JPH0619147A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain the electrophotographic sensitive body improved in electrostatic characteristics and imaging characteristics, especially, superior in reproduction performance of an image high in precision using a liquid developing agent and imaging performance using a scanning exposure system using low-output laser beams. CONSTITUTION:The binder resin of the electrophotographic sensitive body contains at least one kind of a resin [A] of an AB block copolymer low in molecular weight comprising a block A having polar repeating units and a block B having repeating units each represented by formula I; and at least one kind of star type copolymer [B] high in molecular weight having at least 3 polymer chains each having repeating units each represented by formula II and a polar group on one of the terminals of each polymer chain. In formulae I and II, R<11> is a hydrocarbon group; each of a<1> and a<2> is H, halogen, cyano, or a hydrocarbon group: and R<3> is a hydrocarbon group.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Electrophotographic photoreceptors have various structures in order to obtain predetermined characteristics or depending on the type of electrophotographic process applied. Typical 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. Especially in the electrostatic characteristics, the charge retention ratio in the dark (D.R.
R. ) And light sensitivity are greatly affected.

On the other hand, various techniques for improving smoothness and electrostatic characteristics have been studied by using a resin having a relatively low molecular weight (about 10 ³ to 10 ⁴ ) containing an acidic group as a binder resin. ing. For example, JP-A 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.

Further, in order to make the mechanical strength of the photoconductive layer sufficient by using only these low molecular weight resins,
Various techniques of using other resins of medium to high molecular weight in combination have been studied. For example, JP-A-2-68561 discloses a thermosetting resin which forms a crosslinked structure between polymers, and JP-A-2-6856.
No. 562, a resin partially having a cross-linked structure, disclosed in JP-A-2-
No. 69759 describes a resin having an acidic group bonded to the end of the main chain of a graft copolymer. Further, by using a specific medium to high molecular weight resin, a technique for maintaining relatively stable performance even when the environment is remarkably changed has been studied. For example, JP-A-3-29954 and 3-7.
7954, 3-92861 and 3-53257.
JP-A No. 1994-237 describes a resin that binds an acidic group to the end of the graft portion of the graft copolymer or a resin that contains an acidic group in the graft portion of the graft copolymer. Further, according to JP-A-3-206464 and 4-25849,
By using a graft type copolymer having an AB block type copolymer consisting of an acidic group-containing A block and an acidic group-free B block in the graft portion, environmental changes and semiconductor laser light can be used. It was revealed that the comparatively high performance was maintained even when the scanning exposure method was used.

[0007]

However, even if various low molecular weight resins containing these acidic groups, and further various medium to high molecular weight resins are used in combination with these resins, the environment is high and high temperature. It has been found that it is still insufficient to maintain stable performance when the humidity significantly changes from low temperature to low humidity. The scanning exposure method that uses a semiconductor laser beam has a longer exposure time than the conventional simultaneous full-exposure method that uses visible light, and also has a limited exposure intensity, so electrostatic characteristics, especially dark charge retention characteristics, are used. In terms of photosensitivity, higher performance is required.

Particularly, in the electrophotographic lithographic printing plate precursor, when a scanning exposure method using a semiconductor laser beam is adopted, when actually tested with a conventional photoconductor, the above electrostatic characteristics are sufficiently obtained. This is not satisfactory, and especially the difference between E _1/2 and E _1/10 is large, the gradation of the copied image becomes soft, and it becomes difficult to reduce the residual potential after exposure, causing fog in the copied image. Became noticeable, and again
Even when printing as an offset master, a problem such as a print original sticking mark on the printed matter appeared.

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

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

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

[0012]

The above object is to provide an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye and a binder resin, wherein the binder resin is ] And at least one of the following resins [B] are respectively contained in the electrophotographic photosensitive member.

Resin [A] has a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , and -P
O ₃ H ₂ group, -COOH group, -SO ₃ H group, a phenolic OH group, -P (= O) (OH ) R 1 {R 1 is a hydrocarbon group or -OR ² (R ² is a hydrocarbon group A group consisting of at least one polymer group containing at least one polar group selected from the group consisting of (1) and a cyclic acid anhydride-containing group, and a polymer component represented by the following general formula (I) AB comprising at least a B block containing
Block copolymer.

[0014]

[Chemical 5]

[In the formula (I), R ¹¹ represents a hydrocarbon group. Resin [B] A polymer chain having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ and containing at least 30% by weight of a repeating unit represented by the following general formula (II) as a polymer component, at least three bound star copolymer comprising in the organic molecule and a main chain terminal of the opposite side attached to the organic molecule of the respective polymer chains, -PO ₃ H ₂ group, -COOH group, -SO ₃
A resin formed by bonding at least one group selected from an H group, a -P (= O) (OH) R ¹ [R ¹ represents the same as the above] group, and a cyclic acid anhydride-containing group.

[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. Preferably, a ¹ is a hydrogen atom,
This is the case where a ² is a methyl group. ]

That is, the binder resin of the present invention comprises an A block containing the above-mentioned specific polar group-containing component and the above general formula (I).
A low molecular weight AB type block copolymer (resin [A]) with a B block containing a polymer component represented by the following formula, and a polymer chain containing at least the polymer component represented by the general formula (II) above. And a high molecular weight star-type copolymer (resin [B]) having at least three polymer chains each having one of the above-mentioned specific polar groups bonded to the organic molecule.

