JP3115365B2 - Electrophotographic photoreceptor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor,
More specifically, the present invention relates to an electrophotographic photosensitive member having excellent electrostatic characteristics and moisture resistance.

[0002]

2. Description of the Related Art Electrophotographic photoreceptors have various configurations in order to obtain predetermined characteristics or according to the type of electrophotographic process to be applied.

[0003] As typical electrophotographic photoreceptors, there are a photoreceptor having a photoconductive layer formed on a support and a photoreceptor having an insulating layer on the surface, and are widely used. A photoreceptor composed of a support and at least one photoconductive layer is produced by the most common electrophotographic processes, namely charging,
It is used for image exposure and development and, if necessary, image formation by transfer.

Further, a method of using an electrophotographic photosensitive member as an offset master for direct plate making has been widely used. In particular, in recent years, direct electrophotographic lithographic printing has become important as a method for printing high-quality printed matter with a print number of several hundreds to several thousands. Under these circumstances, the binder resin used to form the photoconductive layer of the electrophotographic photoreceptor has excellent film forming properties of itself and excellent dispersibility of the photoconductive powder in the binder resin. The adhesion of the formed recording layer to the substrate is good, and the photoconductive layer of the recording layer has excellent charging ability, low dark decay, large light decay, low pre-exposure fatigue, and photography. It is necessary to have various electrostatic characteristics such as the necessity of maintaining these characteristics stably due to changes in humidity at the time, and excellent imaging properties.

Further, research on a lithographic printing original plate using an electrophotographic photosensitive member has been enthusiastically performed, and a lithographic printing original plate for a photoconductive layer having both electrostatic characteristics as an electrophotographic photosensitive member and printing characteristics as a printing original plate has been achieved. Binder resin is required.

In a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye, and a binder resin, it has been found that not only smoothness but also electrostatic characteristics are greatly affected by the chemical structure of the binder resin. Was. In particular, in the electrostatic characteristics, the charge retention in the dark (DRR) and the light sensitivity are greatly affected.

On the other hand, Japanese Patent Application Laid-Open No. 63-217354 discloses
According to the techniques described in JP-A Nos. 64-70761, JP-A-2-67563 and JP-A-2-247656, a resin having a low molecular weight in which an acidic group-containing polymerization component is randomly present in a polymer main chain is used. A low molecular weight resin formed by bonding an acidic group to one end of the coalesced main chain or a low molecular weight graft copolymer resin formed by bonding an acidic group to one end of the polymer main chain;
By using a low molecular weight graft copolymer resin or the like containing an acidic group in the graft portion as a binder resin, the smoothness and electrostatic properties of the photoconductive layer can be improved. These include that the low molecular weight resin has an effect of sufficiently dispersing the photoconductor and suppressing aggregation between the photoconductors, and the inorganic material without alienating the adsorption between the photoconductor and the spectral sensitizing dye. This is presumed to be due to the fact that the photoconductor is sufficiently adsorbed to the stoichiometric defect and that the surface of the photoconductor is covered slowly and sufficiently.

Due to its mechanism of action, even if the stoichiometric defect of the inorganic photoconductor fluctuates to some extent, it has a sufficient adsorption area, so that the inorganic photoconductor, the spectral sensitizing dye and the resin are relatively stable. It is inferred that the mutual interaction is maintained.

In order to sufficiently enhance the mechanical strength of the photoconductive layer, it is not sufficient to use only these low-molecular-weight resins alone. Japanese Patent Application Laid-Open Nos. 64-564, 63-220149, etc.
No. 63-220148, JP-A-1-280761,
1-16-1664, 1-169455, 1-
No. 211766, No. 2-34859, No. 2-5306
No. 4, 2-56558, Japanese Patent Application No. 1-163796
And Nos. 1-212994, 1-229379 and 1-189245.

[0010]

However, even if these resins or combinations of resins are used, it is still insufficient to maintain stable performance when the environment fluctuates significantly from high temperature and high humidity to low temperature and low humidity. I found it to be. The scanning exposure method using a semiconductor laser beam has a longer exposure time and a limited exposure intensity than the conventional simultaneous exposure method using visible light, so the electrostatic characteristics, especially the dark charge retention characteristics, are limited. , For light sensitivity,
Higher performance is required.

In particular, when a scanning exposure method using a semiconductor laser beam is employed in an electrophotographic lithographic printing original plate, when the conventional photosensitive member is actually tested, the above electrostatic characteristics are sufficiently improved. It is not satisfactory, especially the difference between E _1/2 and E _1/10 is large, the tone of the copied image is soft, and it is difficult to reduce the residual potential after exposure, and the fog of the copied image is reduced. It becomes noticeable,
Even when printing as a lithographic printing original plate ( offset master ) , problems such as sticking traces of printed originals appear on printed matter.

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 tones using a liquid developer. The above-mentioned known techniques have not been able to sufficiently satisfy these demands.

In the known technique, the medium to high molecular weight resin used in combination with the low molecular weight resin sometimes lowers the electrostatic properties of the low molecular weight resin which have been improved in performance. An electrophotographic photoreceptor having a photoconductive layer used in combination with these known resins has high reproducibility of a high-definition image (especially a continuous tone image) faithful copy image or low output. It has been clarified that a problem may occur with respect to the imaging performance by the scanning exposure method using laser light.

The present invention is to improve the problems of the above-described known electrophotographic photosensitive members. SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photoreceptor having a stable and good electrostatic property, always having a clear and high-quality image, even when the environment at the time of forming a copy image fluctuates such as low temperature and low humidity or high temperature and high humidity. It is to provide.

Another object of the present invention is to provide a CPC electrophotographic photosensitive member having excellent electrostatic characteristics and low environmental dependency. Another object of the present invention is to provide an electrophotographic photosensitive member effective for a scanning exposure method using a semiconductor laser beam.

A further object of the present invention is to reproduce a copied image which has excellent electrostatic characteristics (especially dark charge retention and light sensitivity) and which is faithful to an original image (especially a high-resolution continuous tone image). ,
Entirely uniform scumming of the printed matter even without generating course punctate stain, and to provide an excellent electrophotographic lithographic printing <br/> precursor printing durability.

[0017]

An object of the present invention is to provide an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye and a binder resin, wherein the binder resin comprises the following resin [A ₁ ) and at least one of the resins [A ₂ ] and at least one of the following resins [B]. . Resin [A ₁ ] One of polymer main chains having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and containing 30% by weight or more of a repeating unit represented by the following general formula (I) as a polymer component. A monofunctional macromonomer (M ₁ ) having a weight-average molecular weight of 2 × 10 ⁴ or less which is obtained by bonding a polymerizable double bond group represented by the following general formula (II) only to the terminal of And a monomer corresponding to a repeating unit represented by the formula: wherein -PO is located at one end of the main chain of the copolymer.
_{3 H 2, -SO 3 H,} -COOH, -P (= O) (O
H) Resins formed by bonding at least one polar group selected from R ¹ [R ¹ represents a hydrocarbon group or —OR ² (R ² represents a hydrocarbon group)] and a cyclic acid anhydride group . Resin [A ₂ ] having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , containing 30% by weight or more of a repeating unit represented by the following general formula (I) as a polymer component, and the above resin [A ₁ ] Polymerization represented by the following general formula (II) only at one end of a polymer main chain containing 1 to 50% by weight of a polymer component containing at least one polar group selected from the specific polar groups shown. Weight average molecular weight of 2 × 10 ^{4 formed} by bonding a functional double bond group
A resin which is a copolymer comprising at least the following monofunctional macromonomer (M ₂ ) and a monomer corresponding to the repeating unit represented by formula (I).

[0018]

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[In the formula (I), a ¹ and a ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. Z
Represents a hydrocarbon group. Preferably, a ¹ is a hydrogen atom, a ²
Is a methyl group. ]

[0020]

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[In the formula (II), R ³ is -COO-, -O
_{CO -, - CH 2 OCO -} , - CH 2 COO -, - O
_{-, - SO 2 -, -} CO -, - CONR 4 -, - SO 2
NR ⁴ — (where R ⁴ represents a hydrogen atom or a hydrocarbon group), —CONHCOO—, —CONHCONH— or —C ₆ H ₄ —.

B ¹ and b ² may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COOR ⁵ or —COOR ⁵ via a hydrocarbon.
⁵ (where R ⁵ represents an optionally substituted hydrocarbon group). Resin [B] A polymer component (a) having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ and comprising a repeating unit represented by the general formula (I) in the resin [A1] and the resin [B] a _1] at least three identical have a certain polymer component (b) and consists of at least contains a polymer chain containing at least one polar group selected from among the polar groups represented by
Become attached to the machine molecule, polymer component (b) 30 wt% or more and the polymer component (b) 0.05 to 10 wt%
A resin comprising a star-type copolymer.

