JPH06266124A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To provide an electrophotographic sensitive body improved in image reproducibility, moisture resistance and surface strength, excellent in reproducibility of a high definition image especially with a liq. developer and also excellent in image pickup property by a scanning exposure system with a low output laser light. CONSTITUTION:This electrophotographic sensitive body contains a low mol.wt. AB block copolymer resin consisting of block A contg. a polymer component having a specified polar group and block B contg. a polymer component represented by formula I and a medium to high mol.wt. AB and/or ABA block copolymer resin consisting of block A contg. a polymer component represented by formula II and block B contg. a monofunctional macromonomer contg. a component having a specified polar group as binding resins. In the formula I, R<11> is a hydrocarbon. In the formula II, each of a<1> and a<2> is H, a halogen, cyano or hydrocarbon and R<11> is a hydrocarbon.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor,
More specifically, it relates to an electrophotographic photoreceptor having excellent image reproducibility, moisture resistance and surface strength.

[0002]

2. Description of the Related Art Electrophotographic photoreceptors have various structures in order to obtain predetermined characteristics or depending on the type of electrophotographic process applied. Typical electrophotographic photoconductors are a photoconductor having a photoconductive layer formed on a support and a photoconductor having an insulating layer on the surface thereof, which are widely used.

Photoreceptors composed of a support and at least one photoconductive layer are used for image formation by the most common electrophotographic processes, ie charging, imagewise exposure and development, and optionally transfer. Further, a method of using an electrophotographic photosensitive member as an offset original plate for direct plate making is widely used. Particularly in recent years, the direct electrophotographic lithographic printing plate has become important as a method for printing high-quality printed matter by printing several hundred to several thousand sheets. In such a situation, the binder resin used for forming the photoconductive layer of the electrophotographic photosensitive member has excellent film-forming property of itself and dispersibility in the binder resin of the photoconductive powder,
The formed recording layer has good adhesion to the substrate, and the photoconductive layer of the recording layer has excellent charging ability, small dark decay, large light decay, little pre-exposure fatigue, and shooting It is necessary to have various electrostatic characteristics such as being required to stably maintain these characteristics due to changes in humidity with time, and excellent image pickup properties.

Further, research on a lithographic printing original plate using an electrophotographic photosensitive member has been earnestly conducted, and a photoconductive layer for a photoconductive layer having both electrostatic characteristics as an electrophotographic photosensitive member and printing characteristics as a printing original plate has been made. Binder resin is required. Inorganic photoconductive material,
It has been found that, in the photoconductive layer containing at least the spectral sensitizing dye and the binder resin, not only the smoothness but also the electrostatic properties are greatly affected by the chemical structure of the binder resin. Particularly in the electrostatic characteristics, the dark charge retention rate (D.R.
R. ) And light sensitivity are greatly affected.

On the other hand, various techniques for improving smoothness and electrostatic characteristics have been studied by using a resin having a relatively low molecular weight (about 10 ³ to 10 ⁴ ) containing an acidic group as a binder resin. ing. For example, JP-A No. 63-217354 discloses a resin in which an acidic group-containing polymerization component is randomly present in the polymer main chain, and JP-A No. 64-70761 has an acidic group bonded to one end of the polymer main chain. Resin, JP-A-2-67563
Nos. 2,236,561, 2,238,458, 2,236,562, and 2,247,656, etc., each have a resin or an acidic group formed by bonding an acidic group to the end of the main chain of the graft copolymer. Resins contained in the graft portion of the graft type copolymer, and JP-A No. 3-181948 describe AB type block copolymers containing an acidic group as a block. These are such that the low molecular weight resin has an effect of sufficiently dispersing the photoconductor and suppressing the aggregation of the photoconductors, and the inorganic substance without alienating the adsorption between the photoconductor and the spectral sensitizing dye. It is presumed that this is due to the fact that the photoconductor is sufficiently adsorbed to the stoichiometric defects and the surface of the photoconductor is covered gently and sufficiently.

Due to its mechanism of action, the inorganic photoconductor, the spectral sensitizing dye, and the resin are relatively stable because they have a sufficient adsorption region even if the stoichiometric defects of the inorganic photoconductor fluctuate to some extent. It is inferred that mutual interaction is maintained. Furthermore,
In order to make the mechanical strength of the photoconductive layer sufficient by using only these low molecular weight resins, the technique of using another resin of medium to high molecular weight or the resin containing a curable group is used in combination. Various studies have been conducted on a technique of curing after film formation, or a technique of maintaining a relatively high performance even when an environment change or a semiconductor laser beam is used. For example, JP-A-64-564, JP-A-63-220149,
63-220148, JP-A-1-280761,
No. 1-116643, No. 1-169455, No. 1-
No. 211766, No. 2-34859, No. 2-5306
No. 4, No. 2-56558, No. 3-29954, No. 3
-77954, 3-92861, 3-5325.
No. 7, No. 3-92863, No. 3-206464, No. 3-225344, No. 3-181948, No. 3-2.
No. 38462, No. 4-22961, No. 4-30169
No. 4-29243, 4-27951, 4-
No. 25849, No. 4-31866 and No. 4-3285.
No. 0, etc.

[0007]

However, even if various low molecular weight resins containing these acidic groups, and further various medium to high molecular weight resins are used in combination, the photoconductive property in practical use is reduced. It has been found that problems can occur in the mechanical strength of the layers. For example, when the photoconductor is used in a copying machine (or a plate making machine) in the form of a sheet or a roll, the photoconductive layer surface of the photoconductor is always in contact with the back surface of the photoconductor, and the photoconductor is sometimes violently violent. It's inevitable that you'll be costed. At such time, through the electrophotographic process,
When a copied image is formed and viewed, there is a problem that the image is missing or the non-image portion is smeared at the distorted portion.

Further, it is desirable that the reproduced image reproducibility with respect to the original is kept good and stable even when the environment changes remarkably from high temperature / high humidity to low temperature / low humidity. In particular, the scanning exposure method using semiconductor laser light has a longer exposure time than the conventional simultaneous full-time exposure method using visible light, and there is also a restriction on the exposure intensity, so electrostatic characteristics, especially dark charge retention, are retained. For characteristics and light sensitivity,
Higher performance is required.

Further, in recent years, it has been desired to realize a technique for faithfully reproducing not only a copied image of an image composed of line drawings and halftone dots but also a high-definition image composed of continuous gradations by using a liquid developer. When actually testing the image reproducibility with a conventional photoconductor, the gradation of the copied image becomes soft, or
There was a trace of pasting the original. Alternatively, the electrostatic characteristics are good, but the actual copy image has uneven density in the continuous tone portion.

In particular, when a scanning exposure method using a semiconductor laser beam is adopted in an electrophotographic lithographic printing plate, the printed matter may have white spots in a solid image area under uneven density in gradation areas or under low humidity conditions. The unevenness has occurred. In the conventionally known technique, the medium to high molecular weight resin used in combination with the low molecular weight resin may reduce the actual image reproducibility which is improved by the low molecular weight resin. The electrophotographic photoreceptor having a photoconductive layer used in combination with these known resins is a reproducible copy image of a high-definition image (especially continuous tone image) as described above, or a low output laser. It has become clear that a problem may occur with respect to the imaging property of the scanning exposure method using light.

The present invention is intended to improve the problems of the above-described conventionally known electrophotographic photoreceptors. An object of the present invention is to provide an electrophotographic photosensitive member having a sharp and high-quality image with excellent reproducibility of copied images, in which the photoconductive layer has extremely good resistance to abrasion. Another object of the present invention is to always maintain stable and good electrostatic characteristics even when the environment during copy image formation changes such as low temperature low humidity or high temperature high humidity.
An object is to provide an electrophotographic photosensitive member having a clear and high-quality image.

Another object of the present invention is to provide a CPC electrophotographic photosensitive member which is excellent in electrostatic characteristics and has little environmental dependence. Another object of the present invention is to provide an electrophotographic photosensitive member effective for a scanning exposure system using a semiconductor laser beam. A further object of the present invention is to have excellent electrostatic properties (especially dark charge retention and photosensitivity), reproduce a faithful copy image with respect to an original image (especially a high-definition continuous tone image), and obtain a printed matter. An object of the present invention is to provide an electrophotographic lithographic printing original plate which does not generate spot stains as well as uniform stains on the entire surface and has excellent printing durability.

