JPH05323628A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To always maintain stable and good electrostatic characteristics and to obtain high definition and good picture images by incorporating specified resin into a binder resin. CONSTITUTION:The binder resin consists of at least a resin [A1] and/or resin [A2] and a medium to high mol.wt. resin [B]. The resin [A1] is a copolymer containing macromonomers (M1) and monomers expressed by formula I and the end of this copolymer is coupled with a specified polar group. The resin [A2] is a copolymer consisting of macromonomers (M2) having a component containing a specified polar group and of monomers expressed by formula II. The resin [B] is an AB-block copolymer consisting of block A having a component containing a specified polar group and of block B containing a polymer component expressed by formula II in which a specified polar group is coupled with the end of the polymer main chain of the block A opposite to the end coupled with the block B. In formula I, a<1> and a<2> are hydrogen atoms, etc., and R<3> is a hydrocarbon group. In formula II, R<4> is -COO-, etc., b<1> and b<2> are hydrogen atoms, halogen atoms, etc., which may be same or different.

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 electrophotographic photoconductors are a photoconductor having a photoconductive layer formed on a support and a photoconductor having an insulating layer on the surface thereof, which are widely used.

Photoreceptors comprising a support and at least one photoconductive layer are used in the most common electrophotographic processes, ie, charging, imagewise exposure and development, and optionally, image formation by transfer. Furthermore, 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 conducted, 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. Inorganic photoconductive material,
It has been found that, in the photoconductive layer containing at least the spectral sensitizing dye and the binder resin, not only the smoothness but also the electrostatic properties are greatly affected by the chemical structure of the binder resin. Especially in the electrostatic characteristics, the charge retention ratio in the dark (D.R.
R. ) And light sensitivity are greatly affected.

On the other hand, various techniques for improving smoothness and electrostatic characteristics have been studied by using a resin having a relatively low molecular weight (about 10 ³ to 10 ⁴ ) containing an acidic group as a binder resin. ing. For example, JP-A-63-217354 discloses a resin in which an acidic group-containing polymerization component is randomly present in the polymer main chain, and JP-A No. 64-70761 is a resin in which an acidic group is bonded to one end of the polymer main chain. Resin, JP-A-2-67563
Nos. 2,236,561, 2,238,458, 2,236,562, and 2,247,656, etc., each have a resin or an acidic group formed by bonding an acidic group to the end of the main chain of the graft copolymer. Resins contained in the graft portion of the graft type copolymer, and JP-A No. 3-181948 describe AB type block copolymers containing an acidic group as a block. 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.

Further, in order to make the mechanical strength of the photoconductive layer sufficient by using only these low molecular weight resins,
Various techniques of using other resins of medium to high molecular weight in combination have been studied. For example, JP-A-2-68561 discloses a thermosetting resin which forms a crosslinked structure between polymers, and JP-A-2-6856.
No. 562, a resin partially having a cross-linked structure, disclosed in JP-A-2-
No. 69759 describes a resin having an acidic group bonded to the end of the main chain of a graft copolymer. Further, by using a specific medium to high molecular weight resin, a technique for maintaining a relatively stable performance even when the environment is significantly changed has been studied. For example, JP-A-3-29954 and JP-A-3-7795.
No. 54, No. 3-92861, and No. 3-53257, there is a resin that binds an acidic group to the end of the graft portion of the graft copolymer or a resin that contains an acidic group in the graft portion of the graft copolymer. Have been described. Furthermore, 3-20
No. 6464, No. 3-23846 and No. 4-1565
According to No. 5, by using a graft type copolymer having an AB block type copolymer composed of an acidic group-containing A block and an acidic group-free B block in a graft portion, environmental changes and semiconductor lasers can be improved. It has been revealed that a relatively high performance is maintained even when the scanning exposure method using the light is used.

[0007]

However, even if various low molecular weight resins containing these acidic groups, and further various medium to high molecular weight resins are used in combination with these resins, the environment at high temperature and high temperature is high. It was found that it is still insufficient to maintain stable performance when there is a significant change from humidity to low temperature / low humidity. 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. In terms of photosensitivity, higher performance is required.

In particular, in the electrophotographic lithographic printing plate precursor, when a scanning exposure method using a semiconductor laser beam was adopted, when actually tested with a conventional photoreceptor, the above electrostatic characteristics were found to be sufficient. 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, a problem such as a print original sticking mark on the printed matter appeared.

Further, in recent years, it has been desired to realize a technique for faithfully reproducing not only a copied image of an image composed of line drawings and halftone dots but also a high-definition image composed of continuous gradations by using a liquid developer. However, the above-mentioned known technology has not been able to sufficiently satisfy these demands. In the conventionally known technology, the medium to high molecular weight resin used in combination with the low molecular weight resin may lower the electrostatic properties of the high performance of the low molecular weight resin. The electrophotographic photosensitive member having a photoconductive layer used in combination with a known resin is capable of reproducing a faithful copy image of a high-definition image (especially continuous tone image) as described above or a low-output laser beam. For the imaging ability by the scanning exposure method used,
It became clear that it could cause problems.

The present invention is to improve the problems of the above-described conventionally known electrophotographic photoreceptors. 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 as an electrophotographic lithographic printing original plate, which is excellent in electrostatic properties (particularly dark charge retention and photosensitivity) and has an original image (particularly a high-definition continuous tone image).
Reproduces a copy image that is faithful to, and does not generate spot stains as well as uniform stains on the entire printed matter.
Another object is to provide a lithographic printing original plate having excellent printing durability.

[0012]

The above object is to provide an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor, a spectral sensitizing dye and a binder resin. ₁ ] and at least one resin [A ₂ ] and at least one resin [B] below, respectively.

