JPH05142795A - Electroph0tographic sensitive body - Google Patents

Abstract

PURPOSE:To improve the reproducibility of high-fineness images and definition by using an ABA block copolymer as resins of middle to high mol.wts. to be combined with a resin of a low mol.wt. CONSTITUTION:A binder resin is constituted of at least the low mol.wt. AB type block copolymer (resin [A]) consisting of the A block contg. a prescribed polar group-contg. component and the B block contg. the polymer component expressed by formula I and the ABA type block copolymer (resin [B]) contg. the A block contg. the polymer component expressed by formula II and the B block contg. the prescribed polar group-contg. component. The resin [A of the low mol.wt. polymer sufficiently disperses the photoconductor particles by sufficiently adsorbing on these particles and suppress the flocculation thereof since the high-polymer chains thereof are extremely short. In addition, the mechanical strength of the photoconductive layer is sufficiently held by using the ABA block copolymers of the middle to high mol.wts. Further, the block B part has a polar group and, therefore, the adsorption estrangement of spectral sensitizing dyestuff is suppressed.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor,
More specifically, it relates to an electrophotographic photoreceptor having excellent electrostatic characteristics and moisture resistance.

[0002]

2. Description of the Related Art Electrophotographic photoreceptors have various structures in order to obtain predetermined characteristics or depending on the type of electrophotographic process applied.

Typical of electrophotographic photoreceptors are a photoreceptor having a photoconductive layer formed on a support and a photoreceptor having an insulating layer on the surface thereof, which are widely used. Photoreceptors composed of a support and at least one photoconductive layer are produced by the most common electrophotographic process, namely charging.
It is used for image exposure and development and, if necessary, for image formation by transfer.

Further, a method of using an electrophotographic photosensitive member as an offset original plate for direct plate making is widely used. In recent years, in particular, direct electrophotographic lithographic printing plates have become important as a method of printing high-quality printed matter with a printing number of several hundreds to several thousands. In such a situation, the binder resin used to form the photoconductive layer of the electrophotographic photosensitive member has excellent film-forming property of itself and dispersibility in the binder resin of the photoconductive powder, The formed recording layer has good adhesion to the substrate, and the photoconductive layer of the recording layer has excellent charging ability, small dark decay, large light decay, little pre-exposure fatigue, and shooting It is necessary to have various electrostatic characteristics such as that these characteristics need to be stably maintained due to changes in humidity with time, and excellent image pickup properties.

Further, research on a lithographic printing plate precursor using an electrophotographic photosensitive member has been earnestly conducted, and a photoconductive layer for a photoconductive layer having both electrostatic properties as an electrophotographic photosensitive member and printing properties as a printing original plate has been made. Binder resin is required.

In a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye and a binder resin, it has been found that not only smoothness but also electrostatic properties are greatly affected by the chemical structure of the binder resin. It was Particularly in the electrostatic characteristics, the charge retention ratio in the dark (D.R.R.) and the photosensitivity are greatly influenced.

On the other hand, Japanese Unexamined Patent Publication No. 63-217354
No. 64-70761, JP-A-2-67563,
No. 2-236651, No. 2-238458, No. 2-
According to the technique described in No. 236562 and No. 2-247656, an acidic group-containing polymerization component is a low molecular weight resin randomly present in the polymer main chain, and an acidic group is bonded to one end of the polymer main chain. Low molecular weight resin or low molecular weight graft copolymer resin having an acidic group bonded to one end of the polymer main chain, low molecular weight graft copolymer resin containing an acidic group in the graft portion It became possible to improve smoothness and electrostatic characteristics by using, for example, as a binder resin. These are such that the low molecular weight resin has an effect of sufficiently dispersing the photoconductor and suppressing the aggregation of the photoconductors, and the adsorption of the photoconductor and the spectral sensitizing dye is not excluded from the inorganic substance. It is presumed that this is due to the fact that the photoconductor is sufficiently adsorbed to the stoichiometric defects and the surface of the photoconductor is covered gently and sufficiently.

Due to its mechanism of action, the inorganic photoconductor, the spectral sensitizing dye, and the resin are relatively stable because they have a sufficient adsorption area even if the stoichiometric defects of the inorganic photoconductor fluctuate to some extent. It is inferred that mutual interaction is maintained.

In order to make the mechanical strength of the photoconductive layer insufficient by using only these low molecular weight resins, a technique of using another resin of medium to high molecular weight or a resin containing a curable group is used. Japanese Patent Application Laid-Open Nos. 64-564, 63-220149, and 63-220149, which are used together to cure after film formation,
63-220148, JP-A-1-280761,
No. 1-116643, No. 1-169455, No. 1-
No. 211766, No. 2-34859, No. 2-5306
No. 4, No. 2-56558, No. 3-29954, No. 3
-77954, 3-92861, 3-5325.
No. 7 etc.

According to Japanese Patent Laid-Open No. 3-181948,
By using an AB block copolymer composed of a block containing a polar group and a block containing no polar group as a low molecular weight resin,
It has been clarified that a relatively high performance is maintained even when a scanning exposure method using semiconductor laser light is used due to changes in the environment. It was also found that the mechanical strength is improved by incorporating a high molecular weight resin containing an acidic group at random together with the low molecular weight resin in the binder resin.

[0011]

However, even if these resins or a combination of these resins are used, especially in the electrophotographic lithographic printing plate precursor, when the scanning exposure method using the semiconductor laser light is adopted, When actually tested with a photoconductor, the above electrostatic characteristics are not sufficiently satisfied, and especially the difference between E _1/2 and E _1/10 is large, and the gradation of the copied image becomes soft. Makes it difficult to reduce the residual potential after exposure, and the fog on the copied image becomes noticeable. Also, even when printing as an offset master, there are problems such as a printed original sticking mark on the printed matter. Appeared.

Further, in recent years, it has been desired to realize a technique for faithfully reproducing not only a copied image of an image composed of line drawings and halftone dots but also a high-definition image composed of continuous gradations by using a liquid developer. However, the above-mentioned known technology has not been able to sufficiently satisfy these demands.

In the conventionally known technique, the medium-to-high molecular weight resin used in combination with the low-molecular weight resin may lower the electrostatic properties of the low-molecular weight resin, which has been improved in performance. The electrophotographic photosensitive member having a photoconductive layer used in combination with these known resins as described above has high reproducibility of reproduced images of high definition images (especially continuous tone images) or low output. It was clarified that a problem can occur with respect to the imaging property of the scanning exposure method using laser light.

The present invention is to improve the problems of the above-described conventionally known electrophotographic photosensitive members. An object of the present invention is to provide an electrophotographic photosensitive member having a clear and high-quality image which constantly maintains good electrostatic characteristics even when the environment for forming a copied image changes such as low temperature and low humidity or high temperature and high humidity. Is to provide.

Another object of the present invention is to provide a CPC electrophotographic photosensitive member which is excellent in electrostatic characteristics and has little environmental dependence. Another object of the present invention is to provide an electrophotographic photosensitive member effective for a scanning exposure system using a semiconductor laser beam.

A further object of the present invention is an electrophotographic lithographic printing original plate which is excellent in electrostatic properties (particularly dark charge retention and photosensitivity) and is faithful to an original image (particularly a high-definition continuous tone image). Another object of the present invention is to provide a lithographic printing original plate which reproduces a simple copy image, does not cause spot stains as well as uniform stains on the entire surface of a printed matter, and has excellent printing durability.

[0017]

The above-mentioned object is an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor, a spectral sensitizing dye and a binder resin, and the binder resin is shown below. It has been found to be achieved by an electrophotographic photosensitive member characterized by containing at least one resin [A] and at least one resin [B] below. Resin [A] having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ ,
O ₃ H ₂ group, -COOH group, -SO ₃ H group, a phenolic OH group, -P (= O) (OH ) R 1 {R 1 is a hydrocarbon group or -OR ² (R ² is a hydrocarbon group A group consisting of at least one polymer group containing at least one polar group selected from the group consisting of (1) and a cyclic acid anhydride-containing group, and a polymer component represented by the following general formula (I) AB comprising at least a B block containing
Block copolymer.

[0018]

[Chemical 5]

[In the formula (I), R ¹¹ represents a hydrocarbon group. Resin [B] Block A part having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ and containing 30% by weight or more of a repeating unit represented by the following general formula (II) as at least one polymer component. a -PO ₃ H ₂ group, -SO ₃ H group, -COOH group, -P
(= O) (OH) R ³ (R ³ has the same meaning as R ¹ ) and at least one selected from cyclic acid anhydride groups.
A resin composed of an ABA type block copolymer containing a block B part containing 0.05 to 10% by weight of a polymer component containing at least one polar group selected from among various polar groups.

[0020]

[Chemical 6]

[In the formula (II), a ¹ and a ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R
¹² represents a hydrocarbon group. That is, the binder resin of the present invention comprises a low molecular weight AB type block copolymer of an A block containing the specific polar group-containing component and a B block containing the polymer component represented by the general formula (I). ABA type block copolymer (resin [resin [A])), an A block containing the polymer component represented by the general formula (II) and a B block containing the specific polar group-containing component And [B]).

Further, as described above, in the known technique in which the low molecular weight acidic group-containing resin is used in combination with the medium to high molecular weight resin, the medium to high molecular weight resin used in combination improves the performance of the low molecular weight resin. It was found that the generated electrostatic characteristics may deteriorate. It is more important than expected that these medium to high molecular weight resins interact more appropriately with the photoconductor, the spectral sensitizing dye, and the low molecular weight resin in the photoconductive layer. Has become clear.

