JP2640140B2 - Electrophotographic photoreceptor - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an electrophotographic photoreceptor, and more particularly, to an electrophotographic photosensitive member,
The present invention relates to an electrophotographic photosensitive member having excellent moisture resistance and durability.

(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.

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. A photoreceptor composed of a support and at least one photoconductive layer is used for image formation by the most common electrophotographic processes, ie, 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.

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, as well as the base of the formed recording material layer. It has good adhesion to materials, and the photoconductive layer of the recording layer has excellent charging ability, low dark decay, large light decay, low pre-exposure fatigue, and these characteristics due to changes in humidity during imaging. It is necessary to have various electrostatic characteristics, such as a need to stably hold, 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 material using these resins, 1) the affinity with the photoconductive powder is insufficient, and the dispersibility of the coating liquid is poor. 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) at the time of creating the copied image 5) Photosensitive layer However, when used as an offset master, there is a problem that the photosensitive layer is detached during offset printing and the number of printed sheets cannot be increased.

Various methods have been proposed as methods 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 in an aromatic ring or a furan ring, or an anhydride of a dicarboxylic acid. And JP-B-42-6878 and JP-B-45-3073 disclose a method of coexisting them in a photoconductive layer. However, even the photosensitive materials improved by these methods do not have sufficient electrostatic characteristics, and no material having particularly excellent light attenuation characteristics has 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 into the photoconductive layer has been adopted.However, the light-sensitive material produced by such a method significantly deteriorates whiteness and causes deterioration in quality as a recording medium. Causes deterioration of the dark decay of the photosensitive material,
There was a problem that a sufficient copied image could not 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, PP
A technique for improving the reproducibility as a C photoreceptor), moisture resistance and the like is described.

Furthermore, research on a lithographic printing original plate using an electrophotographic photoreceptor has been earnestly conducted, and a binder resin for a photoconductive layer having both electrostatic characteristics as an electrophotographic photoreceptor and printing characteristics as a printing original plate. For example, in Japanese Patent Publication No. Sho 50-31011, a (meth) acrylate monomer was copolymerized with another monomer in the presence of fumaric acid, and wg 1.8 × 10 ⁴ to 10 × 10 ⁴ and Tg 10
A resin obtained by using a resin at -80 ° C and a copolymer comprising a (meth) acrylate monomer and another monomer other than fumaric acid. JP-A-53-54027 discloses that a carboxylic acid group is converted from an ester bond. Using a terpolymer containing a (meth) acrylic ester having a substituent having at least 7 atoms apart, and JP-A-54-20735, JP-A-57-20254
No. 4 uses a quaternary or pentameric copolymer containing acrylic acid and hydroxyethyl (meth) acrylate,
Japanese Patent Application Laid-Open No. 58-68046 discloses a photoconductive polymer 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 characteristics, moisture resistance and durability, when actually evaluated, particularly the chargeability, the dark charge retention, the photosensitivity electrostatic characteristics, There was a problem in the smoothness of the conductive layer and the like, which was not practically satisfactory.

Also, a binder resin developed as an electrophotographic lithographic printing plate precursor has a problem in the above-mentioned electrostatic characteristics, background contamination of printed matter, etc. when actually evaluated.

Further, in order to solve these problems, a copolymer component containing an acidic group in a side chain of the polymer as a binder resin is added in an amount of 0.05%.
The use of 10% by weight content to the low molecular weight resin (w10 ³ to 10 ^4), the smoothness and electrostatic characteristics of the photoconductive layer was good, yet be obtained without background fouling quality JP 63
No. -217354, thereby further such improved low molecular weight resin by the use in combination with the high molecular weight of the resin (w10 ⁴ or higher), the adequate and tighten printing durability film strength of the photoconductive layer without inhibiting the characteristics JP-A-63-49817, JP-A-63-220
Nos. 148 and 63-220149.

(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 a semiconductor laser beam, the exposure time is longer and the exposure intensity is limited as compared with the conventional simultaneous exposure method using visible light. Higher performance is required for light sensitivity.

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.

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

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

Resin [A]; at least one of polyester-type macromonomers having a weight average molecular weight of 1.0 × 10 ^{3 to} 1.5 × 10 ⁴ represented by the following general formulas (I) and (II) as at least a polymer component: Weight average molecular weight of 1.0 × 10 ^{3 to} 2.0 × 1
0 ⁴ of the copolymer.

General formula (I) General formula (II) [Wherein [] represents a repeating unit.

a ₁ and a ₂ may be the same or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -COOZ or a hydrocarbon group having 1 to 8 carbon atoms. -COOZ (Z represents a hydrocarbon group having 1 to 18 carbon atoms).

X ₁ is a direct bond or -COO-, -OCO-, (L ₁ and l ₂ represent an integer of 1 to 3), (P ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms), -CONHCONH-, -CONHCOO-, -O-, Or -SO ₂ - represent.

Y ₁ represents a group linking X ₁ and —COO—.

W ₁ and W ₂ may be the same or different from each other, and each is a divalent aliphatic group, a divalent aromatic group ｛-O-, -S-, (P ₂ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon _{atoms), - SO 2 -, -} COO -, - OCO -, - CONHCO -, - NHC
ONH-, (P ₃ represents the same content as P ₂₎ (P ₄ represents the same content as P ₂₎ and Or an organic residue composed of a combination of these residues.

b ₁ and b ₂ represent the a ₁ and a _2, X ₂ and X _1, each same content. Y ₂ represents a group linking X ₂ and —COO—.

W ₃ represents a divalent aliphatic group. Resin [B] represented by the following general formula (III) only at one end of a polymer main chain containing at least one of the polymer components represented by the following general formulas (IVa) and (IVb) A copolymer comprising at least a monofunctional macromonomer having a weight average molecular weight of 2 × 10 ⁴ or less formed by bonding a polymerizable double bond group and a monomer represented by the following general formula (V).

General formula (III) Wherein (III), V ₀ is -COO -, - OCO -, - CH 2 OCO-,
_{-CH 2 COO -, - O -} , - SO 2 -, - CO -, - CONHCOO-,
−CONHCONH−, −CONHSO ₂ −, The expressed (P ₅ represents a hydrogen atom or a hydrocarbon group).
c ₁ and c ₂ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COOZ ′ or —COOZ ′ via a hydrocarbon (Z ′ is a hydrogen atom or a substituted Represents a hydrocarbon group which may be substituted). General formula (IVa) General formula (IVa) [In formula (IVa) or (IVb), V ₁ represents the same content as V ₀ in formula (III).

Q ₁ represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms. d ₁ and d ₂ may be the same or different and represent the same contents as c ₁ and c _{2 in} formula (III).

Q ₀ is -CN, -CONH ₂ or Wherein T represents a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group or —COOZ ″ (Z ″ represents an alkyl group, an aralkyl group or an aryl group). General formula (V) (In the formula (V), V ₂ represents the same content as V ₁ in the formula (IVa), and Q ₂ represents the same content as Q ₁ in the formula (IVa). E ₁ , e ₂ May be the same or different, and the formula (II
Represents the same contents as c ₁ and c _{2 in} I). That is, the binder resin used in the present invention may be referred to as a polyester-type macromonomer having a polymerizable double bond group at one end and a carboxyl group at the other end (hereinafter referred to as (MA)). ) As a copolymer component, a low molecular weight graft copolymer [A] and a compound of the general formula (IVa) or (I
A polymerizable double bond group at one end of the polymer main chain containing at least the polymer component of Vb) (a monofunctional macromonomer that binds the general formula (III) (hereinafter sometimes referred to as (MB)) And at least one monomer of the general formula (V)
And a resin [B] composed of a graft copolymer containing a seed.

