JPH0422961A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To maintain stable and good electrostatic characteristics and to obtain sharp and good-quality images by incorporating a specified binder resin, a thermo-and/or photo-setting resin, and a cross-linking agent. CONSTITUTION:The electrophotographic sensitive body has a photoconductive layer comprising at least an inorganic photoconductor and a binder resin composed of the cross-linking agent and the binder resin A having a weight average molecular weight of 1X10<3>-2X10<4> and at least repeating units each having an acid group, such as -PO3H2, -COOH, -SO3H, phenolic -OH, or a cyclic acid anhydride group, and the thermo-or photo-setting binder resin B having repeating units each represented by formula I, R1 being a hydrocarbon group, thus permitting the obtained image to be superior in electrostatic characteristics and of sharp and good image quality.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having excellent electrostatic properties, moisture resistance, and durability.

(Prior Art) Electrophotographic photoreceptors have various configurations in order to obtain predetermined characteristics or depending on the type of electrophotographic process to which they are applied.

As representative electrophotographic photoreceptors, there are photoreceptors having a photoconductive layer formed on a support and photoreceptors having an insulating layer on the surface, which are widely used. Photoreceptors comprising a support and at least one photoconductive layer are used for image formation by most common electrophotographic processes, ie, charging, image exposure and development, and optionally transfer.

Furthermore, a method of using an electrophotographic photoreceptor as an offset original plate for direct plate making is widely used.

The binder used to form the photoconductive layer of the electrophotographic photoreceptor has excellent film-forming properties and dispersibility of the photo-iconductive powder into the binder, and also has excellent properties in the formation of the recording layer formed. It has good adhesion to the substrate, and the photoconductive layer of the recording layer has excellent charging ability, has low dark decay, large light decay, and low pre-exposure fatigue, and can be easily affected by changes in humidity during imaging. It is necessary to have various electrical properties such as stable filter properties and excellent imaging properties.

Furthermore, research is being carried out on lithographic printing original plates using electrophotographic photoreceptors, and a binder for the photoconductive layer that has both the electrostatic properties of an electrophotographic photoreceptor and the printing characteristics of an Si + original plate has been developed. Requires resin.

However, conventionally known resins have many problems, particularly in chargeability, dark charge retention, electrostatic properties of light intensity, smoothness of the photoconductive layer, etc., and are not practically satisfactory.

Furthermore, even in the case of a binder resin which is said to have been developed as an original plate for electrophotographic lithographic printing, when actually evaluated, there were problems with the above-mentioned electrostatic properties, scumming of printed matter, etc.

Furthermore, in order to solve these problems, a copolymer component containing an acidic group in the side chain of the polymer was used as a binder resin.
Low molecular weight resin containing 5-10% by weight (edited lO3-1
0') or a low molecular weight resin C~103~104) in which an acidic group is bonded only to one end of the polymer main chain, the smoothness and electrostatic properties of the photoconductive layer can be improved. , and to obtain image quality without background smearing
-217354, 6470761 and JP-A-2
-67563, respectively.

Also, as a binder resin, a resin containing an acidic group in the side chain of the copolymer or a polymeric component bonded to the end of the main chain of the polymer and containing a heat- and/or photo-curable functional group. Techniques using
9690, and JP-A-1-102573 and JP-A-2-874 disclose a technique of using a resin containing an acidic group in the side chain of the copolymer or bonding to the end of the main chain of the polymer in combination with a crosslinking agent. Furthermore, the low molecular weight resin (weight average molecular weight 103 to 10") is mixed with a high molecular weight resin (weight average molecular weight lO").
The technology used in combination with the above resins was disclosed in Japanese Patent Application Laid-open No. 64-56.
No. 4, No. 63-220149, No. 63-220148
JP-A-1-280761, JP-A-1-116643 and JP-A-1-169455 disclose the technique of using such low molecular weight substances in combination with heat and/or photo-curable resins.
JP-A-211766 and JP-A-2-34859 disclose techniques for using such low molecular weight substances in combination with comb-shaped polymers.
No. 3,254,786, respectively. It is stated that by these techniques, the film strength of the photoconductive layer can be made sufficient and the mechanical strength can be increased without impeding the above-mentioned properties due to the use of a resin containing an acidic group at the side chain or terminal end. has been done.

(Problem to be solved by the invention) However, even when these resins are used, the environment is high temperature and
It has been found that it is still insufficient to maintain stable performance when the temperature fluctuates significantly from high temperature to low temperature and low humidity. In particular, scanning exposure methods using semiconductor laser light require longer exposure times than conventional simultaneous exposure methods using visible light across the entire surface, and there are restrictions on exposure intensity. , higher performance is required in terms of photosensitivity.

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

An object of the present invention is to provide an electrophotographic photoreceptor that stably maintains good electrostatic properties and produces clear, high-quality images even when the environment during copy image formation fluctuates, such as low temperature and low humidity, or high temperature and high humidity. It is to be.

Another object of the present invention is to provide a CPC electrophotographic material having excellent electrostatic properties and low environmental dependence.

Another object of the present invention is to provide an electrophotographic photoreceptor that is effective in a scanning exposure method using semiconductor laser light.

Another object of the present invention is to provide an original plate for electrophotographic planographic printing.
It has excellent electrostatic properties (particularly dark charge retention and photosensitivity), reproduces copied images that are faithful to the original, and does not cause not only full-surface stains on printed materials but also spot-like background stains. ,
Another object of the present invention is to provide a lithographic printing original plate having excellent rigidity resistance.

(Means for Solving the Problems) The above object 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 binder resin [A ], and at least one of a heat and/or photocurable resin [B] and a crosslinking agent. Ta.

Binder resin [A] has an average molecular weight of IXIO' to 2X10', -PO3
Hz group, -COOH group, -5OzH group, phenolic O
An A block consisting of at least one polymer component containing at least one acidic group selected from R group, a hydrocarbon group) and a cyclic acid anhydride-containing group, and an A block represented by the following general formula (1). This is achieved by an electrophotographic photoreceptor characterized by containing an AB type block copolymer constituted by a B block containing at least a polymer component.

General formula (T) CH.

-fl-C)12-C-COO-R In (2N), R1 represents a hydrocarbon group. ) That is, the binder resin used in the present invention contains specific acidic groups (
Block copolymer resin [A] comprising a component containing a cyclic acid anhydride anastomosis group (unless otherwise specified in the acidic group) and a component containing a methacrylate component, respectively. and at least one of a heat and/or photocurable resin (rB) and a crosslinking agent, the electrophotographic properties and mechanical strength of the resulting photoreceptor (when used as a printing plate) In some cases, it was found that the printing durability (printing durability) was improved.

The resin [A] used in the present invention is an AB type block copolymer, the A block is composed of at least one polymeric component containing at least one kind selected from the above-mentioned specific acidic groups, and the B block comprises a polymer component containing at least one methacrylate component represented by formula (1), and has a weight average molecular weight of l.
It is characterized by being Xl0' to 2×10''.

Among the acidic group-containing binder resins known to improve the smoothness and electrostatic properties of the photoconductive layer, those using low molecular weight polymers have acidic group-containing polymeric components randomly present in the polymer main chain. It was a resin made by bonding two acidic groups at one end of a polymer main chain.

On the other hand, the resin iA used in the binder resin of the present invention]
This means that the acidic groups contained in the resin do not exist randomly in the polymer main chain or are bonded only to the ends of the polymer main chain, but rather exist in blocks within the polymer main chain. This is a more specific copolymer.

In the copolymer CA) according to the present invention, the region of the unevenly distributed acidic group on one side of the main chain of the polymer (Q) sufficiently adsorbs the stoichiometric defects of the inorganic photoconductor. At the same time, it is presumed that the other block portion (B block portion) constituting the polymer main chain loosely and sufficiently covers the surface of the photoconductor. Due to its mechanism of action, the copolymer according to the present invention always has a stable inorganic photoconductor and resin [A It is inferred that the interaction between , the photoconductor is sufficiently dispersed to suppress agglomeration, and
It has been found that stable, high-performance electrophotographic properties can be maintained even under significant environmental changes, from high temperatures and high temperatures to low temperatures and low humidity. The heat and/or photocurable resin CB) and/or the crosslinking agent do not impede the high performance of the electrophotographic properties mentioned above due to the use of the resin [A], and the resin [A] alone is insufficient. This ensures sufficient mechanical strength of the photoconductive layer. This is particularly effective when using a scanning exposure method using a semiconductor laser. Moreover, the smoothness of the surface of the photoconductive layer is further improved. When a photoreceptor with a rough photoconductive layer surface is used as an electrophotographic lithographic printing original plate, the dispersion state of the zinc oxide particles that are the photoconductor and the binder resin is not appropriate, and aggregates may be present. Because a photoconductive layer is formed, even if the lower body fatening treatment is performed using a lower body fatening treatment liquid, the non-image areas are not made uniformly and sufficiently hydrophilic, causing printing ink to adhere during printing, and as a result, the printed matter deteriorates. Background stains occur in non-image areas.

