JPH0329954A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To improve electrostatic characteristics and to lessen environmental dependency by specifying the respective weight average mol. wts. of a resin A and a resin B as well as the contents of the basic groups in the resins and the bond positions. CONSTITUTION:This photosensitive body contains one kind of the binder resin A and the binder resin B. The binder resin A contains >=30wt.% copolymn. component which has 1X10<3> to 2X10<4> weight average mol. wt. and is expressed by formula I and 0.5 to 20wt.% copolymn. component contg. -PO3H2 group, etc., and one kind of the acidic group selected from cyclic acid anhydride containing group. The binder resin B is the copolymer of 5X10<4> to 1X10<6> weight average mol. wt. which contains at least one of the polyester type macromonomers of 1X10<3> to 1.5X10<4> wt. average mol. wt. expressed by formula II, etc., as the polymer component. In the formula I, a1, a2 denote a hydrogen atom, etc. In the formula II, c1, c2 denote a hydrogen atom, etc.; X1 is a single bond or -COO-, etc.; Y1 is a group to combine X1 to -COO-; W1, W2 denote a bivalent aliphat. group, etc.; R31 denotes a hydrogen atom, etc. The electrostatic characteristics are improved in this way and the environmental resistance is lessened.

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 typical 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. The photoreceptor, which is composed of a support and at least one photoconductive layer, can be formed by the most common electrophotographic processes, namely electrophotography, image exposure and development, and optionally transfer. used.

Furthermore, a method of using an electrophotographic photoreceptor as an offset original plate for Directrec 1 plate making is widely used.

Zuru Shikawa's binder, which is used to form the photoconductive and electrical layers of electrophotographic photoreceptors, has excellent film-forming properties and the ability to disperse photoconductive powder into the binder, as well as excellent recording properties. The adhesion of the body layer to the base material is good, and the photoconductive layer of the recording layer has excellent charging ability, low dark decay, large light decay, and low pre-exposure fatigue. It is necessary to have various electrostatic properties, such as the need to maintain these properties stably under changes in humidity, and excellent imaging performance.

Examples of resins that have been known for a long time include silicone resin (Japanese Patent Publication No. 34-6670), styrene-butadiene resin (
Japanese Patent Publication No. 35-1960), Alxodo resin, maleic acid resin, boria ξto (Japanese Patent Publication No. 35-11219), vinyl acetate resin (Japanese Patent Publication No. 41-2425), vinyl acetate copolymer (Japanese Patent Publication No. 41-2426) ), acrylic resin (Japanese Patent Publication No. 35-11216), acrylic acid ester copolymer (e.g. Japanese Patent Publication No. 35-11219, Japanese Patent Publication No. 36-8
No. 510, Japanese Patent Publication No. 41-13946, etc.) are known.

However, electrophotographic materials using these resins lack 1) affinity with the photoconductive powder, resulting in poor dispersibility of the coating solution. 2) Low chargeability of the photoconductive layer, 3
4) The quality of the image area of the copied image (particularly halftone reproducibility and resolution) is poor; 4) The environment in which the copied image was edited (e.g. high temperature,
5) The film strength and adhesion of the photosensitive layer are not sufficient, and especially when used as an offset 1 master, the photosensitive layer may come off during offset 1 printing. However, there were problems such as not being able to print a large number of copies.

Various methods have been proposed to improve the electrostatic properties of the photoconductive layer, and one such method is to use a compound containing a carboxyl group or a 21-group in an aromatic ring or a furan ring, or a dicarboxylic acid. Japanese Patent Publication No. 42-6878 and Japanese Patent Publication No. 15-3073 disclose a method of further combining anhydrides of 1 to 1 and coexisting in a photoconductive layer. However, even with the photosensitive materials improved by these methods, their electrostatic properties are still insufficient, and none particularly excellent in light attenuation properties has been obtained. Therefore, in order to improve the lack of sensitivity of this photosensitive material, a method of adding a large amount of sensitizing dye to the photoconductive layer has been conventionally used, but the photosensitive materials prepared by this method have a remarkable whiteness. This has caused problems such as deterioration of the quality of the recording medium and, in some cases, deterioration of the photosensitive + a material due to decay, making it impossible to obtain a sufficient copy image.

On the other hand, Japanese Patent Laid-Open No. 6010254 discloses a method of adjusting the average molecular weight of a resin used as a binder resin for a photoconductive layer. That is, acrylic resin with an acid value of 4 to 50 and an average molecular weight of 103 to 104, and 104 to 104.
A technique has been described for improving electrostatic properties (particularly good repeatability as an RPC photoreceptor), moisture resistance, etc. by using together components having a distribution of 2.times.105.

Furthermore, research is being carried out on lithographic printing original plates using electrophotosensitive photoreceptors, and a crystal for photoconductive layers that has both the electrostatic properties as an electrophotographic photoreceptor and the printability as a printing original plate has been developed. For example, in Japanese Patent Publication No. 31011/1983, as a binder resin, a resin 1.8
0'~IOXIO' and TglO~80'C resin, (
In JP-A No. 53-54027, the carboxylic acid group is reduced from ester viscosity to at least 7 atoms. Those using ternary copolymers containing (meth)acrylic acid esters having individually different substituents, and JP-A-54-20735, JP-A-57-
No. 202544 uses a quaternary or penta-component copolymer containing acrylic acid and hydroxyethyl (meth)acrylate, and JP-A-58-68046 uses a copolymer containing 6 carbon atoms.
3 containing (meth)acrylic acid ester and carboxylic acid-containing vinyl monomer having ~12 alkyl groups as substituents
It is stated that those using the original copolymer are effective in improving the desensitization property of the photoconductive layer. However, even if the resin is said to be effective in the electrostatic properties, moisture resistance properties, and durability mentioned above, when actually evaluated, it shows that the electrostatic properties, especially in chargeability, dark charge retention, and photosensitivity. There were problems with the smoothness of the conductive layer, and it was 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 star resin ()twl03 containing 5-10% by weight
- 104) to improve the smoothness and electrostatic properties of the photoconductive layer and to obtain image quality free from background smear, as described in JP-A-63-217354. The patent application discloses that the rigidity of the photoconductive layer can be improved to ensure sufficient film strength without impeding the above characteristics by using it in combination with a resin (hlO' or higher) or by utilizing a crosslinking reaction. 63-49817
No., JP-A No. 63220148, No. 63-220149
and JP-A No. 1-102573.

(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.

Furthermore, when a scanning exposure method using semiconductor laser light is adopted in an electrophotographic lithographic printing original plate, actual tests using a conventional photoreceptor show that the electrostatic properties described above are unsatisfactory. Especially El/. and EIy+.

The large difference between the
Even when printing as an offset master, serious problems such as pasting marks of the printed original appear on the printed matter.

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 in which a copied image is produced changes, such as low temperature and low humidity or high temperature and high humidity. The goal is to provide the following.

Another object of the present invention is to provide a CPC electrophotographic photoreceptor with 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.
To provide a lithographic printing original plate which does not cause scumming on printed matter and does not leave pasting marks.

(Means for Solving the Problems) The second objective is to provide an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor and a binder resin, in which the binder resin contains the following binder resin ( It has been found that this effect can be achieved by an electrophotographic photoreceptor characterized by containing at least one type of binder resin CB) and at least one type of binder resin CB).

Binder resin [A]: has a weight average molecular weight of 1 x 103 to 2 x 10', contains 30% by weight or more of a copolymer component represented by the following general formula (I) and 1PO3H. group, -So. I+ group, -COOI! group, general formula (nla) 011 group, -doR group {R represents a hydrocarbon group or -OR' group 011 (R' represents a hydrocarbon group)}, and a cyclic carboxylic acid hydrate-containing group A resin containing 0.5 to 20 weight percent of a copolymerized portion containing at least one acidic group.

General formula (1) a a 10Cll-C→1COO-1? In formula (1), a1 and a2 each represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group.

1 represents a hydrocarbon group.

Binder resin (B): At least one of the backs of polyester macromonomers having a weight average molecular weight of i1X103 to 1.5XIO', represented by the following general formulas (n[a) and (lIlb)] Weight average molecular weight contained as weight 5
Copolymer of X10' to IXIO6.

? General formula (I[Ib) C3 C4 CII=C X2 Y2 Coo [Wa CO
O −1 R3 ■Formula [I11al and [IIlbl
The numbers inside [ ] represent repeating units.

c1 and c2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyanocarbon group, a hydrocarbon group having 1 to 8 carbon atoms, Coo-Z+, or a hydrocarbon group having 1 to 8 carbon atoms. -Coo-22 (Zl and Z2 each represent a hydrocarbon group having 1 to 18 carbon atoms).

X, is a single bond or -coo-- -oco-{
−C}12′)j! TCOO-,-{-CH2)HO
CO- (sho.ni, represents d or a hydrocarbon group having 1 to 12 carbon atoms), or ~S
Represents O2-.

YI represents a group connecting x1 and -COO-.

W. and 2 may be the same or different, and each has a divalent aliphatic group and a divalent aromatic group {-0--S--N in the bond of each divalent organic residue. (d2 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms), 5
02 COO OCOd3 CONIICO- -NIICONlb -CON
(d. represents the same content as d2 and d4), ? At least one bonding group selected from O■N (d4 represents the same content as d2) and -Si} or an organic residue constituted by a combination of these residues without expressing it.

