group via the hydrocarbon include a methylene group, an ethylene group, a propylene group, and the like.

More preferably, in ritual (1), vl is OCO
---CIIzOCO-1-C112COO0--CO
NH--3o□til+- or may be a hydrogen atom,
Methyl group, C00Z2 or CIl□C00Z2 (Z
2 more preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.). Even more preferably, one of al+ 82 represents a hydrogen atom.

Furthermore, the B-block may contain a polymer component other than the monomer of formula (1), which corresponds to another repeating unit that can be copolymerized with the polymer component represented by formula (T). Examples of monomers include acrylonitrile, methacrylonitrile, heterocyclic vinyls (e.g. vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene,
vinyl pyrazole, vinyl dioxane, vinyl oxazine, etc.). These other monomers are used in an amount not exceeding 20 parts by weight based on 100 parts by weight of the total polymer components of B-floc. Further, it is preferable that the B block does not contain a polymer component containing an acidic group, which is a constituent component of the A-block. When two or more types of copolymerization components are present in the B block, these two or more types of copolymerization components may be contained in the B block by either random copolymerization or flock copolymerization, but it may be necessary to simplify the synthesis. It is more preferable that the elements are contained randomly.

Next, in the macromonomer (M) of the present invention, a block A consisting of a component containing an acidic group indicated by - and the general formula (1
) A B block consisting of a polymer component shown in A-B is connected in an A-B type and is connected to an 8-floc.
The polymerizable double group connected to the other end of the block will be explained.

Specifically, a polymerizable double bond group shown in the following formula (1) can be mentioned as an example.

-Ritual (I[I) b, b2 CH=C [In formula (III), v2 represents the same content as V+ in formula (I). l) z b2 may be the same or different and represent the same content as al+82 in formula (1). ] That is, as the polymerizable double bond group represented by the -ritual (III), more specifically, CIl□-CH-C-0O
=C-O O=C-O CIl□-C11-0 COO1+ 0 C1l□-C-C112-C-0 Ctl. -Ctl(Cllz)2-Co.

CIl□-CH-CO CH2=CJIICH2)20C- and the like.

The macromonomer (M) used in the present invention is B as described above.
- It has a chemical structure in which a polymerizable double bond group as shown in formula (III) is directly bonded to one end of the bronch or bonded by an arbitrary linking group.

Linking 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.), heteroatoms - It is composed of any combination of atomic groups of heteroatom bonds. That is, specifically,
hydrogen atoms, halogen atoms (for example), nitrogen atoms, chlorine atoms, bromine atoms, etc.), cyano groups, hydroxyl groups, alkyl groups (for example, methyl groups, ethyl groups,
) represents a hydrocarbon group etc. representing the same content as R1 in )] or a linking group composed of an arbitrary combination -U.

If the weight average molecular weight of the macromonomer (M) exceeds 2 x 104, the copolymerizability with other monomers (for example, formula (It)) will decrease, which is undesirable. On the other hand, if the weight average molecular weight is too small, the photosensitive layer Since the effect of improving electrophotographic properties becomes small, it is preferable that the ratio is ■×103 or more.

The macromonomer (M) of the present invention can be produced by a conventionally known synthesis method. For example, in the monomer corresponding to the polymer component containing the specific acidic group, the acidic group is previously protected as a functional group, and the organometallic compound (
Ionic polymerization reactions using hydrogen iodide, iodine, etc. (e.g., alkyllithiums, lithium diisoproamide, alkylmagnesium halides, etc.), photopolymerization reactions using porphyrin metal complexes as catalysts, or group transfer polymerization reactions. In the so-called living polymerization reaction of A
After synthesizing the -B block copolymer, various reagents are reacted at the ends of this living polymer to introduce polymerizable double bond groups. Thereafter, the functional group with the protected acidic group is deprotected by hydrolysis reaction, hydrogenolysis reaction, oxidative decomposition reaction, photolysis reaction, etc. to form an acidic group. One example is shown in reaction scheme (1) below.

For example, P, Lutz, P, Masson et al.
, Polym, Bull.

12, 79 (1984) B, C, Eighters
on, G, D, eight andreiys etalMa
cromolecules, 14. 1601 (1
981) K, tlatada+K.

Ute, etal, Polym, J, 17.977 (
1985), 18.1037 (1986).

Hiroshi Miguchi-1 Ko Hatada-1 Polymer processing, together, 366 (19
87) Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymer Papers, 46.18
9 (1989) Kuroki, M., Aida, T.
, T,Am,Chem,Soc, 1094737
(1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 4
3, 300 (1985) D, Y., Sogah, W.
,R,l1ertler etal Macromole
Living polymers can be easily synthesized according to the synthesis method described in J. C. Cules, 20.1473 (1987), etc. Moreover, as a method for introducing a polymerizable double bond group to the terminal of the living polymer, the macromonomer of the present invention can be easily obtained by following a conventionally known synthesis method of macromonomer method.

Specifically, P, Dreyfuss & R, P, Qu
irk, lEncycPolym, Sci, Eng,
, 1.551 (1987), P.F.RemppE.
, Franta+ ^du,, Polym, Sci,
58.1 (1984), V. Percec+App1.
, Polym, Sci, + signature L-95 (1984),
R, Asami.

M, TakaRi, Makvamol, Chem, 5
upp1.12.163 (1985) P, Rempp,
etal, Makvamol, Chem, 5upp
1.8. 3 (1984) Yuji Kami, Kagaku Kogyo Co., Ltd.
56 (1,987), Yuya Yamashita, polymer, gong, 988
(1982), Shibe Kobayashi, Polymers, Separate.

625 (1981), Toshinobu Higashimura, Japan Adhesive Association Journal Measurement, 536 (1982), Hiroshi Ito-1 Polymer processing, peeling, 2
62 (1986), Nojoki Shibu, Takashi Tsuda, Functional Materials, 19
It can be synthesized according to the methods described in reviews such as No. 87 No. 10.5 and the literature/patents cited therein.

Further, the protecting group that protects the specific acidic group of the present invention and the removal (deprotection reaction) of the protecting group can be easily carried out using conventionally known knowledge. For example, it is variously described in the cited documents mentioned above, and furthermore, Yoshio Iwakura,
Keisuke Kurita, “Reactive Polymer” ■Kodansha (1977)
, T, W, Greene'Protective G
roups in Organic 5ynthesi
John Wiley & 5ous (1981
), J.F.W.McOmierProtecti
ve Groups in Organic Chem
istry” Plenum Press, (1973
Methods described in detail in reviews such as 2010) can be selected as appropriate.