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

Furthermore, it was found that the photosensitivity was better than that of a random copolymer resin containing an acidic group in the side chain connecting to the main chain of the polymer.

The spectral enhancing dye, which is normally used to maintain photosensitivity in the visible to infrared light range, has a sufficient spectral sensitizing effect when adsorbed to the photoconductor. It is assumed that the polymer-containing binder resin interacts appropriately with the photoconductor without inhibiting adsorption of the spectral sensitizing dye. This effect was particularly remarkable in the case of anine 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 can sufficiently adsorb and coat the particle surface, which improves the smoothness of the photoconductive layer. It has good electrostatic properties and provides image quality without background smearing, and also maintains sufficient film strength for use as a CPC photoreceptor or as an offset original plate for printing several tens of sheets. However, by coexisting the resin [B] and/or the crosslinking agent as in the present invention, the function of the resin F A ) is not impaired in any way, and the mechanical properties of the photoconductive layer, which are still insufficient with the resin [A] alone, can be improved. We were able to further improve the target strength. Therefore, the photoreceptor of the present invention has excellent electrostatic properties even under fluctuating environmental conditions, and has sufficient film strength. Such)
However, it is now possible to print at least 6,000 sheets.

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

The amount of the methacrylate component represented by formula (1) in the block portion (B block) containing the methacrylate component represented by general formula ([) is preferably 30% to 100% by weight, more preferably 30% to 100% by weight based on the total weight of the block. is 5
It is 0 to 100% by weight. The weight average molecular weight of the copolymer [A) is lXl0' to 2 x 104, preferably 3 x 103
~lXl0'.

When the molecular weight of the resin [A] is smaller than 1X10', the film forming ability decreases and sufficient film strength cannot be maintained, and when the molecular weight is larger than 2X10', the effect of the resin [A] of the present invention decreases, The electronic properties are comparable to those of known resins.

If the acidic group content in the binder resin [A] is less than 0.5% by weight, the initial potential will be low and sufficient image density cannot be obtained; if the acidic group content is more than 20% by weight, This is not preferable because the dispersibility is lowered, the film smoothness and the high-temperature electrophotographic properties are lowered, and furthermore, when used as an offset master, background smudge is increased.

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

The polymerization component containing a specific acidic group constituting the A block of the AB type block copolymer (resin [A)) of the present invention will be explained in more detail.

As acidic groups, -PO2)12 groups, -COO)H groups,
-3O,H group, 1 phenolic 0) group, -P-OH group (
R represents a hydrocarbon group or -OR' group (R' is a hydrocarbon group) and a cyclic acid anhydride-containing group, preferably -C00)1 group, -5031 (group, phenolic OH
group, and P-OH group.

group (R' represents a hydrocarbon group), and R and R' are preferably aliphatic groups having 1 to 22 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group). , decyl group, dodecyl group, octadecyl group, 2-chloroethyl group, 2methoxoethyl group, 3-
ethoxypropyl group, 71J group, crotonyl group, butenyl group, cyclohexyl group, hensyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorohensyl group, fluorobenzyl group, methoxyhensyl group), or substituted optional aryl groups (e.g., phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group) , acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.).

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

In addition, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride include aliphatic nocarboxylic acid anhydride and aromatic dicarboxylic acid anhydride. It will be done.

Examples of aliphatic dicarboxylic anhydrides include succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclopencune-1,2-dicarboxylic anhydride ring, and fuclohexane-1,2-dicarboxylic acid ring. Examples include anhydride ring, cyclohexene-1,2-dicarboxylic acid anhydride ring, 2,3-bicycloC2,2,2E octanedicarphonic acid anhydride ring, etc. These rings include, for example, chlorine atom, bromine atom halogen atoms such as, alkyl groups such as methyl group, ethyl group, butyl group, hexyl group, etc. may be substituted.

Examples of aromatic dicarboxylic anhydrides include phthalic anhydride rings, naphthalene-dicarboxylic anhydride rings, pyridine-dicarboxylic anhydride rings, thiophene-dicarboxylic anhydride rings, etc. For example, halona atoms such as chlorine atom and bromine atom, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, human quinol group, noa 5' group, nitro group, alkokinocarbonyl! (
The flucoquino group may be substituted with, for example, a methoxy group, an ethoquino group, etc.

A polymer component containing a specific acidic group as shown in "2" below, for example, a polymer component constituting the B block composition: v'1
) Any vinyl compound containing an acidic group can be used as long as it copolymerizes with a corresponding vinyl compound such as a methacrylate component shown in (a) and the like.

For example, it is possible to use vinyl compounds described in the Polymer Data Society of Japan (edited by Handbu, Tsuku: Basic Genus), Baifukan (published in 1986), and specific examples include acrylic acid, α and / or β-substituted acrylic acid (e.g. α-
A-7
amino) methyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylnoryl form, α-noano form, β-
chloro form, β-propepta form, α-chloro-β-methquine form, αβ-dichloro form, etc.), methacrylic acid, itaconic acid,
itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (e.g. 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 71=ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters,
half-ester derivatives of vinyl or allyl groups of maleic acid half-amides, vinyl hanzene carboxylic acid, vinyl hanzene sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, dicarboxylic acids, and ester derivatives of these carboxylic acids or sulfonic acids; Examples include compounds containing the acidic group in a substituent of an amide derivative.

Specific examples of these compounds include the following. However, in each of the following, a is -H, -C
1,, -CL -Br , -CN-1-CLCOOCH
i or -CLCOOII, b is -H or -CHj
, n represents an integer of 2 to 18, m represents an integer of 1 to 12, and f represents an integer of 1 to 4.

(a ■) CHzu 0OH (a 1".

CH= CH 0OH (a CHzuC00(CHz)ncOOH (a CH2=C C0NH(CHz)ncOOH (a CHz COO(CHz)nC00(CHz)noGO(CH z) CH2=C C0NH(CHz)nOcO(CH z) s+cOOH(
a CH2=C C0NHCOO(CHz)ncOOll(a CH,=C CONtlCONH(CHz)ncOOH(a-11) CONHCH CB, C00H (a 〒 (a-14) 〒 (m may be the same or different)) ( a CH.

C) I CHzOCO(CHz)mcOOH (a CHz ”” CH+C82￥-COOI+(a (a CH2=C Coo (CHz) n0cOH= CHC00)I(
a-19) (a-20) (a-21) (a-22) (a-23) 〒 〒 H (a (a 〒 (a-26) (a-27) H H H (a 2 days) (a (a-30) CH,=C C=CC00(CHz):+1I (a φ (a-32) (a (a-34) (a-35) (a-36) (a C00(CHz) z C0N (CHzCHzCOOH)
z(a So,)I (a (a oon (a-41) lh CH (a-42) (a-43) (a-44) CHz=CH CH (a Containing a specific acidic group as above Two or more types of polymerization components may be contained in the A block, and in this case, the two or more types of acidic group-containing components are contained in the A block in either random copolymerization or block copolymerization. Good too.

Further, a component that does not contain the acidic group may be included in the A block, and examples of the component include the components represented by the above-mentioned general formula (2H) or the general formula (ff) described below.

The content of such an acidic group-free component is preferably 0 to 50% by weight, more preferably 0 to 20% by weight in the A Bronc, and most preferably, the acidic group-free component is contained in the A Bronc. Not possible.

Next, in the AB type block copolymer (resin [A]),
The polymerization components constituting the B block component will be explained in detail.

The B block component contains at least a methacrylate component represented by the general formula (1), and the methacrylate component of the formula (r) preferably accounts for 30 to 100% of the B block component.
It is contained in an amount of 50 to 100% by weight, preferably 50 to 100% by weight.