R3l represents a hydrogen atom or a hydrocarbon group.

c3, c4, x2, Y2 and R32 in general formula (II1b) are each CI% C in general formula (Illa)
2, ×1, Y1, and +13.

匈 represents a divalent aliphatic residue.

That is, the binder resin used in the present invention consists of a copolymer component of a specific repeating unit and an acidic group (hereinafter, unless otherwise specified, the term acidic includes a cyclic acid anhydride-containing group). A low molecular weight resin (A) containing a copolymerizable component (which shall also include) and a macromonomer represented by the general formula (I[la) and the macromonomer represented by the general formula (IIIb)]. At least one of the graph 1 type copolymers containing at least one of the high molecular weight resins CB) is used.

Furthermore, the low molecular weight resin (A) has the following general formula (Ila
) and an acidic group-containing resin containing a methacrylate component having a specific substituent containing a Hensen ring or a naphthalene ring having a specific substituent at the 2-position or 2.6-position, represented by the general formula (Ilb) ( A) (hereinafter, this low molecular weight substance will be particularly referred to as tree t(A')) is preferable.

General formula (Ila) C113 Furthermore, the high molecular weight resin CB] contains at least one of the above Macro monomer (M+) and macromonomer (M2), and has a PO3112 group at the end of the polymer main chain, -503H group, 1 COOI group, 1011 fire, 0 General formula (n b) CIL+? In (Ila) and (Ilb), the heart and 82 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, -COD, and -GOOD (0,
and D2 are each carbon #! ! 1 to 10 hydrocarbon groups). However, both A2 and A2 do not represent hydrogen atoms.

B1 and B2 each represent a single bond or a linking group having 1 to 4 linking atoms that connects -COO- to the Hensen ring.

A graph 1 type copolymer having at least one acidic group selected from 011 bonded thereto (hereinafter, this high molecular weight product is particularly referred to as resin [B']) is preferable.

In particular, the general formula (Ina ) and/or (Il
In the macromonomer b) R, Il or It,2
When represents a hydrocarbon group, it is particularly preferable to use a resin in which the acidic group is bonded to the main chain of the polymer.

In the present invention, the acidic group-containing resin (A) containing a specific copolymerization component is such that the acidic group contained in the resin adsorbs to the stoichiometric defects of the inorganic photoconductor, and the low molecular weight Therefore, by improving the coverage of the surface of the photoconductor, the trapping of the photoconductor is compensated for and the humidity characteristics are dramatically improved, while the photoconductor is sufficiently dispersed.
It was found to suppress aggregation. The resin (B) is a material that does not impede the high performance electrophotographic properties obtained by using the resin (A) and provides sufficient mechanical strength to the photoconductive layer, which is insufficient with the resin (A) alone. It is.

According to the present invention, resin [A] and resin [B] are used as a binder resin for an inorganic photoconductor by specifying the weight average molecular weight of each resin, the content of acidic groups in the resin, and the bonding position. This is believed to be due to the ability to appropriately change the strength of the interaction between the photoconductor and the resin. In other words, the resin (A) with stronger interaction selectively adsorbs appropriately to the inorganic photoconductor, while the resin (B) with weaker interaction compared to resin [A] has less weight in the resin. The acidic group bonded to a specific position with respect to the main chain of the coalescence interacts gently with the inorganic photoconductor to the extent that the electrophotographic properties are not affected, and in the case of resin (13) tin, the long molecular length and graph 1. It is presumed that, as mentioned above, both the electrophotographic properties and the mechanical strength of the resin could be significantly improved by the interaction between the molecular chains of the same length.

Furthermore, when resin [A'] is used, the electrophotographic properties (especially V, ., D.R. fl.
An improvement of El/10) can be achieved.

The reason for this is unknown, but one reason is that it is due to the effect of the planar Hensen ring or naphthalone ring, which has a substituent at the or-j position, which is the ester component of mekkryle-1. This is thought to be due to the proper alignment of these polymer molecular chains at the zinc oxide interface in the film.

When resin [B'] is used, electrostatic properties, especially D. Il. l
? and L/+o became better, and the use of resin [A] gave an excellent characteristic η. It is preferable that its effectiveness hardly changes even under environmental changes such as high temperature/high temperature, low temperature/low humidity, etc.

Further, in the present invention, the surface of the photoconductor has smoothness. When a photoreceptor with a rough photoconductive layer surface is used as an electrophotographic planographic original plate, the dispersion state of the inorganic particles as a leading heavy substance and the binder resin is not appropriate, and the photoconductive layer is coated in the presence of aggregates. As a result, even if desensitization treatment is performed using a desensitization treatment liquid, the non-image areas cannot be made evenly and sufficiently hydrophilic, causing printing ink to adhere during printing.
As a sticky substance, the non-image area of the printed matter will be distorted.

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

In the resin (A), the weight average molecular weight is IXIO3-2
X10', preferably 3X1x103 to 1x104, the proportion of the copolymer corresponding to the repeating unit of formula (1) is 30% by weight or more, preferably 50 to 97% by weight, and the copolymerization proportion containing an acidic group is The proportion of polymerization components present is 0.5 to 20% by weight, preferably 1 to 10% by weight.

Formula (Ila) and/or (I
J? 61% number. 1.30% by weight or more"2, b
The proportion of copolymerized components containing acidic groups is 0.5 to 20% by weight, preferably 1% by weight.
~10% by weight.

The glass transition point of the resin (A) is preferably -20°C to 1
10°C, more preferably -10°C to 90°C.

On the other hand, the weight average molecular weight of resin CB) is 5X10' to IX
106, preferably 8X10' to 5X10'.

The abundance ratio of the macromonomer represented by the general formula (ITla) and/or (I[Ib) in the polymer is 0.5
It is preferable that the amount is 80% by weight, especially for general formula (I[
1a) and (Illb), R3. Alternatively, in the case of a macromonomer in which R32 is a hydrogen atom, the proportion thereof is preferably 0.5 to 30% by weight.

The glass transition point of the resin (B) is preferably O° to 110
°C, more preferably 20° to 90°C.

If the molecular weight of the binder resin [A] is smaller than 1 x 103, the film shape will deteriorate and sufficient film strength cannot be maintained, while if the molecular weight is larger than 2 x 10', the product temperature will drop even with the resin of the present invention.・The present invention increases fluctuations in electrophotographic characteristics (especially initial jlJ potential, 11{) decay retention rate) under harsh conditions of high humidity, Gion, and low temperature crystallization, making it possible to obtain stable copied images. The effect of this will be weakened.

If the content of acidic groups in the binder resin (A) is less than 0.5% by weight, the initial potential will be low and sufficient image density will not be obtained. On the other hand, if the acidic group content is more than 20% by weight, the dispersibility decreases no matter how low the molecular weight is.
The film smoothness and high-humidity electrophotographic properties are reduced, and when used as an offset master, background smearing increases.

Furthermore, if the molecular weight of the binder resin CB) is smaller than 5 x 105, the film strength cannot be maintained sufficiently, while if the molecular weight is larger than 106, the dispersibility decreases, the film smoothness deteriorates, and the quality of the copied image deteriorates. The image quality (particularly the reproducibility of fine lines and characters deteriorates) deteriorates, and furthermore, when used as an offset 1 master, background stains become significant.

Macromonomer content in binder resin [B] is 0.5
If it is less than % by weight, the electrophotographic properties (especially dark decay rate, photosensitivity) will decrease, and the electrophotographic properties will fluctuate significantly under environmental conditions, especially in combination with near-infrared to infrared spectral sensitizing dyes. Become. This is thought to be due to the fact that the amount of macromonomer that becomes the graft portion is small, resulting in a composition that is almost the same as a conventional homopolymer or random copolymer.

On the other hand, if the content of the macromonomer exceeds 80%, the copolymerizability of the macromonomer according to the present invention with other monomers corresponding to the copolymerization portion will not be sufficient, and even if it is used as a binder resin, it will not be sufficient. Electrophotographic characteristics cannot be obtained.

Furthermore, R31 or R3 in general formulas (I[la) and (Illb). When the macromonomer is a hydrogen atom and exceeds 30% by weight, the dispersibility decreases, the film smoothness deteriorates, the image quality of copied lines deteriorates, and when used as an offset master, the printed matter becomes smeared (11). . This is thought to be because the macromonomer contains more COOI+ groups, which strengthens the interaction with the inorganic photoconductor due to its dispersibility, causing aggregation of the inorganic photoconductor.

Next, binder resin (A) and binder resin CB used in the present invention
) will be explained.

The resin [A] of the present invention contains a repeating unit represented by formula (1) and a repeating unit containing an acidic group as copolymerization components. Two or more types of each repeating unit may be contained in the resin (A).

