JP2684434B2 - Electrophotographic photoreceptor - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor, and more particularly, to an electrophotographic photoreceptor excellent in electrostatic characteristics and moisture resistance. In particular, it relates to a CPC photosensitive member having excellent performance.

[Conventional technology]

The electrophotographic photosensitive member has various configurations in order to obtain predetermined characteristics or according to the type of an applied electrophotographic process.

Representative electrophotographic photoreceptors include a photoreceptor having a photoconductive layer formed on a support and a photoreceptor having an insulating layer on the surface, and 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, i.e. charging, image exposure and development, and, if necessary, transfer.

Further, a method using an electrophotographic photosensitive member as an offset master for direct plate making has been widely used. In particular, in recent years, direct electrophotographic lithographic printing has become important as a method for printing high-quality printed matter with a print number of several hundreds to several thousands.

The binder resin used to form the photoconductive layer of the electrophotographic photoreceptor has excellent film forming properties of itself and the ability to disperse the photoconductive powder in the binder resin, and the formed recording material layer Has good adhesion to the substrate, and the photoconductive layer of the recording layer has excellent charging ability, low dark decay, large light decay, low pre-exposure fatigue, and changes in humidity during photography. It is necessary to have various electrostatic characteristics, such as a need to stably maintain these characteristics, and excellent imaging properties.

Furthermore, research on a lithographic printing original plate using an electrophotographic photoreceptor has been earnestly conducted, and a binder resin for a photoconductive layer having both electrostatic characteristics as an electrophotographic photoreceptor and printing characteristics as a printing original plate. is required.

However, conventionally known binder resins include, in particular, chargeability,
There are many problems in dark charge retention, electrostatic characteristics such as photosensitivity, and smoothness of the photoconductive layer.

In order to solve these problems, a low molecular weight resin containing 0.05 to 10% by weight of a copolymer component containing an acidic group in the side chain of the polymer as a binder resin or an acidic group at the end of the polymer main chain The use of a low molecular weight resin ( _w 10 ³ to 10 ⁴ ) that binds to the resin improves the smoothness and electrostatic properties of the photoconductive layer, and provides image quality free of background stains. 217354 and JP-A-64-70761.

Further, as a binder resin, a resin containing a polymerization component containing an acidic group in the side chain of the copolymer or bonded to the end of the polymer main chain and containing a heat and / or photocurable functional group. Is disclosed in Japanese Patent Application Laid-Open No. 1-100554 and Japanese Patent Application No. 63-39690, in which a resin containing an acidic group in the side chain of the copolymer or bound to the end of the polymer main chain is used in combination with a crosslinking agent. The techniques are disclosed in JP-A-1-102573 and Japanese Patent Application No. 63-39691, respectively. Further, low molecular weight products of the resin (weight average molecular weight 10 ³ to 1
0 ⁴ ) in combination with a resin having a high molecular weight (weight average molecular weight of 10 ⁴ or more) is disclosed in JP-A 64-564 and 63-220149.
No. 63-220140, Japanese Patent Application No. 62-273547, JP-A-1-
No. 116643 and JP-A No. 1-169455 disclose the techniques of using such a low molecular weight compound in combination with a heat-curable and / or photo-curable resin, respectively, in JP-A No. 1-211766 and Japanese Patent Application No. 63-26561. . According to these techniques, the film strength of the photoconductive layer is further sufficiently leveled and the mechanical strength is increased without impairing the above properties due to the use of a resin containing an acidic group at a side chain or at a terminal. Have been.

(Problems to be Solved by the Invention) However, even if these resins are used, it is still insufficient to maintain stable performance when the environment fluctuates remarkably from high temperature and high humidity to low temperature and low humidity. Was. In particular, in the scanning exposure method using a semiconductor laser beam, the exposure time is longer and the exposure intensity is limited as compared with the conventional simultaneous exposure method using visible light. Higher performance is required for light sensitivity.

Furthermore, in the electrophotographic lithographic printing plate precursor, when the scanning exposure method using the semiconductor laser light is adopted, when the conventional photoconductor is actually tested, the above electrostatic characteristics are unsatisfactory, In particular, the difference between E _1/2 and E _1/10 is large, the tone of the copied image becomes soft, and it becomes difficult to further reduce the residual potential after exposure, and the fog of the copied image becomes remarkable, In addition, even when printing is performed as an offset master, a serious problem such as sticking traces of a printed original appears on a printed material has appeared.

The present invention is to improve the problems of the conventional electrophotographic photoreceptor as described above.

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photoreceptor having stable and good electrostatic characteristics and having a clear and high-quality image even when the environment at the time of forming a copy image fluctuates such as low temperature and low humidity or high temperature and high humidity. To provide.

Another object of the present invention is to provide a CPC electrophotographic photoreceptor having excellent electrostatic characteristics and low environmental dependency.

Another object of the present invention is to provide an electrophotographic photosensitive member effective for a scanning exposure method using a semiconductor laser beam.

A further object of the present invention is to provide an electrophotographic lithographic printing plate precursor having excellent electrostatic properties (particularly dark charge retention and light sensitivity),
By providing a lithographic printing original plate that reproduces a copy image that is faithful to the original image and that does not generate spotted background stains as well as uniform background stains on the printed material and that has excellent printing durability is there.

(Means for Solving the Problems) An object of the present invention is to provide an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor and a binder resin, wherein the binder resin is a resin [A] shown below. It has been found that this can be achieved by an electrophotographic photoreceptor characterized by comprising at least one kind and at least one kind of resin [B].

Resin (A); an average molecular weight of ^{1 × 10 3 ~2 × 10 4} , -PO 3 H 2 group,
-COOH group, -SO ₃ H group, a phenolic OH group, R represents a hydrocarbon group or an -OR 'group (R' is a hydrocarbon group) and A comprises at least one polymer component containing at least one acidic group selected from cyclic acid anhydride-containing groups. A resin containing an AB block copolymer composed of a block and a B block containing at least a polymer component represented by the following general formula (I).

General formula (I) (In the formula (I), R ₁ represents a hydrocarbon group.) Resin [B]; a polymer containing at least one of the polymer components represented by the following general formulas (IV a) and (IV b). A monofunctional macromonomer (hereinafter referred to as macromonomer (MA)) having a weight average molecular weight of 2 × 10 ⁴ or less formed by bonding a polymerizable double bond group represented by the following general formula (III) to only one end of the main chain And a monomer represented by the following general formula (V).

General formula (III) Wherein (III), V ₀ is -COO -, - OCO -, - CH 2 OCO-,
_{-CH 2 COO -, - O -} , - SO 2 -, - CO -, - CONHCOO-,
−CONHCONH−, −CONHSO ₂ −, (P ₃ represents a hydrogen atom or a hydrocarbon group).

c ₁ and c ₂ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-
Z'or -COO-Z 'through a hydrocarbon (Z' represents a hydrogen atom or a hydrocarbon group which may be substituted) is represented. ] [In the formula (IV a) or (IV b), V ₁ is V ₀ in the formula (III).
Represents the same content as.

Q ₁ represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms.

d ₁ and d ₂ may be the same or different from each other;
Represents the same contents as c ₁ and c _{2 in} I).

Q ₀ is -CN, -CONH ₂ or Represents

Here, T represents a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group or -COOZ "(Z" represents an alkyl group, an aralkyl group or an aryl group). General formula (V) Wherein (V), V ₂ represents the V ₁ same contents as in formula (IV a), Q ₂ represents a Q ₁ same contents as in formula (IV a). e ₁ and e ₂ may be the same or different from each other, and are represented by the formula (II
Represents the same contents as c ₁ and c _{2 in} I). The binder resin of the present invention contains an AB block copolymer of an A block containing the specific acidic group-containing component and a B block containing the polymer component represented by the formula (I). The resin [A] and a monofunctional macromonomer having a polymerizable double bond group bonded to one end of the polymer main chain containing at least the polymer component of the general formula (IV a) or (IV b) (MB ) And the monomer of general formula (V) are each at least 1
And a resin [B] made of a comb-type copolymer containing seeds.

Furthermore, as the low molecular weight resin [A], 2-position represented by the following general formulas (Ia) and (Ib), and / or
Or a resin [A] containing a methacrylate component having a specific substituent and an acidic group component containing a benzene ring having a specific substituent at the 2- and 6-positions or an unsubstituted naphthalene ring; It is particularly preferable that the resin is a resin [A '].

[In the formula (I a) or (I b), X ₁ and X ₂ are independent of each other,
Each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, -COZ ₂ or -COOZ ₂ (Z ₂ are each carbon atoms 1
~ 10 hydrocarbon groups). However, X ₁ and X ₂ are never both represent a hydrogen atom.

L ₁ and L ₂ each represent a single bond or a linking group having 1 to 4 linking atoms, each linking —COO— and a benzene ring. The resin [A] used in the present invention is an AB block copolymer, and the A block is composed of at least one polymerization component containing at least one selected from the above-mentioned specific acidic groups, and the B block. Comprises a polymer component containing at least one methacrylate component represented by formula (I) and having a weight average molecular weight of 1 × 10 5.
It is characterized by being ^{3 to} 2 × 10 ⁴ .

Among the acidic group-containing binder resins known to improve the smoothness and electrostatic properties of the photoconductive layer described above, those using a low-molecular-weight compound have an acidic group-containing polymer component randomly present in the polymer main chain. Or a resin having an acidic group bonded only to one terminal of the polymer main chain.