[0013]

The above object is to provide an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye and a binder resin, wherein the binder resin is It was found to be achieved by an electrophotographic photosensitive member characterized by containing at least one kind of A] and at least one kind of the following resin [B]. Resin [A] having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ ,
_{O 3 H 2, -COOH, -SO} 3 H, phenolic OH
Group, -P (= O) (OH ) R 1 [R ¹ is a hydrocarbon group or -OR ² (R ² represents a hydrocarbon group)] at least one selected from and cyclic acid anhydride group An AB-type block copolymer composed of an A block containing a polymer component having a polar group and a B block containing at least a polymer component represented by the following general formula (I).

[0014]

[Chemical 5]

[In the formula (I), R ¹¹ represents a hydrocarbon group. Resin [B] A block having a weight average molecular weight of 3 × 10 ⁴ to 1 × 10 ⁶ and containing at least a polymer component composed of a repeating unit represented by the following general formula (II), and —PO ₃ H ₂ ,
_{-COOH, -SO 3 H, -P (} = O) (OH) R
¹ (R ¹ has the same meaning as described above) and a polymerizable double bond only at one end of the polymer main chain containing a polymer component having at least one polar group selected from cyclic acid anhydride groups. Weight average molecular weight 1 × 10 ³ to 2 formed by bonding a bonding group
An AB-type and / or ABA-type block copolymer composed of a B block containing at least one monofunctional macromonomer (M) of × 10 ⁴ .

[0016]

[Chemical 6]

[In the formula (II), a ¹ and a ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R
¹² represents a hydrocarbon group. ]

That is, the binder resin of the present invention is a low molecular weight resin [A having a block A containing the specific polar group component and a block B containing the polymer component represented by the general formula (I). ], And a monoblock containing at least the polymer component represented by the general formula (II) and not containing the specific polar group component, and the specific polar group component as the polymer component. It is composed at least of a medium to high molecular weight AB type and / or ABA type block copolymer (resin [B]) comprising a B block containing at least a monomer (M) as a copolymerization component.

The binder resin of the photoconductive layer disperses the inorganic photoconductive particles sufficiently uniformly and forms a state in which they do not aggregate.
In addition, it is first important not to prevent the spectral sensitizing dye and the chemical sensitizer from being sufficiently adsorbed on the surface of the grain. The resin [A] and the resin [B] of the present invention appropriately form the above state.

That is, since the resin [A] of the present invention contains a large amount of a specific polar group component which is a low molecular weight substance and has a function of adsorbing to the particles, the resin [A] has a stronger adsorptivity than the resin [B] and is therefore selected. To the particles sufficiently to thereby uniformly disperse the particles. Further, since the polymer chain is very short, it also has a function of suppressing aggregation of the particles. Therefore, even if the stoichiometric defect portion of the inorganic photoconductor fluctuates to some extent, it has a sufficient adsorption region, so that a stable interaction between the inorganic photoconductor and the resin [A] is always maintained. Is also considered to have an important action of preventing the adsorption of additives such as spectral sensitizing dyes and chemical sensitizers.

The resin [B] of the present invention having a medium to high molecular weight to be used in combination with the low molecular weight resin [A] has a specific polar group component content lower than that of the resin [A] used in combination and has the following content. As shown in Chemical formula 7, the polar group is contained at a specific position in the block polymer of the resin [B].

[0022]

[Chemical 7]

Therefore, the resin [B] of the present invention forms a state in which the macromonomer polymer portion of the B block is adsorbed to the inorganic photoconductive particles, and conversely, the A block exists away from the surface of the particles. It is thought that As a result, the adsorbed state of the resin [A] and the additive is not alienated, and a block that adsorbs the photoconductor particles and a block that does not adsorb despite the long polymer chain of the resin. As a result, the non-adsorbed block is not adsorbed between the particles to cause agglomeration of the particles. Furthermore, it is presumed that the A block portion having a sufficiently long chain length is likely to form sufficient entanglement between polymer chains.

From the above, by using the binder resin of the present invention, good and stable reproduced image reproducibility is exhibited even when environmental conditions are changed, and the mechanical strength of the film is dramatically improved. It is considered that the phenomenon of so-called pressure fog is remarkably improved because it has improved durability and durability against forces such as abrasion. This effect was particularly remarkable with polymethine dyes or phthalocyanine pigments, which are particularly effective as dyes for spectral sensitization from near infrared to infrared light.

Further, in the present invention, as the resin [A], a resin [A] containing a methacrylate component having a specific substituent and a polar group component represented by the following general formulas (Ia) and (Ib) ] (Hereinafter, this resin is particularly referred to as a resin [A ']).

[0026]

[Chemical 8]

[0027]

[Chemical 9]

[In the formulas (Ia) and (Ib), A ¹ and A
² are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a cyano group, -COZ ² or -C.
OOZ ² (Z ² represents a hydrocarbon group having 1 to 10 carbon atoms)
And B ¹ and B ² each represent a single bond or a linking group having 1 to 4 connecting atoms for connecting —COO— and a benzene ring.] When the above specific resin [A ′] is used, resin [A] Electrophotographic characteristics (especially V ₁₀ , DRR, E
_With the improvement of _1/10 ), the reproducibility of the actual copied image can be significantly improved. The reason for this is unclear, but one reason is that due to the effect of the planar benzene ring or naphthalene ring, which is the ester component of methacrylate, the alignment of these polymer molecular chains at the photoconductor interface in the film. It is thought that this is due to the fact that

On the other hand, when the electrophotographic photoreceptor of the present invention using photoconductive zinc oxide as the photoconductor is used as a conventionally known direct printing plate, it exhibits excellent image pick-up property and remarkably good water retention. That is, the photoconductor of the present invention on which a copied image is formed through an electrophotographic process is desensitized to a non-image portion by a chemical treatment with a conventionally known desensitizing treatment liquid to prepare a printing original plate, which is subjected to offset printing. It shows excellent performance as an original plate for printing when printed.

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

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

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

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

When the amount of the polar group-containing component in the resin [A] is less than 0.5% by weight, the initial potential is low and a sufficient image density cannot be obtained. On the other hand, when the content of the polar group-containing component is more than 20% by weight, the dispersibility of the photoconductor particles is lowered, no matter how low the molecular weight is, and the film smoothness at high temperature and high humidity and the electrophotographic properties are deteriorated. Moreover, when used as an offset master, the background stain increases.

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

Here, -P (= O) (OH) R ¹ represents a group represented by the following chemical formula ¹⁰ , wherein R ¹ is a hydrocarbon group or an -OR ² group (R ² is a hydrocarbon group. R ¹ is preferably an aliphatic group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, Propenyl group, methoxymethyl group, ethoxymethyl group, 2-ethoxyethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-methoxyethyl group, 2-
Fluoroethyl group, 3-chloropropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 2-methoxybutyl group, allyl group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group , A methylbenzyl group, a chlorobenzyl group, a fluorobenzyl group, a methoxybenzyl group, etc.) or an optionally substituted aryl group (eg, a phenyl group, a tolyl group,
Ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-
Methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.) and R ² has the same content as R ¹ .

[0037]

[Chemical 10]

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

The cyclic acid anhydride group means at least 1
It is a group containing one cyclic acid anhydride, and examples of the cyclic acid anhydride contained therein include an aliphatic dicarboxylic acid anhydride and an aromatic dicarboxylic acid anhydride.

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

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

The "polymer component containing a specific polar group" as described above is, for example, a vinyl group-containing vinyl group copolymerizable with a monomer corresponding to the repeating unit represented by the general formula (I). Any compound may be used as long as it is a system compound, and is described, for example, in "Polymer Data Handbook [Basic Edition]", edited by The Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form,
α- (2-amino) methyl, α-chloro, α-bromo, α-fluoro, α-tributylsilyl, α-cyano, β-chloro, β-bromo, α-chloro- β
-Methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half-esters, itaconic acid half-amides, crotonic acid, 2-alkenylcarboxylic acids (eg 2-pentenoic acid, 2-methyl- 2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4
-Ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, vinyl groups of dicarboxylic acids or allyl. Examples thereof include a half-ester derivative of a group, an ester derivative of a carboxylic acid or a sulfonic acid thereof, and a compound having the polar group in the substituent of an amide derivative.

The polar group-containing copolymer component is exemplified below. Here, b ¹ is -H, -CH _3, -Cl, -
Br, -CN, -CH ₂ COOCH ₃ or -CH ₂ CO
OH, b ² represents —H or —CH ₃ , and f is 2 to
18 is an integer, g is an integer of 1 to 12, and h is 1
Indicates an integer of ˜4.