The graft copolymer used in the resin (A) of the present invention has -PO ₃ H ₂ group, -SO ₃ H group, -COOH
Group, -OH group and {R is a hydrocarbon group or -OR ₀ group (R ₀ represents a hydrocarbon group) represents a} a polar group selected from which may have one or more (hereinafter the resin (A), particularly resin [A ']).

Conventionally known acidic group-containing binder resins as described above are mainly used for offset masters, and have a large molecular weight (for example, 5 × 10 ⁴ or more) in order to improve printing durability by maintaining film strength. Was a random copolymer, and the copolymer component containing an acidic group was randomly present in the polymer main chain.

On the other hand, the resin [A] used in the binder resin of the present invention is a graft-type copolymer, and the acidic group contained in the resin is present at random in the polymer main chain. However, it is a copolymer specifically bonded only at the end of the graft portion or only at the end of the graft portion and the end of the main chain.

Therefore, the portion of the acidic group present at a specific position away from the main chain of the polymer is adsorbed on the stoichiometric defect of the inorganic photoconductor, and the main chain portion of the polymer is exposed on the surface of the photoconductor. It is presumed that the coating is loose and sufficient. As a result, while compensating for the trap of the photoconductor and improving the humidity characteristics, the dispersion of the photoconductor is sufficiently performed, the aggregation is suppressed, and the environmental change is remarkably changed from high temperature and high humidity to low temperature and low humidity. It was found that stable high-performance electrophotographic characteristics were maintained even when it fluctuated. The resin [B] does not hinder the high performance of the electrophotographic properties due to the use of the resin [A] at all, and makes the mechanical strength of the photoconductive layer insufficient with the resin [A] alone. Things. It is particularly effective when a scanning exposure method using a semiconductor laser is used.

Further, in the present invention, the smoothness of the photoconductive layer surface becomes 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 zinc oxide particles as the photoconductor and the binder resin is not appropriate, and a state in which agglomerates are present. Because the photoconductive layer is formed, even if the desensitizing treatment with the desensitizing solution is performed, the non-image area is not sufficiently and sufficiently hydrophilicized, causing the printing ink to adhere during printing, and as a result, The background stain on the non-image portion occurs.

Furthermore, it was found that the photosensitivity was better than that of a random copolymer resin containing a polar group not in the end of the graft portion but in the side chain linked to the polymer main chain.

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

Even when only the low molecular weight resin [A] in the present invention is used as the binder resin, the photoconductor and the binder resin are sufficiently adsorbed, and the surface of the particles can be coated. It has good electrostatic characteristics and an image quality free from background contamination. Further, it has sufficient film strength as a CPC photoreceptor or an offset original plate having thousands of printed sheets. However, by coexisting the resin [B] as in the present invention, the mechanical strength of the photoconductive layer which is still insufficient with the function [A] alone without further alienating the function of the resin [A] is further improved. I was able to. Therefore, the photoreceptor of the present invention has excellent electrostatic characteristics even when environmental conditions fluctuate, has sufficient film strength, and is used under severe printing conditions (for example, when the printing pressure is increased in a large printing machine). Etc.), it is now possible to print more than 7,000 copies.

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 the same content as R). It is preferable that the resin further comprises at least one polar group selected from the group consisting of R (hereinafter, also referred to as resin [B ′]).

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 because 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 of the graft copolymer is 1 × 10 ³ to 2 × 10 ⁴ , preferably 3 × 10 ³ to 1 × 1.
0 ^4, existing ratio is 5 to 80 wt% of a copolymer component of the macromonomer (MA), preferably of the polar group in the 10 to 60% by weight, the polar group at the terminal of the copolymer main chain binds The content ratio in the copolymer is 0.5 to 15% by weight, preferably 1 to 10% by weight. The glass transition point of the resin (A) is preferably from -20 ° C to 120 ° C, more preferably from -10 ° C to 90 ° C.
° C.

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 macromonomer of the present invention as a copolymer component differs 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, a polymer chain). Entanglement), the apparent molecular weight (Mw) may be small.

When the molecular weight of the resin [A] is smaller than 1 × 10 ³ , the film-forming ability is reduced, and sufficient film strength cannot be maintained.
10 is larger than ⁴ when the electrophotographic characteristics be a resin of the present invention (particularly initial potential, dark decay retention rate) is unfavorably degraded. In particular, in the case of such a high molecular weight substance, when the content of the acidic group exceeds 3% by weight, such deterioration of the electrophotographic characteristics is remarkable, and when used as an offset master, background stain becomes remarkable.

Polar group (COOH at the graft end) in the binder resin [A]
If the content 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 content of the polar group 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.

Macromonomer (MA) having a polyester structure and serving as a copolymer component of the graft copolymer resin of the present invention, having a polymerizable double bond group at one end and a carboxyl group at the other end. Will be described more specifically.

In the general formulas (I) and (II), [] indicates that the macromonomer (MA) of the formula (I) and / or (II) has a weight average molecular weight of 1 × 10 ^{3 to} 1.5 × 10 ^4. Represents a repeating unit.

In the macromonomer of the general formula (I), preferably, a ₁ and a ₂ may be the same or different from each other, and each may be a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom,
A fluorine atom), a cyano group, an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, etc.), -COOZ
Or —CH ₂ COOZ ｛Z represents an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, etc.), and an aralkyl group having 7 to 9 carbon atoms. (For example, benzyl group, phenethyl group, 3-
Represents a phenylpropyl group or the like, or an optionally substituted phenyl group (for example, a phenyl group, a tolyl group, a xylyl group, a methoxyphenyl group, etc.).

More preferably, either one of a ₁ and a ₂ represents a hydrogen atom.

X ₁ is preferably, -COO -, - OCO -, - CH 2 COO-,
_{-CH 2 OCO -, - CONH -} , - CONHCONH -, - CONHCOO- or Represents

P ₁ is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group,
Hexyl, octyl, decyl, dodecyl, 2-
Methoxyethyl, 2-chloroethyl, 2-cyanoethyl, benzyl, methylbenzyl, chlorobenzyl, methoxybenzyl, phenethyl, phenyl, tolyl, chlorophenyl, methoxyphenyl, butylphenyl, etc. Represents

Y ₁ represents a group linking X ₁ and —COO—, and represents a group directly bonding or linking. Specifically, as a linking group -COO, -OCO, -O -, - S -, - SO 2 -, -NHCOO-, -NHCONH-, and Or a linking group formed by a combination of these linking groups. Wherein g ₁ and g ₂ may be the same or different, and each represents a hydrogen atom, a halogen atom (preferably, for example, A fluorine atom, a chlorine atom, a bromine atom, etc.) or a hydrocarbon group having 1 to 7 carbon atoms (preferably, for example, a methyl group, an ethyl group, a propyl group, a butyl group,
- chloroethyl group, 2-methoxyethyl group, 2-methoxycarbonylethyl group, a benzyl group, methoxybenzyl group, a phenyl group, methoxyphenyl group, a methoxycarbonylphenyl group and the like), g ₃ is the content of the above P ₁ Represents the same.