In the repeating unit represented by general formula (1), the hydrocarbon group of R1 may be substituted.

R1 preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. The substituent may be any substituent other than the acidic group contained in the polymerization component constituting the A block of the AB type block copolymer,
For example, halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, etc.), 0-Zl, -COO-Zl, 0CO
-Zl (Zl represents an alkyl group having 1 to 22 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc. ), and other substituents. A preferable hydrocarbon group has 1 to 1 carbon atoms.
An optionally substituted alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group) , 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2methoxyethyl group, 3-bromopropyl group, etc.), optionally substituted alkenyl groups having 4 to 18 carbon atoms (for example, 2-methyl -1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2pentenyl group, 1-pentenyl group, ■-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc. ), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group) 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 an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl group, naphthyl group, tolyl group, xylyl group,
propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group,
bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylethyl group, ethoxycarbonylphenyl group, phthoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc.). .

In the hydrocarbon group R+, when It is an aliphatic group, it is preferable that the component represented by formula (1) contains 60% by weight or more of a hydrocarbon group having 1 to 5 carbon atoms.

Furthermore, in the resin [A], some or all of the repeating units represented by the general formula (1) constituting the B block component are repeating units represented by the following general formula (Ia) and/or (Ib). It is preferable that there be. Therefore, at least one repeating unit selected from the following general formulas (Ia) and Nb) in the B block component is 30 in the other block.
It is preferably contained in an amount of 50 to 100% by weight or more, particularly 50 to 100% by weight.

General formula (Ia) CI+3 General formula (I b) Hj −←Cl! -C→- [In formula (Ia) or (Ib), X and x2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom -COZ! or -COOZz(
22 each represents a hydrocarbon group having 1 to 10 carbon atoms. However, both xl and x2 do not represent hydrogen atoms.

Ll and L! each represents a single bond or a linking group having 1 to 4 linking atoms that connects 1000- and a benzene ring. ] By incorporating the repeating unit represented by the formula (Ia) and/or (Ib) into the B bronch that does not contain an acidic group, electrophotographic properties (especially ν1°, D, R,
R-El/IQ) can be improved.

The reason for this is unknown, but one reason is that the effect of the planar benzene ring or naphthalene ring with a substituent at the ortho position, which is the ester component of methacrylate, is due to the effect of the zinc oxide interface in the film. This is thought to be due to proper arrangement of these polymer molecular chains.

In formula (Ia), in addition to hydrogen, chlorine, and bromine atoms as preferred x1 and x2, preferred hydrocarbon groups include alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group). group, butyl group, etc.),
Aralkyl group having 7 to 9 carbon atoms (e.g., hensyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromohensyl group, methylhensyl group, methoxyhensyl group, di-4-methyl-benzyl group, etc.) and aryl groups (e.g. phenyl group, tolyl group, silyl group, bromophenyl group, methoxyphenyl group,
chlorophenyl group, dichloro7, z-nyl group, etc.), -COZz and -COOZz (preferred examples of Z2 include those described as the above-mentioned preferred hydrocarbon groups). However, Xl and x
Both 2 do not represent a hydrogen atom.

In formula (Ia), L is a direct bond connecting -COO- and a benzene ring or +CH2+-T- (nl is 1
~3), CHzCHzOCO-1 (C
H20), 2 (nz represents an integer of l or 2),
-C) Represents a linking group having 1 to 4 linking atoms, such as IZCH20.

It represents the same content as L2 beam in formula (Ib).

Specific examples of the repeating unit represented by formula (la) or ([b)] that are preferably used in the B block of the resin [A) of the present invention are listed below. However, the scope of the invention is
It is not limited to these.

(b-1) (b-2) (b (b-4) Hx C.B.

CHl CH Yu (b-5) (b (b-7) (b-8) Hi C.I.

Shil CH3 (b-9) (b (b-11) (b-12) C.B.

CH.

Z CI(3 r ■3 (b (b (b (b-16) uff CH.

CH.

(b (b (b (b CI(.

I C.I.

C.I. H3 (b-21) (b-22) (b (b-24) Hs CH3 r CH.

I Hs (b (b-26) (b (b-28) CH3 lh CH3 L r b" to 83 (b-29) L (b CH.

1←CH, -C→- (b-31) CI(3 (b-32) L (b-33) HI (b-34) CH.

(b-35) (b CH.

LIUt;H3 (b -37) (b -38) (b -39) (b-40) CHKOHI CHTSC1l! In the B block constituted separately from the A block consisting of the polymerization component containing the specific acidic group, the B block is represented by the formula (■) (preferably (Ia) or (I b) ). may contain two or more types of repeating units, and may further contain other polymeric components other than these, a
When two or more types of polymerization components are contained in the B block that does not contain l-character groups, the AB type block copolymerization components are contained in the B block in either random copolymerization or block copolymerization mode. However, it is preferable that they be contained randomly.

Other polymeric components that may be contained in the B block together with the polymeric components selected from the repeating units represented by formula (1), (Ia) and/or (Ib) described above may be any component that copolymerizes with these components. Either is fine.

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

General formula (II) a, a.

1-7CH-C→- T-R.

[In formula (It), T is -COO-, -0CO-, HL
h+0CO-.

R3Rr −+CH1±-zcOo-, -0-. -5(h-, -C
ON-, -5OJ-.

C0NHCOO-, -CON)ICONH-, or -〇-, "1.lag" each represents an integer of 1 to 2, R1 represents the same content as 1 in formula (1), Rz It represents the same content as R1 in formula (1).

a and a□ 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-Zz, or a hydrocarbon group having 1 to 8 carbon atoms. -Coo-Z3 (Zs represents a hydrocarbon group having 1 to 18 carbon atoms)] More preferably, a
l+ at may be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), -COO-Zx or -CHt.
COO-Zs CZs more preferably has 1 to 18 carbon atoms
represents an alkyl group or alkenyl group, such as methyl group, ethyl group, propyl group, butyl group, hexyl group,
Examples include octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, and these alkyl groups and alkenyl groups are
may have the same substituent as shown in 3).

Monomers constituting repeating units other than these include styrenes (e.g. styrene, vinyltoluene, chlorostyrene, bromostyrene, dichlorostyrene, vinylphenol, methoxystyrene, chloromethylstyrene, methoxymethylstyrene, acetoxystyrene, methoxystyrene, carbonylstyrene, methylcarbamoylstyrene, etc.), acrylonitrile, methacrylonitrile, acrolein, methacrolein, vinyl group-containing hetero II compounds (e.g. N-vinylpyrrolidone, vinylpyridine,
Examples include vinylimidazole, vinylthiophene, etc.) acrylamide, methacrylamide, etc., but other copolymerizable components are not limited thereto.

Furthermore, it is preferable that the resin [A] of the present invention further contains a functional group that performs a curing reaction of the resin by at least one of heat and light, that is, a "thermally and/or photocurable function SJ." That is, in addition to the copolymer component corresponding to formula (I) (including formulas (Ia) and (Ib)), resin [A] further contains a heat and/or photocurable functional group in the B block portion. It is preferable to contain a copolymer component, which further improves the film strength and increases the mechanical strength of the electrophotographic photoreceptor.

The proportion of the above-mentioned "copolymer component containing a thermally and/or photocurable functional group" in the resin [A) of the present invention is determined by
A], preferably 0.5 to 30% by weight. More preferably, it is 1 to 20% by weight.

When heat-curable and/or photo-curable functional groups are present in the binder resin, if the content is less than 1% by weight, the curing reaction will be insufficient and the effect of improving the film strength of the photoconductive layer due to the curable functional groups will not be observed. I can't. On the other hand, if the content exceeds 30% by weight,
Even with the binder resin CAI of the present invention, it is difficult to maintain excellent electrophotographic properties, and the properties deteriorate to the same as those of conventionally known binder resins. This will cause stains on the area.

Specific examples of photocurable functional groups include Hideo Inui, Gentabe Nagamatsu, "Photosensitive Polymer" (Kodansha, published in 1977), Takahiro Tsunoda, "New Photosensitive Resin" (published by Printing Society Publishing Department, published in 1981) Kiyomi Kato, “Ultraviolet curing system Chapters 5 to 7,
General Technology Center (published in 1989), G, E, Gr.
een and B, P, 5trak J,
Macro, Sci.