In the general formula (1), a, a2 are a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom), a cyano group or a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms (
For example, methyl group, ethyl group, proyl group, butyl group, etc.)
represents. R1 is preferably an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, proyl group, butyl group, pentyl group, sil group, octyl group, decyl group, todecyl group). group, 1-litecyl group, tetradecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-methoxyethyl group,
3-hydroxypuchyl group, etc.), optionally substituted alkenyl groups having 2 to 18 carbon atoms (e.g. vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group,
hebutenyl group, octenyl group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g. hensyl group,
cycloalkyl groups having 5 to 8 carbon atoms (e.g., cyclopentyl, cyclohexyl group, cyclobutyl group, etc.), optionally substituted aryl groups (e.g. phenyl ayu, tolyl group, xyl group, mesityl group, naphdyl group, methoxyphenyl group, ethoxyphenyl group, fluorophenyl group) , difluorophenyl group, promophenyl group, chlorophenyl group, dichlorophenyl group, iodophenyl group, methoxycarbonylphenyl group, polyoxysulfonylsoenyl group,
cyanoff, nyl group, 21-lofenyl group, etc.).

Further, preferably, the copolymer component corresponding to the repeating jlIt position of general formula (1) is represented by general formula (ITa) and/or (
Ilb) is a methacrylate containing a specific aryl group (resin (A')).

General 2 Nla) C113 General formula (II b) C1{3 In formula (Ila), preferred 8. and as A2,
In addition to hydrogen, chlorine, and bromine atoms, respectively,
Preferred hydrocarbon groups include alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, probyl group, butyl ayu, etc.), aralkyl groups having 7 to 9 carbon atoms (e.g., Henzyl group,
phenethyl group, 3-phenylpyl group, chlorohenzyl group, dichlorobenzyl group, promohenzyl group, methyl\\benzyl group, methyl-xybenzyl group, chloro-methyl-henzyl group, etc.) and aryl groups (e.g. phenyl group,・Ryl group, silyl group, propophenyl group, meI-xyphenyl group, chlorophenyl convex, dichloro1]phenyl group, etc.), -COD, and -COODz (preferred D1 and D2 are the above-mentioned preferred hydrocarbon groups) However, C. and 8. cannot both represent a hydrogen atom.

In formula (Ila), B1 is a single bond connecting -COO- and the Hensen ring or -+C II (n+ represents an integer from 1 to 3), CIl OCO Cll 2CI+ 2
0CO10Cll. It represents a linking group having 1 to 4 linking atoms, such as o+1r (nz represents an integer of 1 or 2), -CII*CIl*0, and the like.

h in formula (Ilb) does not represent the same content as n.

Some specific examples of copolymerization corresponding to the repeating unit represented by formula (Ila) or (IIb) used in the resin [A'] of the present invention are listed below.

but, The scope of the present invention is not limited thereto.

Also, In each example below, T and T2 are each Cl1 llr or I, R is Cal+2. ．． or show, b represents O or an integer from 1 to 3, C is 1~ Indicates an integer of 3.

l 1) C113 2) C11, 31 ■ 11) 8) CIl:1 9) C113 13) ■ 14) C113 32 CI+3 C113 CI{3 ShiUl (violet 19) CH3? In addition, in the copolymer component containing an acidic group in the resin (A) of the present invention, as a preferable acidic group, -PO3
Examples of R include a 11■ group, a -30311 group, a -COOI+ group, a 01lP-011 group, and a cyclic acid anhydride-containing group.

0 (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, proyl group, butyl group, hexyl group, octyl group). , decyl group, dodecyl group, octadecyl group, 2
-chloroethyl group, 2-methoxyethyl group, 3-ethoxypuchyl group, allyl group, crotonyl group, butenyl group,
cyclohexyl group, benzyl group, phenethyl group, 3-phenylprobyl group, methylhenzyl group, chlorohenzyl group, fluorohendyl group, methoxyhenzyl group, etc.), or optionally substituted aryl groups (for example, phenyl group, tolyl group, ethyl Phenyl group, probylphenyl group, chlorophenyl group, fluorophenyl group, promophenyl group,
chloromonomethylphenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.).

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 dicarboxylic 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, cyclopenkune-1,2-dicarboxylic anhydride ring, and cyclohexane-1,2-dicarboxylic anhydride ring. cyclohexene-1,2-dicarboxylic acid anhydride ring, 2,3-bicyclo(2.2.2)octane dicarboxylic acid anhydride ring, etc. These rings include, for example, chlorine atom, bromine atom, etc. may be substituted with a halokene atom, an alkyl group such as a methyl group, an ethyl group, a butyl group, or a hexyl group.

Examples of aromatic dicarboxylic anhydrides include phthalic anhydride rings, naphthalene-dicarboxylic anhydride rings, pyridine-dicarboxylic anhydride rings, thiophene-dicarboxylic anhydride rings, etc. For example, halogen atoms such as chlorine atom and bromine atom, methyl group, ethyl group,
It may be substituted with an alkyl group such as a probyl group or a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxy carbonyl group (for example, a methoxy group, an ethoxy group, etc.).

The acidic group-containing copolymerizable component of the present invention is, for example, a copolymerizable component that can be copolymerized with a monomer corresponding to a repeating unit represented by general formula (I) (including general formulas (Ila) and (llb)). Any vinyl compound containing an acidic group may be used, and is described, for example, in "Polymer Data Handbook [Basic Edition]" edited by the Society of Polymer Science and Technology, Baifukan (1986). Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2-amino)methyl form, α-chloro form, α-bromo form, α -Fluoro form, α-tributylsilyl form, α-
Cyano form, β-chloro form, β-bromo form, α-chloro-
β-methoxy, α,β-dichloroform, etc.), meccrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half ξ-dos, crotonic acid, 2-alkenylcarboxylic acids (e.g. 2-pentenoic acid, -methyl-2-hexenoic acid,
2-octenoic acid, 4-methyl-2-hexenoic acid, 4? methyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylhenzenesulfonic acid, vinylsulfonic acid,
Examples include half-ester derivatives of the vinyl group or allyl group of vinylphosphonic dicarboxylic acid MM, ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing the acidic group in a substituent of an ado derivative.

An example of copolymerization containing an acidic group will be given below. Here, P
1 indicates H or CL, P2 is ■1, CIl:l or C
H2COOCH3, R and ■ represent an alkyl group having 1 to 4 carbon atoms, RI3 represents an alkyl group having 1 to G carbon atoms, a benzyl group, or a phenyl group, C represents an integer of 1 to 3, and d represents an integer of 1 to 3. represents an integer of 2 to 11; e represents an integer of 1 to 11; f represents an integer of 2 to 4; and g represents an integer of 2 to 10.

ii −1) P, −+CI+. -C→1COOII ii -2 C113 10Cl+ CIl →-COOI+ ii -3) ? 1 ← Cll ■ - C → 1 Coo (CH2) acOOH ii -4) P? f- C It■-C→-CONH (CI+2). C O 0 11ii -5) P P2 1←CH C← C00(CI12)20CO(CI+2)cCOOHi
i -6) P 1-{-CI+ P2 [C→- - COO(CI+2)zococn=c++-coo++
ii -7) P2 ii -9) P1 10Cl1 P2 1 C→-COO(CI+2) rsOall ii -10) 1←CIl2 CH-+-CI13
? O N II C II COC-50311C1
{3 ii -15) P P2 10CH C← 0 C(10(CIlz) z-0-P-OH011 ii -23) Soup COX CIl→-SO. l+ ii -24)? P1C11■ CI+-}- CI12COOI+ ii -25) P P2 ii -26) P P2 1,000CH C-CH CONH (CI+2) 2SO3+1 ii -28) -←Cl+ CIl→1ii -19) COOI+ ? 〇Cl+■ C→ー? H■COOR ii -20) 10Cl+ Cll→-COOI+ COOII ii -21) P2 ii -22) P ii -31) P ii -32) P P2 1←Cll-C→1 ii 37) PI P211 1← Cll -C→1 01i Coo(CH2)90-P-Rll 011 ii -36) PI P2 01{ Furthermore, in the binder resin (A), a copolymer component represented by the above general formula (1) (general formula (including those represented by I[a) or (Ilb)) and an acidic group-containing copolymer component, in addition to the copolymer component containing a thermally and/or photocurable functional group, 1 to It is preferable to contain 20% by weight in order to obtain greater mechanical strength.

"Thermal and/or photocurable functional group-1" refers to a functional group that performs a resin curing reaction using at least one of heat and light.

Specifically, the photocurable functional group is described by Hideo Inui and Nagai? Gentaro, “Photosensitive Polymer” (Kodansha, 1977), Takahiro Tsunoda, “New Photosensitive Resin” (Printing Society Publishing Department, 1981)
Annual), G. E. Green and B. P,St
rak, J. Macro. Sci. Reas. Macr
o Chem. C21(2), 187-273(1
981-82), C. G. Rattey, rPh
otopolymerization of Surfa
ce Coatings” (A. Wiley Inte
rScience Pub. Functional groups used in conventionally known photosensitive resins and the like are used as the photocurable resins cited in reviews such as 1982).

Furthermore, the "thermosetting functional group" in the present invention refers to a functional group other than the above-mentioned acidic group. ),
Yuji Harasaki “Latest Binder Technology Handbook” Chapter 11-1 (
General Technology Center, 1985), Takayuki Otsu, “Coordination, Design and Development of New Applications of Acrylic Resins” (Chubu Business Development Center Publishing Department, 1985), Eizo Omori, “Functional Acrylic Resins” (Techno System, 1985) The functional groups cited in the references can be used in reviews such as those published in Japanese.

