JP2520711B2 - Electrophotographic photoreceptor - Google Patents

Description

TECHNICAL FIELD The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having excellent electrostatic characteristics and moisture resistance. In particular, it relates to a CPC photosensitive member having excellent performance.

(Prior Art) An electrophotographic photosensitive member has various configurations in order to obtain predetermined characteristics or according to the type of an applied electrophotographic process.

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

Photoreceptors composed of a support and at least one photoconductive layer are used for image formation by the most common electrophotographic processes, ie charging, imagewise exposure and development, and optionally transfer.

Further, a method of using an electrophotographic photosensitive member as an offset original plate for direct plate making is widely used. Particularly in recent years, the direct electrophotographic lithographic printing plate has become important as a method for printing high-quality printed matter by printing several hundred to several thousand sheets.

The binder 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, and the formed recording medium layer The adhesion to the substrate is good, and the photoconductive layer of the recording layer has excellent charging ability, low dark decay, large light decay, low pre-exposure fatigue, and changes in humidity during imaging. It is necessary to have various electrostatic characteristics, such as a need to stably maintain the characteristics, and excellent imaging properties.

For example, silicone resins (Japanese Patent Publication No. 34-6670), styrene-butadiene resins (Japanese Patent Publication No. 35-1960), alkyd resins, maleic acid resins,
Polyamide (JP-B 35-11219), vinyl acetate resin (JP-B 41-2425), vinyl acetate copolymer (JP-B 41-2426)
No., acrylic resin (JP-B-35-11216), acrylate copolymer (for example, JP-B-35-11219, JP-B-36
No. -8510, Japanese Patent Publication No. 41-13946, etc.).

However, in the electrophotographic photosensitive materials using these resins, 1) the affinity for the photoconductive powder is insufficient and the dispersibility of the coating liquid becomes poor, and 2) the chargeability of the photoconductive layer is poor. Low,
3) Poor quality of the image portion (particularly halftone dot reproducibility / resolution) of the copied image; 4) The image quality is easily affected by the environment (for example, high temperature, high humidity, low temperature, low humidity, etc.) at the time of creating the copied image. There was a problem.

Various methods have been proposed as a method for improving the electrostatic properties of the photoconductive layer. One of the methods is, for example, a compound containing a carboxyl group or a nitro group on an aromatic ring or a furan ring, or a dicarboxylic acid anhydride. Methods of further combining materials and coexisting in a photoconductive layer are disclosed in JP-B-42-6878 and JP-B-45-3073. However, even the photosensitive materials improved by these methods do not have sufficient electrostatic characteristics, and a material having particularly excellent light attenuation characteristics has not been obtained. Therefore, in order to improve the lack of sensitivity of this photosensitive material,
Conventionally, a method of adding a large amount of a sensitizing dye in a photoconductive layer has been adopted.However, a photosensitive material produced by such a method has a remarkable deterioration in whiteness and a decrease in quality as a recording medium. In some cases, the dark decay of the photosensitive material is deteriorated, and a sufficient copied image cannot be obtained.

On the other hand, Japanese Patent Application Laid-Open No. 60-10254 discloses a method in which the average molecular weight of the resin is adjusted and used as the binder resin used in the photoconductive layer. That is, by using an acrylic resin having an acid value of 4 to 50 and a component having a distribution having an average molecular weight of 10 ³ to 10 ⁴ and a component having a distribution having a distribution of 10 ⁴ to 2 × 10 ⁵ , the electrostatic properties ( Especially
A technique for improving repetition reproducibility as a PPC photoreceptor), moisture resistance and the like is described.

Further, research on a lithographic printing plate precursor using an electrophotographic photosensitive member has been earnestly conducted, and a binder resin for a photoconductive layer which has both electrostatic properties as an electrophotographic photosensitive member and printing properties as a printing plate precursor. As, for example, in Japanese Examined Patent Publication No. 50-31011, (meth) acrylate-based monomer was copolymerized with other monomers in the presence of fumaric acid, _Mw 1.8 ~ 10 × 10 ⁴ Tg 10 ~ 80 ℃.
And a copolymer comprising a (meth) acrylate-based monomer and a monomer other than fumaric acid, and JP-A-53-54027 discloses that a carboxylic acid group has at least a number of atoms from an ester bond. In the case of using a terpolymer containing a (meth) acrylate ester having a substituent which is separated by 7 groups, JP-A-54-20735 and JP-A-57-202544 disclose acrylic acid and hydroxyethyl ( Use of a quaternary or pentameric copolymer containing (meth) acrylate, and JP-A-58-68046 discloses a (meth) acrylic ester and a carboxylic acid containing an alkyl group having 6 to 12 carbon atoms as a substituent. It is described that the use of a terpolymer containing a vinyl monomer is effective in improving the desensitizing property of the photoconductive layer.

(Problems to be Solved by the Invention) However, even if the resin is said to be effective in the above-mentioned electrostatic properties and moisture resistance properties, particularly when it is actually evaluated, it is particularly chargeability, dark charge retention, and photosensitivity. However, there was a problem in the electrostatic characteristics as described above, the smoothness of the photoconductive layer, and the like, which were not practically satisfactory.

Further, even in the case of a binder resin which was developed as an electrophotographic planographic printing plate precursor, when actually evaluated, there were problems with the above-mentioned electrostatic characteristics, background contamination of printed matter, and the like.

The present invention solves the above problems of the conventional electrophotographic photoreceptor.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high-quality electrophotographic photoreceptor having improved electrostatic characteristics (particularly dark charge retention and photosensitivity) and reproducing a copied image faithful to an original image.

Another object of the present invention is to provide an electrophotographic photoreceptor 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.

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

It is another object of the present invention to provide a lithographic printing plate that provides a printed matter that does not cause background stain at all as an electrophotographic lithographic printing original plate.

Another object of the present invention is to provide an electrophotographic photoreceptor that is hardly affected by the type of sensitizing dye that can be used in combination.

(Means for Solving the Problems) The above-mentioned problem is solved in an electrophotographic photosensitive member 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]. It has been found that the problem can be solved by an electrophotographic photoreceptor characterized by containing a seed and at least one of the following resins [B].

Resin [A] having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , and-
PO ₃ H ₂ group, -SO ₃ H group, -COOH group, {R represents a hydrocarbon group having 1 to 10 carbon atoms or an OR 'group (R' represents a hydrocarbon group having 1 to 10 carbon atoms), --SH group, acidic group such as phenolic OH group and cyclic acid A resin obtained by bonding at least one substituent of an anhydride-containing group to an end of a polymer main chain.