W ₁ and W ₂ may be the same or different from each other, each represents a binary organic residue, -O-, -S-, _{-SO -, - SO 2 -,} - COO -, - OCO -, - CONHCO -, - N
HCONH-, Represents a divalent aliphatic group or a divalent aromatic group, or an organic residue composed of a combination of these divalent residues, which may have a bonding group selected from the group consisting of: Where P ₂
To P ₄ are the same meaning as P _1.

As a divalent aliphatic group, for example, The {g ₄ and g ₅ which include, may be the same or different, each represents a hydrogen atom, a halogen atom (e.g. fluorine atom, a chlorine atom, a bromine atom) or an alkyl group (e.g. methyl group having 1 to 12 carbon atoms , Ethyl, propyl, chloromethyl, bromomethyl, butyl, hexyl, octyl, nonyl, decyl, etc.). Z is -O
—, —S— or —NR ₁ —, and R ₁ represents an alkyl group having 1 to 4 carbon atoms, —CH ₂ Cl or —CH ₂ Br.

Examples of the divalent aromatic group include a benzene ring group, a naphthalene ring group and a 5- or 6-membered heterocyclic group (a heteroatom selected from an oxygen atom, a sulfur atom and a nitrogen atom as a heteroatom constituting a heterocyclic ring) At least one). These aromatic groups may have a substituent, for example, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a propyl group) , A butyl group, a hexyl group, an octyl group, etc.) and a C1-C6 alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.) are mentioned as examples of the substituent.

As the heterocyclic group, for example, a furan ring, a thiophene ring,
Pyridine ring, pyrazine ring, piperazine ring, tetrahydrofuran ring, pyrrole ring, tetrahydropyran ring, 1,3-
Oxazoline ring and the like.

In formula (II), preferred b ₁ , b ₂ , X ₂ and Y ₂ each have the same contents as those described as preferred in a ₁ , a ₂ , X ₁ and Y ₂ of formula (I).

W ₃ represents a divalent aliphatic residue, for example, CH _2
n (n represents an integer of 2 to 18), (R ₁ and r ₂ may be the same or different and each represents a hydrogen atom,
Represents an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, and a decyl group. However, r ₁ and r ₂ do not represent a hydrogen atom at the same time), (R ₃ represents an alkyl group having 1 to 12 carbon atoms; specifically,
The same alkyl group as r ₁ and r ₂ can be mentioned. m represents an integer of 3 to 18).

In the macromonomer of the general formula (I) and the general formula (II) The following are specific examples of the portion represented by, but are not limited thereto. However, in the following examples, a is _{-H, -CH 3, -CH 2 COOCH} 3, -μ
g, shows -Br or -CN, b represents -H or -CH _3,
h represents an integer of 2 to 12, and i represents an integer of 1 to 12.

(A-15) CH ₂ = CH-CH ₂ CH _2- (A-16) CH ₂ = CH-CH ₂ -COO (CH ₂ ) _h OCO (CH ₂ ) _{i- (A-23) CH 2 =} CH-CH 2 OCO (CH 2) h - (A-24) CH 2 = CH-SO 2 (CH 2) h - Specific examples of W ₁ and W _2, are set forth below organic residues each, the present invention is not limited thereto. However, in each of the following examples, R ₁ represents an alkyl group having 1 to 4 carbon atoms, —CH ₂ Cl or —CH ₂ Br, and R ₂ has 1 to 4 carbon atoms.
8 _{alkyl, CH 2 l OR 1 (R} 1 represents the abovementioned meaning, l represents an integer of 2~8), - CH ₂ μg or -CH ₂
It indicates br, R ₃ represents -H or -CH _3, R ₄ is 1 to carbon atoms
And Z represents -O-, -S- or -NR ₁
- (R ₁ represents the above meaning) indicates, p represents an integer of 1 to 26, q represents an integer of 0 or 1 to 4, r is 1 to 10
J is 0 or an integer of 1-4, and k is 2
Represents an integer of from 6 to 6.

(B-1) CH _{2 p} (B-2) -CH = CH- (B-3) -C≡C- (R ₂ may be the same or different) (R ₁ may be the same or different) (B-11) CH ₂ CH ₂ O CH ₂ CH _{2 r} OCH ₂ CH _{2 j} (B-12) CH ₂ CH ₂ S CH ₂ CH _{2 r} (B-13) CH ₂ CH ₂ SCH ₂ CH ₂ OCH ₂ CH _{2 r} (B-23) -CH ₂ -C≡C-CH _2- (B-24) -CH ₂ -CH = CH-CH _2- (B-25) -CH ₂ OCH ₂ CH _2- (B-26) −CH ₂ CH ₂ CH ₂ O CH ₂ CH ₂ CH ₂ − (B-27) CH _{2 k} SO ₂ CH _{2 k} (B-28) CH _{2 k} S-SCH _{2 k} The macromonomer represented by the general formula (I) is described in “Polymer Data Handbook [Basic Edition]” edited by The Society of Polymer Science, Japan (1986)
Annual publications) Weight average molecular weight 1 synthesized by a polycondensation reaction of diols with dicarboxylic acids, dicarboxylic anhydrides or dicarboxylic esters, as exemplified in Baifukan, etc.
Only the hydroxyl group at one end of the polyester oligomer of × 10 ^{3 to} 1.5 × 10 ⁴ can be easily produced by a method of introducing a polymerizable double bond group by a polymer reaction.

Polyester is synthesized by a conventionally known polycondensation reaction. Specifically, Eiichiro Takiyama “Polyester Resin Handbook” Nikkan Kogyo Shimbun (1986),
"Polycondensation and Polyaddition", edited by The Society of Polymer Science, Kyoritsu Shuppan (1980), I. Goodman, "Encyclopedia of Polymer Science a"
nd Engineering Vol 12 "p1. John Wiley & Sons (1985
Annual publication) can be synthesized.

A method for introducing a polymerizable dipolymer group into only the hydroxyl group at one end of the polyester oligomer is to synthesize by using a reaction of esterification from alcohols or a reaction of urethane from alcohols in a conventionally known low molecular weight compound. Can be.

That is, a method of synthesizing a macromonomer by reacting with a carboxylic acid containing a polymerizable double bond group in a molecule, a carboxylic acid ester, a carboxylic acid halide or a carboxylic acid anhydride, and synthesizing the macromonomer, or It can be achieved by a method of synthesizing a macromonomer by urethanizing by reacting with a monoisocyanate containing a polymerizable double bond group. Specifically, the Chemical Society of Japan, “New Experimental Chemistry Lecture 1
4. Synthesis and Reaction of Organic Compounds [II], Chapter 5, Maruzen Co., Ltd. (1977), "Synthesis and Reaction of Organic Compounds [III], p. 1652, Maruzen Co., Ltd. (1978) Annual publication) can be synthesized.

The macromonomer represented by the general formula (II) is obtained by synthesizing a polyester oligomer by a self-polycondensation reaction of a carboxylic acid containing a hydroxyl group in the molecule, and then polymerizing the same as the macromonomer synthesis of the general formula (I). Can be produced by a method in which a carboxylic acid having a polymerizable double bond group and a lactone are synthesized by a living polymerization reaction. Specifically, T.
Yasuda, T. Aida and S. Inoue, J. Macromol. Sci. Chem., A, 2
1 , 1035 (1984), T. Yasuda, T. Aida and S. Inoue, Macroml
ecules, 17 , 2217 (1984), S. Sosnowski, S. Stomkowski an
d S. Penczek, Makromol. Chem. 188 , 1347 (1987), Y. Gnano
u and P. Rempp., Makromol. Chem. 188 , 2267 (1987), T. Sh
iota and Y. Goto, J. Appl. Polym. Sci., 11 , 753 (1967) and the like.