Resin [A ₁ ] A polymer 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, in which a polymerizable double bond group represented by the following general formula (II) is bonded to only one end of the chain; A copolymer comprising at least a monomer corresponding to the repeating unit represented by (I), and -PO at one end of the main chain of the copolymer.
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 ]. The polymerizability represented by the following general formula (II) only at one terminal of the 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. Copolymer containing at least a monofunctional macromonomer (M ₂ ) having a weight average molecular weight of 2 × 10 ⁴ or less formed by bonding a double bond group and a monomer corresponding to the repeating unit represented by the general formula (I). Resin that is a united body.

[0014]

[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. ]

[0016]

[Chemical 6]

[In the formula (II), R ⁴ is -COO-, -O
_{CO -, - CH 2 OCO -} , - CH 2 COO -, - O
_{-, - SO 2 -, -} CO -, - CON (R 5) -, - S
^{_{O 2 N (R 5) -}} ( wherein R ⁵ represents a hydrogen atom or a hydrocarbon group), - CONHCOO -, - CONHCON
H- or -C ₆ H ₄ - represents a. b ¹ and b ^2, which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COOR ⁶ (wherein R ⁶ through a -COOR ⁶ or hydrocarbons substituted Represents a good hydrocarbon group). Resin [B] having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ and containing at least one polar group selected from the specific polar groups represented by the above resin [A ₁ ]. An AB block copolymer composed of an A block containing at least one polymer component and a B block containing at least one polymer component represented by the general formula (I) represented by the resin [A ₁ ]. In the A block, at least one polar group selected from the specific polar groups represented by the above resin [A ₁ ] is bonded to the end of the polymer main chain on the opposite side to which the B block is bonded. Resin.

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]), an A block containing the above specific polar group-containing component, and the above general In the AB block copolymer with the B block containing the polymer component represented by the formula (I), in the A block, the above-mentioned specific polar group is bonded to the end of the polymer main chain on the opposite side to which the B block is bonded. And a medium to high molecular weight resin [B].

As a result of various studies, as described above, in the known 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 was found that the high-performance electrostatic properties of the resin may deteriorate. And, these medium to high molecular weight resins are photoconductors in the photoconductive layer,
It has become clear that the more appropriate interaction with the interaction between the spectral sensitizing dye and the resin having a low molecular weight is more important than expected.

As a result of repeated studies, a polar group according to the present invention was used as a medium to high molecular weight resin which should be used in combination with a low molecular weight resin [A] containing a polar group and one end of the polymer main chain and A block. It has been found that the above problems can be effectively solved by using an AB block copolymer contained therein and having the A block and a B block containing no polar group.

This is because, due to the synergistic effect of the binder resins [A] and [B] of the present invention, the photoconductor particles are present in a state in which they are sufficiently dispersed and do not condense, 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. In addition, a medium to high molecular weight AB block copolymer containing the specific polar group of the present invention at one end of the polymer main chain and at the A block and not containing it is used. As a result, the electrostatic characteristics were improved and the mechanical strength of the photoconductive layer was sufficiently maintained. This is this resin [B]
The specific polar group bonded to one end of the main chain of the is selectively adsorbed on the photoconductor particles, and the A block portion has a polar state and is present on the surface of the photoconductor particles and in the vicinity thereof. Therefore, it is presumed that this is due to the formation of a state that facilitates the adsorption of the spectral sensitizing dye, further the chemical sensitizer, etc., to the photoconductor particles.

That is, the interaction between the resin [A] and the polar group bonded to the terminal of the resin [B] and the A block sufficiently traps the active sites of the photoconductor particles to stabilize the electrostatic characteristics. It is considered that the electrostatic properties can be maintained at a high level by forming a state in which the adsorption of various sensitizers to the surface of the photoconductor is not excluded. Further, the B block portion not containing a specific polar group in the resin [B] has a sufficient entanglement effect between polymer chains, and as a result, the mechanical strength of the photoconductive layer is improved. Presumed.

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 treatment liquid to prepare a printing original plate. Shows excellent performance as an original plate for printing when it is printed by offset printing. When the photosensitizer of the present invention is desensitized, the non-image areas are sufficiently hydrophilized and the water retention is improved, so that the number of printed sheets is dramatically improved. This is because the zinc oxide particles are uniformly dispersed and the presence state of the binder resin present on the surface of the zinc oxide particles is appropriate and the desensitizing reaction with the desensitizing treatment liquid is not alienated and quickly. It is considered that this is due to effective progress.

Further, in the present invention, in the low molecular weight resin [A ₁ ] and resin [A ₂ ], the 2-position represented by the following general formula (Ia) and general formula (Ib) as the general formula (I): And / or containing a benzene ring or an unsubstituted naphthalene ring having a specific substituent at the 2- and 6-positions,
A resin containing a methacrylate component having a specific substituent (hereinafter, this low molecular weight compound is particularly referred to as resin [AA])
Is preferred.

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[In the formulas (Ia) and (Ib), A ¹ and A
² are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom (for example, a chlorine atom or a bromine atom), a cyano group, -COR ⁷ or -COOR ⁷ (wherein R ⁷ is a carbon number 1 Represents a hydrocarbon group of 10), B
¹ and B ² each represent a single bond or a connecting group having 1 to 4 connecting atoms for connecting —COO— and the benzene ring. ] When the above-mentioned specific resin [AA] is used, the electrophotographic characteristics (particularly V ₁₀ , DRR, E) are further improved as compared with the case of the resin [A].
_1/10 ) improvement can be achieved.

The reason for this is not clear, but one reason is that due to the effect of a planar benzene ring or naphthalene ring having a substituent at the ortho position, which is an ester component of methacrylate, the zinc oxide interface in the film is affected. It is considered that the arrangement of these polymer molecular chains in 1 is appropriately performed.

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.

[0039] 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 A ¹ and A
^{As 2} , each independently of one another, a hydrogen atom, a chlorine atom and a bromine atom, as a hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group,
Ethyl group, propyl group, butyl group, aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group) , Chloromethylbenzyl group) and aryl groups (eg phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and —COR ⁷ and —COOR
⁷ (preferable R ⁷ includes those described as the above-mentioned preferable hydrocarbon group having 1 to 10 carbon atoms).