For example, -011 group, -811 group, -N11 group, -NI
IR2 group (R2 represents a hydrocarbon group, for example, carbon number 1
~10 optionally substituted alkyl groups (e.g. methyl group, ethyl group, probyl group, butyl group, hexyl group, octyl group, decyl group, 2-chloroethyl group, 2methoxyethyl group, 2-cyanoethyl group, etc.), An optionally substituted cycloalkyl group having 4 to 8 carbon atoms (e.g. cycloheptyl group, cyclohexyl group, etc.), an optionally substituted aralyl group having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group) , 3-phenylprobyl group, chlorobenzyl group,
methylhendyl group, methoxyhendyl group, etc.), optionally substituted aryl groups (e.g. phenyl group, 1-lyl group,
xylyl group, chlorophenyl group, propophenyl group, methoxyphenyl group, naphthyl group, etc.], CONIICH 20R 3 (R 3 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, proyl group, butyl group, hexyl group, octyl group, etc.) ?b+, b2 are hydrogen atoms, halogen atoms (
For example, chlorine atom, bromine atom, etc.) or an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, etc.). In addition, the polymerizable double bond group is specifically C1]2・C11−, CIl■・CII−
C It■? CH. C
H3 0i1111 CIl■-CIl-C-0-, Cll. C-C-0-,
CIl=CIl-C-011 0? I{3 CH, II CHz=CH-CONH-, CIl■=C-CONI+
-, CII=CII-CONII? Il■-Cll-N
IICO-, CIl■. C II - C H ■ 1, N
IICOCI1■・CIl-So■-, CIl■・CI
l-Co-, CI+2・CIl-OCll■=CIl-
S-, etc. can be mentioned.

In the present invention, as a method for making the binder resin contain at least one functional group selected from the group of the curable functional groups, a method of introducing the functional group into the polymer by polymer reaction, or a method of introducing one or more of the functional groups One or more monomers containing the above and the general formula (1) (general formula (Ila) or (Ilb)
It can be obtained by a method of copolymerizing a monomer corresponding to the repeating unit of (including )) and a monomer corresponding to the "acidic group-containing co-flj polymer component".

For polymer reactions, conventional methods for small molecule synthesis reactions can be used as they are; for example, "New Experimental Chemistry Course Vol.
~[V]'' (published by Maruzen Co., Ltd.), Yoshio Iwakura and Keisuke Kurita, ``Reactive Polymers'', etc., are described in detail in known literature cited as review articles.

On the other hand, examples of monomers containing the "functional group that undergoes photo- and/or thermosetting reactions" include - Examples include hinyl compounds containing functional groups. Specifically, examples include those containing the functional group in the same compound as the above-mentioned "acidic group-containing compound".

An example of a repeating unit containing a "thermal/photocurable functional group" is given below. Here, Rz, a, b, and e have the same contents as above, and P and P3 are each H or ? 113,
R14 is -CI1=C112 or -CII■CIl=C
I+■iii-4) P1? 〇Cll■-C→1C00(Cllz)eOco(CHz)h-COO-R
zCHCH3, RI6 is -CII=CI+2, ?
I12CI = CI+■ iii -5) PI P3 represents S or ○, T3 represents OH or Nlh, h represents an integer of 1 to 11, and i represents an integer of 1 to 10.

iii-1) P ? 〇Cll. 1C→■ ? 0 0 C It = C I + ■iii -2) iii-3) ? 1←Cll■1C1〉1 COOC}lzclt=cll■ P+ 1←CH2-C→1 C00 (CI+2). 1Coo-Rl4iii-6) ? I P3 11 →Cll　-C→１ one Coo (CI!■). OCO-R. 5 iii-7) ? I P3 11 -{-Cll-C→■ ? OOCII■C II C II■OOC-RI6! OH Il1 12) P, P3 Il+ 13) P.I. P3 -{-Cl+ ? →1■ ? ONIICII■011 Il+ 14) I1 f! ONllCI12ORI I -{-Cll.

? →■ 1 CON+1 (CH2). COOCH2CHCH200C
-RI5■ 0■ 111 15) P1 P3? IP: 1 11 -f- Cll -C→■■■ COO(CIlz)d-T3/-{-CH CIl→Furthermore, the resin (A) of the present invention is a compound of the above-mentioned general formula (I). In addition to the monomer (including general formulas (I[) and (III)) and the acidic group-containing monomer, other monomers other than these may be contained as copolymerization components. For example, in addition to methacrylic esters, acrylic esters, and crotonic esters containing substituents other than those explained in general formula (1), α-olefins, vinyl carboxylates, or allyl esters (e.g., carboxylic acid esters) (propionic acid, butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (e.g. dimethyl ester, diethyl ester, etc.), acrylamide, methacrylamide styrenes (e.g. styrene, vinyl-1-luene, chlorostyrene, hydroxydistyrene, N,N-dimethylaminomethylstyrene,
・oxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinyl sulfone-containing compounds, vinyl ketone-containing compounds, heterocyclic vinyls (e.g. vinylpyrrolidone, vinylpyridine, vinylimidazur, vinylthiophene, vinylimidublin, vinyl) pyrazole, vinyldioxane, vinylquinoline, vinyltetradules, vinyloxazine, etc.).

Next, preferred embodiments of the resin (Bl) will be described below.

The resin [B] of the present invention has the formula (Illa) and/or the formula (
Weight average molecular weight expressed as I[lb)1. OX103~
It is a graft copolymer having a weight average molecular weight of 5X10' to IXIO', which contains a macromonomer of 1.5X10' as a copolymerized portion, preferably, It is a high-molecular-weight resin having at least one acidic group selected from a -P O 3 Hz group (same content as 0 Lll1 R) and a cyclic acid anhydride-containing group bonded to the terminal.

A macromonomer having a polyester structure with a polymerizable double bond group bonded to one end and a carboxyl group bonded to the other end, which is provided as a copolymerization component of resin (B), will be explained in more detail. .

In the general formulas (Illa) and (Illb), ( )
The formula (Illa) and/or (IIlb) (
The weight average molecular weight of the Dmac0 monomer was set to IXI03 to 1.
5 represents a repeating unit sufficient to exceed XIO'.

In the macromonomer of the general formula (Iffa), preferably c1 and c2 may be the same or different, and each is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom), a cyano group, Alkyl group having 1 to 3 carbon atoms (e.g. methyl group, ethyl group, probyl group, etc.)
, -cooz, or -CI12COOZ2 {Zl and Z2 are each an alkyl group having 1 to 8 carbon atoms (e.g. methyl group, ethyl group, proyl group, butyl group, pentyl group, hexyl group, octyl group, etc.), 7 to 8 carbon atoms 9 aralkyl groups (e.g. henzyl group, phenethyl group, 3-phenyl group
:1 pyl group, etc.) or Im may be) phenyl group (
For example, Ph--nole, B>, 1-lyl group, xylyl group, methoxyphenyl group, etc.).

More preferably c. and c2 represents a hydrogen atom.

X. is preferably -COO-, -OCO-, -CI
hCOO-, CI+20CO-, -CONH-, -CO
N+ICONI+-,-CONIICOO one or? OO
, -oco, -o- -s- -so■-
-N- -CONe5 In addition, d1 is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (e.g., methyl group, ethyl group, proyl group, phthyl group, hexyl group, octyl group, decyl group, dodecyl group,
-Me-1-xyethyl group, 2-chloroethyl group, 2-cyanoethyl group, henzyl group, methylbenzyl group, chlorobenzyl group, methoxyhenzyl group, phenethyl group, fuunyl group, 1-lyl group, chlorophenyl group, methoxyphenyl group , butylphenyl group, etc.).

y. For example, it represents a group that connects X1 and -COO, and represents a monoviscous or connected group. It does not represent a linking group specifically selected as a linking group or a linking group formed by a combination of these linking groups. may be 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 probyl group, Butyl group, 2-chloroethyl group, 2-methoxyethyl group, 2-methoxyluponylethyl group, henzyl group, methoxybenzyl group,
(phenyl group, me1-xyphenyl group, me1-xylphenyl group, etc.), and e5 to e7 represent the same content as d above}.

W and 2 may be the same or different and each represents a divalent organic residue, 10S d. d4 Represents a divalent aliphatic group, a divalent aromatic group, or an organic residue composed of a combination of these divalent residues, which may include an open bonding group.

Here, d2 to d3 are d. represents the same content as .

Examples of the monovalent aliphatic group include (r+ and f2 may be the same or different, and each has a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.) or a carbon number of 1 to 12 alkyl groups (for example, methyl group, ethyl group, probyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.). NR33-, R33 is an alkyl group having 1 to 4 carbon atoms, -CI+21J or -(JI
Jr.}.

Examples of the valent aromatic group include a Hensen ring group, a naphthalene ring group, and a 5- or 6-membered heterocyclic group (as a heteroatom constituting the heterocycle, a heteroatom selected from an oxygen atom, a sulfur atom, and a nitrogen atom) (containing at least one kind of). These aromatic groups may have a substituent, for example, a halogen atom (e.g. fluorine atom, chlorine atom,
bromine atom, etc.), alkyl groups having 1 to 8 carbon atoms (e.g. methyl group, ethyl group, probyl group, butyl group, hexyl group,
Examples of substituents include octyl group, etc.), and alkoxy groups having 1 to 6 carbon atoms (eg, methoxy group, 1-oxy group, propoxy group, butoxy group, etc.).

