JP2568906B2 - Electrophotographic photoreceptor - Google Patents

Description

Description: TECHNICAL FIELD 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.

(Prior Art) An electrophotographic photoreceptor has various configurations in order to obtain a predetermined specification 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 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.

As long-known resins, 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
No. 2426), an acrylic resin (Japanese Patent Publication No. 35-11216), and an acrylate copolymer (for example, Japanese Patent Publication No. 35-11219).
Nos. JP-B-36-8510, JP-B-41-13946, etc.) are known.

However, in the electrophotographic photosensitive material using these resins, 1) the affinity with the photoconductive powder is insufficient, and the dispersibility of the coating liquid becomes poor. 2) low chargeability of the photoconductive layer;
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 the materials to coexist in the 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 sensitivity shortage 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 an average molecular weight of 10 ³ to 10 ⁴ and a component having a distribution of 10 ⁴ to 2 × 10 ⁵ , the electrostatic properties (particularly,
A technique for improving repetition reproducibility as a PPC photoreceptor), moisture resistance and the like is described.

Furthermore, research on a lithographic printing original plate using an electrophotographic photosensitive member has been conducted enthusiastically, and a binder for a photoconductive layer that achieves both electrostatic characteristics as an electrophotographic photosensitive member and printing characteristics as a printing original plate. As a resin, for example, in Japanese Patent Publication No. 50-31011,
Copolymerized with (meth) acrylate monomer and other monomers in the presence of fumaric acid, Tg 10-80 at Mw 1.8-10 × 10 ⁴
C. and a copolymer comprising a (meth) acrylate monomer and a monomer other than fumaric acid. JP-A-53-54027 discloses that a carboxylic acid group is formed by forming at least an atom from an ester bond. Those using a terpolymer containing a (meth) acrylic ester having a substituent which is located at a distance of several sevens, and those disclosed in JP-A-54-20735 and JP-A-57-20254.
No. 4 uses a quaternary or pentameric copolymer containing acrylic acid and hydroxyethyl (meth) acrylate,
JP-A-58-68046 discloses a method using a terpolymer containing a (meth) acrylate ester having an alkyl group having 6 to 12 carbon atoms as a substituent and a carboxylic acid-containing vinyl monomer. It is described that it is effective in improving the desensitizing property of the layer.

However, even if the resin is said to have an effect on the above-mentioned electrostatic properties and moisture resistance properties, especially when actually evaluated, electrostatic properties such as chargeability, dark charge retention, photosensitivity, and photoconductive layer Is problematic in terms of smoothness, etc., is not practically satisfactory, and also in a binder resin that has been developed as an electrophotographic lithographic printing plate precursor, when actually evaluated, the above-mentioned electrostatic properties, There was a problem in background soiling of printed matter, and furthermore, in moisture resistance properties and the like.

Further, in order to solve these problems, a low molecular weight resin (Mw 10 ³ -10 ⁴ ) containing 0.05 to 10% by weight of a copolymer component containing an acidic group as a binder resin is used. Japanese Patent Application Laid-Open No. 63-217354 discloses that the smoothness and electrostatic properties of the layer are improved, and that an image quality free from background contamination is obtained.
By using more such low molecular weight resin in combination with a high molecular weight of the resin (MW10 ⁴ or higher), to improve the adequate and tighten printing durability film strength of the photoconductive layer without inhibiting the characteristics No. Sho Nos. 63-49817, JP-A-63-220148 and 6
No. 3-220149.

(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 semiconductor laser light, 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.

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.

(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] A polymer having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and containing at least one of polymer components represented by the following general formulas (IIa) and (IIb) A monofunctional macromonomer (M) having a weight average molecular weight of 2 × 10 ⁴ or less, which is formed by bonding a polymerizable double bond group represented by the following general formula (I) to only one end of the main chain, and at least made of a copolymer from a monomer represented III), or an and the copolymer main chain at one terminal only -PO ₃ H ₂ group, -SO ₃ H group, -COOH group,
-OH group, -SH group and (R is a hydrocarbon group or -OR 'group (R' represents a hydrocarbon group)) A resin obtained by bonding at least one substituent selected from an acidic group and a cyclic acid anhydride-containing group.

Resin [B] has a weight average molecular weight of 2 × 10 ⁴ or more, and has the following general formula (I)
A polymerizable double bond group represented by the following general formula (I) is bonded to only one terminal of a polymer main chain containing at least one of the polymer components represented by Ia) 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 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 -, - CONHCOO -, -
CONHCONH−, −CONHSO ₂ −, 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 each represents a hydrogen atom, a halogen atom, a cyano atom, 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 represents the same content 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 or different from each other, and represent the same contents as a ₁ and a ₂ in the formula (I).

Q is -CN, -CONH ₂ or Represents a hydrogen atom, a halogen atom, a hydrocarbon group,
Represents an alkoxy group or -COOZ '(Z' represents an alkyl group, an aralkyl group or an aryl group).

General formula (III) In formula (III), X ₁ has the same content as X ₀ in formula (IIa), and Q ₁ has the same content as Q ₀ in formula (II a). c ₁ and c ₂ may be the same or different from each other;
It represents the same contents as a ₁ and a ₂ in the table.