In the formulas (Ia) and (Ib), B ¹ and B ² are each a single bond connecting --COO-- and a benzene ring or-(CH ₂ ) _a- (a represents an integer of 1 to 3). ,-
_{CH 2 OCO -, - CH 2} CH 2 OCO -, - (CH 2
O) _b - _(b represents an integer of 1 or _2), - CH 2 CH
A connecting group having 1 to 4 connecting atoms such as ₂ O- and the like, more preferably, a single bond or a connecting group having 1 to 2 connecting 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 the formula, c is an integer of 1 to 4, d is an integer of 0 or 1 to 3, e is an integer of 1 to 3, and R ⁸ is -CcH _{2c + 1} or-(CH ₂ ) _d -C ₆ H _5. (However, c and d are the same as the above), D ¹ and D ² may be the same or different and each represents a hydrogen atom, —Cl, —Br, or —I.

[0044]

[Chemical 9]

[0045]

[Chemical 10]

[0046]

[Chemical 11]

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 12, wherein R ¹ is a hydrocarbon group or an -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. ..

[0049]

[Chemical formula 12]

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride 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.

In the case of the resin [A ₁ ], the polar group is contained by being bonded to the end of the polymer main chain. The content of the polar group is not particularly limited, but is preferably 0.5 to 15% by weight. The polar group may be directly bonded to the end of the polymer main chain or may be bonded via a linking group. The linking group may be any bonding group,
For example, specifically, -C (R ¹⁶ ) (R ¹⁷ ).
-[Wherein R ¹⁶ and R ¹⁷ may be the same or different,
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, respectively)
Propyl group, butyl group, hexyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), phenyl group, etc.], —CH (R ¹⁶ ) —CH (R ¹⁷ ) —, —C ₆ H
_{10 -, - C 6 H 4} -, - O -, - S -, - N (R 18) -
[Here, R ¹⁸ represents a hydrogen atom or a hydrocarbon group (specifically, a hydrocarbon group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, Decyl group, dodecyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-cyanoethyl group,
Benzyl group, methylbenzyl group, phenethyl group, phenyl group, tolyl group, chlorophenyl group, methoxyphenyl group, butylphenyl group, etc.)}]-
CO -, - COO -, - OCO -, - CON (R 18)
_{-, - SO 2 N (R} 18) -, - SO 2 -, - NHCON
H -, - NHCOO -, - NHSO 2 -, - CONHC
OO-, -CONHCONH-, heterocycle (a 5- or 6-membered ring containing at least one kind of O, S, N etc. as a hetero atom, or a condensed ring thereof may be used, and examples thereof include a thiophene ring, a pyridine ring, and a furan ring. , an imidazole ring, piperidine ring, morpholine ring and the like), or ^{_{-S i (R 19) (R}} 20) - [wherein R ^19, R ²⁰ may be the same or different, each hydrocarbon radical or - OR ²¹
(Wherein R ²¹ represents a hydrocarbon group). Examples of these hydrocarbon groups include the same groups as those listed for R ¹⁸ ] and the like, and a linking group composed of a single bonding group or a combination of two or more thereof.

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, b ³ represents H or CH _3, b ⁴ is H, CH ₃ or CHCOOCH _3, R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms, R ¹¹ is alkyl of 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.

[0056]

[Chemical 13]

[0057]

[Chemical 14]

[0058]

[Chemical 15]

[0059]

[Chemical 16]

[0060]

[Chemical 17]

[0061]

[Chemical 18]

[0062]

[Chemical 19]

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 the 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.

[0066]

[Chemical 20]

[In the formula (II), R^FourIs -COO-, -O
CO-, -CH₂OCO-, -CH ₂COO-, -O
-, -SO₂-, -CO-, -CON (R^Five)-, -S
O₂N (R^Five)-(Where R^FiveIs a hydrogen atom or hydrocarbon
Represents a group), -CONHCOO-, -CONHCON
H- or -C₆H_FourRepresents-.

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 —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 the monomer corresponding to the other repeating unit capable of being polymerized, acrylonitrile, methacrylic acid, etc. 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 as 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 a 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 via 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-mentioned case). The hetero atom is composed of an arbitrary combination of atomic groups such as oxygen atom, sulfur atom, nitrogen atom, silicon atom and the like.

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.

[0082]

[Chemical 21]

The protection reaction and deprotection reaction (for example, 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. Specifically, J. F. W. McOmie, "Pro
tective Groups in Organic
Chemistry "Plenum Press (19
73), T.S. 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.

[0085]

[Chemical formula 22]

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.

[0087]

[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, etc.) or a disulfide compound that 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 —, 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.

[0093]

[Chemical formula 23]

[0094]

[Chemical formula 24]

[0095]

[Chemical 25]

[0096]

[Chemical formula 26]

[0097]

[Chemical 27]

[0098]

[Chemical 28]

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 components include, for example, methacrylic acid esters, acrylic acid esters and crotonic acid esters having a substituent other than those described in the general formula (I), and 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 procedure is required to synthesize 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 the oligomer having one end reactive bond as described above in the synthesis of the macromonomer. Next, the resin [B] of the present invention will be described. The resin [B] is an AB block copolymer and has a specific polar group B in the A block of the polymer main chain.
It is characterized in that it is bound to one end on the opposite side to which it is bound to the block, either directly or through a linking group, and that it is contained as a polymer component in the A block.

The amount of the specific polar group-containing component in the AB block copolymer resin [B] is preferably 0.1 to 5 parts by weight per 100 parts by weight of the copolymer [B].
More preferably, the content is 0.2 to 3 parts by weight.
When the content of the polar group in the binder resin [B] is less than 0.1% by weight, the initial potential is low and a sufficient image density cannot be obtained, and when the content of the polar group is more than 5% by weight. ,
It is not preferable because the dispersibility decreases, the film smoothness and the high temperature and high humidity of the electrophotographic characteristics decrease, and the background stain increases when it is used as an offset master.

