JPH0572755A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To provide the electrophotographic sensitive body improved in electrostatic characteristics and photographing performance, especially, superior in reproduction performance of an image high in precision in the case of using a liquid developer, and photographing performance in the case of the scanning exposure system using low output laser beams. CONSTITUTION:The binder resin to be used for the developer contains at least one kind of low molecular-weight copolymer prepared by combining a group of formula II with one end of a main polymer chain comprising repeating units of formula I, copolymerizing the obtained macromonomer again with a monomer corresponding to the formula I, and a kind of stellate copolymer obtained by forming an AB type block copolymer comprising a block A containing the resin or a macromononer having the polar group on the end of the polymer chain and the resin containing the polymer components of the formula I and a block B containing the polymer components each having the polar group, and inserting >=3 of the AB block copolymer in the polymer chain of the resin B. In the formula I, each of a<1> and a<2> is H, halogen, cyano, or a hydrocarbon group; R<3> is a hydrocarbon group; R<4> is a divalent bonding group; and each of b<1> and b<2> is a hydrocarbon group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor,
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 original plate using an electrophotographic photosensitive member has been earnestly carried out, and a photoconductive layer for a photoconductive layer having both electrostatic characteristics as an electrophotographic photosensitive member and printing characteristics 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
According to the techniques described in JP-A No. 64-70761, JP-A Nos. 2-67563 and 2-247656, a low molecular weight resin in which an acidic group-containing polymerization component is randomly present in the polymer main chain, A low molecular weight resin having an acidic group bonded to one end of the polymer main chain or a low molecular weight graft copolymer resin having an acidic group bonded to one end of the polymer main chain,
It has become possible to improve smoothness and electrostatic properties by using a low molecular weight graft copolymer resin containing an acidic group in the graft portion 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, and Japanese Patent Application No. 1-163796.
No. 1-212994, No. 1-2229379, No. 1-189245, and the like.

[0010]

However, even if these resins or combinations of resins are used, they are still insufficient in maintaining stable performance when the environment changes significantly from high temperature / high humidity to low temperature / low humidity. I knew it was. The scanning exposure method that uses a semiconductor laser beam has a longer exposure time than the conventional simultaneous full-exposure method that uses visible light, and also has a limited exposure intensity, so electrostatic characteristics, especially dark charge retention characteristics, are used. , For light sensitivity,
Higher performance is required.

In particular, when the scanning exposure method using a semiconductor laser beam is adopted in the electrophotographic lithographic printing plate precursor, when actually tested with a conventional photosensitive member, the above electrostatic characteristics are sufficiently obtained. This is not satisfactory, and especially the difference between E _1/2 and E _1/10 is large and the gradation of the copied image becomes soft, and it becomes difficult to reduce the residual potential after exposure, causing fog in the copied image. Became noticeable, and again
Even when printing as an offset master, problems such as a printed original sticking traces 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 properties even when the environment during copy image formation 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 object is to provide 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 ₁ ] and at least one of the resins [A ₂ ] and at least one of the following resins [B], and it has been found to be achieved by an electrophotographic photoreceptor. .. Resin [A ₁ ] One of the polymer main chains having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and containing a repeating unit represented by the following general formula (I) as a polymer component in an amount of 30% by weight or more. A monofunctional macromonomer (M ₁ ) having a weight average molecular weight of 2 × 10 ⁴ or less, which is formed by bonding a polymerizable double bond group represented by the following general formula (II) only to the terminal of the general formula (I) Is a copolymer comprising at least a monomer corresponding to the repeating unit represented by
₃ H ₂ , -SO ₃ H, -COOH, -P (= O) (O
H) R ¹ [R ¹ represents a hydrocarbon group or —OR ² (R ² represents a hydrocarbon group)] and a resin formed by bonding at least one polar group selected from a cyclic acid anhydride group .. Resin [A ₂ ] having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and containing a repeating unit represented by the following general formula (I) as a polymer component in an amount of 30% by weight or more and the above resin [A ₁ ]. Polymerization represented by the following general formula (II) only at one end of a polymer main chain containing 1 to 50% by weight of a polymer component containing at least one polar group selected from the specific polar groups shown. Weight average molecular weight of 2 × 10 ⁴
A resin, which is a copolymer comprising at least the following monofunctional macromonomer (M ₂ ) and a monomer corresponding to the repeating unit represented by the general formula (I).

[0018]

[Chemical 5]

[In the formula (I), a ¹ and a ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R
³ represents a hydrocarbon group. Preferably, a ¹ is a hydrogen atom, a
^This is the case where ² is a methyl group. ]

[0020]

[Chemical 6]

[In the formula (II), R ⁴ is -COO-, -O
_{CO -, - CH 2 OCO -} , - CH 2 COO -, - O
_{-, - SO 2 -, -} CO -, - CONR 5 -, - SO 2
NR ⁵ — (wherein R ⁵ represents a hydrogen atom or a hydrocarbon group), —CONHCOO—, —CONHCONH— or —C ₆ H ₄ —.

B ¹ and b ² may be the same or different and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COOR ⁶ or —COOR ⁶ via a hydrocarbon.
⁶ (wherein R ⁶ represents an optionally substituted hydrocarbon group)
Represents. Resin [B] An A block having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ and containing at least the repeating unit represented by the general formula (I) in the above resin [A ₁ ] as a polymer component. AB type block polymer composed of a B block containing at least one polymer component containing at least one polar group selected from the specific polar groups represented by the resin [A ₁ ]. A resin composed of a star-type copolymer in which at least three chains are bound in an organic molecule.

That is, the binder resin of the present invention has a specific polar group bonded to one end of a copolymer containing the macromonomer (M ₁ ) and the monomer corresponding to the general formula (I). Resin [A ₁ ] and / or resin [A ₂ ] which is a copolymer containing the macromonomer (M ₂ ) containing a specific polar group-containing component and the monomer corresponding to the general formula (I). (Hereinafter, macromonomer (M ₁ ) and (M
₂ ) is collectively referred to as macromonomer (M), and resins [A ₁ ] and [A ₂ ] may be collectively referred to as resin [A]) and a polymer component represented by the above general formula (I). An AB type block polymer chain of the A block and the B block containing the specific polar group-containing component has at least 3 in the organic molecule.
It is composed of at least a star-type copolymer (resin [B]) formed by bonding the individual pieces.

As a result of various studies, as described above, in the technique of using a known low molecular weight polar group-containing resin in combination with a medium to high molecular weight resin, depending on the medium to high molecular weight resin used in combination,
It has been found that the low-molecular weight resin described above may deteriorate the electrostatic characteristics of which performance has been improved. It is also 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. It has become clear that it is the cause.

As a result of repeated studies, a polar group-free block A and a polar group-containing block according to the present invention are used as a medium to high molecular weight resin to be used in combination with a low molecular weight resin [A] containing a polar group. It has been found that the above problems can be effectively solved by using a star-type copolymer having at least three polymer chains composed of an AB-type block having B in an organic molecular chain. Is.

This is due to the synergistic effect of the binder resins [A] and [B] of the present invention, in which the photoconductor particles are present in a state in which they are sufficiently dispersed and not condensed, and the spectral sensitizing dye is photoconductive. It is presumed that this is due to the fact that it is sufficiently adsorbed on the surface of the body particles and that the binder resin sufficiently adsorbs the extra active sites on the surface of the photoconductor to compensate the traps.

That is, the low molecular weight graft type copolymer resin [A] containing a specific polar group is sufficiently adsorbed on the photoconductor particles to uniformly disperse the particles, and the polymer chain is The extremely short length has an important effect of suppressing aggregation and preventing adsorption of the spectral sensitizing dye.

Further, by using a star-type copolymer containing a polymer chain composed of an AB block of a B block containing a specific polar group and an A block not containing the polar group, The mechanical strength was sufficiently retained. It is considered that this is because the block B portion of the resin has a weaker interaction than the photoconductor particles and the resin [A], and the entanglement effect between the polymer chains of the block A portions.

Further, it has the effect of improving the electrostatic characteristics as compared with the known medium-to-high molecular weight resin used in combination, that the block B portion which interacts with the photoconductor particles has polarity. 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 area with a conventionally known desensitizing solution to obtain a printing original plate. Shows excellent performance as an original plate for printing when printed by offset printing.

When the photosensitizer of the present invention is desensitized, the non-image area is 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 rapidly. It is considered that this is due to effective progress.

Furthermore, in the present invention, a low molecular weight resin [A] is used.
In the general formula (I) contained in the macromonomer,
And / or as a general formula (I) copolymerized with a macromonomer, a specific substituent at the 2-position and / or at the 2-position and 6-position represented by the following general formula (Ia) and general formula (Ib). A resin containing a methacrylate component having a specific substituent and containing a benzene ring or an unsubstituted naphthalene ring having a (hereinafter, this low molecular weight compound is particularly referred to as a resin [AA]) is preferable.

[0034]

[Chemical 7]

[0035]

[Chemical 8]

[In the formulas (Ia) and (Ib), R ⁷ and R
⁸ are each independently a hydrogen atom and a carbon number of 1-10.
Hydrocarbon group, chlorine atom, bromine atom, -COR ¹¹ or-
COOR ¹¹ (wherein R ¹¹ represents a hydrocarbon group having 1 to 10 carbon atoms) is represented.

R ⁹ and R ¹⁰ 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 unknown, but one reason is that the effect of the planar benzene ring or naphthalene ring having a substituent at the ortho position, which is the ester component of methacrylate, causes the zinc oxide interface in the film. It is thought that this is due to the proper arrangement of these polymer molecular chains in.