Reas, Macro Chew, C21(2)
, 187-273 (1981-82), C, G, R
atty, 'Photopolywirizat
ior+ of SurfaceCootingsJ(
A. Wiley InterScience Pub
As the photocurable resin, functional groups used in conventionally known photosensitive resins are used as cited in the review articles of , et al., published in 1982).

Furthermore, the "thermosetting functional group" in the present invention refers to a functional group other than the above-mentioned acidic group, and includes, for example, Tsuyoshi Endo, "Refinement of Thermosetting Polymers, published by C, M, C Co., Ltd., 1986. , Yuji Harasaki, "Latest Binder Technology Handbook J Chapters ■-■" (General Technology Center, published in 1985), Yoshiyuki Otsu, "Synthesis, design and development of new applications of acrylic resin" (Chubu Management Development Center Publishing Department, published in 1985), The functional groups cited in the review articles such as Eizo Omori's "Functional Acrylic Resins" (Techno System, 1985) can be used.

For example, -〇H group, -5H group, JIH, group, -NHRsI
[Rs represents a hydrocarbon group, for example, a carbon number of 1 to 10
an optionally substituted alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, 2-chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, etc.), carbon 4 to 8 optionally substituted cycloalkyl groups (e.g. cyclohebutyl group,
cyclohexyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group,
3-phenylpropyl group, chlorohensyl group, methylhensyl group, methoxyhensyl group), optionally substituted aryl groups (e.g. phenyl group, tolyl group, xylyl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, naphthyl group) ), C0NHCH20R&CR& is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, etc.) b+
bz], -N=C・θ group and -C-CH group (b+
and bz each represent a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, etc.). In addition, the polymerizable double bond group is specifically a polymerizable group whose polymerization reactivity is lower than that of the monomer corresponding to the repeating unit of general formula (1), such as CHs CHz・C-C0NH uff, CH=CH-C0NH- CH=CH10-C-1 CH=CH15ow, CH,=CH-C0-1C) I2=CI (-0 is formed.

An example of a repeating unit containing a "thermal/photocurable functional group" is given below.

however, In each case below, b and are H or CH, respectively.

and R1+ is -CI(-CH.

CHl or -C00CR=CH□, RI! Ha~C-〇H
1 or -C [I=CH- CB.

and R+J teeth CH=CH1, C=CH, or -CH=CH-CH.

and R4 represents an alkyl group having 1 to 4 carbon atoms, Ql is -5- or -0- , Q represents -OH or -Ni1z, p and q each represents an integer from 1 to 11, and r represents an integer from 1 to IO, and S represents an integer from 2 to 11, l is as defined above.

→coz-c+- ■ C00CR=CH□ -4-C1, -C- key C00CHzCK=CHt 1←CH, -C-)- Coo(CL)p-Coo-R+ 1 cm4)b -(-CBg-C -≠- C00 (CHz) pOcO (CBg) @-Coo-R
+ ++cI(-c→- COOCIhCHCHzooC-R+ xH +coz-c)- CONH(CHi)r-OCO4+a c-9) + CH! -C)-COOCCHt)1-CM-CKz-0-Co-R+5
O-CO-R+s (R+s may be the same or different) 1,000CH, -C) - CONH(CHt)eCOOCHz-CHCHzooC
-RlgOH c + CI -C→- c-13) b +CB-C→- CONHCHzOH c-14) c 1,000 CU-C+- CONHCHzOR+* c-15) c-18) ÷CB-C→- Coo(C) II), -Q! -←CH-CH← c-21) 1+CO, -C-)-COO(CHz)g-NGO The AB type block copolymer [A] of the present invention can be produced by a conventionally known polymerization reaction method. can. Specifically, in a monomer corresponding to a polymer component containing the specific acidic group, the acidic group is previously protected as a functional group,
Known ionic polymerization reactions using organometallic compounds (e.g. alkyllithiums, lithium diisopropylamide, alkylmagnesium halides, etc.) or hydrogen iodide/iodine systems, photopolymerization reactions using porphyrin metal complexes as catalysts, group transfer polymerization reactions, etc. After synthesizing an AB type block copolymer using the so-called living polymerization reaction,
Examples include a method in which a functional group with a protected acidic group is deprotected by a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction, a photolysis reaction, or the like to form an acidic group. One example is shown in reaction scheme (1) below.

For example, P. Lutz, P. Masson et.
al, Polys, Bull.

u, + 79 (1984), B, C,^nder
son, G, D, ^ndrewsetal, Ma
crowolecules, lj, 1601 (
(1981), K.

Hatada, K, Ute, etal, Po1
ys, J. Q., 977 (1985).

lfi, 1037 (1986), Hiroshi Migashi-1 Ko Hatada-1 Polymer Processing, Dish, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymer Papers, parallel, 189 (1
989), Kuroki, T.

Aida, J, Am, Chew, Soc, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthetic Chemistry, 4fi, 300 (1985), D, Y
, Sogah + It, R, Hertler
etal, Macromolecules+f
It can be easily synthesized according to the synthesis method described in J. I., 1473 (1987).

Furthermore, the A-B type block copolymer [A] can also be synthesized by a photoiniferter polymerization method using a monomer with unprotected acidic groups and using a dithiocarbament compound as an initiator. For example, Otsu Yogyo, polymers, gongs,
24B (1988), Shun Himori-Ryuichi Otsu, Poly
m, Rep, Jap,” Mutual 3508 (1988)
, JP-A-64-111, JP-A-64-26619, and the like.

Further, the protecting group for protecting the specific acidic group of the present invention and the dehydrogenation (deprotection reaction) of the protecting group can be easily carried out using conventionally known knowledge. For example, it is variously described in the cited documents mentioned above, and furthermore, Yoshiyu Iwakura,
Keisuke Kurita, “Reactive Polymer” ■Kodansha (1977)
, T.H., Greene.

rProtective Groups in Org
anic 5ynthesisJ.

John Wiley & 5ons (1981
), J, F, Il, McOmie.

'Protective Groups in Org
anic Chemistry” Plenum Pr
The method described in detail in reviews such as ess+ (1973) can be appropriately selected and carried out.

In the resin [A], the amount of the polymer component containing the specific acidic group in the AB type block copolymer is 0.5 to 20% by weight, preferably 0.5 to 20% by weight based on 100 parts by weight of the resin [A]. It is 3 to 15% by weight. The weight average molecular weight of the resin [A] is preferably 3X10' to 1X10'.

In the present invention, heat and/or photocurable resin CB) that can be used together with resin [A] will be explained.

The resin [B] contains a crosslinkable functional group, that is, a functional group that generates a crosslinking reaction in the film to form a bridge between polymers after forming a photosensitive layer using at least one of heat and light. It is a heat and/or photocurable resin that reacts with the heat and/or photocurable functional group that may be contained in the resin [A] to form a crosslinked structure.

That is, it utilizes a reaction mode in which bonding between molecules by condensation reaction, addition reaction, etc., or crosslinking by polymerization reaction is caused by heat and/or light.

Specifically, the thermosetting functional group includes a functional group having a dissociable hydrogen atom (for example, -OH group, -5H group, NFIRz
+ group (R1+ represents a hydrogen atom, an optionally substituted aliphatic group having 1 to 12 carbon atoms, or an optionally substituted aryl group)), -NC5, and a cyclic dicarboxylic acid anhydride. -CONHCHzOR3z (R2g represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group); Examples include polymerizable double bond groups.

Preferable examples of the functional group having a dissociable hydrogen atom include 100 group, -SO group, and -NHRs+ group.

Specific examples of the polymerizable double bond group and photocurable functional group include those described in the "thermal and/or photocurable functional group" contained in the resin [A]. It will be done.

Examples of the resin [B] of the present invention include polymers or copolymers containing such functional groups. Specifically, Tsuyoshi Endo “Refinement of Thermosetting Polymers” (C0M, C Co., Ltd., 1)
(Published in 1988), Yuji Harasaki, "Latest Binder Technology Handbook" Chapter 1f-1 (Published by Sogo Technological Center, 1985), Yoshiyuki Otsu, "Synthesis, Design and Development of New Applications of Acrylic Resins" (Chubu Business Development Center Publishing Department, Published in 1985) , Eizo Omori, "Functional Acrylic Resins" (published by Technosystem, 1985), and other conventionally known resins are used. Examples include polyester resins, unconverted epoxy resins, polycarbonate resins, vinyl alkanoate resins, modified polyamide resins, phenolic resins, modified alkyd resins, melamine resins, acrylic resins, styrene resins, etc. It is sufficient that it contains a functional group capable of forming a crosslinking reaction. Preferably, these resins that do not contain the acidic group represented by resin [A] or have been modified can be used as the resin of the present invention.