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

The weight average molecular weight of the copolymer [B] is 2 × 1.
0 ⁴ to 1 × 10 ⁶ , preferably 4 × 10 ^{4 to} 5 × 10 ^5.
Is.

When the molecular weight of the resin [B] is less than 2 × 10 ⁴ , the film forming ability is deteriorated and the sufficient film strength cannot be maintained.
On the other hand, when the molecular weight is larger than 1 × 10 ^6, the effect of the resin [B] of the present invention is reduced, and the electronic characteristics are the same as those of the conventionally known resin. The glass transition point of the resin [B] is preferably in the range of -10 ° C to 100 ° C, more preferably 0 ° C to 90 ° C.

Specific examples of the specific polar group contained in the resin [B] of the present invention include those having the same contents as the specific polar group contained in the resin [A] described above. .. In the resin [B], when the polar group is bonded to one end of the polymer main chain, the polar group may be directly bonded to one end of the polymer main chain or may be bonded via a linking group. You may. The linking group may be any bonding group,
Specific examples thereof include those described as the linking group that links the polymer main chain and the polar group in the resin [A ¹ ], and one or more of these linking groups may be mentioned. Is a combination of linking groups.

Specific examples of the polymerization component containing a specific polar group constituting the A block of the AB block copolymer (resin [B]) of the present invention include the specific polar group of the resin [A] described above. The same thing as the polymer component contained can be mentioned.

Two or more kinds of the polymer component containing a specific polar group as described above may be contained in the A block, and in that case, the two or more kinds of polar group containing components are contained in the A block. It may be contained in any form of random copolymerization or block copolymerization. Further, a polymer component other than the polar group-containing polymer component may be contained in the A block, and such a polymer component is preferably a polymer component corresponding to a repeating unit of the following general formula (III). Is mentioned.

[0110]

[Chemical 29]

[In the formula (III), X ¹ is -COO- or -OC.
_{O -, - (CH 2)} p -OCO -, - (CH 2) p -C
OO- (p represents an integer of 1 to 3), -O-, -SO
_{2 -, - CO -, -} CON (Q 2) -, - SO 2 N (Q
_{2) -, - CONHCOO -,} - CONHCONH- or -C ₆ H ₄ - are expressed (here Q ² represents a hydrogen atom or a hydrocarbon group). Q ¹ represents a hydrocarbon group. m ¹
And m ² may be the same as or different from each other and represent the same contents as a ¹ and a ² in the formula (I). ]

Here, Q ² is not only a hydrogen atom, but also a preferable hydrocarbon group is a C 1-18 optionally substituted alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group). Group, hexyl group, octyl group,
Decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-
Methoxyethyl group, 3-bromopropyl group, etc.), alkenyl group having 4 to 18 carbon atoms which may be substituted (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.), aralkyl group having 7 to 12 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group) , A bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), and an alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, a cyclohexyl group, 2- A cyclohexylethyl group, a 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, butoxyf Nyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarboxyphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group , Dodecylylamidophenyl group, etc.).

When X ¹ represents —C ₆ H ₄ —, 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.), alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) and the like.

Q ¹ 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),
X 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 that can be contained in the A block together with the polymer component represented by the formula (III), a unit amount corresponding to another repeating unit copolymerizable with the polymer component of the formula (III). Examples thereof include acrylonitrile, methacrylonitrile, and heterocyclic vinyls (for example, vinyl pyridine, vinyl imidazole, vinyl pyrrolidone, vinyl thiophene, vinyl pyrazole, vinyl dioxane, vinyl oxazine, etc.). These other monomers are used within a range not exceeding 20 parts by weight based on 100 parts by weight of the total polymer component of the A block.

Next, the polymerization components constituting the B block component in the AB block copolymer resin [B] will be described in detail. The B 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 B block component. Preferably 50-
100% by weight is contained.

The specific contents of the component of the general formula (I) are the same as those described for the resin [A]. Examples of the other polymer component that can be contained include the same as those described as the component represented by the general formula (III) that can be contained in the A block or the other components. However, the B block is characterized by not containing the specific polar group-containing component contained in the A block.

The AB block copolymer [B] of the present invention is
It can be produced by a conventionally known polymerization reaction method.
Specifically, in the monomer corresponding to the polymer component containing the specific polar group, the polar group is preliminarily protected as a functional group, and an organometallic compound (eg, alkyllithium, lithium diisopropylamide, alkylmagnesium) is used. Halides, etc.) or ionic polymerization reaction with hydrogen iodide / iodine system, photopolymerization reaction using porphyrin metal complex as catalyst, group transfer polymerization reaction, or other known so-called living polymerization reaction to polymerize the AB block copolymer. After that, a specific polar group is directly introduced at the termination reaction, or a polar group is chemically bonded after introducing a functional group capable of binding the polar group, and then a functional group protecting the polar group in the polymer component is added. Hydrolysis reaction, hydrogenolysis reaction,
A method of forming a polar group by performing a deprotection reaction by an oxidative decomposition reaction, a photodecomposition reaction or the like can be mentioned. One example thereof is shown in the following reaction scheme (1).

[0119]

[Chemical 30]

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

Further, the AB block copolymer [B] is a compound containing a diiocarbamento group containing a specific polar group as a substituent, and / or a monomer containing a polar group not protected. It can also be synthesized by performing a polymerization reaction under light irradiation using a compound containing a xanthate group as an initiator. For example, Takayuki Otsu, Polymer, 37 , 248.
(1988), Shunichi Hinomori, Ryuichi Otsu, Polym. Re
p. Jap. 37 . 3508 (1988), JP-A-64
No. 111, JP-A No. 64-26619, Nobuyuki Higashi, et al., P.
polymer Preprints, Japan, 3
6 , (6), 1511 (1987), M.A. Niwa,
N. Higashi, et al. Macromo
l. Sci. Chem. A24 (5), 567 (198
It can be synthesized according to the synthesis method described in 7) or the like.