That is, the binder resin used in the present invention is a comb-type copolymer containing at least a monofunctional macromer and a monomer represented by the general formula (III), and is provided at one end of the polymer main chain. A low-molecular weight compound comprising a specific acid group and / or a cyclic acid anhydride-containing group (hereinafter, unless otherwise specified, the term "acid group" includes a cyclic acid anhydride-containing group). Resin [A], monofunctional macromonomer and general formula (II
And a high molecular weight resin [B] which is a comb-type copolymer containing at least the monomer represented by I).

In the present invention, the resin (A), which is a comb-type copolymer in which a specific acidic group is bonded only to the terminal of the polymer main chain, has an acidic group bonded to a specific position in the resin. It is adsorbed on stoichiometric defects and is a low molecular weight comb-type copolymer, so it improves photo-conductor surface coverage to compensate for photo-conductor traps and improve humidity characteristics. While improving dramatically, the photoconductor is sufficiently dispersed to suppress aggregation, and to provide stable high-performance electrophotographic characteristics even when the environmental changes vary significantly from high temperature and high humidity to low temperature and low humidity. It turned out to be maintained. Further, the resin [B] does not hinder the high performance of the electronic and photographic properties due to the use of the resin [A] at all, and the resin [A] alone has an insufficient mechanical strength of the photoconductive layer. It was found to close. It is particularly effective when a scanning exposure method using a semiconductor laser is used.

The electrophotographic photoreceptor of the present invention has good smoothness on the surface of the photoconductor layer even when used as an electrophotographic lithographic printing plate precursor, and the inorganic particles as the photoconductor are sufficiently contained in the binder. When the desensitizing treatment is performed with the desensitizing treatment liquid, the non-image area is uniformly and sufficiently hydrophilicized, and the adhesion of the printing ink to the non-image area during printing is suppressed to 10,000 sheets. Even when a large number of printed materials are printed, background smear does not occur.

Furthermore, 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 covered, so that the photoconductive layer has a smooth surface. Although the image quality is good in terms of properties and electrostatic characteristics, free from background contamination and less dependent on the environment, 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 properly performed, and the film strength of the photoconductive layer is maintained.

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 acidic groups in the polymer is 0.5 to 15% by weight, preferably 1 to 1% by weight.
0% by weight. Further, the glass transition point of the resin [A] is preferably −10 ° C. to 100 ° C., more preferably −5 ° C. to 80 ° C.
It is.

In the specification of the present application, the weight-average molecular weight (Mw) of the resin of the present invention is such that a polymer having a Mw of about 1,000 or more has good reproducibility as an experimental value.
The measurement values based on the "C method" are shown. Here, the resin containing the monofunctional macromonomer of the present invention as a copolymer component is different from a linear polymer such as a random polymer in the presence state of its polymer chain in a solution, and has a specific form (for example, Entanglement of polymer chains), the apparent molecular weight (Mw) may be small.

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.

If the content of the acidic group in the resin [A] is less than 0.5% by weight, the initial potential is too low to obtain a sufficient image density. On the other hand, when the acidic group content is more than 15% by weight,
The dispersibility is reduced, the film smoothness and the high humidity property of the electrophotographic properties are reduced, and the background smear increases when used as an offset master.

On the other hand, the resin [B] preferably has a weight average molecular weight of 2
× 10 ⁴ or more comb-type copolymer resin. More preferably, the weight average molecular weight is from 5 × 10 ^{4 to} 5 × 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 resin [A] of the present invention is a low molecular weight comb-type copolymer containing at least a monofunctional macromonomer and a monomer represented by the general formula (III), and is provided at one end of the polymer main chain. Only a specific polar group is bonded.
The resin [B] of the present invention is a high molecular weight comb-type copolymer containing at least a monofunctional macromonomer and a monomer represented by the general formula (III). The monofunctional macromonomer and the monomer of the general formula (III) used in the resin [A] and the resin [B] may be the same or different.

The monofunctional macromonomer used for each of the resin [A] and the resin [B] of the present invention can be obtained by adding a polymerizable double bond group represented by the general formula (I) to the general formulas (IIa) and (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 of the polymer components represented by

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.

 The macromonomer (M) will be described.

In the general formula (I), V represents -COO-, -OCO-,-
_{CH 2 OCO -, - CH 2} COO -, - O -, - SO 2 -, - CO -, - C
ONHCOO−, −CONHCONH−, −CONHSO ₂ −, Or Represents Here, R ₁ is a hydrogen atom, and a preferable hydrocarbon group is 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). 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, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-
A naphthylethyl group, a chlorobenzyl group, a bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms ( For example, a cyclohexyl group, a 2-cyclohexylethyl group,
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 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 groups,
And a propoxy group and a butoxy group).

a ₁ and a ₂ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (for example, a chlorine atom,
A bromine atom, a cyano group, an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), -COO-Z, or COOZ via a 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 via the hydrocarbon include a methylene group, an ethylene group, and a propylene group.

More preferably, in the general formula (I), V is -COO
-, - OCO -, - CH 2 OCO -, - CH 2 COO -, - O -, - CON
HCOO -, - CONHCONH -, - CONH -, - SO 2 NH- or A ₁ and a ₂ may be the same or different from each other, and 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 (for example, a methyl group, ethyl , Propyl, butyl, hexyl, etc.). Even more preferably, _one of a ₁ and a ₂ represents a hydrogen atom.