[0044]

[Chemical 11]

[0045]

[Chemical 12]

[0046]

[Chemical 13]

[0047]

[Chemical 14]

[0048]

[Chemical 15]

Two or more polymer components containing a specific polar group as described above may be contained in the A block. In that case, the two or more polar group-containing components are contained in the A block. It may be contained in any form of random copolymerization or block copolymerization.

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

Next, the polymer component constituting the B block component in the resin [A] which is an AB type block copolymer will be described in detail. The B block component contains at least a methacrylate component represented by the general formula (I), and the methacrylate component of the formula (I) is preferably 30 to 100% by weight, more preferably 5% by weight in the B block component.
It is contained in an amount of 0 to 100% by weight.

In the repeating unit represented by the general formula (I), the hydrocarbon group of R ¹¹ may be substituted. R ¹¹
Is preferably an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. The substituent may be any substituent other than the polar group contained in the polymer component constituting the A block of the AB type block copolymer,
For example, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, ^{etc.), - OZ 1, -COO-} Z 1, -OC
OZ ¹ (Z ¹ represents an alkyl group having 1 to 22 carbon atoms,
Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, an octadecyl group and the like). The preferred hydrocarbon group has 1 to 18 carbon atoms.
An optionally substituted alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2 -Bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), 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.), 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.), even if substituted with 5 to 8 carbon atoms Good cycloaliphatic radicals (eg cyclohexyl, 2-
A cyclohexylethyl group, a 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octyl group) Phenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl Group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.) and the like.

[0053] In the hydrocarbon groups R ^11, R ¹¹ may contain preferably in the case of an aliphatic group or 60% by weight of the component represented a hydrocarbon group having 1 to 5 carbon atoms in formula (I) Is preferred.

Further, in the resin [A], a part or all of the repeating unit represented by the general formula (I) constituting the B block component is represented by the general formula (Ia) and the general formula (Ib).
It is preferable that the methacrylate component having a specific substituent has a benzene ring or an unsubstituted naphthalene ring having a specific substituent at the 2-position and / or the 2-position and the 6-position shown by. Therefore, the general formula (I
At least one repeating unit selected from a) and (Ib) is 30% by weight or more in the B block, especially 50 to 1
It is preferably contained in an amount of 00% by weight.

In formula (Ia), preferred A ¹ and A
² , independently of each other, a hydrogen atom, a halogen atom (for example, a chlorine atom and a bromine atom) and a cyano group, as well as a hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. (For example, methyl group, ethyl group,
Propyl group, butyl group, aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloromethyl group benzyl) and aryl groups (e.g. phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and -COZ ² and -COOZ ² (above carbon number preferred Z ² 1 to 10 may be mentioned). However, neither A ¹ nor A ² represents a hydrogen atom.

In the formulas (Ia) and (Ib), B ¹ and B ² are each a single bond connecting —COO— and the benzene ring or — (CH ₂ ) _a — (a represents an integer of 1 to 3). ,-
_{CH 2 OCO -, - CH 2} CH 2 OCO -, - (CH 2
O) _b - _(b represents an integer of 1 or _2), - CH 2 CH
A connecting group having 1 to 4 connecting atoms such as ₂ O- and the like, and more preferably a single bond or a connecting group having 1 to 2 connecting atoms can be mentioned.

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

[0058]

[Chemical 16]

[0059]

[Chemical 17]

[0060]

[Chemical 18]

[0061]

[Chemical 19]

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

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

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

Further, in the resin [A], in the B block formed separately from the A block composed of the polymer component containing the specific polar group, the above formula (I) {preferably (Ia), (Ib)} or the repeating unit represented by the above formula (II) may be contained in two or more kinds, and may further contain a polymer component other than these.
When two or more polymer components are contained in the B block which does not contain a polar group, the AB block copolymer component is contained in the B block by either random copolymerization or block copolymerization. May be
It is preferably contained randomly. However, the B block is characterized by not containing the specific polar group-containing component contained in the A block.

The other polymer component that can be contained in the B block together with the polymer component selected from the repeating units represented by the above formula (I) or (II) is not limited as long as it is a component copolymerizable with these. But it's okay.

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

[0068]

[Chemical 20]

[In the formula (III), V ¹ Is -COO-, -OC
O-,-(CH ₂ ) _i OCO-,-(CH ₂ ) _i COO
-, -O-, -SO ₂ -, -CON (R ^{twenty two} )-,-SO
₂ N (R ^{twenty two} )-, -CO-, -CONHCOO-, -C
ONHCONH- or -C ₆ H _Four Represents- (where
i represents an integer of 1 to 3 and R ^{twenty two} Is hydrogen atom or carbonized water
Represents the prime). R ¹³ Represents a hydrocarbon group. c ¹ And c
² May be the same or different from each other, and in the above formula (II)
Of a ¹ , A ² And have the same contents respectively. 〕here
And R ^{twenty two} Is a hydrogen atom or a preferable hydrocarbon group.
Is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg,
For example, methyl group, ethyl group, propyl group, butyl group,
Butyl, hexyl, octyl, decyl, dodecyl
Group, hexadecyl group, octadecyl group, 2-chloroene group
Cyl group, 2-bromoethyl group, 2-cyanoethyl group, 2
-Methoxycarbonylethyl group, 2-methoxyethyl
Group, 3-bromopropyl group, etc.), substituted with 4 to 18 carbon atoms
Optionally alkenyl groups (eg 2-methyl-1-
Propenyl group, 2-butenyl group, 2-pentenyl group, 3
-Methyl-2-pentenyl group, 1-pentenyl group, 1-
Hexenyl group, 2-hexenyl group, 4-methyl-2-he
Xenyl group, etc.), an alkyl group having 7 to 12 carbon atoms which may be substituted.
Aralkyl group (eg, benzyl group, phenethyl group, 3-
Phenylpropyl group, naphthylmethyl group, 2-naphthyl
Ethyl group, chlorobenzyl group, bromobenzyl group, methyl
Rubenzyl group, ethylbenzyl group, methoxybenzyl group
Group, dimethylbenzyl group, dimethoxybenzyl group, etc.),
An alicyclic group having 5 to 8 carbon atoms which may be substituted (for example,
Chlorohexyl group, 2-cyclohexylethyl group, 2-cyclohexyl group
(Clopentylethyl group, etc.) or substitution of 6 to 12 carbon atoms
Optionally aromatic groups (eg phenyl, naphthyl)
Group, tolyl group, xylyl group, propylphenyl group, buty
Ruphenyl group, octylphenyl group, dodecylphenyl
Group, methoxyphenyl group, ethoxyphenyl group, butoki
Cyphenyl group, decyloxyphenyl group, chlorophenyl
Group, dichlorophenyl group, bromophenyl group, cyano
Phenyl group, acetylphenyl group, methoxycarbonyl
Phenyl group, ethoxycarboxyphenyl group, butoxy
Carbonylphenyl group, acetamidophenyl group, pro
Pioamidophenyl group, dodecyloylamidophenyl group
Etc.) can be mentioned.

[0070] V ¹ is -C ₆ H ₄ - may represent a benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group,
Chloromethyl group, methoxymethyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) and the like.

R ¹³ represents a hydrocarbon group, and a preferable hydrocarbon group is an optionally substituted alkyl group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group). , Hexyl group, octyl group,
Decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-
Methoxycarbonylethyl group, 2-methoxyethyl group,
3-bromopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms which may be substituted (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-perenyl group). Ntenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), and optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group). Group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), carbon number 5 to 8 optionally substituted alicyclic groups (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc. An optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, Ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, A propioamidophenyl group, a dodecyloylamidophenyl group, etc.).

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

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

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

[0075]

[Chemical 21]

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

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

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

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

Specifically, it should be synthesized by the method described in Akira Ueda, Susumu Nagai, Kobunshi Shinbun, 44 , 469 (1987), Akira Ueda, Osaka Municipal Industrial Research Institute Report, 84 (1989) and the like. You can

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

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

[0083]

[Chemical formula 22]

Next, the resin [B] of the present invention will be described. The resin [B] is a monofunctional macromonomer (A block containing the polymer component represented by the general formula (II) and containing no specific polar group and a specific polar group-containing polymer component ( It is a resin composed of an AB type or ABA type block copolymer containing a B block containing M) as a copolymerization component (the pattern of the polymer is shown in the schematic diagram).