As another method for synthesizing the AB type block copolymer, it can also be synthesized by a photoinifer copolymerization method using a dithiocarhament compound as an initiator. For example, Yoyuki Otsu, Polymer, Gong, 248 (], 988), Inspector-1
Takashi Otsu-1 Polym, Rep, Jap, 37.350
8 (1988), JP-A-64-111, JP-A-64-
It is synthesized according to the synthesis method described in No. 26619 and the like.

The macromonomer of the present invention can be obtained using the macromonomer synthesis method described above.

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. However, in the following compound examples, c, d and e are respectively =■, -
C1, or -CII□COOCH3, f is -II
or -CH3, R1+ is C, lh,. 1 (p is an integer from 1 to 18), -(CO□)QC6H5 (q is 1
~, R12 represents -Csllzs++ (S is an integer of 1 to 8) or -(C; fiz) 9C6+15, Y
2 is C00I+.

, t = an integer from 2 to 12, U is from 2 to 6 Indicates an integer.

(G1) (G2) C1h, -0CH3 or -COCI+3) or (G3) (Toro) (G4) (Door) (G5) (G8) Z (G9) f □ ( M-10) (M-11) (M-16) Monomers that copolymerize with the above-mentioned macromonomer (M) are shown, for example, in the above-mentioned formula (II). In formula (II), R2 represents the same content as R1 in formula (1).

In addition, in the polymer main chain, -PO, l+□ group, -3O31
1 group, C0011 group, -C11 group, -811 group and -P
Preferably, it does not contain a copolymer component containing acidic groups such as O and RI+ groups.

Furthermore, the low molecular weight resin (A) of the present invention has -ritual (na)
) and/or - 2nd place or 2nd indicated by the ritual (Ilb),
A graft copolymer (hereinafter referred to as resin
A') is preferable.

(?l-12) H3 (M-14) (M-15) -S In formula (IIa), in addition to hydrogen, chlorine and bromine atoms as preferred X and x2, respectively, as preferred hydrocarbon groups , an alkyl group having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), an aralkyl group having 7 to 9 carbon atoms (e.g. hensyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group) , dichlorohensyl group, bromohensyl group, methylhensyl group, methoxyhensyl group, chloro-methylhensyl group, etc.) and aryl groups (e.g. phenyl group, tolyl group, silyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group) etc.), and -COZ3 and -COOZ3 (preferred examples of Z3 include those described as the above-mentioned preferred hydrocarbon groups). However, × and x
Both 2 do not represent a hydrogen atom.

In formula (Ila), L is a single bond or +Ctlz + [(IL is 1
(does not represent an integer of ~3), cLcllzOco -1n
ctlz0) Ao2- (mz represents an integer of 1 or 2)
, CH2Cl+20, etc. represents a linking group having 1 to 4 linking atoms.

L2 in formula (Ilb) is L represents the same content as .

Specific examples of the monomer represented by the formula (IIa) or (Ilb) used in the resin (A') of the present invention are listed below.

but, The scope of the present invention is limited to these It is not something that will be done.

CH.

l1i death! C1l:+ CH3 ■4) CH3 CH.

CI+3 C1(3 CH3 r CI+3 C) 13 ■3 C113 CtL+ Ctl+ C11゜ 1li C1(.

CI+3 CH3 C1l□ CH.

CI(2 CH3 C112=C 3G) Ca+3 i -34) CI+3 CH3 CH2=C CH:+ CI+2=(1: Furthermore, in the graft type copolymer of the present invention, copolymerization with the macromonomer (M) described in 1. The component may be a monomer other than (IT), (IIa) or (Ilb), such as α-olefins, vinyl alkanoates or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides,
Methacrylamides, styrenes, heterocyclic vinyls [for example, 5- to 7-membered heterocycles containing 1 to 3 nonmetallic atoms (oxygen atoms, sulfur atoms, etc.) other than nitrogen atoms,
Specific compounds include vinylthiophene, vinyldioxane, vinylfuran, etc.

Preferred examples include vinyl alkanoates or allyl esters having 1 to 3 carbon atoms, acrylonitrile, methacrylonitrile, styrene, and styrene derivatives.
Examples include vinyltoluene, butylstyrene, meth; tocystyrene, chlorostyrene, dichlorostyrene, bromostyrene, and dichlorostyrene.

Furthermore, the resin (A) of the present invention may further contain a functional group that performs a curing reaction of the resin with at least one of heat and light, that is, a "thermal and/or photocurable functional group". preferable. That is, the resin (A) contains, in addition to copolymerization components corresponding to the macromonomer (M) and other monomers (for example, monomers of II (II), preferably (Ila) and (Ilb)), respectively. Furthermore, it is preferable to further contain a copolymer component containing a heat-curable and/or photo-curable functional group, thereby improving the film strength and increasing 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 heat-curable and/or photo-curable functional groups are present in the binder resin, if the content is less than 1% by weight, the curing reaction will be insufficient and the effect of improving the film strength of the photoconductive layer due to the curable functional groups will not be observed. I can't. -If the amount of blade metal exceeds 30%,
Even with the binder resin (A) of the present invention, it becomes difficult to maintain excellent electrophotographic properties, and the properties deteriorate to the same as those of conventionally known binder resins. Furthermore, when used as an offset master, background stains occur in non-image areas of printed matter.

Specific examples of photocurable functional groups include Hideo Inui, Gentabe Nagamatsu, "Photosensitive Polymer" (Kodansha, 1977), Takahiro Tsunoda, "New Photosensitive Resin" (Printing Society Publishing Department, 1981)
Annual publication) Kiyomi Kato, [Ultraviolet curing system Chapters 5 to 7
Chapter, General Technology Center (published in 1989), G, E, Gr.
een and B, I', 5trak, J, Mac
ro, Sci, Reas.

Macro Chem, C2] (2), 187-27
3 (1981-B2), C, GRattey, '
Photopolymerization of 5u
rface Co.

tings” (8, Wiley InterScie
Functional groups used in conventionally known photosensitive resins and the like are used as photocurable resins, as cited in the review articles such as CE Pub, 1982).

Furthermore, the "thermosetting functional group" in the present invention refers to a functional group other than the above-mentioned acidic group, and includes, for example, Tsuyoshi Endo, "Refinement of Thermosetting Polymers J (C, M, C, Annual)
, Yuji Harasaki "Latest Binder Technology Handbook" Chapter H-1 (General Technology Center, published in 1985), Yoshiyuki Otsu "Synthesis, design and development of new applications of acrylic resin" (Chubu Management Development Center Publishing Department, published in 1985), The functional groups cited in the review by Eizo Omori [Functional Acrylic Resins] (Technosyste J1, published in 1985) can be used.