That is, the binder resin of the present invention is obtained by bonding a specific polar group to one end of a copolymer containing the macromonomer (M ₁ ) and the monomer corresponding to the general formula (I). made resin [a _1] and / or the macromonomer containing a specific polar group-containing component (M ₂₎ and the resin [a _2] is a copolymer containing a monomer corresponding to the general formula (I) (Hereinafter, the macromonomers (M ₁ ) and (M ₂ ) are collectively referred to as the macromonomer (M), and the resin [A ₁ ]
And [A ₂ ] may be collectively referred to as a resin [A]), a polymer component represented by the above general formula (I), and at least three polymer chains containing the specific polar group-containing component .
At least a star-type copolymer (resin [B]) bonded to organic molecules .

As a result of various studies, as described above, in the technique of using a known low-molecular-weight polar group-containing resin in combination with a medium- to high-molecular-weight resin, depending on the medium-high-molecular-weight resin used together,
It has been found that the high-performance electrostatic properties of the low-molecular-weight resin may be reduced. It is also unexpectedly important that these medium to high molecular weight resins more appropriately interact with the photoconductor, the spectral sensitizing dye and the low molecular weight resin in the photoconductive layer. It has become clear that this is the cause.

As a result of repeated examinations, as a medium to high molecular weight resin to be used in combination with the low molecular weight resin [A] containing a polar group, the component represented by the general formula (I) according to the present invention and the polar group containing resin 3 or more polymer chains containing the same component
It has been found that the above problem can be effectively solved by using a star-type copolymer having a specific amount bonded to an organic molecule.

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

That is, the low molecular weight graft copolymer resin [A] containing a specific polar group is sufficiently adsorbed on the photoconductor particles to uniformly disperse the particles, and the polymer chains are extremely dispersed. It has important effects such as suppressing aggregation due to its short length, and not causing adsorption and alienation of the spectral sensitizing dye.

Further, by using a star-type copolymer in which at least three polymer chains containing a specific polymer component are bonded to the same molecule, the mechanical strength of the photoconductive layer is sufficiently maintained. At the same time, improvement in electrostatic characteristics (especially, light sensitivity) and improvement in imaging performance (especially, reproducibility of a continuous tone image) were achieved.
Although this is not known in detail, the polymer component block of this resin is restricted to a star type, thereby contributing to the effect of improving the entanglement effect of the polymer and further improving the electrostatic characteristics. From the above, it is considered that, in the interaction between the photoconductor particles, the spectral sensitizing dye, and the resin [A], the resin is appropriately involved in suppressing the adsorption and alienation of the dye or in the electrophotographic interaction. .

This effect was particularly remarkable with a polymethine dye or a phthalocyanine pigment which is particularly effective as a dye for spectral sensitization of near infrared to infrared light. On the other hand, shows a very good water retention with good imaging properties in the case of using the electrophotographic photoreceptor of the present invention using a photoconductive zinc oxide as photoconductor as conventional direct printing YoHara plate.

That is, the photoreceptor of the present invention, on which a copied image is formed through an electrophotographic process, is desensitized by a chemical treatment at a non-image portion using a conventionally known desensitizing solution to form a printing master. Shows excellent performance as a printing original plate when is printed by offset printing.

When the photoreceptor of the present invention was desensitized, the non-image area was sufficiently hydrophilized and the water retention was improved, so that the number of printed sheets was 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 desensitization reaction with the desensitizing treatment solution is quickly performed without alienation. It is considered that the process proceeds effectively.

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

[0033]

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[0034]

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[In the formulas (Ia) and (Ib), R ⁶ and R
⁷ are each independently a hydrogen atom, a carbon number of 1 to 10
Hydrocarbon group, chlorine atom, bromine atom, -COR ¹⁰ or-
COOR ¹⁰ (where R ¹⁰ represents a hydrocarbon group having 1 to ¹⁰ carbon atoms).

R ⁸ and R ⁹ each represent a single bond or a linking group having 1 to 4 linking atoms, each linking —COO— and a benzene ring. When the specific resin [AA] is used, the electrophotographic properties (particularly, V ₁₀ , DRR, E _1/10 ) can be further improved as compared with the case of the resin [A].

Although the reason for this is unknown, one reason is that the zinc oxide interface in the film is caused by the effect of a planar benzene or naphthalene ring having a substituent at the ortho position, which is an ester component of methacrylate. It is considered that the arrangement of the polymer molecular chains in the above is properly performed.

Hereinafter, the binder resin of the present invention will be described in detail. 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). To one end of the main chain of the polymer (resin [A ₁ ])
Or a weight average molecular weight of 1 × 10 ³ to 2 × 1 which is contained in the graft portion (resin [A ₂ ]).
0 is ⁴ low molecular weight of the resin.

If the molecular weight of the resin [A] is smaller than 1 × 10 ³ , the film-forming ability is reduced, and the film cannot maintain sufficient film strength.
On the other hand, if the molecular weight is greater than 2 × 10 ^4, the photosensitive member using near infrared to infrared spectral sensitizing dyes, especially, high temperature and high humidity, dark decay retention rate in severe conditions of low temperature and low humidity and Fluctuations in light sensitivity are somewhat large, and the effect of the present invention that a stable copied image can be obtained is diminished.

The glass transition point of the resin [A] is preferably-
30 ° C to 110 ° C, 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 at least 30% by weight, preferably at least 50% by weight in the resin [A], and the total amount of the component containing a polar group Is 0.5 to 15% by weight, preferably 1 to 10% by weight in the resin [A].

The polar group content in the resin [A] is 0.5
If it is less than 10% by weight, the initial potential is too low to obtain a sufficient image density. On the other hand, if the content of the polar group is more than 15% by weight, the dispersibility of even a low molecular weight substance is reduced, and the background fouling 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 copolymer component corresponding to the macromonomer (M) is less than 1% by weight, the characteristics of the graft copolymer are lost, the electrostatic properties (especially the charge retention in the dark, the sensitivity) are reduced, and the offset copolymer is used for offset printing. When used as a master, the water retention also decreases. If the content exceeds 70% by weight, the copolymerizability of the graft copolymer becomes difficult to progress sufficiently, and as a result, the above-mentioned reduction in electrostatic properties and water retention occurs.

Next, 30% by weight of the copolymer of the resin [A] was used.
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, a chlorine atom or a bromine atom), a cyano group, or an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, etc.); .

Z 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. .

Further, Z preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. As the substituent, any substituent other than the polar group contained in the polar group-containing polymer component in the resin [A] may be used, and examples thereof include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom). ^{etc.), - OR 11, -COOR 11} , -OC
OR ¹¹ (R ¹¹ represents an alkyl group having 1 to 22 carbon atoms,
For example, a substituent such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl and the like can be mentioned. Preferred hydrocarbon groups include those having 1 to 18 carbon atoms.
Which may be substituted (e.g., methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, 2-chloroethyl, -Bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group and the like, and an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2-methyl- 1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group Aralkyl groups 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, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.) Good alicyclic groups (for example, cyclohexyl group, 2-
A cyclohexylethyl group, a 2-cyclopentylethyl group or the like, or an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, Octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonyl Phenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecylylamidophenyl group, etc.).

In the hydrocarbon group represented by Z, when Z is an aliphatic group, it preferably contains at least 60% by weight of the hydrocarbon group having 1 to 5 carbon atoms in the component represented by the formula (I). preferable.

In the repeating unit of the general formula (I), which is a component having the substituent Z, a polymer component of the repeating unit represented by the general formula (Ia) and / or the general formula (Ib) is more preferable. Is mentioned.

In the formula (Ia), preferred R ⁶ and R
^{As 7} independently of each other 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, propyl, butyl), an aralkyl group (e.g. benzyl group having a carbon number of 7 to 9, phenethyl, 3-phenylpropyl, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl Groups, chloromethylbenzyl groups) and aryl groups (eg, phenyl, tolyl, xylyl, bromophenyl, methoxyphenyl, chlorophenyl, dichlorophenyl), and -COR ¹⁰ and -COOR.
¹⁰ (preferable R ¹⁰ includes those described above as preferred hydrocarbon groups having 1 to 10 carbon atoms).

In the formulas (Ia) and (Ib), R ⁸ and R ⁹ 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
It is a linking group having 1 to 4 linking atoms such as ₂ O-, and more preferably a single bond or a linking group having 1 to 2 linking atoms.

The formula (I) used in the resin [A] of the present invention
Specific examples of the repeating unit represented by a) or (Ib) are shown below. However, the scope of the present invention is not limited to this. In addition, the following (a-1) to (a-20)
In, c is an integer of 1 to 4, d is 0 or an integer of 1 to 3, e is an integer of 1-3, R ¹² are both -CCH _{2c + 1} or _{- (CH 2) d -C 6} H 5 (However, c and d are the same as described above), and R ¹³ and R ¹⁴ may be the same or different and represent any of a hydrogen atom, —Cl, —Br, and —I.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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Next, the polar group contained in the low molecular weight resin [A] will be described. Polar group, -PO ₃ H _2, -S
_{O 3 H, -COOH, -P (} = O) (OH) is preferably from R ¹ 及 beauty cyclic acid anhydride-containing group in which the selected at least one kind.

Here, -P (= O) (OH) R ¹ represents a group represented by the following formula: wherein R ¹ is a hydrocarbon group or an -OR ² group (R ² is a hydrocarbon group). Represents)
And 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. .