Hereinafter, formula (I) or (I) which can be used in the present invention.
Specific examples of the macromonomer represented by I) are shown below. However, in each of the following examples, [] indicates a repeating unit sufficient to make the weight-average molecular weight of the macromonomer 1 × 10 ^{3 to} 1.5 × 10 ⁴ , d indicates —H or —CH ₃ , and R
₅ and R ₆ may be the same or different and each is -CH ₃ or -C ₂ H ₅
Wherein R ₇ and R ₈ may be the same or different and each is -Cl,
-Br, indicates -CH ₂ Cl or -CH ₂ Br, s is an integer of 1 to 25, t is an integer of 2 to 12, u represents an integer of 2 to 12, x is 2 to 4 Y represents an integer of 2 to 6, and z represents an integer of 1 to 4.

The resin [A] used in the binder resin of the present invention is at least one selected from the general formulas (I) and (II).
A graft copolymer having at least one macromonomer as a copolymerization component, and the other copolymerization component is a monomer that satisfies the physical properties of the above-described binder resin and that can be radically copolymerized with the macromonomer. Any may be used.

Preferably, a monomer represented by the following general formula (VI) is used as a copolymer component in an amount of 20 to 95% by weight in the copolymer, preferably
It is contained in an amount of 40 to 90% by weight.

General formula (VI) In the general formula (VI), f ₁ and f ₂ represent the same contents as a ₁ and a ₂ in the formula (I), and more preferably represent a hydrogen atom or a methyl group.

X ₃ is -COO -, - OCO- or represents -O-, preferably a -COO-.

Q ₃ represents a hydrocarbon group having 1 to 18 carbon atoms. Preferably, 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 pentyl group, a hexyl group, an octyl group, a decyl group,
Dodecyl group, tridecyl group, tetradecyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-chloroethyl group, 2-cyanoethyl group, 2 -(N, N-dimethylamino) ethyl group, 2,3-dihydroxypropyl group, 3-canivamoylpropyl group, etc., an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group) , Methoxybenzyl, ethoxybenzyl, methylbenzyl, dimethylbenzyl, chlorobenzyl, dichlorobenzyl, dibromobenzyl, acetoxybenzyl, cyanobenzyl, naphthylmethyl, 2-naphthylethyl, etc.), carbon An optionally substituted cycloalkyl group of the formulas 5 to 8 (for example, cyclopentene) Group, a cyclohexyl group, Shikuropuchiru group), an aryl group (e.g., phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group,
Dibromophenyl, chlorobromo-phenyl, acetoxyphenyl, acetylphenyl, chloro-methyl-phenyl, bromo-methyl-phenyl, cyanophenyl, methoxycarbonylphenyl, etc.).

Further, the resin of the present invention has the above-mentioned general formula (I) and / or
Alternatively, other monomers other than these may be contained as a further copolymerization component together with the macromonomer of (II) and the monomer of general formula (VI).

For example, α-olefins, vinyl alkanoate 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 quinoline, vinyl thiazole, vinyl oxazine, etc.).

These other monomers other than the macromonomer of the formula (I) and / or (II) and the monomer of the formula (VI) are used in the copolymer.
It does not exceed 20% by weight.

In the graft copolymer of the present invention, when the amount of the copolymer component corresponding to the macromonomer (formula (I) and / or formula (II)) is 5% by weight or less, dispersion as a photosensitive layer coating material is sufficiently performed. Will be gone. If it exceeds 80% by weight, the copolymerization with the monomer of the general formula (VI) will not proceed sufficiently, and in addition to the desired graft copolymer, the monomer of the general formula (VI) or another monomer It is not preferable because a polymer having only a body can be formed. Furthermore, when these resins are dispersed, aggregation with the photoconductor occurs.

In the resin (A), in addition to a carboxyl group further bonded to the tip of the graft portion, a polar group ｛-PO ₃ H ₂ group, -SO ₃ H group, -COOH group,
-OH group, (R represents a hydrocarbon group or OR ₀ (R ₀ represents a hydrocarbon group)) may be bonded (resin [A ′]), and further combined with a resin [A] having no terminal-bonded acidic group. May be used in combination with the resin [A '].

here, In the above, the hydrocarbon group represented by R and R ₀ has 1 carbon atom
-18 aliphatic groups or C6-C12 aromatic groups. Specifically, an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group,
Decyl group, dodecyl group, 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-diethylamino group, etc.), A cycloalkyl group having 5 to 8 carbon atoms (for example, cycloheptyl group, cyclohexyl group, cyclooctyl group, etc.), an aralkyl group having 7 to 12 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl) Group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, dichlorobenzyl group, methylbenzyl group, chloro-methyl-benzyl group, dimethylbenzyl group, trimethylbenzyl group, methoxybenzyl group, etc.) Aliphatic groups, and further optionally substituted aryl groups having 6 to 12 carbon atoms (for example, phenyl group, tolyl group, xylyl group) Chlorophenyl group, bromophenyl group, dichlorophenyl group, chloro-methyl-
And an aromatic group such as a phenyl group, a methoxyphenyl group, a methoxycarbonylphenyl group, a naphthyl group, and a chloronaphthyl group.

Examples of the OH group include alcohols containing a vinyl group or an allyl group (e.g., ester substituents such as allyl alcohol, methacrylic acid ester and acrylamide, and compounds containing an -OH group in the N-substituent), hydroxyphenol or hydroxyphenol. Examples thereof include methacrylic esters or amides containing a phenyl group as a substituent.

As a method for producing the resin [A '], specifically, a method using a polymerization initiator containing the polar group or a functional group which can be converted into a polar group after being converted, or a method using the polar group or a A method using a chain transfer agent containing a functional group that can be converted to a polar group, a method using both of them, and a method using a termination reaction in an anionic polymerization method to introduce the functional group, etc. be able to.

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
pl. 12 , 163 (1985) and the like.

The binder resin of the present invention may contain two or more kinds of the resin [A] (including the resin [A ']) as described above.

On the other hand, the resin [B] is a resin that satisfies the above-mentioned properties and is composed of a graft copolymer containing at least a monofunctional macromonomer (MB) and a monomer represented by the general formula (V). It is characterized by things.

The resin [B] preferably has a weight average molecular weight of 3 × 10 ⁴
The above is a graft copolymer resin. More weight average molecular weight of ⁵ × 10 ⁴ ~3 × 15 5 preferably.

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

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

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

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

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

c ₁ and c ₂ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (for example, a chlorine atom,
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.), -COOZ 'or -COOZ' (Z '
Represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, and specifically,
Represents a represents) the same contents as those described for P _5.

Examples of the hydrocarbon in the —COOZ ′ group via the above hydrocarbon include a methylene group, an ethylene group, and a propylene group.

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

That is, as the polymerizable double bond group represented by the general formula (III), specifically, And the like.

In the general formula (IVa), V ₁ represents the same content as V ₀ in the formula (III).