For example, -〇i+ group, -5l+ group, -Ni1□ group, -NI
IR7 group [R7 represents a hydrocarbon group, for example, a carbon number of 1
~10 optionally substituted alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, 2-chloroethyl group, 2methoxyethyl group, 2-cyanoethyl group, etc.), An optionally substituted cycloalkyl group having 4 to 8 carbon atoms (e.g., socloheptyl group, cyclohexyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., hensyl group, 1-netyl group, 3-phenylpropyl group) aryl group, which may be substituted (e.g., phenyl group, tolyl group, xylyl group, chloroethyl group, bromophenyl group, methyl xyphenyl group, etc.), C0NIICI+20R8CRo is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, etc.) d,
d2), -Jl-C=O group and -C=C11 group (dI and d2 are each 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.). Further, as the polymerizable double bond group, for example, Cl13CH30 C1+2=C-CONI+-1CIl=CI+,,C0
NH-8CH2・C1l-0-CC1h OO I II lI C1l□:C-0-C-1C1l□=CH-C11□-
0-CC1+2・Cl1-CIL, -NHCO-1C1
12・Cll-802C112=C)1-(1-1C1
12=Cll-C11□0, C1l,=Cll-C0-
1 Examples of repeating units containing [heat/photocurable functional group] are given below. However, on each side below, b and C represent the same meanings as above, and R21 is -CII=CH2 or -C
112CIl=CI+2, R2° is CH3 1i -3) CII=CII. , C1l□ or CII1li -←CH2 C→- CH.

Coo(C1h) represents v-Coo-R2°, I? zs represents C) I=CI+, CIl2 or an integer from 1 to 11 ii -4) 1,000 CH2 C→- an alkyl group, OI represents or Coo(C112) vOCO(CH2) v-COO
-R2, 0□ represents 011 or Nl+□, ■ represents an integer from 1 to 11 (V may be the same or different), X represents an integer from 1 to 10, and represents an integer from 1 to 4 , and Z represents an integer from 2 to 11.

ii -1) -(-c l(2 C→□ Coo-R2 COOC) I=C11□ ii -2) C00(C1vOCO-1?22 1←CH2 C→- COOCII□Cl1=CI+2 ii -8) ii -12) -(-CI"C→-- CONII (CIl2) X-0CO-R24ii -
9) ii -13) -6H2 C→-□ -tel+ C→□□ C00 (CH2), -CIl-CI+□-0-GO-R
zsCONllCI+2011 0~Co-Rzs (R2゜ may be the same or different) ii -14) ii -10) -(-CI C→□□ 1℃I■2 C→-- C0NHCH20R26 CONII (C112)vC00C112-CIIC
11200C-R24ii -15) ii -11) 1+ClI C→- ii -21) b -(-CIl□-C→- COO(Cth) 2-NGO ii -18) c mfc) I -C? COO (CI+2) 2-Q□ ii -19) □ (-CH-CH-ner ii -20) The binder resin of the present invention contains the macromonomer (M) and other monomers (for example, -ritual (n ), and any photo- and/or thermosetting functional group-containing monomer), by copolymerizing at least one compound selected from the following in a desired ratio. I can do it. As the polymerization method, it can be produced by using known methods such as solution polymerization, suspension polymerization, precipitation polymerization, and emulsion polymerization. For example, in solution polymerization, monomers are added in a predetermined ratio in a solvent such as Hensen or toluene, and azobis-based compounds,
A copolymer solution can be obtained by polymerization using a peroxide compound and a radical polymerization initiator. A desired copolymer can be obtained by drying it or adding it to a negative solvent. In suspension polymerization, monomers are suspended in the presence of a dispersant such as polyvinyl alcohol or polyvinylpyrrolidone, and copolymerized in the presence of a radical polymerization initiator to obtain a copolymer.

In the resin (A), the amount of the polymer component containing the specific acidic group in the AB type block copolymer is as follows:
Preferably 1 to 30% by weight in 100 parts by weight of resin (A)
More preferably, it is 3-20%.

The weight average molecular weight of the resin (A) is preferably 3 x 103~
lXl0'.

In the present invention, together with the resin (A) according to the present invention, at least one of heat and/or photo-curable resins CB) or at least one of a crosslinking agent is allowed to coexist. Thereby, the film strength of the electrophotographic photoreceptor can be improved without impairing the properties of the resin (A).

The resin (B) contains a crosslinkable functional group, that is, a functional group that generates a crosslinking reaction in the film to form a bridge between polymers after forming a photosensitive layer using at least one of heat and light. It is a heat and/or photocurable resin that reacts with the heat and/or photocurable 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, -011 group, -sng, N1(1
? 3. (R3 represents a hydrogen atom, an optionally substituted aliphatic group having 1 to 12 carbon atoms, or an optionally substituted allyl group); and NC5, each selected from the group of a cyclic dicarboxylic acid anhydride. or -CON1((:1(201?3□(R3゜ is a hydrogen atom or the number of carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc.) 1 to 6 alkyl groups) or a polymerizable double bond group.

The functional group having a dissociable hydrogen atom is preferably 10
11 groups, -511 groups, and -NIIR3□ groups are given as 4S.

Specifically, the polymerizable double bond group and photocurable functional group include those described in the "thermal and/or photocurable functional group" contained in the resin (A). It will be done.

Polymers or copolymers containing such functional groups are examples of the resins CB) of the invention. Specifically, Tsuyoshi Endo "Refinement of thermosetting polymers" (C1M, C Co., Ltd., 1)
．． 986), Yuji Harasaki “Latest Binder Technology Handbook”
Chapter 11-1 (Published by General Technology Center, 1985), Yoshiyuki Otsu [Synthesis, design and development of new applications of acrylic resins] (Published by Chubu Business Development Center Publishing Department, 1985), Eizo Omori, "Functional Acrylic Resins J ( Techno System (published in 1985)
Conventionally known resins cited in the review of et al. are used. For example, polyester resin, untransformed epoxy resin, polycarbonate resin, vinyl alkanoate resin,
Modified polyamide]・Resin, phenol resin, modified alkyl 7
Examples of the resin include a resin, a melamine resin, an acrylic resin, a styrene resin, etc., as long as these resins contain the functional group for forming the crosslinking reaction described above. Preferably, these resins that do not contain the acidic group represented by resin (A) or have been modified can be used as the resin of the present invention.