[0058]

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The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride. Examples of the cyclic acid anhydride include aliphatic dicarboxylic anhydride and aromatic dicarboxylic anhydride. Things.

Examples of aliphatic dicarboxylic anhydrides include:
Succinic anhydride ring , glutaconic anhydride ring, maleic anhydride ring, cyclopentane-1,2-dicarboxylic anhydride ring, cyclohexane-1,2-dicarboxylic anhydride ring, cyclohexene-1,2- Dicarboxylic anhydride ring,
2,3-bicyclo [2.2.2] octadicarboxylic anhydride ring and the like. These rings are, for example, chlorine atom,
A halogen atom such as a bromine atom, or an alkyl group such as a methyl group, an ethyl group, a butyl group, and a hexyl group may be substituted.

Examples of the aromatic dicarboxylic anhydride include a phthalic anhydride ring, a naphthalene-dicarboxylic anhydride ring, a pyridine-dicarboxylic anhydride ring, and a thiophene-dicarboxylic anhydride ring. These rings are
For example, a chlorine atom, a halogen atom such as a bromine atom, a methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group,
Hydroxyl group, cyano group, nitro group, alkoxycarbonyl 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 bound to one end of the polymer main chain. Resin [A ₁ ]
The content of the polar group-containing binding component in is not particularly limited, but is preferably 0.5 to 15% by weight. The polar group may be directly bonded to one end of the polymer main chain, or may be bonded via a linking group. Such a linking group may be any linking group. For example, specifically, -CR ¹⁵ R ^16- [where R ¹⁵ and R ¹⁶
May be the same or different and each represents a hydrogen atom, a halogen atom (a chlorine atom, a bromine atom, etc.), an OH group, a cyano group,
Alkyl group (methyl group, ethyl group, 2-chloroethyl group, 2-hydroxyethyl group, propyl group, butyl group,
Hexyl group), an aralkyl group (benzyl group, phenethyl group, etc.), a phenyl group, etc.],-(CHR ¹⁵ -CH
_{^{R 16) -, - C 6}} H 10 -, - C 6 H 4 -, - O -, - S
—, —NR ¹⁷ — [where R ¹⁷ is a hydrogen atom or a hydrocarbon group ｛specifically, a hydrocarbon group having 1 to 12 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, Hexyl group, 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.).
Represents-), -CO-, -COO-, -OCO-, -CO
_{^{NR 17 -, - SO 2 NR}} 17 -, - SO 2 -, - NHCON
H -, - NHCOO -, - NHSO 2 -, - CONHC
OO—, —CONHCONH—, a heterocyclic ring (a 5- or 6-membered ring containing at least one kind of O, S, N, or the like as a hetero atom or a condensed ring thereof may be used. For example, a thiophene ring, a pyridine ring, a furan ring , an imidazole ring, piperidine ring, morpholine ring and the like) or -Si R ¹⁸ R ¹⁹ [wherein R ^18, R ¹⁹ may be the same or different, each a hydrocarbon group or -OR ²⁰ (wherein R
²⁰ represents a hydrocarbon group). These hydrocarbon groups, such as single or a linking group constituted by combination of two or more of these linking group] and the like can be exemplified the same groups in R ¹⁷ can be mentioned.

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 copolymer component containing a polar group in the resin [A ₂ ] may be, for example, a compound represented by the following general formula (I):
a) and (Ib)] as long as it is a vinyl compound containing the polar group which can be copolymerized with a monomer corresponding to the repeating unit represented by the following formula: Data Handbook [Basic Edition] "Baifukan (1
986) and the like. Specifically, acrylic acid, alpha and / or β-substituted acrylic acids (e.g., alpha-acetoxy body, alpha-acetoxymethyl body, alpha-(2-amino) an ethyl body, alpha-chloro body, alpha-bromo compound, α- full
Oro form, α-tributylsilyl form, α-cyano form, β-
Chloro form, β-bromo form, α-chloro-β-methoxy form, α, β-dichloro form), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid semiamides,
Crotonic acid, 2-alkenylcarboxylic acids (eg, 2-
Pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-
Octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, half-ester derivatives of vinyl or allyl groups of dicarboxylic acids And a compound containing the polar group in the substituent of the ester derivative or amide derivative of these carboxylic or sulfonic acids.

Examples of the copolymer component containing a polar group are described below. Here, R ²¹ represents H or CH ₃ , R ²² represents H, CH ₃ or CH ₂ COOCH ₃ , R ²³ represents an alkyl group having 1 to 4 carbon atoms, and R ²⁴ represents 1 to 6 carbon atoms. Represents an alkyl group, a benzyl group or a phenyl group;
3 represents an integer, g represents an integer of 2 to 11, and h represents 1 to
11 represents an integer, i represents an integer of 2 to 4, and j represents 2 to
Indicates an integer of 10.

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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

In the resin [A ₁₂ ], the polar group contained as a copolymer component in the macromonomer and the polar group bonded to one end of the polymer main chain may be the same or different. The ratio varies depending on the types and amounts of other binder resins, spectral sensitizing dyes, chemical sensitizers or other additives 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 in the range of 0.5 to 15% by weight.

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

[0080]

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[In the formula (II), R ³ represents —COO—, —O
_{CO -, - CH 2 OCO -} , - CH 2 COO -, - O
_{-, - SO 2 -, -} CO -, - CONR 4 -, - SO 2
NR ⁴ — (where R ⁴ represents a hydrogen atom or a hydrocarbon group), —CONHCOO—, —CONHCONH— or —C ₆ H ₄ —.

B ¹ and b ² may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COOR ⁵ or —COOR ⁵ via a hydrocarbon.
⁵ (where R ⁵ represents an optionally substituted hydrocarbon group)
Represents The weight average molecular weight of the macromonomer (M) is 2
If it exceeds × 10 ⁴ , the copolymerizability with the monomer corresponding to the formula (I) is undesirably reduced. On the other hand, if the weight average molecular weight is too small, the effect of improving the electrophotographic properties of the photosensitive layer will be small, so that it is preferably 1 × 10 ³ or more.

As a polymer component constituting a repeating unit of the monofunctional macromonomer (M) having the polymerizable double bond group bonded to one terminal, general formulas (I), (Ia) and / or
Or the component represented by (Ib) is mentioned, The content is 30 weight% or more in a macromonomer, Preferably it is 50 weight% or more.

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

The macromonomer (M) may further contain other polymer components other than those described above as a polymer component. For example, acrylonitrile, methacrylic Lonitrile, acrylamides, methacrylamides, styrene and derivatives thereof (eg, vinyl toluene, chlorostyrene, bromostyrene, hydroxymethylstyrene, N, N-dimethylaminomethylstyrene, etc.), and heterocyclic vinyls (eg, vinylpyridine, vinyl Imidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.).

When these other monomers are contained,
1 to 30% by weight based on the total polymer component of the macromonomer (M)
It is preferred that In addition, macromonomer (M ₂ )
Is preferably 1 to 50% by weight, more preferably 3 to 30% by weight in the macromonomer.

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 by Z in the general formula (I). Z is -C ₆ H ₄ - may represent a benzene ring may have a substituent. Examples of the substituent include 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 groups,
And a propoxy group and a butoxy group).

B ¹ and b ² may be the same or different, and are preferably a hydrogen atom, a halogen atom (eg, a chlorine atom or a 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 ⁵ or -COO via hydrocarbon
R ⁵ (R ⁵ is preferably an alkyl group having 1 to 18 carbon atoms,
Represents an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, and specific examples thereof include the same as those described in the above Z.

Examples of the hydrocarbon group in the —COOR ⁵ group via the above hydrocarbon include a methylene group, an ethylene group, and a propylene group. More preferably, in the general formula (II), R ³ 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 ⁵ or -CH ₂ COOR ⁵
[R ⁵ more preferably represents an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc.)]. More preferably, b ¹ and b
^{In 2} , either one represents a hydrogen atom.

The macromonomer used in the present invention is a repeating unit represented by the general formula (I), (Ia) and / or (Ib) as described above, and in the case of the macromonomer (M ₂ ), more specifically. The polymerizable double bond represented by the general formula (II) is directly bonded to only one terminal of a random polymer main chain comprising at least a repeating unit containing a polar group, or is bonded by an arbitrary connecting group. Having the chemical structure shown.

Examples of the linking group for linking the component of the formula (II) and the polymer component include a carbon-carbon bond (single bond or double bond), a carbon-heteroatom bond and a heteroatom-heteroatom bond (in the above description, a heteroatom bond) Is constituted by an arbitrary combination of atomic groups such as an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom.

More specific examples of the linking group include those similar to 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.

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

More specifically, P.S. Dreyfuss an
dR. P. Quirk, Encycl. Polym.
Sci. Eng. , 7, 551 (1987); 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, Polymer, 30, Koichi Ito, Polymer Processing, 35, 262 (1986), Higashi Kishiro, Takashi Tsuda, Functional Materials, 1987, No. It can be synthesized according to the methods described in reviews such as 10, 5 and the literatures and patents cited therein.