Resin [B] The polymerizability represented by the following general formula (I) is present only at one end of the polymer main chain containing at least one polymer component represented by the following general formulas (IIa) and (IIb). A resin, which is a copolymer comprising at least a monofunctional macromonomer having a weight average molecular weight of 2 × 10 ⁴ or less formed by binding a double bond group and a monomer represented by the following general formula (III).

General formula (I) Wherein (I), V is -COO -, - OCO -, - CH 2 OCO -, -
_{CH 2 COO -, - O -} , - SO 2 -, - CO-, Or (R ₁ represents a hydrogen atom or a hydrocarbon group).
a ₁ and a ₂ may be the same or different from each other, and represent a hydrogen atom,
Represents a halogen atom, a cyano group, a hydrocarbon group, -COO-Z, or -COO-Z via a hydrocarbon (Z represents a hydrogen atom or a hydrocarbon group which may be substituted). ] General formula (IIa) General formula (IIb) [In formula (IIa) or (IIb), X ₀ has the same meaning as V in formula (I).

Q ₀ represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms. b ₁ and b ₂ may be the same as or different from each other, and have the same contents as a ₁ and a ₂ in the formula (I).

Q is -CN, -CONH ₂ or Where Y represents a hydrogen atom, a halogen atom, an alkoxy group or -COOZ '(Z' represents an alkyl group, an aralkyl group or an aryl group). General formula (III) (In the formula (III), X ₁ represents the same content as X ₀ in the formula (IIa), and Q ₁ represents the same content as Q ₀ in the formula (IIa). C ₁ , c ₂ May be the same or different from each other and have the formula (I)
It has the same contents as a ₁ and a _{2 in the above} . That is, the binder resin used in the present invention includes an acidic group and / or a cyclic acid anhydride-containing group (hereinafter, unless otherwise specified in the present specification, a cyclic acid anhydride-containing group is included in the term of acidic group). A resin having a low molecular weight [A] which does not contain in the side chain connecting to the polymer main chain but binds only to the end of the main chain.
And a resin [B] made of a comb-type copolymer containing at least one kind of each of the macromonomer (M) and the monomer represented by the general formula (III).

In the present invention, in the resin [A] in which the acidic group contained in the resin is bonded to the terminal of the polymer main chain, the acidic group bonded to the terminal of the polymer causes a stoichiometric defect of the inorganic photoconductor. Adsorb,
In addition, since it is a low molecular weight substance, the trapping of the photoconductor is compensated by improving the coverage of the surface of the photoconductor and the humidity characteristics are dramatically improved, while the photoconductor is sufficiently dispersed. It was found that the aggregation was suppressed. The resin [B] does not hinder the high performance of the electrophotographic properties due to the use of the resin [A], and can sufficiently increase the mechanical strength of the photoconductive layer, which is insufficient with the resin [A] alone. It is.

Moreover, in the present invention, the smoothness of the photoconductor surface is smooth. 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 inorganic particles as the photoconductor and the binder resin is not appropriate, and the photoconductive layer is in a state where the aggregates are present. Since the layer is formed, even if the desensitizing treatment with the desensitizing solution is performed, the non-image area is not uniformly and sufficiently hydrophilized, causing the printing ink to adhere during printing, and as a result, the non-image The part will be soiled.

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. Although good image quality can be obtained with good electrostatic characteristics and no background contamination, the film strength is not yet sufficient, and satisfactory results in durability cannot be obtained.

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

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 ″ represents a hydrocarbon group), and is preferably a resin (hereinafter also referred to as a resin [B ′]) in which at least one acidic group selected from the group is further bonded.

When the resin [B '] is used, the electrostatic properties, especially DRR and E
_1/10 is better, does not hinder the excellent properties of using resin [A] at all, and its effect is particularly high temperature, high humidity,
It is preferable that there is almost no change even in environmental changes such as low temperature and low humidity. Further, the film strength is further improved, and the printing durability is improved.

In the resin [A], the weight average molecular weight is 1 × 10 ³ to 2
× 10 ⁴ , preferably 3 × 10 ³ to 1 × 10 ⁴ , the content of the acidic group bonded to the terminal is 0.5 to 15% by weight, preferably 1 to 1% by weight.
It is 0% by weight. The glass transition point of the resin [A] is preferably -10 ° C to 100 ° C, more preferably -5 ° C to 80 ° C.
Is.

If 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. On the other hand, when the molecular weight is larger than 2 × 10 ⁴ , the electrophotographic characteristics (particularly, initial potential and dark decay retention) deteriorate, which is not preferable. In particular, in the case of such a high molecular weight product, when the content of the acidic group exceeds 3%, such deterioration of the electrophotographic characteristics is remarkable, and when used as an offset master, background stain becomes remarkable.

When the content of the terminal acidic group in the resin [A] is less than 0.5% by weight, the initial potential is low and a sufficient image density cannot be obtained. On the other hand, when the content of the acidic group is more than 15% by weight, the dispersibility decreases, the film smoothness and the high-humidity characteristics of the electrophotographic characteristics decrease, and the background stain increases when used as an offset master.

The resin [A] may be any of conventionally known resins as long as it has the above-mentioned physical properties. For example, a polyester resin,
Modified epoxy resin, silicone resin, olefin resin,
Polycarbonate resin, vinyl alkanoate resin, allyl alkanoate resin, modified polyamide resin, phenol resin, fatty acid modified alkyd resin, acrylic resin and the like are used.

More specifically, as an example of the resin [A], a (meth) acrylic copolymer containing a monomer represented by the following general formula (IV) as a copolymer component and containing 30% by weight or more in total is shown. Can be mentioned.

General formula (IV) In the general formula (IV), X represents a hydrogen atom, a halogen atom (for example, a chloro atom or a bromo atom), a cyano group or an alkyl group having 1 to 4 carbon atoms. T has 1 to 18 carbon atoms
An optionally substituted alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, 2-methoxyethyl group) , 2-
Ethoxyethyl group, etc.), an optionally substituted alkenyl group having 2 to 18 carbon atoms (eg, vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.), and carbon number 7 To 12 optionally substituted aralkyl groups (eg, benzyl group, phenethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), and optionally substituted cycloalkyl groups having 5 to 8 carbon atoms (eg, Cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.), aryl group (for example, phenyl group, tolyl group, xyl group, mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group,
Chlorophenyl group, dichlorophenyl group, etc.).