Specific examples of monomers corresponding to copolymer components containing these functional groups include vinyl compounds containing these functional groups.

For example, it is described in the Society of Polymer Science's ``tFAr Polymer Data Handbook (Basic Edition)'' Baifukan (1986).Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoquine α-ace1hexymethyl, α-(2-amino)methyl, α-bromo, α-fluoro, α-tribudylsilyl, α-cyano, β-ri l-colloid, α-bromo, α
-chloro-β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amide F, 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 amide, vinyl In the substituents of benzenesulfonic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylposboxylic acid, half-ester derivatives of vinyl or allyl groups of dicarboxylic acids, and Nisder derivatives and amide derivatives of these carboxylic acids or sulfonic acids, or in the substituent of the styrene derivative,
Examples include vinyl compounds containing the above-mentioned functional groups.

More specifically, as an example of the resin (B), a (meth)acrylic copolymer containing a total amount of 30% by weight or more of the monomer represented by the general formula (I) described above as a copolymerization component. can be mentioned.

The content of the copolymer component j containing a crosslinkable (crosslinkable) functional group in the resin CB) is preferably 0.5 to 40 mol%.

The weight average molecular weight of the resin (13) is preferably 1×103
~1x105, more preferably 5X10'~5X
10'.

Furthermore, the glass transition point of the resin CB) is preferably 20°C.
-120°C1, more preferably 0°C - 100°C.

The ratio of resin [A] and resin CB) used in the present invention varies depending on the type, particle size, and surface condition of the inorganic photoconductive material used, but generally the ratio of resin (A) to resin CB) is 5. ~60:95-40 (weight ratio), preferably 10-40:90-60 (weight ratio).

On the other hand, in the present invention, a crosslinking agent can be used together with the resin [A]. In particular, when the resin (A) and/or the resin [B] contain photo- and/or thermosetting functional groups, a cross-linking agent can be used in combination to promote cross-linking in the film. As the crosslinking agent used, compounds commonly used as crosslinking agents can be used. Specifically, "Crosslinking agent Han F book" edited by Machizo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), "Polymer data Huff 1-
Compounds described in "Book Basic Edition" Baifukan (1986) etc. can be used.

For example, silane coupling of organic silane compounds (e.g., vinyltributoxysilane, vinyltributoxysilane, T-glycidoxypropyltrif-1-quinsilane, γ-mercaptopropyl I-liethoxysilane, T-aminopropyltriethoxysilane, etc.) agents, etc.), polyisocyanate compounds (e.g., toluylene diisocyanate, 0 toluylene diisocyanate, diphenylmethane diisocyanate-1~, 1~riphenylmethane triisocyanate, polymethylene polyphenylisocyanate-1)
・Heximethylene diisocyanate, isopolone diisocyanate, polymeric polyisocyanate, etc.), polyol compounds (for example, 1.4-butanediol, polyoxypropylene glycol, polyoxyargylene glycol, polyamine compounds (e.g., ethylenediamine, T-hydroxypropylated ethylenediamine, phenylenediamine, hexymethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds, and epoxy Resins (for example, compounds described in "Epoxy Resin" edited by Hiroshi Kakiuchi, Shokodo (1985), Kuniyuki Hashimoto (ed. Department,
Compounds described in Hideo Matsunaga (ed.) [Uria Melamine Resin] Nikkan Kogyo Shimbun (1969), etc.), poly(
meth)acrylate compounds (for example, those described in Makoto Okawara, Takeo Saegusa, and Toshinobu Toi, eds., "Oligomer", Kodansha (1976), Eizo Omori, "Functional Acrylic Resin", Technosystem (published in 1985), etc. Compounds are mentioned,
Specifically, polyethylene glycol diacrylate,
Nenopenal glycol diacrylate, 1,6-hexanediol acrylate, trimethylolpropane triacrylate, pentaerythritol polyacrylate I
-, bisphenol A-diglycidyl ether diacrylate, oligoester acrylic I. ), etc. The amount of the crosslinking agent used in the present invention is 0.00% based on the total amount of binder resin.
Preferably it is 5 to 30% by weight, especially 1 to 10% by weight.

In the present invention, a reaction accelerator may be added to the binder resin, if 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 L 1 acid, Hensensulfonic 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, other resins other than the resin of the present invention may 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.

Examples include acrylate-1-butadiene resin and vinyl alkanoate resin.

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 (particularly the improvement of electrostatic properties) are 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 perform a heat treatment. For example, 5~ at 60'C~120°C
Process for 120 minutes. When used together with the reaction accelerators mentioned above,
Can be processed under milder conditions.

Inorganic photoconductive materials used in the present invention include zinc oxide,
Examples include titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, 1'mium selenium, 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 photoconductive couple.

In the present invention, various dyes can be used in combination as spectral sensitizers, if necessary. For example, Harumi Miyamoto, Hidehiko Takei, Imaging 1973 (No. 8) p. 12,
C, J, Young et al., RCA Review 15
469 (1954), Wataru Kiyota, Journal of the Institute of Electrical Communication, 63-C (No, 2) 97 (1980), Yuji Harasaki et al., Industrial Science Journal 78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthine dyes, phthalein dyes, polymethine dyes (e.g., oxonol dyes,
merocyanine pigment, cyanine pigment, logocyanine pigment,
Styryl dyes, etc.), phthalocyanine dyes (which may contain metal), and the like.

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, 05
4, No. 450, and JP-A-57-16456.

oxonol dye, merocyanine dye, cyanine dye,
Polymethine dyes such as rhodacyanine dyes include F,
M.Harmmer “The Cyanine
Dyes and Related Compounds
It is possible to use dyes described in 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. ]
No. 28.179, U.S. Patent No. 3,132.942, U.S. Patent No. 3.622.317, British Patent No. 1,226
, No. 892, British Patent No. 1,309,274, British Patent No. 1,405,898, Japanese Patent Publication No. 4B-7814,
Examples include dyes described in Japanese Patent Publication No. 55-18892.