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

[0096]

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The protection reaction and deprotection reaction (eg, hydrolysis reaction, hydrogenolysis reaction, oxidative decomposition reaction, etc.) of the polar group randomly contained in the macromonomer (M ₂ ) of the present invention are conventionally known. It can be performed by the method of. Specifically, J.I. F. W. McOmie, "Pro
tive Groups in Organic
Chemistry "Plenum Press (19
73); W. Greene, "Protective
e Groups in Organic Synth
esis ", John Wiley and Sous
(1981), Ryohei Oda "Polymer Fine Chemicals" Kodansha (1976), Yoshio Iwakura, Keisuke Kurita "Reactive Polymers" Kodansha (1977), Berner eta
l. Radiation Curing, 198
6, no. 10, p10, JP-A-62-212669.
Nos. 62-286064 and 62-210475
Nos. 62-195684 and 62-258476
No. 63-260439, Japanese Patent Application No. 62-22052
No. 0, 62-226692 and the like.

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

[0099]

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

[0101]

[Table 1]

The chain transfer agents that can be used include:
For example, a mercapto compound containing the polar group or a substituent capable of being subsequently derived into the polar group (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2
-Mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2
-Mercaptoethyl) amino] propionic acid, N- (3
-Mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-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 which is an oxidized form of these mercapto compounds, or an iodized alkyl compound containing the above polar group or substituent (for example, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanol, Iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferred are mercapto compounds.

Examples of the specific reactive group-containing polymerization initiator that can be used include, for example, 2,2′-azobis (2
-Cyanopropanol), 2,2′-azobis (2-cyanopentanol), 4,4′-azobis (4-cyanovaleric acid), 4,4′-azobis (4-cyanovaleric 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]
Or a derivative thereof.

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 following specific examples include those similar to 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 represents -H or -CH, respectively.
CH ₃ or —CH ₂ C00CH ₃ , wherein R ³⁰ is —C _k
H _{2k +} 1 (k is an integer of _{1~18), - CH 2 C 6} H
_{5, -C 6 H 4 (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
_And R ³⁴ is -Cl, -Br, -CN or -OCH
₃ shows, m shows the integer of 2-18, n shows the integer of 2-12, p shows the integer of 2-4.

[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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The resin [A] of the present invention contains, in addition to the monomers corresponding to the aforementioned general formula (I) and the macromonomer (M), other monomers as further copolymerization components. Is also good.

Examples of such other copolymerization components include methacrylates, acrylates, crotonates containing substituents other than those described in the general formula (I), and α-olefins. , Vinyl carboxylate or allylic acid esters (eg, carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalene carboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic esters (eg, Dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrenes (for example, styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinyl) 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.). 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, the resin [A] comprising the above-mentioned polar group bonded to one end of the polymer main chain.
₁ ] or the resin [A ₁₂ ], at least during the polymerization reaction between the macromonomer (M) and the monomer corresponding to the general formula (I), the polar group or a specific group derivable therefrom. This can be achieved by using a polymerization initiator or a chain transfer agent containing a reactive group in the molecule.

Specifically, it can be obtained in the same manner as in the method of the oligomer having a one-terminal reaction bond as described above in the synthesis of the macromonomer. Next, the resin [B] of the present invention will be described.

The resin [B] has at least three polymer chains containing at least the polymer component (a) represented by the above general formula (I) and the specific polar group-containing polymer component (b).
Bound to pieces same organic component child is a resin made of a so-called star copolymers. That is, the polymer is schematically represented, for example, as follows.

[0118]

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[0119]

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In the above, X represents an organic molecule, and [P
[olimer] represents a polymer chain. Here, the three or more polymer chains bonded to the organic molecule may be structurally the same or different, respectively, and at least the polymer component represented by the general formula (I) and the polar group-containing It suffices if the components are contained in the above proportions. Further, the length of each polymer chain may be the same or different.

The weight average molecular weight of the resin [B] is 2 × 10 ⁴
１1 × 10 ⁶ , preferably 3 × 10 ⁴ -5 × 10 ⁵ . When the molecular weight of the resin [B] is less than 2 × 10 ⁴ , the film-forming ability is reduced and sufficient film strength cannot be maintained, and when the molecular weight is more than 1 × 10 ⁶ , the resin [B] of the present invention may be used.
Effect is reduced, and the electronic properties are almost the same as those of conventionally known resins.

The glass transition point of the resin [B] is -10 ° C.
It is preferably in the range of 100C to 100C, more preferably 0C to 90C. The resin [B] is a star-type copolymer branched as described above, but the proportion of each polymer component in the entire copolymer is the same as described above.

The specific contents of the polymerization component represented by the general formula (I), which is a copolymerization component contained in the resin [B], and the specific polar group-containing component are the same as those described for the resin [A]. Similar ones can be mentioned.

In the star-type copolymer [B], the amount of the polymer component of the specific polar group-containing component was 10%.
0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 0 parts by weight.

When the polar group content in the resin [B] is 0.0
If the amount is less than 5% by weight, the initial potential is low and sufficient image density cannot be obtained. If the content of the polar group is more than 10% by weight, the dispersibility is reduced, and the film smoothness and electrophotographic characteristics are reduced. It is not preferable because the high-temperature and high-humidity properties are reduced, and the background stain increases when used as an offset master.

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

The polymer component containing the specific polar group as described above may be contained in the polymer chain in two or more kinds. On the other hand, in the resin [B], the amount of the polymer component comprising the repeating unit represented by the general formula (I) is at least 30% by weight, preferably from 30% by weight to 9% by weight of the total copolymer weight.
9.95% by weight, more preferably 50% to 99.5% by weight
% By weight.

The resin [B] may contain other copolymer components in addition to the above-mentioned polymer components. Such a polymer component preferably corresponds to a repeating unit of the following general formula (III): Polymer component.

[0129]

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[In the formula (III), D ¹ is -COO-,-
_{OCO -, - (CH 2)} q -OCO -, - (CH 2) q
-COO- (q represents an integer of 1 to 3), -O-,-
SO _2- , -CO-, -CON-D ^3- , -SO ₂ N-
Represents D ³ —, —CONHCOO—, —CONHCONH— or —C ₆ H ₄ — (where D ³ represents a hydrogen atom or a hydrocarbon group); and D ² represents a hydrocarbon group.

R ¹ and r ² may be the same or different from each other and represent the same contents as a ¹ and a ² in the formula (I). Here, in addition to the hydrogen atom, D ³ is preferably a hydrocarbon group which may be substituted with an alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, Hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2
-Cyanoethyl group, 2-methoxycarbonylethyl group,
2-methoxyethyl group, 3-bromopropyl group and the like, an alkenyl group having 4 to 18 carbon atoms which may be substituted (for example, 2-methyl-1-propenyl group, 2-butenyl group,
2-pentenyl group, 3-methyl-2-pentenyl group, 1
-Pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), having 7 to 1 carbon atoms
2 optionally substituted aralkyl groups (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., an alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, cyclohexyl group, 2-cyclohexyl) An ethyl group, a 2-cyclopentylethyl group or the like, or an optionally substituted aromatic group having 6 to 12 carbon atoms (for example,
Phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl Bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarboxyphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecylylamidophenyl group, etc.).

When D ¹ represents —C ₆ H ₄ —, the benzene ring may have a substituent. Examples of the substituent include a halogen atom (eg, a chlorine atom, a bromine atom, etc.), an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group,
Chloromethyl group, methoxymethyl group, etc.) and alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.).

D ² represents a hydrocarbon group. Preferred examples of the hydrocarbon group include an alkyl group having 1 to 22 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group). , Hexyl group, octyl group,
Decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-
Methoxycarbonylethyl group, 2-methoxyethyl group,
3-bromopropyl group, etc., an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-−２) An phenyl group, a 1-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 4-methyl-2-hexenyl group and the like, an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, 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 to 8 optionally substituted alicyclic groups (for example, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group and the like) An optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, Ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, A propioamidophenyl group, a dodecylylamidophenyl group, etc.).

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

Further, as a polymer component which can be contained in the resin [B] together with the polymer component represented by the formula (III), other repeating units copolymerizable with the polymer component of the formula (III) Monomers such as acrylonitrile, methacrylonitrile, and heterocyclic vinyls (eg, vinylpyridine, vinylimidazole, vinylpyrrolidone,
Vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.). These other monomers account for 20 per 100 parts by weight of the total polymer component of the resin [B].
Used within a range of not more than parts by weight.

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

However, when using this reaction, the "specific polar group" of the present invention is used as a protected functional group, and after polymerization, the protective group is eliminated. The protection of the specific polar group of the present invention by a protective group and the elimination of the protective group (deprotection reaction) can be easily carried out by utilizing conventionally known knowledge. For example, various descriptions are given in the above cited references, and furthermore, Yoshio Iwakura and Keisuke Kurita, "Reactive Polymers", Kodansha Co., Ltd. (1977); W.
Greene, “Protective Groups
in Organic Synthesis ", Jo
hnWiley & Sons (1981);
F. W. McOmie, "Protective Gr
ups in Organic Chemistr
y ", Plenum Press, (1973) and the like.