On the other hand, the resin [A] used in the binder resin of the present invention binds only to the terminal of the polymer main chain even if the acidic group contained in the resin is randomly present in the polymer main chain. However, the copolymer is not specified, but is further specified so as to exist as a block in the polymer main chain.

The copolymer according to the present invention, while the region of the portion of the acidic group unevenly distributed to one side portion of either one of the main chain of the polymer is sufficiently adsorbed to the stoichiometric defect of the inorganic photoconductor, It is presumed that the other block portions constituting the polymer main chain cover the surface of the photoconductor slowly and sufficiently. Due to its action mechanism, the copolymer according to the present invention has a sufficient adsorption area even if the stoichiometric defect of the inorganic photoconductor fluctuates somewhat, so that the inorganic photoconductor and the resin [A According to the present invention, it is inferred that according to the present invention, the photoconductor traps can be more sufficiently compensated and the humidity characteristics can be improved more excellently than the conventionally known acidic group-containing resin, while the light characteristics can be improved. The conductor is sufficiently dispersed,
It has been found that aggregation is suppressed.

The resin [B] does not hinder the high performance of the electrophotographic properties due to the use of the resin [A] at all, and the resin [A] alone provides sufficient mechanical strength of the photoconductive layer, which is insufficient. It has been found that a sufficiently good imaging performance can be obtained even when the environment fluctuates as described above or a low output laser beam is used.

This is a resin [A] as a binder resin for the inorganic photoconductor.
And the resin [B] by specifying the weight average molecular weight of the resin and the content and bonding position of the acidic group in the resin,
It is presumed that the strength of the interaction between the inorganic photoconductor and the resin was appropriately changed. That is, the resin [A] having a stronger interaction selectively and appropriately adsorbs to the inorganic photoconductor, while the resin [B] having a weaker interaction than the resin [A] inhibits the electrophotographic properties. It is presumed that by gently interacting with the inorganic photoconductor to such an extent that both the electrophotographic characteristics and the mechanical strength were remarkably improved as described above.

Further, when the resin [A '] is used, the electrophotographic properties (especially V ₁₀ , DRR, E _1/10 ) are higher than those of the resin [A].
Can be improved.

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

Further, in the present invention, the smoothness of the photoconductive layer surface becomes smooth. On the other hand, when a photoconductor having a rough surface of the photoconductive layer is used as the electrophotographic lithographic printing plate precursor, the dispersion state of the zinc oxide particles as the photoconductor and the binder resin is not appropriate, and an aggregate exists. Since the photoconductive layer is formed in the state, even if the desensitizing treatment with the desensitizing solution is performed, the non-image portion is not sufficiently and sufficiently hydrophilized, causing adhesion of the printing ink during printing, and as a result, The background stain on the non-image portion of the printed matter occurs.

When the resin of the present invention is used, the interaction between the adsorption and coating of the photoconductor and the binder resin is appropriately performed, and the film strength of the photoconductive layer is maintained.

Even when only the low molecular weight resin [A] in the present invention is used as the binder resin, the photoconductor and the binder resin are sufficiently adsorbed, and the surface of the particles can be coated. It has good electrostatic characteristics and an image quality free from background contamination. Further, it has sufficient film strength as a CPC photoreceptor or an offset original plate having thousands of printed sheets. However, by coexisting the resin [B] as in the present invention, the mechanical strength of the photoconductive layer which is still insufficient with the resin [A] alone without further alienating the function of the resin [A] is further improved. I was able to. Accordingly, the photoreceptor of the present invention has excellent electrostatic characteristics even when environmental conditions fluctuate, has sufficient film strength, and is subjected to severe printing conditions (for example,
Even when the printing pressure is increased with a large printing press), it is possible to print more than 10,000 sheets.

Furthermore, the resin (B), said comb copolymer mainly at one end of the chain only -PO ₃ H ₂ group, -SO ₃ H group, -COOH group, -OH group, -SH
Group and {R ₀ represents a hydrocarbon group or a —OR ₀ ′ (R ₀ ′ represents a hydrocarbon group) group} and a resin (hereinafter referred to as resin [B ′]) further bound with at least one acidic group selected from (Sometimes referred to)).

When the resin [B '] is used, the electrostatic characteristics, especially DRR and E _1/10 are improved, and the excellent characteristics due to the use of the resin [A] cannot be prevented at all. It is preferable because there is almost no change even in environmental changes such as humidity, low temperature, and low humidity. Further, the film strength is further improved, and the printing durability is improved.

Spectral sensitizing dyes that are usually used to maintain photosensitivity in the visible light to infrared light regions are those whose spectral sensitizing function sufficiently functions by being adsorbed to a photoconductor, and are therefore common to the present invention. It is assumed that the binder resin containing the polymer appropriately interacts with the photoconductor without inhibiting the adsorption of the spectral sensitizing dye. This effect was particularly remarkable with cyanine dyes or phthalocyanine pigments, which are particularly effective as dyes for spectral sensitization of near infrared to infrared light.

In the block copolymer [A], the polymer component amount of the specific acidic group-containing component is preferably 0.5 to 20 parts by weight, more preferably 3 to 15 parts by weight per 100 parts by weight of the copolymer [A]. It is contained in.

The amount of the methacrylate component represented by the formula (I) in the block portion (B block) containing the methacrylate component represented by the general formula (I) is calculated based on the total weight of the block.
Preferably from 30% to 100% by weight, more preferably from 50 to 1%
00% by weight. The weight average molecular weight of the copolymer [A] is 1
It is x10 ^{3 to} 2x10 ⁴ , preferably 2x10 ³ to 1x10 ⁴ .

When the molecular weight of the resin [A] is less than 1 × 10 ³ , the film-forming ability is reduced and sufficient film strength cannot be maintained. When the molecular weight is more than 2 × 10 ⁴ , the effect of the resin [A] of the present invention may be reduced. And the electronic properties are about the same as those of conventionally known resins.

When the content of the acid group in the binder resin [A] is less than 0.5% by weight, the initial potential is low and a sufficient image density cannot be obtained, and when the content of the acidic group is more than 20% by weight,
It is not preferable because the dispersibility is reduced, the film smoothness and the high humidity property of the electrophotographic properties are reduced, and furthermore, the background smear increases when used as an offset master.

The glass transition point of the resin [A] is preferably in the range of -10C to 100C, more preferably -5C to 85C.

The polymerization component containing a specific acidic group constituting the A block of the AB block copolymer (resin [A]) of the present invention will be described more specifically.

The acidic group, -PO ₃ H ₂ group, -COOH group, -SO ₃ H group,
Phenolic OH group, {R is a hydrocarbon group or -OR 'group (R' is a hydrocarbon group),} and include cyclic acid anhydride-containing group, preferably, -COOH group, -SO ₃ H groups, phenolic OH groups ,as well as It is.

In the above, R represents a hydrocarbon group or an -OR 'group (R' represents a hydrocarbon group), and R and R 'are preferably an aliphatic group having 1 to 22 carbon atoms (for example, a methyl group, an ethyl group, Propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, 2-chloroethyl, 2-methoxyethyl, 3-ethoxypropyl,
Allyl group, crotonyl group, butynyl 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 (For example, 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.).

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

Further, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and the cyclic acid anhydride contained therein includes an aliphatic dicarboxylic acid anhydride and an aromatic dicarboxylic acid anhydride. To be

Examples of the aliphatic dicarboxylic anhydride include a succinic anhydride ring, a glutaconic anhydride ring, a maleic anhydride ring,
Cyclopentane-1,2-dicarboxylic anhydride ring, cyclohexane-1,2-dicarboxylic anhydride ring, cyclohexene-1,2-dicarboxylic anhydride ring, 2,3-picyclo [2.2.
2] octanedicarboxylic anhydride rings and the like, and these rings are substituted with, for example, halogen atoms such as chlorine atom and bromine atom, and alkyl groups such as methyl group, ethyl group, butyl group and hexyl group. Is also good.

Examples of the aromatic dicarboxylic anhydride include a phthalic anhydride ring, a naphthalene-dicarboxylic anhydride ring, a pyridine-dicarboxylic anhydride ring, a thiophene-dicarboxylic anhydride ring, and the like. Is, for example, a chlorine atom, a halogen atom such as a bromine atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (for the alkoxy group, for example, Methoxy group, ethoxy group, etc.) may be substituted.

Examples of the above-mentioned “polymer component containing a specific acidic group” include a polymer component constituting the B block component in the resin [A] of the present invention, that is, a methacrylate component represented by the general formula (I), and the like. Any vinyl compound containing the acidic group, which copolymerizes with the corresponding vinyl compound, can be used.

For example, vinyl compounds described in “Polymer Data Handbook [Basic Edition]” edited by The Society of Polymer Science, Baifukan (1986) and the like can be used. Specifically, acrylic acid, α and / or β Substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino)
Methyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α-chloro-β-methoxy form,
α, β-dichloro form), 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), maleic acid, maleic acid half esters,
Maleic acid semi-amides, vinyl benzene carboxylic acid, vinyl benzene sulfonic acid, vinyl sulfonic acid, vinyl phosphoic acid, vinyl or allyl group half-ester derivatives of dicarboxylic acids, and ester or amide derivatives of these carboxylic or sulfonic acids And a compound containing the acidic group in the substituent.