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 resin [A] is a graft copolymer containing at least a monomer corresponding to the polymer component represented by the general formula (I) and a monofunctional macromonomer (M), and further has a specific polar group. At one end of the main chain of the polymer (resin [A ₁ ])
Alternatively, each of them is contained in the graft portion (resin [A ₂ ]), and has a weight average molecular weight of 1 × 10 ³ to 2 × 1.
It is a low molecular weight resin of 0 ⁴ .

When the molecular weight of the resin [A] is less than 1 × 10 ³ , the film forming ability is deteriorated and 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 glass transition point of the resin [A] is preferably −
It is 30 ° C to 110 ° C, and more preferably -20 ° C to 90 ° C. The proportion of the polymer component corresponding to the repeating unit of the general formula (I) in the resin [A] is 30% by weight or more, preferably 50% by weight or more in the resin [A], and the total amount of the components containing a polar group. Is 0.5 to 15% by weight, preferably 1 to 10% by weight in the resin [A].

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 15% by weight, dispersibility of the low molecular weight compound decreases, and scumming increases when used as an offset master.

Macromonomer (M) in resin [A]
Is 1 to 70% by weight, preferably 5 to 50% by weight in the resin [A]. When the amount of the copolymerization component corresponding to the macromonomer (M) is less than 1% by weight, the characteristics of the graft type copolymer are lost and the electrostatic properties (particularly the charge retention ratio in the dark and the sensitivity) are deteriorated, and the offset printing is performed. When used as an original plate, water retention is also reduced. If the content exceeds 70% by weight, the copolymerizability of the graft-type copolymer will not sufficiently proceed, and as a result, the above-mentioned electrostatic properties and water retention will be deteriorated.

Next, 30% by weight in the copolymer of resin [A]
The repeating unit represented by the general formula (I) contained above will be further described. a ¹ and a ² each represent a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), a cyano group, or an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.) and the like. ..

R ³ 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.

Further, R ³ preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. The substituent may be any substituent other than the polar group contained in the polar group-containing polymer component in the resin [A], and examples thereof include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom). Etc.), -OR ¹² , -COOR ¹² , -O.
COR ¹² (R ¹² represents an alkyl group having 1 to 22 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group,
Hexadecyl group, octadecyl group, etc.) and the like. The preferred hydrocarbon group has 1 carbon atom.
To 18 optionally substituted alkyl groups (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-
A bromoethyl group, a 2-cyanoethyl group, a 2-methoxycarbonylethyl group, a 2-methoxyethyl group, a 3-bromopropyl group, and the like, an alkenyl group having 4 to 18 carbon atoms which may be substituted (for example, 2-methyl-1 A 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.), aralkyl group having 7 to 12 carbon atoms and optionally substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2- Naphthylethyl group,
Chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), carbon number 5-8
An optionally substituted alicyclic group (for example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (for example, a 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, dodecyl Roylamidophenyl group, etc.) and the like.

[0047] In the hydrocarbon group represented by R ^3, preferably when R ³ is an aliphatic group containing more than 60 wt% in component represented a hydrocarbon group having 1 to 5 carbon atoms in formula (I) Preferably.

In the repeating unit of the general formula (I) which is a component having such a substituent R ³ , a polymer of the repeating unit represented by the general formula (Ia) and / or the general formula (Ib) is more preferable. Ingredients are included.

In formula (Ia), preferred R ⁷ and R
As ⁸ are each a hydrogen atom independently of one another, out of the chlorine atom and a bromine atom, a hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group (e.g. methyl group having 1 to 4 carbon atoms,
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 (for example, phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and -COR ¹¹ and -COOR.
¹¹ (preferable R ¹¹ includes those described as the above-mentioned preferable hydrocarbon group having 1 to 10 carbon atoms).

In the formulas (Ia) and (Ib), R ⁹ and R ¹⁰ are each a single bond connecting —COO— and the benzene ring or — (CH ₂ ) _a — (a represents an integer of 1 to 3). ,-
_{CH 2 OCO -, - CH 2} CH 2 OCO -, - (C
H _{2) b} - _(b represents an integer of 1 or _2), - CH 2 C
A connecting group having 1 to 4 connecting atoms such as H ₂ O-,
More preferably, a single bond or a linking group having 1 to 2 bonding atoms 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. In addition, the following (a-1) to (a-20)
In, c is an integer of 1 to 4, d is 0 or an integer of 1 to 3, e is an integer of 1-3, R ¹³ are both -CCH _{2c + 1} or _{- (CH 2) d -C 6} H 5 (However, c and d are the same as the above), R ¹⁴ and R ¹⁵ may be the same or different and each represents a hydrogen atom, —Cl, —Br, or —I.

[0052]

[Chemical 9]

[0053]

[Chemical 10]

[0054]

[Chemical 11]

[0055]

[Chemical formula 12]

[0056]

[Chemical 13]

Next, the polar group contained in the low molecular weight resin [A] will be described. Polar group, -PO ₃ H _2, -S
At least one selected from O ₃ H, —COOH, —P (═O) (OH) R ¹ — and cyclic acid anhydride-containing groups is preferred.

Here, -P (= O) (OH) R ¹ represents a group represented by the following chemical formula 14, wherein R ¹ is a hydrocarbon group or a -OR ² group (R ² is a hydrocarbon group. Represents)
Specifically, R ¹ is a hydrocarbon group having 1 to 6 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2 -Fluoroethyl group, 3-chloropropyl group,
3-methoxypropyl group, 2-methoxybutyl group, benzyl group, phenyl group, propenyl group, methoxymethyl group, ethoxymethyl group, 2-ethoxyethyl group) and the like, and R ² represents the same content as R ^1. ..

[0059]

[Chemical 14]

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 aliphatic dicarboxylic acid anhydride and 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.

Resin [A₁], The polar group is polymerized.
It is bound to the end of the main chain and contained. Inclusion of the polar group
The amount is not particularly limited, but is 0.5 to 15% by weight.
Preferably. The polar group is directly attached to the end of the polymer main chain.
It may be bonded or may be bonded via a linking group. Or
The linking group may be any bonding group,
For example, -CR¹⁶R¹⁷-[Here
And R¹⁶, R¹⁷May be the same or different, each hydrogen
Atom, halogen atom (chlorine atom, bromine atom, etc.), OH
Group, cyano group, alkyl group (methyl group, ethyl group, 2-
Chloroethyl group, 2-hydroxyethyl group, propyl
Group, butyl group, hexyl group, etc.), aralkyl group (benzyl
Group, phenethyl group, etc.), phenyl group, etc.], −
(CHR¹⁶-CHR¹⁷)-, -C₆H_Ten-, -C₆H_Four
-, -O-, -S-, -NR¹⁸-[Here R¹⁸Is hydrogen
Child or hydrocarbon group (specifically, carbon number as hydrocarbon group
1-12 hydrocarbon groups (eg methyl, ethyl,
Ropyl group, butyl group, hexyl group, octyl group, decyl group
Group, dodecyl group, 2-methoxyethyl group, 2-chloroethyl group
Cyl group, 2-cyanoethyl group, benzyl group, methylben
Zyl group, phenethyl group, phenyl group, tolyl group, chloro
Phenyl group, methoxyphenyl group, butylphenyl group
And the like)}, -CO-, -COO-,
-OCO-, -CONR¹⁸-, -SO₂NR¹⁸-, -S
O₂-, -NHCONH-, -NHCOO-, -NHS
O₂-, -CONHCOO-, -CONHCONH-,
Heterocycle (at least one of O, S, N, etc. as a hetero atom)
Seed-containing 5- or 6-membered ring or condensed ring thereof
It may be any, for example, thiophene ring, pyridine ring,
Furan ring, imidazole ring, piperidine ring, morpholine
Ring and the like) or -S_iR ¹⁹R²⁰ Where R¹⁹,
R²⁰May be the same or different and each is a hydrocarbon group or
Is -OR^{twenty one}(Where R^{twenty one}Represents a hydrocarbon group).
These hydrocarbon groups include R¹⁸Similar to those listed in
Or a bonding group such as
Examples include linking groups composed of a combination of two or more of these.
Be done.

On the other hand, in the case of the resin [A ₂ ], the polar group is contained in the polymer component in the monofunctional macromonomer (M ₂ ). The copolymerizable component containing a polar group in the resin [A ₂ ] is, for example, represented by the general formula (I) [the general formula (I
a) and (Ib)], any vinyl-based compound containing the polar group that can be copolymerized with the monomer corresponding to the repeating unit represented by the formula: Data Handbook [Basic] "Baifukan (1
986) and the like. Specifically, acrylic acid, α- and / or β-substituted acrylic acid (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-cyano form, β-chloro form, β-bromo form, α-chloro-β-methoxy form,
α, β-dichloro form, etc.), methacrylic acid, itaconic acid,
Itaconic acid half-esters, itaconic acid half-amides, crotonic acid, 2-alkenylcarboxylic acids (for example, 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half-esters,
Maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, half-ester derivatives of vinyl group or allyl group of dicarboxylic acids and ester derivatives and amide derivatives of these carboxylic or sulfonic acids Examples thereof include compounds having the polar group in the substituent.