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

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

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

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

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

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

In the formula (IVb), Q ₀ is -CN, -CONH ₂ or T 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, A methoxy group, an ethoxy group or the like) or -COOZ "(Z" preferably represents an alkyl group having 1 to 8 carbon atoms, an aralkyl group or an aryl group having 7 to 12 carbon atoms).

The macromonomer (MB) may contain two or more polymer components represented by the formula (IVa) or (IVb). In the formula (IVa), when Q ₁ is an aliphatic group, the aliphatic group having 6 to 12 carbon atoms may be used in an amount not exceeding 20% by weight of the total polymer components in the macromonomer (MB). preferable.

Further, when V ₁ in the general formula (IVa) is —COO—, the polymer component represented by the formula (IVa) is at least 30% by weight or more in all the polymer components in the macromonomer (MB). It is preferable to be contained.

In the macromonomer (MB), acrylonitrile, methacrylonitrile, acrylamides, methacrylic acid, etc. may be used as a monomer corresponding to a repeating unit copolymerizable with the polymer component represented by the formula (IVa) and / or (IVb). 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.).

The macromonomer (MB) used in the present invention is, as described above, a compound represented by the general formula (III) only at one end of the polymer main chain composed of the repeating units represented by the general formulas (IVa) and / or (IVb). The polymerizable double bond group represented by ()) has a chemical structure directly bonded or bonded by an arbitrary linking group. Examples of the group linking the component of the formula (III) and the component of the formula (IVa) or (IVb) include a carbon-carbon bond (single bond or double bond) and a carbon-heteroatom bond (for example, an oxygen atom, Sulfur atom,
Nitrogen atom, silicon atom, etc.) and any combination of heteroatom-heteroatom bond atomic groups.

Preferred among the macromonomers (MB) of the present invention are those represented by formula (VIIa) or (VIIb).

Formula (VIIa) Formula (VIIb) In the formula (VIIa) or (VIIb), c ₁ , c ₂ , d ₁ , d ₂ , V ₀ ,
V ₁ , Q ₁ and Q ₀ are respectively represented by the formula (III), the formula (IVa) and the formula (IV
Represents the same content as described in b).

W ₀ is a simple bond or [H ₁ and h ₂ each 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.) Show], CH = CH, -O-, -S-, -COO -, - SO ₂ -, -NHCOO-, -NHCONH-, [H ₃ and h ₄ each represent a hydrogen atom or a hydrocarbon group having the same content as Q ₁ in the formula (IVa)], or a single linking group selected from an atomic group or an arbitrary combination thereof. Represents a linking group.

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

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

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. Et al, Makramol, Chem. Suppl.
8 , 3 (1984), Yusuke Kawakami, Chemical Industry, 38 , 56 (1987), Yuya Yamashita, Polymer, 31 , 988 (1982), Shiro Kobayashi, Polymer,
30 , 625 (1981), Toshinobu Higashimura, Journal of the Adhesion Society of Japan 18 , 536 (19
82), Koichi Ito, Polymer Processing, 35 , 262 (1986), Higashi Kishiro, Takashi Tsuda, Functional Materials, 1987 No.10,5, etc. 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.

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

The monomer copolymerized with the macromonomer (MB) is represented by the general formula (V). In the formula (V), e ₁ ,
e ₂ may be the same or different from each other;
Represents the same content as c ₁ and c ₂ . V ₂ is equal to V ₁ of the formula (IVa) and Q
₂ represents the same contents as Q ₁ in the formula (IVa).

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

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

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

The above-mentioned vinyl compound containing an acidic group is described, for example, in “Polymer Data Handbook [Basic Edition]” edited by The Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α-acetoxy form)
(2-amino) methyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α-chloro-β-
Methoxy, α, β-dichloro), methacrylic acid,
Itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (eg, 2-pentenoic acid, 2-methyl-2-hexenoic acid,
-Octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinyl Examples include half-ester derivatives of vinyl or allyl groups of sulfonic acids, vinylphosphonic acids and dicarboxylic acids, and ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing an acidic group in the substituents of the amide derivatives.

In the case where the "vinyl compound having 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.

Further, the resin [B '] which can be used as a preferred embodiment of the present invention contains at least one kind of a repeating unit represented by the general formula (V) and at least one kind of a repeating unit represented by a macromonomer (MB). at one end of the polymer main chain only, -PO ₃ H ₂ group, -SO ₃ H group, -COOH group, -OH
This is a polymer formed by bonding at least one polar group selected from a group, a SH group and a PO ₃ R′H group.

Here, R ′ in the —PO ₃ R′H group represents the same content as the above-mentioned R {hydrocarbon group or —OR ₀ group (R ₀ represents a hydrocarbon group)}. The same ones as described above can be mentioned as specific examples.

When the above-mentioned polar group is bonded to one end of the polymer main chain, the polymer main chain should not contain a copolymer component containing a carboxyl group, a sulfo group, a hydroxyl group, or a phosphono group. Is preferred.

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

Examples of the bonding group include a carbon-carbon bond (single bond or double bond), a carbon-heteroatom bond (for example, an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom), and a heteroatom-heteroatom bond. It is composed of any combination of atomic groups. For example, (H _5, h ₆ represents h _1, h ₂ same contents as the), CH
= CH, -0-, -S-, -COO -, - SO ₂ -, -NHCOO-, -NHCONH-, (Each h _7, h ₈ represents the h _3, h ₄ same contents as above)
And the like, or a single linking group selected from an atomic group such as the above, or a linking group composed of an arbitrary combination.

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

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

Specifically, P. Dreyfuss, RPQuirk, Encycl.Polym.Sc
Review of 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 resin [B] are used in a ratio of 5 to 80 to 95 to 20 (weight ratio).
And preferably 10 to 60 to 90 to 40 (weight ratio).

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

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 et al., RC
A Review 15 , 469 (1954), Kohei Kiyota, IEICE Transactions J 63-C (No.2), 97 (1980), Yuji Harasaki et al., 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.
No. 0334, JP-A-50-114227, JP-A-53-39130, JP-A-53-82353, U.S. Pat.No. 3,052,540, U.S. Pat.
54,450 and JP-A-57-16456.

Oxonol dyes, merocyanine dyes, cyanine dyes, polymethine dyes such as 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 No.3,121,008, U.S. Patent No.3,125,447, U.S. Patent No.3,128,179, U.S. Patent No.3,132,942, U.S. Patent No.3,622,317, U.K. Patent No.1,226,892, U.K. Patent No.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 that spectrally sensitizes 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, Showa 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
No. 27551, U.S. Pat.No. 3,619,154, U.S. Pat.
Issue 6, Research Disclosure, 1982, 216, 117-11
Those described on page 8 and the like can be mentioned. The photoreceptor of the present invention is excellent in that even when 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 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 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 μm, particularly preferably from 10 to 50 μm.

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

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

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

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

As the resin used for forming the insulating layer or the charge transport layer, typical ones are polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-copolymer resin, A thermoplastic resin 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 an example of a conductor substrate or a conductive material, Yukio Sakamoto, Electrophotography, 14, (No. 1), p2-11 (197)
5), Hiroyuki Moriga, “Chemistry of Introductory Special Paper”, Polymer Publishing Association (1
975), MF Hoover, J. Macromol. Sci. Chem. A-4 (6),
Those described in pages 1327 to 1417 (1970) and the like are used.

Examples of the binder resin of the present invention include the resin [A] described above. (Examples) Examples of the present invention will be described below, but the content of the present invention is not limited thereto.