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

As a result of repeated studies, a polymer chain having a polar group according to the present invention bonded to one end as a medium to high molecular weight resin to be used in combination with a low molecular weight resin [A] containing a polar group. It has been found that the above problems can be effectively solved by using a star-type copolymer having at least 3 in the organic molecule. This is due to the synergistic effect of the binder resins [A] and [B] of the present invention, in which the photoconductor particles are sufficiently dispersed and not condensed, and the spectral sensitizing dye is added to the surface of the photoconductor particles. It is presumed that this is due to the fact that the binder resin is sufficiently adsorbed on the photoconductor and that the binder resin sufficiently adsorbs the extra active sites on the surface of the photoconductor to compensate the trap.

That is, the low molecular weight resin [A] containing a specific polar group in a block is sufficiently adsorbed to the photoconductor particles to uniformly disperse the particles, and the polymer chain is very short. Has an important effect of suppressing aggregation and preventing adsorption of the spectral sensitizing dye. In addition, by using a star-type copolymer containing a polymer chain in which a specific polar group is bonded to one end of the present invention, electrostatic properties (especially photosensitivity) and image pickup property (especially continuous tone images) Reproducibility) was improved and the mechanical strength of the photoconductive layer was sufficiently retained.

Although the details are not clear, the effect of entanglement between polymer chains due to the star-shaped regulation of the polymer component block of this resin is improved, and polar groups are further added to the ends of the polymer chains. It is believed that it is due to the proper interaction with the photoconductor because it is bonded. Further, in the present invention, as the resin [B], among the A block containing at least the repeating unit represented by the general formula (II) as a polymer component, the polymer chain that binds to the organic molecule, and the specific polar group It is preferable that the resin is composed of an AB type block composed of a B block containing at least one polymer component having at least one polar group selected from B '].). This is because the polar group at one end of the polymer chain of this resin [B '] and the portion of the B block adjacent thereto interact weaker than the photoconductor particles with the resin [A], and the spectral sensitization is performed. It is considered that this is due to the formation of an environment in which the dye can be sufficiently adsorbed with the photoconductor particles, the entanglement effect between the polymer chains in the A block portion, and the like.

As a result, the electrostatic characteristics are improved as compared with the known medium to high molecular weight resins used in combination.

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

That is, the photoconductor of the present invention, on which a copied image is formed through an electrophotographic process, is desensitized by chemically treating the non-image area with a conventionally known desensitizing treatment liquid to prepare a printing original plate. Shows excellent performance as an original plate for printing when it is printed by offset printing. When the photosensitizer of the present invention was desensitized, the non-image area was sufficiently hydrophilized and the water retention property was improved, resulting in a dramatic increase in the number of printed sheets. This is because the zinc oxide particles are uniformly dispersed and the presence state of the binder resin present on the surface of the zinc oxide particles is appropriate and the desensitizing reaction with the desensitizing treatment liquid is not alienated and quickly. It is considered that this is due to effective progress.

Further, in the present invention, the low molecular weight resin [A] is represented by the following general formula (Ia) and general formula (Ib).
Containing a benzene ring or a naphthalene ring having a specific substituent at the 2-position, and / or a 2-position and a 6-position, and a methacrylate component having a specific substituent and an acidic group component. It is preferable that the resin [A] (hereinafter, this low molecular weight substance is particularly referred to as resin [AA]).

[0027]

[Chemical 7]

[0028]

[Chemical 8]

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

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

The binder resin of the present invention will be described in detail below. First, the resin [A] of the present invention will be described. The 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. Fluctuations in dark decay retention rate and light sensitivity at
The effect of the present invention that a stable copy image is obtained is diminished.

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

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

Next, the polymerization component containing a specific polar group 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
Group, a phenolic OH group, a -P (= O) (OH) R ¹ group and a cyclic acid anhydride-containing group, and preferably -SO.
₃ H group, -COOH group, -P (= O) (OH) R ¹ group and phenolic OH group are mentioned.

Here, -P (= O) (OH) R ¹ represents a group represented by the following chemical formula 9, 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, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group, etc.) or an aryl group which may be substituted (eg, phenyl group, tolyl group, ethylphenyl) Group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group,
Acetylphenyl group, butoxyphenyl group, etc.) and R ² has the same content as R ¹ .

[0037]

[Chemical 9]

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

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

Examples of aromatic dicarboxylic acid anhydrides include phthalic anhydride ring, naphthalene-dicarboxylic acid anhydride ring, pyridine-dicarboxylic acid anhydride ring, thiophene-dicarboxylic acid anhydride ring, and the like. These rings are
For example, chlorine atom, halogen atom such as bromine atom, 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 copolymerization component is exemplified below. Here, b ¹ is -H, -CH _3, -Cl, -B
r, -CN, -CH ₂ COOCH ₃ or -CH ₂ COO
Indicates H, b ² represents -H or -CH _3, f is 2 to 1
8 is an integer, g is an integer of 1 to 12, and h is 1 to
Indicates an integer of 4.

[0044]

[Chemical 10]

[0045]

[Chemical 11]

[0046]

[Chemical 12]

[0047]

[Chemical 13]

[0048]

[Chemical 14]

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

A component 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 polymerization 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),
The methacrylate component of the formula (I) is preferably 30 to 100% by weight, more preferably 50 to 100% by weight in the B block component.
100% by weight is contained.

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

[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, at least one repeating unit selected from the following general formulas (Ia) and (Ib) in the B block component is 30% by weight or more, particularly 50 or more, in the B block.
It is preferable that the content is ˜100 wt%.