That is, as the polymerizable double bond group represented by the general formula (I), specifically, CH ₂ = CH-CONH-, And the like.

In the general formula (IIa) or (IIb), X ₀ is a group represented by the formula (I)
Represents the same content as V in. 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 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 group, tridecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group,-
2-hydroxyethyl 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.), C5-8 cycloalkyl group (for example, cycloheptyl group, cyclohexyl group, cyclooctyl group, etc.), C7-12 carbon atom Optionally substituted aralkyl groups (e.g., benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl, chlorobenzyl, bromobenzyl, dichlorobenzyl, methylbenzyl, chloro) -Methyl-benzyl group, dimethylbenzyl group, trimethylbenzyl group,
Methoxybenzyl group, etc.).

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

In the formula (IIa), X ₀ is preferably -COO-, -OCO
_{-, - CH 2 COO -,} - CH 2 OCO -, - O -, - CO -, - CONH
COO -, - CONHCONH -, - 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 general formula (IIb), Q represents -CN, -CONH ₂ or Y 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.), an alkoxy group (eg, Methoxy, ethoxy, propoxy, butoxy, etc.) or -COOZ '
(Z 'preferably represents 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) has the formula (IIa) and / or (II)
The polymer component represented by b) may be contained in two or more kinds. When Q ₀ is an aliphatic group, the aliphatic group having 6 to 12 carbon atoms is preferably used in an amount not exceeding 20% by weight of all the polymer components in the macromonomer (M).

Furthermore, when X ₀ in the general formula (IIa) is —COO—, in all the polymer components in the macromonomer (M),
It is preferable that the polymer component represented by the formula (IIa) is contained in an amount of 30% by weight or more. In the macromonomer (M), acrylonitrile, methacrylonitrile, methacrylonitrile, and the like may be used as monomers corresponding to other repeating units copolymerizable with the polymer component represented by the formula (IIa) and / or (IIb).
Acrylamides, methacrylamides, styrene and derivatives thereof (for example, vinyl toluene, chlorostyrene,
Dichlorostyrene, bromostyrene, hydroxymethylstyrene, N, N-dimethylaminomethylstyrene, etc.),
Heterocyclic vinyls (for example, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.)
And the like.

The macromonomer used in the present invention is, as described above, a compound represented by the general formula (I) only at one end of a polymer main chain comprising a repeating unit represented by the general formula (IIa) and / or (IIb). Is a polymerizable double bond group having a chemical structure directly bonded or bonded with an arbitrary linking group. Formula (I) component and formula (IIa) or (II
b) Copolymerization for connecting the components includes a carbon-carbon bond (single bond or double bond), a carbon-heteroatom bond (for example, an oxygen atom, a 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 following formula (IVa) or (IVb).

In the formula (IV), a ₁ , a ₂ , b ₁ , b ₂ , X ₀ , Q ₀ , Q, V are
They represent the same contents as those described in Formula (I), Formula (IIa) and Formula (IIb), respectively.

W is a simple bond or [R ₂ and R ₃ 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-, [R ₄ represents a hydrogen atom, a hydrocarbon group having the same content as Q ₀ in the formula (IIa), etc.] or a single linking group selected from an atomic group or an arbitrary combination thereof. Represents a linking group.

More preferably, in the resin [A] and / or the resin [B], as a repeating unit of a macromonomer and / or as a repeating unit corresponding to the monomer represented by the general formula (III), the following general formula (V) And at least one of the copolymer components represented by (VI) is 30% of the total polymer components.
Preferably, it is contained in an amount of at least% by weight. Especially resin [A]
In the above, it is preferable that the copolymer component represented by the following formula (V) or (VI) is contained as a repeating unit corresponding to the monomer represented by the formula (III) in an amount of 30% by weight or more of the whole polymer component.

Wherein A ₁ and A ₂ are each independently a hydrogen atom,
Hydrocarbon group having 1 to 10 carbon atoms, chlorine atom, bromine atom, -CO
D ₁ or -COOD ₂ (D ₁ and D ₂ each represents a hydrocarbon group having 1 to 10 carbon atoms) represent.

Each B ₁ and B ₂ bind the -COO- and the benzene ring, represents a direct bond or a linking atoms 1-4 linking groups. In the formula (V), preferred A ₁ and A ₂ are, in addition to a hydrogen atom, a chlorine atom and a bromine atom, respectively, and preferred hydrocarbon groups include an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group). , A propyl group, a butyl group, etc.), an 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,
Xylyl group, bromophenyl group, methoxyphenyl group,
Chlorophenyl group, dichlorophenyl group, etc.), and-
COD ₁ and -COOD ₂ (preferable D ₁ and D ₂ include those described as the preferable hydrocarbon groups above).

In the formula (V), B ₁ is a direct bond or CH _{2 n} (n represents an integer of 1 to 3), —CH ₂ CH ₂ OCO—, CH ₂ O _m (--COO— and a benzene ring are bonded. m represents an integer of 1 or 2), -CH ₂ CH ₂ O- or the like;
Represents 4 linking groups.