The polar group-containing copolymerization component will be exemplified below. Here, R ²² represents H or CH ₃ , R ²³ represents H, CH ₃ or CHCOOCH ₃ , R ²⁴ represents an alkyl group having 1 to 4 carbon atoms, and R ²⁵ represents alkyl group having 1 to 6 carbon atoms. Group, benzyl group or phenyl group, and f is 1 to 3
Is an integer, g is an integer of 2 to 11, and h is 1 to 1.
1 represents an integer, i represents an integer of 2 to 4, and j represents 2-1.
Indicates an integer of 0.

[0066]

[Chemical 15]

[0067]

[Chemical 16]

[0068]

[Chemical 17]

[0069]

[Chemical 18]

[0070]

[Chemical 19]

[0071]

[Chemical 20]

[0072]

[Chemical 21]

[0073]

[Chemical formula 22]

[0074]

[Chemical formula 23]

[0075]

[Chemical formula 24]

[0076]

[Chemical 25]

[0077]

[Chemical formula 26]

In the present invention, the resin [A ₂ ] containing a polar group in the macromonomer may further have at least one of the polar groups bonded to the end of the polymer main chain ( Such a resin is sometimes called a resin [A ₁₂ ]).

In the resin [A ₁₂ ], the polar group contained as a copolymerization component in the macromonomer and the polar group bonded to one end of the polymer main chain may be the same or different, and their presence The ratio varies depending on the kind and amount of other binder resin, spectral sensitizing dye, chemical sensitizer or other additive constituting the photoconductive layer of the present invention, and the ratio is preferably adjusted arbitrarily. .. What is important is that the total amount of both polar groups is used within the range of 0.5 to 15% by weight.

Further, the monofunctional macromonomer (M) to be used as a copolymerization component of the graft type copolymer resin of the present invention will be described in detail. Monofunctional macromonomer (M
₁ ) is at least one of the polymer components represented by the above general formula (I) [also includes the general formulas (Ia) and (Ib)], the polymerizable double bond group represented by the general formula (II). Formed by bonding only to one end of the polymer main chain containing
The weight average molecular weight is 2 × 10 ⁴ or less, and the macromonomer (M ₂ ) further contains the same specific polar group as described above as a polymer component which is a repeating unit of the macromonomer (M ₁ ). It contains at least one of the polymer components.

[0081]

[Chemical 27]

[In the formula (II), R ⁴ is —COO—, —O
_{CO -, - CH 2 OCO -} , - CH 2 COO -, - O
_{-, - SO 2 -, -} CO -, - CONR 5 -, - SO 2
NR ⁵ — (wherein R ⁵ represents a hydrogen atom or a hydrocarbon group), —CONHCOO—, —CONHCONH— or —C ₆ H ₄ —.

B ¹ and b 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, —COOR ⁶ or —COOR ⁶ via a hydrocarbon.
⁶ (wherein R ⁶ represents an optionally substituted hydrocarbon group)
Represents. When the weight average molecular weight of the macromonomer (M) exceeds 2 × 10 ⁴ , the copolymerizability with the monomer corresponding to the formula (I) decreases, which is not preferable. On the other hand, when the weight average molecular weight is too small, the effect of improving the electrophotographic characteristics of the photosensitive layer becomes small, so that it is preferably 1 × 10 ³ or more.

As the polymer component constituting the repeating unit of the monofunctional macromonomer (M) having the polymerizable double bond group bonded to one end, one of the general formulas (I), (Ia) and / or
Alternatively, the component represented by (Ib) may be mentioned, and the content thereof is 30% by weight or more, preferably 50% by weight or more in the macromonomer.

These general formulas (I), (Ia) and (I)
The specific description of the polymer component represented by b) is as described for the above-mentioned copolymerizable component that can be copolymerized with the macromonomer, and specific examples thereof include the same ones as described above. In the resin [A], the component of the formula (I) contained as a copolymer component of the resin [A] and the macromonomer (M)
It may be the same as or different from the component of formula (I) contained as a polymerization component therein.

Further, as the polymer component in the macromonomer (M), a polymer component other than the above may be contained. For example, as a monomer corresponding to another polymerizable repeating unit, acrylonitrile or methacrylic acid may be used. Ronitrile, acrylamides, methacrylamides, styrene and derivatives thereof (eg vinyltoluene, chlorostyrene, bromostyrene, hydroxymethylstyrene, N, N-dimethylaminomethylstyrene, etc.), heterocyclic vinyls (eg vinylpyridine, vinyl) Imidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.) and the like.

When these other monomers are contained,
1 to 30% by weight in all polymer components of macromonomer (M)
Is preferred. In addition, macromonomer (M ₂ )
In the macromonomer, the specific polar group-containing component further contained in 1 is preferably 1 to 50% by weight, more preferably 3 to 30% by weight.

On the other hand, in the general formula (II), the specific content of the hydrocarbon group is the same as the content of the hydrocarbon group described for R ³ in the general formula (I). R ⁴ is -C ₆ H ₄ -
When represented by, the 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.), an alkoxy group (eg, methoxy group, Ethoxy group,
Propoxy group, butoxy group, etc.) and the like.

B ¹ and b ² may be the same or different from each other, and preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom), a cyano group, an alkyl group having 1 to 4 carbon atoms (eg methyl group, (Ethyl group, propyl group, butyl group, etc.), -COOR ⁶ or -COO via hydrocarbon
R ⁶ (R ⁶ is preferably an alkyl group having 1 to 18 carbon atoms,
It represents an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, and specific examples thereof include those described for R ³ .

Examples of the hydrocarbon group in the —COOR ⁶ group through the above hydrocarbon include a methylene group, an ethylene group, a propylene group and the like. More preferably, in the general formula (II), R ⁴ is -COO -, - OCO -, -
_{CH 2 OCO -, - CH 2} COO -, - O -, - CON
H -, - SO ₂ NH- or -C ₆ H ₄ - represents, b ¹ and b ² may be the same as or different from each other, each represents a hydrogen atom, a methyl group, -COOR ⁶ or -CH ₂ COOR ⁶
[R ⁶ more preferably represents an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.)]. More preferably b ¹ and b
^{In 2} , one of them represents a hydrogen atom.

The macromonomer used in the present invention is further specified in the case of the repeating unit represented by the general formula (I), (Ia) and / or (Ib) as described above, and the macromonomer (M ₂ ). The polymerizable double bond group represented by the general formula (II) is bonded directly to only one terminal of the main chain of the random polymer including at least repeating units containing a polar group of It has a defined chemical structure.

The linking group for linking the component of the formula (II) and the polymer component part includes a carbon-carbon bond (single bond or double bond), a carbon-heteroatom bond and a heteroatom-heteroatom bond (in the above, a heteroatom). As, for example, any combination of atomic groups of oxygen atom, sulfur atom, nitrogen atom, silicon atom, etc.).

Specific examples of the linking group include the same as those described as the linking group for linking the polymer main chain and the polar group in the resin [A ₁ ]. Or a combination of two or more linking groups.

Macromonomer (M) used in the present invention
Can be produced by a conventionally known synthesis method. Specifically, radical polymerization using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a carboxyl group, a carboxyhalide group, a hydroxyl group, an amino group, a halogen atom and an epoxy group in a molecule. It is synthesized by a method such as a radical polymerization method in which the obtained oligomer having a terminal reactive group bond is reacted with various reagents to form a macromer.

Specifically, P. Dreyfuss an
d R. P. Quirk, Encycl. Polym.
Sci. Eng. 7, 551 (1987), p. F.
Rempp, E .; Franta, Adu. Polym.
Sci, 58, 1 (1984), Yusuke Kawakami, Chemical Industry,
38, 56 (1987), Yuya Yamashita, Polymer, 31, 9
88 (1982), Shiro Kobayashi, High Polymer, 30, Koichi Ito, Polymer Processing, 35,262 (1986), Kishiro Azuma, Takashi Tsuda, Functional Materials, 1987, No. It can be synthesized according to the methods described in the review articles of 10, 5 and the like and references therein, patents and the like.

However, the macromonomer (M ₂ ) of the present invention
Contains the above polar group as a component of its repeating unit, and is thus synthesized in consideration of the following points. As one of the methods, for example, as shown in the reaction formula (A), a radical polymerization and a terminal reactive group are carried out by the above method using a monomer containing a functional group in which the polar group is protected. It is to be introduced.

[0097]

[Chemical 28]

The protection reaction and deprotection reaction (eg, hydrolysis reaction, hydrogenolysis reaction, oxidative decomposition reaction, etc.) of the polar group randomly contained in the macromonomer (M ₂ ) of the present invention are conventionally known. It can be performed by the method of. Specifically, J. F. W. McOmie, "Pro
tective Groups in Organic
Chemistry "Plenum Press (19
73), T.W. W. Greene, "Protectiv
e Groups in Organic Synth
sis ", John Wiley and Sous
(1981), Ryohei Oda "Polymer Fine Chemicals" Kodansha (1976), Yoshio Iwakura, Keisuke Kurita "Reactive Polymer" Kodansha (1977), G.I. Berner eta
1, J.I. Radiation Curing, 198
6, No. 10, p10, JP-A-62-212669
No. 62-286064, No. 62-210475.
No. 62-195648, 62-258476.
No. 63-260439, Japanese Patent Application No. 62-22052
It can be synthesized using the method described in No. 0, No. 62-226692 and the like.

As another method, for example, as shown in the reaction formula (B), after synthesizing an oligomer as described above, a specific reactive group bonded to one end of the oligomer and It is a method of synthesizing by reacting with a reagent containing a polymerizable double bond group, which reacts only with a specific reactive group, by utilizing the difference in reactivity of the contained polar groups.