Examples of the heterocyclic group include a furan ring, a thiophene ring, a pyridine ring, a pyracine ring, a piperazine ring, and a ? 1. Lahydrofuran ring, pyrrole ring, Te1. Lahydrobilane ring, 1,
Examples include 3-oxazoline ring.

Ihl preferably represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and specific examples of the hydrocarbon group include C,,C
The same examples as those mentioned above in 2 can be mentioned.

Formula (Illb), odor, preferred c3, c4, x2
, v2 and R32 are C, , c2, X+ . of formula (nla).
．． Each represents the same contents as those described as preferable in YI and R3■.

W3 represents a divalent aliphatic residue, specifically -{-
Cll. →■ (m+ is an integer from 2 to 1H), g2 represents an alkyl group such as a ru group, an ethyl group, a probyl group, and both 13l and g2 represent a hydrogen atom; a pyru group, a butyl group, a hexyl group , octyl group, etc.), m
2 represents an integer from 1 to 16).

In the macromonomer in general formula (Illa) and general formula (Illb)? Specific examples of the portion 1 L YI X2 Y2 include, but are not limited to, the following. However, in each of the following examples,
OI is -11, -CI+3, -Cll zC;OOC
II 3, CI, -Br or -CN, 0■ is -1
1 or -Cl13, n represents an integer of 2 to 12,
m represents an integer of 1 to 12.

(A-1) Ql (A-2) C
ll:1CH2=C −
CIl=C? COO (CI+■).

alkyl groups (e.g. methyl group, ethyl group, pro(A-
5) 01 C CONH (CH2) ,l (^-6) C113 C CONIICONH{CH2)I1 (8-7) C113 C ■ CONIICOO{-CI+ 2)n (A-8) 02 C ? 00(CIl■)llOCO(CI1■). (A-9
) 02 C? ONII (Cll■). OCO (Cll 2) -
02 C? oo(CH2)rlSO■NH(CH2)Il02 C COO(Ctlz) 3Nl'lCOO(Cllz).

(A-19) Ro2 C COO(CI{z)3NH (A-11) OCO(CHz)Ll (A-12) COO (Cll z)nOcOcIl(A-13) (A-15) ? Il■CH2 (8122)? OOCII■C II C It■OOC(CI+2
)l, (8123)? Il■OCO(Cll■).

(A-24) 302(CH2)Il (A-25) CON(CH2)I1 (A-26) (A-27) ? 8-28) 0■ (B-3) C-C? , and W2 include the following organic residues, but the present invention is not limited thereto. However, in each of the following examples, R41 has 1 to 1 carbon atoms.
4 alkyl group, -cuzcr or -CIlBr, R42 is an alkyl group having 1 to B carbon atoms, -←C}12
→TOR41 (R■ stands for one meaning, l is 2
~8), -CII■ (J or -CII
zBr, R43 represents -■ or -CH3, R4
4 represents an alkyl group having 1 to 4 carbon atoms, Q represents -0-, -S-, or -NR41 (R41 represents the above meaning), p represents an integer of 1 to 26, and q represents O or represents an integer of 1 to 4, r represents an integer of 1 to 10, and j represents O or 1
An integer of ~4 is shown, and k is an integer of 2-6.

(84) -{- CI+2→T (B-5) (B-6) (B-7) (B-8) R41 1 ←CH-CH2-+-r- R421142 11 ←Cl(-Cll → -?R4■ may be the same or different)? 4 1 C-CI1■ 2 R41 (R4. may be the same or different) (11-2) -CIl=CI+ R44 R4a(l'l 10)? II C II■EOCI12CII■→,OC
II2C (l?44 may be the same or different) (B~
11)? CII■Cll. O CI1zCtl■-→Tba OC
11■C1] 2 Ugo~ (B 12)? -CII■CII2S Cl12CIl■→'(B 13)? CIhCtl■SCtlzCII. OCIhCII2
→Shimoichi 73 (B-23)? Il■-C壬C-CHZ 74 (B-24) CI+. - CIl = Cll - CI! 2(B-
25)? Il■OCHzCIh (B-26)? uzcu■Cli■oC11. CI12CII■(B
-27)? 〇Cl+■÷1-so2 -{- CI+2→r(B
-28) +C112-)-T-S-S+CH2-)TCH3-C]13 The macromonomer represented by the general formula (nla) is described in "Polymer Data Handbook [Basic W] J
(Published in 1986) Baifukan et al., which are synthesized by polycondensation reaction of diols and dicarboxylic acids, dicarboxylic acid anhydrides, or dicarboxylic acid esters, and have a weight average molecular weight of 1 x 103 to 1.5 x 104. Only in the hydroxyl group at one end of the polyester oligomer,
It can be easily produced by introducing a polymerizable double bond group through a polymer reaction.

Polyester is synthesized by a conventionally known polycondensation reaction, specifically, Eiichiro Takiyama, "Polyester Resin Handbook," Nikkan Kogyo Shimbunsha (published in 1986)
, edited by The Society of Polymer Science and Technology, “Polycondensation and Weighting Force” (formerly Kyoritsu Shuppan (1980)
Annual), I. Goodman rEncyc1op
edia of Polymer Science a
nd Engineering VOI 12J pi.
John Wiley & Sons (1985
The merger can be carried out according to the method described in the annual publication) etc.

A method for introducing a polymerizable double group only into the hydroxyl group at one end of a polyester oligomer uses a conventionally known reaction of esterifying alcohols or urethanizing alcohols in low-molecular compounds. We can come to an agreement.

That is, a method in which macromonomers are synthesized by esterification by reaction with carboxylic acids, carboxylic esters, carboxylic acid halides, or carboxylic anhydrides containing a polymerizable double bond group in the molecule; This can be achieved by a method in which urethane is formed by a reaction with an isocyanate containing a polymerizable double viscous group, and then a macromonomer is combined.

Specifically, the Chemical Society of Japan, "New Experimental Chemistry Course ■, Synthesis and Reactions of Organic Compounds (II) J, Chapter 5, Maruzen ■, (19
Coalescence can be carried out using the method described in detail in ``Coordination and Reactions of Organic Compounds [■]'', p. 1652, Maruzen ■ (published in 1978), etc.

The macromonomer represented by the general formula (l [b)] is synthesized by a self-polycondensation reaction of a carboxylic acid containing a hydroxyl group in the molecule, and then the macromonomer represented by the general formula (II [a)] is synthesized. A method for synthesizing a macromonomer through a similar polymer reaction can be a method in which a carboxylic acid containing a polymerizable double bond group and a lactone are combined through a living polymerization reaction. Specifically, T. Yasuda, T. 8ida and
Sjnoue J. Macromol. Sci
．． Chem. , 8, 21. 1035 (
1984), T. Yasuda, T. Aid
aand S. Inoue, Macromlecule
es+ 17+ 2217 (1984)+S. Sos
Nowski, S. Stomkowski and
S. Penczek Makromol. Chem
．． 188. 1347 (1987L Y. Gnan
ou andP. Rempp. , Makromol.
Chem. 188 2267 (1987), T. S
Hiota and Y. Goto, J. Appl.
Polym. Sci. , 11+753 (1967)
It can be manufactured by the method described in et al.

Specific examples of macromonomers represented by formula (Illa) or (Illb) that can be used in the present invention are shown below. However, in each example below, the weight average molecular weight of the macromonomer is 1 x 103 to 1.5
Indicates sufficient repeat<1'i position to make iO', and b. indicates the same content as above, and b.は-■or-c11
3, R45 and R46 may be the same or different and each represents C113 or -C 2 I+ 5, R4? and R48 may be the same or different and each -CL -Br
, -CH2cl or -Cll2Br, and S is 1 to
25 is an integer, t is an integer from 2 to 12, and U is 2.
Indicates an integer from ~12, X represents an integer from 2 to 4, and y represents 2
~G is an integer, and Z is an integer from 1 to 4.

(Gate-1) Q3 (G2) O (M-3) 0, (M-4) (G5) CIL+ (M-9) 0 (M-6) 0 (M-10) Q1 (M-11 ) CH. (M-12) Q 8l 82 (M-13) (M-15) (M-21) (M-22) (Gate-23) (M-24) (M-16) (M47) 0. (M-20) 0 (M-25) 0 (M-26) The resin [B] used in the binder resin of the present invention is selected from the general formula (I[[a] and (Illb)) described above. A copolymer containing at least one macromonomer as a copolymerization component, and the other copolymerization component is a copolymer that satisfies the physical properties of the binder resin described above and is radical copolymerizable with the macromonomer. Any monomer can be used as long as it can be obtained.

Preferably, the copolymer contains 30% to 99% by weight of a monomer corresponding to the copolymerization amount of general formula (1) shown in the resin [A].

86 Resin CB) may contain other copolymerization components other than the copolymerization component represented by general formula (1), specifically, other copolymerization components described for resin (A). Examples include monomers corresponding to the following.

The proportion of these other monomers as a copolymerized portion is
It is preferable that the amount of citrus [B) in the total polymer does not exceed 30% by weight at most, and more preferably 20% by weight or less.