Furthermore, as a polymethine dye that spectrally sensitizes the near-infrared to infrared light region with a long wavelength of 700 nm or more, JP-A No. 47840,
JP 47-44180, JP 51-41061, JP 49-5034, JP 49-45122, JP 5746245, JP 56-35141, JP 57- No. 157254, JP-A-61-2604
No. 4, JP-A No. 61-27551, U.S. Patent No. 3,61
No. 9,154, U.S. Pat. No. 4,175,956, rR
search Disclosure J 1982
216, pp. 117-118. The photoreceptor of the present invention is excellent in that even when various sensitizing dyes are used in combination, its performance does not easily change due to the sensitizing dye. Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers such as chemical sensitizers can be used in combination. For example, the above-mentioned review/imaging 1
9F 3 (No. 8), p. 12, etc., of the review citations for electron-accepting compounds (e.g., halogens, henzquinone, chloranil, acid anhydrides, organic carboxylic acids, etc.), Hiroshi Komon et al., "Recent Photoconductive Materials" and development of photoreceptors.

"Practical Application" Chapters 4 to 6: Japan Scientific Information Co., Ltd. Publishing Department (
Examples include polyarylalkane compounds, hindered phenol compounds, P-phenylenediamine compounds, etc. cited in the review of 1986).

The amount of these various additives added is not particularly limited, but
Normally o, ooot to 2.0% 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 of a photoconductor with a stacked structure of a charge generation layer and a charge transport layer, the thickness of the charge generation layer is preferably 0.01 to 1μ, particularly 0.05 to 0.5μ. It is.

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 polyvinyl carhasol, oxazole dyes, birapurin 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 effective resins such as acrylic resin, polyolefin resin, urethane resin, polyester resin, epoxy resin, melamine resin, and silicone resin 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, metal, paper, plastic sheet, etc. are basically impregnated with a low-resistance substance, just as in the conventional case. those that have been subjected to conductive treatment, such as those that are coated with at least one layer for the purpose of imparting conductivity to the back side of the base (the side opposite to the side on which the photosensitive layer is provided) and 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, a conductive plastic base is coated with 8, etc. You can use paper laminated.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, electronic photography, 14 (No, 1), P2-11 (
1975), Hiroyuki Moriga, “Introductory Special Paper Chemistry” Kobunshi Publishing (1975), M. F., Hoover, J.
Macromol, Sci.

Chem, A 4 (6), No. 1327-141
7 (1970) etc. is used.

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

Synthesis example of macromonomer (M): (M-1) Triphenylmethyl methacrylate 1.30 g and toluene 100
The mixed solution of g was thoroughly degassed under a nitrogen stream and cooled to -20°C. 1,1-diphenylbutyllithium 1.0g
was added and reacted for 10 hours.

Further, a mixed solution of 70 g of ethyl methacrylate and 100 g of toluene was added to this mixed solution after sufficiently degassing under a nitrogen stream, and the mixture was reacted for further 10 hours.

After bringing this mixture to 0°C, add 60 #lIl/of carbon dioxide gas.
Aeration was carried out for 30 minutes at a flow rate of min to stop the polymerization reaction.

The resulting reaction solution was brought to a temperature of 25°C with stirring, and 6 g of 2-hydroxyl methacrylate was added, followed by a mixed solution of 2 g of cyclohexyl methacrylate FL, 1.0 g of 4N,N-dimethylaminopyridine, and 20 g of methylene chloride. was added dropwise over 30 minutes, and the mixture was stirred for 3 hours.

After filtering out the precipitated insoluble matter, 10 ml of a 30% hydrogen chloride ethanol solution was added to the mixed solution, and the mixture was stirred for 1 hour.

Next, the solvent was distilled off from the reaction mixture under reduced pressure until the total volume was reduced to half, and then reprecipitated into petroleum ether 11. The polymer obtained by collecting the precipitate and drying it under reduced pressure is Few
6.5XIO', the yield was 56 g (M-1) lh Synthesis example 2 of macromonomer (M); (M-2) 5 g of hensyl methacrylate (tetraphenylborufinate) aluminum methyl O, Ig and methylene chloride 6
0 g of the mixed solution was brought to a temperature of 30° C. under a nitrogen stream. This was irradiated with 300 m xenon lamp light from a distance of 25 marks through a glass filter, and reacted for 12 hours.

Furthermore, 45 g of butyl methacrylate was added to this mixture,
After 8 hours of light irradiation, this anti-Tj5 mixture was irradiated with 4-
10 g of bromomethylstyrene was added and stirred for 30 minutes to stop the reaction.

Next, Pd-C was added to this reaction mixture, and a catalytic reduction reaction was carried out at a temperature of 25°C for 1 hour.

After filtering out insoluble matter, the mixture was reprecipitated into 500 mR of petroleum ether, and the precipitate was collected and dried. The obtained polymer had a yield of 33
g and day w7×101.

(M-2) Synthesis example 3 of macromonomer (M): (M-3)4
-A mixed solution of 20 g of vinylphenyloxytrimethylsilane and 100 g of toluene was sufficiently degassed under a nitrogen stream and cooled to 0°C. 2 g of 1,1-diphenyl3-methylpentyllithium was added and stirred for 6 hours. Further, a mixed solution of 80 g of 2-chloro-6 methylphenyl methacrylate and 100 g of toluene was added to this mixture after sufficiently degassing under a nitrogen stream, and the mixture was reacted for 8 hours. After thoroughly stirring (while stirring) ethylene onitozide was aerated at a flow rate of 30 mR/min for 30 minutes, the reaction mixture was cooled to a temperature of 15°C, and 12 g of methacrylic acid chloride was added at 30 mR/min.
The mixture was added dropwise over a period of minutes, and the mixture was further stirred for 3 hours.

Next, add 30% hydrogen chloride ethanol solution to this reaction mixture]
After adding Og and stirring at 25°C for 1 hour, the mixture was reprecipitated into 1p of petroleum ether, and the collected precipitate was washed twice with 300ml of diethyl ether and dried. The obtained polymer is
The yield was 55g and Ftw7.8XIQ''.

(M~3) Synthesis example 4 of CIL+ macromonomer (M): (M-/l)
A mixed solution of 40 g of triphenylmethyl methacrylate and 100 g of toluene was thoroughly degassed under a nitrogen stream, and -2
Cooled to 0°C.

2 g of 5ec-butyllithium was added and reacted for 10 hours.

Next, this mixture? After thoroughly degassing a mixed solution of 60 g of styrene and 100 g of toluene to the 8 liquid under a nitrogen stream,
The mixture was added and reacted for 12 hours. After the mixture was brought to O'C, 1.g of benzylpromyelin was added and reacted for 1 hour, and further reacted for 2 hours at a temperature of 25°C.