As another method, a monomer having a specific polar group of the present invention which is not protected is used, and a compound containing a disiocarbamate group and / or a compound containing a xanthate group is used as an initiator. It can also be synthesized by performing a polymerization reaction under light irradiation. For example, Takatsu Otsu, polymer, 3
7 , 248 (1988), Shunichi Himori, Ryuichi Otsu, Pol
ym. Rep. Jap. 37 . 3508 (1988),
JP-A-64-111, JP-A-64-26619, Nobuyuki Higashi, Polymer Preprints, Japan
an, 36 , (6), 1511 (1987); Ni
wa, N.M. Higashi, et al. Macro
mol. Sci. Chem. A24 (5), 567 (1
987) and the like.

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

Examples of other resins that can be used in combination are, for example, vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer, methacrylate copolymer, and 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
Page, Koichi Nakamura, "Practical Technology of Binders for Insulating Materials", Chapter 10, C.I. H. C. Publishing (1985); D.
Tatt, S.M. C. Heidecker, Tappi,
4 9 (No.10), 439 ( 1966), E. S. B
altazzi, R.A. G. FIG. Blanklotte et
al, Photo. Sci. Eng. 16 (No.
5), 354 (1972), Nguyen Chan K, Isamu Shimizu, Eiichi Inoue, Journal of the Society of Electrographic Photography 18 (No. 2),
28 (1980), JP-B-50-31011, JP-A-53-54027, JP-A-54-20735, and 57-
The resins disclosed in JP-A-202544 and JP-A-58-68046 are exemplified.

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

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

[0144] When the total amount of the binder resin is less than 10 parts by weight, the film strength of the photoconductive layer can not be maintained. If the amount is more than 100 parts by weight, the electrostatic characteristics are reduced, and the copied image is deteriorated even in the actual image pickup performance.

If the weight ratio of the resin [A] to the resin [A] of the present invention is 0.05 or less in the usage ratio of the resin [A] and the resin [B], the effect of improving the electrostatic properties is diminished. 0.8
Above this, there may be cases where the film strength of the photoconductive layer cannot be sufficiently maintained (particularly as an electrophotographic lithographic printing original plate).

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 (N
o. 8) Page 12, C.I. J. Young et al., RCA R
view 15 , 469 (1054), Kohei Kiyota,
IEICE Transactions J63 - C (No. 2 ), 97
(1980), Yuji such as Yuji, industrial scientific journals 66 78 and 188 (1963), Tadaaki Tani, Journal of the Japan Society of Photographic Science and Technology 35, 2
08 (1972), etc.
Diphenylmethane dye, triphenylmethane dye, xanthene dye, phthalein dye, polymethine dye (for example, oxonol dye, merocyanine dye, cyanine dye, rhodacyanine dye, styryl dye, etc.), phthalocyanine dye (which may contain metal), etc. Is mentioned.

More specifically, those using mainly carbonium dyes, triphenylmethane dyes, xanthene dyes and phthalein dyes are described in JP-B-51-45.
No. 2, JP-A-50-90334 and JP-A-50-11422
No. 7, No. 53-39130, No. 53-82353,
U.S. Pat. Nos. 3,052,540 and 4,054,45
0 and JP-A-57-16456.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes, and rhodacyanine dyes are described in F.A. M. H am er "The Cyanine
Dyes and Related Component
d) and the like, and more specifically, US Pat. Nos. 3,047,384 and 3,110,
No. 591, No. 3, 121, 008, No. 3, 125, 4
No. 47, No. 3,128,179, No. 3,132,94
No. 2, No. 3, 622, 317, British Patent No. 1, 22
6,892, 1,309,274, 1,40
5,898, JP-B-48-7814, and 55-18
No. 892 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 No.
No. 7-840, No. 47-44180, Japanese Patent Publication No. 51-4
No. 1061, JP-A-49-5034 and JP-A-49-451
No. 22, No. 57-46245, No. 56-35141
No., 57-157254, 61-26044,
No. 61-27551, U.S. Pat. No. 3,619,154
No. 4,175,956, “Research D
isclosure ", 1982, 216, 117-
And those described on page 118 and the like. The photoreceptor of the present invention is excellent in that even when various sensitizing dyes are used in combination, the performance is hardly changed by the sensitizing dye. Furthermore, various conventionally known additives for an electrophotographic photosensitive layer such as a chemical sensitizer can be used in combination, if necessary. For example,
Review mentioned above: Imaging 1973 (No. 8) No. 1
" Recent development and commercialization of photoconductive materials and photoreceptors", e.g., electron accepting compounds (for example, halogen, benzoquinone, chloranil, acid anhydride organic carboxylic acid, etc.) and Hiroshi Komon, etc. Chapters 4 to 6 include polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, and the like, which are reviewed in Japanese Science Information Co., Ltd., Publishing Division (1986).

The amounts of these various additives are not particularly limited, but are usually 0.04 parts by weight based on 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, especially 10 to 50μ is preferred.

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

In some cases, an insulating layer is provided for the main purpose of protecting the photosensitive member, improving the durability, and improving the dark attenuation characteristics.
At this time, the insulating layer is set relatively thin, and the insulating layer provided when the photosensitive member is used in a specific electrophotographic process is set relatively thick.

In the latter case, the thickness of the insulating layer is 5 to 70
μ, especially 10 to 50 μ. Examples of the charge transport material of the laminated photoreceptor include polyvinyl carbazole, oxazole dyes, pyrazoline dyes, and triphenylmethane dyes. 5 to 4 as the thickness of the charge transport layer
0μ, especially 10 to 30μ is suitable.

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

The photoconductive layer according to the present invention can be provided on a conventionally known support. Support of the electrophotographic photosensitive layer is say generally is preferably electrically conductive, the conductive support, just as the conventional, for example, metal, paper, a low resistance material on the basis of the plastic sheet those conductive treatment by, for example, impregnating, those conductivity is imparted to the back surface of the base body (surface opposite to the surface on which the photosensitive layer), and further coated with at least one or more layers for the purpose of achieving anti-curl,
A substrate provided with a water-resistant adhesive layer on the surface of the support, a substrate provided with at least one or more pre-coat layers on the surface layer of the support as required, a base conductive plastic on which Al or the like is deposited on paper, Can be used.

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

The electrophotographic photoreceptor of the present invention can be used in applications utilizing all conventionally known electrophotographic processes. That is, the photoreceptor of the present invention can be used for any of the recording methods of the PPC method and the CPC method.
The developer can be used in any combination of a dry developer and a liquid developer.

In particular, since a high-definition original faithful copy image can be formed, the effects of the present invention can be further enhanced when used in combination with a liquid developer. In addition, by combining with a color developer, not only black-and-white copy images,
It can also be applied to color copied images (for example, Kuro Takizawa, “Photo Industry” 33 , 34 (1975), Masayasu Anzai, “IEEJ Technical Report 77 , 17 (197)
7)).

Further, the present invention is also effective in a system for other uses utilizing the recent electrophotographic process. For example, the photoreceptor of the present invention using photoconductive zinc oxide as the photoconductor is used as an offset lithographic printing plate precursor, and is also non-polluting and has good whiteness and good photoconductive zinc oxide or photoconductive titanium oxide. The photoreceptor can be used as an underprint material or a color group used in an offset printing process.

[0161]

[Synthesis of Macromonomer (M)]

Synthesis Example 1 of Macromonomer: (MM-1) 75 g of methyl methacrylate, 25 of methyl acrylate
g, 5 g of thioglycolic acid and 200 g of toluene were heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 2,2'-azobisisobutyronitrile (abbreviation A.
I. B. N. ) 1.0 g, and reacted for 8 hours. Next, 8 g of glycidyl methacrylate, N, N
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 a white powder. The weight average molecular weight (Mw) of the macromonomer was 3.8 × 10 ³ .

[0162]

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Synthesis Example 2 of Macromonomer: (MM-2) 90 g of butyl methacrylate, 10 g of methacrylic acid,
4 g of 2-mercaptoethanol, 2 of tetrahydrofuran
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.

Next, 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 added dropwise with stirring at a temperature of 25 ° C. or lower. After the addition, the mixture was further stirred for 1 hour. Thereafter, 0.5 g of t-butylhydroquinone was added, and the temperature was adjusted to 60.
C. 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 and allowed to stand, and then water was removed by decantation. After two more water washes, 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 yield of the obtained viscous material was 65 g and Mw 3.3 × 1.
0 was ^3.

[0165]

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

A. I. B. N. 1.5 g was added and reacted for 4 hours. I. B. N. 0.5 g was added and reacted for 4 hours. Next, the reaction solution was cooled to a temperature of 20 ° C.
For 1 hour. Next, 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 over about 10 minutes while stirring in 1 liter of water, stirred for 1 hour and allowed to stand, and water was removed by decantation. After repeating the washing with water twice more, it was dissolved in 100 ml of tetrahydrofuran and reprecipitated in 2 liter of petroleum ether. The precipitate was collected by decantation and dried under reduced pressure. The yield of the obtained viscous material was 70 g and Mw was 6 × 10 ³ .