The following are specific examples of these compounds. However, in each of the following examples, a is -H,-
_{CH 3, -Cl, -Br, -CN} -, - CH 2 COOCH 3 or -CH ₂ COOH
Are shown, b represents -H or -CH _3, n is an integer of 2 to 18, m represents an integer of 1 to 12, l is an integer of 1-4.

_{(A-15) CH 2 =} CHCH 2 OCO (CH 2) mCOOH (a-16) CH 2 = CHCH 2 lCOOH Two or more types of polymerization components containing the specific acidic group as described above may be contained in the A block, and in that case, the two or more types of acidic group-containing components may be randomly copolymerized in the A block. It may be contained in any form of block copolymerization.

Further, the component not containing the acidic group may be contained in the A block, and examples of the component include components represented by the general formula (I) or (II). The content of the acidic group-free component is preferably 0 to 50% by weight, more preferably 0 to 20% by weight in the A block, and most preferably, the acidic group-free component is not contained in the A block. .

Next, the polymerization component constituting the B block component in the AB block copolymer [A] will be described in detail.

The B block component contains at least a methacrylate component represented by the general formula (I), and the methacrylate component of the formula (I) is preferably 30 to 100% by weight, more preferably 50 to 100% by weight in the B block component. Contained.

In the repeating unit represented by the general formula (I), the hydrocarbon group of R ₁ may be substituted.

R ₁ preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. As the substituent, any substituent may be used as long as it is a substituent other than the acidic group contained in the polymerization component constituting the A block of the AB block copolymer. For example, a halogen atom (for example, a fluorine atom, a chlorine atom, bromine _{atom) -O-Z 1, -COO-} Z 1, -OCO-Z 1, (Z 1 is
Represents an alkyl group having 1 to 22 carbon atoms, for example, a methyl group,
And a substituent such as 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). Preferred hydrocarbon groups include alkyl groups having 1 to 18 carbon atoms which may be substituted (for example, 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-
A methoxyethyl group, a 3-bromopropyl group and the like, and an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2-
Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc. ), An optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group,
-Naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (E.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or 6 to 12 carbon atoms.
Which may be substituted (for example, phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl) Group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, Dodecyloylamidophenyl group, etc.).

In the hydrocarbon group of R _1, preferably when R ₁ is an aliphatic group, preferably not less than 60% by weight of the component represented a hydrocarbon group having 1 to 5 carbon atoms in formula (I) .

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 a repeating unit represented by the following general formula (Ia) and / or (Ib). It is preferred that Therefore, at least one repeating unit selected from the following general formulas (Ia) and (Ib) in the B block component accounts for 30% by weight in the other block.
As described above, it is particularly preferable to contain 50 to 100% by weight.

[In the formula (I a) or (I b), X ₁ and X ₂ are independent of each other,
Each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom -COZ ₂ or -COOZ ₂ (Z ₂ each having a carbon number 1 to 1
0 represents a hydrocarbon group). However, X ₁ and X ₂ are never both represent a hydrogen atom.

L ₁ and L ₂ each represent a single bond or a linking group having 1 to 4 linking atoms, each linking —COO— and a benzene ring. By containing the repeating unit represented by the formula (Ia) and / or (Ib) in a B block containing no acidic group, the electrophotographic properties (particularly, V ₁₀ , DRR, E
_1/10 ) improvement can be achieved.

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

In formula (I a), preferable X ₁ and X ₂ are a hydrogen atom, a chlorine atom and a bromine atom, respectively, and a preferable hydrocarbon group is an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, Propyl group, butyl group, etc.), aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group,
A dichlorobenzyl group, a bromobenzyl group, a methylbenzyl group, a methoxybenzyl group, a chloro-methyl-benzyl group and the like; and an aryl group (for example, a phenyl group, a tolyl group,
Silyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group, etc.), and -CO
Z ₂ and —COOZ ₂ (preferable Z _{2 can} include those described as preferable hydrocarbon groups above). However, X ₁ and X ₂ are never both represent a hydrogen atom.

In the formula (I a), L ₁ is a direct bond or CH _{2 n1} (n ₁ represents an integer of ₁ to 3) that bonds —COO— and the benzene ring, —CH ₂ CH ₂ OCO—, (CH ₂ O) _n2 (n ₁ represents an integer of 1 or _{2), - CH 2 CH 2} O- number such linking atom, such as 1
Represents 4 linking groups.

L ₂ in the formula (I b) is the same meaning as L _1.

Specific examples of the repeating unit represented by the formula (Ia) or (Ib), which is preferably used in the B block of the resin [A] of the present invention, are shown below. However, the scope of the present invention is:
It is not limited to these.

In the B block formed separately from the A block comprising the specific acidic group-containing polymerization component, the repeating unit represented by the formula (I) {preferably (Ia) or (Ib)} is Two or more kinds may be contained, and other polymerization components other than these may be contained. When two or more polymerization components are contained in the B block containing no acidic group, the AB block copolymer component is contained in the B block in any mode of random copolymerization or block copolymerization. However, it is preferable to be contained at random.

Other polymerization components which can be contained in the B block together with the polymerization components selected from the repeating units represented by the above formulas (I), (Ia) and / or (Ib) are components copolymerized with these. Any may be used.

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

General formula (II) Wherein (II), T is _{-COO -, - OCO-, CH 2} m1 OCO
−, CH _{2 m2} COO−, _−O− , −SO ₂ −, -CONHCOO-, CONHCONH-, or And m ₁ and m ₂ each represent an integer of 1 to 2;
₃ represents the same contents as R ₁ in the formula (I). R ₂ is the same meaning as R ₁ in formula (I).

a ₁ and a ₂ may be the same or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -COO-Z ₃ or a hydrocarbon group having 1 to 8 carbon atoms. Represents —COO—Z ₃ (Z ₃ represents a hydrocarbon group having 1 to 18 carbon atoms). More preferably, a ₁ and a ₂ may be the same or different from each other, and represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, etc.), —COO—Z ₃ or _{-CH 2 COO-Z 3 (Z} 3 more preferably represents an alkyl or alkenyl group having 1 to 18 carbon atoms, e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl Group, dodecyl group,
Tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, pentenyl group, hexenyl group, octenyl group, decenyl group and the like, and these alkyl group and alkenyl group have the same substituents as those described for R ₁ above. ).

As a monomer constituting a repeating unit other than these,
Further, styrenes (for example, styrene, vinyltoluene, chlorostyrene, bromostyrene, dichlorostyrene, vinylphenol, methoxystyrene, chloromethylstyrene, methoxymethylstyrene, acetoxystyrene,
Methoxycarbonylstyrene, methylcarbamoylstyrene, etc.), acrylonitrile, methacrylonitrile,
Acrolein, methacrolein, vinyl group-containing heterocyclic compounds (eg, N-vinylpyrrolidone, vinylpyridine,
Vinyl imidazole, vinyl thiophene, etc.), acrylamide, methacrylamide and the like.
These other copolymer components are not limited to these.

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

For example, P. Lutz, P. Masson etal, Polym. Bull. 12 .
(1984), BCAnderson, GDAndrews etal, Macromolecu
les, 14 , 1601, (1981), K. Hatada, K. Ute. et al., Polym. J. 1
7, 977 (1985), 18, 1037 (1986), the right hand Koichi, Koichi Hatada, polymer processing, 36, 366 (1987), Higashimura Satoshinobe, Mitsuo Sawamoto, polymer Collected Papers, 46, 189 (1989), M.Kuroki, T.Aida,
J. Am. Chem. Soc. 109 , 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43 , 300 (1985), DYSogah, WRHe
Macromolecules, 20 , 1473 (1987), etc. can be easily synthesized.

Further, the AB block copolymer [A] can also be synthesized by a photoiniferter polymerization method using a monomer without protecting the acidic group and using a disiocarbamate compound as an initiator. For example, Takayuki Otsu, polymeric, 37, 248 (19
88), Shunichi Hinomori, Ryuichi Otsu, Polym. Rep. Jap. 37. 3508 (1
988), JP-A-64-111, JP-A-64-26619, and the like.

Further, the protecting group for protecting the specific acidic group of the present invention and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing conventionally known knowledge. For example, various descriptions are given in the above cited references, and furthermore, Yoshio Iwakura, Keisuke Kurita, “Reactive Polymers” published by Kodansha (1977)
TWGreene, "Protective Groups in Organic Sy
nthesis ", John Wiley & Sons (1981), JFW McOmi
e, `` Protective Groups in Organic Chemistry '' Plenum
Press, (1973) and the like can be carried out by appropriately selecting a method described in detail.

In the present invention, when the binder resin further contains at least one of the above-mentioned resin [A] and the above-mentioned high molecular weight (resin [B] having a weight average molecular weight of 3 × 10 ⁴ or more), the electrophotographic photoreceptor is further improved. It was found that the mechanical strength of the photoconductive layer was improved.

The resin [B] makes the mechanical strength of the photoconductive layer sufficient when the resin [A] alone is insufficient.

In addition, a low molecular weight resin [A] and a high molecular weight resin [B]
The electrophotographic photosensitive member of the present invention which is used in combination has a good smoothness of the photoconductive layer surface even when used as an electrophotographic lithographic printing original plate, and the zinc oxide particles as the photoconductive material are bound. Since it is well dispersed in the agent, the desensitizing treatment with the desensitizing treatment liquid makes the non-image area hydrophilic enough to prevent the adhesion of printing ink to the non-image area during printing. Therefore, even if a large number of printed matter such as 10,000 sheets are printed, the background stain is not generated.