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

On the other hand, in the resin [B] of the present invention, it is preferable that the B block has a longer polymer chain than the A block.
As the binder resin used for the photoconductive layer of the present invention, the above-mentioned known resins for inorganic photoconductors may be used in combination in addition to the resins [A] and [B] of the present invention. However, the ratio of these other resins used is 3 in 100 parts by weight of the total binder resin.
A range not exceeding 0% 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 0.05 to 0.05 by weight ratio of resin [A] / resin [B].
It is preferably 0.6 / 0.95 to 0.40, and more preferably 0.10 to 0.40 / 0.90 to 0.60.
Is. When the total amount ratio of the binder resin is 10 parts by weight or less,
The film strength of the photoconductive layer cannot be maintained. On the other hand, when the amount is 100 parts by weight or more, the electrostatic characteristics are deteriorated and the copy image is deteriorated in the actual image pickup property.

If the weight ratio of the resin [A] to the resin [A] and the resin [B] of the present invention is 0.05 or less, the effect of improving the electrostatic characteristics is diminished. On the other hand, 0.6
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. As the spectral sensitizing dye used in the present invention, various dyes are used alone or in combination as necessary. For example, Harumi Miyamoto, Hidehiko Takei, Imaging 1973 (No. 8), page 12,
C. J. Young et al., RCA Review 15 ,
469 (1054), Kouhei Kiyota et al., IEICE Transactions
J63 - C (No. 2 ), 97 (1980), Yuji Harasaki et al., Industrial Science Magazines 66 78 and 188 (196).
3), Tadaaki Tani, Journal of the Photographic Society of Japan 35 , 208 (197).
2) Carbonyl dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanines Examples thereof include dyes (which may contain a metal).

More specifically, those mainly containing carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes are disclosed in Japanese Examined Patent Publication No. 51-45.
No. 2, JP-A Nos. 50-90334 and 50-11422.
No. 7, No. 53-39130, No. 53-82353,
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.
No. 0,591, No. 3,121,008, No. 3,1
No. 25,447, No. 3,128,179, No. 3,
132,942, 3,622,317, British Patents 1,226,892, 1,309,274.
No. 1,405,898, JP-B-48-7814
No. 55-18892 and the like.

Further, as a polymethine dye for spectrally sensitizing the near infrared to infrared light region having a long wavelength of 700 nm or more, JP-A-4,
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
Disclosure ", 1982, 216, 117.
To those described on page 118 and the like. 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, the aforementioned review article: Imaging 1973 (No. 8)
Electron-accepting compounds (for example, halogen, benzoquinone, chloranil, organic carboxylic acid anhydrides, etc.) in the review article on page 12, etc., Hiroshi Komon, et al. Chapter 4 to Chapter 6 • Polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds and the like, which are cited as reference articles 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 from 0.01 to
1 μ, particularly 0.05 to 0.5 μ is preferable.

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
It is set to ˜70 μ, particularly 10 to 50 μ.

Examples of the charge transport material for the laminated type photoreceptor include polyvinylcarbazole, oxazole dyes, pyrazoline dyes and triphenylmethane dyes. The thickness of the charge transport layer is preferably 5 to 40 μ, particularly 10 to 30 μ. Typical resins used for forming the insulating layer or the charge transport layer are polystyrene resin, polyester resin, cellulose resin, polyether resin,
Vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl chloride copolymer resin, polyacrylic resin, polyolefin resin, urethane resin, polyester resin, epoxy resin, melamine resin, silicone resin thermoplastic resin and effective 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, having a precoat layer of at least one phase or more provided on the surface layer of the support, and a conductive electroconductive plastic substrate on which Al or the like is vapor-deposited. It is possible to use those laminated to.

Concrete examples of the conductive substrate or the conductive material are Yukio Sakamoto, Electrophotography, 14 (No.
1), P2-11 (1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry", Polymer Publishing (1975), M.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 using 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 can be more exerted when 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 copy images (for example, Kuro Takizawa, “Photo Industry” 33 , 34 (1975), Masayasu Anzai, “Technical Report of IEICE 77 , 17 (197).
7 years) and the like).

Further, it is also 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.

[0141]

[Synthesis of macromonomer (M)]

Macromonomer Synthesis Example 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 .

[0142]

[Chemical 31]

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 was cooled in a water bath to a temperature of 20.
C., 10.2 g of triethylamine was added, and 14.5 g of methacrylic acid chloride was 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 warmed 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 .

[0145]

[Chemical 32]

Synthesis Example 3 of Macromonomer: (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 .

[0148]

[Chemical 33]

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 to 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 .

[0150]

[Chemical 34]

[0151]

[Chemical 35]

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.

[0154]

[Chemical 36]

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 .

[0156]

[Chemical 37]

[Synthesis of Resin [A]] Synthesis Example 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 was 1.0 ×.
It was 10 ⁴ .

[0158]

[Chemical 38]

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 .

[0160]

[Chemical Formula 39]

Synthesis Examples 3 to 9 of Resin [A]: [A-3] to
[A-9] In the synthesis example of the resin [A], instead of 80 g of 2-chlorophenyl methacrylate and 20 g of macromonomer,
Copolymers were produced in the same manner as in Synthesis Example 2 of Resin [A] except that the monomers and macromonomers corresponding to the following Table-A were replaced. Mw of each polymer is 7.5 × 10 ^{3 to} 9 × 1.
It was in the range of 0 ³ .

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

[0163]

[Table 2]

[0164]

[Table 3]

Synthesis Example 10 of resin [A]: [A-10] benzyl methacrylate 70 g, 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 .

[0167]

[Chemical 40]

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 Mw was 6.5 × 10.
63 g of a viscous product of ³ was obtained.

[0170]

[Chemical 41]

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 .

[0173]

[Table 4]

[0174]

[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.

[0177]

[Chemical 42]

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.