In formula (Ia), preferred A ¹ and A
As ² are each a hydrogen atom independently of one another, a halogen atom (e.g., chlorine atom and bromine atom) outside and a cyano group, 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 A benzyl group) and an aryl group (for example, a phenyl group, a tolyl group, a xylyl group, a bromophenyl group, a methoxyphenyl group, a chlorophenyl group, a dichlorophenyl group), and -COR ⁴ and -COOR ⁴ (preferred R ⁴ has the above carbon number. 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, 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 15]

[0059]

[Chemical 16]

[0060]

[Chemical 17]

[0061]

[Chemical 18]

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).

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

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

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

[0068]

[Chemical 19]

[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. d ¹ And d
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 copolymerization component constituting the repeating unit other than these, which may be further contained, for example, methacrylic acid esters, acrylic acid esters, crotonic acid esters containing substituents other than those explained in the general formula (I). In addition, α-olefins, vinyl carboxylates or allyl esters (for example, as carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, Itaconic acid esters (eg, dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrenes (eg, styrene, vinyltoluene, chlorostyrene, hydroxystyrene, etc.)
N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinylsulfone-containing compound, vinylketone-containing compound, heterocyclic vinyls (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 20]

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 block A is equivalent to synthesizing an azobis compound (that is, a high molecular weight azobis initiator) containing any part of the block B and using this as an initiator to form the other block. 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 block A-containing polymer initiator is preferable. For example, the reaction can be carried out according to the reaction scheme (2) shown below.

[0083]

[Chemical 21]

Next, the resin [B] of the present invention will be described. The resin [B] has a polymer chain containing at least 30% by weight of the polymer component represented by the general formula (II),
It is a star-type copolymer having at least three bonds in an organic molecule, and at the end of the main chain on the opposite side of each polymer chain bonded to the organic molecule, the specific polymer contained in the resin [A] is added. It is a star-type copolymer formed by bonding at least one polar group selected from the same groups as the polar groups.

More preferably, the polymer chain constituting the star of the resin [B] is represented by the A block containing 30% by weight or more of the polymer component represented by the general formula (II) and the resin [B]. An AB type block polymer chain composed of a B block containing at least a polymer component containing at least one polar group selected from the specific polar groups It is composed of a polymer chain having the above-mentioned specific polar group bonded to the terminal (resin [B ']).

That is, the polymer is schematically shown below.
It becomes like 2.

[0087]

[Chemical formula 22]

[Where X represents an organic molecule, (A) represents an A block, (B) represents a B block, and (A)-
(B) represents a polymer chain. -W represents a specific polar group. Further, the polymer chain constituting the star of the resin [B] has an upper limit of 15 in the organic molecule at most,
Usually, it is about 10. The weight average molecular weight of the resin [B] is 2 × 10 ⁴ to 1 × 10 ⁶ , preferably 3 × 10 ^{4 to} 5 ×.
It is 10 ⁵ . When the molecular weight of the resin [B] is less than 2 × 10 ⁴ , the film forming ability is lowered and sufficient film strength cannot be maintained, and when the molecular weight is more than 1 × 10 ⁶ , the effect of the resin [B] of the present invention is obtained. The amount is reduced, and the electronic characteristics are the same as those of conventionally known resins.

The glass transition point of the resin [B] is −10 ° C.
The temperature is preferably in the range of -100 to 100 ° C, more preferably 0 to 90 ° C. Each component constituting the polymer chain of the star type copolymer (resin [B]) of the present invention has the following characteristics.

The polymer component represented by the repeating unit represented by the general formula (II) contained in at least the polymer chain is preferably 30 to 100% by weight, more preferably 5% by weight.
It is contained in an amount of 0 to 100% by weight. Also, in the A block of the polymer chain of the resin [B ′], the amount of the polymer component present is preferably 30 to 1 in all polymer components of the A block.
It is preferably 50 to 100% by weight, more preferably 00 to 100% by weight.

Further, the A block in the resin [B '] of the present invention is characterized by not containing the specific polar group-containing component contained in the B block.

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

Further, as a polymer component which can be contained together with the polymer component represented by the formula (III), a monomer corresponding to another repeating unit copolymerizable with the polymer component represented by the formula (III), For example, acrylonitrile, methacrylonitrile,
Heterocyclic vinyls (eg vinyl pyridine, vinyl imidazole, vinyl pyrrolidone, vinyl thiophene, vinyl pyrazole, vinyl dioxane, vinyl oxazine, etc.)
Etc. These other monomers are used within a range not exceeding 20 parts by weight based on 100 parts by weight of all polymer components in the polymer chain.

The content of the polar group bonded to the polymer chain end in the resin [B] of the present invention is 0.
It is 01 to 15% by weight, preferably 0.05 to 8% by weight. When the polar group content is less than 0.01% by weight, the initial potential is low and a sufficient image density cannot be obtained.
On the other hand, when the polar group content is more than 15% by weight, the dispersibility of the photoconductor particles is lowered, the film smoothness at high temperature and high humidity and the electrophotographic characteristics are lowered, and when used as an offset master. It is not preferable because the amount of soiling increases.

The resin [B] of the present invention comprises at least one polar group selected from the above-mentioned specific polar groups bonded to the end of the main chain of each polymer chain. The specific polar group may be directly bonded to the main chain of the polymer chain, or may be bonded via an arbitrary linking group. Specific examples of the specific polar group include polar groups having the same contents as those described in the resin [A].