B ₂ in formula (VI) is the same meaning as B _1.

If the weight average molecular weight of the macromonomer exceeds 2 × 10 ⁴ , the copolymerizability with the monomer of the formula (III) is undesirably reduced. On the other hand, if the weight average molecular weight is too small,
Since the effect of improving the electrophotographic properties of the photosensitive layer is reduced, 1
It is preferably at least × 10 ³ .

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

Specifically, P.Dreyfuss & R.P.Quirk, Encycl, Polym.S
ci.Eng., 7, 551 (1987), PFRempp, E.Franta, Adu., Poly
m.Sci. 58 , 1 (1984), V. Percec, Appl., Polym. Sci., 285, 9
5 (1984), R. Asami, M. TakaRi, Makvamol. Chem. Suppl. 12 ,
163 (1985), P. Rempp. Et al, Makvamol. Chem. Suppl. 8, 3
(1984), Yusuke Kawakami, Chemical Industry, 38 , 56 (1987), Yuya Yamashita, Polymer, 31 , 988 (1982), Shiro Kobayashi, Polymer, 3
0, 625 (1981), Higashimura Satoshinobe, Journal of the Adhesion Society of Japan 18, 536 (1
982), Koichi Ito, Polymer Processing, 35 , 262 (1986), Higashi Kishiro, Takashi Tsuda, Functional Materials, 1987 No. 10, 5, synthesized according to the methods described in the literature and patents can do.

Specific examples of the macromonomer (M) of the present invention include the following compounds. However, the scope of the present invention is not limited to these.

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

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

Moreover, in the polymer main chain, -PO ₃ H ₂ group, -SO ₃ H group, -COO
Those which do not contain a copolymer component containing a polar group such as H group, -OH group, -SH group and -PO ₃ RH group are preferred.

On the other hand, the resin [A] of the present invention further comprises only one end of a polymer main chain containing at least one repeating unit represented by the general formula (III) and at least one repeating unit represented by a macromonomer. -PO ₃ H ₂ group, -SO ₃ H group, -COO
H group, a -OH group, formed by combining at least one acidic group selected from -SH group and -PO ₂ RH group and a cyclic acid anhydride-containing group polymer. Here, 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, the same or a plurality of linking groups similar to those described for W can be mentioned.

In addition, In the above, 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, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group Or an optionally substituted aryl group (eg, phenyl, tolyl, ethylphenyl, propylphenyl, chlorophenyl, fluorophenyl, bromophenyl, chloro-methyl-phenyl, dichlorophenyl, methoxy) Phenyl group,
Cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.).

Further, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and as the cyclic acid anhydride contained, an aliphatic dicarboxylic anhydride and an aromatic dicarboxylic anhydride are included. No.

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

Examples of the aromatic dicarboxylic anhydride include a phthalic anhydride ring, a naphthalenedicarboxylic anhydride ring, a pyridine dicarboxylic anhydride ring, a thiophenedicarboxylic anhydride ring, and the like. , Chlorine atom,
Halogen atom such as bromine atom, alkyl group such as methyl group, ethyl group, propyl group, butyl group, hydroxyl group, cyano group, nitro group, alkoxycarbonyl group (alkoxy group includes, for example, methoxy group, ethoxy group, etc.) Etc. may be substituted.

The resin [A] of the present invention comprising a specific acidic group bonded to only one terminal of the polymer main chain is prepared by a method of reacting various reagents with the terminal of a living polymer obtained by conventionally known anionic or cationic polymerization. (Method by ionic polymerization), radical polymerization using a polymerization initiator and / or chain transfer agent containing a specific acidic group in the molecule (radical polymerization), or ionic polymerization as described above or 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) and the methods cited in the references cited therein.

Further, the resin [B] contains at least one macromonomer.
Polymerization can be easily carried out by a conventionally known ionic polymerization method or radical polymerization method in the presence of at least one of the species and the monomer of the general formula (III).

The resin [A] and 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, vinyl compounds containing an acidic group, α-olefins, acrylonitrile methacrylonitrile, acrylamide, methacrylamide, styrene, vinyl group-containing naphthalene compounds (eg, vinyl naphthalene, 1-isoperopenenyl naphthalene, etc.), and vinyl group-containing Heterocyclic compounds (for example, vinylpyridine, vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyl-1,3
-Dioxolan, vinylimidazole, vinylthiazole, vinyloxazoline, etc.).

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

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.

In the present invention, a resin other than the resins [A] and [B] may be used in combination. Examples of such resins include alkyd resins, polybutyral resins, polyolefins, ethylene-vinyl acetate copolymers, styrene resins, styrene-butadiene resins, acrylate butadiene resins,
And vinyl alkanoate resins.

When the other resin exceeds 30% (weight ratio) of the total amount of the binder resin using the resin of the present invention, the effect of the present invention (especially, improvement of electrostatic characteristics) is lost.

The ratio of the amount of the resin [A] and the amount of the resin [B] used in the present invention varies depending on the type, particle size, and surface state of the inorganic photoconductive material to be used, but generally the resin [A] and the resin [B] are used. The ratio is 5 to 80 to 95 to 20 (weight ratio), preferably 10 to 50 to 90 to 50 (weight ratio).