Specific examples of monomers corresponding to the coelectric component containing these functional groups include vinyl compounds containing these functional groups.

For example, see the Polymer Data Handbook published by the Polymer Science Society of Japan.
Basic Edition] Baifukan (published in 1986), etc.

Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2-aminomethyl form, α-chloro form, α-bromo form, α- Fluoro form, α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α-chloro-β-
methoxy form, α, β-dichloro form, etc.), methacrylic acid,
Itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (e.g. 2-pentenoic acid, 2-methyl-2-hexenoic acid,
-Octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octene tcJ), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylsulfone Half ester derivatives of vinyl or allyl groups of acids, vinylphosphonic acids, dicarboxylic acids, and ester derivatives and amide derivatives of these carboxylates or sulfonic acids, or in substituents of styrene derivatives, Examples include vinyl compounds containing groups.

More specifically, a (meth)acrylic copolymer containing a total of 30% by weight or more of the monomer represented by the general formula (It) described above as a copolymerization component is cited as an example of resin CB). be able to.

The content of the "copolymer component containing a crosslinkable (crosslinkable) functional group" in the resin [B] is preferably 0.5 to 30% by weight.

The weight average molecular weight of the resin [B] is preferably 1×I03~
lXl0', more preferably 5X10' to 5X1
0'.

The ratio of resin [A3] and resin [B] used in the present invention varies depending on the type, particle size, and surface condition of the inorganic photoconductive material used, but in general, the ratio of resin [A] and resin [B] used is The ratio is 5 to 80 to 95 to 20 (weight ratio), preferably 10 to 50 to 90 to 50 (weight ratio).

On the other hand, in the present invention, a crosslinking agent can be contained together with the resin [A]. When containing a crosslinking agent,
It is preferable that the resin [A] contains a photo- and/or thermosetting functional group and/or that resin CB) is used in combination. Crosslinking in the membrane can be promoted by using a crosslinking agent.

As the crosslinking agent used, compounds that are usually used as crosslinking agents can be used. Specifically, Shinzo Yamashita and Tosuke Kaneko ed. “Crosslinking Agent Handbook” published by Taiseisha (19
1981) Compounds described in the Society of Polymer Science, "Komunshi Data Handbook Basic Edition", Baifukan (1986), etc. can be used.

For example, silane coupling of organic silane compounds (e.g., vinyltrimethoxysilane, vinyltributoxysilane, γ-glycidoxypropyltrimethoxy7rane, T-mercaptopropinitriethoxysilane, T-aminopropyltriethoxysilane, etc.) agents), polyisocyanate compounds (e.g. toluylene diisocyanate, O-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, isocyanate, polymeric polyisocyanate, etc.), polyol compounds (e.g., 1.4 butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1
．． 11-trimethylolpropane, etc.), polyamine compounds (e.g., ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds, and Epoxy resins (e.g. compounds described in "Epoxy Resins" edited by Hiroshi Kakiuchi, Shokodo (1985), "Epoxy Resins" edited by Kuniyuki Hashimoto, Nikkan Kogyo Shimbunsha (1969), etc.), melamine resins (e.g. Miwa) A portion of “Uria Melamine Resin” edited by Hideo Matsunaga, Nikkan Kogyo Shimbunsha (196
Poly(meth)acrylate compounds (e.g. Shin Okawara, Takeo Saegusa, Toshinobu Higashimura "Oligomer" Kodansha (1976) Eizo Omori "
Examples include compounds described in Functional Acrylic Resin J Techno System (published in 1985), and specifically, polyethylene glycol diacrylate, nenopentyl glycol diacrylate, 1,6-hexanediol acrylate, Methylolpropane triacrylate, pentaerythritol polyacrylate, bisphenol A-diglycidyl ether diacrylate, oligoester acrylate: methacrylates of these, and the like. ) etc. The amount of crosslinking agent used in the present invention is 0.5 to 30% by weight based on the total amount of binder resin.
, particularly preferably 1 to 10% by weight.

In the present invention, a reaction accelerator may be added to the binder resin as necessary in order to promote the crosslinking reaction in the photosensitive layer.

When the crosslinking reaction is a reaction mode in which a chemical bond is formed between functional groups, examples thereof include organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.).

When the crosslinking reaction is a polymerizable reaction mode, a polymerization initiator (peroxide, azobis compound, etc.) may be used, and preferably,
azobis polymerization initiator), polyfunctional polymerizable monomers (e.g. vinyl methacrylate, allyl methacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, divinyl succinate, divinyl adipate, diallyl succinate) , 2-methylvinyl methacrylate, divinylbenzene, etc.).

Furthermore, in the present invention, resins other than the resin of the present invention can also be used in combination. Examples of these resins include:
Examples include alkyd resins, polybutyral resins, polyolefins, ethylene-vinyl acetate copolymers, styrene resins, styrene-butadiene resins, acrylate-butadiene resins, vinyl alkanoate resins, and the like.

Examples include acrylate butadiene resin, vinyl alkanoate resin, and the like.

If the above-mentioned other resin exceeds 30% (weight ratio) of the total binder resin amount using the resin of the present invention, the effects of the present invention (especially improvement in electrostatic properties) will be lost.

The binder resin of the present invention is crosslinked or thermally cured after applying the photosensitive layer forming material. To perform crosslinking or thermosetting,
For example, the drying conditions may be made stricter than the drying conditions used in conventional photoreceptor production.For example, the drying conditions may be set to a high temperature and/or a long period of time. Alternatively, after drying the coating solvent, it is preferable to further perform a heat treatment. For example, 5 to 12 at 60℃ to 120℃
Process for 0 minutes.

When the above-mentioned reaction accelerator is used in combination, the treatment can be carried out under milder conditions.

Inorganic photoconductive materials used in the present invention include zinc oxide,
Examples include titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, lead sulfide, and the like.

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

In the present invention, various dyes can be used in combination as spectral aggravating agents if necessary. For example, Harumi Miyamoto, Hidehiko Takei, Imaging 1l (Na8), p. 12, C, J, Y
Oung et al., RCA Review and 469 (1954
), Wataru Kiyota, Journal of the Institute of Electrical Communication, UL-CLh2
)-97 (1980), Yuji Harasaki et al., Industrial Science Magazine i7
Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthine dyes, phthalein dyes, polymethine dyes (e.g., oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain metal), and the like.

More specifically, examples using mainly carbonium dyes, triphenylmethane dyes, xanthine dyes, and phthalein dyes include Japanese Patent Publication No. 51452 and Japanese Patent Publication No. 5
0-90334, JP 50-114227, JP 53-39130, JP 53-82353, U.S. Patent No. 3,052,540, U.S. Patent No. 4,054
, No. 450, and JP-A-57-16456.

oxonol dye, merocyanine dye, cyanine dye,
Polymethine dyes such as logcyanine dyes include F,
M, Harmwer'The Cyanine
Dyes aridRelated Compound
It is possible to use dyes described in US Pat. No. 3,047,384 and US Pat.
．． No. 110,591, U.S. Patent No. 3,121.008, U.S. Patent No. 3.125.447, U.S. Patent No. 3,1
No. 28.179, U.S. Patent No. 3.132.942, U.S. Patent No. 3.622.317, British Patent No. 1.226
．． 892, British Patent No. 1,309.274, British Patent No. L405,898, Japanese Patent Publication No. 48-7814, Japanese Patent Publication No. 55-18892, and the like.