The group to be linked is, for example, a carbon-carbon bond.
Compound (single bond or double bond), carbon-heteroatom bond
(As a hetero atom, for example, oxygen atom, sulfur atom
Child, nitrogen atom, silicon atom, etc.), hetero atom-hetero atom
Composed of any combination of atomic groups of child bonds
It That is, specifically, a mere bond or -C (Z^Four)
(Z^Four)-[Z^FourCan be the same or different,
Child, halogen atom (eg, fluorine atom, chlorine atom, odor)
Elementary atom, etc.), cyano group, hydroxyl group, alkyl group
(Eg, methyl, ethyl, propyl, etc.)
],-(CH = CH)-, -C₆H_Ten-, -C₆H_Four
-, -O-, -S-, -CO-, -N (Z^Five)-, -C
OO-, -C (= S)-, -Si (Z^Five)₂-, -SO
₂-, -CON (Z ^Five)-,-SO₂N (Z^Five)-,-
NHCOO-, -NHCONH-, -C (Z^Five)
(Z^Five)-[Z^FiveAre each a hydrogen atom,
R in (I)¹¹Hydrocarbon groups, etc. that have the same contents as
A single linking group selected from atomic groups such as
It represents a linking group composed of any combination.

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

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

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

Further, a polymer component other than the above polar group-containing polymer component may be contained in the B block, and such polymer component is preferably the above-mentioned general formula (I),
Examples thereof include polymer components corresponding to the repeating units of (II) and (III), and the same as those described as other components. The content of the specific polar group-containing component in the resin [B '] is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total polymerization components of the resin [B']. It is contained in the ratio of.

When the content of the polar group in the binder resin [B '] is less than 0.05% by weight, the initial potential is low and a sufficient image density cannot be obtained, and the content of the polar group is 15% by weight. If the amount is larger than the above range, the dispersibility is lowered, the high temperature and high humidity of the film smoothness and the electrophotographic characteristics are lowered, and further, the background stain is increased when it is used as an offset master, which is not preferable.

In the resin [B ′] of the present invention, the kind of the specific polar group contained in the B block of the polymer chain composed of the AB block and the kind of polar group bonded to the end of the polymer chain are It may be the same or different. In the resin [B ′] of the present invention, the proportion of the polar group contained as a copolymerization component and the polar group bonded to one end of the polymer main chain constitutes the photoconductive layer of the present invention. Types of other binder resins, spectral sensitizing dyes, chemical sensitizers or other additives
It depends on the amount, and it is preferable to adjust the ratio arbitrarily. The important thing is that the total amount of both polar groups is 0.05
It is to be used within the range of 15% by weight.

What is important in the resin [B ′] of the present invention is that the ratio of the specific polar group-containing substitution component present in the resin [B ′] in 100 parts by weight is 0.05% as described above. It is within the range of 15 to 15% by weight, and in the resin [B ′], when it is present in both the polymer chain component of the resin [B ′] and one end of the main chain, the above-mentioned abundance ratio is It is arbitrarily divided within the range.

Preferably, the abundance ratio in the polymer chain component is 0.1 to 1.0, where 1.0 is that in the terminal component.
Is the ratio of

On the other hand, in resin [B '], A block and B block
The weight ratio of all the polymer components of the block is such that the proportion of the A block present in 100 parts by weight of the total polymer is preferably 50 to 9
It is 5% by weight, more preferably 60 to 90% by weight.
Further, in the block polymer chain, it is preferable that the block A has a larger weight average molecular weight than the block B.

On the other hand, the organic molecule according to the present invention formed by binding at least three polymer chains is not particularly limited as long as the molecular weight of the molecule is 1,000 or less. Examples include trivalent hydrocarbon residues such as Chemical formula 23.

[0107]

[Chemical formula 23]

[0108] (wherein, in () .r ¹ ~r ⁴ which represents a repeating unit represents a hydrogen atom or a hydrocarbon group. Provided that at least one of r ¹ and r ² or r ³ and r ⁴ are high These organic residues are constituted alone or in any combination thereof, and in the case of a combination, —O—, —S—, —N (r ⁷ ) —, —CO—,
-CS -, - COO -, - CON (r 7) -, - SO 2
_{-, - SO 2 N (r} 7) - ( wherein each represent r ⁷ hydrogen atom or a hydrocarbon group), - NHCOO -, - NH
A heterocyclic group containing a hetero atom such as CONH-, oxygen atom, sulfur atom, nitrogen atom (eg, thiophene ring, pyridine ring, pyran ring, imidazole ring, benzimidazole ring, furan ring, piperidine ring, pyrazine) Ring, pyrrole ring, piperazine ring, etc.) and the like.

Examples of other organic molecules which bond the polymer chains include those composed of a combination of the following chemical formula 24 and the above-mentioned bonding unit. However, specific examples of the organic molecule according to the present invention are not limited to these.

[0110]

[Chemical formula 24]

The star copolymer [B] 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. Halides, etc.) or ionic polymerization reaction with hydrogen iodide / iodine system, photopolymerization reaction using porphyrin metal complex as catalyst, group transfer polymerization reaction, or other known so-called living polymerization reaction to polymerize the AB block copolymer. After that, during the termination reaction, a specific polar group is directly introduced, or a functional group capable of binding the polar group is introduced, and then the polar group is chemically bonded. Thereafter, a deprotection reaction is carried out by a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction, a photolysis reaction or the like of the functional group which protects the polar group in the polymer component,
The method of forming a polar group is mentioned.