[0100]

[Chemical 29]

As shown in the reaction formula (B), specific examples of combinations of specific functional groups are shown in Table 1 below. However, the present invention is not limited to these, and importantly, by utilizing the selectivity of the reaction in a normal organic chemical reaction, macromonomerization can be achieved without protecting the polar group in the oligomer. It should be done.

[0102]

[Table 1]

As chain transfer agents that can be used,
For example, the polar group or a substituent-containing mercapto compound that can be induced to the polar group later (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2
-Mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2
-Mercaptoethyl) amino] propionic acid, N- (3
-Mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol , 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2
-Mercapto-3-pyridinol or the like) or a disulfide compound which is an oxidized form of these mercapto compounds, or an iodinated alkyl compound having the polar group or the substituent (for example, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2- Iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.) and the like. Preferred are mercapto compounds.

Specific examples of the reactive group-containing polymerization initiator that can be used include 2,2′-azobis (2
-Cyanopropanol), 2,2'-azobis (2-cyanopentanol), 4,4'-azobis (4-cyanovaleric acid), 4,4'-azobis (4-cyanovaleric acid chloride), 2, 2'-azobis [2- (5-methyl-2
-Imidazolin-2-yl) propane], 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane], 2,2'-azobis {2-
[1- (2-hydroxyethyl) -2-imidazoline-
2-yl] propane}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide]
Etc. or their derivatives and the like.

The amount of each of these chain transfer agents or polymerization initiators is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on all monomers.

Specific examples of the macromonomer (M) of the present invention include the following compounds. However,
As the macromonomer (M ₁ ), the same as the following specific examples may be mentioned as those containing no polar group-containing component.

In each of the following examples, R ²⁶ represents -H or -CH ₃ , and R ²⁷ , R ²⁸ or R ²⁹ represent -H or -H, respectively.
CH ₃ or indicates -CH ₂ COOCH _3, R ³⁰ is -C _k
H _{2k + 1} (k represents an integer of 1 to 18), —CH ₂ C ₆ H
_{5, -C 6 H 5 (R} 31) (R 32), (R 31, R 32 are each -
Shows H, -Cl, -Br, and -CH ₃ or _{-COOCH 3), - C 10 H} 7 or indicates _{-CH 2 -C 10 H 7, R} 33
-CN is, -OCOCH _3, -CONH ₂ or -C ₆ H
₅ shows a, R ³⁴ is -Cl, -Br, -CN or -OCH
₃ , m is an integer of 2 to 18, n is an integer of 2 to 12, and p is an integer of 2 to 4.

[0108]

[Chemical 30]

[0109]

[Chemical 31]

[0110]

[Chemical 32]

[0111]

[Chemical 33]

[0112]

[Chemical 34]

[0113]

[Chemical 35]

Further, the resin [A] of the present invention contains a monomer corresponding to the above-mentioned general formula (I) and macromonomer (M) together with a monomer other than these as a further copolymerization component. Good.

Examples of such other copolymerization component include, in addition to methacrylic acid esters, acrylic acid esters, crotonic acid esters containing a substituent other than those described in the general formula (I), 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 (for example, Dimethyl ester, diethyl ester, etc., acrylamides, methacrylamides, styrenes (for example, styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinyl chloride) Naphthalene), vinyl sulfone-containing compounds, vinyl ketones containing compounds, heterocyclic vinyl compounds (e.g., vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline,
Vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.) and the like. However, it is preferable that these other monomers do not exceed 20% by weight in the copolymer of the resin [A].

In the resin [A] used in the present invention, at least the above-mentioned method is required for synthesizing the resin [A ₁ ] or the resin [A ₁₂ ] in which the polar group is bonded to the terminal of the polymer main chain. During the polymerization reaction of the macromonomer (M) and the monomer corresponding to the general formula (I), a polymerization initiator or a chain transfer agent containing the polar group or a specific reactive group that can be induced in the polar group is used in combination. It is achieved by doing.

Specifically, it can be obtained in the same manner as in the method of oligomers with one end reactive bond as described above in the synthesis of macromonomers. Next, the resin [B] of the present invention will be described.

The resin [B] comprises a block A containing at least the polymer component represented by the general formula (I) and at least one polar group selected from the specific polar groups represented by the resin [A]. It is a star-type copolymer in which at least three AB-type block polymer chains composed of a block B containing at least the polymer component contained therein are bound in an organic molecule.

Here, the order of arrangement of the block A and the block B in the polymer chain may be any. That is, the following is a schematic representation of the polymer.

[0120]

[Chemical 36]

[0121]

[Chemical 37]

[Wherein X represents an organic molecule, (A) represents block A, (B) represents block B, and (A)-
(B) represents a polymer chain. Further, the upper limit of such AB type block polymer chains contained in the organic molecule is at most 15, usually about 10.

The content of the specific polar group-containing component in the resin [B] is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the resin [B]. Contained.

When the content of the polar group in the binder resin [B] is less than 0.05% by weight, the initial potential is low and a sufficient image density cannot be obtained, and the content of the polar group is less than 15% by weight. If it is too much, 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 it is used as an offset master, which is not preferable.

In the resin [B], the total amount of the specific polar group-containing polymer component contained in all the copolymers is equal to the specific polar group-containing polymer component contained in the resin [A]. Is preferably 10% by weight to 50% by weight with respect to the total amount of. When the total amount of the resin [B] is less than 10% by weight of that of the resin [A], the electrophotographic properties (especially the charge retention in the dark) and the photosensitivity are significantly lowered, and the film strength is also lowered. On the other hand, when 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 master plate.

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. Each block constituting the polymer chain of the star type copolymer (resin [B]) of the present invention has the following characteristics.

The A block component contains at least a polymer component represented by the repeating unit represented by the general formula (I), and the component represented by the formula (I) is preferably 30 to 100% by weight in the A block component. %, More preferably 50 to
100% by weight is contained. Further, the block A is characterized by not containing the specific polar group-containing component contained in the block B.

The specific contents of the component of the general formula (I) are the same as those described for the resin [A]. Examples of other polymer components that can be contained include components represented by the following general formula (III).

[0130]

[Chemical 38]

[In the formula (III), D ¹ is -COO-,-
_{OCO -, - (CH 2)} q -OCO -, - (CH 2) q
-COO- (q represents an integer of 1 to 3), -O-, -S.
_{O 2 -, - CO -,} - CON-D 3 -, - SO 2 N-D
^{3 -, - CONHCOO -, -} CONHCONH- or -C ₆ H ₄ - are expressed (here D ³ represents a hydrogen atom or a hydrocarbon group).

D ² represents a hydrocarbon group. m ¹ and m
² may be the same as or different from each other, and have the same contents as a ¹ and a ² in the formula (I). Here, in addition to a hydrogen atom, D ³ is preferably a hydrocarbon group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 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.), C4-18 An optionally substituted alkenyl group (eg, 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.), and optionally substituted aralkyl groups having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-
Naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), alicyclic group having 5 to 8 carbon atoms which may be substituted ( For example, a cyclohexyl group, a 2-cyclohexylethyl group,
2-cyclopentylethyl group, etc.) or an 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, ethoxycarboxyphenyl group, butoxycarbonylphenyl group, acetamidophenyl group,
Propioamidophenyl group, dodecyloylamidophenyl group, etc.).

[0133] D 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 ² represents a hydrocarbon group, and a preferable hydrocarbon group is an optionally substituted alkyl group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group). , Hexyl group, octyl group,
Decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-
Methoxycarbonylethyl group, 2-methoxyethyl group,
3-bromopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms and which may be substituted (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-perenyl group). Mentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.) and optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group). Group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), carbon number 5-8 optionally substituted alicyclic groups (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc. An 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, etc.).

More preferably, in the general formula (III), D ¹ is -COO-, -OCO-, -CH ₂ OCO.
_{-, - CH 2 COO -,} - O -, - CONH -, - SO
₂ NH- or -C ₆ H ₄ - represents a.

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). Monomers, such as acrylonitrile, methacrylonitrile, heterocyclic vinyls (eg vinyl pyridine, vinyl imidazole, vinyl pyrrolidone,
Vinyl thiophene, vinyl pyrazole, vinyl dioxane, vinyl oxazine, etc.) and the like. These other monomers are 20 parts in 100 parts by weight of the total polymer component of the A block.
It is used within the range of not exceeding parts by weight.

Next, the B block component constituting the polymer chain of the star type copolymer [B] will be described in detail. Specific examples of the polymer component containing a specific polar group that constitutes the block B include the same as the polymer component containing a specific polar group of the resin [A] described above.

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

Further, a polymer component other than the above-mentioned polar group-containing polymer component may be contained in the block B, and such a polymer component is preferably a repeating unit of the above general formulas (I) and (III). The polymer component corresponding to the unit, and the same components as those described as other components can be mentioned.

On the other hand, the organic molecule according to the present invention formed by bonding at least three polymer chains is not particularly limited as long as the molecular weight of the molecule is 1,000 or less. Examples include trivalent hydrocarbon residues such as Chemical formula 39.