Furthermore, as a polymethine dye that spectrally sensitizes the near-infrared to infrared light region with a long wavelength of 700 nm or more, JP-A No. 47840,
JP 47-44180, JP 51-41061, JP 49-5034, JP 49-45122, JP 57-46245, JP 56-35141
No., JP 57457254, JP 61-2604
No. 4, JP-A No. 61-27551, U.S. Patent No. 3.61
No. 9.154, U.S. Pat. No. 4,175,956, rR
search Disclosure J 1982
216, pp. 117-118. The photoreceptor of the present invention is excellent in that its performance does not easily vary depending on the sensitizing dye, even when various sensitizing dyes are used together. Furthermore, if necessary, various conventionally known addition amounts for electrophotographic photosensitive layers, such as chemical sensitization, can be used in combination.For example, in the above-mentioned review: Imaging
Electron-accepting compounds (e.g., halogens, benzoquinone, chloranil, acid anhydrides, organic carboxylic acids, etc.) cited in reviews such as N(Na8), page 12, Hiroshi Komon et al., ``Recent research on photoconductive materials and photoreceptors''"Development and Practical Application", Chapters 4 to 6, Nihon Kagaku Information Co., Ltd. Publishing Department (1986), cited in the review of polyaryl alkane compounds, hindered phenol compounds,
Examples include P-phenylenediamine compounds.

The amounts of these various additives are not particularly limited, but
Usually 0.0001 to 2.0 parts per 100 parts by weight of photoconductor.
It is 0 parts by weight.

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

In addition, when a photoconductive layer is used as a charge generation layer of a photoconductor with a stacked structure of a charge generation layer and a charge transport layer, the thickness of the charge generation layer is preferably 0.01 to 1μ, particularly 0.05 to 0.5μ. It is.

In some cases, an insulating layer is added mainly for the purpose of protecting the photoreceptor, improving its durability, dark decay characteristics, etc.

At this time, the insulating layer is set to be relatively thin, and when the photoreceptor is used for a specific electrophotographic process, the insulating layer provided is set to be relatively thick.

In the latter case, the thickness of the insulating layer is between 5 and 70μ, in particular 1
It is set to 0 to 50μ.

Charge transport materials for the laminated photoreceptor include polyvinylcarbazole, oxazole dyes, pyrazoline dyes, triphenylmethane dyes, and the like.

The thickness of the charge transport layer is 5 to 40 μm, particularly 10 to 3 μm.
0μ is suitable.

Typical resins used to form the insulating layer or charge transport layer include polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl oxide copolymer resin, Thermoplastic resins and effective resins such as polyacrylic resins, polyolefin resins, urethane resins, polyester resins, epoxy resins, melamine resins, and silicone resins are used as appropriate.

The photoconductive layer according to the invention can be provided on a conventionally known support. Generally speaking, the support for the electrophotographic photosensitive layer is preferably electrically conductive.As the electrically conductive support, for example, metal, paper, plastic sheet, etc. are basically impregnated with a low-resistance substance, just as in the conventional case. those that have been subjected to conductive treatment, such as those that have been coated with at least one layer for the purpose of imparting conductivity to the back side of the base (the side opposite to the surface on which the photosensitive layer is provided) and to prevent curling, and those that have been coated with at least one layer for the purpose of preventing curling, etc. Those with a water-resistant adhesive layer on the surface of the body, those with at least one or more pre-coated layers provided on the surface layer of the support as required, and those with a conductive plastic base coated with vapor-deposited material, etc., laminated onto paper. You can use the ones that have been prepared.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, electrophotography, 14(N[Ll), P2-11(
1975), Hiroyuki Moriga, “Introductory Chemistry of Special Papers” Kobunshi Publishing (1975), A, F, 1 (oover, J
, Macrowol, Sci.

Chew, A-4(6), No. 1327-1417
(1970) etc. are used.

(Example) Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto.

[Synthesis of resin [A]] Synthesis example 1 of resin [A]: (A-13 95 g of engineered methyl methacrylate and 2 of tetrahydrofuran
00g of the mixed solution was sufficiently degassed under a nitrogen stream to -20
Cooled to ℃. 1. l-diphenylbutyllithium 1.
5 g was added and reacted for 12 hours. Furthermore, to this mixed solution,
A mixed solution of 5 g of triphenylmethyl methacrylate and 5 g of tetrahydrofuran was added after sufficient degassing under a nitrogen stream, and the mixture was reacted for further 8 hours. After the mixture was cooled to 0° C., 10 d of methanol was added and reacted for 30 minutes to terminate the polymerization. The obtained polymer solution was heated to a temperature of 30°C while stirring.
℃, 3 m of 30% hydrogen chloride ethanol solution was added thereto, and the mixture was stirred for 1 hour.Next, the solvent was distilled off from the reaction mixture under reduced pressure until the total volume became half, and petroleum ether Il was added.
It sank back inside.

The polymer obtained by collecting the precipitate and drying it under reduced pressure was -8
, 5 x 10' and the yield was 70 g.

(A-1) (Weight ratio) b = Indicates niblock combination (same below) Synthesis example 2 of resin [A]: (A-23 46 g of n-butyl methacrylate, (tetraphenylborufinate)
A mixed solution of 0.5 g of aluminum methyl and 60 g of methylene chloride was brought to a temperature of 30° C. under a nitrogen stream. 3 to this
Light from a 00W xenon lamp was irradiated from a distance of 25 cm through a glass filter, and the reaction was carried out for 12 hours. Furthermore, 4 g of benzyl methacrylate was added to this mixture, and after light irradiation for 8 hours, 3 g of methanol was added to this reaction mixture and stirred for 30 minutes to stop the reaction.Next, Pd-C was added to this reaction mixture. A catalytic reduction reaction was carried out at a temperature of 25° C. for 1 hour.

After filtering out insoluble matter, it was reprecipitated in 500 m of petroleum ether,
The precipitate was collected and dried. The yield of the obtained polymer was 33g.
It was ~9.3X10'.

C00C4H*(n) Cool resin [A]
Synthesis Example 3: (A-3) 90 g of 2-chloro-6-methylphenyl methacrylate
A mixed solution of 200 g of toluene was thoroughly degassed under a nitrogen stream and cooled to 0°C.
- 2.5 g of methylpentyl lithium was added and stirred for 6 hours. This mixture was further stirred with 4-vinylphenyloxytrimethylsilane LOg'firm for 6 hours, and then 3 g of methanol was added and stirred for 30 minutes.

Next, add 1 part of 30% hydrogen chloride ethanol solution to this reaction mixture.
After adding 0 g of petroleum ether and stirring at 25°C for 1 hour,
The precipitate reprecipitated and collected in 300 g of diethyl ether
Washed twice with m and dried. The obtained polymer had a yield of 58
G? ~7.8 x 102.

(A-3) Synthesis Example 4 of Resin [A]: (A-4) A mixture of 95 g of phenyl methacrylate, Hensyl N, and 4.8 g of N-diethyldithiocarhamate was sealed in a container under a nitrogen stream, and the temperature was increased. It was heated to 60°C.

This was irradiated with light for 10 hours using a 400H high-pressure mercury lamp from a distance of 10 cm through a glass filter for photopolymerization.

Add to this 5 g of acrylic acid and 180 g of methyl ethyl ketone.
After adding , the atmosphere was replaced with nitrogen, and light was irradiated again for 10 hours.

The obtained reaction product was reprecipitated in hexane 1,51, collected and dried. The resulting polymer was 68 g and ˜9.5×10 3 .

CA-4,) H3 Synthesis Examples 5 to 16 of Resin [A] Resin [A] shown in Table 1 below was synthesized in the same manner as in the synthesis example of resin [A].

table CHl -C)1. -C″JTb-fY士T COOR.

Each resin [A) book is 6X10” ~9.5xlO' And It was.

Synthesis Examples 19 to 23 of Resin [A] The following Table 1 was carried out in the same manner as in Synthesis Example [4] of Resin [A].
Resin [A] shown in -2 was synthesized. ~ of each resin is 8X1
0' to lXl0'.

Examples 1 to 2 and Comparative Examples A-C Example 1 2 og (as a solid content) of the resin (A-t) produced in Synthesis Example 1, 200 g of zinc oxide, and 0. 02g phthalate ma water sO, 15g
After dispersing a mixture of 300 g of toluene in a ball mill for 4 hours, a resin (B-1) having the following structure was added.15.
Then, 5 g of N, N', N'-trimethylethylenediamine was added and dispersed for 5 minutes. This was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 22 g/m'', dried at 100°C for 1 hour, and then kept in the dark at 20°C and 65% RH for 24 hours. An electrophotographic light-sensitive material was produced by allowing the mixture to stand for a period of time.

Resin (B-1) CH.