These are, for example, P.M. Lutz, P.M. M
asson et al, Polym. Bull. 1
2 . 79 (1984), B.I. C. Anderson,
G. D. Andrews et al, Macromol
ecules, 14 , 1601 (1981), K.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 is prepared by using a monomer in which a polar group is not protected and using a compound containing a dithiocarbament 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, it can be synthesized according to the literature described in the method of synthesizing resin [A].

The protection of the specific polar group of the present invention with a protective group and the elimination of the protective group (deprotection reaction) are as follows:
This can be easily performed by utilizing the conventionally known knowledge.
For example, various descriptions are given in the above cited document, and further,
The method described in detail in the review article described in the method of synthesizing resin [A] can be appropriately selected and performed.

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

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

Specifically, Ryuji Shibata, Jiro Ishiwata, "Polymer," Vol. 17, 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 resin [A] and the resin [B] of the present invention are used in an amount of 0.05 to 0.05 by weight ratio of resin [A] / resin [B].
It is preferably 0.6 / 0.95 to 0.40, more preferably 0.10 to 0.50 / 0.90 to 0.50.
Is.

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

When the weight ratio of the resin [A] to the resin [A] and the resin [B] of the present invention is 0.05 or less, the effect of improving the electrostatic characteristics is diminished. On the other hand, 0.6
If the above is the case, the film strength of the photoconductive layer cannot be sufficiently maintained (particularly as an electrophotographic lithographic printing plate precursor).

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

The spectral sensitizing dye used in the present invention includes
If necessary, various dyes are used alone or in combination. For example, Harumi Miyamoto, Hidehiko Takei, Imaging 1973 (N
o. 8) Page 12, C.I. J. Young et al., RCA R
view 15 , 469 (1054), Kouhei Kiyota,
IEICE Transactions J63 - C (No. 2 ), 97
(1980), Yuji Harasaki et al., Industrial Science Magazines 66 78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35 ,
Carbon dioxide dyes, diphenylmethane dyes, triphenylmethane dyes, such as 208 (1972)
Examples thereof include xanthene dyes, phthalein dyes, polymethine dyes (eg, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain a metal), and the like.

More specifically, as those mainly containing carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes, Japanese Patent Publication No. 51-45 is available.
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 a near-infrared region to an infrared region having a long wavelength of 700 nm or more, JP-A No. 4 (1994)-
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 cited as reference articles of the Japanese Scientific Information Co., Ltd. Publishing Department (1986).

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

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

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

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

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

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably conductive, and as the conductive support, just as in the conventional case, for example, metal, paper, plastic sheet or the like is basically impregnated with a low resistance substance. Conductive treated by, for example, the basic back surface (the surface opposite to the surface on which the photosensitive layer is provided) to have conductivity, and at least one layer coated for the purpose of preventing curling,
Paper having a water-resistant adhesive layer provided on the surface of the support, 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), P2-11 (1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry", Polymer Publishing (1975), M.M. F. Hoo
ver., J. Macromol. Sci. Chem. A
-4 (6), 1327 to 1417 (1970) and the like are used.

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

In particular, since it is possible to form a copy image of a high-definition original faithfully, the effect of the present invention is more exerted when it is used in combination with a liquid developer. Also, by combining with a color developer, not only black and white copy images,
It can also be applied to color reproduction images (for example, Kuro Takizawa, “Photo Industry” 33 , 34 (1975), Masayasu Anzai, “Technical Research Report of the Institute of Electronics and Communication Engineers” 77 , 17 (19).
1977) etc.).

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

[0137]

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.

[0139]

[Chemical 25]

Synthesis Example 2 of Resin [A]: [A-2] A mixed solution of 46 g of n-butyl methacrylate, (tetraphenylporphinato) aluminum methyl 0.5 g and 60 g of methylene chloride was heated at 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.

[0142]

[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.

Then, 10 g of 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.

[0145]

[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.

[0148]

[Chemical 28]

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

[0150]

[Table 1]

[0151]

[Table 2]

[0152]

[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 .

[0154]

[Table 4]

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

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

[0157]

[Chemical 29]

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

[0159]

[Chemical 30]

Synthesis Example 2 of Resin [B]: [B-2] A mixture of 50.3 g of methyl methacrylate, 24.7 g of methyl acrylate, 8.0 g of an initiator [I-2] having the following structure and 75 g of tetrahydrofuran was used as a nitrogen stream. Warmed to a temperature of 50 ° C below. In this solution, 6 under the same conditions as in Synthesis Example 1
It was irradiated with light for an hour and photopolymerized.

[0161]

[Chemical 31]

Methyl methacrylate 23 was added to this polymer.
g, acrylonitrile (2.0 g) and tetrahydrofuran (25 g) were added, and the temperature was adjusted to 6
The mixture was heated to 0 ° C. and subjected to light irradiation for 12 hours to carry out photopolymerization in the same manner as above. The obtained reaction product was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried to give a yield of 75 g and a Mw.
1.2 × 10 ⁵ polymer was obtained.

[0163]

[Chemical 32]

Synthesis Examples 3 to 10 of Resin [B]: [B-3]
~ [B-10] A mixture of 65 g of methyl methacrylate and 0.008 mol of each initiator shown in Table C below was subjected to a photopolymerization reaction in the same manner as in Synthesis Example 1 of Resin [B].