As a result of repeated studies, a polar group-free block A and a polar group-containing block according to the present invention were selected as medium to high molecular weight resins to be used in combination with the polar group-containing low molecular weight resin [A]. It has been found that the above problems can be effectively solved by using an ABA block copolymer containing B. This is due to the synergistic effect of the binder resins [A] and [B] of the present invention, in which the photoconductor particles are sufficiently dispersed and not condensed, and the spectral sensitizing dye is added to the surface of the photoconductor particles. It is presumed that this is due to the fact that the binder resin is sufficiently adsorbed on the photoconductor and that the binder resin sufficiently adsorbs the extra active sites on the surface of the photoconductor to compensate the trap.

That is, the low molecular weight resin [A] containing a specific polar group as an A block, as described above, is sufficiently adsorbed on the photoconductor particles to uniformly disperse the particles, and the polymer chain Is very short to prevent aggregation, and
It has an important effect such as preventing adsorption of the spectral sensitizing dye.

Further, a medium A composed of a block A containing no specific polar group of the present invention and a block B containing the same is used.
The mechanical strength of the photoconductive layer was sufficiently retained by using the high molecular weight ABA block copolymer. This is because although the block B portion of this resin has some interaction with the photoconductor particles, it is weaker than the resin [A], and the entanglement effect between the polymer chains of the block A partial comrades, etc. It is thought to be due to.

Further, it has the effect of improving the electrostatic characteristics as compared with the known medium to high molecular weight resins used in combination, that the block B portion interacting with the photoconductor particles has a polar group. Therefore, it is considered that it has a function of suppressing the adsorption of the spectral sensitizing dye.

This effect was particularly remarkable with polymethine dyes or phthalocyanine pigments which are particularly effective as dyes for spectral sensitization from near infrared to infrared light. On the other hand, when the electrophotographic photoreceptor of the present invention using photoconductive zinc oxide as the photoconductor is used as a conventionally known direct printing plate, it exhibits excellent image pick-up property and remarkably good water retention.

That is, the photoconductor of the present invention on which a copied image is formed through an electrophotographic process is desensitized by chemically treating the non-image portion with a conventionally known desensitizing treatment liquid to prepare a printing original plate. It shows excellent performance as a printing original plate when printed by offset printing.

When the photosensitizer of the present invention is desensitized, the non-image areas are sufficiently hydrophilized and the water retention is improved, so that the number of printed sheets is dramatically improved. This is because the zinc oxide particles are uniformly dispersed and the presence state of the binder resin present on the surface of the zinc oxide particles is appropriate and the desensitizing reaction with the desensitizing treatment liquid is not alienated and quickly. It is considered that this is due to effective progress.

The binder resin of the present invention will be described in detail below. First, the resin [A] of the present invention will be described. The weight average molecular weight of the resin [A] is 1 × 10 ³ to 2 × 1.
0 ⁴ , preferably 2 × 10 ³ to 1 × 10 ⁴ , and the glass transition point of the resin [A] is preferably −10 ° C. to 100 ° C.
It is preferably in the range of, but more preferably -5 ° C to 8 ° C.
It is 5 ° C.

When the molecular weight of the resin [A] is less than 1 × 10 ³ , the film forming ability is deteriorated and the sufficient film strength cannot be maintained.
On the other hand, when the molecular weight is more than 2 × 10 ⁴ , even in the case of the resin of the present invention, particularly in a photoreceptor using a near infrared to infrared spectral sensitizing dye, high temperature / high humidity, low temperature / low humidity under severe conditions. Fluctuations in dark decay retention rate and light sensitivity at
The effect of the present invention that a stable copy image is obtained is diminished.

The amount of the specific polar group-containing component in the AB type block copolymer of the resin [A] is preferably 0.5 to 20 parts by weight, more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the copolymer [A]. It is preferably contained in a proportion of 3 to 15 parts by weight.

The content of polar groups in the resin [A] is 0.5
If it is less than wt%, the initial potential is low and a sufficient image density cannot be obtained. On the other hand, when the content of the polar group is more than 20% by weight, the dispersibility of the low molecular weight compound is lowered, the film smoothness and the high humidity property of the electrophotographic properties are deteriorated, and further when used as an offset master. The dirt on the ground increases.

Next, the polymerization component containing a specific polar group which constitutes the A block of the AB block copolymer which is the resin [A] will be described more specifically. The polar group, -PO ₃ H ₂ group, -SO ₃ H group, -COOH
Group, a phenolic OH group, a -P (= O) (OH) R ¹ group and a cyclic acid anhydride-containing group, and preferably -SO.
₃ H group, -COOH group, -P (= O) (OH) R ¹ group and phenolic OH group are mentioned.

Here, -P (= O) (OH) R ¹ represents a group represented by the following chemical formula 7, wherein R ¹ is a hydrocarbon group or a -OR ² group (R ² is a hydrocarbon group. R ¹ is preferably an aliphatic group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, Propenyl group, methoxymethyl group, ethoxymethyl group, 2-ethoxyethyl group, 2-chloroethyl group,
2-bromoethyl group, 2-methoxyethyl group, 2-fluoroethyl group, 3-chloropropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 2-methoxybutyl group, allyl group, crotonyl group, butenyl group, cyclohexyl Group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group, etc.) or an aryl group which may be substituted (eg, phenyl group, tolyl group, ethylphenyl) Group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group,
Acetylphenyl group, butoxyphenyl group, etc.) and R ² has the same content as R ¹ .

[0036]

[Chemical 7]

Examples of the phenolic OH group may include methacrylic acid esters or amides containing a hydroxyphenol or hydroxyphenyl group as a substituent.

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride to be contained include an aliphatic dicarboxylic acid anhydride and an aromatic dicarboxylic acid anhydride. Things can be mentioned.

Examples of the aliphatic dicarboxylic acid anhydride include:
Succinic anhydride, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-1,2-dicarboxylic acid anhydride ring, cyclohexane-1,2-dicarboxylic acid anhydride ring, cyclohexene-1,2- Dicarboxylic acid anhydride ring,
2,3-bicyclo [2.2.2] octadicarboxylic acid anhydride ring and the like can be mentioned, 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 and a hexyl group may be substituted.

Examples of aromatic dicarboxylic acid anhydrides include phthalic anhydride ring, naphthalene-dicarboxylic acid anhydride ring, pyridine-dicarboxylic acid anhydride ring, thiophene-dicarboxylic acid anhydride ring, and the like. These rings are
For example, chlorine atom, halogen atom such as bromine atom, alkyl group such as methyl group, ethyl group, propyl group and butyl group,
Hydroxyl group, cyano group, nitro group, alkoxycarbonyl group (as the alkoxy group, for example, methoxy group,
Ethoxy group etc.) may be substituted.

The "polymer component containing a specific polar group" as described above is, for example, a vinyl group-containing vinyl group copolymerizable with a monomer corresponding to the repeating unit represented by the general formula (I). Any compound may be used as long as it is a system compound, and it is described, for example, in "Polymer Data Handbook [Basic Edition]" edited by the Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form,
α- (2-amino) methyl, α-chloro, α-bromo, α-fluoro, α-tributylsilyl, α-cyano, β-chloro, β-bromo, 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 (eg 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, vinyl groups of dicarboxylic acids or allyl. Examples thereof include a half-ester derivative of a group, an ester derivative of a carboxylic acid or a sulfonic acid thereof, and a compound having the polar group in the substituent of an amide derivative.

The polar group-containing copolymerization component is exemplified below. Where b ^{1 is} —H, —CH ₃ , —Cl, —B
r, --CN, --CH ₂ COOCH ₃ or --CH ₂ COO
H, b ² represents —H or —CH ₃ , and f represents 2 to 1
8 is an integer, g is an integer of 1 to 12, and h is 1 to
Indicates an integer of 4.

[0043]

[Chemical 8]

[0044]

[Chemical 9]

[0045]

[Chemical 10]

[0046]

[Chemical 11]

[0047]

[Chemical 12]

Two or more kinds of the above-mentioned polymerization component containing a specific polar group may be contained in the A block,
In that case, the two or more kinds of polar group-containing components may be contained in the A block in any mode of random copolymerization or block copolymerization.

A component not containing the polar group may be contained in the A block, and examples of the component include B.
The same as the components that can be contained in the block, for example, the components represented by the general formula (I), (II) or (III) described below or the components listed as other components can be mentioned. The content of such a polar group-free component in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, but it is most preferable that such a polar group-free component is not contained in the A block. preferable.

Next, the polymerization component constituting the B block component in the AB type block copolymer [A] will be described in detail. The B block component is at least represented by the general formula (I)
The methacrylate component represented by the formula (I) is preferably 3 in the B block component.
0-100% by weight, more preferably 50-100% by weight
Contained.