Further, the resin [A] of the present invention may contain, in addition to the monomer of the general formula (IV), a monomer other than these as a copolymerization component.

For example, α-olefins, vinyl alkanoates or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, heterocyclic vinyls (for example, vinylpyrrolidone, vinylpyridine, vinylimidazole,
Vinyl thiophene, vinyl imidazoline, vinyl pyrazole, vinyl-dioxane, vinyl kirin, vinyl thiazole, vinyl oxazine, etc.) and the like. Particularly, vinyl acetate, allyl acetate, acrylonitrile, methacrylonitrile, styrenes and the like are preferable components from the viewpoint of improving the film strength.

Further, among the acidic groups bonded to the ends of the main chain in the resin [A] of the present invention, preferable acidic groups are —PO ₃ H ₂ groups and —SO ₃ groups.
H group, -COOH group, Mention may be made of a cyclic acid anhydride-containing group.

In, R represents a hydrocarbon group or OR '(R' represents a hydrocarbon group), and R and R'preferably have 1 carbon atom.
To 22 aliphatic groups (e.g., methyl, ethyl, propyl, butyl, hexyl, octyl, decyl,
Dodecyl group, octadecyl group, 2-chloroethyl group, 2
-Methoxyethyl group, 3-ethoxypropyl group, allyl group, crotryl group, butethyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group Etc.) or an aryl group which may be substituted (eg, phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxy Phenyl group,
Cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.).

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride to be contained include an aliphatic dicarboxylic acid anhydride and an aromatic dicarboxylic acid anhydride. To be

Examples of the aliphatic dicarboxylic acid anhydride, succinic anhydride ring glutaconic anhydride ring, maleic anhydride ring, cyclopentane-1,2-dicarboxylic acid anhydride ring, cyclohexane-1,2-dicarboxylic acid anhydride Ring, cyclohexene-1,2-dicarboxylic acid anhydride ring, 2,3-bicyclo [2,2,
2] 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 aromatic dicarboxylic acid anhydrides include phthalic anhydride ring, naphthalene / dicarboxylic acid anhydride ring, pyridine-dicarboxylic acid anhydride ring, thiophene / dicarboxylic acid anhydride ring, and the like. , For example, halogen atom such as chlorine atom, bromine atom, methyl group, ethyl group,
An alkyl group such as a propyl group and a butyl group, a hydroxyl group, a cyano group, a nitro group, and an alkoxycarbonyl group (eg, an alkoxy group such as a methoxy group and an ethoxy group) may be substituted.

The resin [A] may be synthesized from these copolymerization components so that the acidic group is bonded to the terminal of the main chain of the copolymer. Specifically, a method using a polymerization initiator containing the acidic group or a functional group that can be converted into an acidic group after conversion, or a chain containing the acidic group or a functional group that can be converted into the acidic group later It can be produced by a method using a transfer agent, a method using both of them, or a method using an end reaction in an anionic polymerization method to introduce the functional group.

For example, P. Dreyfuss, RPQuirk, Encycl.Polym.Sci.En
g. 7 , 551 (1987), V. Percec, Appl. Polym. Sci. 285 , 95 (1
985), PFRempp, E.Franta, Adv.Polym.Sci. 58 , 1 (198
4), Y.Yamashita, J.Appl.Polym.Sci, Appl.Polym.Symp.
36 , 193 (1981), R. Asami, M. Takaki, Makromol. Chem, Sup
It can be produced by the synthetic method described in the review article such as pl. 12 , 163 (1985).

The resin [B] is a resin which satisfies the above-mentioned physical properties and is composed of a comb-type copolymer containing at least the monofunctional macromonomer (M) and the monomer represented by the general formula (III). Characterize.

The resin [B] preferably has a weight average molecular weight of 2 × 10 ⁴
The above is a comb-type 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 (M) is formed by adding a polymerizable double bond group represented by the general formula (I) to the general formula (IIa) or (IIb)
Having 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 the formula:

In the general formulas (I), (IIa) and (IIb), a ₁ ,
The hydrocarbon groups contained in a ₂ , V, b ₁ , b ₂ , X ₀ , Q ₀ and Q each have the indicated carbon number (as an unsubstituted hydrocarbon group). It may have a substituent.

In the general formula (I) representing the macromonomer (M),
V is -COO -, - OCO -, - CH 2 OCO -, - CH 2 COO -, - O
−, −SO ₂ −, −CO−, Represents Here, in addition to a hydrogen atom, R ₁ is preferably a hydrocarbon group which may be a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a 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, etc.), having 4 to 18 carbon atoms.
Optionally substituted alkenyl groups (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 and the like, and optionally substituted aralkyl groups 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 is When represented by, 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.).

a ₁ and a ₂ may be the same or different from each other, 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 (for example, methyl group, ethyl group, propyl group, butyl group, etc.), -COO-Z or COOZ through hydrocarbon (Z is a hydrogen atom) Or an alkyl group having 1 to 18 carbon atoms, an alkenyl group,
Represents an aralkyl group, an alicyclic group or an aryl group, which may be substituted, specifically, represent represent) the same contents as those described above R _1.

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

More preferably, in the general formula (I), V is -CO
O -, - OCO -, - CH 2 OCO -, - CH 2 COO -, - O -, - CO
NH -, - SO ₂ NH- or Represents a ₁ and a ₂ may be the same or different, and each represents a hydrogen atom, a methyl group, —COOZ or —CH ₂ COOZ (Z is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, a methyl group,
Ethyl group, propyl group, butyl group, hexyl group, etc.). Even more preferably, one of a ₁ and a ₂ always represents a hydrogen atom.

That is, as the polymerizable double bond group represented by the general formula (I), specifically, Etc.

In formula (IIa), X ₀ has the same meaning as V in formula (I).

b ₁ and b ₂ may be the same or different and represent the same contents as a ₁ and a ₂ in the formula (I).

Q ₀ represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms.

Specifically, an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group,
Dodecyl group, tridecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 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.), cycloalkyl group having 5 to 8 carbon atoms (eg, cycloheptyl group, cyclohexyl group, cyclooctyl group, etc.), substitution having 7 to 12 carbon atoms An aralkyl group which may be represented (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group,
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 group, tolyl group, xylyl group, chlorophenyl group, bromophenyl group, dichlorophenyl group, chloro-methyl-phenyl group, methoxyphenyl group, methoxycarbonylphenyl group). , Naphthyl group, chloronaphthyl group, etc.) and the like.