The ratio of the weight average molecular weight of the resin [A] to the resin [B] is preferably 1.2 or more, more preferably 2.0 or more.

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 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), Wataru equality Kiyota, Telecommunications Society of J63-C (No.2), 97 (1980), Yuji like Yuji, Industrial Chemistry Journal 66 78 and 188 (1963), Tadaaki Tani, Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, etc., as described in the review articles of the Photographic Society of Japan 35 , 208 (1972), etc.
Xanthene dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, and the like), phthalocyanine dyes (which may contain metals), and the like.

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

Oxonol dyes, merocyanine dyes, cyanine dyes, polymethine dyes such as rhodacyanine dyes, F.
M. Hanmer `` The Cyanine Dyes and Related Compounds ''
More specifically, dyes described in U.S. Pat.No. 3,047,384, U.S. Pat.No. 3,110,591, U.S. Pat.No. 3,121,008, U.S. Pat.No. 3,125,447, U.S. Pat.
No. 3,128,179, U.S. Pat.No. 3,132,942, U.S. Pat.
2,317, UK Patent 1,226,892, UK Patent 1,309,27
No. 4, British Patent No. 1,405,898, JP-B-48-7814, JP-B-55-18892, and the like.

Further, as polymethine dyes 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, and JP-A-51-41061 49−5034
No., JP-A-49-45122, JP-A-57-46245, JP-A-56
No. -35141, JP-A-57-157254, JP-A-61-26044,
JP-A-61-27551, U.S. Pat.No. 3,619,154, U.S. Pat.No.4,175,956, `` Research Disclosure '' 1982, 21
6, pages 117 to 118 and the like. The photoreceptor of the present invention is excellent in that even if various sensitizing dyes are used in combination, the performance is hardly changed by the sensitizing dye. Furthermore, various conventionally known additives for an electrophotographic photosensitive layer such as a chemical sensitizer can be used in combination, if necessary.
For example, the review mentioned above: Imaging 1973 (No. 8) No. 12
"Recent development and commercialization of photoconductive materials and photoreceptors", e.g., electron accepting compounds (e.g., halogen, benzoquinone, chloranil, acid anhydride, organic carboxylic acid, etc.) and Hiroshi Komon, which are described in pages and other reviews. Chapters 4 to 6 include polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, and the like, which are reviewed in Japanese Science Information Co., Ltd., Publishing Division (1986).

The amounts of these various additives are not particularly limited, but are usually 0.0001 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 µ, particularly preferably from 10 to 50 µ.

When a photoconductive layer is used as the charge generation layer of the photoreceptor in which the charge generation layer and the charge transport layer are stacked, 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 of a polyacryl resin, a polyolefin resin, a urethane resin, an epoxy resin, a melamine resin, a silicone resin, and a curable resin are appropriately used.

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally, the support of the electrophotographic photosensitive layer is preferably conductive. As the conductive support, a base material such as a metal, paper, or a plastic sheet is impregnated with a low-resistance substance in the same manner as in the related art. A substrate that has been subjected to a conductive treatment, for example, by applying a conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided), and further coated with at least one layer for the purpose of preventing curling and the like. A substrate provided with a water-resistant adhesive layer on its surface, a substrate provided with at least one or more precoat layers as necessary on the surface layer of the support, or a substrate conductive plastic on which Al or the like is deposited is laminated on paper. Can be used.

Specifically, as examples of the conductive substrate or the conductive material, Yukio Sakamoto, Electrophotography, 14 (No. 1), P2-11 (197
5), Hiroyuki Moriga, “Introduction to Special Paper Chemistry,” Polymer Publishing Association (1
975), MFHoover, J. Macromol. Sci. Chem, A-4.
(6), and 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.

Production Example 1 of Macromonomer 1: A mixed solution of 96 g of M-1 benzyl methacrylate, 4 g of thioglycolic acid and 200 g of toluene was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 1.0 g of 4,4'-azobis (4-cyanovaleric acid) (abbreviated as ACV) was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate was added to the reaction solution,
1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in methanol 2,
82 g of a white powder was obtained. The weight average molecular weight of the polymer was 8,300 (a GPC measurement value in terms of polystyrene; the same applies hereinafter).

Production Example 2 of Macromonomer: M-2 96 g of benzyl methacrylate, 4 g of thioglycolic acid and 200 g of toluene while stirring under a nitrogen stream,
Heated to a temperature of 70 ° C. 0.8 g of 2,2'-azobis (isobutyronitrile) (abbreviation: AIBN) was added and reacted for 8 hours. Next, glycidyl methacrylate 7.
5 g, N, N-dimethyldodecylamine 1.0 g and t-butylhydroquinone 0.8 g were added, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in methanol 2 to obtain 85 g of a colorless and transparent viscous substance. The weight average molecular weight of the polymer was 5,600.

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

Next, the reaction solution was cooled in a water bath to a temperature of 20 ° C.,
Triethylamine (10.2 g) was added, and methacrylate chloride (14.5 g) was added dropwise with stirring at a temperature of 25 ° C. or lower. After the addition, the mixture was further stirred for 1 hour. Thereafter, 0.5 g of t-butylhydroquinone was added, the mixture was heated to a temperature of 60 ° C., and stirred for 4 hours. After cooling, the precipitate was reprecipitated in methanol 2 to obtain 79 g of a colorless and transparent viscous substance. The weight average molecular weight was 6,000.