[0141]

[Chemical Formula 39]

(Here, r ^{1 to} r ⁶ represent a hydrogen atom or a hydrocarbon group, provided that at least one of r ¹ and r ² or r ^{3 to} r ⁶ is linked to the polymer chain.) The organic residue is composed of one or a combination of any of these, and in the case of a combination, -O-, -S
^{-, - N (r 7)} -, - COO -, - CON (r 7)
_{-, - SO 2 -, -} SO 2 N (r 7) - ( wherein each represent r ⁷ hydrogen atom or a hydrocarbon group), - NHCO
O-, -NHCONH-, a heterocyclic group containing a hetero atom such as an oxygen atom, a sulfur atom and a nitrogen atom (for example, a thiophene ring, a pyridine ring, a pyran ring, an imidazole ring, a benzimidazole ring, a furan ring, A piperidine ring, a pyrazine ring, a pyrrole ring, a piperazine ring, etc.) and the like.

Other organic molecules which bond the polymer chains include those formed by a combination of Chemical formula 40 or Chemical formula 41 and the above-mentioned bonding unit. However, specific examples of the organic molecule according to the present invention are not limited to these.

[0144]

[Chemical 40]

[0145]

[Chemical 41]

The star type copolymer [B] of the present invention can be synthesized by utilizing a conventionally known method for synthesizing a star type polymer of a monomer containing a polar group and having a polymerizable double bond group. it can. For example, one of them is a polymerization reaction using carbanion as an initiator. Specifically, M. Mort
on, T.W. E. Helminiak et al. P
olym. Sci. 57, 471 (1962), B.I.
Gordon III, M .; Blumenthal, J. et al.
E. Loftus, et al, Polym. Bul
l. 11, 349 (1984), R.I. B. Bate
S.W. A. Beavers, et al. Org.
Chem. , 44, 3800 (1979).

However, when this reaction is used, the "specific polar group" of the present invention is used as a protected functional group and polymerized, and then the protective group is eliminated. The protection of the specific polar group of the invention with a protecting group and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing the conventionally known knowledge. For example, various references are given in the above cited document, and further, Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer" Kodansha Co., Ltd. (1977), T.S. W.
Greene, "Protective Groups
in Organic Synthesis ”, Jo
hnWiley & Sons (1981), J. Am.
F. W. McOmie, "Protective Gr
oops in Organic Chemistr
The method described in detail in the review article such as "y" Plenum Press, (1973) can be appropriately selected and performed.

As another method, a monomer of the present invention which does not protect a specific polar group is used, and a compound containing a dithiocarbament group and / or a compound containing a xanthate group is used as an initiator. It can also be synthesized by performing a polymerization reaction under light irradiation. 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.

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 copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer, methacrylate copolymer, acrylate copolymer. , Vinyl acetate copolymer, polyvinyl butyral, alkyd resin, silicone resin, epoxy resin, epoxy ester resin, polyester resin and the like.

Specifically, Ryuji Shibata and Jiro Ishiwata, “Polymer”, Vol. 17, p. 278 (1968), Harumi Miyamoto.
Hidehiko Takei "Imaging" 1973 (No.8) 9th
P., 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 .; 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, 54-20735, 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 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 from 0.05 to 0.05 in terms of the resin [A] / resin [B] weight ratio.
It is preferably 0.8 / 0.95 to 0.20, more preferably 0.10 to 0.50 / 0.90 to 0.50.
Is.

If 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.

Further, when the weight ratio of the resin [A] to the resin [A] and the resin [B] used in the present invention is 0.05 or less, 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), Kyohei 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 described in JP-B-51-45.
No. 2, JP-A Nos. 50-90334 and 50-11422.
No. 7, No. 53-39130, No. 53-82353,
U.S. 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
No. 5,447, No. 3,128,179, No. 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 near-infrared to infrared light region having a long wavelength of 700 nm or more, Japanese Patent Application Laid-Open Publication No. 4 (1999) -43
No. 7-840, No. 47-44180, 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 may 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 thickness of the photoconductive layer is 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.
It is set to μ, particularly 10 to 50 μ. Examples of the charge transport material of the laminated type 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 suitable.

Typical resins used for forming the insulating layer or the charge transport layer are polystyrene resin, polyester resin, cellulose resin, polyether resin,
Thermoplastic resin and effective resin such as vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl chloride copolymer resin, polyacrylic resin, polyolefin resin, urethane resin, polyester resin, epoxy resin, melamine resin, and silicone 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, a basic back surface (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.

Specifically, as examples of the conductive substrate or the conductive material, Yukio Sakamoto, Electrophotography, 14 (No.
1), P2-11 (1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry", Polymer Publishing (1975), M.P. 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 Report of IEICE" 77 , 17 (19).
1977) etc.).

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.

[0171]

EXAMPLES Examples of the present invention will be illustrated below, but the contents of the present invention are not limited thereto. [Synthesis of macromonomer (M)] Synthesis example of macromonomer 1: (MM-1) 75 g of methyl methacrylate, 25 methyl acrylate
A mixed solution of g, 5 g of thioglycolic acid and 200 g of toluene was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 2,2'-azobisisobutyronitrile (abbreviation A.
I. B. N. ) 1.0 g was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate, N, N was added to this reaction solution.
-1.0 g of dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added, and the mixture was stirred at a temperature of 100 ° C for 12 hours. After cooling, the reaction solution was reprecipitated in 2 liters of n-hexane to obtain 82 g of white powder. The weight average molecular weight (Mw) of the polymer was 3.8 × 10 ³ .

[0172]

[Chemical 42]

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

Then, the reaction solution is cooled in a water bath to a temperature of 20.
C., 10.2 g of triethylamine was added, and 14.5 g of methacrylic acid chloride was stirred and added dropwise at a temperature of 25.degree. After dropping, the mixture was further stirred for 1 hour as it was. Then, 0.5 g of t-butyl hydroquinone was added and the temperature was adjusted to 60.
The mixture was heated to ℃ and stirred for 4 hours. After cooling, the mixture was dropped into 1 liter of water with stirring (about 10 minutes), stirred for 1 hour as it was, and allowed to stand, and then water was removed by decantation. After washing with water twice more, tetrahydrofuran 1
It was dissolved in 00 ml and reprecipitated in 2 liters of petroleum ether. The precipitate was collected by decantation and dried under reduced pressure. The obtained viscous product had a yield of 65 g and had a Mw of 3.3 × 1.
It was 0 ³ .

[0175]

[Chemical 43]

Macromonomer Synthesis Example 3: (MM-3) benzyl methacrylate 95 g, 2-phosphonoethyl methacrylate 5 g, 2-aminoethyl mercaptan 6 g
And a mixture of 200 g of tetrahydrofuran were heated to a temperature of 70 ° C. with stirring under a nitrogen stream.

A. I. B. N. 1.5 g was added and the reaction was carried out for 4 hours. I. B. N. 0.5 g was added and reacted for 4 hours. Next, this reaction solution is cooled to a temperature of 20 ° C., 10 g of acrylic anhydride is added, and the temperature is 20 to 25 ° C.
It was stirred for 1 hour. Then t-butyl hydroquinone 1.
0 g was added and the mixture was stirred at a temperature of 50 to 60 ° C. for 4 hours. After cooling, the reaction mixture was added dropwise to water (1 liter) with stirring for about 10 minutes, and the mixture was stirred for 1 hour and allowed to stand, and water was removed by decantation. The washing with water was repeated twice more, then, the residue was dissolved in 100 ml of tetrahydrofuran and reprecipitated in 2 liters of petroleum ether. The precipitate was collected by decantation and dried under reduced pressure. The yield of the obtained viscous product was 70 g, and the Mw was 6 × 10 ³ .

[0178]

[Chemical 44]

Macromonomer Synthesis Example 4: (MM-4) A mixed solution of 90 g of 2-chlorophenyl methacrylate, 10 g of the monomer of the following structure (I), 4 g of thioglycolic acid and 200 g of toluene was heated at 70 ° C. under a nitrogen stream. Warmed to. A. I. B. N. 1.5 g was added and reacted for 5 hours. I. B. N. 0.5 g was added and reacted for 4 hours. Next, 12.4 g of glycidyl methacrylate, N,
1.0 g of N-dimethyldodecylamine and 1.5 g of t-butylhydroquinone were added and the reaction was carried out at a temperature of 110 ° C. for 8 hours. After cooling, the reaction mixture was added with p-toluenesulfonic acid 3 g, 90 vol% tetrahydrofuran aqueous solution 100 m.
The solution was added to 1 and stirred at a temperature of 30 to 35 ° C. for 1 hour.
The above mixture was reprecipitated in 2 liters of a mixed solution of water / ethanol [(1/3) volume), and the precipitate was collected by decantation. This precipitate was added to tetrahydrofuran 200
It was dissolved in ml and reprecipitated in 2 liters of n-hexane to obtain 58 g of powder. The Mw was 7.6 × 10 ³ .

[0180]

[Chemical 45]

[0181]

[Chemical 46]

Macromonomer Synthesis Example 5: (MM-5) 2,6-dichlorophenyl methacrylate 95 g, 3-
A mixed solution of 5 g of (2′-nitrobenzyloxysulfonyl) propyl methacrylate, 150 g of toluene and 50 g of isopropyl alcohol was placed under a nitrogen stream at a temperature of 80 ° C.
Warmed to. 2,2'-azobis (2-cyanovaleric acid)
(Abbreviation: ACV) 5.0 g was added and reacted for 5 hours,
Furthermore, A. C. V. 1.0g was added and it reacted for 4 hours.
After cooling, the reaction product was reprecipitated in 2 liters of methanol, the powder was collected by filtration, and dried under reduced pressure.