Next, 100 g of tetrahydrofuran was added to and dissolved in this, and further, 32.2 g of methyl acrylate,
N-vinylpyrrolidone 2.0 g and methacrylic acid 0.8
After adding g, photopolymerization and reprecipitation were performed in the same manner as in Synthesis Example 1. The Mw of the obtained polymer was 8 × 10 ^{4 to} 1.0 ×.
It was in the range of 10 ⁵ .

[0166]

[Table 5]

[0167]

[Table 6]

[0168]

[Table 7]

Synthesis Examples 11 to 16 of Resin [B]: [B-1
1] to [B-16] In Synthesis Example 1 of Resin [B], instead of methyl methacrylate, methyl acrylate and acrylic acid, each monomer corresponding to the polymerization component shown in Table-D was used. Each polymer was obtained by operating under the same conditions as in Synthesis Example 1.
The Mw of the obtained polymer was in the range of 5 × 10 ^{4 to} 6 × 10 ⁴ .

[0170]

[Table 8]

[0171]

[Table 9]

Synthesis Examples 17 to 23 of Resin [B]: [B-1
7] to [B-23] Methyl methacrylate 63.6 g, methyl acrylate 31.4 g, 2-hydroxyethyl methacrylate 5
g, a mixed solution of (1 × 10 ⁻³ ) mol of the initiator shown in Table E below and 100 g of tetrahydrofuran was irradiated in the same manner as in Synthesis Example 1 for 8 hours. The obtained polymer was reprecipitated in 1.5 liter of methanol, and the precipitate was collected by filtration and dried to obtain 70 to 80 g of each polymer. The Mw of the obtained polymer was in the range of 8 × 10 ⁴ to 10 × 10 ⁴ .

[0173]

[Table 10]

[0174]

[Table 11]

[0175]

[Table 12]

Synthesis Examples 24 to 28 of Resin [B]: [B-2
4] to [B-28] A mixture of a monomer corresponding to the polymer component shown in the following Table-F and 15.4 g of the above initiator [I-2] was added at a temperature of 4 under a nitrogen stream.
The mixture was heated to 0 ° C., and the following operations were carried out in the same manner as in Synthesis Example 1 to irradiate with light and polymerize for 5 hours.

The solid substance was taken out, and tetrahydrofuran 1
After dissolving in 00 g, 19.5 g of methyl acrylate and 0.5 g of acrylic acid were added, and the temperature was further increased under a nitrogen stream at 50
The mixture was heated to ° C and irradiated with light in the same manner as above to polymerize.
The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. Yield of each polymer is 65-75g
The Mw was 9 × 10 ^{4 to} 1.2 × 10 ⁵ .

[0178]

[Table 13]

Synthesis Examples 29 to 35 of Resin [B]: [B-2
9] to [B-35] 57 g of methyl methacrylate, 28 of methyl acrylate
g and a mixture of 1.3 g of an initiator [I-18] having the following structure were heated to a temperature of 40 ° C. under a nitrogen stream, and then the following operation was carried out in the same manner as in Synthesis Example 1 to perform light irradiation for polymerization for 4 hours. .

[0180]

[Chemical 33]

After dissolving the solid substance in 100 g of tetrahydrofuran, each monomer corresponding to the polymerization components shown in Table G below was added, and the mixture was further heated to 50 ° C. under a nitrogen stream and irradiated with light in the same manner as above. And polymerized. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. The yield of each polymer is 70 to 80 g, and the Mw is 9 × 10.
It was in the range of ^{4 to} 1.1 × 10 ⁵ .

[0182]

[Table 14]

[0183]

[Table 15]

Example 1 and Comparative Examples 1 to 6 Resin [A-5] 6 g (as solid content), Resin [B-
1] 34 g (as solid content), photoconductive zinc oxide 20
0 g, a mixture of 0.018 g of methine dye [I] having the following structure, 0.3 g of phthalic anhydride and 300 g of toluene in a homogenizer (manufactured by Nippon Seiki Co., Ltd.), the rotation speed was 6 × 10 ^3.
A photosensitive layer-formed product was prepared by dispersing at rpm for 6 minutes, and 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 was produced.

[0185]

[Chemical 34]

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

[0187]

[Chemical 35]

Comparative Example 2: In Example 1, the resin [B-
1] 34 g of resin [R-2] having the following structure instead of 34 g
An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that.

[0189]

[Chemical 36]

Comparative Example 3: In Example 1, the resin [B-
1] 34 g of resin [R-3] having the following structure instead of 34 g
An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that.

[0191]

[Chemical 37]

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

[0193]

[Table 16]

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

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

Environmental conditions at the time of imaging are 20 ° C. and 65% RH
(I) and 30 ° C. 80% RH (II). As shown in Table-H, the light-sensitive material of the present invention had good electrostatic characteristics, and the actual copied image had no background fog and the copied image quality was clear. On the other hand, Comparative Examples 1 to 3 are photosensitivity (E _1/10 and E 1
_1/100 ), and even in the actual copied image, fine lines, letters, etc., and slight background fog remained even after the rinsing process.

Further, although it does not match the electrostatic characteristic, unevenness occurs in the intermediate density of the continuous tone portion of the copy document. The photoreceptor of the present invention and the photoreceptor of the comparative example have E _1/100
The values differ greatly. The E _1/100 value indicates how much potential remains in the non-image portion (exposed portion) after exposure in the actual image pickup property. It indicates that the image area is free from background stains.

Specifically, it is necessary to set the residual potential to −10 V or less, that is, how much exposure amount is required to set V _R −10 V or less. In the scanning exposure method according to ( _3), setting VR to −10 V or less with a small exposure amount is
This is very important in designing the optical system of the copying machine (cost of the device, accuracy of optical path of optical system, etc.).