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

[0180]

[Table 6]

[0181]

[Table 7]

[0182]

[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 .

[0184]

[Chemical 43]

[Synthesis of Resin (B)] Synthesis Example of Resin [B] 1: [B-1] 42.5 g of methyl acrylate, 2.5 g of acrylic acid,
2-Carboxyethyl N, N-diethyldithiocarbamate: [I-1] 7.6 g and tetrahydrofuran 50
The mixture of g was sealed in a container under a nitrogen stream and the temperature was 50 ° C.
Warmed to. 10 cm with a 400 W high pressure mercury lamp
Light was irradiated from a distance of 8 hours through a glass filter for 8 hours for photopolymerization.

The reaction product was reprecipitated in 500 ml of petroleum ether, and the precipitate was collected and dried. The yield of the obtained polymer was 41 g, and the Mw was 1.0 × 10 ⁴ . Further, a mixture of 10 g of the above-mentioned polymer (which serves as a polymer initiator), 65 g of methyl methacrylate, 25 g of methyl acrylate and 100 g of tetrahydrofuran was heated to 50 ° C. under a nitrogen stream. This is irradiated with light under the same conditions as above, and 1
Photopolymerized for 0 hours. The obtained mixture was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. The yield of the obtained block polymer was 85 g, and the Mw was 8.5 × 10 ⁴ .

[0187]

[Chemical 44]

Synthesis Example 2 of Resin [B-2]: [B-2] 67 g of methyl methacrylate, 33 g of methyl acrylate
g, benzyl N-ethyl-N- (2-carboxyethyldithiocarbamate: [I-2] 2.2 g and a mixed solution of 100 g of tetrahydrofuran under a nitrogen stream at a temperature of 50.
℃ was made. This was photopolymerized under the same light irradiation conditions as in Synthesis Example 1 for 8 hours. The reaction mixture was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to obtain a polymer having a Mw of 8 × 10 ^{4 in} a yield of 85 g. A mixture of 85 g of the above polymer, 14 g of methyl methacrylate, 1 g of methacrylic acid and 150 g of tetrahydrofuran was heated to 50 ° C. under a nitrogen stream. This was photopolymerized for 16 hours under the same light irradiation conditions as in Synthesis Example 1. The reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to obtain a block copolymer with an Mw of 9.5 × 10 ^{4 in} a yield of 83 g.

[0189]

[Chemical 45]

Synthesis Example 3 of Resin [B]: [B-3] A mixed solution of 80 g of ethyl methacrylate and 200 g of toluene was sufficiently deaerated under a nitrogen stream and cooled to -20 ° C. Next, 2.0 g of 1,1-diphenyl-3-methylpentyllithium was added, and the mixture was stirred for 12 hours. Further, 19 g of methyl methacrylate and 1.5 g of 4-vinylphenylcarbonyloxytrimethylsilane were added to this mixture and reacted for 12 hours, then reacted for 2 hours as it was under a carbon dioxide stream, and further reacted for 2 hours at a temperature of 0 ° C.

To this reaction mixture, 1 liter of a methanol solution containing 10 g of 30% hydrochloric acid was added dropwise over 30 minutes with stirring, and the mixture was stirred for 1 hour as it was. The precipitated powder was filtered off, washed with methanol and dried. A block copolymer having an Mw of 6.5 × 10 ⁴ was obtained with a yield of 75 g.

[0192]

[Chemical 46]

Synthesis Examples 4 to 13 of Resin [B]: [B-4]
~ [B-13] In the same reaction method as in Synthesis Example 2 of Resin [B], the following Table-D was used.
The resin [B] shown in was synthesized. Mw of each polymer obtained
Was in the range of 7 × 10 ^{4 to} 9 × 10 ⁴ .

[0194]

[Table 9]

[0195]

[Table 10]

[0196]

[Table 11]

Synthesis Examples 14 to 20 of Resin [B]: [B-1
4] to [B-20] In the synthesis example of the resin [B-1], the initiator [I-1]
Instead of 7.6 g, 4.2 x 1 of each initiator shown in Table-E below.
0 ^-3 other with moles, in the same manner as in Synthesis Example 1, it was synthesized the block copolymer. Mw of each copolymer is 8 × 10
It was in the range of ⁴ to 10 × 10 ⁴ .

[0198]

[Table 12]

Synthesis Examples 21 to 30 of Resin [B]: [B-2
1] to [B-30] Each polymer corresponding to the following Table-F was polymerized by a photopolymerization reaction in the same manner as in the method of Synthesis Example [B-2].

[0200]

[Table 13]

[0201]

[Table 14]

Example 1 and Comparative Examples 1 to 3 (Example 1) 7 g of resin [A-7] (as solid content),
33 g of resin [B-1] having the following structure (as solid content),
A mixture of 200 g of photoconductive zinc oxide, 0.017 g of methine dye [I] having the following structure, 0.18 g of phthalic anhydride and 300 g of toluene was added in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 6 × 10 ³ r.p. p. m. Was dispersed for 7 minutes at the rotation speed of. This photosensitive layer-forming dispersion 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 100 ° C. for 30 seconds. Then, the mixture was left in the dark at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material.

[0203]

[Chemical 47]

Comparative Example 1 In Example 1, the resin [B-
1] 33 g of resin [R-1] having the following structure instead of 33 g
An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that was used.

[0205]

[Chemical 48]

Comparative Example 2: In Example 1, the resin [B-
1] 33 g of resin [R-2] having the following structure instead of 33 g
An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that.

[0207]

[Chemical 49]

Comparative Example 3: In Example 1, the resin [B-
1] 33 g of resin [R-3] having the following structure instead of 33 g
An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that.

[0209]

[Chemical 50]

For these photosensitive materials, the electrostatic characteristics,
Imaging and environmental conditions (20 ° C, 65% RH) and (30
The image pick-up property when the temperature was 80 ° C. and 80% RH was examined. The above results are shown in Table-G.