When the resin [B] is an ABA type block copolymer, the A blocks at both ends may be structurally the same or different, and at least the B blocks in each B block are the same. It suffices that it does not contain the polar group component and also contains the polymer component represented by the general formula (II). The length of each polymer chain may be the same or different.

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

The glass transition point of the resin [B] is −10 ° C.
The temperature is preferably in the range of -100 to 100 ° C, more preferably 0 to 90 ° C. The monofunctional macromonomer (M) used in the present invention is contained in the B block in an amount of 1 to 60% by weight, preferably 5 to 40% by weight, based on the whole polymer. Content of monofunctional macromonomer (M) is 1% by weight
When the amount is below, the effect of making the B block a graft structure is diminished, and the electrophotographic characteristics and water retention are deteriorated. On the other hand, when it is 60% by weight or more, the copolymerizability with other copolymerization components is lowered, which is not preferable.

The amount of the polymer component of the specific polar group-containing component in the block copolymer resin [B] is 0.05 to 10 per 100 parts by weight of the total amount of all the polymers in the copolymer resin [B].
It is contained in an amount of 0.5 part by weight, preferably 0.5 to 8 parts by weight. The amount of the polar group-containing component in the resin [B] is 0.05
If it is less than 10% by weight, the initial potential is low and a sufficient image density cannot be obtained, and if the content of the polar group is more than 10% by weight, the dispersibility of the photoconductor particles is lowered and the high temperature and high humidity are increased. In this case, the film smoothness and the electrophotographic characteristics in Example 2 are deteriorated, and the background stain is increased when used as an offset master, which is not preferable.

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

Next, the polymer component of the A block in the resin [B] will be described. The main polymer component of the A block is a repeating unit represented by the general formula (II),
The content is preferably 30% by weight to 100% by weight, more preferably 50% by weight based on the total weight of the A block.
% To 100% by weight. Specific examples of the polymer component represented by the general formula (II) include those having the same contents as those exemplified for the resin [A].

Further, in the A block of the resin [B],
In addition to the above-mentioned polymer components, other copolymer components may be contained, and the copolymer weight in the description of the B block of the resin [A] may be represented by the general formula (I) or other components. The same content as the combined component can be mentioned. These other monomers are used in an amount not exceeding 30 parts by weight based on 100 parts by weight of the total polymer component of the A block.

Next, the polymer component of the B block in the resin [B] will be described. The B block contains at least one monofunctional macromonomer (M) containing a specific polar group, and does not contain the specific polar group-containing polymer component as another polymer component. Characterize. The monofunctional macromonomer (M) has a weight average molecular weight of 1 × 1.
0 ^{3 to} 2 × 10 ⁴ , preferably 3 × 10 ³ to 1 ×
It is 10 ⁴ .

When the weight average molecular weight of the macromonomer (M) exceeds 2 × 10 ⁴ , the copolymerizability with other monomers decreases, which is not preferable. On the other hand, if the weight average molecular weight is too small, the effect of improving the electrophotographic characteristics of the photosensitive layer becomes small, so that it is preferably 1 × 10 ³ or more. The macromonomer (M) is formed by binding a polymerizable double bond group to one end of the polymer main chain, and specific examples thereof include the double bond group represented by the general formula (IV).

[0094]

[Chemical formula 23]

[In the formula (IV), e ¹ and e ² each represent a hydrogen atom, a halogen atom, a trifluoromethyl group, a cyano group or a hydrocarbon group. V ² is -COO-, -OCO-,
_{- (CH 2) m3 OCO -} , - (CH 2) m3 COO- (m
₃ represents an integer of 1~3), - O -, - SO 2 -, - C
^{O -, - CON (T 1} ) -, - SO 2 N (T 1) -, -
CONHCOO -, - CONHCONH- or -C ₆ H
₄ - represents a (wherein, T ¹ represents a hydrogen atom or a hydrocarbon group).

Here, T ¹ is not only a hydrogen atom but also a preferable hydrocarbon group is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group). Group, hexyl group, octyl group,
Decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-
Methoxyethyl group, 3-bromopropyl group, etc.), alkenyl group having 4 to 18 carbon atoms which may be substituted (eg, 2
-Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-
Methyl-2-hexenyl group, etc.), C7-C12 optionally substituted aralkyl group (eg, 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.), an alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, cyclohexyl group, 2 -Cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or C6
To 12 optionally substituted aromatic groups (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, Butoxyphenyl group, decyloxyphenyl group,
Chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc. )can give.

When V ² represents —C ₆ H ₄ —, the benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group,
Chloromethyl group, methoxymethyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) and the like.

E ¹ and e ² may be the same as or different from each other, preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a trifluoromethyl group, a cyano group, a carbon number of 1 to 4 An alkyl group (for example, a methyl group,
Ethyl, propyl, butyl, etc.), - COOZ ³ or -COOZ ³ (Z ³ through the hydrocarbon is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group Or an aryl group, which may be substituted, and specifically represents the same contents as those described above for T ¹ .

Examples of the hydrocarbon in -COOZ ³ via the above hydrocarbon include a methylene group, an ethylene group, a propylene group and the like. More preferably, the general formula (IV)
In, V ² is -COO-, -OCO-, -CH ₂ O.
_{CO -, - CH 2 COO -} , - O -, - CONH -, -
SO ₂ NH- or -C ₆ H ₄ - represents, e ¹ and e ²
May be the same or different from each other, and are preferably a hydrogen atom, a methyl group, -COOZ ³ or -CH ₂ COOZ ³ {Z ³ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, propyl). Group, butyl group, hexyl group, etc.)). Even more preferably, e ¹
And one of e ² represents a hydrogen atom.

In the macromonomer (M) used in the present invention, the polymerizable double bond group represented by the general formula (IV) is directly bonded to one end of the polymer main chain, or any linking is carried out. It has a chemical structure bonded by a group.
As the group to be linked, carbon-carbon bond (single bond or double bond), carbon-hetero atom bond (as a hetero atom, for example, oxygen atom, sulfur atom, nitrogen atom, silicon atom, etc.), hetero atom-hetero atom It is composed of any combination of bonding atomic groups.

The specific content of the optional linking group is-[C (d
₁ ) (d ₂ )]-(d ₁ and d ₂ may be the same or different and each is a hydrogen atom, a halogen atom (chlorine atom, bromine atom, etc.), an OH group, a cyano group, an alkyl group (a methyl group, ethyl group). Group, 2-chloroethyl group, 2-hydroxyethyl group,
Propyl group, butyl group, hexyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), phenyl group, etc.),-[(C (d ₃ ) = C (d ₄ )]-(d ₃ , d
₄ represents the same content as d ₁ and d ₂ ), -C ₆ H _10- ,
_{-C 6 H 4 -, - O} -, - S -, - N (d 5) - [d ₅
Represents a hydrogen atom or a hydrocarbon group (specifically, a hydrocarbon group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-cyanoethyl group, benzyl group, methylbenzyl group, phenethyl group, phenyl group,
Tolyl group, chlorophenyl group, methoxyphenyl group, butylphenyl group, etc.)], -CO-, -C.
OO -, - OCO -, - CON (d 5) -, - SO 2 N
_{(D 5) -, - SO} 2 -, - NHCONH -, - NHC
_{OO -, - NHSO 2 -,} - CONHCOO -, - CO
NHCONH-, heterocycle (as a hetero atom, O, S,
It may be any 5- or 6-membered ring containing at least one N or the like or a condensed ring thereof: for example, a thiophene ring,
Pyridine ring, furan ring, imidazole ring, piperidine ring, morpholine ring and the like) or -Si (d ₆ ).
_{(D 7) -. (D} 6, d 7 , which may be the same or different, represent a hydrocarbon group or -Od ₈ (d ₈ represents a hydrocarbon group) as these hydrocarbon groups, mentioned in d ₅ The same as those mentioned above) can be used alone or a linking group constituted by a combination thereof.

The polymer component of the macromonomer (M) contains at least one polymer component containing a specific polar group. In the resin (B), -PO ₃ H ₂ These specific polar group, -COOH, -SO ₃ H, -
P (═O) (OH) R ¹ (R ¹ has the same meanings as described above) and cyclic acid anhydride groups are mentioned, and the specific contents of the polar group-containing polymer component are described in Resin [A ] The same thing as the polymer component illustrated in [] is mentioned.