In the repeating unit represented by the general formula (I), the hydrocarbon group of R ¹¹ may be substituted. R ¹¹
Is preferably an optionally substituted hydrocarbon group having 1 to 22 carbon atoms. The substituent may be any substituent other than the polar group contained in the polymerization component constituting the A block of the AB type block copolymer, and examples thereof include a halogen atom (for example, a fluorine atom and a chlorine atom). ,
A bromine atom), over ^{OZ 1, -COO-Z 1,} -OCOZ
¹ (Z ¹ represents an alkyl group having 1 to 22 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, and an octadecyl group.) And the like. The preferred hydrocarbon group is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group,
Octyl group, decyl group, dodecyl group, hexadecyl group,
Octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), which may be substituted with 4 to 18 carbon atoms. Alkenyl group (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), carbon number 7
To 12 optionally substituted aralkyl groups (eg, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group) , A methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, etc.) or Optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group, tolyl group, xylyl group,
Propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group,
Bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group and the like).

[0052] In the hydrocarbon groups R ^11, R ¹¹ may contain preferably in the case of an aliphatic group or 60% by weight of the component represented a hydrocarbon group having 1 to 5 carbon atoms in formula (I) Is preferred.

Further, in the resin [A], some or all of the repeating units represented by the general formula (I) constituting the B block component are represented by the following general formula (Ia) and general formula (Ib).
It is preferable that the methacrylate component having a specific substituent containing a benzene ring or an unsubstituted naphthalene ring having a specific substituent at the 2-position and / or the 2-position and the 6-position shown by This low molecular weight compound is especially used for resin [A
A]). Therefore, at least one repeating unit selected from the following general formulas (Ia) and (Ib) in the B block component is 30% by weight or more, particularly 50 or more, in the B block.
It is preferable that the content is ˜100 wt%.

[0054]

[Chemical 13]

[0055]

[Chemical 14]

[In the formulas (Ia) and (Ib), A ¹ and A
² are each independently a hydrogen atom and a carbon number of 1 to 10
Hydrocarbon group, chlorine atom, bromine atom, -COZ ² or-
COOZ ² (Z ² represents a hydrocarbon group having 1 to 10 carbon atoms) is represented.

B ¹ and B ² each represent a single bond or a linking group having 1 to 4 linking atoms, which bonds —COO— and the benzene ring. ] When the above-mentioned specific resin [AA] is used, the electrophotographic characteristics (particularly V ₁₀ , DRR, E) are further improved as compared with the case of the resin [A].
_1/10 ) improvement can be achieved.

The reason for this is not clear, but one reason is that due to the effect of the planar benzene ring or naphthalene ring having a substituent at the ortho position, which is the ester component of methacrylate, the zinc oxide interface in the film is affected. It is thought that this is due to the proper arrangement of these polymer molecular chains in.

In formula (Ia), preferred A ¹ and A
^{As 2} , each independently of one another, a hydrogen atom, a chlorine atom and a bromine atom, as a hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group,
Ethyl group, propyl group, butyl group, aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group) , Chloromethylbenzyl group) and aryl groups (eg phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and —COZ ² and —COOZ
² (preferable Z ² includes those described as the preferable hydrocarbon group having 1 to 10 carbon atoms). However, neither A ¹ nor A ² represents a hydrogen atom.

In the formulas (Ia) and (Ib), B¹Over
And B²Is a single bond connecting -COO- and the benzene ring.
Or- (CH₂)_a-(A represents an integer of 1 to 3),-
CH₂OCO-, -CH₂CH₂OCO-,-(CH₂
O )_b-(B represents an integer of 1 or 2), -CH₂CH
₂A connecting group having 1 to 4 connecting atoms such as O-,
More preferably, a single bond or a linking group having 1 to 2 bonding atoms is used.
Can be mentioned.

The formula (I) used in the resin [A] of the present invention is
Specific examples of the repeating unit represented by a) or (Ib) are shown below. However, the scope of the present invention is not limited to this.

[0062]

[Chemical 15]

[0063]

[Chemical 16]

[0064]

[Chemical 17]

[0065]

[Chemical 18]

Further, in this resin [A], the monomer represented by the general formula (II) is preferable as a component other than the general formula (I) and the polar group-containing component.

In the polymer component represented by the general formula (II), a ¹ and a ² are each a hydrogen atom, a halogen atom (for example, chlorine atom, bromine atom, etc.), a cyano group or a carbon number of 1 to 4
Represents an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, etc.) and the like. Particularly, it is preferable that a ¹ represents a hydrogen atom and a ² represents a methyl group.

R ¹² represents a hydrocarbon group, specifically an alkyl group, an aralkyl group or an aromatic group, preferably an aralkyl group or an aromatic group which is a hydrocarbon group containing a benzene ring or a naphthalene ring. is there. More specific R ¹²
Examples of the same include the same as R ¹¹ described in the above formula (I).

In the resin [A], in the B block formed separately from the A block composed of the above-mentioned polymerization component containing a specific polar group, the above formula (I) (preferably (Ia), ( Ib)} or the repeating unit represented by the above formula (II) may be contained in two or more kinds, and may further contain other polymerization components other than these. When two or more polymerization components are contained in the B block containing no polar group, the AB block copolymerization component is contained in the B block in any of random copolymerization and block copolymerization modes. Although it may be contained, it is preferably contained at random. However, the block B is characterized by not containing the specific polar group-containing component contained in the block A.

The other polymerization component which can be contained in the B block together with the polymerization component selected from the repeating units represented by the above formula (I) or (II) may be any component as long as it can be copolymerized with these. ..

For example, a repeating unit represented by the following general formula (III) can be mentioned.

[0072]

[Chemical 19]

[In the formula (III), V ¹ is -COO- or -OC.
_{O -, - (CH 2)} i OCO -, - (CH 2) i COO
-, - O -, - SO 2 -, - CON (R 22) -, - SO
₂ N (R ²² )-, -CO-, -CONHCOO-, -C
ONHCONH- or -C ₆ H ₄ - are presented (here,
i represents an integer of 1 or 2, and R ²² is R ¹¹ in the formula (I).
Represents the same content as). R ¹³ has the same meaning as R ¹¹ in formula (I).

[0074] V ¹ is -C ₆ H ₄ - may represent a benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group,
Chloromethyl group, methoxymethyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) and the like.

D ¹ and d ² may be the same as or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, —COOZ ³ or 1 to 8 carbon atoms.
-COOZ ³ (wherein Z ³ represents a hydrocarbon group having 1 to 18 carbon atoms) via a hydrocarbon group represent. More preferably, d ¹ and d ² may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), —COOZ ³ or — CH ₂ COOZ ³ (wherein Z ³ more preferably represents an alkyl group or an alkenyl group having 1 to 18 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, Examples thereof include dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, and the like, and these alkyl groups and alkenyl groups have the same substituents as those described above for R ^11. May be used).

As the copolymerization component constituting the repeating unit other than these, which may be further contained, for example, methacrylic acid esters, acrylic acid esters, crotonic acid esters containing substituents other than those explained in the general formula (I). In addition, α-olefins, vinyl carboxylates or allyl esters (for example, as carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, Itaconic acid esters (eg, dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrenes (eg, styrene, vinyltoluene, chlorostyrene, hydroxystyrene, etc.)
N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinylsulfone-containing compound, vinylketone-containing compound, heterocyclic vinyls (for example, vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, Vinyl imidazoline, vinyl pyrazole, vinyl dioxane, vinyl quinoline, vinyl tetrazole, vinyl oxazine and the like).

The AB block copolymer used in the resin [A] of the present invention can be produced by a conventionally known polymerization reaction method. Specifically, in the monomer corresponding to the polymer component containing the specific polar group, the polar group is preliminarily protected as a functional group, and an organometallic compound (eg, alkyllithium, lithium diisopropylamide, alkylmagnesium) is used. After synthesizing an AB block copolymer by a known so-called living polymerization reaction such as an ionic polymerization reaction with a halide or the like) or a hydrogen iodide / iodine system, a photopolymerization reaction using a porphyrin metal complex as a catalyst, or a group transfer polymerization reaction A method of forming a polar group by performing a deprotection reaction on a functional group having a protected polar group by a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction, a photodecomposition reaction, or the like. One example thereof is shown in the following reaction scheme (1).

[0078]

[Chemical 20]

These are, for example, P.M. Lutz, P.M. M
asson et al, Polym. Bull. 1
2 . , 79 (1984), B.I. C. Anderson,
G. D. Andrews et al, Macromol
ecules, 14 , 1601 (1981), K .; Ha
tada, K .; Ute. et al, Polym. J. 1
7 , 977 (1985), 18 , 1037 (198)
6), Koichi Right Hand, Koichi Hatada, Polymer Processing, 36 , 366
(1987), Toshinobu Higashimura, Mitsuo Sawamoto, Transactions on Polymers, 4
6 , 189 (1989), M.S. Kuroki, T .; Ai
da, J. Am. Chem. Soc. 109 , 4737
(1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 4.
3 , 300 (1985), D.I. Y. Sogah, W.C.
R. Hertletal. Macromolecule
It can be easily synthesized according to the synthetic method described in Les, 20 , 1473 (1987) and the like.

Further, the AB block copolymer uses a monomer in which the polar group is not protected and is irradiated with light by using a compound containing a disiocarbament group and / or a compound containing a xanthate group as an initiator. It can also be synthesized by performing a polymerization reaction below. For example, Takayuki Otsu, Polymer, 3
7 , 248 (1988), Shunichi Hinomori, Ryuichi Otsu, Pol
ym. Rep. Jap. 37 . 3508 (1988),
JP-A-64-111, JP-A-64-26619, Nobuyuki Higashi, etc., Polymer Preprints, Jap
an, 36 , (6), 1511 (1987), M.A. Ni
wa, N.W. Higashi, et al. Macro
mol. Sci. Chem. A24 (5), 567 (1
987) and the like.