In the formula (IIa), X ₀ is preferably -COO-, -OCO
_{-, - CH 2 COO -,} - CH 2 OCO -, - O -, - CO -, - CONH
−, −SO ₂ NH− or Represents

Preferred examples of b ₁ and b ₂ represent the same contents as those of a ₁ and a ₂ described above.

In the formula (IIb), Q represents —CN, —CONH ₂ or Represents a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkoxy group (eg, methoxy group,
Ethoxy group) or -COOR '(R' is preferably an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryl group).

The macromonomer (M) may contain two or more polymer components represented by the formula (IIa) or (IIb). Further, when Q ₀ is an aliphatic group in the formula (IIa), the aliphatic group having 6 to 12 carbon atoms should be used within a range not exceeding 20% by weight based on the total polymer components in the macromonomer (M). preferable.

Further, when X ₀ in the general formula (IIa) is —COO—, the polymer component represented by the formula (IIa) is at least 30% by weight or more in all the polymer components in the macromonomer (M). It is preferable to be contained.

Further, in the macromonomer (M), acrylonitrile, methacrylonitrile, acrylamides, methacryl, etc. may be used as a monomer corresponding to a repeating unit that can be copolymerized with the polymer component represented by the formula (IIa) and / or (IIb). Amides, styrene and derivatives thereof (eg vinyltoluene, chlorostyrene, dichlorostyrene, bromostyrene, hydroxymethylstyrene, N, N-dimethylaminomethylstyrene, etc.), heterocyclic vinyls (eg vinylpyridine, vinylimidazole, vinylpyrrolidone) , Vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.) and the like.

The macromonomer used in the present invention is represented by the general formula (I) only at one end of the polymer main chain composed of the repeating units represented by the general formulas (IIa) and / or (IIb) as described above. The polymerizable double bond group has a chemical structure in which it is directly bonded or bonded with an arbitrary linking group. Formula (I) component and formula (IIa) or (IIb)
The group connecting the components, carbon-carbon bond (single bond or double bond), carbon-heteroatom bond (hetero atoms include, for example, oxygen atom, sulfur atom, nitrogen atom,
Silicon atom, etc.), and any combination of heteroatom-heteroatom bond atomic groups.

Preferred among the macromonomers (M) of the present invention are those represented by the formula (Va) or (Vb).

In formula (Va) or (Vb), a ₁ , a ₂ , b ₁ , b ₂ , V, X ₀ , Q ₀ , Q are respectively described in formula (I), formula (IIa) and formula (IIb). Indicates the same content as the one that was done.

W is a simple bond or [R ₂ and R ₃ represent a hydrogen atom, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), cyano group, hydroxyl group, alkyl group (eg, methyl group, ethyl group, propyl group, etc.), etc. ], CH = CH, -O-, -S-, −COO−, −SO ₂ −, -NHCOO-, -NHCONH-, [R ₄ represents a hydrogen atom, a hydrocarbon group having the same meaning as Q ₀ in the above formula (IIa)] or a single linking group selected from atomic groups or a linking group composed of any combination. Represents

When the weight average molecular weight of the macromonomer (M) exceeds 2 × 10 ⁴ , copolymerizability with the monomer represented by the formula (III) decreases. On the other hand, if the molecular weight is too small, the effect of improving the electrophotographic characteristics of the photosensitive layer becomes small, so 1 × 10 ³ or more is preferable.

The macromonomer (M) of the present invention can be produced by a conventionally known synthesis method. For example, a method by an ionic polymerization method of reacting various reagents to the end of a living polymer obtained by anionic polymerization or cationic polymerization to form a macromer, a carboxyl group in the molecule,
Using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a hydroxyl group and an amino group, an oligomer having a terminal reactive group bond obtained by radical polymerization is reacted with various reagents to form a macromer. A method by a radical polymerization method, a method by a polyaddition condensation method in which a polymerizable double bond group is introduced into an oligomer obtained by a polyaddition or polycondensation reaction in the same manner as the above-mentioned radical polymerization method, and the like can be mentioned.

Specifically, P.Dreyfuss & RPQuirk, Encycl, Poly
m.Sci.Eng., 7 , 551 (1987), PFRempp E.Franta, Adu., P
olym.Sci. 58 , 1 (1984), V.Percec, Appl., Polym.Sci., 28
5 , 95 (1984), R. Asami, M. TakaRi, Makvamol. Chem. Suppl.
12 , 163 (1985), P.Rempp.etal, Makvamol, Chem.Suppl. 8 ,
3 (1984), Kawakami press, chemical industry, 38, 56 (1987), Yuya Yamashita, polymeric, 31, 988 (1982), Shiro Kobayashi, polymer, 3
0, 625 (1981), Higashimura Satoshinobe, Journal of the Adhesion Society of Japan 18, 536 (198
2), Koichi Ito, polymer processing, 35, 262 (1986), AzumaTakashi Shiro, Takashi Tsuda, functional material, synthesized according to the method described in the review and its literature, patents, etc. references such as 1987 Nanba10,5 can do.

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

The monomer that copolymerizes the macromonomer (M) is represented by the general formula (III). In formula (III),
c ₁ and c ₂ may be the same or different from each other, and a in the formula (I)
₁ represents a ₂ same content as. X ₁ is X _{0 in} formula (IIa) and Q ₁
Represents the same contents as Q _{0 in} formula (IIa).

Further, the resin [B] of the present invention may contain, in addition to the macromonomer (M) and the monomer of the general formula (III), other monomers other than these as a copolymerization component.

For example, the vinyl compound represented by the above formula (IV) in the resin [A], α-olefins, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, styrene, vinyl group-containing naphthalene compound (for example, vinyl-naphthalene, 1- Compounds such as isoperopenylnaphthalene, etc.) vinyl group-containing heterocyclic compounds (for example, vinyl pyridine, vinyl pyrrolidone, vinyl thiophene, vinyl-tetrahydrofuran, vinyl-1,3-dioxolane, vinyl imidazole, vinyl thiazole, vinyl oxazoline, etc.) To be

In the resin [B], the composition ratio of the copolymer component having a macromer (M) as a repeating unit and the copolymer component having a monomer represented by the general formula (III) as a repeating unit is 1 to 90.
/ 99 to 10 (weight composition ratio), preferably 5 to 60/95 to
40 weight composition ratio.