(Synthesis Example of Macronomer Used for Resin [A]) Synthesis Example 1 of Macromonomer 1: 90.1 g of MM-1 1,4-butanediol, 105.1 g of succinic anhydride, p
A mixture of 1.6 g of toluenesulfonic acid monohydrate and 200 g of toluene was heated under reflux for 4 hours with stirring in a flask equipped with a Dean-Stark reflux apparatus. The amount of water distilled off azeotropically with the toluene solvent was 17.5 g.

Next, a mixed solution of 17.2 g of acrylic acid and 150 g of toluene and 1.0 g of t-butylhydroquinone were added to the above reaction product, and the mixture was further reacted under reflux with stirring for 4 hours. After cooling to room temperature, the precipitate was reprecipitated in 2 l of methanol, and the precipitated solid was collected by filtration and dried under reduced pressure.

The yield was 135 g and the (MM-1) weight average molecular weight of the obtained macromonomer was 6.8 × 10 ³ .

_{(MM-1) CH 2 =} CH-COOCH 2 4 OCOCH 2 2 COOH synthesis of Macromonomer Example 2: MM-2 1,6- hexanediol 120 g, anhydrous glutaric acid 114.1
g, p-toluenesulfonic acid monohydrate 3.0 g and toluene 2
50 g of the mixture was reacted under the same conditions as in Synthesis Example 1 of the macromonomer. The amount of water distilled off azeotropically was 17.5 g.

After cooling to room temperature, the precipitate was reprecipitated in 2 l of n-hexane. The liquid was decanted, collected and dried under reduced pressure.

The carboxyl group content was measured by a method in which the above reaction product was dissolved in toluene and neutralized and titrated with a 0.1N methanolic potassium hydroxide solution to give 500 μmol / gr.

A mixture of 100 g of the above solid, 8.6 g of methacrylic acid, 1.0 g of t-butylhydroquinone and 200 g of methylene chloride was dissolved at room temperature with stirring.

Dicyclohexylcarbodiimide (DCC) 20.3 g, 4
A mixed solution of 0.5 g of-(N, N-dimethyl) aminopyridine and 100 g of methylene chloride was titrated to the above mixture with stirring for 1 hour. The mixture was further stirred for 4 hours.

As the DCC solution was added dropwise, insoluble crystals precipitated. The reaction mixture was filtered through a 200 mesh nylon cloth to remove insolubles.

The filtrate was reprecipitated in 2 l of hexane, and the powder was collected by filtration. After 500 ml of acetone was added thereto and the mixture was stirred for 1 hour, the insoluble matter was subjected to gravity filtration using filter paper. After the filtrate was concentrated under reduced pressure until the total volume became half, this solution was added to ether 1 and stirred for 1 hour. The precipitated solid was collected by filtration and dried under reduced pressure.

The weight average molecular weight of the macromonomer (MM-2) obtained in a yield of 53 g was 8.2 × 10 ³ .

Synthesis Example 3 of Macromonomer: MM-3 500 g of 12-hydroxystearic acid was stirred in an oil bath at an external temperature of 150 ° C. under a reduced pressure of 10 to 15 mmHg for 10 hours while distilling off generated water.

The carboxyl group content of the obtained liquid is 600 μmol / gr
Met. 100 g of the above liquid material, methacrylic anhydride 18.5
g, a mixed solution of 1.5 g of t-butylhydroquinone and 200 g of tetrahydrofuran were stirred at a temperature of 40 to 45 ° C. for 6 hours. The reaction mixture was added dropwise to water 1 with stirring for 1 hour and further stirred for 1 hour. After standing, the precipitated liquid was taken out by decantation, dissolved in 200 g of THF, and reprecipitated in methanol 1. The sedimented liquid was taken out by decantation and dried under reduced pressure.

In a yield of 62 g, the weight average molecular weight of the macromonomer (MM-3) was 6.7 × 10 ³ .

Synthesis Example 4 of Macromonomer: MM-4 According to the synthesis method described in S. Penczek et al. Makromol. Chem. 188.1347 (1987), a macromonomer having the following structure (MM
-4) was synthesized.

Weight average molecular weight: 7.3 × 10 ³ (Synthesis example of resin [A]) Synthesis example 1: Resin [A] 60 g of A-1 benzyl methacrylate, 20 methyl acrylate
g, a mixture of 20 g of the compound (MM-1) of Synthesis Example 1 of macromonomer and 200 g of toluene were heated to 90 ° C. under a nitrogen stream. 2,2'-azobisisobutyronitrile (abbreviation AI
BN) was added and stirred for 4 hours. Further, 2 g of AIBN was added, followed by 2 hours, and then 1 g of AIBN was further added, followed by stirring for 3 hours. The weight average molecular weight of the obtained copolymer [A-1] is 9.
It was 6 × 10 ³ .

Synthesis Example 2: Resin [A]: A-2 50 g of benzyl methacrylate, 50 g of compound (MM-2) of Synthesis Example 2 of macromonomer, n-dodecyl mercaptan
A mixed solution of 1.0 g and toluene 200 g was heated to a temperature of 75 under a nitrogen stream.
Warmed to ° C.

2,2'-azobisisobutyronitrile (AIBN) 1.0
g was added and stirred for 4 hours. Add AIBN 0.4g and add 2
After that, 0.2 g of AIBN was added, followed by stirring for 3 hours.

The weight average molecular weight of the obtained copolymer [A-2] is 7.5.
× was 10 ^3.

Synthesis Example 3 of Resin [A]: A-3 A mixed solution of 47 g of 2-bromophenyl methacrylate, 50 g of the compound of Synthesis Example 3 (MM-3) of macromonomer, 3.0 g of thioglycolic acid and 200 g of toluene was placed in a nitrogen stream. To a temperature of 75 ° C. Add 1.5g of AIBN and stir for 4 hours
Add 0.4g of AIBN and 2 hours, then add more AIBN
0.2 g was added and stirred for 3 hours. The obtained copolymer [A-
3] had a weight average molecular weight of 7.0 × 10 ³ .

Synthesis Example 4: Resin [A]: A-4 A mixture of 60 g of 2-chlorophenyl methacrylate, 40 g of the compound (MM-4) of Synthesis Example 4 of macromonomer, 150 g of toluene and 50 g of isopropyl alcohol was heated at 85 ° C. under a nitrogen stream. Was heated. 5.0 g of 4,4'-azobis (2-cyanovaleric acid) (abbreviation: ACV) was added and stirred for 4 hours.
Next, 1 g of ACV was added and the mixture was stirred for 2 hours, and then 1 g of ACV was added and stirred for 3 hours. The weight average molecular weight of the obtained copolymer [A-4] was 8.5 × 10 ³ .

Synthesis Examples 5 to 14 of Resin [A]: A-5 to A-14 Resins [A] shown in Table 1 below were produced in the same manner as in Synthesis Example 1 of Resin [A]. The weight average molecular weight of each of the obtained resins was 8.5 × 10 ^{3 to} 1.0 × 10 ⁴ .

Synthesis Examples 15-20 of Resin [A]: A-15-20 In Synthesis Example 3 of Resin [A], 3 g of thioglycolic acid was used.
Each resin [A] was produced in the same manner as in Synthesis Example 3 of resin [A] except that 3 g of each of the mercapto compounds (chain transfer agents) shown in Table 2 below was used instead of the above.