[0211]

[Table 15]

Embodiments of the evaluation items shown in Table-G are as follows. Note 1) Strength of photoconductive layer: The surface of the obtained light-sensitive material was emery paper (# 100) with a load of 50 g / cm ² using Haydon-14 type surface test material (manufactured by Shinto Chemical Co., Ltd.).
0) was repeated 1000 times to remove the abrasion powder, and the residual film rate (%) was calculated from the weight reduction of the photosensitive layer to obtain the mechanical strength. Note 2) Electrostatic characteristics: In a dark room at a temperature of 20 ° C and 65% RH,
-6k using a paper analyzer (Paper Analyzer SP-428 manufactured by Kawaguchi Electric Co., Ltd.) for each light-sensitive material
After corona discharge was performed for 20 seconds at V, the surface potential V ₁₀ at this time was measured after standing for 10 seconds. Then, the potential V ₁₀₀ after standing still in the dark for 90 seconds was measured, and the potential retention after dark decay for 90 seconds, that is, the dark decay retention rate [DRR (%)] was calculated as (V ₁₀₀ / V ₁₀ ) × 100 (%).

The surface of the photoconductive layer was -40 by corona discharge.
After being charged to 0 V, the surface of the photoconductive layer was gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm).
The time until the surface potential (V ₁₀ ) is attenuated to 1/10 by irradiation with light is calculated, and from this, the exposure amount E _1/10 (erg / cm
² ) is calculated. Also, the same surface potential (V ₁₀ ) is 1/1
The time until it decays to 00 is calculated, and from this, the exposure amount E
Calculate _1/100 (erg / cm ² ). Environmental conditions at the time of measurement are 20 ° C, 65% RH (I) and 30 ° C, 80% RH
(II). Note 3) Imaging property: After leaving each light-sensitive material under the following environmental conditions for one day and night, each light-sensitive material is charged at −6 kV, and a 2.8 mW output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm) is used as a light source. With a pitch of 25 μm on the surface of the photosensitive material under an irradiation amount of 64 erg / cm ^2.
And, after speed exposure with a scanning speed of 300 m / sec, as a liquid developer, ELP-T (manufactured by Fuji Photo Film Co., Ltd.) was used for development and isoparaffin Isopar G (manufactured by Esso Chemical Co., Ltd.) as a solvent rinse solution. The copied image (fogging, image quality) obtained by fixing after washing was visually evaluated.

Environmental conditions at the time of imaging are 20 ° C. and 65% RH
(I) and 30 ° C. 80% RH (II). As shown in Table-G, the light-sensitive material of the present invention had good electrostatic characteristics, and the actual copied image had no background fog and the copied image quality was clear. On the other hand, in Comparative Examples 1, 2 and 3, the photosensitivity (E _1/10 and E _1/100 ) was lowered, and even in the actual copy image, fine lines, letters and the like were scratched, and the background was observed even after the rinse treatment. The fog remained without being removed. Further, although it does not match the electrostatic characteristic, unevenness occurs in the intermediate density of the continuous tone portion of the copy document.

[0215] The photoreceptor of the present invention and the photoreceptor of the comparative example have 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 amount is required to set V _R −10 V or less,
The scanning exposure method according to the semiconductor laser beam, to a V _R below -10V with a small amount of exposure, (cost of the device, the accuracy of the optical system optical path, etc.) optical system design of the copying machine is very important is there.

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, and it is particularly advantageous for a semiconductor laser light scanning exposure type photosensitive system. It became clear. Example 2 Resin [A-9] 6 g (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-
Hydroxymaleimide 0.20g and toluene 30
An electrophotographic light-sensitive material was produced by operating 0 g of the mixture in the same manner as in Example 1.

[0217]

[Chemical 51]

The film properties (surface smoothness) of this photosensitive material,
The electrostatic characteristics, the imaging characteristics, and the electrostatic characteristics and the imaging characteristics were examined when the environmental conditions were 30 ° C. and 80% RH. Furthermore, the printability when used as an original plate for electrophotographic lithographic printing was examined. The results are shown in Table-H.

[0219]

[Table 16]

Embodiments of the evaluation items shown in Table-H are as follows. Note 4) Smoothness of surface layer: The photosensitive material obtained was measured using a Beck's smoothness tester (manufactured by Kumagai Riko Co., Ltd.) with an air capacity of 1 c.
The smoothness (sec / cc) was measured under the condition of c. Note 5) Contact angle with water: Each photosensitive material is desensitized EP
A solution of L-EX (manufactured by Fuji Photo Film Co., Ltd.) diluted with distilled water twice is used for an etching processor.
The surface of the photoconductive layer is passed around to be desensitized, and then a drop of distilled water (2 μl) is placed on the surface, and the contact angle with the formed water is measured with a goniometer. Note 6) Printing durability: Under the same conditions as those of the above-mentioned Note 2), plate making was performed to form a toner image, and desensitization processing was performed under the same conditions as the above Note 5), and this was used as an offset master. Shows the number of prints that can be printed on an offset printing machine (Oliver 52 type, manufactured by Sakurai Seisakusho Co., Ltd.) without causing scumming on the non-image area of the printed matter and on the image quality of the image area. As shown in Table-H, the light-sensitive material of the present invention has good mechanical strength and electrostatic properties of the smooth film of the photoconductive layer, and the actual copy image has no background fog. The copy quality was also 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 it is used as an offset master original plate, the desensitizing treatment is sufficiently advanced by the desensitizing treatment liquid, the contact angle with water of the non-image area is as small as 0 °, and it is sufficiently hydrophilized. I know that there is. 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.

As described above, the resin [A] and the resin [B] of the present invention appropriately interact with the zinc oxide particles, and the desensitizing reaction by the desensitizing treatment liquid easily and easily proceeds. It shows that the state is formed and the film strength is remarkably improved by the action of the resin [B]. Examples 3 to 20 In Example 2, resin [A-9] and resin [B-2]
Instead of, each resin [A] and each resin [B] in the following Table-I
In the same manner as in Example 2 except that the above was replaced with, electrophotographic photosensitive members were produced.