From the above, an electrophotographic photosensitive member satisfying the electrostatic characteristics and the image pick-up property can be obtained only when the resin of the present invention is used, and it is particularly advantageous for a semiconductor laser light scanning exposure type photosensitive system. It became clear. Example 2 5 g of resin [A-23] (as solid content), resin [B-
2] 35 g (as solid content), photoconductive zinc oxide 20
0 g, 0.020 g of methine dye (II) having the following structure, N-
Hydroxymaleinimide 0.20 g and toluene 30
An electrophotographic light-sensitive material was produced by operating 0 g of the mixture in the same manner as in Example 1.

[0200]

[Chemical 38]

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

[0202]

[Table 17]

Embodiments of the evaluation items shown in Table-I are as follows. Note 3) Smoothness of surface layer: The photosensitive material obtained was measured using a Beck's smoothness tester (manufactured by Kumagai Riko Co., Ltd.) with an air capacity of 1 c.
The smoothness (sec / cc) was measured under the condition of c. Note 4) Contact angle with water: Each photosensitive material is desensitized EP
A solution of L-EX (manufactured by Fuji Photo Film Co., Ltd.) diluted with distilled water by a factor of 2 was used for an etching processor.
After passing through the surface of the photoconductive layer to desensitize it, a drop of distilled water (2 μl) is placed on the surface, and the contact angle with the formed water is measured with a goniometer. Note 5) Printing durability: Under the same conditions as in Note 2) above, plate making was performed to form a toner image, and desensitization was performed under the same conditions as Note 4) above, and this was used as an offset master. Shows the number of sheets that can be printed on an offset printing machine (Oliver 52 type, manufactured by Sakurai Seisakusho Co., Ltd.) without causing scumming in the non-image area of the printed matter and in the image quality of the image area. As shown in Table I, the light-sensitive material of the present invention had good electrostatic characteristics, and the actual copied image was free of background fog and the copied image quality was clear. The mechanical strength of the smooth film of the photoconductive layer was examined and found to be good. It is presumed that this is because the photoconductor and the binder resin are sufficiently adsorbed and the particle surface is covered. For the same reason, even when it is used as an offset master original plate, the desensitizing treatment with the desensitizing treatment solution proceeds sufficiently, the contact angle with water of the non-image area is as small as 10 degrees or less, and it is sufficiently hydrophilized. You can see that Even when the print was actually printed and the print stain was observed, the print stain was not recognized at all, and 10,000 prints with clear image quality were obtained.

From the above, the resin [A] and the resin [B] of the present invention properly interact with the zinc oxide particles, and the desensitizing reaction by the desensitizing treatment liquid easily and easily proceeds. It shows that the state is formed and that the film strength is remarkably improved by the action of the resin [B]. Examples 3 to 24 In Example 2, the resin [A-23] and the resin [B-
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that each resin [A] and each resin [B] in Table-J below were used instead of 2].

The electrostatic characteristics were measured in the same manner as in Example 2.

[0206]

[Table 18]

Further, when the actual image pick-up property of these light-sensitive materials was examined, it was possible to obtain a clear copy image having good reproducibility of fine lines / characters, no unevenness of halftone and no background fog. It was

When used as an offset master original plate and printed in the same manner as in Example 2, at least 10,000 or more sheets could be printed. From the above, each of the light-sensitive materials of the present invention was good in all aspects of smoothness, film strength, electrostatic properties and printability of the photoconductive layer.

Furthermore, it was found that the electrostatic characteristics were further improved by using the resin [AA]. Examples 25 to 28 Electrophotographic photosensitive materials were produced under the same conditions as in Example 1 except that the methine dye [I] used in Example 1 was replaced with the dyes shown in Table K below.

[0210]

[Table 19]

[0211]

[Table 20]

The light-sensitive materials of the present invention are all excellent in chargeability, dark charge retention rate, and photosensitivity, and the actual copied images can be produced even under severe conditions of high temperature and high humidity (30 ° C., 80% RH).
It gave a clear image with no background fog. Examples 29 and 30 and Comparative Example 4 Resin [A-19] (Example 29) or Resin [A-7]
Any 6 g of (Example 30), resin [B-25] 34
g, zinc oxide 200 g, uranine 0.02 g, methine dye [VII] 0.03 g having the following structure, methine dye [VIII] 0.03 g having the following structure, p-hydroxybenzoic acid 0.1
A mixture of 8 g and 300 g of toluene was rotated in a homogenizer at a rotation speed of 7 × 10 ³ r. p. m. For 5 minutes to prepare a photosensitive layer-formed product, which was coated on a conductive-treated paper with a wire bar so that the dry adhesion amount was 22 g / m ² and 1
It was dried at 10 ° C. for 20 seconds. Then in the dark at 20 ℃, 65
Each electrophotographic photosensitive member was produced by leaving it under a condition of% RH for 24 hours.

[0213]

[Chemical Formula 39]

[0214]

[Chemical 40]

Comparative Example 4 A photosensitive material was prepared in the same manner as in Example 29 except that 34 g of resin [R-4] having the following structure was used instead of 34 g of resin [B-25] in Example 29. did.