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 temperature of the reaction solution was adjusted to 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 60 ° C. for 6 hours.

After cooling the obtained reaction product, it was reprecipitated in methanol 2 to obtain 75 g of a colorless and transparent viscous substance. Weight average molecular weight is 8.5
00.

Production Example 5 of Macromonomer: M-5 A mixture of 93 g of 2-chlorobenzyl 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, the precipitate was reprecipitated in methanol 2 and heated to 50 ° C. under reduced pressure to distill off the solvent. The obtained viscous substance is washed with toluene
The mixture was dissolved in 200 g, and 16 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecyl methacrylate and 1.0 g of t-butylhydroquinone were added to the mixed solution, followed by stirring at 110 ° C. for 10 hours. This reaction solution was reprecipitated in methanol 2 again. The weight average molecular weight of the obtained pale yellow viscous material was 5,
It was 200.

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 75 ° C. while stirring under a nitrogen stream. 1.5 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 methanol 2 to obtain 86 g of a white powder. The weight average molecular weight was 3,600.

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 brought 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., followed by further stirring for 1 hour. 2,2 ′
-Methylenebis- (6-t-butyl-p-cresol)
0.5 g was added, and the mixture was stirred at a temperature of 40 ° C. for 3 hours. After cooling, this solution was reprecipitated in methanol 2 to obtain 83 g of a viscous substance. The weight average molecular weight was 3,400.

Production Example 8 of Macromonomer: M-8 A mixed solution of 95 g of methyl methacrylate, 150 g of toluene and 50 g of ethanol was heated to a temperature of 75 ° C. in a nitrogen stream. 5 g of ACV was added and reacted for 8 hours. Next, glycidyl acrylate 15 g, N, N-dimethyldodecylamine 1.0 g
And 1.0 g of 2,2'-methylenebis- (6-t-butyl-p-cresol), and the mixture was stirred at a temperature of 100 ° C for 15 hours. After cooling, the reaction solution was reprecipitated in methanol 2 to obtain 83 g of a transparent viscous substance. The weight average molecular weight was 4,800.

Macromonomer Production Examples 9 to 18: M-9 to M-18 In Macromolecule Production Example 3, except that the acid halide compounds in Table 1 were used instead of methacrylic acid chloride, the same as in Production Example 3 Operate the macromonomer M
-9 to M-18 were produced. The weight average molecular weight of each macromonomer was approximately 6,000.

Macromonomer Preparation Examples 19 to 27: M-19 to M-27 The procedure of Preparation Example 2 was repeated except that the monomers of Table 2 were used instead of benzyl methacrylate in Preparation Example 2 of the macromonomer. And the macromonomers M-19 to M-27
Was manufactured.

Macromonomer Production Examples 28 to 32: M-28 to M-32 In Macromolecule Production Example 2, except that the monomers shown in the following table were used instead of benzyl methacrylate, the same operation as in Production Example 2 was performed. Macromonomers were each produced.

Production Example 1: Resin [A] 1: [A] -1 70 g of ethyl methacrylate, macromonomer (M-
2) 30 g and a mixed solution of 150 g of toluene and 50 g of isopropanol were heated to a temperature of 80 ° C. under a nitrogen stream. Next, 4,4 '
6 g of -azobis (4-cyanovaleric acid) was added and reacted for 10 hours. The weight average molecular weight (Mw) of the obtained copolymer [A] -1 was 8.5 × 10 ³ .

Composition formula of resin (1) Production Examples 2 to 9 of Resin [A]: Resin [A] -2 to 9 In Production Example 1 of Resin [A], the macromonomer (M
Each resin [A] was produced in the same manner as in Production Example 1 except that the macromonomer shown in Table 4 below was used instead of -2). The Mw of each resin was 8.0 × 10 ^{3 to} 9 × 10 ³ .

Production Example 10 of resin [A]: resin [A] -10 propyl methacrylate 80 g, macromonomer (M-
1) A mixed solution of 20 g, 2.0 g of thioglycolic acid, 100 g of toluene and 50 g of isopropanol was heated to 70 ° C. under a nitrogen stream.
Was heated. 2,2'-azobis (isobutyronitrile)
(Abbreviated name: AIBN) 1.0g and stirred for 4 hours, then AIB
N. 0.5 g was added and the mixture was stirred for 4 hours. The Mw of the obtained polymer was 6 × 10 ³ .

Composition of Resin [A] -10 Production Examples 11 to 17 of Resin [A]: Resin [A] -11 to 17 Same as Production Example 10 except that the compounds in the following table were used instead of thioglycolic acid in Production Example 10 of Resin [A]. To produce a polymer.

Production Examples 18 to 24 of Resin [A]: Resin [A] -18 to 24 In Production Example 1 of Resin [A], instead of 4,4′-azobis (4-cyanovaleric acid), Except for using the system compound, operations were performed in the same manner as in Production Example 1 to produce polymers.