Regarding protection of a specific polar group with a protecting group and elimination of the protecting group (deprotection reaction) of the present invention,
This can be easily performed by utilizing the conventionally known knowledge.
For example, various descriptions are given in the above cited document, and further,
Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer" published by Kodansha Ltd. (1977), T.S. W. Greene, "Prote
ctive Groups in Organic S
"Thensis", John Wiley & So
ns (1981), J. F. W. McOmie, "P
Protective Groups in Organ
icChemistry "Plenum Press,
The method described in detail in the review article (1973) and the like can be appropriately selected and performed.

Further, the block A is equivalent to synthesizing an azobis compound (that is, a high molecular weight azobis initiator) containing any part of the block B and using this as an initiator to form the other block. A method of synthesizing the above-mentioned monomers by radical polymerization reaction can also be used.

Specifically, it can be synthesized by the method described in Akira Ueda, Susumu Nagai, Kobunshi Shinbun, 44 , 469 (1987), Akira Ueda, Osaka City Institute of Industrial Research, 84 (1989), etc. You can

In the case of synthesizing by utilizing this reaction, the weight average molecular weight of the polymer azobis initiator is 2 × because of the ease of synthesis of the polymer azobis initiator and the regularity of the polymerization reaction of blocking. It is preferably 10 ⁴ or less.

From the above, when synthesizing by this reaction,
A method using a block A-containing polymer initiator is preferable. For example, the reaction can be carried out according to the reaction scheme (2) shown below.

[0086]

[Chemical 21]

Next, the resin [B] of the present invention will be described. The resin [B] contains the polymer component represented by the general formula (II) in an amount of 30% by weight or more and does not contain a specific polar group, and a block A portion and a specific polar group-containing polymer component.
It is a resin composed of an ABA type block copolymer containing 5 to 10% by weight of a block B part, and the polymer is schematically shown below.

(Block A Part)-(Block B Part)-
(Block A Part) Here, the block A parts at both ends may be structurally the same or different and each does not contain at least the polar group component in the block B part and is represented by the general formula (II). The polymer component may be included. The length of each polymer chain may be the same or different.

The weight average molecular weight of the resin [B] is 2 × 10 ^4.
˜1 × 10 ⁶ , preferably 3 × 10 ^{4 to} 5 × 10 ⁵ . When the molecular weight of the resin [B] is less than 2 × 10 ⁴ , the film forming ability is lowered and sufficient film strength cannot be maintained, and when the molecular weight is more than 1 × 10 ⁶ , the resin [B] of the present invention is used.
Is less effective, and the electronic characteristics are the same as those of conventionally known resins.

The glass transition point of the resin [B] is −10 ° C.
The temperature is preferably in the range of -100 to 100 ° C, more preferably 0 to 90 ° C. Resin [B] is ABA as described above.
Although it is a block copolymer of the type, the ratio of each polymer component in the whole copolymer is the same as the above.

The specific contents of the copolymer component represented by the general formula (II) and the specific polar group-containing component contained in the resin [B] are the same as those described in the resin [A]. The same thing is mentioned.

The amount of the specific polar group-containing component in the block copolymer [B] is 0.05 to 10 parts by weight per 100 parts by weight of the block B in the copolymer [B].
It is preferably contained in a proportion of 0.5 to 8 parts by weight.

The content of the polar group in the resin [B] is 0.
If it is less than 05% by weight, the initial potential is low and a sufficient image density cannot be obtained, and the polar group content is 10% by weight.
If the amount is larger than the above range, the dispersibility is lowered, the film smoothness and the high temperature and high humidity of the electrophotographic characteristic are lowered, and further, the background stain is increased when used as an offset master, which is not preferable.

Further, the specific polar group-containing polymer component contained in the resin [B] is 10% by weight based on the total amount of the specific polar group-containing polymer component contained in the resin [A]. ~
It is preferably used in the range of 50% by weight. If the amount is less than 10% by weight, the electrophotographic properties (particularly the charge retention in the dark and the photosensitivity) are significantly deteriorated, and the strength of the film is also decreased. On the other hand, if it exceeds 50% by weight, the homogenization of dispersion becomes insufficient, the electrophotographic characteristics are deteriorated, and the water retention property is lowered as an offset original plate.

On the other hand, the amount of the polymer component represented by the general formula (II) contained at least as the polymer component of the block A portion in the resin [B] is preferably 30% by weight in the total weight of the block A portion. % To 100% by weight, more preferably 50% to 100% by weight.

Further, in the block A portion of the resin [B], other copolymer component may be contained in addition to the above-mentioned polymer component, and such polymer component is preferably represented by the general formula (III). The polymer component corresponding to a repeating unit is mentioned.

Further, as a polymer component which can be contained in the A block together with the polymer component represented by the formula (III), it corresponds to another repeating unit copolymerizable with the polymer component represented by the formula (III). Examples thereof include acrylonitrile, methacrylonitrile, and heterocyclic vinyls (eg, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, 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 component of the resin [B].

Next, the polymer component in the block B portion of the resin [B] will be described. Specific examples of the polymerization component containing a specific polar group in the block B portion of the ABA type block copolymer (resin [B]) of the present invention include the polymer containing a specific polar group of the resin [A] described above. The same as the united components can be mentioned.

Two or more kinds of the polymerization component containing the specific polar group as described above may be contained in the block B part, and in that case, the two or more kinds of the polar group-containing component are contained in the block B part. In the above, it may be contained in any form of random copolymerization or block copolymerization.

In addition, in the block B part, other copolymer component may be contained in addition to the above polar group-containing polymer component. Examples of the other copolymerization component include the polymer components that can be contained in the block A part, that is, those described as the general formulas (II) and (III) and other polymerization components. These polymerization components are 90 to 99.95 parts by weight in 100 parts by weight of block B.

Preferred components other than the polar group-containing component of the block B portion as the polymerization component are those represented by the general formula (I
In the component represented by I), both a ¹ and a ² represent a hydrogen atom, and the hydrocarbon of R ¹² has 1 to 6 carbon atoms.
An optionally substituted alkyl group (for example, a methyl group,
Ethyl group, propyl group, butyl group, pentyl group, hexyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-
Methoxyethyl group, 2-thienylethyl group, 2,3-dichloropropyl group, etc.) can be mentioned. Further, in the component represented by the general formula (III), d ¹
Also, those in which both of d and d ² represent a hydrogen atom and the hydrocarbon of R ¹³ represents the same as those described above as preferable in R ¹² are also preferable components. Further, those listed as other components can be used, but in this case, it is preferable that the amount of these copolymerization components is 0.5 to 10 parts by weight in 100 parts by weight of block B.

ABA type block copolymer of the present invention [B]
Can be produced by a conventionally known polymerization reaction method. Specific examples include those described in the synthesis of resin [A]. One example is the reaction formula (C) below.
It was shown to.

[0103]

[Chemical formula 22]

These include, for example, the references cited in the synthesis of the resin [A], M. Morton, T .;
E. Helminiak et al. Polym.
Sci. 57 , 471 (1962), B.I. Gordo
n III, M.N. Blumenthal, J. et al. E. Lo
ftus, Polym. Bull. , 11 , 349
(1984), R.A. B. Bates, W.C. A. Beav
ers et al. Org. Chem. , 44 , 3
It can be easily synthesized according to the synthesis method described in 800 (1979) and the like.

Regarding protection of a specific polar group of the present invention with a protecting group and elimination of the protecting group (deprotection reaction),
It can be easily carried out by utilizing the conventionally known knowledge as described in the synthesis of the resin [A].

Further, an ABA type block copolymer [B]
Is the same as in the case of synthesizing the resin [A], using a monomer that does not protect the polar group, and using a compound containing a dithiocarbamate group and / or a compound containing a xanthate group as an initiator, It can also be synthesized by performing a polymerization reaction under irradiation.

As the binder resin used for the photoconductive layer of the present invention, in addition to the resins [A] and [B] of the present invention, known resins for inorganic photoconductors described above can be used in combination.
However, the proportion of these other resins used is the total amount of the binder resin 10
A range not exceeding 30 parts by weight in 0 parts by weight is preferable. If this ratio is exceeded, the effect of the present invention will be significantly reduced.

Typical other resins that can be used in combination are, for example, vinyl chloride-vinyl acetate copolymers, styrene-butadiene copolymers, styrene-methacrylate copolymers, methacrylate copolymers, acrylate copolymers. , Vinyl acetate copolymer, polyvinyl butyral, alkyd resin, silicone resin, epoxy resin, epoxy ester resin, polyester resin and the like.

Specifically, Ryuji Shibata, Jiro Ishiwata, "Polymer," Vol. 17, p. 278 (1968), Harumi Miyamoto.
Hidehiko Takei "Imaging" 1973 (No.8) 9th
Pp. Koichi Nakamura, "Practical Technology of Binders for Insulating Materials," Chapter 10, C.I. H. C. Published (1985), D.M. D.
Tatt, S. C. Heidecker, Tappi,
49 (No. 10), 439 (1966), E.I. S. B
Altazzi, R.A. G. Blanklotte et
al, Photo. Sci. Eng. 16 (No.
5), 354 (1972), Nguyen Chan Kay, Isamu Shimizu, Eiichi Inoue, The Institute of Electrophotography 18 (No. 2),
28 (1980), JP-B-50-31011, JP-A-53-54027, JP-A-54-20735, and JP-A-57-57.
The resins disclosed in JP-A-202544 and JP-A-58-68046 are cited.