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

[0217]

[Chemical 41]

[0218]

[Table 21]

In the above measurement, the same operations as in Example 1 were carried out except that the electrostatic characteristics and the image pickup properties were in accordance with the following operations. Note 6) Method for measuring E _1/10 and E _1/100 of electrostatic characteristics After charging the surface of the photoconductive layer to −400 V by corona discharge, the surface of the photoconductive layer was exposed to visible light with an illuminance of 2.0 lux. After irradiation, the time until the surface potential (V ₁₀ ) is attenuated to 1/10 or 1/100 is obtained, and from this, the exposure amount E _1/10 or E _1/100 (lux seconds) is calculated. Note 7) Imaging property After leaving each light-sensitive material for 1 day under the following environmental conditions, fully automatic plate-making machine EPL-404V (Fuji Photo Film Co., Ltd.)
Manufactured by EPL-T as a toner, and a copy image (fog, image quality of the image) obtained by plate making was visually evaluated. The environmental conditions at the time of imaging are 20 ° C 65% RH (I) and 30 ° C 8
Performed at 0% RH (II). However, the original for copying (that is, the original copy) was prepared by cutting out and pasting other originals.

No difference was observed in the smoothness of the photoconductive layer in each light-sensitive material. However, in the electrostatic characteristics, Comparative Example 4 had a particularly large value of the photosensitivity E _1/100 , which was further promoted and deteriorated at high temperature and high humidity. The photosensitive material of the present invention has good electrostatic characteristics, and Example 30 using the resin [AA] having a specific substituent is very good, and particularly, the value of E _1/100 is small. It was

Examination of the actual image pickup property shows that Comparative Example 4
In addition to the original as a copy image, the frame (that is, the trace of pasting) of the part cut out and stuck was recognized as the background stain of the non-image part. However, in all cases of the present invention, clear images having no background stain were obtained.

Further, when these were subjected to desensitization treatment as offset printing original plates and printed, all of the present invention produced 10,000 printed matters with clear image quality without scumming.
However, in Comparative Example 4, the above-mentioned sticking mark was not removed even by the desensitizing treatment, and was generated from the printed matter printed out.

From the above, only the light-sensitive material of the present invention could give good characteristics. Example 31 5 g of resin [A-21] and 35 g of resin [B-30], 200 g of zinc oxide, 0.02 g of uranine, 0.04 g of rose bengal, 0.03 g of bromphenol blue, 0.40 g of phthalic anhydride and 300 g of toluene. A mixture of
A light-sensitive material was prepared by the same procedure as in Example 29.

The light-sensitive material of the present invention was operated in the same manner as in Example 29, and its performances were examined. All were excellent in chargeability, dark charge retention rate and photosensitivity, and the actual copied image was high temperature and high humidity. (30 ° C., 80% RH), even under severe conditions, a clear image with no background fog was provided.

Further, when this was used as an original plate of an offset master and printed, a printed matter having clear image quality was obtained even at 10,000 sheets. Examples 32 to 43 In Example 31, except that 5 g of resin [A-21] and 35 g of resin [B-30] were replaced with 6 g of resin [A] and 34 g of resin [B] shown in Table M below. Each light-sensitive material was prepared in the same manner as in Example 31.

[0226]

[Table 22]

The light-sensitive materials of the present invention are all excellent in chargeability, dark charge retention rate, and photosensitivity, and actual copy images also cause background fog even under severe conditions of high temperature and high humidity (30 ° C., 80% RH). It gave a clear image without the occurrence of fine line skipping.

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

[0229]

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

Claims (4)

[Claims] 1. An electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye and a binder resin, wherein the binder resin is 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 group, -COOH group, -SO ₃ H group, a phenolic OH group, -P (= O) (OH ) R 1 {R 1 is a hydrocarbon group or -OR ² (R ² is a hydrocarbon group A group consisting of at least one polymer group containing at least one polar group selected from the group consisting of (1) and a cyclic acid anhydride-containing group, and a polymer component represented by the following general formula (I) AB comprising at least a B block containing
Block copolymer. [Chemical 1] [In the formula (I), R ¹¹ represents a hydrocarbon group. Resin [B] A polymer chain having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ and containing at least 30% by weight of a repeating unit represented by the following general formula (II) as a polymer component, at least three bound star copolymer comprising in the organic molecule and a main chain terminal of the opposite side attached to the organic molecule of the respective polymer chains, -PO ₃ H ₂ group, -COOH group, -SO ₃
A resin formed by bonding at least one group selected from an H group, a -P (= O) (OH) R ¹ [R ¹ represents the same as the above] group, and a cyclic acid anhydride-containing group. [Chemical 2] [In the formula (II), a ¹ and a ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ¹² represents a hydrocarbon group. ] 2. The above-mentioned resin [A] is one of the aryl group-containing methacrylate components represented by the following general formula (Ia) and general formula (Ib) as a copolymer component represented by the general formula (I). The electrophotographic photosensitive member according to claim 1, further comprising at least one. [Chemical 3] [Chemical 4] [In formulas (Ia) and (Ib), A ¹ and A ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a cyano group, —COR ⁴ or —COOR ⁴ (R
⁴ 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 polymer chain that binds to an organic molecule comprises an A block containing at least the repeating unit represented by the general formula (II) as a polymer component and the resin [B]. It is composed of an AB type block composed of a B block containing at least one polymer component having at least one polar group selected from the specific polar groups shown, and one end of the A block is The electrophotographic photosensitive member according to claim 1 or 2, wherein the electrophotographic photosensitive member is bound to an organic molecule and the other end is bound to a B block. 4. 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, wherein the content is 10% by weight to 50% by weight based on the total amount of the components.