Production Example 25 of Resin [A]: Resin [A] -25 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 88 ° C. under a nitrogen stream. Next, 4,4 '
6 g of -azobis (4-cyanovaleric acid) was added and reacted for 10 hours. The weight average molecular weight of the obtained copolymer was 4.6 × 10 ³ (the composition formula of the resin [A] -25 was the same as that of the resin [A] -1).
Same as).

Production Examples 26-30 of Resin [A]: Resin [A] -26-30 Resin [A] -26-30 A mixed solution of 75 g of a monomer, 25 g of a macromonomer (M-28), 150 g of toluene and 50 g of ethanol in the following table was heated at a temperature of nitrogen under a nitrogen stream. Heated to 80 ° C. Next, 4,4'-azobis (4
5 g of (cyanovaleric acid) was added thereto, and the mixture was reacted for 10 hours to obtain a polymer shown in the following table.

Production Example 31 of Resin [A]: Resin [A] -31 60 g of ethyl methacrylate, macromonomer: AN-6
(Toa Gosei Chemical Co., Ltd .: repeating unit part: styrene / acrylonitrile) A mixed solution of 40 g, toluene 150 g and isopropanol 50 g was heated to a temperature of 80 ° C. 4.0 g of 4,4'-azobis (4-cyanovaleric acid) was added and reacted for 8 hours. Mw of the obtained polymer was 1.2 × 10 ⁴ .

Production Examples 32 to 41 of Resin [A]: Resin [A] -32 to 41 In Production Example 31 of Resin [A], instead of ethyl methacrylate and macromonomer: AN-6, compounds shown in Table 8 below, respectively. Other than replacing with, in the same manner as in Production Example 31,
Each polymer was prepared.

The Mw of each polymer was 9.0 × 10 ^{3 to} 1.5 × 10 ⁴ .

Production Example 1: Resin [B] 1: [B] -1 69.2 g of ethyl methacrylate, macromonomer (M-
1) A mixed solution of 30 g, 0.8 g of acrylic acid and 150 g of toluene was heated to a temperature of 70 ° C. under a nitrogen stream. Next, AIBN 0.5g
Was added and reacted for 10 hours. The obtained copolymer [B]-
1 had a weight average molecular weight of 9.8 × 10 ⁴ and a glass transition point of 72 ° C.

Example 1 8 g of the resin [A] -1 produced in each of the above Production Examples
32 g (as solid content) of resin [B] -1; 200 g of zinc oxide; cyanine dye 0.018 having the following structure
g, a mixture of 0.10 g of phthalic anhydride and 300 g of toluene were dispersed in a ball mill for 2 hours to prepare a photosensitive layer-formed product, and this was subjected to conductive treatment on paper so that the dry adhesion amount was 18 g / m ² . Then, the resultant was coated with a wire bar, dried at 110 ° C. for 30 seconds, and then left in a dark place at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material.

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 the 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 (as a solid content) of the resin [B] -1 was used as the binder resin.

Comparative Example C As a binder resin, only resin [C] -1 having the following structure was used.
An electrophotographic photosensitive material C was produced in the same manner as in Example 1 except that g was used.

Weight average molecular weight 35,000 Glass transition point 46 ℃ The film properties (surface smoothness), film strength, electrostatic properties, imaging properties of these photosensitive materials and the imaging properties when the environmental conditions were set to 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).

 The above results are summarized in Table-9.

The embodiments of the evaluation items shown in Table-9 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 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 mechanical strength.

Note 3) Electrostatic properties: Paper analyzer (Kawaguchi Electric Co., Ltd. paper analyzer) 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.
Next, the potential V ₇₀ after standing still in the dark for 60 seconds was measured, and the potential retention after dark decay for 60 seconds, that is, the dark decay retention rate [DRR (%) was (V ₇₀ / V ₁₀ ) × It was determined by 100 (%).

After charging the surface of the photoconductive layer to −400 V by corona discharge, the surface is irradiated with monochromatic light having a wavelength of 780 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 ).

Note 4) Image-capturability: Each photosensitive material was allowed to stand for one day under the following environmental conditions. Next, it is charged at -5 Kv, and as a light source, gallium-aluminum-arsenic with 2.8 mW output, a semiconductor laser (oscillation wavelength 780 nm)
Developed using ELP-T (manufactured by Fuji Photo Film Co., Ltd.) as a liquid developer after exposure at a pitch of 25 μm and a scanning speed of 300 m / sec under a radiation dose of 64 erg / cm ² on the surface of the photosensitive material using Then, a copied image (fog, 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 photosensitive material was treated with a desensitizing solution ELP-EX (manufactured by Fuji Photo Film Co., Ltd.), and applied to an etching processor.
After passing through the surface to desensitize the surface of the photoconductive layer, a drop of 2 μm of distilled water is placed thereon, and the contact angle with the formed water is measured with a goniometer.

Note 6) Printing durability Each of the photosensitive materials is subjected to plate making under the same conditions as above Note 4) to form a toner image, and subjected to desensitization treatment under the same conditions as above Note 5). Indicates the number of sheets that can be printed on an offset printing machine (Oliver 52, manufactured by Sakurai Seisakusho Co., Ltd.) without causing background contamination in the non-image area of the printed matter and no problem with the image quality of the image area. Is good).