As another copolymerization component, a “vinyl compound containing an acidic group” can be contained as a repeating unit. In that case, the acidic group-containing copolymerization component is contained in the copolymer.
It is preferable not to exceed 10% by weight.

If 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 ′] that can be used as a preferred embodiment of the present invention contains at least one repeating unit represented by the general formula (III) and at least one repeating unit represented by the macromonomer (M). at one end of the polymer main chain only, -PO ₃ H ₂ group, -SO ₃ H group, -COOH group, -O
It is a polymer formed by bonding at least one acidic group selected from H group, SH group and PO ₃ R ″ H group.

Here, a hydrocarbon group is represented by R ″ in the —PO ₃ R ″ H group, and specific examples thereof include the hydrocarbon groups described above for R.

When the acidic group is bonded to one end of the polymer main chain, the polymer main chain may not contain a copolymerization component containing a polar group such as a carboxyl group, a sulfo group, a hydroxyl group and a phosphono group. preferable. In the resin [B ′], the acidic group is directly bonded to one end of the polymer main chain,
Alternatively, it has a chemical structure linked 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, (R ₅ and R ₆ represent the same contents as R ₂ and R ₃ above), CH
= CH, -O-, -S-, -COO -, - SO ₂ -, -NHCOO-, -NHCONH-, (R ₇ represents the same content as R ₄ described above), and a single linking group selected from atomic groups or a linking group composed of any 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 reacted with various reagents at 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
Review articles such as 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), etc. 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 ratio of resin [B] used is 5 to 80:95 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.

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 together as a spectral sensitizer, if necessary. For example, Harumi Miyamoto, Hidehiko Takei, Imaging 1973 (No.8) page 12, CJ Young et al., RC
A Review 15 , 469 (1954), Kouhei Kiyota, The Institute of Electrical Communication, J 63-C (No.2), 97 (1980), Yuji Harasaki, etc., Journal of Industrial Chemistry 66 78 and 188 (1963), Tadaaki Tani. , Journal of the Photographic Society of Japan
35, 208 (1972) carbonium-based dyes review references such as, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (e.g., oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes And the like, and phthalocyanine dyes (which may contain metals).

More specifically, examples of those mainly using a carbonium dye, a triphenylmethane dye, a xanthene dye, and a phthalein dye are described in JP-B-51-452 and JP-A-50-9.
0334, JP-A-50-114227, JP-A-53-39130, JP-A-53-82353, U.S. Pat.No. 3,052,540, U.S. Pat.No. 4,0
54,450 and JP-A-57-16456.

As polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes, F.
M. Harmmar `` The Cyanine Dyes and Related Compound
s '' and the like can be used, and more specifically, U.S. Pat.No. 3,047,384, U.S. Pat.No.3,110,591,
U.S. Patent 3,121,008, U.S. Patent 3,125,447, U.S. Patent 3,128,179, U.S. Patent 3,132,942, U.S. Patent 3,622,317, U.S. Patent 1,226,892, U.K. Patent 1,
No. 309,274, UK Patent No. 1,405,898, JP-B-48-7814
And the dyes described in JP-B-55-18892.

Further, as a polymethine dye for spectrally sensitizing the near-infrared to infrared light region having a long wavelength of 700 nm or more, JP-A-47-840, JP-A-47-44180, JP-B-51-41061, Sho 49-5034,
JP-A-49-45122, JP-A-57-46245, JP-A-56-35141
No., JP-A-57-157254, JP-A-61-26044, JP-A-61-26044
27551, U.S. Pat.No. 3,619,154, U.S. Pat.No. 4,175,95
No. 6, "Research Disclosure", 1982, 216, Nos. 117-11
Those described on page 8 and the like can be mentioned. The photoconductor of the present invention is excellent in that the performance thereof hardly changes depending on the sensitizing dye even when various sensitizing dyes are used in combination. Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers such as chemical sensitizers can be used in combination. For example, the above-mentioned review articles: Electron accepting compounds (for example, halogen, benzoquinone, chloranil, acid anhydride, organic carboxylic acid, etc.) described in the review articles such as Imaging 1973 (No. 8), page 12, etc .; Recent Developments and Practical Applications of Photoconductive Materials and Photoconductors "Chapters 4 to 6: Polyarylalkane compounds, hindered phenol compounds, p- And phenylenediamine compounds.

The addition amount of these various additives is not particularly limited, but is usually 0.0001 to 2.0 parts by weight with respect to 100 parts by weight of the photoconductor.

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

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

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

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

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

Typical resins used for forming the insulating layer or the charge transport layer are polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl chloride copolymer resin, Thermoplastic resins and curable resins such as polyacrylic resins, polyolefin resins, urethane resins, polyester resins, epoxy resins, melamine resins, and silicone resins are appropriately used.

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

Specifically, as an example of a conductor substrate or a conductive material, Yukio Sakamoto, Electrophotography, 14, (No. 1), p2-11 (197)
5), Hiroyuki Moriga, “Introduction to Special Paper Chemistry”, Polymer Society (1
975), MF Hoover, J. Macromol. Sci. Chem. A-4 (6),
Those described on pages 1327 to 1417 (1970) and the like are used.

(Examples) Examples of the present invention will be illustrated below, but the contents of the present invention are not limited thereto.

Synthesis Example of Resin [A] 1: Resin [A] -1 A mixed solution of 95 g of benzyl methacrylate and 200 g of toluene was heated to a temperature of 90 ° C. under a nitrogen stream, and then 4,4′-
5 g of azobis (4-cyanovaleric acid) (hereinafter abbreviated as ABCV) was added and reacted for 10 hours.

The weight average molecular weight of the obtained polymer [A] -1 was 8,300.
Met.

Synthesis Example 2 of Resin [A]: Resin [A] -2 A mixed solution of 95 g of ethyl methacrylate, 5 g of thioglycolic acid, and 200 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream, and then azobisisobutyronitrile. 1.0g was added and it was made to react for 8 hours.

The weight average molecular weight of the obtained polymer [A] -2 was 7,800.

Synthetic Examples 3 to 8 of Resin [A]: Resin [A] -3 to 15 The same as Synthetic Example 2 except that the thioglycolic acid used in Synthetic Example 2 of Resin [A] is replaced with the compound of Table-1. Each polymer [A] was synthesized under the conditions of.