-SCHz-C'f'i'TtCL-1j1 Shishin "Ya c
ut-co Imaichi 1-2 3.6 × 104 (weight ratio) Noanine dye [A] Example 2 In Example 1, instead of 20 g of resin CA-1,
An electrophotographic light-sensitive material was prepared in the same manner as in Example 1, except that 20 g (in terms of solid content) of resin (A5) was used.

Comparative Example A An electrophotographic light-sensitive material was produced in the same manner as in Example 1, except that 20 g of resin (R-1) having the following structure was used in place of 20 g of resin [A-1]. .

Comparative resin (R-13 CI(, C1l.

)k:6X10' (random copolymer) Comparative Example B Same as Example 1 except that 20 g of resin (R-2) having the following structure was used in place of 20 g of resin (A-1). An electrophotographic light-sensitive material was produced by this operation.

(R-2) cHffHOOC-CH
I-5+CH! -C+ C00C, H5 Mw 8.0x103 Comparative Example C In Example 1, instead of 20 g of resin (A-1),
An electrophotographic material was prepared in the same manner as in Example 1, except that 20 g of resin (R-3) having the following structure was used.

(R-3) υ 8.5XI03 (weight ratio) For these photosensitive materials, the electrostatic properties, imaging properties, and environmental conditions were determined at (20'C165%R11) and (30°C58
0% 12Fl) was investigated. The results are shown in Table 2.

The implementation aspects of the evaluation items listed in Table-2 are as follows.

Note 1) Electrostatic properties: In a dark room at a temperature of 20°C and 165% RH, each photosensitive material was subjected to corona discharge at -6 kV for 20 seconds using a paper analyzer (Paper Analyzer 5P-428 model manufactured by Kawaguchi Electric Co., Ltd.). After that, leave it for 10 seconds, and the surface potential at this time is V. 0 and then left to stand in the dark for 90 seconds, the potential v1. . The potential retention property after dark decaying for 90 seconds, that is, the dark decay retention rate (DRR (%)
] was determined by (Vl@@/Lll)×100(%).

Further, after the surface of the photoconductive layer was charged to -400V by corona discharge, the surface of the photoconductive layer was irradiated with light from a gallium-aluminum-arsenide semiconductor laser (oscillation wavelength: 780 nm), and the surface potential (V+O) was attenuated to 1710V. Find the time until
Calculate.

The environmental conditions at the time of measurement were 20°C, 65%RH (I), and 30°C.
It was carried out at 80% RH (II).

Note 2) Imaging properties: After leaving each photosensitive material for one day and night under the following environmental conditions, each photosensitive material was charged with ν to -6, and a 268-output gallium-aluminum-arsenide semiconductor laser (oscillation wavelength 780 ns) was used as a photoelectric charge. ) on the surface of the photosensitive material.
After exposure at a pitch of 25a and a scanning speed of 300 m/sec under an irradiation dose of "g/cm", the film is developed and fixed using ELP-T (manufactured by Fuji Photo Film Co., Ltd.) as a liquid developer. The copied image (fogging, image quality) obtained was visually evaluated.

The environmental conditions at the time of imaging were 20'C65%l? H(1) and 3
It was carried out at 0°C and 80% RH (I[).

As shown in Table 2, each of the photosensitive materials of the present invention had good electrostatic properties, and the actual copied images were clear with no blurring and both copies were clear.

On the other hand, Comparative Examples A-C are Obi! A decrease in electric potential (ν1°) or a decrease in photosensitivity (E'/+J) occurs, and even in actual copied images, the image density (D9) decreases, resulting in fading of fine lines, characters, etc., and occurrence of ground blur. I was born alive.

From the above, an electrophotographic photoreceptor that satisfies electrostatic properties can be obtained only when the resin of the present invention is used.

Furthermore, even when using the resin of the present invention, the resin (A) containing a methacrylate component having a specific substituent
It has become clear that Example 2, which consists of the following, has improved electrostatic properties5 compared to Example 1, and is particularly advantageous over the photoconductor system using the semiconductor laser beam scanning exposure method.

Example 3 10 g (as solid content) of the resin (A-6) produced in Synthesis Example 6, 10 g of resin CB-2 having the following structure, 20 g of zinc oxide
A mixture of 0 g, cyanine dye 3B) having the following structure, 0.30 g of phthalic anhydride, and 300 g of toluene was dispersed in a ball mill for 4 hours, 4 g of glutaconic acid was added to this dispersion, and the mixture was further dispersed in a ball mill for 10 minutes. The photosensitive layer was dispersed to prepare a photosensitive layer-forming product, which was coated onto electrically conductive treated paper using a wire bar so that the dry adhesion amount was 22 g/m'', dried at 100°C for 30 seconds, and then coated at 120°C. 'C
It was heated for 1 hour.

Then, an electrophotographic light-sensitive material was prepared by leaving it for 24 hours in a dark place at 20"C and 65% RH.

cyanine dye CB) (cHz) asoie (C1lz)-5(hK Resin [B 2] CH3 CH.

C00CtHs 0NHZ COOCHz (JICHz \1 to: 4.5 × 104 Film properties (surface smoothness), film strength, electrostatic properties, imaging performance, and static when the environmental conditions are 30゛C180%RH) The electrical properties and imaging properties were investigated.

The above results are summarized in Table 3.

The implementation modes of the evaluation items shown in Table 3 are as follows.

Note 3) Smoothness of photoconductive layer: The obtained photosensitive material was tested using a Henk smoothness tester (Kumagai Riko).
The smoothness (sec/cc) was measured under the condition of an air volume of 111 cc.

Note 4) Contact angle with water: Is each photosensitive material desensitized? F1. Using a solution prepared by diluting ELP-E (manufactured by Fuji Photo Film Co., Ltd.) twice with residual water, the surface of the photoconductive layer was desensitized by passing it through the Etching Prosensor once. ! A drop of water is placed on it, and the contact angle with the water formed is measured using a goniometer.

Note 5] Printing durability After making a plate in the same manner as in the imaging property of property 2) above, it was desensitized under the same conditions as property 4) above, and this was used as an offset master in an offset printing machine (Sakurai Seisakusho Co., Ltd.). This indicates the number of sheets that can be printed using high-quality paper (manufactured by Oliver Model 52) as the printing paper without causing problems with scumming in the non-image areas and image quality in the image areas (the higher the number of sheets printed, the better the rigidity resistance. (represents something).

As shown in Table 3, in the photosensitive material of the present invention, the smooth film of the photoconductive layer had good mechanical strength and electrostatic properties, and the actual copied images had no blurring and the quality of the copied images was clear. . This is presumed to be due to the photoconductor and the binder resin being sufficiently adsorbed and covering the particle surface. For the same reason, even when used as an offset master original, the desensitizing treatment with the desensitizing treatment liquid progresses sufficiently, and the contact angle with water in the non-image area is as small as 10 degrees or less, making it sufficiently hydrophilic. It can be seen that When actually printing and observing the background smear on the printed matter, no background smudge was observed, and 8,000 printed matter with clear image quality were obtained.

The above can be achieved by the function of resin [B] or resin [B] and crosslinking agent without alienating the effect of resin [A).
This shows that the strength of the film has been significantly improved.

Example 4 A mixture of 38 g (as solid content) of the resin (A-13) produced in Synthesis Example 13, 200 g of zinc oxide, 0.020 g of methine dye (C) having the following structure, 0.30 g of maleic anhydride, and 300 g of toluene was ball milled. After dispersing in a ball mill for 4 hours, 4 g of 1,3-xylylene diisocyanate was added, and the mixture was further dispersed in a ball mill for 10 minutes.

This was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 22 g/at, heated at 100"C for 15 seconds, then heated at 120"C for 2 hours, then heated at 20°C in the dark. An electrophotographic light-sensitive material was prepared by leaving it for 24 hours under the conditions of C365%R1.

Methine dye (C) In the same manner as in Example 3, each characteristic was measured and shown in the table below.
2) In place of 30 g and 4 g of glutaconic acid as a crosslinking agent, each resin and crosslinking agent shown in Table 5 below was used, and in place of cyan dye [B], cyanine dye [D] having the following structure was used.
] Each photosensitive material was produced in the same manner as in Example 3, except that 0.020 g of .

Cyanine dye (Dl C2H5CJs) Each characteristic was measured in the same manner as in Example 3. Table 5 shows (
The electrostatic properties were shown under conditions (30° C., 80% RH).