[0168]

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Synthesis Example 4 of Macromonomer: (MM-4) A mixed solution of 90 g of 2-chlorophenyl methacrylate, 10 g of a 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. Was heated. 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 reacted at 110 ° C. for 8 hours. After cooling, the reaction mixture was mixed with 3 g of p-toluenesulfonic acid, 100 m of 90 vol% aqueous solution of tetrahydrofuran.
The solution was added to 1 and stirred at a temperature of 30 to 35 ° C. for 1 hour.
The 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 is washed with tetrahydrofuran 200
The solution was dissolved in 2 ml of n-hexane and reprecipitated in 2 l of n-hexane to obtain 58 g of powder. Mw was 7.6 × 10 ³ .

[0170]

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[0171]

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Synthesis Example 5 of Macromonomer: (MM-5) 95 g of 2,6-dichlorophenyl methacrylate, 3-g
A mixed solution of 5 g of (2'-nitrobenzyloxysulfonyl) propyl methacrylate, 150 g of toluene and 50 g of isopropyl alcohol was heated at 80 ° C. under a nitrogen stream.
Was heated. 2,2'-azobis (2-cyanovaleric acid)
(Abbreviation: ACV) 5.0 g was added and reacted for 5 hours.
Further, A. C. V. 1.0 g was added and reacted for 4 hours.
After cooling, the reaction product was reprecipitated in 2 liters of methanol, and 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
-1.0 g of butyl hydroquinone and 100 g of toluene
Was stirred at a temperature of 110 ° C. for 10 hours. After cooling to room temperature, the mixture was stirred for 1 hour with an 80 W high-pressure mercury lamp.
Irradiated for hours. Thereafter, the reaction mixture was reprecipitated in 1 liter of methanol, and the powder was collected by filtration and dried under reduced pressure. Yield 34
g was 7.3 × 10 ³ .

[0174]

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Synthesis Example 6 of Macromonomer: (MM-6) 80 g of ethyl methacrylate, N-vinylpyrrolidone 5
g, 29 g of trimethylsilyl methacrylate, 3 g of β-mercaptoethanol and 200 g of tetrahydrofuran
Was heated to 70 ° C. while stirring under a nitrogen stream. A. I. B. N. 1 g was added and reacted for 4 hours. I. B. N. 0.5 g was added and reacted for 4 hours. After cooling the reaction mixture and setting the temperature at 25 ° C., 6.6 g of methacrylic acid was added, and 8 g of dicarboxylcarboxylic diimide (DCC) and 4- (N, N
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 for 4 hours. The reaction mixture is then added to formic acid 10
g was added and stirred for 1 hour. After filtering out the precipitated insoluble matter, the filtrate was reprecipitated in 1 liter of methanol, and the oily substance was collected by filtration. Further, this oily substance was added to tetrahydrofuran 200
g, and the insoluble material was separated by filtration and reprecipitated again in 1 liter of methanol. M in 65g yield
w7 × 10 ³ .

[0176]

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[Synthesis of Resin [A]] Synthesis Example 1 of Resin [A]: [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. Add 5 g and react for 4 hours,
Further, A. C. V. 0.5 g was added and reacted for 4 hours. The weight average molecular weight (Mw) of the obtained copolymer is 1.0 × 1
0 was ^4.

[0178]

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Synthesis Example 2 of Resin [A]: [A-2] 80 g of 2-chlorophenyl methacrylate, macromonomer (MM-7) having the following structure (Mw 5 × 10 ³ ) 20
g, β-mercaptopropionic acid 3 g and toluene 20
0 g of the mixed solution was heated to a temperature of 75 ° C. under a nitrogen stream.
In addition, A. I. B. N. 1.5 g was added and reacted for 4 hours, and further 0.5 g was added and reacted for 4 hours. Mw of the obtained copolymer was 8.8 × 10 ³ .

[0180]

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Synthesis Examples 3 to 9 of Resin [A]: [A-3] to
[A-9] In Synthesis Example 2 of Resin [A], instead of 80 g of 2-chloromethacrylate and 20 g of macromonomer, each of the monomers corresponding to Table-A below and the macromonomer were replaced with resin [A]. In the same manner as in Synthesis Example 2). Mw of each polymer was in the range of 7.5 × 10 ^{3 to} 9 × 10 ³ .

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

[0183]

[Table 2]

[0184]

[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 .

[0187]

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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 mixed with nitrogen. The mixture was heated to a temperature of 75 ° C. under an air stream. A. I. B. N. 1.0 g was added and reacted 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, and the precipitate was collected and dried.
63 g of the viscous material of ³ was obtained.

[0190]

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Synthesis Examples 12 to 19 of Resin [A]: [A-1]
2] to [A-19] In Synthesis Example 11 of Resin [A], monomers and macromonomers corresponding to the polymerization components shown in Table-B below were used instead of the monomers and macromonomers. Except for the above, reaction was carried out in the same manner as in Synthesis Example 11 to produce each polymer.

The Mw of each copolymer is from 6 × 10 ³ to 8 × 10
The range was ³ .

[0193]

[Table 4]

[0194]

[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. 80
Warmed to ° C. A. I. B. N. 1.0 g was added and reacted for 4 hours. I. B. N. Add 0.5 g for 2 hours, then add 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.

[0197]

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

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

[0200]

[Table 6]

[0201]

[Table 7]

[0202]

[Table 8]

Synthesis Example 29 of Resin [A] of the Invention: [A-
29] 2-chloro-6-methylphenyl methacrylate 60
g, 25 g of macromonomer (MM-4), 15 g of methyl acrylate, 150 g of toluene and 50 g of isopropanol were 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. Mw of the obtained copolymer was 9.8 × 10 ³ .

[0204]

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[Synthesis of Resin [B]] Synthesis Example 1 of Resin [B] [B-1] 67 g of methyl methacrylate, 32 of methyl acrylate
g, acrylic acid 1 g and an initiator [I-1] 1 having the following structure
A mixed solution of 7.5 g and 150 g of tetrahydrofuran was heated to a temperature of 50 ° C. under a nitrogen stream. 400
The mixture was irradiated with light from a high-pressure mercury lamp of W for 10 hours through a glass filter from a distance of 10 cm to carry out photopolymerization. The obtained reaction product was reprecipitated in 1 liter of methanol, the precipitate was collected and dried, and the weight average molecular weight was obtained in a yield of 72 g (Mw: Mw in resin [B] is a value obtained by a GPC method in terms of polystyrene). A 5 × 10 ⁴ polymer was obtained.

[0206]

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[0207]

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Synthesis Example 2 of Resin [B]: [B-2] In Synthesis Example 1 of Resin [B], the initiator [I-1] 1
Instead of 7.5 g, an initiator [I-2] 10 having the following structure was used.
The operation was carried out under the same conditions as in Synthesis Example 1 except that g was used. The yield of the obtained polymer was 75 g and Mw was 6 × 10 ⁴ .

[0209]

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[0210]

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Synthesis Examples 3 to 9 of Resin [B]: [B-3] to
[B-9] Methyl methacrylate 65 g, methyl acrylate 30
g, 4 g of N-vinylpyrrolidone, 1 g of methacrylic acid, 0.0312 mol of an initiator shown in Table D below, and 100 g of tetrahydrofuran, and operated under the same conditions as in Synthesis Example 1 to obtain each polymer. Was.

The Mw of each of the obtained polymers was 6 × 10 ⁴ to 8
× 10 ⁴ range.

[0213]

[Table 9]

[0214]

[Table 10]

[0215]

[Table 11]

Synthesis Examples 10 to 15 of Resin [B]: [B-1
0] to [B-15] In Synthesis Example 1 of Resin [B], except that instead of methyl methacrylate, methyl acrylate and acrylic acid, respective monomers corresponding to the polymerization components described in Table-E were used. By operating under the same conditions as in Synthesis Example 1, each polymer was obtained.
The Mw of each of the obtained polymers was in the range of 5 × 10 ^{4 to} 6 × 10 ⁴ .

[0219]

[Table 12]

[0218]

[Table 13]

Synthesis Examples 16 to 19 of Resin [B]: [B-1
6] to [B-19] 71.5 g of methyl methacrylate, 25 g of methyl acrylate, 2.5 g of acrylonitrile, 1 g of acrylic acid,
Each polymer was obtained by operating under the same conditions as in Synthesis Example 1 except that the initiator in Table F below was a mixed solution of 0.0315 mol and 100 g of tetrahydrofuran.

The Mw of each polymer obtained was 5 × 10 ⁴ to 8
× 10 ⁴ range.

[0221]

[Table 14]

[0222]

[Table 15]

Synthetic Examples 20 to 24 of Resin [B]: [B-2
0] to [B-24] A mixture of 11.3 g of the initiator [I-2] and a monomer corresponding to each polymer component shown in Table G below was heated to a temperature of 40 ° C under a nitrogen stream. Heated.

The following procedures were performed in the same manner as in Synthesis Example 1 to irradiate with light and polymerize. The solid matter was taken out, dissolved in 250 ml of tetrahydrofuran, and then reprecipitated in 1.5 liter of methanol to remove the precipitate. It was collected by filtration and dried. The yield of each polymer was 60 to 75 g, and the Mw was 6 × 10 ⁴ to 8 × 10 ⁴ .