Synthesis Example 16 of Resin [A]: A mixture of 95 g of Resin [A] -16n-propylmethacrylate and 200 g of tetrahydrofuran was heated to a temperature of 70 ° C. under a nitrogen stream, and then 4,4′-acylbis (4-cyano) was used. 6 g of valeric acid chloride) was added and reacted for 10 hours. Next, after cooling to a temperature of 10 ° C. or lower, 3 g of pyridine was added with stirring, and a mixed solution of 4 g of glycolic acid and 10 ml of acetone was added dropwise so that the temperature did not exceed 10 ° C. After reacting for 1 hour as it was, it was reacted for 4 hours at a temperature of 20 ° C.

The reaction mixture was reprecipitated in 2 l of methanol, the solution was decanted off and the viscous material was dried.

 The weight average molecular weight of the obtained polymer was 10,800.

Synthesis Examples 17 to 27 of Resin [A]: Resins [A] -17 to 27 Synthesis was carried out except that the ethyl methacrylate and thioglycolic acid used in Synthesis Example 2 of Resin [A] were replaced with the compounds of Table 2 respectively. By operating under the same conditions as in Example 2, each polymer [A] was synthesized.

Production Example 1 of Macromonomer 1: A mixed solution of 95 g of M-1 methyl methacrylate, 5 g of thioglycolic acid, and 200 g of toluene was stirred under a nitrogen stream.
The temperature was raised to 75 ° C. 1.0 g of 2,2'-azobis (cyanovaleric acid) (abbreviated as ACV) was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to the reaction solution, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was re-precipitated in 2 l of methanol, and a white powder was obtained.
82 g were obtained. The number average molecular weight of the polymer (M-1) was 6,500.

Production Example 2 of Macromonomer: A mixed solution of 95 g of M-2 methyl methacrylate, 5 g of thioglycolic acid and 200 g of toluene was heated to 70 ° C while stirring under a nitrogen stream. 1.5 g of 2,2'-azobis (isobutylnitrile) (abbreviation: AIBN) was added and reacted for 8 hours.
Next, to this reaction solution, 7.5 g of glycidyl methacrylate,
1.0 g of N, N-dimethyldodecylamine and 0.8 g of t-butylhydroquinone were added, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in 2 l of methanol,
85 g of a colorless and transparent viscous substance was obtained. The number average molecular weight of the polymer (M-2) was 2,400.

Production Example 3 of Macromonomer: A mixed solution of 94 g of M-3 propyl methacrylate, 6 g of 2-mercaptoethanol and 200 g of toluene was heated to 70 ° C. under a nitrogen stream.
Was heated. 1.2 g of AIBN was added and reacted for 8 hours.

The reaction solution is then cooled in a water bath to a temperature of 20 ° C,
Triethylamine (10.2 g) was added, and methacrylic acid chloride (14.5 g) was added dropwise with stirring at a temperature of 25 ° C. or lower. After dropping, the mixture was further stirred for 1 hour as it was. Thereafter, 0.5 g of t-butylhydroquinone was added, the mixture was heated to a temperature of 60 ° C, and stirred for 4 hours. After cooling, the precipitate was reprecipitated in 2 l of methanol to obtain 79 g of a colorless and transparent viscous substance. The number average molecular weight of the polymer (M-3) is 4,500.
Met.

Production Example 4 of Macromonomer: M-4 A mixed solution of 95 g of ethyl methacrylate and 200 g of toluene was heated to a temperature of 70 ° C. under a nitrogen stream. 5 g of 2,2'-azobis (cyanoheptanol) was added and reacted for 8 hours.

After cooling, the reaction solution was brought to a temperature of 20 ° C. in a water bath, 1.0 g of triethylamine and 21 g of methacrylic anhydride were added, and the mixture was stirred for 1 hour and then at a temperature of 60 ° C. for 6 hours.

The obtained reaction product was cooled and then reprecipitated in 2 l of methanol to obtain a colorless transparent viscous product (75 g). The number average molecular weight of the polymer (M-4) was 6,200.

Production Example 5 of Macromonomer: M-5 A mixture of 93 g of benzyl methacrylate, 7 g of 3-mercaptopropionic acid, 170 g of toluene and 30 g of isopropanol was heated to a temperature of 70 ° C. under a nitrogen stream to obtain a homogeneous solution. 2.0 g of AIBN was added and reacted for 8 hours. After cooling, reprecipitate in 2 l of methanol and heat to 50 ° C. under reduced pressure.
The solvent was distilled off. The obtained viscous substance was dissolved in 200 g of toluene, and glycidyl methacrylate 16 g, N, N
-Dimethyldodecyl methacrylate (1.0 g) and t-butylhydroquinone (1.0 g) were added, and the mixture was stirred at 110 ° C for 10 hours. The reaction solution was reprecipitated again in 2 l of methanol. The number average molecular weight of the obtained pale yellow viscous substance (M-5) was 3,40.
It was 0.

Production Example 6 of Macromonomer: A mixed solution of 95 g of M-6 propyl methacrylate, 5 g of thioglycolic acid and 200 g of toluene was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 1.0 g of AIBN was added and reacted for 8 hours. Next, glycidyl methacrylate 13 g, N, N
1.0 g of -dimethyldodecylamine and 1.0 g of t-butylhydroquinone were added, and the mixture was stirred at 110 ° C for 10 hours. After cooling, the reaction solution was reprecipitated in 2 l of methanol to obtain 86 g of a white powder. The number average molecular weight of the polymer (M-6) is 3,500.
Met.

Production example 7 of macromonomer: M-7 methyl methacrylate 40 g, ethyl methacrylate 54
g, a mixture of 6 g of 2-mercaptoethylamine, 150 g of toluene and 50 g of tetrahydrofuran were heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 2.0 g of AIBN was added and reacted for 8 hours. Next, the reaction solution was heated to a temperature of 20 ° C. in a water bath, and 23 g of methacrylic anhydride was added dropwise thereto so that the temperature did not exceed 25 ° C., and the mixture was further stirred for 1 hour. 2,
0.5 g of 2'-methylenebis (6-t-butyl-p-cresol) was added, and the mixture was stirred at a temperature of 40 ° C for 3 hours. After cooling,
This solution was reprecipitated in 2 l of methanol to obtain 83 g of a viscous substance. The number average molecular weight of the polymer (M-7) was 2,200.