Each of the photosensitive materials of the present invention has excellent chargeability, dark charge retention, and photosensitivity, and can be used at high temperatures (30°C, 180% R
Even under the harsh conditions of 1(), clear images were produced without any occurrence of ground blur or fine line skipping.

All of the places printed as off-cent master originals,
We were able to print over 6,000 sheets with clear images and no background smudges.

Examples 13 to 16 8 g of resin [A] in Table 6 below, resin CB in Table 6 below)
Group X 20g, zinc oxide 200g, the cyanine dye (A
) O, OlBg, maleic anhydride 0.30g and toluene 300. The mixture was dispersed in a ball mill for 4 hours.

To this was added 12 g of resin [B) group Y shown in Table 6 below, and further dispersed in a ball mill for 10 minutes. This was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 25 g/s+'', and after heating at 100°C for 15 seconds,
Further heating was performed for 2 hours at °C. Then 20'C165%
An electrophotographic light-sensitive material was prepared by leaving it for 24 hours under the conditions of R1.

Each of the photosensitive materials of the present invention has chargeability, dark charge retention,
The photosensitivity Q is excellent, and the actual copied images can be printed at high temperatures (30°C).
Even under the harsh conditions of 180% R, clear images were obtained with no soil burrs.

Furthermore, when this was used as an offset master master plate for printing, clear prints with clear image quality were obtained even after 6000 sheets.

Example 17 Resin (A-5) 10g, following resin CB-1,5) 1
．． 8g, oxidized bent lead 200g, rose hengal 0.50g
g, 0.25 g of tetrabromophenol blue, 0.30 g of uranine, 0.3 g of tetrahydrophthalic anhydride
0g and 240ga of toluene were combined and dispersed in a ball mill for 4 hours. To this, the following resin [B-15) 1
2g was added and dispersed for 10 minutes. This was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 20 g/m2, heated at 110'C for 30 seconds, and heated to 120°C.
The mixture was heated at C for 2 hours. Next, an electrophotographic light-sensitive material was prepared by allowing the mixture to stand for 24 hours at 20° C. and 165% RH.

Resin: 5-tS) CH3CH3 11 knee CH2-C--hB-↑CH,-C-light "-
C00C1lZC611, C00(CL) zOco(
C12COOH9 3. OXIO" (Weight composition ratio) The following results were obtained when τ and each characteristic were measured in the same manner as in Example 1.

Smoothness of photoconductive layer: 500 (cc/5ea) Electrostatic properties V,, (V) D, R, R (:) E, /, 0 (f
fi , , se0 imaging performance, (20°C165χRH
) and (30°C, 180χRH) good copied images were obtained under both conditions.

Rigidity resistance: Good printed images were obtained up to 6000 sheets.

As described above, the photosensitive material of the present invention was able to obtain excellent electrophotographic properties and high printing durability.

However, the electrostatic properties and imageability were determined as follows.

Electrostatic properties: Temperature 20°C 265% I? After corona discharge was applied to each photosensitive material for 20 seconds at 6 kV using a paper analyzer (Paper Analyzer 5P-428 model, manufactured by Kawaguchi Electric Co., Ltd.) in a dark room at 100 m, the surface potential at this time was measured. ν,. was measured. Next, the potential v7° was measured after being left in the dark for 60 seconds, and the retention of the potential after dark decay for 60 seconds, that is, the dark decay retention rate (DRR) was measured.
] was determined by (V70/VIO) x 100(χ).

Further, after the surface of the photoconductive layer is charged to -400 V by corona discharge, the surface of the photoconductive layer is irradiated with visible light of 2.0 lux, and the surface potential (V,.) is attenuated to 1/10. Find the time until the exposure I E ly +. (
lux seconds).

Side imageability: The photosensitive material was plate-made by using ELP-T as a toner with a fully automatic plate-making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) to form a toner image.

Examples 18 and 19 Resin CA-22] and C123) 6.3 g each, Table 7 below
Resin (S) 33.7g each, zinc oxide 200g, uranine 0.02g, rose hengal 0.04g, fromphenol blue 0.03g, phthalic anhydride 0.40
A mixture of 300 g of toluene and 300 g of toluene was
The photosensitive material was prepared by dispersing it over time, and then applied with a wire bar to a conductive coating with a dry coating weight of 24 g/m'' and dried at 110'C for 1 minute.Next. After 3 minutes of exposure with a high-pressure mercury lamp, it was then exposed to light for 20 minutes in the dark.
Each electrophotographic photoreceptor was prepared by leaving it for 24 hours under the conditions of "C265%R1". The characteristics of the obtained photoreceptor are shown in Table 8.

The photosensitive material of the present invention has chargeability, dark charge retention,
It has excellent photosensitivity, and the actual copied images can be used even at high temperatures (30°).
Even under the harsh conditions of (C-80% RH), clear images were produced with no soil blurring.

Furthermore, using this as the original version of Offcent Master,
When printed, even 5,000 to 6,000 sheets were obtained with clear image quality.

Examples 20 to 28 As a binder resin, resin [A] 6.5 shown in Table 9 below
g and resin (B) 33.5g, zinc oxide 200g
A mixture of 0.05 g of Rose Bengal, 0.03 g of tetrabromophenol blue, 0.02 g of uranine, 0.01 g of phthalic anhydride, and 240 g of toluene was dispersed in a ball mill for 2 hours. A predetermined amount of the crosslinking agent shown in Table 8 below was added to this dispersion, and the mixture was further dispersed in a ball mill for 10 minutes. This was applied to conductive treated paper with a dry adhesion amount of 18g/
Apply it with a wire parr so that it becomes l12, and apply it at 110℃ to 30
An electrophotographic photoluminescent material was produced by heating for a second, then heating at 120°C for 2 hours, and then leaving it for 24 hours at 20°C and 165% RH.

The photosensitive material of the present invention has chargeability, dark charge retention,
It has excellent photosensitivity, and the actual copied images can be used even at high temperatures (30°).
Even under the harsh conditions of C-80%R1 (), clear images were provided with no soil blurring.

Furthermore, when printing was performed using this as an original plate of an off-cent master, prints with clear image quality were obtained even after printing 8,000 sheets.

(Effects of the Invention) According to the present invention, an electrophotographic flashlight that has excellent electrostatic properties (especially electrostatic properties under harsh conditions), clear and high-quality images, and furthermore has excellent mechanical strength. You can get a body. This is particularly effective for scanning exposure methods using semiconductor laser light.

By using a repeating unit containing a specific methacrylate component represented by formula (Ia) or (Ib) in the resin of the present invention, the electrostatic properties are further improved.

(3 others)

Claims (1)

Scope of Claims: (1) An electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor and a binder resin, wherein the binder resin is at least one of the following binder resins [A]. 1. An electrophotographic photoreceptor comprising at least one of a thermosetting resin [B] and a crosslinking agent. Binder resin [A] has a weight average molecular weight of 1 x 10^3 to 2 x 10^4,
-PO_3H_2 group, -COOH group, -SO_3H group,
Phenolic OH group, ▲ Numerical formula, chemical formula, table, etc. ▼ group {R represents a hydrocarbon group or -OR' group (R' indicates a hydrocarbon group)} and cyclic acid anhydride-containing group An AB type block copolymer comprising an A block comprising at least one polymer component containing at least one acidic group and a B block comprising at least a polymer component represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In formula (I), R_1 represents a hydrocarbon group.) (2
) A claim characterized in that the B block in the AB type block copolymer contains 30% by weight or more of at least one repeating unit selected from the following general formulas (Ia) and (Ib). 1) The electrophotographic photoreceptor described above. General formula ( I a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula ( I b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In formula ( I a) or ( I b), X_1 and X_2 are mutually independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, -COZ_2 or -CO
OZ_2 (Z_2 each represents a hydrocarbon group having 1 to 10 carbon atoms). However, both X_1 and X_2 do not represent hydrogen atoms. L_1 and L_2 each represent a single bond or a linking group having 1 to 4 linking atoms that connects -COO- to the benzene ring. ] (3) The resin [A] further contains 1 to 3 repeating units containing heat and/or photocurable functional groups as a copolymer component.
Claim (1) or (2) characterized in that it contains 0% by weight.
) The electrophotographic photoreceptor described above.