Further, in some cases, the electrophotographic photoreceptor of the present invention is desired to have greater mechanical strength while maintaining its excellent electrophotographic properties. For this purpose, a method of introducing heat-curable and/or photocurable functional groups similar to those described for resin (A) into the main chain of the graft copolymer can be applied.

That is, also in resin CB), the above formula (I[la)
and/or (Illb) macromonomer and preferably the monomer represented by general formula (1), a monomer containing at least one thermally and/or photocurable functional group may be contained as a copolymerization component. preferable. Such heat-curable and/or photo-curable functional groups suitably crosslink the polymers, thereby strengthening the interaction between the polymers and improving the strength of the film. Therefore, the resin of the present invention further containing such heat-curable and/or photo-curable functional groups,
This has the effect of strengthening the interaction between the binder resin without impeding proper adsorption and coating between the surface of the zinc oxide particles and the binder resin, and as a result, the film strength is further improved.

The resin [B'] of Wood's invention, in which a specific acidic group is bonded only to one end of the polymer main chain, is obtained by attaching various reagents to the end of a living polymer obtained by conventionally known anionic or cationic polymerization. A reaction method (ionic polymerization method), a radical polymerization method using a polymerization initiator and/or chain transfer agent containing a specific acidic group in the molecule (radical polymerization method), or the above ion A polymer containing a reactive group (for example, an amino group, a halogen atom, an epoxy group, an acid halide group, etc.) at the end obtained by a polymerization method or a radical polymerization method is converted into the specific acidic group of the present invention by a polymer reaction. It can be easily manufactured by a combination of methods and the like.

Specifically, P. Dreyfuss, R. P
．． Quirk Encycle, Polym.
Sci. Eng, 7, 551 (19 8
7. ), Yoshiki Nakajo, Yuya Yamashita "Dye and Medicine", ■,
232 (1985), Akira Ueda, Susumu Nagai “Science and Industry”
It can be produced by the methods described in reviews such as Goritsu, 57 (1986) and the literature cited therein.

Specifically, the chain transfer agent used is, for example, a mercapto compound containing the acidic group or the above-mentioned reactive group (i.e., a group that can be induced into the acidic group) (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid). , 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopionyl)glycine, 2-mercaptonicotinic acid, 3- [N (2-
Mercaptoethyl)carbamoyl]propionic acid, 3(
N-(2-mercaptoethyl)amino]propionic acid,
N-(3-mercaptobioyl)alanine, 2-mercaptoecune sulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercapto-1 ethanol, 3-mercapto-1,2-propanediol, ■-Mercapto-2-propanol, 3-mercap 1,2-butanol, mercaptophenol 2-
Mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3pyridinol, 4-(2mercaptoethyloxycarbonyl)phthalic anhydride, 2-mercaptoethylphosphonoic acid, 2mercaptoethylbosphonic acid monomethyl ester, etc. ), or iodized alkyl compounds containing the above polar groups or substituents (e.g. iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanol,
iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferred are mercapto compounds.

Specific examples of the polymerization initiator containing the acidic group or a specific reactive group include 4,4'-azobis(4-cyanovaleric acid), 4,4''-azobis(4-cyanovaleric acid chloride) ), 2.2''-azobis(2-cyanopropanol), 2,2゜-azobis(2-cyanopentanol), 2.2'-azobis[2-medyru N-(2-
hydroxyethyl)-propioamyl='L2,2゜-
Azobis(2-methyl-N[1,1-bis(hydroxymethyl)-2-hydroxyethyl)propioamide l
, 2'-azobist2-[1-(2-hydroxyethyl)-2-imidlin-2-yl]propane l
, 2,2"-azobis(2-(2imidazolin-2-yl)propane)2,2"-azobis(2-(4,
5,6.7-tetrahy-1-lowill-L3-diazopin-2-yl)propane] and the like.

The amount of each of these chain transfer agents or polymerization initiators is 0.05 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total monomers.

In the present invention, resin (A) and resin CB) (according to the present invention)
In addition to (including Bl), other resins can also be used in combination. Examples of such resins include Alkit resin, polybutyral resin, polyolefins, ethylene-vinyl acetate copolymer, styrene resin, styrene-butadiene resin, acrylate-1-butadiene resin, and vinyl alkanoate resin.

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

In addition, when the resin (A) and/or CB) of the present invention contains the thermosetting functional group, the necessary C reaction may be added to promote the crosslinking reaction in the photosensitive layer. A reaction accelerator may also be added. In the case of a reaction mode that forms a chemical bond between functional groups, for example, ira acid (acetic acid, propionic acid, butyric acid, Hensensulfonic acid, p-toluenesulfonic acid, etc.)
, a crosslinking agent, and the like.

As a crosslinking agent, specifically, Shinzo Yamashita and Tosuke Kaneko ed.
Compounds described in "Crosslinking Agent Handbook" published by Taiseisha (1981) and the like can be used. For example, commonly used crosslinking agents such as organic silanes, polyurethanes, and polyisocyanates, and curing agents such as epoxy resins and melanin resins can be used.

In the case of a polymerizable reaction mode, a polymerization initiator (peroxides, azobis-based compounds, etc. are mentioned, preferably an azobis-based polymerization initiator), a monomer containing a polyfunctional polymerizable group (for example, vinylmethacrylate), etc. -1・, allyl methacrylate,
To ethylene glycol diacrylate-1, volumetric glycol diacrylate, divinyl succinate,
divinyl adibate, diallyl succinate, 2-methylvinylmethacrylate-1, divinylhensen, etc.).

Further, in the present invention, when using a binder resin containing such a thermosetting functional group, a thermosetting treatment is performed. This heat curing treatment can be performed by tightening the drying conditions during conventional photoreceptor production. For example, 60°C~
The treatment may be carried out at 120"C for 5 minutes to 120 minutes. If the above-mentioned reaction accelerator is used in combination, the treatment can be carried out under milder conditions.

The ratio of the amount of resin CA) (including (A')) and resin (including rD (CB')) used in the present invention varies depending on the type, particle size, and surface condition of the inorganic photoconductive material used. Generally, the ratio of resin (A) to resin CB) is 5 to 80:95 to 20 (weight ratio), preferably 10 to 60:90 to 40 (weight ratio).

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 photoconductor.

In the present invention, various dyes can be used in combination as spectral sensitizers, if necessary. For example, Harumi Miyagi, Hidehiko Takei, Imaging 1973 (No. 8) p. 12,
C. J, Young et al., RCA Review 5,
469 (1954) Wataru Kiyota, Transactions of the Institute of Electrical Communication Engineers J 63-C- (No. 2) 97 (1980),
Yuji Harasaki et al., industrial chemistry journals 78 and 188 (1
963), Tadaaki Tani, Journal of the Photographic Society of Japan 208 (1
Carbonium dyes, diphenylmethane dyes, 1-rifhenylmethane dyes, xanthene dyes, phthalein dyes, and polymethine dyes (e.g.,
oxonol dye, merocyanine dye, cyanine dye,
Rhodacyanine dyes, styryl dyes, etc.), lidocyanine dyes (which may contain metal), and the like.

More specifically, examples using mainly carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes include JP-B No. 51452 and JP-A 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-5746456.

oxonol dye, merocyanine dye, cyanine dye,
Examples of polymethine dyes such as logcyanine dyes include F. M
．． Harmmar rThe Cyaninc Dy
es andRelated Compounds J
It is possible to use the pigments described in et al., and more specifically,
U.S. Patent No. 3.0117,384, U.S. Patent No. 3.1
No. 10,591, U.S. Patent No. 3. 121008, U.S. Patent No. 3,125,447, U.S. Patent No. 3,12
8,179, U.S. Patent No. 3,132,942, U.S. Patent No. 3,622,317, British Patent No. 1. 2
26,892, British Patent No. L309,274,
British Patent No. L405,1398 Blade, Special Publication 1978-781
4, Japanese Patent Publication No. 55-18892, and the like.

Furthermore, as a vorimethine dye that spectrally sensitizes the near-infrared to infrared light region with a long wavelength of 700 nm or more, JP-A-47840, JP-A-47-44180, and JP-B-Sho 51-41061 are used.
No., JP-A-49-5034, JP-A-49-45122
No., JP-A-5746245, JP-A-56-35141
No., JP-A-57-157254, JP-A-61-260
No. 44, JP-A No. 61-27551, U.S. Patent No. 3,6
No. 19,154, U.S. Pat. No. 4,175,956, r
Research Disclosure” 1982
2B, 216, pages 117-118, etc.
I can't get enough of it. 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 additives for electrophotographic photosensitive layers such as chemical sensitizers can be used in combination. For example, the electron-accepting compounds (e.g., halogens, henzoquinone, chloranil, acid anhydrides, organic carboxylic acids, etc.) cited in the aforementioned review: Imaging 1973 (No. 8) page 12, Hiroshi Komon et al. Recent Development and Practical Application of Photoconductive Materials and Photoreceptors” No. 4
Chapter ~ Chapter 6 Nippon Scientific Information Co., Ltd. Publishing Department (1986)
Polyarylalkane compounds cited in the review, Hinder 1
- Phenol compounds, p-phenylenediamine compounds, etc. can be mentioned.

Addition of these various additives? Although not particularly limited, it is usually 0.0001 to 2 parts by weight per 100 parts by weight of the photoconductor.
．． It is 0 parts by weight.