Production Example 8 of Macromonomer A mixed solution of 95 g of M-8 methyl methacrylate, 150 g of toluene and 150 g of ethanol was heated to a temperature of 75 ° C. under a nitrogen stream. ACV5g was added and reacted for 8 hours. Next, glycidyl acrylate 15 g, N, N-dimethyldodecylamine 1.0 g
Then, 1.0 g of 2,2'-methylenebis- (6-t-butyl-p-cresol) was added, and the mixture was stirred at a temperature of 100 ° C for 15 hours. After cooling, the reaction solution was reprecipitated in 2 l of methanol to obtain 83 g of a transparent viscous material. The number average molecular weight of the polymer (M-8) is 3,6.
00.

Production Examples 9 to 18 of Macromonomer: M-9 to M-18 The same as Production Example 3 except that the acid halide compound of Table 3 was used in place of the methacrylic acid chloride in Production Example 3 of the macromonomer. By operation, macromonomers M-9 to M-18 were produced, respectively.

The _N of the macromonomers M-9 to M-18 is 4,000.
It was ~ 5,000.

Production Examples 19 to 27 of Macromonomer: M-19 to M-27 The same procedure as in Production Example 2 except that the monomers shown in Table 4 were used in place of methyl methacrylate in Production Example 2 of macromonomer. Macromonomer (M-19) ~ (M
-27) was produced.

Production Example 1: 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 was 9.8 × 1.
0 Glass transition point ⁴ was 72 ° C..

Production Examples 2 to 15 of Resin [B]: Resin [B] -2 to 15 Under the same polymerization conditions as in Production Example 1 of Resin [B], the following Table-
Resin [B] of No. 5 was produced. _W of each resin is 8 × 10 ⁴ ~
The range was 1.5 × 10 ⁵ .

Production Example 16 of Resin [B]: Resin [B] -16 Ethyl methacrylate 70 g, 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. Then 4,4 ′
-Azobif (0.8 g of 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 .

Composition formula of [B] -16 Production Examples 17 to 24 of Resin [B]: Resin [B] -17 to 24 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 the macromonomer shown in Table 6 below was 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]: Resin [B] -25 to 31 In Production Example 16 of Resin [B], instead of ACV,
Except that the azobis compound shown in Table 7 below was used,
In the same manner as in the above, polymers were each produced.

Production example 32 of resin [B]: 80 g of [B] -32 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 under a nitrogen stream at a temperature of 80 ° C.
Was heated. 0.5 g of 1,1 'azobis (cyclohexane-1-carbonitrile) (abbreviated as ACHN) was added and stirred for 4 hours, and 0.3 g of ACHN was further added and stirred for 4 hours. The polymer obtained had a _W of 8 × 10 ⁴ and a glass transition point of 41 ° C.

Composition of resin [B] -32 Production Examples 33 to 39 of Resin [B]: [B] -33 to [B] -39 Production Examples of Resin [B] except that the compounds of Table 8 below were used instead of thioglycolic acid. A polymer was produced in the same manner as in Example 32.

Production Examples 40 to 48 of Resin [B]: [B] -40 to 48 Under the same polymerization conditions as in Production Example 26 of Resin [B], Table 9 below was used.
Was produced. _W of each resin is 9.5 × 10 ^{4 to} 1.2
× 10 ⁵ range.

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

Examples 1 and 2 and Comparative Examples A to D Example 1 6 g of resin [A] -1 produced in Production Example 1 of resin [A]
(As solid content), 34 g of resin [B] -1 produced in Production Example 1 of resin [B] (as solid content), zinc oxide 200
g, a mixture of 0.018 g of the cyanine dye [A] having the following structure, 0.05 g of phthalic anhydride and 300 g of toluene in a ball mill.
And time dispersion, a photosensitive layer formation was prepared, which on conductive treated papers, as dry coverage is 22 g / m ^2, was coated with a wire bar, and dried for 30 seconds at 110 ° C., and then the dark 20 ℃ 6
An electrophotographic light-sensitive material was prepared by being left under a condition of 5% RH for 24 hours.

Example 2 An electrophotographic photosensitive material was produced in the same manner as in Example 1, except that the resin [B] -16 and 34 g were used instead of the resin [B] -1 and 34 g. .

Comparative Example A Resin [A]-used as binder resin in Example 1
Instead of 1 and [B] -1, only resin [A] -1 was used for 40
An electrophotographic photosensitive material A was produced in the same manner as in Example 1 except that g (as solid content) was used.

Comparative Example B An electrophotographic photosensitive material B was produced in the same manner as in Example 1, except that only 40 g of the following resin [R] -1 was used as the binder resin.

Resin [R] -1 Comparative Example C Resin [R] -1, 6 g and Resin [B] -as the binder resin
An electrophotographic photosensitive material C was produced in the same manner as in Example 1 except that 1 34 g (as solid content) was used.

Comparative Example D Only 40 g of resin [R] -2 having the following structure was used as a binder resin.
An electrophotographic photosensitive material D was produced in the same manner as in Example 1 except for using the same.

Resin [R] -2 The film properties (surface smoothness), film strength, electrostatic properties, imaging properties of these photosensitive materials, and the electrostatic property imaging body when the environmental conditions were set to 30 ° C. and 80% RH were examined. Furthermore, when these photosensitive materials are used as a master plate for an offset master, the photoconductive desensitizing property (represented by the contact angle with water of the photoconductive layer after the desensitizing process) and printability (background stain, Printing durability).

 The above results are summarized in Table-11.

The embodiments of the evaluation items shown in Table 11 are as follows.

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

Note 2) Mechanical strength of the photoconductive layer: The surface of the obtained photosensitive material was applied to an emery paper (#) with a load of 50 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 characteristics: A paper analyzer (Kawaguchi Electric Co., Ltd. paper analyzer) was applied to each photosensitive material in a dark room at a temperature of 20 ° C and 65% RH.
After the 20 seconds corona discharge -6kV with SP-428 type), allowed to stand for 10 seconds to measure the surface potential V ₁₀ at this time.
Then measuring the potential V ₁₀₀ after allowing to stand for 90 seconds in as dark, retention of potential after being 90 seconds dark decay, i.e., dark decay retention rate [DRR (%) of (V ₉₀ / V ₁₀₎ × 100 (%).

After charging the surface of the photoconductive layer to -400 V by corona discharge, the surface potential (V ₁₀ ) was changed by irradiation with monochromatic light with a wavelength of 780 nm.
Calculate the time to 1/10 decay and calculate the exposure E
Calculate _1/10 (erg / cm ² ).