The total amount of the binder resin used in the photoconductive layer of the present invention is 1 part with respect to 100 parts by weight of the inorganic photoconductor.
The amount is preferably 0 to 100 parts by weight, more preferably 15 to 50 parts by weight.

The ratio of the resin [A] and the resin [B] used in the present invention is 0.05 to 0.05 by weight ratio of resin [A] / resin [B].
It is preferably 0.8 / 0.95 to 0.20, more preferably 0.10 to 0.50 / 0.90 to 0.50.
Is.

When the total amount ratio of the binder resin is 10 parts by weight or less, the film strength of the photoconductive layer cannot be maintained. On the other hand, when the amount is 100 parts by weight or more, the electrostatic characteristics are deteriorated and the copy image is deteriorated in the actual image pickup property.

If the weight ratio of the resin [A] to the resin [A] and the resin [B] of the present invention is not more than 0.05, the effect of improving the electrostatic characteristics is diminished. On the other hand, 0.8
If the above is the case, the film strength of the photoconductive layer cannot be sufficiently maintained (particularly as an electrophotographic lithographic printing plate precursor).

Examples of the inorganic photoconductive material used in the present invention include zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide and lead sulfide.

The spectral sensitizing dye used in the present invention includes
If necessary, various dyes are used alone or in combination. For example, Harumi Miyamoto, Hidehiko Takei, Imaging 1973 (N
o. 8) Page 12, C.I. J. Young et al., RCA R
view 15 , 469 (1054), Kouhei Kiyota,
IEICE Transactions J63 - C (No. 2 ), 97
(1980), Yuji Harasaki et al., Industrial Science Magazines 66 78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35 , 2
08 (1972) and other general reference carbonium dyes,
Diphenylmethane dye, triphenylmethane dye, xanthene dye, phthalein dye, polymethine dye (for example, oxonol dye, merocyanine dye, cyanine dye, rhodacyanine dye, styryl dye, etc.), phthalocyanine dye (may contain metal), etc. Is mentioned.

More specifically, those mainly containing carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes are disclosed in Japanese Examined Patent Publication No. 51-45.
No. 2, JP-A Nos. 50-90334 and 50-11422.
No. 7, No. 53-39130, No. 53-82353,
US Pat. Nos. 3,052,540 and 4,054,45
No. 0, those described in JP-A-57-16456, and the like.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include F.I. M. Harmmer "The Cyani
neDyes and Related Compou
The dyes described in "nd" and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384 and 3,11.
0,591, 3,121,008, 3,12
5,447, 3,128,179 and 3,13
2,942, 3,622,317, British Patents 1,226,892, 1,309,274, 1,405,898, Japanese Patent Publication Nos. 48-7814, 5
Examples thereof include dyes described in No. 5-18892.

Further, as a polymethine dye for spectrally sensitizing a near-infrared region to an infrared region having a long wavelength of 700 nm or more, JP-A No. 4/1992 has been proposed.
No. 7-840, No. 47-44180, and Japanese Patent Publication No. 51-4
1061, JP-A-49-5034, and JP-A-49-451.
No. 22, No. 57-46245, No. 56-35141.
No. 57-157254, No. 61-26044,
No. 61-27551, U.S. Pat. No. 3,619,154.
No. 4,175,956, "Research D
isclosure ", 1982, 216, 117-
Examples thereof include those described on page 118. The photoconductor of the present invention is excellent in that its performance does not easily change depending on the sensitizing dye even when various sensitizing dyes are used in combination. Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers such as chemical sensitizers can be used in combination. For example,
Review Article: Imaging 1973 (No. 8) No. 1
Electron-accepting compounds (for example, halogen, benzoquinone, chloranil, acid anhydride organic carboxylic acid, etc.) in the review article on page 2, etc., Hiroshi Komon, et al., "Development and practical application of bacterial photoconductive materials and photoconductors" Chapters 4 to 6 • Polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, and the like, which are the reference examples of the Japanese Science Information Publishing Co., Ltd. (1986).

The addition amount of these various additives is not particularly limited, but usually 0.0 to 100 parts by weight of the photoconductor.
001 to 2.0 parts by weight. The photoconductive layer has a thickness of 1 to 1.
00μ, particularly 10 to 50μ is suitable.

When the photoconductive layer is used as the charge generation layer of the laminated type photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is 0.01 to 1 .mu.m, particularly 0.05 to 0. 5
μ is preferred.

In some cases, an insulating layer may be additionally provided for the purpose of protecting the photoreceptor and improving durability and dark decay characteristics.
At this time, the insulating layer is set to be relatively thin, and the insulating layer provided when the photoconductor is used in a specific electrophotographic process is set to be relatively thick.

In the latter case, the insulating layer has a thickness of 5 to 70.
μ, particularly 10 to 50 μ. Examples of the charge transport material for the laminated photoreceptor include polyvinyl carbazole, oxazole dyes, pyrazoline dyes, triphenylmethane dyes and the like. The thickness of the charge transport layer is 5 to 4
0 μ, particularly 10 to 30 μ is preferable.

Typical resins used for forming the insulating layer or the charge transport layer are polystyrene resin, polyester resin, cellulose resin, polyether resin,
Vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl chloride copolymer resin, polyacrylic resin, polyolefin resin, urethane resin, polyester resin, epoxy resin, melamine resin, silicone resin thermoplastic resin and curable resin are appropriately used. ..

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably conductive, and as the conductive support, just as in the conventional case, for example, metal, paper, plastic sheet or the like is basically impregnated with a low resistance substance. Conductive treated by, for example, the basic back surface (the surface opposite to the surface on which the photosensitive layer is provided) to have conductivity, and at least one layer coated for the purpose of preventing curling,
Paper having a water-resistant adhesive layer provided on the surface of the support, one having at least one precoat layer provided on the surface layer of the support as required, and a substrate made of electroconductive plastic such as Al vapor-deposited into paper. Those laminated to can be used.

Concrete examples of the conductive substrate or the conductive material are Yukio Sakamoto, Electrophotography, 14 (No.
1), P2-11 (1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry", Polymer Publishing (1975), M.M. F. Hoo
ver., J. Macromol. Sci. Chem. A
-4 (6), 1327 to 1417 (1970) and the like are used.

The electrophotographic photosensitive member of the present invention can be used in applications utilizing any conventionally known electrophotographic process. That is, the photoconductor of the present invention can be used for both PPC and CPC recording systems, and
As the developer, any combination of a dry developer and a liquid developer can be used.

In particular, since it is possible to form a copy image of a high-definition original faithfully, the effect of the present invention is more exerted when it is used in combination with a liquid developer. Also, by combining with a color developer, not only black and white copy images,
It can also be applied to color reproduction images (for example, Kuro Takizawa, “Photo Industry” 33 , 34 (1975), Masayasu Anzai, “Technical Research Report of IEICE 77 , 17 (197)”.
7 years) and the like).

Further, it is effective in a system used for other purposes using the electrophotographic process in recent years. For example, the photoconductor of the present invention using photoconductive zinc oxide as a photoconductor is used as an offset lithographic printing plate precursor and is made of photoconductive zinc oxide or photoconductive titanium oxide which is pollution-free and has a good whiteness. The photoconductor can be used as an underprinting material used in an offset printing process, a color group, or the like.

[0129]

EXAMPLES Examples of the present invention will be illustrated below, but the contents of the present invention are not limited thereto. [Synthesis of Resin [A]] Synthesis Example 1 of Resin [A] 1: [A-1] 95 g of ethyl methacrylate and tetrahydrofuran 2
Thoroughly degas the mixed solution of 00g under nitrogen stream, and
Cooled to ° C. 1,1-diphenylbutyllithium 1.
5 g was added and reacted for 12 hours. Furthermore, in this mixed solution,
A mixed solution of 5 g of triphenylmethyl methacrylate and 5 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream and then added, and the mixture was further reacted for 8 hours. After this mixture was heated to 0 ° C., 10 ml of methanol was added and reacted for 30 minutes to terminate the polymerization. The resulting polymer solution was stirred at a temperature of 30
The temperature was adjusted to 0 ° C., 3 ml of a 30% hydrogen chloride ethanol solution was added thereto, and the mixture was stirred for 1 hour. Then, the solvent was distilled off from the reaction mixture under reduced pressure until the total amount was halved, followed by reprecipitation in 1 liter of petroleum ether.

The weight average molecular weight (Mw) of the polymer obtained by collecting the precipitate and drying it under reduced pressure was 8.5 × 10 ³ , and the yield was 7
It was 0 g.

[0131]

[Chemical formula 23]

Synthesis Example 2 of Resin [A]: [A-2] A mixed solution of 46 g of n-butyl methacrylate, 0.5 g of (tetraphenylporphinato) aluminum methyl and 60 g of methylene chloride was heated at a temperature of 30 ° C. under a nitrogen stream. And This was irradiated with 300 W-xenon lamp light from a distance of 25 cm through a glass filter and reacted for 12 hours. This mixture was further mixed with benzyl methacrylate 4
After irradiating with light for 8 hours in the same manner, 3 g of methanol was added to this reaction mixture and stirred for 30 minutes to stop the reaction. Then Pd-C was added to the reaction mixture at a temperature of 25
The catalytic reduction reaction was carried out at 0 ° C for 1 hour.