To this reaction mixture, g of a 30% hydrogen chloride-containing ethanol solution was added, and the mixture was stirred for 2 hours. After the container was filtered, the precipitate was reprecipitated in n-hexane IF, and the precipitate was collected and dried under reduced pressure. The yield of the obtained polymer was 58g TFiW4.5X1
It was 03.

(M-4) Then, light was irradiated again for 10 hours.

To the obtained reaction mixture, 1.12 g of 2-isocyanatoethyl methacrylate was added dropwise at a temperature of 30° C. over 1 hour, and the mixture was further stirred for 2 hours.

The obtained reaction product was reprecipitated in 1.5 ρ of hexane, collected, and dried. The obtained polymer weighed 68 g T: ~6. O×1
It was 03.

(M-5) CI+3 Synthesis Example 5 of Macromonomer (M): (M-5) Phenylmethacryle-1-70g, Hensyl-N-hydroxylethyl-N-ethyldithiocarhano-1.4. The mixture of h was sealed in a container under nitrogen flow and heated to a temperature of 60°C. This was irradiated with light for 10 hours from a distance of 10 cm through a glass filter using a high-pressure mercury lamp of just under 400 liters for photopolymerization. After adding 30 g of acrylic acid and 180 g of methane, a nitrogen-substituted resin [synthesis example of Al],
:[A-1] Ethyl methacrylate-1・80g1 macromonomer (M-
1) A mixed solution of 120 g and 150 g of luene was heated to a temperature of 95°C under a nitrogen stream. 2.2'-Azubis (
Add 6 g of isobutyronitrile (AI[N) and react for 3 hours, and then add A, 1. -B, N2g was added and reacted.

The spacing of the obtained copolymer was 9XI03.

[A1] Synthesis Example 2 of Resin (A): l:A-2] 2-r1r7 phenylmerocryl 1-70 g, Maclvmo)mer (M-2) 30 g, n-dodecyl mercaptan 2 g, and A mixed solution of 100 g of toluene was heated to a temperature of 80° C. under a nitrogen stream. Add 3 g of 2,2'-azobis(isovaleronitrile) (AIVN) and add 3
time reaction, and further A, 1. V, 11.1 g was added and reacted for 2 hours.

Next ^, 1. 1 g of B and N were added, heated to 90°C, and reacted for 3 hours. The spacing of the obtained copolymer was 7.
It was 6XIO'.

(Left below) Synthesis examples 3 to 18 of resin [A]: fA-31 to [A4
8] Copolymers shown in Table 1 below were synthesized under the same polymerization conditions as in Synthesis Example J of Resin [A), except that ethyl methacrylate was replaced with another monomer. h of each obtained polymer is 5 x 103~9
It was XIO'.

Table-1 CII3CI+, + x + y + 20 = 100 (weight ratio) Synthesis examples 19 to 35 of resin (A): [A-19] to [
In Synthesis Example 2 of A-351 tree [A], the polymerization conditions shown in Table 2 below were carried out under the same polymerization conditions as Synthesis Example 2, except that another macromonomer (M) was used instead of the macromonomer (M-2). A copolymer was synthesized. The distance between each polymer obtained is 2X10'
~lXl0'.

1 to 2 "A-B Resin (A-1) 6g (as solid content), Resin CB- with the following structure], ) 30g (as solid content), Cyanine dye (1:) with the following structure 0.018g, A mixture of 0.1.5 g of salicylic acid and 300 g of toluene was dispersed in a ball mill for 4 hours, and 3 g of glutaric anhydride was further added and dispersed in a ball mill for 5 minutes to prepare a photosensitive layer-forming product, and conductive treatment was performed to remove dirt. 1>2 drying amount on paper: 25g
/% with a wire bar, ] 10
After drying at 120°C for 30 seconds, it was further heated at 120°C for 2 hours. Then, an electrophotographic light-sensitive material was prepared by leaving it for 24 hours at 20° C. and 65% R1+ in a dark place.

Resin CB-1) Cyanine dye (1) (CH2)4SO.

(CI+2) Example 2 for 4SO3 Same as Example 1 except that 6 g (as solid content) of resin [A-2] was used instead of 6 g (7) of resin [A-1] in Example 1. An electrophotographic light-sensitive photographic material was produced by the following steps.

Kitakyou A: An electrophotographic light-sensitive material was produced in the same manner as in Example 1, except that 6 g of resin [R-1] shown below was used instead of 6 g of resin [A-1]. did.

[R-1) CI(3C1(:1 1011□-C-)■"□+C++Z-C±" (Weight ratio) COOC211s COCooH6X
IO3 (random copolymer) [T] 澹W; Same operation as in Example] except that 6 g of resin [R-2] shown below was used instead of 6 g of resin (A-1) in Example 1. An electrophotographic light-sensitive material was prepared.

(R-2) C1l.

1100cmCI+. -5-(CI+ 2-C)--C
OOC2115 Mw 8.0
%RH) was investigated.

The above results are summarized in Table 3.

(Left below) ■ ■ The implementation of the evaluation items shown in Table 3 is as follows.

Note 1) Electrostatic properties: After each photosensitive material was subjected to corona discharge at -6kV for 20 seconds using a paper analyzer (Kawaguchi Electric Q Kiku Paper Analyzer 5P-428 model) in a dark room at a temperature of 20°C and 165% R11. , left for 10 seconds, and the surface potential at this time is V. was measured. Next, the potential V100 was measured after being allowed to stand still in the dark for 90 seconds, and the retention of the potential after dark decay for 90 seconds, that is, the dark decay retention rate CDIIR (
) was determined by (V+oo/Lo) x100 (%).

Further, after the surface of the photoconductive layer is charged to -400 μm by corona discharge, the surface of the photoconductive layer is irradiated with light from a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength: 780 nm).
The time required for the surface potential (V+O) to attenuate to 1/10 is determined, and exposure tE+z+o (erg/CA) is calculated from this time. Similarly, the surface potential (V+) is 1/100
Find the time it takes for the light to attenuate and calculate the exposure amount E1z+ from this
Calculate oo(erg/cJ). The environmental conditions at the time of measurement were 20°C 65% R11 (1) and 30°C 980% R1.
1 (II).

Note 2) 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 2.8m-output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780nm) at the surface of the photosensitive material.
Copied image obtained by developing and fixing using ELP-T (manufactured by Fuji Photo Film ■) as a liquid developer after exposure under an irradiation dose of 0 erg/cJ, a pitch of 25 μl, and a scanning speed of 300 m/see. (Fog, image quality) were visually evaluated.

The environmental conditions during imaging were 20°C, 65% 1711 (1) and 30°C, 80% R11 (II).