[0225]

[Table 16]

[0226]

[Table 17]

Example 1 and Comparative Examples 1 and 2 Resin [A-2] 6 g (as solid content), resin [B-
1 (as solid content) 34g, photoconductive zinc oxide 20
0 g, in methine dyes (I) 0.018g of the following structure, homogenizer a mixture of phthalic anhydride 0.15g and toluene 300 g (manufactured by Nippon Seiki Co.), rotational speed 6 × 10
Disperse at ³ rpm for 10 minutes to prepare a photosensitive layer forming product,
This was applied to a conductive-treated paper with a wire bar so that the dry adhesion amount was 25 g / m ² , dried at 110 ° C. for 10 seconds, and then dried in a dark place at 20 ° C. and 65% RH at 2%.
By leaving it for 4 hours, an electrophotographic photosensitive material was produced.

[0228]

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

[0230]

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Comparative Example 2: The resin [B-
1] 34 g of resin [R-2] having the following structure instead of 34 g
Other than the above, an electrophotographic photosensitive material was produced in the same manner as in Example 1.

[0232]

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[0233] These light-sensitive materials, environmental conditions (2
0 ° C., 65% RH), (30 ° C., 80% RH) and (1
At 5 ° C. and 30% RH), the electrostatic characteristics and the imaging properties were examined.

The above results are shown in Table-H.

[0235]

[Table 18]

The embodiments of the evaluation items shown in Table-H are as follows. Note 1) Electrostatic characteristics: in a dark room at a temperature of 20 ° C. and 65% RH.
-6k using a paper analyzer (Paper Analyzer SP-428 manufactured by Kawaguchi Electric Co., Ltd.) for each photosensitive material
After 20 seconds corona discharge V, left for 10 seconds to measure the surface potential V ₁₀ at this time. Then measuring the potential V ₁₀₀ after allowed to stand for 90 seconds in as dark, retention of potential after being 90 seconds dark decay, i.e., dark decay retention rate [DRR (%)] (V ₁₀₀ / V ₁₀ ) × 100 (%).

Further, the surface of the photoconductive layer was changed to −40 by corona discharge.
After charging to 0 V, the surface of the photoconductive layer was gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm).
Irradiation with light was performed to determine the time required for the surface potential (V ₁₀ ) to decay to 1/10, and the exposure amount E _1/10 (erg / cm
² ) Calculate. Environmental conditions during measurement: 20 ° C, 65%
RH (I), 30 ° C., 80% RH (II) and 15 ° C.
Performed at 30% RH (III). Note 2) imaging properties: After standing for one day at each of the photosensitive material following environmental conditions, each photosensitive material was charged at -6 kV, gallium 2.8mW output as a light source - aluminum - arsenide Motohan conductor laser (oscillation wavelength 780 nm) and 64er on the surface of the photosensitive material.
g / cm ^2, an exposure dose of 25 μm and a scanning speed of 300 m / sec after a speed exposure of 300 g / sec. A copy image (fog, image quality) obtained by fixing with a rinse solution of a solvent (manufactured by Chemical Co., Ltd.) was visually evaluated.

Environmental conditions during imaging are 20 ° C. and 65% RH
(I), 30 ° C, 80% RH (II) and 15 ° C, 30%
Performed on RH (III). As shown in Table-H, the photosensitive material of the present invention had good electrostatic characteristics even when the environmental conditions were changed, and the actual copied image was free of ground fog and the copied image quality was clear. On the other hand, Comparative Examples 1 and 2 exhibited good imaging performance under the conditions of normal temperature and normal humidity (I), but did not necessarily correspond to the electrostatic characteristics under the conditions of high temperature and high humidity (II). In addition, unevenness occurs at an intermediate density in a continuous tone portion of a copy original which is a high-resolution copy original. Further, even after the rinsing treatment, slight ground fog remained without being removed.

Further, under the condition of low temperature and low humidity (III), fine white spots were randomly generated in the solid image portion. As described above, only when the resin of the present invention is used, the electrostatic characteristics and the imaging performance (particularly, high-definition images)
It was clarified that an electrophotographic photoreceptor satisfying the above condition was obtained, and in particular, was superior to a photoreceptor system of a semiconductor laser light scanning exposure type. Example 2 and Comparative Examples 3 and 4 Resin [A-15] 5 g (as solid content), resin [B-
2] 35 g (as solid content), photoconductive zinc oxide 20
0 g, 0.020 g of methine dye (II) having the following structure, N-
0.20 g of hydroxymaleimide and 30 of toluene
By operating 0 g of the mixture in the same manner as in Example 1, an electrophotographic photosensitive material was produced.

[0240]

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

[0242]

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

[0244]

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[0245] film-forming property of the photosensitive material (surface smoothness), the mechanical strength of the photoconductive layer, 20 ° C. The 及 beauty environmental conditions, 65% R
H and 30 ° C., and 80% RH and 15 ° C. and 30% RH were examined for electrostatic characteristics and imaging properties. Further, printability when used as an electrophotographic lithographic printing original plate was examined.

[0246]

[Table 19]

The embodiments of the evaluation items shown in Table-I are as follows. Note 3) Smoothness of surface layer: The obtained photosensitive material was measured for its smoothness (sec / cc) using a Beck smoothness tester (manufactured by Kumagai Riko Co., Ltd.) under the condition of an air volume of 1 cc. did. Note 4) Mechanical strength of photoconductive layer: The surface of the obtained photosensitive material was measured using a Haydon-14 type surface test material (manufactured by Shinto Chemical Co., Ltd.) with a load of 75 g / cm ² and emery paper ( film residual rate from the weight reduction of the photosensitive layer removed 1000 times repetitive rubbing <br/> Ri abrasion powder in ♯1000) (%)
And determined the mechanical strength. Note 5) Raw plate water retention: Desensitizing processing solution EPL for each photosensitive material (without plate making)
-EX (manufactured by Fuji Photo Film Co., Ltd.) diluted 5 times with distilled water and passed twice through an etching processor to desensitize the photoconductive layer surface, and then distilled water was used as dampening water. It was applied to an offset printing machine (manufactured by Hamada Printing Machinery Co., Ltd., Model 611XLA-II), and the degree of background staining of the 50th printed matter from the start of printing was visually evaluated (the original plate subjected to desensitization processing). (Equivalent to the forced condition for examining the degree of water retention). Note 6) Printing durability: Under the same conditions as in the above-mentioned Note 2), plate making and toner image formation, followed by passing twice through an etching processor using ELP-EX to desensitize the ink. Then, using this as an offset master, an offset printing machine (Oliver 52, manufactured by Sakurai Seisakusho Co., Ltd.) is used to indicate the number of sheets that can be printed without causing a problem in background stain on a non-image portion of the printed matter and image quality of the image portion. The greater the number, the better the printing durability.)

As shown in Table I, the light-sensitive material of the present invention
The mechanical strength and electrostatic properties of the smooth film of the photoconductive layer were good, and the actual copied image had no ground fog and the copied image quality was clear. This is presumed to be due to the photoconductor and the binder resin being sufficiently adsorbed and covering the particle surface. For the same reason, even when used as an offset master master, the desensitizing treatment with the desensitizing solution proceeds sufficiently, and even when the water retention under forced conditions is evaluated, it is sufficiently hydrophilized, and ink adhesion does not occur at all. I was not able to admit. Even when the printed matter was actually printed and the background stain was observed, no background stain was observed at all, and 10,000 prints of clear image quality were obtained.

On the other hand, in Comparative Examples 3 and 4, when the conditions at the time of imaging were severe, the background was slightly but slightly stained in the non-image portion, and the unevenness was generated in the high-resolution continuous tone image portion. Alternatively, problems such as white dropout and unevenness of the solid image portion occur.

Further, as the offset master original plate, ink adhesion appeared in the water retention of the raw plate subjected to desensitization treatment. The actual printing durability was also limited to 4 to 6,000 sheets. The above is
The resin [A] and the resin [B] of the present invention properly interact with the zinc oxide particles to form a state in which the desensitization reaction with the desensitizing solution easily and sufficiently proceeds. This shows that the film strength has been remarkably improved by the action of the resin [B]. Examples 3 to 22 In Example 2, the resin [A-15] and the resin [B-
Each electrophotographic photoreceptor was produced in the same manner as in Example 2 except that each resin [A] and each resin [B] shown in Table J below were used instead of [2].

[0251]

[0252]

[Table 20]

The electrostatic properties and image-capturing properties of each photosensitive material were measured in the same manner as in Example 1. All photosensitive materials had good electrostatic characteristics, and the actual imaging performance of these photosensitive materials was examined. The reproducibility of fine lines and characters was good, there was no halftone unevenness, and there was no background fog. A copy image was obtained.

Further, when printing was performed in the same manner as in Example 2 using the offset master master, at least 10,000 or more sheets could be printed. From the above, each photosensitive material of the present invention was excellent in all aspects of the smoothness, film strength, electrostatic properties and printability of the photoconductive layer. Examples 23 to 26 Electrophotographic photosensitive materials were produced under the same conditions as in Example 1 except that the methine dye [I] used in Example 1 was replaced with the dye shown in Table K below.