After filtering off the insoluble matter, 500 ml of petroleum ether
The precipitate was collected and dried. The polymer obtained had Mw of 9.3 × 10 ³ and a yield of 33 g.

[0134]

[Chemical formula 24]

Synthesis Example 3 of resin [A]: [A-3] 90 g of 2-chloro-6-methylphenyl methacrylate
A mixed solution of toluene and 200 g of toluene was thoroughly degassed under a nitrogen stream and cooled to 0 ° C. Then 1,1-diphenyl-3
-Methylpentyllithium (2.5 g) was added, and the mixture was stirred for 6 hours. Further, 10 g of 4-vinylphenyloxytrimethylsilane was added to this mixture and stirred for 6 hours, then 3 g of methanol was added and stirred for 30 minutes.

Then, 10 g of a 30% hydrogen chloride ethanol solution was added to this reaction mixture, and the mixture was stirred at 25 ° C. for 1 hour, then reprecipitated in 1 liter of petroleum ether and the collected precipitate was washed twice with 300 ml of diethyl ether. Dried. The polymer obtained had Mw of 7.8 × 10 ³ and a yield of 58 g.

[0137]

[Chemical 25]

Synthesis Example 4 of resin [A]: [A-4] A mixture of 95 g of phenyl methacrylate and 4.8 g of benzyl N, N-diethyldithiocarbamate was sealed in a container under a nitrogen stream and heated to a temperature of 60 ° C. Warmed. To this, 4
Photopolymerization was carried out by irradiating with a 00W high pressure mercury lamp from a distance of 10 cm through a glass filter for 10 hours.

Acrylic acid (5 g) and methyl ethyl ketone (180 g) were added thereto, the atmosphere was replaced with nitrogen, and light was again irradiated for 10 hours. The obtained reaction product was reprecipitated in 1.5 liters of hexane, collected, and dried. The polymer obtained has a Mw of 9.5 × 1.
0 ³ and the yield was 68 g.

[0140]

[Chemical formula 26]

Synthesis Examples 5 to 19 of Resin [A]: [A-5]
~ [A-18] A resin [A] shown in Table A below was synthesized in the same manner as in Synthesis Example 1 of the resin [A]. Mw of each resin is 6 × 10 ³ ~
It was 9.5 × 10 ³ .

[0142]

[Table 1]

[0143]

[Table 2]

[0144]

[Table 3]

Synthesis Examples 19 to 23 of Resin [A]: [A-1
9] to [A-23] Resin [A] shown in Table B below was synthesized in the same manner as in Synthesis Example 4 of resin [A]. Mw of each resin is 8 × 10 ³ ~
It was 1 × 10 ⁴ .

[0146]

[Table 4]

[Synthesis of Resin [B]] Synthesis Example of Resin [B] 1: [B-1] A mixed solution of 90 g of methyl acrylate, 10 g of acrylic acid and 13.4 g of an initiator [I-1] having the following structure was prepared. The temperature was raised to 40 ° C. under a nitrogen stream. This solution was irradiated with light from a high-pressure mercury lamp of 400 W at a distance of 10 cm through a glass filter for 10 hours for photopolymerization. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to give a weight average molecular weight (Mw) of 2 × 10 7 in a yield of 78 g.
⁴ (hereinafter Mw in Resin [B] is a GPC method value in terms of polystyrene) was obtained.

[0148]

[Chemical 27]

A mixed solution of 10 g of the above polymer, 65 g of methyl methacrylate, 25 g of methyl acrylate and 100 g of tetrahydrofuran was heated to a temperature of 50 ° C. under a nitrogen stream. This mixture was irradiated with light under the same conditions as above.
It was carried out for 5 hours.

The reaction product was reprecipitated in 1.5 liters of methanol, and the precipitate was collected and dried to obtain a polymer having a yield of 75 g and a Mw of 8 × 10 ⁴ .

[0151]

[Chemical 28]

Synthesis Example 2 of Resin [B]: [B-2] In Synthesis Example 1 of Resin [B], the initiator [I-1] 1
A reaction treatment was conducted under the same conditions as in Synthesis Example 1 except that 14.8 g of an initiator having the following structure was used instead of 3.4 g, and M
73 g of a polymer of w5 × 10 ⁴ was obtained.

[0153]

[Chemical 29]

[0154]

[Chemical 30]

Synthesis Example 3 of Resin [B]: [B-3] 80 g of methyl methacrylate, 20 of ethyl acrylate
g, a mixed solution of 13.5 g of an initiator [I-3] having the following structure and 150 g of tetrahydrofuran was heated at a temperature of 50 under a nitrogen stream.
Warmed to ° C. This mixture was irradiated with light under the same conditions as in Synthesis Example 1 for 10 hours.

[0156]

[Chemical 31]

The reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected by filtration and dried. A mixed solution of 60 g of the polymer, 30 g of methyl acrylate, 10 g of methacrylic acid and 100 g of tetrahydrofuran was heated under a nitrogen stream at a temperature of 5
The temperature was set to 0 ° C. and light irradiation was performed for 10 hours in the same manner as above.

The reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to obtain 73 g of powder. Further, 60 g of this polymer, 30 g of ethyl methacrylate, 10 g of methyl acrylate and 100 g of tetrahydrofuran.
The mixed solution of was heated to a temperature of 50 ° C. in a nitrogen stream. This was irradiated with light for 10 hours in the same manner as above.

The reaction product was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried to obtain 76 g of a polymer having Mw of 9 × 10 ⁴ .

[0160]

[Chemical 32]

Synthesis Example 4 of resin [B]: [B-4] 50 g of methyl methacrylate and tetrahydrofuran 1
Thoroughly degas the mixed solution of 00g under nitrogen stream, and
Cooled to ° C. 1,1-diphenylpentyltium 1.
2 g was added and reacted for 12 hours. Furthermore, in this mixed solution,
A mixed solution of 30 g of methyl acrylate, 3 g of triphenylmethyl methacrylate and 50 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream and added, and the mixture was reacted for 8 hours. Further, a mixed solution of 50 g of methyl methacrylate and 50 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream, then added to the above reaction solution, and reacted for 10 hours.

After the mixture was brought to 0 ° C., methanol 1
Polymerization was stopped by adding 0 ml and reacting for 30 minutes. The resulting polymer solution was heated to a temperature of 30 ° C. under stirring, and
3 ml of 0% hydrogen chloride ethanol solution was added and stirred for 1 hour. Next, the solvent was distilled off from the reaction mixture under reduced pressure until the total amount became half, and the mixture was reprecipitated in 1 liter of methanol.

The polymer obtained by collecting the precipitate and drying under reduced pressure had a Mw of 8.5 × 10 ⁴ and a yield of 65 g.

[0164]

[Chemical 33]

Synthesis Example 5 of Resin [B]: [B-5] Methyl methacrylate 70 g, methyl acrylate 30
A mixed solution of 0.5 g of g (tetraphenylporphinate) aluminum methyl and 200 g of methylene chloride was heated to a temperature of 30 ° C. under a nitrogen stream. This was irradiated with light of 300 W-xenon lamp through a glass filter from a distance of 25 cm and reacted for 12 hours. Further to this mixture
40 g of ethyl acrylate and 6.4 g of benzyl methacrylate were added, and the mixture was reacted in the same manner for 10 hours under light irradiation. Furthermore, 70 g of methyl methacrylate was added to this mixture.
And 30 g of methyl acrylate were added, and the mixture was similarly reacted under light irradiation for 12 hours. 3 g of methanol was added to this reaction mixture.
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 the insoluble matter was filtered off, it was reprecipitated in 2 liters of methanol, and the precipitate was collected by filtration and dried to give a polymer 180.
g was obtained. Its Mw was 8.5 × 10 ⁴ .

[0167]

[Chemical 34]

Synthesis Examples 6 to 15 of Resin [B]: [B-6]
~ [B-15] In the same reaction method as in Synthesis Example 2 of Resin [B], the following Table-C was used.
The resin [B] shown in was synthesized.

The Mw of the obtained copolymer was 5 × 10 ^{4 to} 7
It was in the range of × 10 ⁴ .

[0170]

[Table 5]

[0171]

[Table 6]

[0172]

[Table 7]

Synthesis Examples 16 to 19 of Resin [B]: [B-1
6] to [B-19] In the synthesis example 1 of the resin [B], the initiator [I-1] 1
5 × 10 each of the initiators in Table D below was used instead of 3.4 g.
^{The same procedure} as in Synthesis Example 1 was carried out ^{except that -2} mol was used.
-1] was obtained.

The Mw of each polymer is 7 × 10 ^{4 to} 8.5 × 1.
It was 0 ⁴ .

[0175]

[Table 8]

Synthesis Examples 20 to 26 of Resin [B]: [B-2
0] to [B-26] A mixed solution of 90 g of benzyl methacrylate, 10 g of acrylic acid and 7.8 g of an initiator [I-8] having the following structure was heated to a temperature of 40 ° C under a nitrogen stream. This was reacted for 5 hours under the same light irradiation conditions as in Example 1. The polymer obtained was dissolved in 200 g of tetrahydrofuran, and then methanol 1.0
It reprecipitated in liter, and the precipitate was collected by filtration and dried.

[0177]

[Chemical 35]

A mixed solution of 20 g of this polymer, each of the monomers corresponding to the polymer components shown in Table E below, and 100 g of tetrahydrofuran was treated in the same manner as above and irradiated with light to react for 15 hours. ..