That is, in the present invention, when the resin [A] and the resin [B] are used together, the interaction between adsorption and coating of the inorganic photoconductor and the binder resin is appropriately performed, and the film strength of the photoconductive layer is further improved. It is well retained.

In the resin [A], the amount of the specific acidic group-containing polymer component in the AB block copolymer is 0.5 to 20% by weight, preferably 3 to 20% by weight in 100 parts by weight of the resin [A].
15% by weight. The weight average molecular weight of the resin [A] is preferably 3 × 10 ³ to 1 × 10 ⁴ .

Next, the resin [B] used in the present invention will be described.

The resin [B] is a resin which is a graft type copolymer that satisfies the above-mentioned physical properties and contains at least a monofunctional macromonomer (MB) and a monomer represented by the general formula (V). Characterize.

The resin [B] preferably has a weight average molecular weight of 3 × 10 ⁴
The above is a graft copolymer resin. More preferably, the weight average molecular weight is from 5 × 10 ^{4 to} 3 × 10 ⁵ .

The glass transition point of the resin [B] is preferably 0 ° C to 120 ° C.
And more preferably from 10 ° C to 90 ° C.

The monofunctional macromonomer (MB) has a polymerizable double bond group represented by the general formula (III), a general formula (IV a) or (IV
It has a weight-average molecular weight of 2 × 10 ⁴ or less which is bonded to only one end of a polymer main chain containing at least one polymer component represented by b).

In the general formulas (III), (IVa) and (IVb),
The hydrocarbon groups contained in c ₁ , c ₂ , V ₀ , d ₁ , d ₂ , V ₁ , Q ₁ and Q ₀ each have the indicated carbon number (as an unsubstituted hydrocarbon group), These hydrocarbon groups may have a substituent.

Formula showing the macromonomer (MB) in (III), V ₀ is -COO -, - OCO -, - CH 2 OCO -, - CH 2 COO-,
_{-O -, - SO 2 -,} - CO -, - CONHCOO -, - CONHCONH
−, −CONHSO ₂ −, Represents Here, P ₃ is, in addition to a hydrogen atom, a preferable hydrocarbon group as an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group). 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 and the like, and an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, , 2-methyl-
1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), An optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group,
-Naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (E.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or C6-C6.
12 optionally substituted aromatic groups (for example, phenyl group,
Naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl Group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.).

V ₀ In the case where is represented, the benzene ring may have a substituent.
Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group, Ethoxy group, propoxy group, butoxy group, etc.).

c ₁ and c ₂ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (for example, a chlorine atom,
Bromine atom, etc.), cyano group, alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.), -COO-Z 'or -COO-Z' via hydrocarbon.
(Z 'represents a hydrogen atom or an alkyl group, alkenyl group, aralkyl group, alicyclic group or aryl group having 1 to 18 carbon atoms, which may be substituted, and specifically,
It represents the same contents as those described for P ₃ above).

Examples of the hydrocarbon in the -COO-Z 'group through the hydrocarbon include a methylene group, an ethylene group, a propylene group and the like.

More preferably, in the general formula (III), V ₀ is -C
OO -, - OCO -, - CH 2 OCO -, - CH 2 COO -, - O -, - C
ONHCOO -, - CONHCONH -, - CONH, -SO 2 NH- or And c ₁ and c ₂ may be the same or different from each other, and are a hydrogen atom, a methyl group, —COO—Z ′ or —CH ₂ COOZ ′ (Z ′.
Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc.). Even more preferably, one of c ₁ and c ₂ always represents a hydrogen atom.

That is, as the polymerizable double bond group represented by the general formula (III), specifically, CH ₂ = CH-O-, Is mentioned.

In general formula (IV a), V ₁ has the same meaning as V ₀ in formula (III).

d ₁ and d ₂ may be the same or different from each other, and have the formula (III)
Represents the same content as c ₁ and c _{2 in} .

Q ₁ represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms.

Specifically, an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, an octyl group, a decyl group,
Dodecyl, tridecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2
-Hydroxylethyl group, 2-methoxyethyl group, 2-
Ethoxyethyl group, 2-cyanoethyl group, 3-chloropropyl group, 2- (trimethoxysilyl) ethyl group, 2-
Tetrahydrofuryl group, 2-thienylethyl group, 2-N,
N-dimethylaminoethyl group, 2-N, N-diethylaminoethyl group, etc., C5-C8 cycloalkyl group (for example, cycloheptyl group, cyclohexyl group, cyclooctyl group, etc.), C7-C12 substitution Aralkyl groups (eg, benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl,
Aliphatic groups such as chlorobenzyl group, bromobenzyl group, dichlorobenzyl group, methylbenzyl group, chloro-methyl-benzyl group, dimethylbenzyl group, trimethylbenzyl group, and methoxybenzyl group.

Further, an optionally substituted aryl group having 6 to 12 carbon atoms (eg, phenyl, tolyl, xylyl, chlorophenyl, bromophenyl, dichlorophenyl, chloro-methyl-phenyl, methoxyphenyl, methoxycarbonylphenyl) , A naphthyl group, a chloronaphthyl group, etc.).

In the formula (IVa), preferably V ₁ is -COO-, -OCO.
_{-, - CH 2 COO -,} - CH 2 OCO -, - O -, - CO -, - CONH
COO -, - CONHCONH -, - CONH -, - SO 2 NH-, or Represents

Preferred examples of d ₁ and d ₂ represent the same contents as those of c ₁ and c ₂ described above.

In formula (IV b), Q ₀ represents —CN, —CONH ₂ or Represents a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), a hydrocarbon group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, phenyl group, etc.), alkoxy group, ( For example, a methoxy group, an ethoxy group, etc.) or -COO-Z "(Z" is preferably 1 carbon atom.
Represents an alkyl group having 8 to 8, an aralkyl group having 7 to 12 carbon atoms or an aryl group).

The macromonomer (MB) may contain two or more polymer components represented by the formula (IV a) or (IV b). Or in (IV a), when Q ₁ is an aliphatic group, it has 6 to 12 carbon atoms.
It is preferable to use the aliphatic group in a range not exceeding 20% by weight based on the total polymer components in the macromonomer (MB).

Furthermore, when V ₁ in the general formula (IV a) is —COO—, in all the polymer components in the macromonomer (MB),
At least 30% by weight of the polymer component of the formula (IVa)
It is preferable to contain the above.

Further, in the macromonomer (MB), acrylonitrile, methacrylonitrile, acrylamides as monomers corresponding to repeating units that can be copolymerized with the polymer component represented by the formula (IV a) and / or (IV b) , Methacrylamide, styrene and its derivatives (eg vinyltoluene, chlorostyrene, dichlorostyrene, bromostyrene, hydroxymethylstyrene, N, N-dimethylaminomethylstyrene, etc.), heterocyclic vinyls (eg vinylpyridine, vinylimidozole) , Vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.) and the like.

The macromonomer (MB) provided in the resin [B] of the present invention has the general formula (IV a) and / or (IV
The polymerizable double bond group represented by the general formula (III) is directly bonded to only one end of the polymer main chain composed of the repeating unit represented by b), or is bonded by any linking group. It has a different chemical structure. The group connecting the formula (III) component and the formula (IV a) or (IV b) component includes a carbon-carbon bond (single bond or double bond), a carbon-heteroatom bond (hetero atom is, for example, an oxygen atom). , Sulfur atom, nitrogen atom, silicon atom, etc.), and any combination of atomic groups of heteroatom-heteroatom bond.

Preferred among the macromonomers (MB) of the present invention are those represented by the formula (VI a) or (VI b).

In formula (VI a) or (VI b), c ₁ , c ₂ , d ₁ , d ₂ , V ₀ ,
V ₁ , Q ₁ and Q ₀ are the formula (III), the formula (IV a) and the formula (IV
Represents the same content as described in b).

W ₀ is a simple bond or [H ₁ and h ₂ represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.) ], CH = CH, -O-, -S-, -COO -, - SO ₂ -, -NHCOO-, -NHCONH-, [H ₃ and h ₄ each represent a hydrogen atom, a hydrocarbon group having the same content as Q ₁ in the above formula (IV a)] or the like, and a single linking group selected from atomic groups or any combination thereof. Represents a linked group.

When the weight average molecular weight of the macromonomer (MB) exceeds 2 × 10 ⁴ , the copolymerizability with the monomer represented by the formula (V) decreases. On the other hand, if the molecular weight is too small, the effect of improving the electrophotographic properties of the photosensitive layer will be small, so that it is preferably 1 × 10 ³ or more.

The macromonomer (MB) used for the resin [B] in the present invention can be produced by a conventionally known synthesis method. For example, a method by an ionic polymerization method in which various reagents are reacted with the ends of a living polymer obtained by anionic polymerization or cationic polymerization to form a macromer,
Oligomers of terminal reactive group bond obtained by radical polymerization using a polymerization initiator and / or chain transfer agent containing a reactive group such as carboxyl group, hydroxyl group, amino group in the molecule and various reagents By a radical polymerization method of reacting with a polymer to form a macromer, a polyaddition condensation method of introducing a polymerizable double bond group into the oligomer obtained by a polyaddition or polycondensation reaction in the same manner as the above radical polymerization method. Is mentioned.