Examples of the other copolymerizable component to be contained together with the polar group-containing polymer component include the polymer component represented by the general formula (II), and the total polymer component 100 of the macromonomer (M) can be mentioned. 30 to 99.5% by weight in parts by weight,
It is preferably 50 to 99% by weight. Further, it may contain other polymer components, and corresponds to a monomer copolymerized with the monomers corresponding to the polar group-containing polymer component and the polymer component represented by the general formula (II), respectively. Any polymerization component can be used. The content of these other polymer components is preferably 30% by weight or less, more preferably 20% by weight or less.

Examples of these other polymer components include the same compounds as those of the above-mentioned resin B, the general formulas (I) and (III) of the B block of the resin [A]. Further, the polymer component containing the specific polar group may be contained in the polymer main chain of the macromonomer (M) in any mode of random copolymerization or AB type block copolymerization.

However, when it is contained by block copolymerization, a polar group-containing polymer component is contained in the block on the side opposite to the side where the polymerizable double bond group is bonded. Further, the block containing the polar group-containing component may contain other polymer component, and specifically, it may be contained in the block [B] of the resin [B] other than the polar group-containing polymer component. It may be any of the other polymer components.

The macromonomer (M) of the present invention can be produced by a conventionally known synthesis method. For example,
In the monomer corresponding to the polymer component containing the specific polar group, the polar group is preliminarily protected as a functional group, and an organometallic compound (eg, alkyllithium, lithium diisopyramide, alkylmagnesium halide) is used. Etc.) or an ionic polymerization reaction with a hydrogen iodide / iodine system, a photopolymerization reaction using a porphyrin metal complex as a catalyst,
Alternatively, after a copolymer is synthesized by a known so-called living polymerization reaction such as a group transfer polymerization reaction, various reagents are reacted with the ends of this living polymer to introduce a polymerizable double bond group.

After that, a functional group having a protected polar group is subjected to a deprotection reaction by a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction, a photolysis reaction or the like to form a polar group. One example thereof is shown in the following reaction scheme (3).

[0108]

[Chemical formula 24]

For example, P. Lutz, P.M. Masson
et al, Polym. Bull. , 12, 79
(1984), B.I. C. Anderson, G.M. D. A
ndrews et al, Macromolecule
es, 14, 1601 (1981), K.S. Hatad
a, K. Ute et al, Polym. J. 17,
977 (1985), 18, 1037 (1986), Koichi Right Hand, Koichi Hatada, Polymer Processing, 36, 366 (198).
7), Toshinobu Higashimura, Mitsuo Sawamoto, Transactions on Polymers, 46, 18
9 (1989), M.A. Kuroki, T .; Aida,
J. Am. Chem. Soc. 109, 4737 (19
87), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 3
00 (1985), D.I. Y. Sogoh, W.A. R. He
rtler et al, Macromolecule
The living polymer can be easily synthesized according to the synthetic method described in S., 20, 1473 (1987) or the like. Further, as a method for introducing a polymerizable double bond group to the terminal of the living polymer, the macromonomer of the present invention can be easily obtained according to a conventionally known synthesis method of a macromonomer method.

Specifically, P.I. Dreyfuss an
d R. P. Quirk, Encycl. Polym.
Sci. Eng. 7 , 551 (1987), p. F.
Rempp, E. Franta, Adv. Polym.
Sci. 58, 1 (1984), V.I. Percec,
Appl. Polym. Sci. , 285, 95 (19
84), R.A. Asami, M .; Takari, Makr
amol. Chem. Suppl. , 12,163 (1
985), P. Rempp et al, Makram
ol. Chem. Suppl. , 8, 3 (1984),
Yusuke Kawakami, Kagaku Kogyo, 38, 56 (1987), Yuya Yamashita, Polymer, 31, 988 (1982), Kobayashi Shiro, Polymer, 30, 625 (1981), Toshinobu Higashimura, Journal of Japan Adhesion Society 18, 536 (1982), Koichi Ito, Polymer Processing, 35, 262 (1986), Kishiro Azuma, Takashi Tsuda, Functional Materials, 1987, No. It can be synthesized according to the methods described in the reviews such as 10, 5 and the references and patents cited therein.

The protecting group for protecting the specific polar group of the present invention and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing the conventionally known knowledge. For example, various references are given in the above-mentioned references, and further, Yoshio Iwakura, Keisuke Kurita "Reactive Polymer", Kodansha Co., Ltd. (1977), T.S. W. Greene, "Prot
active Groups in Organic
"Synthesis" John Wiley and
Sons (1981), J. Am. F. W. McOmie,
"Protective Groups in Org
anic Chemistry "Plenum Pre
The method described in detail in the review article such as ss (1973) can be appropriately selected and performed.

As another synthetic method, a photoiniferter polymerization method using a disiocarbamate compound as an initiator can be used. For example, Takayuki Otsu, polymer, 3
7, 248 (1988), Shunichi Hinomori, Ryuichi Otsu, Po
lym. Rep. Jap. 37, 3508 (1988
Year), JP-A-64-111, JP-A-64-26619
The macromonomer of the present invention can be obtained by utilizing the above-mentioned macromonomer synthesis method.

More specific methods for synthesizing the macromonomer of the present invention include US Pat. Nos. 5,550,017 and 6,389.
It is more specifically described in the specification such as No. 22. In the resin [B] of the present invention, the A block / B block ratio is 50 to 99/50 to 1 (weight ratio), preferably 60.
˜95 / 40 to 5 (weight ratio). The resin [B] of the present invention provided in the photoconductive layer may be AB type or ABA.
Any one type of type copolymer may be contained, and AB
Both type and ABA type copolymers may be included.

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

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

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

The total amount of the binder resin used in the photoconductive layer of the present invention is 1 with respect to 100 parts by weight of the inorganic photoconductor.
The amount is preferably 0 to 100 parts by weight, more preferably 15 to 50 parts by weight. The ratio of the resin [A] and the resin [B] used in the present invention is 0.05 to 0.8 / 0.95 to 0.2 in terms of a resin [A] / resin [B] weight ratio.
It is preferably 0, and more preferably 0.10.
It is 0.50 / 0.90 to 0.50.

If the total amount ratio of the binder resin is 10 parts by weight or less, the film strength of the photoconductive layer cannot be maintained. On the other hand, when the amount is 100 parts by weight or more, the electrostatic characteristics are deteriorated and the copy image is deteriorated in the actual image pickup property. In addition, the resin [A] and the resin [B] of the present invention are used in the ratio of
If the weight ratio is less than or equal to 0.05, the effect of improving the electrostatic characteristics is diminished. On the other hand, when it is 0.8 or more, the film strength of the photoconductive layer cannot be sufficiently maintained (particularly as an electrophotographic lithographic printing plate precursor).

As the inorganic photoconductive material used in the present invention, zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, lead sulfide, etc. may be used in combination. Good. As the spectral sensitizing dye used in the present invention, various dyes are used alone or in combination as necessary. For example, Harumi Miyamoto,
Hidehiko Takei, Imaging 1973 (No. 8) No. 12
Page, C.I. J. Young et al., RCA Review 1
5 , 469 (1054), Kouhei Kiyota, The Institute of Electrical Communication, J63- C (No. 2), 97 (1980), Yuji Harasaki, etc., Industrial Science Journals 66 , 78 and 188 (196).
3), Tadaaki Tani, Journal of the Photographic Society of Japan 35 , 208 (197).
2) Carbonyl dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, cythylyl dyes, etc.), phthalocyanines Examples thereof include dyes (which may contain a metal).

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

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

Further, as a polymethine dye for spectrally sensitizing the near infrared to infrared light region having a long wavelength of 700 nm or more, JP-A-4,
No. 7-840, No. 47-44180, and Japanese Patent Publication No. 51-4
1061, JP-A-49-5034, and JP-A-49-451.
No. 22, No. 57-46245, No. 56-35141.
No. 57-157254, No. 61-26044,
No. 61-27551, U.S. Pat. No. 3,619,154.
No. 4,175,956, "Research D
isclosure ", 1982, 216, 117-
Examples thereof include those described on page 118. The photoconductor of the present invention is excellent in that the performance thereof hardly changes depending on the sensitizing dye even when various sensitizing dyes are used in combination. Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers such as chemical sensitizers can be used in combination. For example,
Review Article: Imaging 1973 (No. 8) No. 1
Electron-accepting compounds (eg halogen, benzoquinone, chloranil, organic carboxylic acid anhydrides, etc.) in the review article on page 2 etc., Hiroshi Komon, et al., "Recent Developments and Commercialization of Photoconductive Materials and Photoconductors" Chapter 4 to Chapter 6: Polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, and the like, which are the reference examples of the Japanese Scientific Information Co., Ltd. Publishing (1986).