[0255]

[Table 21]

[0256]

[Table 22]

The light-sensitive materials of the present invention are all excellent in chargeability, dark charge retention, and photosensitivity, and the actual copied images are high-temperature and high-humidity (30 ° C., 80% RH) and low-temperature low-humidity (15%).
(30 ° C., 30% RH), a clear image without background fog was obtained. Examples 27 and 28 and Comparative Example 5 6.5 g of either resin [A-1] (Example 27) or resin [A-7] (Example 28), resin [B-21] 3
3.5 g, photoconductive zinc oxide 200 g, uranine 0.0
A mixture of 2 g, 0.03 g of a methine dye [VII] having the following structure, 0.03 g of a methine dye [VIII] having the following structure, 0.18 g of p-hydroxybenzoic acid and 300 g of toluene in a homogenizer was rotated at 7 × 10 ³ rpm. For 10 minutes to prepare a photosensitive layer-formed product, which was applied to a conductive treated paper with a wire bar so that the dry adhesion amount was 25 g / m ^2, and dried at 110 ° C. for 20 seconds. Next, each electrophotographic photoreceptor was manufactured by being left in a dark place at 20 ° C. and 65% RH for 24 hours.

[0258]

Embedded image

[0259]

Embedded image

Comparative Example 5 In Example 27, the resin [B-
21] Instead of 33.5 g, a resin [R-
5] A light-sensitive material was produced in the same manner as in Example 27 except that 33.5 g was used.

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

[0262]

Embedded image

[0263]

[Table 23]

In the above measurement, the same operation as in Example 1 was carried out except that the following operation was carried out for the electrostatic characteristics and the image pickup properties. Note 7) Measurement method of E _1/10 of electrostatic characteristics After charging the surface of the photoconductive layer to −400 V by corona discharge, irradiating the surface of the photoconductive layer with visible light having an illuminance of 2.0 lux, the surface potential was measured. The time until (V ₁₀ ) attenuates to 1/10 is obtained, and the exposure amount E _1/10 (looks / second) is calculated from this. Note 8) Imaging properties After each photosensitive material was left for one day and night under the following environmental conditions, a fully automatic plate making machine EPL-404V (Fuji Photo Film Co., Ltd.)
Manufactured), and a copy image (fog, image quality) obtained by making a plate using EPL-T as a toner was visually evaluated. Environmental conditions at the time of imaging are: 20 ° C. 65% RH (I), 30 ° C. 8
Performed at 0% RH (II) and 15 ° C., 30% RH (III). However, a copy original (that is, a copy original) was prepared by cutting and pasting another original.

In all of the photosensitive materials of the present invention, the mechanical strength of the photoconductive layer was good, but Comparative Example 5 was lower than these. The electrostatic properties showed good performance at normal temperature and normal humidity (I), but especially at low temperature and low humidity (II).
In I), E _1/10 decreased.

The photosensitive material of the present invention has good electrostatic properties. Further, Example 28 using the resin (A) having a specific substituent is very good, and particularly has a value of E _1/100 . Has become smaller. Examining the actual imaging performance, Comparative Example 5
In addition, in addition to the original as a copy image, the frame of the cut and pasted portion (that is, the trace of pasting) was recognized as background stain on the non-image portion. Further, when the environmental conditions at the time of imaging are high temperature and high humidity (II) and low temperature and low humidity (III), unevenness occurs in the halftone region of the continuous tone portion of the copied image, and minute white voids in the solid image portion. The occurrence of unevenness was observed.

Further, when these were subjected to desensitization processing as an offset printing original plate and then printed, 10,000 sheets of clear images without any background stain were obtained in any of the present invention.
However, in Comparative Example 5, the above-mentioned sticking mark was not removed even by the desensitization treatment, and was generated from the printed material.

As described above, only the light-sensitive material of the present invention was able to give good characteristics. Example 29 5.5 g of resin [A-24] and resin [B-21]
5 g, zinc oxide 200 g, uranine 0.02 g, rose bengal 0.04 g, bromophenol blue 0.03
g, a mixture of 0.40 g of phthalic anhydride and 300 g of toluene were processed in the same manner as in Example 27 to prepare a photosensitive material.

The photographic material of the present invention was operated in the same manner as in Example 27, and the performance was examined. All of the characteristics were excellent in chargeability, dark charge retention, and photosensitivity. (30 ° C, 80% RH) and low temperature / low humidity (15 ° C, 30%
% RH), and gave a clear image without generation of background fog.

Further, when this was used as a master for an offset master and printing was performed on 10,000 sheets, a printed matter of clear image quality was obtained. Examples 30 to 53 In Example 29, instead of 5.5 g of the resin [A-24] and 34.5 g of the resin [B-21], 5 g of the resin [A] and 35 g of the resin [B] shown in the following Table-M were used. Except for using, each photosensitive material was produced in the same manner as in Example 29.

[0271]

[Table 24]

The light-sensitive materials of the present invention are all excellent in chargeability, dark charge retention and photosensitivity, and actual copied images can be obtained at high temperature and high humidity (30 ° C., 80% RH) and low temperature and low humidity (15 ° C., 30%).
% RH), and provided a clear image free from occurrence of background fogging and fine line skipping.

Further, when printing was performed as an offset master master, a printed matter of clear image quality free of background stain was obtained even after printing 10,000 sheets.

[0274]

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

The use of a repeating unit containing a specific methacrylate component represented by the formula (Ia) or (Ib) in the resin of the present invention further improves the electrostatic properties.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03G 5/05 101

Claims (4)

(57) [Claims] 1. An electrophotographic photosensitive member having a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye and a binder resin, wherein the binder resin comprises the following resin [A ₁ ] and resin [A ₂ ], And at least one of the following resins [B]. Resin [A ₁ ] One of polymer main chains having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and containing 30% by weight or more of a repeating unit represented by the following general formula (I) as a polymer component. A monofunctional macromonomer (M ₁ ) having a weight-average molecular weight of 2 × 10 ⁴ or less which is obtained by bonding a polymerizable double bond group represented by the following general formula (II) only to the terminal of And a monomer comprising a monomer corresponding to the repeating unit represented by the formula: and -PO ₃ at one end of the main chain of the copolymer.
_{H 2, -SO 3 H, -COOH} , -P (= O) (OH) R
^{1 A} resin obtained by bonding at least one polar group selected from [R ¹ represents a hydrocarbon group or —OR ² (R ² represents a hydrocarbon group)] and a cyclic acid anhydride group. Resin [A ₂ ] having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , containing 30% by weight or more of a repeating unit represented by the following general formula (I) as a polymer component, and the above resin [A ₁ ] Polymerization represented by the following general formula (II) only at one end of a polymer main chain containing 1 to 50% by weight of a polymer component containing at least one polar group selected from the specific polar groups shown. A monofunctional macromonomer (M ₂ ) having a weight average molecular weight of 2 × 10 ⁴ or less formed by bonding a functional double bond group and a monomer corresponding to the repeating unit represented by the general formula (I). A resin that is a polymer. Embedded image [In the formula (I), a ¹ and a ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. Z represents a hydrocarbon group. [Chemical formula 2] [In the formula (II), R ³ represents -COO-, -OCO-, -C
_{H 2 OCO -, - CH 2} COO -, - O -, - SO 2 -,
—CO—, —CONR ⁴ —, —SO ₂ NR ⁴ — (where R ⁴
Represents a hydrogen atom or a hydrocarbon group), -CONHC
OO -, - CONHCONH- or -C ₆ H ₄ - represents a. b ¹ and b ² may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group,
COOR ⁵ or —COOR ⁵ through a hydrocarbon (where R
⁵ represents an optionally substituted hydrocarbon group). Resin [B] A polymer component (a) having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ and comprising a repeating unit represented by the general formula (I) in the resin [A ₁ ] and the resin At least three polymer chains comprising at least one polymer component (b) containing at least one polar group selected from the specific polar groups represented by [A ₁ ];
Become attached to the machine molecule, polymer component (b) 30 wt% or more and the polymer component (b) 0.05 to 10 wt%
Star-type copolymer contained. 2. The resin [A ₂ ] further binds at least one polar group selected from the specific polar groups represented by the resin [A ₁ ] to one end of the copolymer main chain. The electrophotographic photoreceptor according to claim 1, wherein 3. The resin [A ₁ ] or [A ₂ ] as a polymer component represented by the following general formula (I):
The electrophotographic photosensitive member according to claim 1, further comprising at least one of a methacrylate component containing an aryl group represented by the following general formula (Ib): Embedded image Embedded image [In the formulas (Ia) and (Ib), R ⁶ and R ⁷ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom , a bromine atom, —COR ¹⁰ or —COOR ¹⁰ (here, R
¹⁰ represents a represents) a hydrocarbon group having 1 to 10 carbon atoms, R ⁸
And R ⁹ each represent a single bond or a linking group having 1 to 4 linking atoms that connects -COO- and a benzene ring. ] 4. In the resin [B], the content (weight ) of a specific polar group-containing polymer component contained in the whole copolymer
%) Is the content (% by weight) of the specific polar group-containing polymer component contained in the resins [A1] and [A2] .
3. The method according to claim 1, wherein the amount is 10% to 50%.
The electrophotographic photosensitive member according to the above.