Specifically, P.Dreyfuse & RPQuirk, Encycl.Poly
m.Sci.Eng., 7 , 551 (1987), PFRempp, E.Franta, Adv.P
olym. Sci., 58 , 1 (1984), V. Percec, Appl. Polym. Sci., 28
5 , 95 (1984), R. Asami, M.TaKaRi, Makvamol.Chem.Supp
l., 12 , 163 (1985), P. Rempp et al, Makvamol. Chem. Supp
l., 8 , 3 (1984), Yusuke Kawakami, Chemical Industry, 38 , 56 (198
7), Yuya Yamashita, Polymer, 31 , 988 (1982), Shiro Kobayashi,
Polymer, 30, 625 (1981), Higashimura Satoshinobe, Journal of the Adhesion Society of Japan 1
8, 536 (1982), Koichi Ito, polymer processing, 35, 262 (198
6), can be synthesized according to the method described in the reviews such as Kishiro Higashi, Takashi Tsuda, Functional Materials, 1987 No. 10,5, and references and patents cited therein.

The macromonomer (MB) of the present invention is specifically,
The following compounds may be mentioned as examples: However, the scope of the present invention is not limited to these.

However, in each of the following examples, c ₁ represents -H or -CH ₃ , d ₁ represents -H or -CH ₃ , and d ₂ represents -H, -CH ₃ or -CH ₂ COOCH ₃ . , R ₁₁ is -C _d H _{2d + 1} , -CH ₂ C ₆ H ₅ , -C ₆
H ₅ or Wherein R ₁₂ is -C _d H _{2d + 1} , CH _{2 e} C ₆ H ₅ or Are shown, R ₁₃ is -C _d H _{2d +} 1, shows a -CH ₂ C ₆ H ₅ or -C ₆ H _5, R ₁₄ represents a -C _d H _{2d + 1} or -CH ₂ C ₆ H ₅ , R ₁₅ is -C _d H
_{2d + 1, -CH 2 C 6} H 5 or R ₁₆ represents -C _d H _{2d + 1} , R ₁₇ represents -C _d H _{2d + 1} , -CH
₂ C ₆ H ₅ or Wherein R ₁₈ is -C _d H _{2d + 1} , -CH ₂ C ₆ H ₅ or V ₁ represents -COOCH ₃ , -C ₆ H ₅ or -CN, and V ₂ represents-
OC _d H _{2d + 1} , -OCOC _d H _{2d + 1} , -COOCH ₃ , -C ₆ H ₅ or -CN, and V ₃ is -COOCH ₃ , -C ₆ H ₅ , Or indicates -CN, V ₄ is _{-OCOC d H 2d + 1, -CN} , shows a -CONH ₂ or -C ₆ H _5, V ₅ represents -CN, a -CONH ₂ or -C ₆ H _5, V ₆ is -COOCH ₃ , -C ₆ H ₅ or And T ₁ represents -CH ₃ , -Cl, -Br or -OCH ₃ , and T ₂
Represents a -CH _3, -Cl or -Br, T ₃ is -H, -Cl, -B
r, -CH _3, shows a -CN or -COOCH _3, T ₄ is -CH _3, -Cl
Or indicates -Br, T ₅ is -Cl, -Br, -F, -OH or -CN
Wherein T ₆ is -H, -CH ₃ , -Cl, -Br, -OCH ₃ or -C
Indicates OOCH _3, d is an integer of 1 to 18, e is an integer of 1 to 3, f is an integer of 2-4.

The monomer copolymerized with the macromonomer (MB) is represented by the general formula (V). In the formula (V), e ₁ ,
e ₂ may be the same or different from each other;
Represents the same content as c ₁ and c ₂ . V ₂ is V ₁ of the formula (IV a),
Q ₂ has the same contents as Q _{1 in} formula (IV a).

Further, the resin [B] of the present invention may contain other monomers as copolymer components in addition to the above-mentioned macromonomer (MB) and the monomer of the general formula (V).

For example, vinyl compounds containing an acidic group, α-olefins, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, styrene, vinyl group-containing naphthalene compounds (for example, vinyl-naphthalene,
-Isoperopenylnaphthalene, etc.) vinyl group-containing heterocyclic compounds (for example, vinylpyridine, vinylpyrrolidone, vinylthiophene, vinyl-tetrahydrofuran, vinyl-
Compounds such as 1,3-dioxolan, vinylimidazole, vinylthiazole, and vinyloxazoline).

In the resin [B], the composition ratio of the copolymer component having a macromer (MB) as a repeating unit and the copolymer component having a monomer represented by the general formula (V) as a repeating unit is 1 to 80/9.
9-20 (weight composition ratio), preferably 5-60 / 95-40
It is a weight composition ratio.

The above-mentioned vinyl compound containing an acidic group 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-acetoxy form)
(2-amino) methyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α-chloro-β-
Methoxy, α, β-dichloro), 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,
-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, vinyl Examples include half-ester derivatives of vinyl or allyl groups of sulfonic acids, vinylphosphonic acids and dicarboxylic acids, and ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing an acidic group in the substituents of the amide derivatives.

When the "vinyl compound containing an acidic group" is contained as a repeating unit as another copolymerization component, the acidic group-containing copolymerization component preferably does not exceed 10% by weight in the copolymer.

When the content of the acidic group-containing component exceeds 10% by weight, the interaction with the inorganic photoconductor particles becomes remarkable, and the smoothness of the photoreceptor surface is impaired. As a result, electrophotographic properties (particularly, chargeability, charge in the dark) (Retention) is deteriorated.

Further, the resin [B ′] which can be used as a preferred embodiment of the present invention contains at least one repeating unit represented by the general formula (V) and at least one repeating unit represented by the macromonomer (MB). Only at one end of the polymer main chain to -PO ₃ H ₂ group, -SO ₃ H group, -COOH group, -O
H group, -SH group and (R ₀ represents a hydrocarbon group or a —OR ₀ ′ (R ₀ ′ represents a hydrocarbon group) group}, and is a polymer having at least one acidic group bonded thereto.

Here, R ₀ , as the hydrocarbon group represented by R ₀ ′, an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group,
Octyl, decyl, dodecyl, tetradecyl,
Octadecyl group, 2-methoxyethyl group, 3-methoxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, etc.) and aralkyl groups having 7 to 9 carbon atoms which may be substituted (eg, benzyl group, phenethyl group, 3 -Phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group, chlorobenzyl group, etc.), alicyclic group having 5 to 8 carbon atoms (eg cyclobenzyl group, cyclohexyl group, etc.), substitution having 6 to 12 carbon atoms Optionally aromatic group (eg, phenyl group, tolyl group, xylyl group, naphthyl group,
Chlorophenyl group, bromophenyl group, alkoxyphenyl group (as alkyl group, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, etc.), acetoxyphenyl group, methyl -Chloro-phenyl group, propylphenyl group, butylphenyl group, decylphenyl group, etc.) and the like.

When the acidic group is bonded to one end of the polymer main chain, the polymer main chain does not contain a copolymerization component containing a polar group such as a carboxyl group, a sulfo group, a hydroxyl group, or a phosphono group. It is preferable.

In the resin [B '], the acidic group has a chemical structure in which it is directly bonded to one end of the polymer main chain or is bonded via an arbitrary linking group.

Examples of the bonding group include a carbon-carbon bond (single bond or double bond), a carbon-heteroatom bond (for example, an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom), and a heteroatom-heteroatom bond. It is composed of any combination of atomic groups. For example, [H ₅ and h ₆ represent the same contents as the above h ₁ and h ₂ ) CH = CH
, (Where h ₇ and h ₈ represent the same contents as h ₃ and h ₄ above)
And the like, or a single linking group selected from an atomic group such as the above, or a linking group composed of an arbitrary combination.

In the resin [B '], the content of the acidic group bonded only to one end of the polymer main chain is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight per 100 parts by weight of the resin [B']. %. If the amount is less than 0.1% by weight, the effect of improving the film strength is small, and if the amount is 15% by weight or more, the photoconductor is not uniformly dispersed at the time of preparing the photoconductor dispersion, so that aggregation occurs, and a uniform coating film is not formed.

The resin [B '] of the present invention comprising a specific acidic group bonded to only one terminal of the polymer main chain is prepared by reacting various reagents with the terminal of a living polymer obtained by conventionally known anionic or cationic polymerization. Method (method by ionic polymerization), method of radical polymerization using a polymerization initiator and / or chain transfer agent containing a specific acidic group in the molecule (method by radical polymerization), or ionic polymerization as described above Alternatively, it can be easily produced by a synthesis method such as a method of converting a polymer having a terminal reactive group obtained by a radical polymerization method into a specific acidic group of the present invention by a polymer reaction.

Specifically, P. Dreyfuss, RPQuirk, Encycl.Polym.Sc
i.Eng., 7 : 551 (1987), Yoshiki Chujo, Yuya Yamashita, "Dyes and Chemicals", 30 , 232 (1985), Akira Ueda, Susumu Nagai, "Science and Industry" 60 , 57 (1986) In addition, it can be produced by the method described in the cited document or the like.

The ratio of the amount of the resin [A] used in the present invention to the amount of the resin [B] (including [B ']) varies depending on the type, particle size and surface state of the inorganic photoconductive material used, but generally the resin [A]
And the resin [B] are used in a ratio of 5 to 80 to 95 to 20 (weight ratio).
And preferably 10 to 60 to 90 to 40 (weight ratio).