As shown in Table 3, the photosensitive material of the present invention had good electrostatic properties, and the actual copied images had no blurring and the quality of the copied images was clear. On the other hand, in Comparative Examples A and B, the charging potential (V+O) decreased or the photosensitivity (IEI/+o and E+/+Oo
), and even in actual copied images, the image density (DH
), which resulted in fading of fine lines, letters, etc., and the occurrence of burrs.

In particular, the photoreceptor of the present invention and the photoreceptor of the comparative example are E+z+
oo values are significantly different. E, 7. . . The value is the non-image area (already exposed area) after exposure in actual imaging performance.
This value indicates how much potential remains in the image, and the smaller this value is, the less background smear will occur in the non-image area after development.

Specifically, it is necessary to make the residual potential below -10V, that is, in order to actually make it below -10V,
How much exposure is required? In the scanning exposure method using semiconductor laser light, it is important to reduce , accuracy of the optical system optical path, etc.) is very important.

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

Furthermore, even when the resin of the present invention is used, the resin [A] containing a methacrylate component having a specific substituent
It has become clear that Example 2, consisting of the following, has better electrostatic properties than Example 1, and is particularly useful for semiconductor laser optical scanning exposure type photoreceptor systems.

Example 3 Resin (A-19) 5.4g (as solid content),
Resin CB-2) with the following structure: 30.6 g, zinc oxide: 200 g, cyanine dye with the following structure (II'J O,
A mixture of 018 g and 300 g of toluene was dispersed in a ball mill for 4 hours.

Furthermore, 1,3-gysilylene diisocyanate 2.
5 g was added and dispersed in a ball mill for 5 minutes. This was applied to electrically conductive treated paper using a wire bar so that the dry adhesion amount was 22 g/nT, and dried at 00°C for 30 seconds. It was then heated at 120°C for 1.5 hours.

Then, an electrophotographic light-sensitive material was prepared by leaving it for 24 hours in a dark place at 20° C. and 165% R11.

Resin (B-2) Mw 3.8 'C, 80% R1+, the electrostatic properties, imaging properties, and printability were investigated.

The results are shown in Table 4.

(The following is a blank space) The manner in which the evaluation items shown in Table 4 are implemented is as follows.

Note 3) Smoothness of surface layer: The obtained photosensitive material was tested using a Henk smoothness tester (Kumagai Riko).
The smoothness (
sec/cc) was measured.

Note 4) Mechanical strength of photoconductive layer: The obtained photosensitive material was tested using a Heyton-14 type surface tester (manufactured by Shinrai Kagaku ■) with a weight of 70 g/cm2/later with emery paper (11000) at 500 g/cm2. The residual film ratio (χ) was determined from the weight loss of the photosensitive layer by repeatedly removing abrasion powder and using it as mechanical strength.

Note 5) Contact angle with water: Each photosensitive material is exposed to light by passing it through an etching processor once using a solution prepared by diluting the desensitizing liquid EPL-EX (manufactured by Fuji Photo Film) twice with distilled water. After desensitizing the surface of the conductive layer, droplets of 2Al distilled water were placed on it,
The formed contact angle with water is measured with a goniometer.

Note 6) Printing durability: Each photosensitive material is plate-made to form a toner image under the same conditions as the imaging performance in property 2) above, and then desensitized under the same conditions as property 5) above. As an offset master, apply it to an offset printing machine (Sakurai Seisakusho Oliver 52 model),
It indicates the number of prints that can be printed without causing problems with background stains in non-image areas and image quality in image areas of printed matter (the higher the number of prints, the better the rigidity resistance).

As shown in Table 4, in the photosensitive material of the present invention, the smooth film of the photoconductive layer had good mechanical strength and electrostatic properties, and the actual copied images had no blurring 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 desensitization treatment with the desensitization 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 is clear that it has been done. When actually printing and observing the background smudges on the printed matter, no background smudge was observed, and 10,000 prints with clear image quality were obtained.

The above can be achieved by the action of resin [B] or resin CB) and crosslinking agent without alienating the action of resin (A).
This shows that the strength of the film has been significantly improved.

Examples 4 to 11 In Example 3, resin [A-In 2.4 g, resin CB
In place of 30.6 g of -2'J and 1.2.5 g of 1,3-xylylene diisocyanate as a crosslinking agent, each resin and crosslinking agent shown in Table 5 below was used, and cyan dye CB
) with 0.02 cyanine dye [D] having the following structure.
A CC photosensitive material was prepared in the same manner as in Example 3, except that 0 g was used.

Cyanine dye CD) C2Hs C2II 5 In the same manner as in Example 3, each characteristic was measured. Table 5 shows (30°
The electrostatic properties under C580%RH) condition were shown.

Each of the photosensitive materials of the present invention has excellent chargeability, dark charge retention, and photosensitivity, and can be used at high temperatures and high humidity (30" C180% R
11) Even under the harsh conditions described above, clear images were produced without any occurrence of ground blur or fine line skipping.

Any place printed as an offset master master plate,
It was possible to print more than 10,000 sheets with clear images and no background smudges.

Examples 12 to I5 6 g of resin (A) in Table 6 below, resin (B) in Table 6 below
Group X 18g, zinc oxide 200g,
) and 300 g of toluene were dispersed in a ball mill for 3 hours.

To this was added 12 g of Resin (B) Group Y shown in Table 6 below, and further dispersed in a ball mill for 10 minutes. This was applied to conductive-treated paper using a wire spar so that the dry adhesion amount was 20 g/m2, heated at 100°C for 15 seconds, and heated to 120°C.
Further heating was performed at C for 2 hours. Then, 20°C 165%R
An electrophotographic light-sensitive material was prepared by leaving it for 24 hours under H conditions.

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°C8).
Even under the harsh conditions of 80% RH), clear images with no soil burr were obtained.

Furthermore, when this was used as an off-cent master original plate for printing, a print with clear image quality was obtained even with a cane.

Example J6 Resin [A-15] 6 g, following resin CB-15)
18g, zinc oxide 200g, rose hengal 0.50g
g, 0.25 g of tetrabromophenol blue,
Mix 3 og of uranine and 240 g of toluene,
Dispersion was carried out in a ball mill for 4 hours. Add the following resin (B
-15) 12g was added and dispersed for 5 minutes. This was applied to electrically conductive treated paper using a wire bar so that the dry adhesion amount was 20 g (7 m2), heated at 110°C for 30 seconds, and then heated at 120°C for 2 hours. Then, 20℃, 6
An electrophotographic light-sensitive material was prepared by leaving it for 24 hours under the condition of 5% R11.