Each of the obtained polymers was reprecipitated in 1.5 liter of methanol, and the precipitate was collected by filtration and dried to obtain Mw 4 × 1.
60 × 70 g of a polymer of 0 ^{4 to} 7 × 10 ⁴ was obtained.

[0180]

[Table 9]

[0181]

[Table 10]

Example 1 and Comparative Examples 1 and 2 6 g of resin [A-3] (as solid content), resin [B-
1] 34 g (as solid content), photoconductive zinc oxide 20
A mixture of 0 g, 0.018 g of the cyanine dye [I] having the following structure, 0.15 g of phthalic anhydride and 300 g of toluene in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) was rotated at a rotation speed of 6 × 1.
Disperse at 0 ³ rpm for 8 minutes to prepare a photosensitive layer-formed product,
This is applied to a conductively treated paper with a wire bar so that the dry adhesion amount becomes 25 g / m ² , dried at 110 ° C for 10 seconds, and then left in the dark at 20 ° C and 65% RH for 24 hours. By doing so, an electrophotographic photosensitive material was produced.

[0183]

[Chemical 36]

Comparative Example 1 Example 1 was repeated except that 34 g of resin [R-1] having the following structure was used instead of 34 g of resin [B-1] in Example 1.
An electrophotographic photosensitive material was produced in the same manner as in.

[0185]

[Chemical 37]

Comparative Example 2 An electrophotographic photosensitive material was prepared in the same manner as in Example 1, except that 34 g of the resin [B-1] was replaced with the resin [R-2] having the following structure. did.

[0187]

[Chemical 38]

With respect to these photosensitive materials, electrostatic characteristics, image pick-up properties and environmental conditions (20 ° C., 65% RH), (30
The imaging properties were examined under the conditions of (° C., 80% RH) and (15 ° C., 30% RH).

The above results are shown in Table-F.

[0190]

[Table 11]

Embodiments of the evaluation items shown in Table-F are as follows. Note 1) Electrostatic characteristics: In a dark room at a temperature of 20 ° C and 65% RH,
-6k using a paper analyzer (Paper Analyzer SP-428 manufactured by Kawaguchi Electric Co., Ltd.) for each light-sensitive material
After corona discharge was performed for 20 seconds at V, the surface potential V ₁₀ at this time was measured after standing for 10 seconds. Then, the potential V ₁₀₀ after standing still in the dark for 90 seconds was measured, and the potential retention after dark decay for 90 seconds, that is, the dark decay retention rate [DRR (%)] was calculated as (V ₁₀₀ / V ₁₀ ) × 100 (%).

The surface of the photoconductive layer was -40 by corona discharge.
After being charged to 0 V, the surface of the photoconductive layer was gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm).
The time until the surface potential (V ₁₀ ) is attenuated to 1/10 by irradiation with light is obtained. From this, the exposure amount E _1/10 (erg / cm
² ) is calculated. Environmental conditions at the time of measurement are 20 ° C and 65% R
H (I), 30 ° C 80% RH (II) and 15 ° C 30% R
Performed with H (III). Note 2) Imaging property: After leaving each light-sensitive material under the following environmental conditions for one day and night, charge each light-sensitive material at −6 kV, and use 2.8 mW output gallium-aluminum-arsenic as a light source and a semiconductor laser (oscillation wavelength 780 nm). ), A pitch of 25 μm on the surface of the photosensitive material under an irradiation amount of 64 erg / cm ^2.
m and a scanning speed of 300 m / sec. After speed exposure, ELP-T (manufactured by Fuji Photo Film Co., Ltd.) was used as a liquid developer, and was developed, and isoparaffin Isopar G (manufactured by Esso Kagaku) was used as a solvent rinse. Copy image (fogging and image quality) obtained by fixing after washing with liquid
Was visually evaluated.

Environmental conditions at the time of imaging are 20 ° C. and 65% RH
(I), 30 ° C 80% RH (II) and 15 ° C 30% RH
Conducted in (III). As shown in Table-H, the light-sensitive material of the present invention had good electrostatic characteristics even when environmental conditions changed, and the actual copied image was free of background fog and the copied image quality was clear. On the other hand, Comparative Examples 1 and 2 showed good imaging properties under normal temperature and normal humidity (I) conditions, but under high temperature and high humidity conditions (II),
Although it does not necessarily correspond to the electrostatic characteristic, unevenness occurs in the intermediate density of the continuous tone portion of the copy document which is a high-definition copy image.

Further, even after the rinsing treatment, a slight background fog remained without being removed. Further, under the condition of low temperature and low humidity (III), minute white spots were randomly generated in the solid image area.

From the above, an electrophotographic photoreceptor satisfying electrostatic characteristics and image pick-up properties (especially high-definition images) can be obtained only when the resin of the present invention is used, and particularly, a semiconductor laser light scanning exposure method is used. It became clear that it would be superior to the photoconductor system of. Example 2 and Comparative Examples 3 and 4 5 g of resin [A-21] (as solid content), resin [B-
2] 35 g (as solid content), photoconductive zinc oxide 20
0 g, 0.020 g of methine dye (II) having the following structure, N-
Hydroxymaleimide 0.20g and toluene 30
An electrophotographic light-sensitive material was produced by operating 0 g of the mixture in the same manner as in Example 1.

[0196]

[Chemical Formula 39]

Comparative Example 3 Example 2 was repeated except that 35 g of the resin [R-3] having the following structure was used in place of 35 g of the resin [B-2] in Example 2.
An electrophotographic photosensitive material was produced in the same manner as in.

[0198]

[Chemical 40]

Comparative Example 4 Example 2 was repeated except that 35 g of the resin [R-4] having the following structure was used in place of 35 g of the resin [B-2] in Example 2.
An electrophotographic photosensitive material was produced in the same manner as in.

[0200]

[Chemical 41]

The film properties (smoothness of the surface) of each light-sensitive material, the mechanical strength of the photoconductive layer, the electrostatic property, the image pick-up property, and the environmental conditions were 30 ° C., 80% RH and 15 ° C., 30% RH. The electrostatic characteristics and the image pickup property at the time were examined. Furthermore, the printability when used as an original plate for electrophotographic lithographic printing was examined. The results are shown in Table-G.

[0202]

[Table 12]

Embodiments of the evaluation items shown in Table-G are as follows. Note 3) Smoothness of surface layer: The photosensitive material obtained was measured using a Beck's smoothness tester (manufactured by Kumagai Riko Co., Ltd.) with an air capacity of 1 c.
The smoothness (sec / cc) was measured under the condition of c. Note 4) Mechanical strength of photoconductive layer: Emery paper (#) was applied to the surface of the obtained light-sensitive material using Haydon-14 type surface test material (manufactured by Shinto Chemical Co., Ltd.) with a load of 75 g / cm ^2. 10
00) was repeated 1000 times to remove the abrasion powder, and the residual film rate (%) was calculated from the weight reduction of the photosensitive layer and defined as the mechanical strength. Note 5) Raw plate water retention: Desensitizing treatment liquid EPL-EX (Fuji Photo Film Co., Ltd.) for each light-sensitive material (not plate-making)
Solution) was diluted 5 times with distilled water and passed through an etching processor twice to desensitize the surface of the photoconductive layer. Then, distilled water was used as fountain solution to prepare an offset printing machine (( ) Hamada Printing Machinery Works 611XLA-II type)
Then, the degree of background stain of the 50th printed material after printing was visually evaluated (corresponding to a forced condition for examining the degree of water retention of the desensitized original plate). Note 6) Printing durability: After making a plate under the same conditions as in Note 2) above to form a toner image and forming a toner image, the plate was passed twice through an etching processor using ELP-EX to be desensitized.
This is used as an offset master and applied to an offset printing machine (Oliver 52 type manufactured by Sakurai Seisakusho Co., Ltd.) to show the number of prints that can be made without causing stains on the non-image area of the printed matter and on the image quality of the image area (the number of printed sheets is The larger the number, the better the printability.)

As shown in Table-G, the light-sensitive material of the present invention comprises
The smooth film of the photoconductive layer had good mechanical strength and electrostatic properties, and the actual copied image had no background fog and the copied image quality was clear. It is presumed that this is because the photoconductor and the binder resin are sufficiently adsorbed and the particle surface is covered. For the same reason, even when used as an offset master original plate, the desensitizing treatment with the desensitizing treatment liquid proceeds sufficiently, and even if the water retention under the forced condition is evaluated, it is sufficiently hydrophilized, and the ink adhesion does not occur at all. I was not able to admit. Even when the print was actually printed and the print stain was observed, the print stain was not recognized at all, and 10,000 prints with clear image quality were obtained.

On the other hand, in Comparative Example 3 and Comparative Example 4, when the image capturing condition becomes severe, the non-image portion is slightly stained, and unevenness occurs in the high-definition continuous gradation portion. A problem such as white unevenness in the solid image portion occurred.

Further, ink adhesion appeared in the water retention of the stencil plate which was desensitized as the offset master original plate. The actual printability was only 4 to 6,000 sheets. The above is a condition in which the resin [A] and the resin [B] of the present invention properly interact with the zinc oxide particles, and the desensitizing reaction by the desensitizing treatment liquid easily and sufficiently proceeds. It shows that the film is formed and that the film strength is remarkably improved by the action of the resin [B]. Examples 3 to 22 Resin [A-21] and resin [B-2] in Example 2
Instead of, each resin [A] and each resin [B] in the following Table-H
In the same manner as in Example 2 except that the above was replaced with, electrophotographic photosensitive members were produced.