Note 7) Dm (image density) Indicates the maximum value of the solid toner image density (measureable with a Macbeth reflection densitometer).

As shown in Table 9, the photosensitive material of the present invention and Comparative Example A had good photoconductive layer smoothness and electrostatic properties, and the actual copied image had no ground fog and the copied image quality was clear. This is presumed to be due to the fact that the photoconductivity and the binder resin were sufficiently adsorbed and covered the back surface of the particles.

For the same reason, even when used as an offset master master, the desensitizing treatment with the desensitizing solution proceeds sufficiently, and the contact angle with water in the non-image area is 15 ° or less and sufficiently hydrophilized. ing. Even when the printed matter was actually printed and the background stain was observed, no stain 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 serious problem occurred in durability.

In each of the photoreceptors of Comparative Example B and Comparative Example C, the film strength was sufficient, but the electrostatic characteristics, especially DRR and E1 / 10 (corresponding to high sensitivity) were significantly reduced, and the actual image was taken. However, a sufficient copied image could not be obtained. Comparative Example C
Is a polymer using a resin in which the acid component is reduced. When a high-molecular-weight polymer containing the same amount of the acid component as in Example 1 was used, it was agglomerated in dispersion with zinc oxide, and a dispersion could not be formed.

As described above, only the photosensitive material of the present invention was excellent in all aspects of the smoothness, film strength, electrostatic properties and printability of the photoconductive layer.

Examples 2 to 12 The same operation as in Example 1 except that the above resin [A] -1 and resin [B] shown in Table 10 below were used in combination at a weight ratio of (1/4). Was used to produce each photosensitive material. Example 1
In the same manner as described above, the smoothness, film strength and electrostatic characteristics of each photosensitive material were measured.

Each of the photosensitive materials of the present invention has good photoconductive layer strength and electrostatic properties, and the actual copied image has clear image quality without background fog even under high temperature and high humidity (30 ° C. and 80% RH). there were.

Example 13 Instead of the resin [A] -1 and 8 g used in Example 1, 8 g of each of the resins [A] -2 to [A] -10 produced in the same manner as in the production example of the resin [A] in 2 to 10 An electrophotographic photosensitive material was prepared in the same manner as in Example 1 except for using the same, and the same results as in Example 1 were obtained.

Example 14 Instead of 30 g of the macromonomer (M-1) used in Production Example 1 of the resin [B], the macromonomers (M-2) to (M-2) obtained in Macromonomer Production Examples 2 to 27 were obtained.
Resins [B] -13 to 38 were produced in the same manner as in Production Example 1 of Resin [B] except that 30 g of each of 7) was used. 32 g of these resins [B] used in Example 1 [B] -1, 32 g
An electrophotographic photoreceptor was produced in the same manner as in Example 1 except that each was used in place of, and the same results as in Example 1 were obtained.

 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-47-34833 (JP, A) JP-A-61-73962 (JP, A) JP-A-62-14657 (JP, A) JP-A-53-348 12623 (JP, A) JP-A-63-197964 (JP, A) JP-A-63-309971 (JP, A) JP-A-57-161863 (JP, A) JP-B-40-8221 (JP, B1)

Claims (1)

(57) [Claims] 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] and at least one of the following resins [B]. An electrophotographic photoreceptor comprising one kind. Resin [A] A polymer having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and containing at least one of polymer components represented by the following general formulas (IIa) and (IIb) A monofunctional macromonomer having a weight average molecular weight of 2 × 10 ⁴ or less, which is obtained by bonding a polymerizable double bond group represented by the following general formula (I) to only one end of the main chain, and a compound represented by the following general formula (III) a copolymer at least comprising a monomer represented, and the copolymer main chain at one terminal only -PO ₃ H ₂ group, -SO ₃ H group, -COOH group, -OH
Group, -SH group and (R is a hydrocarbon group or -OR 'group (R' represents a hydrocarbon group)) A resin obtained by bonding at least one substituent selected from an acidic group and a cyclic acid anhydride-containing group. Resin [B] has a weight average molecular weight of 2 × 10 ⁴ or more, and has the following general formula (II)
a) a polymerizable double bond group represented by the following general formula (I) bonded to only one terminal of a polymer main chain containing at least one of the polymer components represented by (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 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 -, - CONHCOO -, - CO
NHCONH−, −CONHSO ₂ −, (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 each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COOZ or -COO-Z via a hydrocarbon (Z is a hydrogen atom or Represents a good hydrocarbon group). General formula (IIa) General formula (IIb) In formula (IIa) or (IIb), X ₀ represents the same content 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 or different from each other, and have the formula (I)
It represents the same contents as a ₁ and a ₂ in the table. Q is -CN, -CONH ₂ or Represents a hydrogen atom, a halogen atom, a hydrocarbon group,
Represents an alkoxy group or -COOZ '(Z' represents an alkyl group, an aralkyl group or an aryl group). General formula (III) In formula (III), X ₁ has the same content as X ₀ in formula (IIa), and Q ₁ has the same content as Q ₀ in formula (II a).
c ₁ and c ₂ may be the same or different from each other, and in the formula (I)
Represents the same contents as a ₁ and a ₂ .