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. Preferably, zinc oxide, titanium oxide and the like are used.

The total amount of the binder resin used for the inorganic photoconductive material is 10 to 100 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the photoconductor.

In the present invention, various dyes can be used as spectral sensitizers as needed. For example, Harumiya Miyamoto, Hidehiko Takei, Imaging 1973 (No.8) page 12, CJ Young, R
CA Review 15 , 469 (1954), Kouhei Kiyota, The Institute of Electrical Communication, J63-C (No.2), 97 (1980), Yuji Harasaki, etc.,
Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, which are cited as references in industrial chemistry magazines 66 , 78 and 188 (1963), Tadaaki Tani, Japan Photographic Society magazine 35 , 208 (1972), etc. Examples thereof include polymethine dyes (for example, oxonol, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes), phthalocyanine dyes (which may contain a metal), and the like.

More specifically, those using mainly carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes are described in JP-B-51-452,
0-90334, JP-A-50-114227, JP-A-53-39130
And JP-A-53-82353, U.S. Pat. No. 3,052,540, U.S. Pat. No. 4,054,450, and JP-A-57-16456.

Polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes, and rhodacyanine dyes are FM
Hammer, `` The Cyanine Dyes and Related Compounds ''
Can be used, more specifically, more specifically,
U.S. Patent No. 3047384, U.S. Patent No.3110591, U.S. Patent No.3121008, U.S. Patent No.3125447, U.S. Patent No.
No. 9, U.S. Pat.No. 3,31,942, U.S. Pat.No. 36224317, U.K. Pat.No. 1226892, U.K. Pat.No. 1309274, U.K. Pat.
Dyes described in JP 1405898, JP-B-48-7814, JP-B-55-18892 and the like can be mentioned.

Further, as a polymethine dye for spectrally sensitizing the near infrared to infrared light region having a long wavelength of 700 nm or more, JP-A-47-840, JP-A-47-44180, JP-B-51-41061, 1949-5034
No., JP-A-49-45122, JP-A-57-46245, JP-A-56
No. -35141, JP-A-57-157254, JP-A-61-26044,
JP-A-51-27551, U.S. Pat.No. 3619154, U.S. Pat.
4175956, "Research Disclosure", 1982, 216, No. 1
And those described on pages 17 to 118 and the like.

The photoreceptor of the present invention is also excellent in that even when various sensitizing dyes are used in combination, the performance is not easily changed by the sensitizing dye.

Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers, such as an sensitizer for a charge amount, can be used in combination. For example, the above-mentioned general installation: Imaging 1973 (No.8)
"Recent development and commercialization of photoconductive materials and photoreceptors", e.g., electron accepting compounds (eg, halogen, benzoquinone, cranyl, acid anhydride, organic carboxylic acid, etc.) described in the reviews on page 12, etc. Chapters 4 to 6: Polyarylalkane compounds, which are reviewed in Japanese Science Information Publishing Co., Ltd. (1986)
Hindered phenol compounds, p-phenylenediamine compounds, and the like.

The amount of these various additives is not particularly limited,
Usually, it is 0.001 to 2.0 parts by weight based on 100 parts by weight of the photoconductor.

The thickness of the photoconductive layer is preferably from 1 to 100 μm, particularly preferably from 10 to 50 μm.

When a photoconductive layer is used as the charge generation layer of the photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is preferably 0.01 to 1 μm, particularly preferably 0.05 to 0.5 μm.

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

In the latter case, the thickness of the insulating layer is between 5 and 70 μm, especially 10
Set to ~ 50μ.

Examples of the charge transport material of the laminated photoreceptor include polyvinyl carbazole, oxazole dyes, pyrazoline dyes, and triphenylmethane dyes. The thickness of the charge transport layer is preferably 5 to 40 μm, particularly preferably 10 to 30 μm.

As the resin used for forming the insulating layer or the charge transport layer, typical ones are polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-copolymer resin, A thermoplastic resin and a curable resin such as a polyacryl resin, a polyolefin resin, a urethane resin, an epoxy resin, a melamine resin, and a silicone resin are appropriately used.

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

Specifically, as an example of a conductive substrate or a conductive material, Yukio Sakamoto, Electrophotography, 14, (No. 1), pp. 2-11 (1975), Hiroyuki Moriga, “Chemistry of Introductory Specialty Paper” Molecular Publishing Association (1975), MFHoover, J. Macromol. Sci. Chem. A-4
(6), those described in pages 1327 to 1417 (1970) and the like are used.

(Examples) Examples of the present invention will be described 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 200 of tetrahydrofuran
g of the mixed solution was sufficiently degassed under a nitrogen stream and cooled to -20 ° C. 1.5 g of 1,1-diphenylbutyllithium was added and 12
Reacted for hours. Further, to this mixed solution, a mixed solution of 5 g of triphenylmethyl methacrylate and 5 g of tetrahydrofuran was sufficiently degassed under a nitrogen stream, and then added, and the mixture was further reacted for 8 hours. The mixture was brought to 0 ° C.,
ml was added and reacted for 30 minutes to terminate the polymerization. The temperature of the resulting polymer solution was adjusted to 30 ° C. with stirring, to which 3 ml of a 30% ethanol solution of hydrogen chloride was added, followed by stirring for 1 hour. Next, the solvent was distilled off under reduced pressure until the total amount of the reaction mixture became half, and the reaction mixture was reprecipitated in petroleum ether 1.

The polymer obtained by collecting the precipitate and drying under reduced pressure is:
The yield was 70 g with a weight of 8.5 x 10 ³ .

[A-1] (Weight ratio) b: Shows a block bond (same below) Synthesis Example 2 of resin [A]: [A-2] 46 g of n-butyl methacrylate, 0.5 g of (tetraphenylporphenate) aluminum methyl and 60 g of methylene chloride. The temperature of the mixed solution was 30 ° C. under a nitrogen stream. This was irradiated with light from a 300 W-xenon lamp through a glass filter from a distance of 25 cm, and reacted for 12 hours. To this mixture was further added 4 g of benzyl methacrylate.
After irradiating with light for a period of time, 3 g of methanol was added to this reaction mixture and stirred for 3 minutes to stop the reaction. Next, Pd-C was added to the reaction mixture, and a catalytic reduction reaction was performed at a temperature of 25 ° C. for 1 hour.

After filtering off the insoluble matter, the precipitate was reprecipitated in 500 ml of petroleum ether,
The precipitate was collected and dried. The obtained polymer was obtained in a yield of 33 g.
It was w9.3 × 10 ³ .

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

The reaction mixture is then added to a 10% 30% hydrogen chloride ethanol solution.
g, and the mixture was stirred at 25 ° C. for 1 hour. The precipitate was reprecipitated in petroleum ether 1 and the collected precipitate was extracted with 300 ml of diethyl ether.
Washed and dried twice. The obtained polymer was w7 with a yield of 58 g.
It was 8 × 10 ³ .

[A-3] Synthesis Example 4: 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 vessel under a nitrogen stream, and heated to a temperature of 60 ° C. This was irradiated with light for 10 hours through a glass filter from a distance of 10 cm with a 400 W high-pressure mercury lamp, and photopolymerized.

To this were added 5 g of acrylic acid and 180 g of methyl ethyl ketone, followed by purging with nitrogen and light irradiation again for 10 hours.

The obtained reaction product was reprecipitated in hexane 1.5, collected and dried. The obtained polymer had a weight of 9.5 × 10 ³ in 68 g.

[A-4] (Production Example of Resin [B]) Production Example 1 of Resin [B] 1: Resin [B-1] 70 g of ethyl methacrylate, macromonomer (M-
1) A mixed solution of 30 g and 150 g of toluene was heated under a nitrogen stream at a temperature of 7
Warmed to 0 ° C. Next, 0.5 g of AIBN was added and reacted for 4 hours. Further, 0.3 g of AIBN was added and reacted for 6 hours.
The weight average molecular weight of the obtained copolymer [B-1] is 9.8 × 1
Glass transition point was 72 ° C. at 0 ⁴ Resin [B-1] (Weight Ratio) Production Examples 2 to 15 of Resin [B]: Resins [B-2] to [B-1]
5] Under the same polymerization conditions as in Production Example 1 of Resin [B], the following Table-
Resin No. 1 [B] was produced. The w of each resin is 8 × 10 ⁴ ~
The range was 1.5 × 10 ⁵ .

Production Example 16 of Resin [B]: Resin [B-16] 70 g of ethyl methacrylate, macromonomer (M-
2) A mixed solution of 30 g, 150 g of toluene and 50 g of isopropanol was heated to a temperature of 70 ° C. under a nitrogen stream. Next, 4,4 '
0.8 g of -azobis (4-cyanovaleric acid was added and reacted for 10 hours. The weight average molecular weight (w) of the obtained copolymer was
The glass transition point was 72 ° C. at 9.8 × 10 ⁴ .

Resin [B-16] Production Examples 17 to 24 of Resin [B]: Resins [B-17] to [B-2]
4] In Production Example 16 of Resin [B], the macromonomer (M
Each resin [B] was produced in the same manner as in Production Example 16 except that macromonomers shown in Table 2 below were used instead of -2). The w of each resin was 9 × 10 ^{4 to} 1.2 × 10 ⁵ .