50 g of the above powder, 14 g of glycidyl methacrylate, 0.6 g of N, N-dimethyldecylamine, t
-Butyl hydroquinone 1.0 g and toluene 100 g
The mixture was stirred at a temperature of 110 ° C. for 10 hours. After cooling to room temperature, the mixture was stirred with an 80W high pressure mercury lamp for 1 hour.
Irradiated for hours. Then, the reaction mixture was reprecipitated in 1 liter of methanol, and the powder was collected by filtration and dried under reduced pressure. Yield 34
Mw was 7.3 × 10 ³ in g.

[0184]

[Chemical 47]

Synthesis Example 6 of Macromonomer: (MM-6) 80 g of ethyl methacrylate, 5 of N-vinylpyrrolidone
g, trimethylsilyl methacrylate 29 g, β-mercaptoethanol 3 g and tetrahydrofuran 200 g
The mixed solution of (1) was heated to 70 ° C while stirring under a nitrogen stream. A. I. B. N. 1 g was added and the reaction was carried out for 4 hours. I. B. N. 0.5 g was added and reacted for 4 hours. After the reaction mixture was cooled and the temperature was set to 25 ° C., 6.6 g of methacrylic acid was added, to which 8 g of dicarboxylcarboxylic diimide (D.C.C.) and 4- (N, N) were added.
A mixed solution of 0.2 g of dimethylamino) pyridine and 20 g of methylene chloride was added dropwise at a temperature of 25 to 30 ° C., and the mixture was further stirred as it was for 4 hours. The reaction mixture was then charged with formic acid 10
g was added and the mixture was stirred for 1 hour. The precipitated insoluble matter was filtered off, the filtrate was reprecipitated in 1 liter of methanol, and an oily matter was collected by filtration. Furthermore, this oily substance was added to tetrahydrofuran 200
It was dissolved in g, the insoluble matter was filtered off, and then reprecipitated again in 1 liter of methanol, and an oily matter was collected and dried. Yield 65g M
It was w7 × 10 ³ .

[0186]

[Chemical 48]

[Synthesis of Resin [A]] Synthesis Example 1 of Resin [A] 1: [A-1] 70 g of benzyl methacrylate, macromonomer (MM
-1) A mixed solution of 30 g, 150 g of toluene and 50 g of isopropanol was heated to a temperature of 80 ° C under a nitrogen stream. A. C. V. 5g was added and reacted for 4 hours,
Furthermore, A. C. V. 0.5 g was added and reacted for 4 hours. The weight average molecular weight (Mw) of the obtained copolymer is 1.0 × 1.
It was 0 ⁴ .

[0188]

[Chemical 49]

Synthesis Example 2 of Resin [A]: [A-2] 80 g of 2-chlorophenyl methacrylate, 20 g of macromonomer (Mw 5 × 10 ³ ) corresponding to the following structure, β
-A mixed solution of 3 g of mercaptopropionic acid and 200 g of toluene was heated to a temperature of 75 ° C under a nitrogen stream. In addition to this, I. B. N. 1.5g was added and reacted for 4 hours,
Further, 0.5 g was added and reacted for 4 hours. The Mw of the obtained copolymer was 8.8 × 10 ³ .

[0190]

[Chemical 50]

Synthesis Examples 3 to 9 of Resin [A]: [A-3] to
[A-9] In the synthesis example of the resin [A], instead of 2-chloromethacrylate 80 g and macromonomer 20 g, the following table-
Copolymers were produced in the same manner as in Synthesis Example 2 of Resin [A] except that each monomer corresponding to A and the macromonomer were replaced. The Mw of each polymer was in the range of 7.5 × 10 ^{3 to} 9 × 10 ³ .

The Mw of each macromonomer used was 3.
It was in the range of 5 × 10 ^{3 to} 5 × 10 ³ .

[0193]

[Table 2]

[0194]

[Table 3]

Synthesis Example 10 of Resin [A]: [A-10] 70 g of benzyl methacrylate, macromonomer (MM
-4) A mixed solution of 30 g and 200 g of toluene was heated to a temperature of 80 ° C under a nitrogen stream. 8 g of 2,2'-azobisvaleronitrile (AIVN) was added and reacted for 3 hours. I. V. N. 1 g was added and reacted for 4 hours.

The Mw of the obtained polymer was 8.5 × 10 ³ .

[0197]

[Chemical 51]

Synthesis Example 11 of Resin [A]: [A-11] A mixed solution of 60 g of 2-chlorophenyl methacrylate, 35 g of macromonomer (MM-2), 5 g of 2-methoxyethyl methacrylate, 3 g of octadecyl methacrylate and 200 g of toluene was added with nitrogen. The temperature was raised to 75 ° C. under an air stream. A. I. B. N. 1.0 g was added and the reaction was carried out for 3 hours. I. B. N. The operation of adding 0.5 g and reacting for 3 hours was continued twice.

After cooling, the reaction product was reprecipitated in 1 liter of ether, the precipitate was collected and dried, and the Mw was 6.5 × 10.
63 g of a viscous product of ³ was obtained.

[0200]

[Chemical 52]

Synthesis Examples 12 to 19 of Resin [A]: [A-1
2] to [A-19] In Synthesis Example 11 of resin [A], instead of each monomer and macromonomer, each monomer and macromonomer corresponding to the polymerization component shown in Table B below was used. Others were reacted in the same manner as in Synthesis Example 11 to produce each polymer.

The Mw of each copolymer is 6 × 10 ³ to 8 × 10.
It was in the range of ³ .

[0203]

[Table 4]

[0204]

[Table 5]

Synthesis Example 20 of Resin [A]: [A-20] A mixed solution of 70 g of 2-chlorophenyl methacrylate, 30 g of macromonomer (MM-3), 3.0 g of thioglycolic acid and 150 g of toluene was heated under a nitrogen stream at a temperature. 80
Warmed to ° C. A. I. B. N. 1.0 g was added and reacted for 4 hours. I. B. N. 0.5 g was added for 2 hours, and A. I. B. N. 0.3 g was added and reacted for 3 hours.

The Mw of the obtained copolymer was 8.5 × 10 ^3.
Met.

[0207]

[Chemical 53]

Synthesis Examples 21 to 28 of Resin [A]: [A-2
1] to [A-28] In the same manner as in Synthesis Example 20 of Resin [A], 60 g of a monomer corresponding to the components shown in Table C below and 40 g of a macromonomer.
And 0.04 mol of the mercapto compound was used to carry out the polymerization reaction.

Mw of the obtained copolymer was 6 × 10 ^{3 to} 9
It was × 10 ³ .

[0210]

[Table 6]

[0211]

[Table 7]

[0212]

[Table 8]

Synthesis Example 29 of Resin [A] of the Present Invention: [A-
29] 2-chloro-6-methylphenyl methacrylate 60
A mixed solution of g, 25 g of macromonomer (MM-4), 15 g of methyl acrylate, 150 g of toluene and 50 g of isopropanol was heated to a temperature of 80 ° C. under a nitrogen stream.
A. C. V. 5 g was added and reacted for 5 hours. C.
V. 1.0 g was added and reacted for 4 hours. The Mw of the obtained copolymer was 9.8 × 10 ³ .

[0214]

[Chemical 54]

[Synthesis of Resin [B]] Synthesis Example of Resin [B]: [B-1] 74 g of methyl methacrylate and an initiator of the following structure [I
-1] The mixture of 12.4 g was heated at a temperature of 50 ° C under a nitrogen stream.
Warmed to. 10c of this solution with 400W high pressure mercury lamp
Photopolymerization was carried out by irradiating with light from a distance of m through a glass filter for 5 hours.

Tetrahydrofuran 100 was added to this polymer.
g was added and dissolved, 25 g of methyl acrylate and 1.0 g of acrylic acid were further added, and then the mixture was heated again to a temperature of 50 ° C. under a nitrogen stream.

[0217]

[Chemical 55]

Then, after irradiating with light for 10 hours in the same manner as described above, the obtained reaction product was reprecipitated in 2 liters of methanol, and the precipitate was collected and dried to obtain a weight of 78 g. Average molecular weight (Mw: Mw is G in terms of polystyrene)
A value of 6 × 10 ⁴ by PC method was obtained.

[0219]

[Chemical 56]

Synthesis Example 2 of Resin [B]: [B-2] In the synthesis example of Resin [B-1], the initiator [I-1] 1
In place of 2.4 g, an initiator [I-2] having the structure shown below 16.
It operated on the same conditions as the synthesis example 1 except having used 0g.
The yield of the obtained polymer was 72 g, and the Mw was 6 × 10 ⁴ .

[0221]

[Chemical 57]

[0222]

[Chemical 58]

Synthesis Examples 3 to 9 of Resin [B]: [B-3] to
[B-9] A mixture of 65 g of methyl methacrylate and 0.013 mol of each initiator shown in Table D below was subjected to a photopolymerization reaction in the same manner as in Synthesis Example 1 of Resin [B].

Next, 100 g of tetrahydrofuran was added to and dissolved in this, and further 30 g of methyl acrylate and N-
After adding 4 g of vinylpyrrolidone and 1 g of methacrylic acid, photopolymerization and reprecipitation were carried out in the same manner as in Synthesis Example 1. The Mw of the obtained polymer was in the range of 5 × 10 ⁴ to 8 × 10 ⁴ .