The addition amount of these various additives is not particularly limited, but usually 0.0 to 100 parts by weight of the photoconductor.
001 to 2.0 parts by weight. The photoconductive layer has a thickness of 1 to 1.
00 μm, particularly 10 to 50 μm is suitable. Further, when the photoconductive layer is used as the charge generation layer of the laminated type photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is 0.0
1 to 1 μm, particularly 0.05 to 0.5 μm is suitable.

In some cases, an insulating layer may be additionally provided for the purpose of protecting the photoreceptor and improving durability and dark decay characteristics.
At this time, the insulating layer is set to be relatively thin, and the insulating layer provided when the photoconductor is used in a specific electrophotographic process is set to be relatively thick. In the latter case, the thickness of the insulating layer is 5
˜70 μm, especially 10 to 50 μm.

As the charge transport material for the laminated type photoreceptor, there are polyvinyl carbazole, oxazole dyes, pyrazoline dyes, triphenylmethane dyes and the like. The thickness of the charge transport layer is 5 to 40 μm, particularly 10 to 30 μm.
m is preferred. As the resin used for forming the insulating layer or the charge transport layer, typical ones are polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl chloride copolymer resin, Polyacrylic resin, polyolefin resin,
A urethane resin, an epoxy resin, a melamine resin, a thermoplastic resin such as a silicone resin, and a curable resin are appropriately used.

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

Specifically, as an example of the conductive substrate or the conductive material, Yukio Sakamoto, Electrophotography, 14 (No. 1)
2-11 (1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry," Polymer Publishing (1975), M.S. F. Hoove
r, J. Macromol. Sci. Chem. A-4
(6), those described on pages 1327 to 1417 (1970) and the like are used.

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

In particular, since it is possible to form a copy image of a high-definition original faithfully, the effect of the present invention is more exerted when it is used in combination with a liquid developer. Also, by combining with a color developer, not only black and white copy images,
It can also be applied to color copy images (for example, Kuro Takizawa "Photo Industry" 33 , 34 (1975), Masayasu Anzai "Technical Research Report of the Institute of Electronics and Communication Engineers" 77 , 17 (1977).
Year)) etc.)).

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

[0131]

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

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

[0133]

[Chemical 25]

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

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

[0136]

[Chemical formula 26]

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

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

[0139]

[Chemical 27]

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

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

[0142]

[Chemical 28]

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

[0144]

[Table 1]

[0145]

[Table 2]

[0146]

[Table 3]

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

[0148]

[Table 4]

[Synthesis of Resin [B]] [Synthesis of Macromonomer] Synthesis Example 1 of Macromonomer (M) 1: (MM-1) A mixed solution of 10 g of triphenylmethyl methacrylate and 100 g of toluene was thoroughly passed under a nitrogen stream. Degassed-20
Cooled to ° C. 1,1-diphenylbutyllithium 0.
02 g was added and reacted for 10 hours. Furthermore, in this mixed solution,
A mixed solution of 90 g of ethyl methacrylate and 100 g of toluene was thoroughly degassed under a nitrogen stream, and then added.
Reacted for 0 hours. After the temperature of this mixture was set to 0 ° C., carbon dioxide gas was bubbled at a flow rate of 60 ml / min for 30 minutes to stop the polymerization reaction. The resulting reaction liquid was heated to 25 ° C. with stirring, 6 g of 2-hydroxyethyl methacrylate was added,
Furthermore, dicyclohexylcarbodiimide 10 g, 4-
A mixed solution of 0.2 g of N, N-dimethylaminopyridine and 30 g of methylene chloride was added dropwise over 30 minutes, and the mixture was kept at 3
Stir for hours.

The precipitated insoluble matter was filtered off, and then 10 ml of a 30% by weight hydrogen chloride / ethanol solution was added to this mixed solution to obtain 1
Stir for hours. Next, the solvent was distilled off from the reaction mixture under reduced pressure until the total amount was halved, followed by reprecipitation in 1 liter of petroleum ether. The polymer obtained by collecting the precipitate and drying it under reduced pressure had a Mw of 6.5 × 10 ³ and a yield of 56 g.

[0151]

[Chemical 29]

Synthesis Example 2 of Macromonomer (M): (MM-2) A mixed solution of 5 g of benzyl methacrylate, 0.01 g of (tetraphenylporphinato) aluminum methyl and 60 g of methylene chloride was heated to 30 ° C. under a nitrogen stream. . This was irradiated with light of 300 W-xenon lamp through a glass filter from a distance of 25 cm and reacted for 18 hours. Add 45 g of butyl methacrylate to this mixture.
After irradiating for 20 hours in the same manner, 8 g of 2-bromoethyl methacrylate was added to this reaction mixture, and the reaction was stopped by stirring for 3 minutes.

Next, Pd-C was added to this reaction mixture, and catalytic reduction reaction was carried out at a temperature of 25 ° C. for 1 hour. The insoluble material was filtered off and then reprecipitated in 500 ml of petroleum ether, and the precipitate was collected and dried. The obtained polymer had a yield of 33 g and Mw.
It was 7 × 10 ³ .

[0154]

[Chemical 30]

Synthesis Example 3 of Macromonomer (M): (MM-3) Methyl Methacrylate 60 g, Methyl Acrylate 20
g, benzyl-N-hydroxyethyl-N-ethyldithiocarbamate 6.3 g and tetrahydrofuran 80 g
The mixture of (1) was sealed in a container under a nitrogen stream and heated to a temperature of 60 ° C. This was irradiated with light from a high pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 10 hours to perform photopolymerization. After 10 g of acrylic acid, 10 g of methyl methacrylate and 40 g of tetrahydrofuran were added thereto, the atmosphere was replaced with nitrogen, and light was irradiated again for 10 hours.

6 g of 2-isocyanatoethyl methacrylate and 0.01 g of tetrabutoxy titanate were added dropwise to the obtained reaction mixture at a temperature of 30 ° C. over 1 hour, and the mixture was further stirred for 4 hours. The resulting reaction product was reprecipitated in 1.5 liters of hexane, collected, and dried. The polymer obtained is 68
The Mw was 8.0 × 10 ³ in g.

[0157]

[Chemical 31]

Synthesis Example 4 of Macromonomer (M): (MM-4) 66.5 g of methyl methacrylate, 28.5 g of methyl acrylate, 6.8 trimethylsilyl methacrylate
g, thioglycolic acid 2.5 g, and tetrahydrofuran 200 g were mixed at a temperature of 75 ° C. under a nitrogen stream. To this, 0.8 g of 2,2'-azobisisobutyronitrile (abbreviation AIBN) was added and reacted for 4 hours. I. B. N. 0.3 g was added and reacted for 4 hours. After cooling to a temperature of 25 ° C., 7.0 g of 2-hydroxyethyl methacrylate was added to the reaction mixture, and 10.0 g of dicyclohexylcarbodiimide (abbreviation D.C.C.), 4-
A mixed solution of 0.1 g of N, N-dimethylaminopyridine and 20 g of methylene chloride was added dropwise with stirring for 1 hour, and the reaction was further continued for 4 hours.

Next, 10 g of an 85% formic acid aqueous solution was added to the reaction product.
Was added and stirred for 2 hours, and then the precipitate was filtered off by suction filtration. The filtrate was reprecipitated in 1 liter of methanol, and the precipitate was collected by decantation. This precipitate was dissolved in 300 g of toluene, the insoluble material was filtered off, and the filtrate was n-
The precipitate was collected again by reprecipitation in 1 liter of a hexane / ethanol (3/1) ratio solution. The polymer obtained by drying under reduced pressure was 7 × 10 ³ and the yield was 58 g.