Synthesis Example 21 of Resin [A]: A-21 A mixture of 50 g of 2,6-dichlorophenyl methacrylate, 50 g of the compound of Synthesis Example 1 (MM-1) of macromonomer, 2 g of thioglycolic acid, 150 g of toluene and 50 g of ethanol was passed through a nitrogen stream. Below, it was heated to a temperature of 80 ° C. 3 g of ACV was added and reacted for 4 hours, and 1.0 g of ACV was further added and reacted for 4 hours. The weight average molecular weight of the obtained copolymer [A-21] was 8.5 × 10 ³ .

Resin [A] Synthesis Examples 22 and 23: [A-22] and [A-23] The following resin [A-] was synthesized in the same manner as in Resin [A] Synthesis Example 3.
22] and [A-23] were each produced.

Weight average molecular weight: 8.6 × 10 ³ Weight average molecular weight: 8.1 × 10 ³ (weight composition ratio) Synthesis Examples 24 to 25 of Resin [A] Resins shown in Table 3 below were produced in the same manner as in Synthesis Example 3 of Resin [A]. The weight average molecular weight of each resin obtained is
It was 3.0 × 10 ³ to 8 × 10 ⁴ .

(Production Example of Macromonomer Used for Resin [B]) 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 while stirring.
Heated to a temperature of 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: M-2 A mixed solution of 95 g of methyl methacrylate, 5 g of thioglycolic acid and 200 g of toluene was stirred under a nitrogen stream,
Heated to a temperature of 70 ° C. 1.5 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 2 l of methanol to obtain 85 g of a colorless and transparent viscous substance. 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.

Next, the reaction solution was 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 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 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 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.

The obtained reaction product was cooled and then reprecipitated in 2 l of methanol to obtain 75 g of a colorless and transparent viscous substance. 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
1.0 g of -dimethyldodecyl methacrylate and 1.0 g of t-butylhydroquinone were added, and the mixture was stirred at 110 ° C for 10 hours. This reaction solution was reprecipitated again in 21 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 70 ° C. while stirring under a nitrogen stream. 1.0 g of AIBN was added and reacted for 8 hours. Next, glycidyl methacrylate 13 was added to the reaction solution.
g, 1.0 g of N, N-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,
86 g of a white powder was obtained. The number average molecular weight of the polymer (M-6) was 3,500.

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., followed by further stirring 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: M-8 95 g of 2-chlorophenyl methacrylate, 150 g of toluene
g and ethanol 150 g in a nitrogen stream at a temperature of 75
Warmed to ° C. 5 g of ACV was added and reacted for 8 hours. Next, 15 g of glycidyl acrylate, 1.0 g of N, N-dimethyldodecylamine and 1.0 g of 2,2′-methylenebis- (6-t-butyl-p-cresol) were 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 substance. The number average molecular weight of the polymer (M-8) was 3,600.

Macromonomer Production Examples 9 to 18: M-9 to M-18 The same as Production Example 3 except that the acid halide compounds in Table 4 were used instead of methacrylic acid chloride in Macromonomer Production Example 3. To produce macromonomers (M-9) to (M-18), respectively.

In addition, w of the macromonomer of (M-9) to (M-18) is 4.
000-5,000.

Macromonomer Preparation Examples 19 to 27: M-19 to M-27 In the same manner as in Preparation Example 2, except that the monomers of Table 5 were used instead of methyl methacrylate in Preparation Example 2 of the macromonomer. Macro monomer (M-19) ~ (M-2
7) Manufactured.

(Production Example of Resin [B]) Production Example 1 of Resin [B] 1: [B-1] 70 g of ethyl methacrylate, macromonomer (M-
1) A mixed solution of 30 g and 150 g of toluene was heated under a nitrogen stream at a temperature of 7
Warmed to 0 ° C. Next, 0.5 g of AIBN was added and reacted for 4 hours. Further, 0.3 g of AIBN was added and reacted for 6 hours.
The weight average molecular weight of the obtained copolymer [B-1] is 9.8 × 1
0 Glass transition point ⁴ was 72 ° C..

Production Examples 2 to 15 of Resin [B]: Resins [B-2] to [B-15] Under the same polymerization conditions as in Production Example 1 of Resin [B], the following Table-
Resin [B] of No. 6 was produced. The w of each resin is 8 × 10 ⁴ ~
The range was 1.5 × 10 ⁵ .

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

Production Examples 17 to 24 of Resin [B]: Resins [B-17] to [B-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 7 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): Resins (B-25) to (B-31) In Production Example 16 of Resin (B), instead of ACV,
Except that the azobis compound shown in Table 8 below was used,
By operating in the same manner as in the above, each of the polymers was manufactured in the same manner.

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

Production Examples 33 to 39 of Resin [B]: Resins [B-33] to [B-39] Except for using the compounds of Table 9 below in place of thioglycolic acid in Production Example 32 of Resin [B], A polymer was produced in the same manner as in Production Example 32.

Production Examples 40 to 48 of Resin (B): [B-40] to [B-48] The same polymerization conditions as in Production Example 26 of Resin (B) shown in Table 10 below.
Was produced. W of each resin is 9.5 × 10 ^{4 to} 1.2
× 10 ⁵ range.

Production Examples 49 to 56 of Resin (B): (B-49) to (B-56) Under the same polymerization conditions as in Production Example 16 of Resin (B),
Each resin shown in Table 11 below was produced. Each resin obtained [B]
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-4] produced in Synthesis Example 4 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 a cyanine dye [A] having the following structure, 0.40 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 20 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 34 g of the resin [B-16] was used instead of 34 g of the resin [B-1].

Comparative Example A The resin used as a binder resin in Example 1 [A-
In place of [4] and [B-1], only resin [A-4] was used.
An electrophotographic photosensitive material A was produced in the same manner as in Example 1 except that 40 g (as a 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.

w: 6,500 Tg 40 ° C [weight composition ratio] Comparative Example C The same operation as in Example 1 except that 6 g of the above-mentioned resin [R-1] and 34 g of the above-mentioned resin [B-1] (as solid content) were used as the binder resin. To prepare an electrophotographic photosensitive material C.

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.

w: 4,500 Tg 46 ° C [Weight composition ratio] The film properties of these photosensitive materials (surface smoothness), film strength, electrostatic properties, imaging properties, and static electricity when the environmental conditions are 30 ° C and 80% RH The characteristic imaging body was 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-12.

The embodiments of the evaluation items shown in Table-12 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 the mechanical strength.

Note 3) Electrostatic characteristics: Paper analyzer (paper analyzer manufactured by Kawaguchi Electric Co., Ltd.) in a dark room at a humidity 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, the potential V ₁₉₀ after standing still in the dark for 180 seconds was measured, and the retention of the potential after dark decay for 180 seconds, that is, the dark decay retention rate [DRR (%) was (V ₁₉₀ / V ₁₀ ) × 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.
Calculate the time to 1/10 decay and calculate 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, 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.

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

Note 5) Contact angle with water: Using a solution obtained by diluting each photosensitive material ELP-EX (manufactured by Fuji Photo Film Co., Ltd.) twice with distilled water,
After passing through an etching processor once to desensitize the surface of the photoconductive layer, a drop of 2 μl 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 in Note 4) above to form a toner image, and is subjected to desensitization treatment under the same conditions as in Note 5) above. (Oliver 52 type manufactured by Sakurai Seisakusho Co., Ltd.) indicates the number of sheets that can be printed without causing background contamination in the non-image area of the printed matter and no problem in the image quality of the image area. Represents that).