Production Examples 25 to 31 of Resin [B]: Resins [B-25] to [B-3]
1] In Production Example 16 of Resin [B], instead of ACV,
The production example except that the azobis compounds shown in Table 3 below were used.
By operating in the same manner as in 16, each polymer was produced.

Production Example 32 of Resin [B]: Resin [B-32] 80 g of butyl methacrylate, macromonomer (M-
8) A mixed solution of 20 g, 1.0 g of thioglycolic acid, 100 g of toluene and 50 g of isopropanol was heated to 80 ° C. under a nitrogen stream.
Was heated. 1,1'-azobis (cyclohexane-1-
(Carbonitrile) (abbreviation: ACHN) (0.5 g) was added and stirred for 4 hours. ACHN (0.3 g) was further added and stirred for 4 hours. The w of the obtained polymer was 8.0 × 10 ⁴ and the glass transition point was 41 ° C.

Resin [B-32] Production Examples 33 to 39 of Resin [B]: Resins [B-33] to [B-3]
9] A polymer was produced in the same manner as in Production Example 32 of Resin [B] except that the compounds shown in Table 4 below were used instead of thioglycolic acid.

Production Examples 40 to 48 of Resin [B]: Resins [B-40] to [B-4]
8] The following Table 5 was used under the same polymerization conditions as in Production Example 26 of Resin [B].
Was produced.

The w of each resin ranged from 9.5 × 10 ^{4 to} 1.2 × 10 ⁵ .

Production Examples 49 to 56 of Resin [B]: [B-49] to [B-56] Under the same polymerization conditions as in Production Example 16 of Resin [B],
The resins shown in Table 6 below were produced. Each resin obtained [B]
W was 9.5 × 10 ^{4 to} 1.1 × 10 ⁵ .

Example 1 and Comparative Examples AC Resin [A-4] 6 g (as solid content), Resin [B-1
9] 34 g (as solid content), a mixture of cyanine dye [I] 0.018 g having the following structure and toluene 300 g was dispersed in a ball mill for 4 hours to prepare a photosensitive layer-forming material, which was applied to a conductive-treated paper. Apply with a wire bar so that the dry adhesion amount becomes 25 g / m ² , dry at 110 ° C for 30 seconds, and then 2 in the dark.
An electrophotographic light-sensitive material was prepared by being left at 0 ° C. and 65% RH for 24 hours.

Cyanine dye [I] Comparative Example A: Instead of the binder resin used in Example 1, 6 g of resin [R-1] having the following structure and 34 g of poly (ethyl methacrylate) (w2.4 × 10 ⁵ ): resin [R-2] were used. An electrophotographic photosensitive material was prepared in the same manner as in Example 1 except for using it.

Comparative Example B: The procedure of Example 1 was repeated, except that 6 g of the resin [R-3] and 34 g of the resin [R-2] having the following structure were used instead of the binder resin used in Example 1. A photographic light-sensitive material was prepared.

Comparative Example C: The procedure of Example 1 was repeated, except that 6 g of resin [R-3] and 34 g of resin [R-4] having the following structure were used instead of the binder resin used in Example 1. A photographic light-sensitive material was prepared.

The film properties (surface smoothness), electrostatic properties, imaging properties, and imaging properties of these photosensitive materials when the environmental conditions were 30 ° C. and 80% RH were examined. Further, when these photosensitive materials are used as an offset master, the photoconductive desensitizing property (expressed by the contact angle of the photoconductive layer with water after the desensitizing treatment) and printability (ground stain, Printing durability).

 Table 7 summarizes the above results.

The embodiments of the evaluation items shown in Table-7 are as follows.

Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was measured for its smoothness (sec / cc) using a Beck smoothness tester (manufactured by Kumagaya Riko Co., Ltd.) under the condition of an air capacity of 1 cc. It was measured.

Note 2) Mechanical strength of photoconductive layer: The surface of the obtained photosensitive material was emery paper (#) with a load of 60 g / cm ² using a Haydon-14 type surface test material (manufactured by Shinto Chemical Co., Ltd.). The abrasion powder was removed 1000 times repeatedly to remove the abrasion powder, and the remaining film rate (%) was determined from the weight loss of the photosensitive layer, and the resulting value was defined as the mechanical strength.

Note 3) Electrostatic properties: Paper sensitizers (Kawaguchi Electric Co., Ltd. Paper Analyzer SP) are applied to each photosensitive material in a dark room at a temperature of 20 ° C and 65% RH
-428 type) and after corona discharge for 20 seconds at -6kV,
It was left for 10 seconds, and the surface potential V ₁₀ at this time was measured. Then measure the potential V ₁₈₀ after leaving still for 180 seconds in the dark as it is, holding the potential after dark decay for 180 seconds, that is,
Dark decay retention rate [DRR (%)] (V ₁₈₀ / V ₁₀ ) × 100 (%)
I asked for it.

After charging the surface of the photoconductive layer to −500 V by corona discharge, the surface is irradiated with monochromatic light having a wavelength of 785 nm, and the surface potential (V ₁₀ ) is reduced.
The time required to decay to 1/10 is determined, and the exposure E
Calculate _1/10 (erg / cm ² ). Furthermore, after charging to -500 V by corona discharge in the same manner as in E _1/10 measurement, irradiation with monochromatic light having a wavelength of 785 nm was performed, and the time until the surface potential (V ₁₀ ) attenuated to 1/100 was determined. The quantity E _1/100 (erg / cm ² ) is calculated.

Note 4) Image-capturability: Each photosensitive material was allowed to stand for one day under the following environmental conditions. Next, gallium-aluminum-arsenic of 2.8 mW output and semiconductor laser (oscillation wavelength 785 nm) charged at -5 kV were used, and a pitch of 25 μm and scanning speed were applied on the surface of the photosensitive material at an irradiation dose of 50 erg / cm ^2. After speed exposure at 330 m / sec, ELP-T (manufactured by Fuji Photo Film Co., Ltd.) was used as a liquid developer, and the copied image (fogging, image quality) obtained by fixing was visually evaluated. .

Environmental conditions at the time of imaging were 20 ° C 65% RH and 30 ° C 80% RH.

Note 5) Contact angle with water: Each light-sensitive material was passed through an etching processor once using a desensitizing solution EPL-EX (manufactured by Fuji Photo Film Co., Ltd.) diluted twice with distilled water. After desensitizing the surface of the photoconductive layer with water, a drop of distilled water 2III- is placed on the surface, and the contact angle with the formed water is measured with a goniometer.

Note 6) Printing durability: Each light-sensitive material is subjected to plate making under the same conditions as in Note 4) above to form a toner image, and subjected to desensitization treatment under the same conditions as in Note 5) above, and this is used as an offset master. The number of sheets that can be printed on an offset printing machine (Oliver 52 type, Sakurai Mfg. Co., Ltd.) without causing stains on the non-image area of the printed matter and on the image quality of the image area. Is good].

As shown in Table 7, the photosensitive material of the present invention had good strength and electrostatic properties of the smooth film of the photoconductive layer, and the actual copied image was free of background fog and the copied image quality was clear. This is presumed to be due to the photoconductor and the binder resin being sufficiently adsorbed and covering the particle surface. For the same reason, even when used as an offset master master, the desensitizing treatment with the desensitizing solution proceeds sufficiently, the contact angle with water of the non-image area is as small as 10 degrees or less, and the hydrophilicity is sufficiently increased. You can see that Even when the printed matter was actually examined and the background stain was observed, no background stain was observed.

Comparative Examples A to C are compared with the photosensitive material of the present invention.
The electrostatic characteristics have deteriorated. In Comparative Example C, the film strength was improved, and the electrostatic properties were also V ₁₀ , DRR, and E _1/10 .
Almost satisfactory values were obtained. However, looking at the E _1/100 value, it was more than twice as large as that of the light-sensitive material of the present invention. 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. This indicates that the value stains on the image area will not occur.

Specifically, it is necessary to set the residual potential to -10 V or less, that is, scanning with a semiconductor laser beam depends on how much exposure is required in order to actually make V _R -10 V or less. With the exposure method, a small exposure
To the V _R below -10V, the (cost of the device, the accuracy of an optical system an optical path) optical system design of the copying machine is very important for.

From the above, when an image was actually taken with an apparatus with a slightly reduced exposure dose, Comparative Example A had a remarkably low DRR, and a satisfactory copy image was not obtained. In Comparative Example B, the image deteriorated remarkably under the conditions of high temperature and high humidity, and the density of the image portion was reduced, thin lines and characters were blurred, and the ground fog was generated in the non-image portion. In Comparative Example C, the image was almost satisfactory under the condition of normal temperature and normal humidity, but under the condition of high temperature and high humidity, the occurrence of ground fogging and the thinning of the thin line in the image portion occurred. Further, even when used as an offset master, under the printing conditions that the photosensitive material of the present invention can print 10,000 sheets or more, in each of Comparative Examples A to C, non-image area stains are generated from printed printouts. have done.
This was because a clear copied image was not obtained, and ground fog could not be removed by the desensitizing treatment.

As described above, an electrophotographic photosensitive member that satisfies electrostatic characteristics and printability only when the resin of the present invention is used is obtained.

Examples 2 to 17 In Example 1, the resin [A-4] and the resin [B-1
9] was replaced with each resin [A] and each resin [B] shown in Table 11 below, and each electrophotographic photosensitive member was produced in the same manner as in Example 1.