[0160]

[Chemical 32]

Synthesis Example 5 of Macromonomer (M): (MM-5) A mixed solution of 96 g of ethyl methacrylate, 4 g of 3-sulfopropyl methacrylate, 3 g of 2-mercaptoethanol, 150 g of tetrahydrofuran and 50 g of methanol was stirred under a nitrogen stream. While heating to a temperature of 65 ° C.
To this, 0.8 g of 2,2'-azobisisovaleronitrile (abbreviation A.I.V.N) was added and reacted for 4 hours. I. V. N. 0.5 g was added and reacted for 4 hours. After cooling, it was reprecipitated in 1 liter of methanol. The precipitate was collected and dried under reduced pressure to obtain 63 g of a polymer.

50 g of this polymer was added to tetrahydrofuran 1
It was dissolved in 00 g, 5.5 g of acrylic acid was added, and the temperature was raised to 25 ° C. with stirring. D. C. C. 15.9 g, 4- (N,
A mixed solution of 0.6 g of N-dimethylamino) pyridine and 20 g of methylene chloride was added dropwise over 1 hour, and the mixture was further added as it was to 3
Stir for hours. After adding 8 g of 85% formic acid aqueous solution and stirring for 1 hour, the insoluble matter was filtered off by suction filtration.

The filtrate was reprecipitated in 700 ml of a hexane / ethanol (3/1) solution, and the precipitate was collected and dried under reduced pressure to obtain a polymer of 6 × 10 ³ .

[0164]

[Chemical 33]

Synthesis Example of Resin [B] 1: [B-1] 54 g of methyl methacrylate, 26 of methyl acrylate
g, n-butyl-N, N-diethyldithiocarbamate 1.7 g and a mixed solution of 80 g of tetrahydrofuran,
The container was sealed under a nitrogen stream and heated to a temperature of 50 ° C. This was irradiated with light from a high pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 8 hours to perform photopolymerization. To this, 10 g of methyl acrylate, macromonomer (MM
-1) After adding 10 g and 30 g of tetrahydrofuran, the atmosphere was replaced with nitrogen, and light irradiation was again performed for 18 hours.

This reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected by filtration and dried under reduced pressure to obtain Mw 8.5 × 10.
75 g of ⁴ polymer was obtained.

[0167]

[Chemical 34]

Synthesis Example 2 of Resin [B]: [B-2] 75 g of methyl methacrylate, macromonomer (MM-
2) A mixed solution of 25 g, 5.4 g of an initiator [I-1] having the following structure and 105.4 g of tetrahydrofuran was sealed in a container under a nitrogen stream. Photopolymerization was carried out at a temperature of 50 ° C. for 12 hours under the same photopolymerization reaction conditions as in Synthesis Example 1.

[0169]

[Chemical 35]

20 g of the above polymer (solid content 10 g), methylmethanol 58 g, methyl acrylate 19.5
A mixed solution of g, 2.5 g of N-vinylpyrrolidone and 100 g of tetrahydrofuran was sealed in a container under a nitrogen stream. Photopolymerization was carried out at a temperature of 50 ° C. for 10 hours under the above photopolymerization reaction conditions. Next, it was reprecipitated in 1 liter of methanol, and the precipitate was collected by filtration and dried under reduced pressure to obtain 80 g of a polymer having Mw of 1.2 × 10 ⁵ .

[0171]

[Chemical 36]

Synthesis Example 3 of Resin [B]: [B-3] 70 g of methyl methacrylate, macromonomer (MM-
3) A mixed solution of 30 g, 4.3 g of an initiator [I-2] having the following structure and 104.3 g of tetrahydrofuran was added to [B-
Photopolymerization was carried out under the same conditions as in the synthesis example 2).

[0173]

[Chemical 37]

10 g of the above polymer (solid content 5 g), 60.3 g of methylmethanol, 29.7 of methyl acrylate.
A mixed solution of 100 g of tetrahydrofuran and 100 g of tetrahydrofuran was further photopolymerized in the same manner as in the synthesis example of [B-2] above.
Next, it was reprecipitated in 1 liter of methanol, and the precipitate was collected by filtration and dried under reduced pressure to obtain 76 g of a polymer having Mw of 1 × 10 ⁵ .

[0175]

[Chemical 38]

Synthesis Example 4 of Resin [B]: [B-4] 67 g of methyl methacrylate, 3 of butyl methacrylate
A mixed solution of 3 g, benzyl-N, N-dimethyldithiocarbamate 0.8 g and tetrahydrofuran 100 g was photopolymerized under the same conditions as in the synthesis example of [B-1]. After mixing a mixed solution of 24 g of ethyl methacrylate, 6 g of macromonomer (MM-5) and 30 g of tetrahydrofuran with this polymer solution, photopolymerization was further performed under the same conditions as above.

A mixed solution of 42 g of methyl methacrylate, 18 g of ethyl acrylate and 60 g of tetrahydrofuran was mixed with this polymer solution, and then photopolymerization was conducted under the same conditions as above. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to obtain Mw 1.1 × 1.
This gave 152 g of a polymer of 0 ⁵ .

[0178]

[Chemical Formula 39]

Synthesis Examples 5 to 11 of Resin [B]: [B-5]
-[B-11] Each polymer of the following Table-C was synthesize | combined by the method similar to the synthesis example of [B-1]. The Mw of the obtained polymer was 8 × 10 ⁴ to
The range was 1 × 10 ⁵ .

[0180]

[Table 5]

[0181]

[Table 6]

Synthesis Examples 12 to 36 of Resin [B]: [B-1
2] to [B-36] In the same manner as in the synthesis example of [B-3], the following Table-D and Table-D are shown.
The resin [B] of E was synthesized. Mw of each resin [B] is 9x
It was in the range of 10 ^{4 to} 2 × 10 ⁵ .

[0183]

[Table 7]

[0184]

[Table 8]

[0185]

[Table 9]

[0186]

[Table 10]

[0187]

[Table 11]

[0188]

[Table 12]

[0189]

[Table 13]

[0190]

[Table 14]

Example 1 and Comparative Examples 1 and 2 6 g of resin [A-7] (as solid content), resin [B-
2] 34 g (as solid content), photoconductive zinc oxide 20
A mixture of 0 g, 0.018 g of the dye [I] having the following structure, 0.15 g of phthalic anhydride and 300 g of toluene was placed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to rotate at 7 × 10 ³ rp.
m to disperse for 8 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 10 seconds, Then, by leaving it in the dark at 20 ° C. and 65% RH for 24 hours, an electrophotographic photosensitive material (hereinafter sometimes referred to as a sensitive material) was produced.

[0192]

[Chemical 40]

Comparative Example 1 Example 1 was repeated except that 34 g of resin [R-1] having the following structure was used in place of 34 g of resin [B-2] in Example 1.
An electrophotographic photosensitive material was produced in the same manner as in.

[0194]

[Chemical 41]

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

[0196]

[Chemical 42]

Regarding these photosensitive materials, the smoothness of the photoconductive layer, abrasion resistance, printability and environmental conditions (20 ° C., 6
5% RH), (30 ° C, 80% RH) and (15 ° C, 3
The imaging property when 0% RH) was examined. The above results are shown in Table-F.

[0198]

[Table 15]

Embodiments of the evaluation items shown in Table-F are as follows. Note 1) Smoothness of surface layer: The photosensitive material was measured for its smoothness (sec / cc) using a Beck's smoothness tester (manufactured by Kumagai Riko Co., Ltd.) under an air volume of 1 cc. Note 2) Imaging property: After the photosensitive material was left for one day under the following environmental conditions, the photosensitive material was charged at −6 kV, and a 2.8 mW output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm) was used as a light source. And a pitch of 25 μm on the surface of the photosensitive material under an irradiation amount of 64 erg / cm ^2.
After speed exposure at a scanning speed of 300 m / sec, ELP-T (manufactured by Fuji Photo Film Co., Ltd.) was used as a liquid developer and developed, and a rinse liquid of isoparaffin Isopar G (manufactured by Esso Kagaku) was used. The copied image (fog, image quality) obtained by fixing after washing was visually evaluated.

The environmental conditions at the time of imaging are 20 ° C. and 65% RH.
(I), 30 ° C 80% RH (II) and 15 ° C 30% R
Performed with H (III). Note 3) Scratch resistance The same photosensitive material is placed on the surface of the photosensitive material so that it overlaps with the back surface, a weight of 75 g is placed on it, and the upper photosensitive layer is pulled slowly in the horizontal direction. A photosensitive material having a photoconductive layer was used to perform plate making (that is, formation of a copy image) in the same manner as in Note 2), and the image of the portion costly with the weight and the image of the non-image portion were visually evaluated. . The environmental conditions at the time of imaging were (20 ° C. 65% RH) (I).