Jugetsuji (B-15) C1h CIL.

+CHz-C-hT-fC1lz C-h-COOC
H2C6H5C00(C112)20CO(CI+2)
2COOIIMw 3. OXIO' (weight composition ratio)
When each characteristic was measured in the same manner as in Example 1, the following results were obtained.

Smoothness of photoconductive layer: 430 (cc/5ec) Strength of photoconductive layer: 97% Imaging property: (20°C165χR11) and (30'C,
80χR1+) A good copy image was obtained under both conditions.

Printing durability: Good printed images were obtained up to 10,000 sheets.

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

However, electrostatic properties and imaging performance were determined as follows.

Electrostatic properties: After each photosensitive material was subjected to corona discharge for 20 seconds at 6 kV using a Pever Analyzer (Paper Analyzer 5P-428 model manufactured by Kawaguchi Electric Co., Ltd.) in a dark room at a temperature of 20°C, 165% R11. , and the surface potential VIG at this time was measured. Next, the potential V70 was measured after leaving it in the dark for 60 seconds, and the retention of the potential after dark decaying for 60 seconds, that is, the dark decay retention rate (DRR (χ))
was determined by (V7o/V+o)X100(χ).

In addition, 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 of 2.0 lux, and the time required for the surface potential (V + O) to attenuate to 1710 V is determined. From this, the exposure amount El/In (runx seconds) is calculated.

Imaging properties: The plate making of the photosensitive material was carried out using a fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) using E L PT as a toner to form a toner image.

Examples 17 and 18 7 g each of resins (A-3) and [A-21], 29 g each of resin [I3] in Table 7 below, 200 g of zinc oxide, uranine o,
A mixture of 2 g of o, 0.04 g of rose hengal, 0.03 g of bromophenol blue, and 300 g of toluene,
Disperse in a ball mill for 4 hours to prepare a photosensitive layer formed product,
The dry adhesion amount is 25g/m2 on conductive treated paper.
Apply it with a wire bar so that it becomes 1 at 10'C.
Dry for a minute. Next, after exposure for 3 minutes with a high-pressure mercury lamp,
Next, each electrophotographic photoreceptor was prepared by leaving it for 24 hours at 20° C. and 165% R1+ in a dark place. The characteristics of the obtained photoreceptor are shown in Table 8.

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

Furthermore, using this as the original version of Offcent Master,
Even when printing 8,500 to 9,000 sheets, prints with clear image quality were obtained.

Examples 19 to 27 As a binder resin, resin [A] 5.4 shown in Table 9 below was used.
g and resin (B) 30.6g, zinc oxide 200g
, Rose Hengal 0.05g, Tetrabromophenol Blue 0.03g, Uranine 0.02g and Toluene 240g? The mixture was dispersed in a ball mill for 4 hours.

A predetermined amount of the crosslinking agent shown in Table 9 below was added to this dispersion, and the mixture was further dispersed in a ball mill for 5 minutes. The dry adhesion amount on conductive-treated paper was 20 g/mi! Apply with a wire bar and heat at 110'C for 30 seconds.
Heated at °C for 2 hours. Next, an electrophotographic light-sensitive material was prepared by leaving it for 24 hours at 20° C. and 165% RH.

The photosensitive material of the present invention has chargeability, dark charge retention,
It has excellent light sensitivity, and the actual copied images can be used even under high temperature and high humidity conditions (30°).
Even under the harsh conditions of C-80%R1+), clear images were provided without any ground blurring.

Furthermore, when printing was performed using this as an original plate for an offset master, prints with clear image quality were obtained even after printing 8,000 sheets.

(Effects of the Invention) According to the present invention, it is possible to obtain an electrophotographic photoreceptor that has excellent electrostatic properties (especially electrostatic properties under severe conditions) and has clear and high-quality images. This is particularly effective for scanning exposure methods using semiconductor laser light.

Further, in particular, in the resin [A], the electrophotographic properties are further improved by using a polymerization component consisting of a monomer represented by the formula (Ha) and/or (nb) together with the macromonomer (M).

Furthermore, the mechanical strength of the electrophotographic photoreceptor obtained is increased by incorporating a thermally and/or photocurable functional group into the resin of the present invention.

Furthermore, the mechanical strength of the electrophotographic photoreceptor can also be increased by using the resin of the present invention in combination with a heat and/or photocurable resin and/or a crosslinking agent.

Claims (3)

[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 of the following resins [A] and a heat and/or photocurable resin [ B] and at least one of a crosslinking agent. Resin [A]; -PO_3H_2 group, -COOH group, -SO_3H group,
Selected from phenolic OH groups, ▲mathematical formulas, chemical formulas, tables, etc.▼ groups {R represents a hydrocarbon group or -OR' group (R' represents a hydrocarbon group)} and cyclic acid anhydride-containing groups. A block containing at least one kind of polymer component containing at least one acidic group, and the following general formula (I
) and a B block containing at least a polymer component represented by Weight average molecular weight 1 x 10^3 to 2 containing at least one macromonomer (M) as a copolymerization component
×10^4 graft type copolymer. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In formula (I), a_1 and a_2 each represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group. V_1 is -COO-, -OCO-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(
l_1, l_2 represent integers from 1 to 3), -O-, -SO_2-, -CO-, ▲ Formula,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -CONHCOO-, -CONHCONH-
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (here, Z_1 represents a hydrogen atom or a hydrocarbon group). R_1 represents a hydrocarbon group. However, V_1 is ▲formula,
There are chemical formulas, tables, etc. When representing ▼, R_1 represents a hydrogen atom or a hydrocarbon group. ] (2) The resin [A] further contains 1 to 30 repeating units containing heat and/or photocurable functional groups as a polymer component.
The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor contains % by weight. (3) In the resin [A], the macromonomer (M)
Claim (1) characterized in that it contains at least 30% by weight of at least one of the monomers represented by the following general formula (IIa) and general formula (IIb) as a copolymerization component.
Or the electrophotographic photoreceptor described in (2). General formula (IIa) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (IIb) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X_1 and 10 hydrocarbon groups, chlorine atom, bromine atom, -COZ_3 or -COOZ_3 (Z_3 each represents a hydrocarbon group having 1 to 10 carbon atoms). however,
Both X_1 and X_2 do not represent hydrogen atoms. L_1 and L_2 each represent a single bond or a linking group having 1 to 4 linking atoms that connects -COO- to the benzene ring. ]