[0225]

[Table 9]

[0226]

[Table 10]

[0227]

[Table 11]

Synthesis Examples 10 to 15 of Resin [B]: [B-1
0] to [B-15] In Synthesis Example 1 of resin [B], each monomer corresponding to the polymerization component shown in Table-E was used instead of methyl methacrylate, methyl acrylate and acrylic acid. Each polymer was obtained by operating under the same conditions as in Synthesis Example 1.
The Mw of the obtained polymer was in the range of 5 × 10 ^{4 to} 6 × 10 ⁴ .

[0229]

[Table 12]

[0230]

[Table 13]

Synthesis Examples 16 to 21 of Resin [B]: [B-1
6] to [B-21] 16.5 g of methyl acrylate, acrylonitrile 2.
5 g, 1.0 g of acrylic acid, and the initiator of the following Table-F were added to 0.5 g.
A mixed solution of 0072 mol and 20 g of tetrahydrofuran was irradiated with light in the same manner as in Synthesis Example 1 for 15 hours. Then, to this reaction product, methyl methacrylate 60 was added.
g, 20 g of methyl acrylate and 80 g of tetrahydrofuran were added, and then a polymerization reaction and reprecipitation were performed in the same manner as in Synthesis Example 1. The Mw of the obtained polymer was 5 × 10 ⁴ to 8
It was in the range of × 10 ⁴ .

[0232]

[Table 14]

[0233]

[Table 15]

[0234]

[Table 16]

Synthesis Examples 22 to 26 of Resin [B]: [B-2
2] to [B-26] A mixture of a monomer corresponding to the polymer component shown in Table G below and 14 g of the above initiator [I-2] was added at a temperature of 40 ° C. under a nitrogen stream.
The mixture was heated to, and the following operations were carried out in the same manner as in Example 1 to irradiate with light and polymerize for 5 hours.

The solid is taken out and tetrahydrofuran 1
After dissolving in 00 g, 25 g of methyl acrylate and 1.5 g of acrylic acid were added, and the mixture was further heated to a temperature of 50 ° C. under a nitrogen stream and irradiated with light to polymerize in the same manner as above. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. The yield of each polymer is 65-75 g and M
w was 5 × 10 ^{4 to} 7 × 10 ⁴ .

[0237]

[Table 17]

Synthesis Examples 27 to 33 of Resin [B]: [B-2
7] to [B-33] methyl methacrylate 56 g, methyl acrylate 24
A mixture of g and 10 g of the initiator [I-16] having the following structure was heated to a temperature of 40 ° C. under a nitrogen stream, and the following operations were carried out in the same manner as in Example 1 to irradiate with light for polymerization for 4 hours.

After dissolving the solid substance in 100 g of tetrahydrofuran, each monomer corresponding to the polymerization component shown in Table H below was added, and the mixture was further heated to a temperature of 50 ° C. under a nitrogen stream and irradiated with light in the same manner as above. And polymerized. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. The yield of each polymer was 65 to 75 g, and the Mw was 4 × 10 ^4.
Was about 7 × 10 ⁴ .

[0240]

[Chemical 59]

[0241]

[Table 18]

[0242]

[Table 19]

Example 1 and Comparative Examples 1 and 2 8 g of resin [A-7] (as solid content), resin [B-
1] 32 g (as solid content), optical electrode zinc oxide 20
0g Cyanine dye [I] having the following structure 0.018g A mixture of 0.45g salicylic acid and 300g toluene in a homogenizer (manufactured by Nippon Seiki Co., Ltd.), rotation speed 7 × 10 ³ r
Dispersion was carried out for 10 minutes at pm to prepare a photosensitive layer-formed product, which was applied to a conductive-treated paper with a wire bar so that the dry adhesion amount was 25 g / m ^2, and dried at 110 ° C. for 10 seconds. Then, it was left in the dark at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material.

[0244]

[Chemical 60]

Comparative Example 1: In Example 1, the resin [B-
1] 32 g of resin [R-1] having the following structure instead of 32 g
An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that was used.

[0246]

[Chemical formula 61]

Comparative Example 2: In Example 1, the resin [B-
1] 32 g of resin [R-2] having the following structure instead of 32 g
An electrophotographic photosensitive material was prepared in the same manner as in Example 1 except that

[0248]

[Chemical formula 62]

With respect to these photosensitive materials, electrostatic characteristics, image pick-up properties and environmental conditions (20 ° C., 65% RH), (30 ° C.,
The image pick-up property at 80% RH) and (15 ° C., 30% RH) was examined.

The above results are shown in Table-I.

[0251]

[Table 20]

Embodiments of the evaluation items shown in Table-I 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 type 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 (%).

Further, 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 calculated, and from this, the exposure amount E _1/10 (erg / cm
² ) is calculated. Similarly, the surface potential (V ₁₀ ) is 1/1
The time until it decays to 00 is calculated, and the exposure amount E
Calculate _1/10 (erg / cm ² ). Environmental conditions at the time of measurement are 20 ° C, 65% RH (I), 30 ° C, 80% RH
(II) and 15 ° C., 30% RH (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 an isoparaffin Isopar G (manufactured by Esso Chemical Co., Ltd.) solvent rinse solution was used. The copied image (fogging, image quality of the image) obtained by fixing after washing with (1) was visually evaluated.

The environmental conditions at the time of imaging are 20 ° C. and 65% RH.
(I), 30 ° C 80% RH (II) and 15 ° C, 30% R
Performed with H (III). As shown in Table I, the light-sensitive material of the present invention had good electrostatic characteristics, 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
If the environmental conditions change, the photosensitivity E _1/10 and E _1/100 will drop, and even in the actual copy image, fine lines, letters, etc. will not be removed, and even after rinsing, slight background fog remains without being removed. have done.

Although it does not match the electrostatic characteristic, unevenness occurs in the intermediate density of the continuous tone part of the copy original especially under the environmental condition (II). A slight white drop was generated in the area.

When the photoconductor of the present invention and the photoconductor of the comparative example are E
_1/100 value is greatly different. The E _1/100 value indicates how much potential remains in the non-image portion (exposed portion) after exposure in the actual image pickup property. It indicates that the image area is free of background stains.

Specifically, it is necessary to set the residual potential to −10 V or less, that is, how much exposure dose is required to set V _R −10 V or less. In the scanning exposure method according to ( _1), setting VR to −10 V or less with a small exposure amount is
This is very important in designing the optical system of the copying machine (cost of the device, accuracy of optical path of optical system, etc.).

From the above, an electrophotographic photosensitive member satisfying the electrostatic characteristics and the image pick-up property can be obtained only when the resin of the present invention is used, which is particularly advantageous for a semiconductor laser light scanning exposure type photosensitive system. It became clear. Example 2 and Comparative Examples 3 and 4 6 g of resin [A-23] (as solid content), resin [B-
2] 34 g (as solid content), photoconductive zinc oxide 20
0 g, 0.020 g of methine dye (II) having the following structure, N-
Hydroxyphthalimide 0.23 g and toluene 300
The mixture of g was operated in the same manner as in Example 1 to prepare an electrophotographic photosensitive material.

[0259]

[Chemical 63]

Comparative Example 3: In Example 2, the resin [B-
2] 34 g instead of resin [R-3] 34 having the following structure
An electrophotographic photosensitive material was produced in the same manner as in Example 2 except that g was used.

[0261]

[Chemical 64]

Comparative Example 4: In Example 2, the resin [B-
2] 34 g instead of resin [R-4] 34 having the following structure
An electrophotographic photosensitive material was produced in the same manner as in Example 2 except that g was used.

[0263]

[Chemical 65]

The film properties (surface smoothness) of this photosensitive material,
The electrostatic characteristics, the imaging characteristics and the imaging characteristics were examined when the environmental conditions were 30 ° C., 80% RH and 15 ° C., 30% RH. Further, the printability when used as an electrophotographic lithographic printing plate precursor was investigated.

[0265]

[Table 21]

Embodiments of the evaluation items shown in Table-J are as follows. Note 3) Smoothness of surface layer: The obtained light-sensitive material was measured using a Beck's smoothness tester (produced 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: The surface of the obtained light-sensitive material was tested with Haydon-14 type surface test material (manufactured by Shinto Chemical Co., Ltd.) under a load of 75 g / cm ² with emery paper ( # 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 solution EPL-EX (Fuji Photo Film Co., Ltd.)
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 Machine Co., Ltd., 611XLA-II
Then, the degree of background stain of the printing press on the 50th sheet after printing was evaluated (corresponding to the forced condition for examining the degree of water retention of the desensitized original plate). Note 6) Printing durability: Under the same conditions as in Note 2) above, after making a plate to form a toner image, ELP-EX is used to pass twice through an etching processor to desensitize. Then, using this as an offset master, it is applied to an offset printing machine (Oliver 52 type manufactured by Sakurai Mfg. Co., Ltd.) to show the number of prints that can be made without causing scumming in the non-image area of the printed matter and in the image quality of the image area (printing). The larger the number, the better the printing durability.) As shown in Table-J, in the light-sensitive material of the present invention, the smooth film of the photoconductive layer had good mechanical strength and electrostatic properties, and the actual copied image was free of 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 observed 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 conditions at the time of image pickup are severe, the non-image part is slightly stained, and unevenness is generated in the high-definition continuous tone image part. Alternatively, problems such as white spots and unevenness in the solid image portion occurred.

Further, in the offset master-original plate, the degreasing-processed plate water retention showed ink adhesion. The actual printing durability was 4 to 6,000 sheets. The above is
The resin [A] and the resin [B] of the present invention properly interact with the zinc oxide particles to form a pan state in which the desensitizing reaction by the desensitizing treatment solution easily and sufficiently proceeds. And that the film strength is remarkably improved by the action of the resin [B]. Examples 3 to 22 In Example 2, the resin [A-23] and the resin [B-
Each electrophotographic photosensitive member was produced in the same manner as in Example 2 except that each resin [A] and each resin [B] shown in Table K below were used instead of 2].