[0222]

[Table 17]

When electrostatic properties were measured in the same manner as in Example 2, all showed good results. Further, when the actual operability of these light-sensitive materials was examined, fine reproducibility of fine lines / characters was not generated, halftone unevenness was not generated, and clear copy images having no background fog were obtained. When used as an offset master original plate and printed in the same manner as in Example 2, at least 10,000 sheets or more 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 21 to 24 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 J below.

[0225]

[Table 18]

[0226]

[Table 19]

The light-sensitive materials of the present invention are all excellent in chargeability, dark charge retention rate, and photosensitivity, and actual copied images can be obtained even under severe conditions of high temperature and high humidity (30 ° C., 8% RH). It gave a clear image with no background fog. Examples 25 and 26 and Comparative Example 4 Resin [A-19] (Example 25) or Resin [A-29]
6.5 g of any of (Example 26), resin [B-6] 3
A mixture of 3.5 g, 200 g of zinc oxide, 0.02 g of uranine, 0.035 g of rose bengal, 0.025 g of bromphenol blue, 0.18 g of p-hydroxybenzoic acid and 300 g of toluene was rotated in a homogenizer at a rotation speed of 7 × 10 ³ r. ． p. m. For 5 minutes to prepare a photosensitive layer-formed product, and apply it to a paper that has been subjected to conductive treatment so that the dry adhesion amount is 25
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. Comparative Example 4 A photosensitive material was prepared in the same manner as in Example 25 except that 33.5 g of the resin [B-6] was used instead of 33.5 g of the resin [B-6]. It was made.

In the same manner as in Example 2, each characteristic of each photosensitive material was examined. The results are summarized in Table-K below.

[0229]

[Table 20]

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 6) Method for measuring E _1/10 and E _1/100 of electrostatic characteristics After charging the surface of the photoconductive layer to −400 V by corona discharge, the surface of the photoconductive layer was exposed to visible light with an illuminance of 2.0 lux. The time until the surface potential (V ₁₀ ) decays to 1/10 or E _1/100 after irradiation is determined, and from this, the exposure amount E _1/10 or E
Calculate _1/100 (lux seconds). Note 7) 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 a copy image (fog, image quality of the image) obtained by plate making was visually evaluated. The environmental conditions at the time of imaging are 20 ° C 65% RH (I) and 30 ° C 8
Performed at 0% RH (II). However, the original for copying (that is, the original copy) was prepared by cutting out and pasting other originals.

In each light-sensitive material, no difference was observed in the smoothness and strength of the photoconductive layer. The electrostatic characteristics of the photographic material of the present invention are good, and Example 26 using the resin [A] having a specific substituent is very good, and especially the value of E _1/100 is small. It was

Examination of the actual image pickup property shows that Comparative Example 4
In addition to the original as a copy image, the frame (that is, the trace of pasting) of the part cut out and stuck was recognized as the background stain of the non-image part. However, in all cases of the present invention, clear images having no background stain were obtained. Further, when these were subjected to a desensitizing treatment as offset printing original plates and printed, all of the present invention produced 10,000 printed matters with clear image quality without background stains. However, in Comparative Example 4, the above-mentioned sticking mark was not removed even by the desensitizing treatment, and was generated from the printed matter.

From the above, only the light-sensitive material of the present invention could give good characteristics. Examples 27 to 42 In Example 25, instead of 6.5 g of resin [A-19] and 33.5 g of resin [B-6], 6.5 g of resin [A] and resin [B] of the following Table-L. Each light-sensitive material was produced in the same manner as in Example 25 except that 33.5 g was used.

[0234]

[Table 21]

The light-sensitive materials of the present invention are all excellent in chargeability, dark charge retention rate and photosensitivity, and the actual copied image also causes fog in the harsh conditions of high temperature and high humidity (30 ° C., 80% RH). Gave a clear image. Further, when printed as an offset master original plate, a printed matter having a clear image quality with no background stain was obtained even after printing 10,000 sheets.

Further, the photoreceptor of the resin [A] containing a methacrylate having a specific aryl group as a substituent showed better performance.

[0237]

According to the present invention, an electrophotographic photoreceptor having a clear and high-quality image excellent in electrostatic characteristics (especially electrostatic characteristics under severe conditions) and further having excellent mechanical strength. Can be obtained. In particular, it is effective for a scanning exposure method using semiconductor laser light. Formula (Ia) or (I
By using the repeating unit containing the specific methacrylate component represented by b) in the resin of the present invention, the electrostatic characteristics are further improved.

Claims (4)

[Claims] 1. An electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye, and a binder resin, wherein the binder resin is 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 ]. The polymerizability represented by the following general formula (II) only at one terminal of the 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. Copolymer containing at least a monofunctional macromonomer (M ₂ ) having a weight average molecular weight of 2 × 10 ⁴ or less formed by bonding a double bond group and a monomer corresponding to the repeating unit represented by the general formula (I). Resin that is a united body. [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 -, -} CON (R 5) -, - SO 2 N (R
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, which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COOR ⁶ (wherein R ⁶ through a -COOR ⁶ or hydrocarbons substituted Represents a good hydrocarbon group). Resin [B] having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ and containing at least one polar group selected from the specific polar groups represented by the above resin [A ₁ ]. An AB block copolymer composed of an A block containing at least one polymer component and a B block containing at least one polymer component represented by the general formula (I) represented by the resin [A ₁ ]. In the A block, at least one polar group selected from the specific polar groups represented by the above resin [A ₁ ] is bonded to the end of the polymer main chain on the opposite side to which the B block is bonded. Resin. 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), A ¹ and A ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a cyano group, —COR ⁷ or —COOR ⁷ (R
⁷ represents a hydrocarbon group having 1 to 10 carbon atoms), and B ¹
And B ² each represent a single bond or a connecting group having 1 to 4 connecting atoms for connecting —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