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

Further, when a photoconductive layer is used as the charge generation layer of a photoreceptor with a stacked charge generation layer and a charge transport layer, the thickness of the charge generation layer is 0. OI~1μ, especially 0.05~0.5μ is suitable.

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

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 polyvinyl ruhazole, oxazole dyes, birapurin dyes, 1-
Examples include liphenylmethane dyes.

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

Typical resins used for the insulation layer or charge transport layer include polystyrene #AJIu, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride copolymer resin. , polyacrylic resin, polyolefin resin, urethane resin,
Thermoplastic resins and curable resins such as epoxy resins, plastic 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 of the electrophotographic photosensitive layer is preferably electrically conductive, and the electrically conductive support may be made of a low-resistance material such as metal, paper, or plastic sheet. those that have been subjected to conductive treatment by impregnating them, those that have been coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and further preventing curling, etc. A water-resistant adhesive layer is provided on the surface of the support, at least one pre-coat layer is provided on the surface layer of the support as required, and a conductive plastic base is coated with AN or the like. You can use paper laminated.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakaki, Electrophotography, 14, (No.l),
p2-11 (1975), Hiroyuki Moriga. "Introductory Chemistry of Special Papers" Kobunshi Publishing (1975), M. F. II
oover, J. Macromol. Sci
．． Chem. A-4 (6). 1327th ~
1417 (1970) etc. is used.

(Example) The invention will now be illustrated by examples.

Example 1 of the resin (A) of the present invention: [A-1] 95 g of pendyl methacrylate, 5 g of acrylic acid, and 2 g of toluene
After heating 00 g of the mixed solution to a temperature of 90'C under a nitrogen stream, 2,2゛-azobisisobutyroni-1-IJ J
l/ (abbreviation A.I.B.N) 6.0g to jJDe4
The time response was U゜. Furthermore, A. lIl. N. 2g
was added and reacted for 2 hours.

Weight average molecular weight (abbreviation ~) of the obtained copolymer (A-1)
) was 8500.

Synthesis examples 2 to 28 of resins CA) of the present invention: [^-21 to [
A-28] Each resin [A] in Table 1 below was synthesized under the same polymerization conditions as in Synthesis Example 1 of Resin (A).

99 100 Synthesis example 29 of resin (A) of the present invention: [A-2912
A mixed solution of 95 g of 6-dichlorophenyl methacrylate, 5 g of acrylic acid, 2 g of n-dodecylbutane, and 200 g of toluene was heated to a temperature of 80°C under a nitrogen stream. I. B. N. 2 g was added and reacted for 4 hours, then A. I. B. N. Add 0.5g and continue for 2 hours. lB. N. 0.5 g was added and reacted for 3 hours. After cooling, it was reprecipitated into a mixed solution 22 of methanol/water (9/1), and the precipitate was collected by decantation and dried under reduced pressure. The yield of the waxy copolymer obtained was 78 g and the weight was 6.3 XIO3.

Macromonomer combination example 1: MM-1 1,4-butanediol 90.1g, succinic anhydride 10
A mixture of 5.1 g, p-toluenesulfonic acid monohydrate, 1.6 g, and toluene 200 g was
4 hours under reflux with stirring in a flask equipped with a reflux device.
heated for an hour. 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 L-butylhydroquinone were added to the above reaction mixture, and the mixture was reacted under reflux for 4 hours with further stirring. After cooling to room temperature, it was reprecipitated into 2 liters of methanol, and the precipitated solid was collected by filtration and dried under reduced pressure.

The yield was 135 g, and the obtained macromonomer (MM-
1) Weight average molecular weight was 6.8XIO3.

(MM-1) Synthesis example 2 of macromonomer: MM-2 120 g of 1,6-hexanediol, 1 gluconic anhydride
14.1g, p-}luenesulfonic acid monohydrate 3
．． A mixture of 0 g and 250 g of toluene was reacted under the same conditions as in Example 1 for the synthesis of macromonomers. The amount of water distilled off azeotropically was 17.5 g.

After cooling to room temperature, n-hexane 2I! ．． The liquid was collected after decantation and dried under reduced pressure.

The above reaction product was dissolved in 1.0% luene. When the carboxyl group content was measured by neutralization titration with IN potassium hydroxide methanol solution, it was found to be 500 μmol/g.
r. It became.

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

Dicyclohexyllupodiimide (D.C.C.) 20.
3g, 4-(N,N-dimethyl)aminopyridine 0.5
A mixed solution of 100 g of methylene chloride and 100 g of methylene chloride was titrated into the above mixture for 1 hour while stirring. The mixture was further stirred for 4 hours.

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

The filtrate was reprecipitated into 2 liters of hexane, and the powder was collected by filtration. After adding 500 me of acetone and stirring for 1 hour, the insoluble matter was filtered by gravity using a filter paper. After the filtrate was concentrated under reduced pressure until the total volume was 2, this solution was added to ether lffi 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″.

(MM-2) Macromonomer synthesis example 3: MM-3 500 g of 12-hydroxystearic acid was heated at an external temperature of 150 g.
The mixture was stirred for 10 hours in an oil bath at °C under a reduced pressure of 10 to 15 mmlll while distilling off some of the water.

The carboxyl group content of the obtained liquid was 600 μmol.
/gr. 100 g of the above liquid, 18.5 g of methacrylic anhydride, t-butylhytroquinone 1.
A mixed solution of 5 g of tetrahydrofuran and 200 g of tetrahydrofuran was stirred at a temperature of 40 to 45°C for 6 hours. Add 1 part of the reaction mixture to 1 part of water.
It was added dropwise into ffi over 1 hour while stirring, and the mixture was further stirred and pressed for 1 hour. The precipitated liquid was taken out by decantation, dissolved in 200 g of TIIP, and reprecipitated in 1R methanol. The precipitated liquid was taken out by decantation and dried under reduced pressure.

The yield was 62 g, and the weight average molecular weight of the macromonomer (MM-3) was 6.7 XIO''.

(MM-3) CB-1) CI+3. Synthesis example 4 of CH3 macromonomer: MM-4 S. Penczek et al. Makromol
．． Chem. 188. 1347 (1987), a macromonomer (MM-
4) was synthesized.

Weight average molecular weight: 7.3X103 Resin of the present invention CB) Synthesis Example 1: A mixture of 85 g of [B-1] ethyl methacrylate, 15 g of the compound (MM-1) of macromonomer synthesis example 1, and 200 g of toluene was heated under a nitrogen stream. It was then heated to a temperature of 75°C.

■, 0.6 g of 1''-azobis(cyclohexane-I-carponitrile) (abbreviation 8, B.C.C.) was added and stirred for 4 hours.Furthermore, 0.3 g of A.B.C.C. The mixture was added for 3 hours, and then 0.2 g of 8.B.C.C. was added and stirred for 4 hours.The resulting copolymer was 9.IXIO.
'Met.

Synthesis Example 2 of Resin [B] of the Invention: Synthesis Example 4 of [B-21 Henzyl Methacrylate-1.95g, Macromonomer]
A mixture of 5 g of compound (MM-4) and 200 g of toluene was heated to 75°C under a nitrogen stream. 44'
-Azobis(2-cyanovaleric acid) (abbreviation: A.C.
V. ) and stirred for 4 hours. Next, A. C
．． V. 0.3g was added for 3 hours, and then A,C. V.
0.2 g was added and stirred for 3 hours. The weight average molecular weight of the obtained copolymer was 1.2×105.

(B-2) Examples 3 to 13 of combination of resin CB of the present invention: [B-3 to
[8-13] Polymerization strip A9 similar to Example 1 of resin paste (B)
The resins were combined with each resin shown in Table 2 below.

1 1 3 Synthesis Examples 14 to 23 of the resin (B) of the present invention: [B-13
Synthesis of H~[11-231 Resin CB) In Example 1, the following mercapto compounds were used as chain transfer agents and the resins CB) in Table 3 were produced under similar polymerization conditions.

Examples 24 to 31 of combinations of resins CB) of the present invention: [11-2
4]~(u-311 resin (In Synthesis Example 2 of Bl, as the azobis compound, C.C.V. was replaced with another azobis compound, and under the same polymerization conditions, resin C of Table 4 was used.
13] were produced respectively. Each resin (Bl Nonba 8.0
It was IO'~2xl05.

119 Examples 32 to 41 of resin CB) of the present invention: [8-3
21 to [8-41] Resin CB] Each resin CB) in Table 5 below was synthesized under the same polymerization conditions as in Example 1.

The book of the obtained copolymer is 9. O XIO' ~ 1.2 X
It was IO5. .

Example 1 and Comparative Examples A-B Resin 1: A-10) 6 g (as solid content) Resin (B-1) 34 g (as solid content), zinc oxide 200
g, heptamethine cyanine dye shown by the following structural formula (
A mixture of 0.02 g of 1'3, 0.05 g of phthalic anhydride, and 300 g of toluene was dispersed in a Pall mill for 2 hours to prepare a photosensitive layer shape, and this was applied to conductive-treated paper with a dry adhesion amount. It was coated with a wire bar at a concentration of 18 g/m and dried at 100°C for 30 seconds.