Note 4) Printability In the same manner as in Note 3), the surface of the photoconductor was subjected to a scoring operation, and then plate making was carried out under the same conditions as in Note 2) above to form a toner image. The ELP-EX was passed through an etching processor twice for desensitization, and this was applied as an offset master to an offset printing machine (Oliver 52 type manufactured by Sakurai Seisakusho Co., Ltd.) to remove scumming in the non-image area of the printed matter. Indicates the number of prints that can be printed without causing a problem in the image quality of the image area (the larger the number of prints, the better the printability).

As shown in Table-F, the light-sensitive material of the present invention is
Even if the environmental conditions changed, the electrostatic characteristics were good, and the actual copied image had no background fog and the copied image quality was clear. On the other hand, in Comparative Examples 1 and 2, when the environmental conditions changed, unevenness at intermediate density occurred in the continuous tone part of the copy document which is a high-definition copy image. Further, in a kosuri test in which a load was applied to the surface of the photoconductive layer, the photosensitive material of the present invention showed good images regardless of the presence or absence of kosuri. However, the light-sensitive materials of Comparative Examples 1 and 2 are those of the copied image which cannot be put to practical use because the image portion of the worn portion is greatly scratched and the non-image portion is significantly smeared by the kosuri test. It is had.

Further, when these photosensitive materials after plate-making were subjected to desensitization treatment and printed as an offset printing plate with a printing machine, the printing plate of the present invention showed clear images with clear images and no background stains. I got 10,000 copies. On the other hand, in Comparative Examples 1 and 2, the blurring of the image portion appears in the image of the printed matter as it is, and the stain of the non-image portion is not removed even by the desensitizing treatment, and as the background stain of the non-image portion of the printed matter, It occurred from the printing.

From the above, an electrophotographic photosensitive member having excellent image pick-up resistance (especially high-definition image) can be obtained only when the resin of the present invention is used, and particularly semiconductor laser light scanning It was clarified that it was superior to the exposure type photoreceptor system and that it exhibited extremely good printing plate performance even when used as an electrophotographic lithographic printing original plate. Example 2 and Example 3 Resin [A-22] 5 g (as solid content) (Example 2)
Alternatively, resin [A-19] 5 g (as solid content) (Example 3), resin [B-3] 35 g (as solid content), photoconductive zinc oxide 200 g, dye [II] 0.0 having the following structure:
A mixture of 20 g, N-hydroxymaleinimide 0.20 g and toluene 300 g was treated in the same manner as in Example 1 to prepare an electrophotographic photosensitive material.

[0205]

[Chemical 43]

The film properties (surface smoothness), abrasion resistance, printability and environmental conditions of each light-sensitive material were set to 20 ° C., 65% RH,
The imaging properties at 30 ° C., 80% RH and 15 ° C., 30% RH were examined in the same manner as in Example 1. Table of the results
Shown in G.

[0207]

[Table 16]

When the respective performances of the respective light-sensitive materials were examined in the same manner as in Example 1, all the performances were good. In particular, Example 2 using the resin [A] containing a specific substituent,
It showed a better imaging property. Examples 4 to 6 Instead of the dye [I] used in Example 1, the following table-
An electrophotographic photosensitive material was prepared under the same conditions as in Example 1 except that the dye of H was used instead.

[0209]

[Table 17]

In each of the light-sensitive materials of the present invention, all copied images have high temperature and high humidity (30 ° C., 80% RH) and low temperature and low humidity (1
Even under the severe conditions of 5 ° C. and 30% RH), a clear image with no background fog was provided. Also, the anti-corrosion property
It was extremely good, and when printed as an offset printing plate, a good printed matter could be obtained even after printing 10,000 sheets. Examples 7 to 26 In Example 1, 6 g of resin [A-7] and resin [B-
2] Instead of 34 g, 6 g of each resin [A] in Table I below.
And each photosensitive material was prepared in the same manner as in Example 1 except that 34 g of each resin [B] was used.

[0211]

[Table 18]

The image pickup property of each light-sensitive material was measured in the same manner as in Example 1. The actual image pick-up of each of the light-sensitive materials was excellent in reproducibility of fine lines and characters, no generation of halftone unevenness, and clear copy images with no background fog were obtained. The abrasion resistance was also extremely good. Further, when printing was performed in the same manner as in Example 2 using the offset master original plate, at least 10,000 or more sheets could be printed favorably.

From the above, each of the light-sensitive materials of the present invention was good in all aspects of the smoothness, film strength, electrostatic properties and printability of the photoconductive layer. Example 27 and Comparative Example 3 5 g of resin [A-18] and 35 g of resin [B-17], 200 g of photoconductive zinc oxide, 0.02 g of uranine, 0.04 g of rose bengal, 0.03 g of bromphenol blue.
g, 0.40 g of phthalic anhydride, and 300 g of toluene were dispersed in a homogenizer at a rotation speed of 8 × 10 ³ rpm for 6 minutes to prepare a photosensitive layer-forming material, which was dried and attached to a conductive-treated paper. Of 25 g / m ² was applied with a wire bar and dried at 110 ° C. for 20 seconds. Then, each electrophotographic photosensitive material was produced by leaving it in the dark at 20 ° C. and 65% RH for 24 hours. Comparative Example 3 An electrophotographic photosensitive material was produced in the same manner as in Example 27, except that the resin [R-2] was used instead of the resin [B-17] in Example 27.

The smoothness / imaging property, the abrasion resistance and the printability of each light-sensitive material were measured in the same manner as in Example 1. The results are shown in Table-J.

[0215]

[Table 19]

In Table-J, the image pickup property and the abrasion resistance were the same as in Example 1 except for the following operations. Note 5) Imaging property: Obtained by leaving the light-sensitive material to stand for one day under the following environmental conditions and then making a plate using EPL-T as a toner with a fully automatic plate-making machine EPL-404V (manufactured by Fuji Photo Film Co., Ltd.). The copied image (fog, image quality) was visually evaluated. Environmental conditions during imaging are 20 ° C and 65% RH
(I), 30 ° C 80% RH (II) and 15 ° C 30% R
Performed with H (III). However, the manuscript for copying (that is,
The original copy) was prepared by cutting out and pasting other originals. Note 6) Corrosion resistance In the Kossure resistance test of Note 3), the same method as Note 3) was used except that the image capturing method was changed to Note 5).

In both the light-sensitive material of the present invention and Comparative Example 3, the smoothness of the photoconductive layer was good. As a result of examining the actual image pick-up property, in Comparative Example 3, the frame (that is, the sticking mark) of the cut-out and stuck part was recognized as the background image of the non-image part in addition to the original as the copied image. Furthermore, when the environmental conditions at the time of image pickup are high temperature and high humidity (II) and low temperature and low humidity (III), unevenness occurs in the halftone region of the continuous tone part of the copy image, and minute unevenness of white spots in the solid image part occurs. Etc. were seen. However, in all cases of the present invention, clear images having no background stain were obtained.

The abrasion resistance of the present invention was extremely good, however, in Comparative Example 3, the abrasion was observed in the image portion and the background stain was remarkable in the non-image portion. Admitted. Further, when these were subjected to a desensitizing treatment as offset printing original plates and printed, all of the present invention produced 10,000 printed matters with clear image quality without background stains. However, in Comparative Example 3, the above-mentioned sticking mark is not removed even by the desensitizing treatment, and further, the background stain of the non-image portion of the worn portion and the blurring of the image portion are generated from the printed matter. Oops.

From the above, the light-sensitive material of the present invention was good in all aspects of image pick-up property, abrasion resistance and printability. Examples 28 to 51 In Example 27, instead of 5 g of the resin [A-18] and 35 g of the resin [B-17], 6 g of each resin [A] and 34 g of the resin [B] shown in Table K below were used. Photosensitive materials were produced in the same manner as in Example 27 except that the above was used.

[0220]

[Table 20]

Each of the light-sensitive materials of the present invention showed good performance in image pick-up, abrasion resistance and printability as in Example 27.

[0222]

According to the present invention, it is possible to obtain an electrophotographic photosensitive member having a clear and high-quality image and further having excellent image reproducibility, moisture resistance and surface strength. In particular, it is effective for a scanning exposure method using semiconductor laser light.
By using the repeating unit containing the specific methacrylate component represented by the formula (Ia) or (Ib) in the present invention, the image reproducibility is further improved.

Claims (3)

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