[0207]

[Table 13]

The electrostatic characteristics and the image pickup property of each light-sensitive material were measured in the same manner as in Example 1. Each of the photosensitive materials had good electrostatic characteristics. When the actual imaging properties of these light-sensitive materials were examined, it was possible to obtain a clear copy image with good reproducibility of fine lines and characters, no generation of halftone unevenness, and no background fog.

Further, when printing was carried out in the same manner as in Example 2 using the offset master original plate, at least 10,000 sheets or more could be printed satisfactorily. From the above, each photosensitive material of the present invention, the smoothness of the photoconductive layer,
It was good in all respects of film strength, electrostatic properties and printability. Examples 23 to 26 An electrophotographic photosensitive material was prepared under the same conditions as in Example 1 except that the methine dye [I] used in Example 1 was replaced with the dye shown in Table I below.

[0210]

[Table 14]

[0211]

[Table 15]

The light-sensitive materials of the present invention are all excellent in chargeability, dark charge retention rate, and photosensitivity, and actually copied images are high temperature / high humidity (30 ° C., 80% RH) and low temperature / low humidity (15 ° C., 30).
% RH), a clear image with no background fog was obtained even under severe conditions. Examples 27 and 28 and Comparative Example 5 6.5 g of either resin [A-1] (Example 27) or resin [A-7] (Example 28), resin [B-23] 3
A mixture of 3.5 g, zinc oxide 200 g, uranine 0.02 g, methine dye (VII) 0.03 g having the following structure, methine dye (VIII) 0.03 g having the following structure, p-hydroxybenzoic acid 0.18 g and toluene 300 g. Was dispersed in a homogenizer at a rotation speed of 7 × 10 ³ rpm for 6 minutes to prepare a photosensitive layer-formed product, which was coated on a conductive-treated paper with a wire bar so that the dry adhesion amount was 25 g / m ^2. Then 1
It was dried at 10 ° C. for 20 seconds. Then in the dark at 20 ℃, 65
Each electrophotographic photosensitive member was produced by leaving it under a condition of% RH for 24 hours.

[0213]

[Chemical 42]

[0214]

[Chemical 43]

Comparative Example 5 In place of the resin [B-23] used in Example 27, 33.5 g of the resin [R-2] used in Comparative Example 2 was used.
A light-sensitive material was prepared in the same manner as in Example 27. Each characteristic of each light-sensitive material was examined in the same manner as in Example 1. The results are summarized in Table-J below.

[0216]

[Table 16]

In the above measurement, the same operation as in Example 1 was performed except that the electrostatic characteristic and the image pickup property were in accordance with the following operations. Note 7) Method for measuring E _1/10 of electrostatic characteristics: After the surface of the photoconductive layer was charged to −400 V by corona discharge, the surface of the photoconductive layer was irradiated with visible light with an illuminance of 2.0 lux, and the surface The time until the potential (V ₁₀ ) decays to 1/10 is obtained, and the exposure amount E _1/10 (lux · sec) is calculated from this. Note 8) Imaging property: Obtained by allowing each light-sensitive material to stand for one day under the following environmental conditions and then using EPL-404V (manufactured by Fuji Photo Film Co., Ltd.) as a toner to make a plate using a fully automatic plate-making machine EPL-404V. The copied images (fog, image quality) thus obtained were visually evaluated. Environmental conditions during imaging are 20 ° C and 65% RH
(I), 30 ° C 80% RH (II) and 15 ° C 30% RH
Conducted in (III). However, the original for copying (that is, the original copy) was prepared by cutting out and pasting other originals.

In each of the light-sensitive materials of the present invention, the mechanical strength of the photoconductive layer was good, but Comparative Example 5 was lower than this. As for the electrostatic properties, they all showed good performance at room temperature and normal humidity (I), but E _1/10 decreased especially at low temperature and low humidity. The photosensitive material of the present invention has good electrostatic characteristics, and
Example 28 using a resin [AA] having a specific substituent
Was very good, and in particular, the value of E _1/10 was small.

Examination of the actual image pickup property shows that Comparative Example 5
In addition to the original as a copy image, the frame (that is, the trace of pasting) of the part cut out and stuck was recognized as the background stain of the non-image part. Furthermore, the environmental conditions during imaging are high temperature and high humidity (I
I), under low temperature and low humidity (III), unevenness was observed in the halftone region of the continuous tone part of the copied image, and slight unevenness of white spots was observed in the solid image part. However, in all cases of the present invention, clear images having no background stain were obtained.

Further, when these were subjected to desensitization treatment as offset printing original plates and printed, all of the present invention produced 10,000 printed matters with clear image quality without scumming.
However, in Comparative Example 5, the above-mentioned sticking mark was not removed even by the desensitizing treatment, and was generated from the printed matter.

From the above, each of the light-sensitive materials of the present invention was good in all aspects of smoothness, film strength, electrostatic properties and printability of the photoconductive layer. Furthermore, it has been found that the electrostatic characteristics are further improved by using the resin [AA]. Example 29 5 g of resin [A-23] and 35 g of resin [B-22], 200 g of zinc oxide, 0.02 g of uranine, 0.04 g of rose bengal, 0.03 g of bromphenol blue, 0.40 g of phthalic anhydride and 300 g of toluene. A mixture of
A light-sensitive material was prepared in the same manner as in Example 27, following the steps below.

The light-sensitive material of the present invention was operated in the same manner as in Example 27 and examined for each performance. All were excellent in chargeability, dark charge retention rate and photosensitivity, and the actual copy image was high temperature / high humidity ( Thirty
℃, -80% RH and low temperature and low humidity (15 ℃, 30% R)
Even under the harsh conditions of H), no background fog occurs,
Gave a clear image.

Further, when this was used as an original plate of an offset master and printed, a printed matter having clear image quality was obtained even at 10,000 sheets. Examples 30 to 53 In Example 29, 5 g of resin [A-23] and 35 g of resin [B-22] were used instead of 5 g of resin [A-23] and 35 g of resin [B-22], and 35 g of resin [A] shown in Table K below. Each photographic material was prepared in the same manner as in Example 29.

[0224]

[Table 17]

The light-sensitive materials of the present invention are all excellent in chargeability, dark charge retention rate and photosensitivity, and the actual copied images are high temperature and high humidity (30 ° C., 80% RH) and low temperature and low humidity (15 ° C., 30%).
Even under the severe conditions of (RH), a clear image with no background fog or fine line skipping was provided.

Further, when printed as an offset master original plate, a printed matter having a clear image quality without generation of scumming was obtained even after printing 10,000 sheets.

[0227]

According to the present invention, an electrophotographic photoreceptor having a clear and high-quality image excellent in electrostatic characteristics (especially electrostatic characteristics under severe conditions) and further having excellent mechanical strength. Can be obtained. In particular, it is effective for a scanning exposure method using semiconductor laser light.

By using the repeating unit containing the specific methacrylate component represented by the formula (Ia) or (Ib) in the resin of the present invention, the electrostatic property is further improved.

Claims (3)

[Claims] 1. An electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye and a binder resin, wherein the binder resin is at least one of the following resins [A] and the following: An electrophotographic photosensitive member comprising at least one resin [B]. Resin [A] having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ ,
O ₃ H ₂ group, -COOH group, -SO ₃ H group, a phenolic OH group, -P (= O) (OH ) R 1 {R 1 is a hydrocarbon group or -OR ² (R ² is a hydrocarbon group A group consisting of at least one polymer group containing at least one polar group selected from the group consisting of (1) and a cyclic acid anhydride-containing group, and a polymer component represented by the following general formula (I) AB comprising at least a B block containing
Block copolymer. [Chemical 1] [In the formula (I), R ¹¹ represents a hydrocarbon group. Resin [B] Block A part having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ and containing 30% by weight or more of a repeating unit represented by the following general formula (II) as at least one polymer component. a -PO ₃ H ₂ group, -SO ₃ H group, -COOH group, -P
(= O) (OH) R ³ (R ³ has the same meaning as R ¹ ) and at least one selected from cyclic acid anhydride groups.
A resin composed of an ABA type block copolymer containing a block B part containing 0.05 to 10% by weight of a polymer component containing at least one polar group selected from among various polar groups. [Chemical 2] [In the formula (II), a ¹ and a ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ¹² represents a hydrocarbon group. ] 2. The above-mentioned resin [A] is one of the aryl group-containing methacrylate components represented by the following general formula (Ia) and general formula (Ib) as a copolymer component represented by the general formula (I). The electrophotographic photosensitive member according to claim 1, further comprising at least one. [Chemical 3] [Chemical 4] [In Formulas (Ia) and (Ib), A ¹ and A ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, —COZ ² or —COOZ ² (Z ² is the number of carbon atoms. 1 to
10 represents a hydrocarbon group), and B ¹ and B ² each represent a single bond for connecting —COO— and the benzene ring or a connecting group having 1 to 4 connecting atoms. ] 3. In the resin [B], the total amount of the specific polar group-containing polymer component contained in all the copolymers is the specific polar group-containing polymer contained in the resin [A]. 3. The electrophotographic photosensitive member according to claim 1, which is 10% by weight to 50% by weight based on the total amount of the components.