As shown in Table 12, only Comparative Example D using a conventionally known resin was extremely poor in the smoothness and electrostatic properties of the photosensitive layer.

In Comparative Examples B and C, the environmental conditions were high temperature and high humidity (30 degrees, 80%
RH), the electrostatic characteristics fluctuate and decrease, especially
The DRR worsened for 180 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. Comparative Example D has film strength,
Neither the electrostatic property nor the printing property was at a level that could withstand practical use.

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 master plate, the desensitizing treatment with the desensitizing solution has sufficiently proceeded, and the contact angle with water of the non-image portion is as small as 15 ° or less, and is sufficiently hydrophilic. 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 problem occurred in durability.

Further, in the photosensitive material of the present invention, Example 2 in which the binder resin contained a polar group in the binder resin [B] had further improved film strength compared to Example 1 in terms of the number of printings as an offset master master. Improved.

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

Examples 3 to 22 In Example 1, 6 g of the resin [A-4] and the resin [B-
1) 6 g of each of the resins [A] in Table 13 below in place of 34 g,
Resin [B] was used in an amount of 34 g each, and cyanine dye [A] 0.0
Instead of 18 g, cyanine dye [B] having the following structure: 0.018 g
Each photosensitive material was produced in the same manner as in Example 1 except that the above was used.

As shown in Table 13, excellent results were obtained in the present invention. When the resin [B] contains a polymer component containing an acidic group or contains a terminal polar group, the printing durability is particularly improved.

Examples 23 to 36 In Example 1, 6 g of resin [A-4] and resin [B-
1) 6 g of each of the resins [A] in Table 14 below in place of 34 g,
Resin [B] was used in an amount of 34 g each, and cyanine dye [A] 0.018
Each photosensitive material was prepared in the same manner as in Example 1 except that 0.016 g of methine dye [C] having the following structure was used instead of 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 severe conditions (80% RH), clear images without fog were obtained.

Examples 37 to 40 As a binder resin, the resin [A] 6.5 g described in Table 15 below
And resin [B] 33.5 g, zinc oxide 200 g, Rose Bengal
0.05 g, bromophenol blue 0.03 g, uranine 0.02
g, phthalic anhydride 0.3 g and toluene 240 g were dispersed in a ball mill for 3 hours. With this in conductive treated paper, as a dry coverage of 20 g / m ² was coated with a wire bar
Heated at 110 ° C. for 30 seconds. Then, the mixture was allowed to stand at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material.

The photosensitive materials of the present invention are all excellent in chargeability, dark charge retention, and photosensitivity.
Even under severe conditions (.degree. C.-80% RH), clear images without fog were obtained.

Further, a printed material having a clear image quality was obtained in a place where printing was performed by using this as an original master of the offset master and in a place where the number of printings was as shown in Table-9.

However, in E _1/10 of the electrostatic characteristics, the surface of the photoconductive layer was charged to −400 V by corona discharge, and then the surface of the photoconductive layer was irradiated with visible light having an illuminance of 2.0 lux, and the surface potential (V ₁₀ )
The time until the light decay to 1/10 is calculated.
_1/10 (looks / second) was calculated.

In the plate making of the photosensitive material, a toner image was formed by using a fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) using ELP-T as a toner.

(Effects of the Invention) According to the present invention, an electrophotographic photosensitive member having excellent electrostatic characteristics and mechanical strength can be obtained.

Claims (3)

(57) [Claims] An electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor and a binder resin, wherein the binder resin comprises at least one of the following resins [A] and a resin [B An electrophotographic photoreceptor comprising at least one of the following: Resin [A]; at least one of polyester-type macromonomers having a weight average molecular weight of 1.0 × 10 ^{3 to} 1.5 × 10 ⁴ represented by the following general formulas (I) and (II) as at least a polymer component: Weight average molecular weight of 1.0 × 10 ^{3 to} 2.0 × 10 ⁴
Copolymer. General formula (I) General formula (II) [Wherein [] represents a repeating unit. a ₁ and a ₂ may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -COO-Z or a hydrocarbon group having 1 to 8 carbon atoms. -Z-COO-Z (Z represents a hydrocarbon group having 1 to 18 carbon atoms). X ₁ is a direct bond or -COO-, -OCO-, (L ₁ and l ₂ represent an integer of 1 to 3), (P ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms), -CONHCONH-, -CONHCOO-, -O-, Or -SO ₂ - represent. Y ₁ represents a group linking X ₁ and —COO—. W ₁ and W ₂ may be the same or different from each other, and each is a divalent aliphatic group, a divalent aromatic group ｛-O-, -S-, (P ₂ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon _{atoms), - SO 2, -COO -} , - OCO -, - CONHCO -, - NHCON
H-, (P ₃ represents the same content as P _2), (P ₄ represents the same content as P ₂₎ and Or an organic residue composed of a combination of these residues. b ₁ and b ₂ represent the same contents as a ₁ and a ₂ , X ₂ and X ₁ , respectively. Y ₂ represents a group linking X ₂ and —COO—. W ₃ represents a divalent aliphatic residue. Resin [B] represented by the following general formula (III) only at one end of a polymer main chain containing at least one of the polymer components represented by the following general formulas (IVa) and (IVb) A copolymer comprising at least a monofunctional macromonomer having a weight average molecular weight of 2 × 10 ⁴ or less formed by bonding a polymerizable double bond group and a monomer represented by the following general formula (V). General formula (III) Wherein (III), V ₀ is -COO -, - OCO -, - CH 2 OCO-,
_{-CH 2 COO -, - O -} , - SO 2 -, - CO -, - CONHCOO-,
−CONHCONH−, −CONHSO ₂ −, The expressed (P ₅ represents a hydrogen atom or a hydrocarbon group).
c ₁ and c ₂ may be the same or different, and each may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COOZ ′
Or -COO-Z 'through a hydrocarbon (Z' represents a hydrogen atom or a hydrocarbon group which may be substituted). General formula (IVa) General formula (IVb) [In formula (IVa) or (IVb), V ₁ represents the same content as V ₀ in formula (III). Q ₁ represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms. d ₁ and d ₂ may be the same or different and represent the same contents as c ₁ and c _{2 in} formula (III). Q ₀ is -CN, -CONH ₂ or Wherein T represents a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, or -COOZ ″ (Z ″ represents an alkyl group,
Represents an aralkyl group or an aryl group). General formula (V) Wherein (V), V ₂ represents the V ₁ same contents as in the formula (IVa), Q ₂ represents Q ₁ same contents as in the formula (IVa).
e ₁ and e ₂ may be the same or different and represent the same contents as c ₁ and c _{2 in} formula (III). ] 2. The copolymer of resin [A] further comprises -PO ₃ H ₂ ,
-SO ₃ H group, -COOH group, and -OH group {R represents a hydrocarbon group or —OR ₀ group (R ₀ represents a hydrocarbon group)}, and at least one polar group selected from the above is bonded to one end of the main chain of the copolymer. The electrophotographic photosensitive member according to claim 1, wherein: 3. The copolymer of resin [B] further comprises -PO ₃ H
₂ group, -SO ₃ H group, -COOH group, -OH group, -SH group and (1) or (2), wherein at least one polar group selected from (R 'represents the same content as R) is bonded to one end of the main chain of the copolymer. Electrophotographic photoreceptor.