Note 4) Imaging: Each light-sensitive material was left for one day under the following environmental conditions. Next, charged at −5 kV, using a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 750 nm) with a 2.8 mW output as a light source, a pitch of 25 μm and a scanning speed on the surface of the photosensitive material under an irradiation dose of 64 erg / cm ² Visually evaluate the copied image (fog, image quality) obtained by developing and fixing using ELP-T (manufactured by Fuji Photo Film Co., Ltd.) as a liquid developer after 300 m / sec speed exposure. did.

The environmental conditions during imaging were 20 ° C 65% RH and 30 ° C 80% RH.

Note 5) Contact angle with water: Each photosensitive material was passed through an etching processor once using a desensitizing solution ELP-EX (manufactured by Fuji Photo Film Co., Ltd.) to desensitize the photoconductive layer surface. After that, a drop of distilled water (2 μl) is put on this, 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 is subjected to desensitization processing under the same conditions as in Note 5) above. (Oliver 52 type manufactured by Sakurai Mfg. Co., Ltd.) shows the number of prints that can be made without causing scumming in the non-image area of the printed matter and in the image quality of the image area (the higher the number of printed sheets, the better the printing durability. It means that).

As shown in Table-11, only the comparative example D using the conventionally known resin had remarkably poor smoothness and electrostatic characteristics of the photosensitive layer.

In Comparative Examples B and C, the environmental conditions were high temperature and high humidity (30 degrees, 80% R
H), the electrostatic characteristics fluctuate and decrease, especially 9
The DRR worsened for 0 seconds. As a result, the actual imageability due to the scanning exposure was reduced in the copied image.

In Comparative Example A, almost no change in the electrostatic characteristics and imaging performance due to changes in environmental conditions as in Comparative Examples B and C was observed, and the electrostatic characteristics at room temperature and normal humidity were also compared with Comparative Example B. It was excellent. This is extremely effective in a scanning exposure method using a low-power semiconductor laser beam.

The photosensitive material of the present invention has the same electrostatic properties and image-capturing properties as Comparative Example A, and the film strength of the photosensitive layer is significantly improved.

Even when this is used as an offset master original plate, the desensitizing treatment with the desensitizing treatment liquid has proceeded sufficiently, and the contact angle with water of the non-image area is as small as 15 degrees or less, and it is sufficiently hydrophilized. When actually printed and observed the background stain of the printed matter, nothing was observed. However, in the case of Comparative Example A, when the strength test and the printing durability test of the photoconductive layer were performed, the film strength was not sufficient, and a problem occurred in durability.

Further, in the light-sensitive material of the present invention, Example 2 in which the binder resin [B] contains a polar group has a film strength higher than that of Example 1 in terms of the number of printed sheets as an offset master original plate. Improved.

From the above, the photosensitive material of the present invention has a smoothness of the photoconductive layer,
It was good in all respects of film strength, electrostatic properties and printability.

Examples 3 to 22 Resin [A] -1, 6 g and resin [B] in Example 1
-1 and 34 g each of resin [A] in Table 12 below 6
g, resin [B] using 34 g each, and cyanine dye [A]
Instead of 0.018 g, the cyanine dye of the following structure [B] 0.01
Each photosensitive material was produced in the same manner as in Example 1 except that 8 g was used.

Examples 23 to 36 In Example 1, resin [A] -1, 6 g and resin [B]
Each of the resin [A] in Table 13 below was replaced with 6
g, resin (B) 34 g each, and cyanine dye (A) 0.
Each photosensitive material was prepared in the same manner as in Example 1 except that 0.016 g of the methine dye [C] having the following structure was used instead of 018 g.

Each characteristic was measured in the same manner as in Example 1. The smoothness and film strength of each light-sensitive material exhibited almost the same characteristics as those of the sample of Example 1.

Each of the light-sensitive materials of the present invention is excellent in chargeability, dark charge retention rate, and photosensitivity, and the actual copied image is high temperature and high humidity (30 ° C.
Even under the harsh conditions of 80% RH, clear images were obtained with no background fog.

Claims (1)

(57) [Claims] 1. 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] and at least the following resins [B]. An electrophotographic photoreceptor containing one kind. Resin [A] having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and -PO
₃ H ₂ group, -SO ₃ H group, -COOH group, {R represents a hydrocarbon group having 1 to 10 carbon atoms or an OR 'group (R' represents a hydrocarbon group having 1 to 10 carbon atoms), --SH group, acidic group such as phenolic OH group and cyclic acid A resin obtained by bonding at least one substituent of an anhydride-containing group to an end of a polymer main chain. Resin [B] The polymerizability represented by the following general formula (I) is present only at one end of the polymer main chain containing at least one polymer component represented by the following general formulas (IIa) and (IIb). A resin, which is a copolymer comprising at least a monofunctional macromonomer having a weight average molecular weight of 2 × 10 ⁴ or less formed by binding a double bond group and a monomer represented by the following general formula (III). General formula (I) Wherein (I), V is -COO -, - OCO -, - CH 2 OCO -, -
_{CH 2 COO -, - O -} , - SO 2 -, - CO-, Or (R ₁ represents a hydrogen atom or a hydrocarbon group).
a ₁ and a 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 via a hydrocarbon (Z represents a hydrogen atom or a hydrocarbon group which may be substituted). ] General formula (IIa) General formula (IIb) [In formula (IIa) or (IIb), X ₀ has the same meaning as V in formula (I). Q ₀ represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms. b ₁ and b ₂ may be the same as or different from each other, and have the same contents as a ₁ and a ₂ in the formula (I). Q is -CN, -CONH ₂ or Where Y represents a hydrogen atom, a halogen atom, an alkoxy group or -COOZ '(Z' represents an alkyl group, an aralkyl group or an aryl group). General formula (III) (In the formula (III), X ₁ represents the same content as X ₀ in the formula (IIa), and Q ₁ represents the same content as Q ₀ in the formula (IIa). C ₁ , c ₂ May be the same or different from each other and have the formula (I)
It has the same contents as a ₁ and a _{2 in the above} . (2) The resin [B] further comprises a —PO ₃ H ₂ group, a —SO ₃ H group, a —COOH group, a —OH group, a —SH group, and only at one end of the main chain of the copolymer. The electrophotographic photoreceptor according to claim 1, wherein the resin is a resin formed by bonding at least one acidic group selected from the group consisting of (R "represents a hydrocarbon group).