The electrostatic characteristics were measured in the same manner as in Example 1. The results are shown in Table-8.

Example 1 was used as an offset master master.
When printing was performed in the same manner as described above, all of them could print 10,000 sheets or more.

From the above, each photosensitive material of the present invention, the smoothness of the photoconductive layer,
The film strength, electrostatic properties, and printability were all favorable.

Furthermore, it was found that the use of the resin [A '] further improved electrostatic characteristics.

Examples 18 to 33 In Example 1, the binder resin was replaced by 7.6 g of resin [A] and 34 g of resin [B] shown in Table 12 below, and instead of 0.02 g of cyanine dye [I], a dye having the following structure [ II) 0.019g
An electrophotographic photosensitive material was produced under the same conditions as in Example 1 except that the above was changed to.

Dye (II) The photosensitive materials of the present invention are all excellent in chargeability, dark charge retention, and photosensitivity.
(80 ° C., 80% RH), a clear image without fog was obtained.

Furthermore, when this was used as an offset master master, 10,000 or more printed materials with clear image quality without background fog could be printed.

Examples 34 and 35 and Comparative Example D Resin [A-1] (Example 34) or Resin [A-10] (Example 35) 6.5 g, Resin [B-16] 33.5 g, Zinc oxide 200 g , Uranine 0.02 g, rose bengal 0.04 g, bromphenol blue 0.03 g, phthalic anhydride 0.20 g and toluene 300 g were dispersed in a ball mill for 4 hours to prepare a photosensitive layer-forming material, which was then applied to electroconductive paper. Then, it was applied with a wire bar so that the dry adhesion amount was 20 g / m ^2, and dried at 110 ° C. for 1 minute. Then, in the dark, at 20 ° C and 65% RH
Each electrophotographic photoreceptor was prepared by being left for 24 hours.

Comparative Example D In Example 34, 6.5 g of resin [A-2] and 6.5 g of resin [B-
16] A photosensitive material was produced in the same manner as in Example 34 except that 6.5 g of resin [R-3] and 33.5 g of resin [R-4] were used instead of 33.5 g.

As in Example 1, each characteristic of each photosensitive material was examined. The results are summarized in Table 10 below.

In the above measurement, the same operation as in Example 1 was performed, except that the following operation was performed for the electrostatic characteristics and the image capturing property.

Note 7) 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, irradiating the surface of the photoconductive layer with visible light having an illuminance of 2.0 lux. The time required for the surface potential (V ₁₀ ) to decay to 1/10 or E _1/100 is determined, and the exposure amount E _1/10 or E _1/100 (lux seconds) is calculated from this.

Note 8) Imaging characteristics After each photosensitive material is left for one day and night under the following environmental conditions, E is used with a fully automatic plate making machine EPL-404V (Fuji Photo Film Co., Ltd.).
A copy image (fog, image quality) obtained by making a plate using PL-T as a toner was visually evaluated. Environmental conditions at the time of imaging were 20 ° C. and 65% RH (I) and 30 ° C. and 80% RH (II). However, a copy original (that is, a copy original) was prepared by cutting and pasting another original.

In each photosensitive material, no difference was observed in the smoothness and strength of the photoconductive layer. However, in Comparative Example D, the value of the light sensitivity E _1/100 was particularly large in the electrostatic characteristics. The photosensitive material of the present invention has good electrostatic characteristics, and furthermore, the photosensitive material of Example 35 using the resin [A] having a specific substituent was used.
Was very good, and the value of E _1/100 was particularly small.

Investigation of the actual imaging performance revealed that in Comparative Example D, in addition to the original as a copy image, the frame of the cut and pasted portion (that is, the pasted trace) was recognized as background stain in the non-image portion. However, in each case of the present invention, clear images without background stains were obtained.

Further, when these were subjected to desensitization processing as an offset printing original plate and then printed, 10,000 sheets of clear images having no background stain were obtained in any of the present invention. However, in Comparative Example D, the sticking marks were not removed even by the desensitizing treatment, and were generated from the printed material.

As described above, only the photosensitive material of the present invention was able to give good characteristics.

Examples 36 to 49 In Example 34, 6.5 g of resin [A-2] and resin [B
-16] Instead of 33.5g, resin [A] 6.5g in Table-11 below
Each photosensitive material was produced in the same manner as in Example 34 except that 33.5 g of the resin [B] was used.

All photosensitive materials of the present invention are chargeable, dark charge retention,
Excellent light sensitivity, real copy image is high temperature and humidity (30 ℃, 80%
Even under severe conditions (RH), a clear image was obtained without occurrence of ground fogging or fine line skipping.

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

Examples 50 and 51 6.5 g of either resin [A-14] (Example 50) or resin [A-15] (Example 51), resin [B-2] 33.5 g, zinc oxide 200 g, uranine 0.02 g. A mixture of 0.04 g of rose bengal, 0.03 g of bromphenol blue, 0.200 of phthalic anhydride and 300 g of toluene was dispersed in a ball mill for 3 hours. Next, 0.6 g of glutaric acid (Example 50) or 1,6-
Hexanediol 0.5 g (Example 51) was added, and further dispersed by a ball mill for 10 minutes.

This was applied to a conductive treated paper with a wire bar so that the dry adhesion amount was 20 g / m ² , dried at 110 ° C. for 1 minute, and further heated at 120 ° C. for 1.5 hours. Next, in a dark place, 20 ° C, 65% RH
Each electrophotographic photoreceptor was prepared by allowing to stand for 24 hours under the above conditions.

When these photosensitive materials were examined for electrostatic properties and imaging properties in the same manner as in Example 34, they showed good performance.

Further, when printed as an original plate for offset printing, it is possible to print more than 10,000 sheets.

(Effects of the Invention) According to the present invention, it is possible to obtain an electrophotographic photosensitive member having excellent electrostatic characteristics and mechanical strength even under severe conditions. Further, the photoreceptor of the present invention is effective for a scanning exposure method using a semiconductor laser beam.

Claims (3)

(57) [Claims] An electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material and a binder resin, wherein the binder resin is at least one of the following resins [A]:
An electrophotographic photosensitive member comprising a seed and at least one kind of resin [B]. Resin (A); 1 × 10 ³ has a weight average molecular weight of ~2 × 10 ^4, -PO ₃ H
₂ group, -COOH group, -SO ₃ H groups, phenolic OH groups, R represents a hydrocarbon group or an -OR 'group (R' is a hydrocarbon group) and A comprises at least one polymer component containing at least one acidic group selected from cyclic acid anhydride-containing groups. A resin containing an AB block copolymer composed of a block and a B block containing at least a polymer component represented by the following general formula (I). General formula (I) (In the formula (I), R ₁ represents a hydrocarbon group.) Resin [B]; a polymer containing at least one of the polymer components represented by the following general formulas (IV a) and (IV b). A monofunctional macromonomer having a weight average molecular weight of 2 × 10 ⁴ or less formed by bonding a polymerizable double bond group represented by the following general formula (III) to only one end of the united main chain and the following general formula (V) A resin which is a copolymer comprising at least a monomer represented by: General formula (III) Wherein (III), V ₀ is -COO -, - OCO -, - CH 2 OCO-,
_{-CH 2 COO -, - O -} , - SO 2 -, - CO -, - CONHCOO-,
−CONHCONH−, −CONHSO ₂ −, (P ₃ represents a hydrogen atom or a hydrocarbon group). c ₁ and c ₂ may be the same or different from each other, and represent a hydrogen atom,
It represents a halogen atom, a cyano group, a hydrocarbon group, -COO-Z 'or a hydrocarbon-mediated -COO-Z' (Z 'represents a hydrogen atom or an optionally substituted hydrocarbon group). ] [In the formula (IV a) or (IV b), V ₁ is V ₀ in the formula (III).
Represents the same content as. Q ₁ represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms. d ₁ and d ₂ may be the same or different from each other, and have the formula (III)
Represents the same content as c ₁ and c _{2 in} . Q ₀ is -CN, -CONH ₂ or Represents Here, T represents a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group or -COOZ "(Z" represents an alkyl group, an aralkyl group or an aryl group). General formula (V) [In the formula (V), V ₂ represents the same content as V ₁ in the formula (IV a). Q ₂ has the same meaning as Q ₁ in formula (IV a). e ₁ and e ₂ may be the same or different and represent the same contents as c ₁ and c _{2 in} formula (III). ] 2. The AB block copolymer, wherein the B block contains at least 30% by weight of at least one repeating unit selected from the following formulas (Ia) and (Ib). The electrophotographic photosensitive member according to claim 1. [In the formula (I a) or (I b), X ₁ and X ₂ are independent of each other,
Each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, -COZ ₂ or -COOZ ₂ (Z ₂ are each carbon atoms 1
~ 10 hydrocarbon groups). However, X ₁ and X ₂ are never both represent a hydrogen atom. L ₁ and L ₂ each connect -COO- and a benzene ring,
It represents a single bond or a linking group having 1 to 4 linking atoms. ] 3. The copolymer in the resin [B] further comprises:
PO ₃ H ₂ group, -SO ₃ H group, -COOH group, -OH group, and -SH group At least one acidic group selected from {R ₀ represents a hydrocarbon group or a --OR ₀ ′ group (R ₀ ′ represents a hydrocarbon group)} is bonded to one end of the main chain of the copolymer. The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is provided.