The electrostatic characteristics were measured in the same manner as in Example 2. The results are shown in Table-K.

[0270]

[Table 22]

The electrostatic characteristics and the image pickup property of each light-sensitive material were measured in the same manner as in Example 1. All of the photosensitive materials have good electrostatic characteristics, and when the actual imaging properties of these photosensitive materials were examined, the reproducibility of fine lines and characters was good, there was no unevenness in the halftone, and there was no clear background fog. A duplicate image was obtained.

When used as an offset master original plate and printed in the same manner as in Example 2, at least 10,000 or more sheets could be printed. From the above, each of the light-sensitive materials of the present invention was good in all of the smoothness, film strength, electrostatic properties and printability of the photoconductive layer. Examples 23 to 26 Electrophotographic photosensitive materials were produced under the same conditions as in Example 1 except that the methine dye [I] used in Example 1 was replaced with the dyes shown in Table L below.

[0273]

[Table 23]

[0274]

[Table 24]

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).
Even under severe conditions (° C., 30% RH), a clear image with no background fog was obtained. Examples 27 and 28 and Comparative Example 5 Resin [A-1] (Example 27) or Resin [A-22]
6.5 g of any of (Example 28), resin [B-26]
33.5 g, zinc oxide 200 g, uranine 0.02 g,
0.03 g of methine dye [VII] having the following structure, 0.03 g of methine dye [VIII] having the following structure, 0.18 phthalic anhydride
g and 300 g of toluene were dispersed in a homogenizer at a rotation speed of 7 × 10 ³ rpm for 8 minutes to prepare a photosensitive layer-formed product, which was applied to a conductive-treated paper with a dry adhesion amount of 20.
It was coated with a wire bar so as to be g / m ² and dried at 110 ° C. for 20 seconds. Next, each electrophotographic photosensitive member was prepared by leaving it in the dark at 20 ° C. and 65% RH for 24 hours.

[0276]

[Chemical 66]

[0277]

[Chemical 67]

Comparative Example 5 In the same manner as in Example 27 except that 33.5 g of the resin [R-5] having the following structure was used instead of 33.5 g of the resin [B-26] in Example 27. A photosensitive material was prepared.

In the same manner as in Example 1, each characteristic of each photosensitive material was examined. The results are summarized in Table-M below.

[0280]

[Chemical 68]

[0281]

[Table 25]

In the above measurement, the electrostatic properties and the image pickup properties were the same as in Example 1 except that the following operations were performed. Note 7) Method for measuring E _1/10 of electrostatic characteristics After charging the surface of the photoconductive layer to −400 V by corona discharge, the surface of the photoconductive layer was irradiated with visible light having an illuminance of 2.0 lux to obtain the surface potential. The time required for (V ₁₀ ) to decay to _1/10 is calculated, and the exposure dose E _1/10 (lux · sec) is calculated from this. Note 8) Imaging property After leaving each light-sensitive material for 1 day under the following environmental conditions, fully automatic plate-making machine EPL-404V (Fuji Photo Film Co., Ltd.)
Manufactured by EPL-T as a toner, and the copy image (fog, image quality of the image) obtained by plate making was visually evaluated. Environmental conditions at the time of imaging are 20 ° C 65% RH (I), 30 ° C 8
Performed at 0% RH (II) and 15 ° C., 30% RH (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 in Comparative Example 5, it was lower than these. The electrostatic properties showed good performance at room temperature and humidity (I), but especially at low temperature and low humidity (II).
In I), E _1/10 decreased.

The light-sensitive material of the present invention has good electrostatic characteristics, and Example 28 using the resin [A] having a specific substituent is very good, and particularly, the value of E _1/100 . Has become smaller. As a result of examining the actual image pickup property, Comparative Example 5
In addition to the original as a copy image, the frame of the cut-out portion (that is, the trace of attachment) was recognized as the background stain of the non-image portion. Furthermore, when the environmental conditions at the time of image pickup are high temperature / high humidity (II) and low temperature / low humidity (III), unevenness occurs in the halftone region of the continuous tone part of the copy image, and white spots in the solid image part are minute. Occurrence of unevenness was observed.

Further, when these were subjected to desensitizing 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 trace was not removed even by the desensitizing treatment, and was generated from the printed matter printed out.

From the above, only the light-sensitive material of the present invention can provide good characteristics. Example 29 Resin [A-7] 5 g and resin [B-8] 35 g, zinc oxide 200 g, uranine 0.02 g, rose bengal 0.
A mixture of 04 g, bromphenol blue 0.03 g, phthalic anhydride 0.40 g and toluene 300 g was treated in the same manner as in Example 27 to prepare a light-sensitive material.

The performance of the light-sensitive material of the present invention was examined in the same manner as in Example 27. As a result, all were excellent in chargeability, dark charge retention rate and photosensitivity. (30 ℃, 80% RH) and low temperature / low humidity (15 ℃, 30
% RH), a clear image with no background fog was obtained even under severe conditions.

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-7] and resin [B
-8] 5 g of resin [A] shown in Table N below instead of 35 g
Each photosensitive material was prepared in the same manner as in Example 27 except that 35 g of Resin [B] was used.

[0289]

[Table 26]

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).
% RH), a clear image with no background fog or fine line skipping was provided even under severe conditions.

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

[0292]

According to the present invention, an electrophotographic photoreceptor having a clear and high-quality image having excellent electrostatic characteristics (electrostatic characteristics under particularly 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 (4)

[Claims] 1. An electrophotographic photosensitive member having a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye and a binder resin, wherein the binder resin is the following resin [A ₁ ] or resin [A ₂ ] ] And at least one of the following resins [B], an electrophotographic photosensitive member comprising: Resin [A ₁ ] One of the polymer main chains having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and containing a repeating unit represented by the following general formula (I) as a polymer component in an amount of 30% by weight or more. A monofunctional macromonomer (M ₁ ) having a weight average molecular weight of 2 × 10 ⁴ or less, which is formed by bonding a polymerizable double bond group represented by the following general formula (II) only to the terminal of the general formula (I) Is a copolymer comprising at least a monomer corresponding to the repeating unit represented by
₃ H ₂ , -SO ₃ H, -COOH, -P (= O) (O
H) R ¹ [R ¹ represents a hydrocarbon group or —OR ² (R ² represents a hydrocarbon group)] and a resin formed by bonding at least one polar group selected from a cyclic acid anhydride group .. Resin [A ₂ ] having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and containing a repeating unit represented by the following general formula (I) as a polymer component in an amount of 30% by weight or more and the above resin [A ₁ ]. Polymerization represented by the following general formula (II) only at one end of a polymer main chain containing 1 to 50% by weight of a polymer component containing at least one polar group selected from the specific polar groups shown. Weight average molecular weight of 2 × 10 ⁴
A resin, which is a copolymer comprising at least the following monofunctional macromonomer (M ₂ ) and a monomer corresponding to the repeating unit represented by the general formula (I). [Chemical 1] [In the formula (I), a ¹ and a ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ³ represents a hydrocarbon group. ] [Chemical 2] [In the formula (II), R ⁴ is —COO—, —OCO—, —C
_{H 2 OCO -, - CH 2} COO -, - O -, - SO
_{2 -, - CO -, -} CONR 5 -, - SO 2 NR 5 -
(Wherein R ⁵ represents a hydrogen atom or a hydrocarbon group),
CONHCOO -, - CONHCONH- or -C ₆ H
₄ - represents a. b ¹ and b ² may be the same or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COOR ⁶ or —COO via a hydrocarbon.
R ⁶ (wherein R ⁶ represents an optionally substituted hydrocarbon group) is represented. Resin [B] An A block having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ and containing at least the repeating unit represented by the general formula (I) in the above resin [A ₁ ] as a polymer component. AB type block polymer composed of a B block containing at least one polymer component containing at least one polar group selected from the specific polar groups represented by the resin [A ₁ ]. A resin composed of a star-type copolymer in which at least three chains are bound in an organic molecule. 2. The resin [A ₂ ] further comprises the resin [A ₂ ].
_[1 ] The electrophotographic photosensitive member according to claim 1, wherein at least one polar group selected from the specific polar groups represented by [ ₁ ] is bonded to the terminal of the main chain of the copolymer. 3. The resin [A ₁ ] or [A ₂ ] as a polymer component represented by the general formula (I) is represented by the following general formula (I
The electrophotographic photosensitive member according to claim 1 or 2, containing at least one of a) and an aryl group-containing methacrylate component represented by the following general formula (Ib). [Chemical 3] [Chemical 4] [In formulas (Ia) and (Ib), R ⁷ and R ⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, —COR ¹¹ or —COOR ¹¹ (wherein R ¹¹ is Represents a hydrocarbon group having 1 to 10 carbon atoms), R ⁹ and R ¹⁰
Each represent a single bond or a linking group having 1 to 4 linking atoms for linking -COO- and the benzene ring. ] 4. In the resin [B], the total amount of the specific polar group-containing polymer component contained in all the copolymers is specified in the resins [A ₁ ] and [A ₂ ]. 10% to 50% by weight based on the total amount of the polar group-containing polymer component
The electrophotographic photosensitive member according to claim 1, wherein