Then, in the dark under the conditions of 20°C and 65% R I-1.
By leaving it for 4 hours, an electrophotographic light-sensitive material was produced.

Cyanine dye (1) Comparative example A. In Example 1, instead of 34 g of resin CB-1), poly(ethyl methacrylate) Olw: 2.4 x
An electrophotographic light-sensitive material was prepared in the same manner as in Example 1, except that 34 g of 10') was used.

Comparative Example B The same procedure as in Example 1 was carried out, except that resin [R1] having the following structure was used instead of 6 g of resin [:A-10) and 34 g of resin CB-1) in Example 1. An electrophotographic light-sensitive material was produced.

(R-1) Edited by: 3.8 Examined. Furthermore, when these photosensitive materials are used as original plates for offset masters, the photoconductive desensitization property (represented by the contact angle with water of the photoconductive layer after desensitization treatment) and printability (background smudge, Rigidity resistance, etc.) were investigated.

The above results are summarized in Table 6.

The implementation aspects of the evaluation items shown in Table 6 are as follows.

Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was tested using a Heck smoothness tester (Kumagai Riko).
The smoothness (sec/cc) was measured under the condition of an air volume of 1 cc.

Note 2) Mechanical strength of photoconductive layer: The surface of the photosensitive material obtained was tested using a Hayton-14 type surface test material (
(manufactured by Shinto Kagaku ■) with a load of 55 g/c+], and was repeatedly probed with emery paper (#1000) 1000 times to remove abrasion powder and determine the residual film rate (%) from the weight loss of the photosensitive layer. did.

Note 3) Electrostatic properties: In a dark room at a temperature of 20°C and 65% RH, each photosensitive material was subjected to corona discharge at -6 kV for 20 seconds using a paper analyzer (Paper Analyzer SP-428 model manufactured by Kawaguchi Electric). After allowing it to stand for 10 seconds, the surface potential VIO at this time was measured. The potential VI9 was then left to stand in the dark for 180 seconds. The retention of the potential after dark decaying for 180 seconds, that is, the dark decay retention rate (DRR)
(%) was determined by (VI90/VIO) XIOO (%).

After the surface of the photoconductive layer was charged to -500V by corona discharge, it was irradiated with monochromatic light with a wavelength of 785 nm to increase the surface potential (
V,. ) is attenuated to 1/10, and the exposure amount El/10 (erg/cfl) is calculated from this. Furthermore, as in the El/10 measurement, 50
After charging to 0V, it was irradiated with monochromatic light with a wavelength of 785 nm, and the surface potential (V+O) was 18. . Determine the time it takes for the light to attenuate, and then calculate the exposure amount E17. Calculate o(erg/cM).

Note 4) Imaging performance: Each photosensitive material was left for one day and night under the following environmental conditions.

Next, it is charged with -5kV and used as a light source. Using a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm) with an output of 8 mW, a 50 e
Copied image obtained by developing and fixing using ELP-T (manufactured by Fuji Photo Film ■) as a liquid developer after exposure under an irradiation dose of RG/CFL at a pitch of 25μ and a scanning speed of 300m/sec. (Kabri,
Image quality) was visually evaluated.

The environmental conditions during imaging were 20°C65%R11 and 30°C8.
It was performed at 0% Rll. Copied manuscripts are word processor characters,
I used letters cut out from straw paper and pasted on.

Note 5) Contact angle with water: Each photosensitive material was processed in an etching processor using a desensitizing liquid ELP-EX (manufactured by Fuji Photo Film).
After passing through the photoconductive layer to desensitize the photoconductive layer surface, a droplet of 2 pl of distilled water is placed on the photoconductive layer, and the contact angle with the water formed is measured using a goniometer.

Note 6) Rigidity Resistance Each photosensitive material is plate-made under the same conditions as Note 4) above to form a toner image, desensitized under the same conditions as Note 5) above, and used as an offset master to print on an offset printing machine. (Oliver Model 52 manufactured by Sakurai Seisakusho) indicates the number of sheets that can be printed without causing background stains in the non-image areas of the printed matter or problems with the image quality of the image areas (the higher the number of printed sheets, the better the printing durability. ).

As shown in Table 6, in each of the photosensitive materials of the present invention, the strength and electrostatic properties of the smooth film of the photoconductive layer were good, and the actual copied images had no ground blur 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.

Comparative example B is D. R. R. was low and E,,, o was also large, and furthermore, under conditions of high temperature and high humidity, satisfactory photoconductivity could not be obtained. Comparative Example A has electrostatic properties under conditions of normal temperature and normal humidity. R. R.
A nearly satisfactory value for EI/10 was obtained. However, El
/100, the value was more than twice that of the photosensitive abrasive of the present invention. Furthermore, under conditions of high temperature and high humidity,
D. R. R. EI/I. A decreasing trend was observed. Also, E
At l/+00, the decrease was even greater. IE+/10G
In actual imaging performance, the value indicates how much potential remains in the non-image area (already exposed area) after exposure. Indicates that stains will no longer occur.

Specifically, it is necessary to make the residual potential below -10V, that is, how much exposure is required to actually make VR below -10V, so we decided to use a scanning exposure method using semiconductor laser light. Therefore, it is very important to reduce (1) to -10 V or less with a small exposure amount in terms of the design of the optical system of a copying machine (device cost, accuracy of optical system optical path, etc.).

From this fact, when an image was actually taken using an apparatus with a slightly lower exposure dose, the light-sensitive material of Comparative Example A had blurring in the non-image areas.

Furthermore, even when used as an offset master original plate, under printing conditions that allow printing of 10,000 or more sheets of the photosensitive dye of the present invention,
It was limited to 000 pieces.

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

Examples 2 to 17 In Example 1, resin (A-10) and resin (B-1
) Each electrophotographic photoreceptor was produced in the same manner as in Example 1, except that each resin (A) and each resin (B) shown in Table 7 below were used instead of (1).

Table 7 Furthermore, when printing was performed in the same manner as in Example 1 using the offset master original plate, more than 10,000 sheets could be printed in all cases.

From the above, each of the photosensitive materials of the present invention was good in all respects of the smoothness of the photoconductive layer, film strength, electrostatic properties, and printability.

Examples 18 to 25 In Example 1, the binder resin was replaced with resin (A) shown in Table 8 below.
Same conditions as in Example 1, except that 6.5 g and 33.5 g of resin (B) were replaced, and 0.018 g of the dye (U) having the following structure was used instead of 0.02 g of the cyanine dye (1). An electrophotographic light-sensitive material was produced.

The electrostatic properties of dye (II) (22-4SIU3) can be obtained as shown in Table 8, the measured values under the conditions (30°C, 80% Rl+). This is effective for scanning exposure methods.

Claims (3)

[Claims] (1) In an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor and a binder resin, the binder resin includes at least one of the following binder resins [A] and binder resin [B]. An electrophotographic photoreceptor characterized by containing at least one of the following. Binder resin [A]: has a weight average molecular weight of 1 x 10^3 to 2 x 10^4,
30% by weight of the copolymerization component represented by the following general formula (I)
The above and -PO_3H_2 group, -SO_3H group, -C
Select from OOH group, -OH group, ▲mathematical formula, chemical formula, table, etc.▼{R represents a hydrocarbon group or -OR' group (R' represents a hydrocarbon group)}, and cyclic acid anhydride-containing group The copolymerization component containing at least one kind of acidic group is 0.
Resin containing 5 to 20% by weight. General Formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In formula (I), a_1 and a_2 each represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group. R_1 represents a hydrocarbon group. Binder resin [B]: represented by the following general formula (IIIa) and general formula (IIIb),
Weight average molecular weight 5x containing at least one polyester type macromonomer having a weight average molecular weight of 1x10^3 to 1.5x10^4 as a polymer component
10^4 to 1 x 10^6 copolymer. General formula (IIIa) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIIb) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ In formulas [IIIa] and [IIIb], the brackets [ ] represent repeating units. c_1 and c_2 may be the same or different from each other,
Each hydrogen atom, halogen atom, cyano group, carbon number 1-8
hydrocarbon group, -COO-Z_1 or -COO-Z_2 (Z_1 and Z_
2 each represents a hydrocarbon group having 1 to 18 carbon atoms. X_1 is a single bond or -COO-, -OCO-, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (l_1, l_2 represent integers from 1 to 3), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (d_1 is a hydrogen atom or (represents a hydrocarbon group having 1 to 12 carbon atoms), -CONHCONH-, -CONHC
Represents OO-, -O-, ▲mathematical formulas, chemical formulas, tables, etc.▼ or -SO_2-. Y_1 represents a group connecting X_1 and -COO-. W_1 and W_2 may be the same or different from each other,
Divalent aliphatic group, divalent aromatic group {-O-, -S-, -N- (d_2 is a hydrogen atom or a carbon number of 1 to 12 in the bond of each divalent organic residue) (represents a hydrocarbon group),
-SO_2-, -COO-, -OCO-, -CONHC
O-, -NHCONH-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (d_3 represents the same content as d_2), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (d_4 represents the same content as d_2) and ▲ may contain at least one bonding group selected from ▼ which includes mathematical formulas, chemical formulas, tables, etc.} or represents an organic residue constituted by a combination of these residues. R_3_1 represents a hydrogen atom or a hydrocarbon group. c_3, c_4, X_2, Y in general formula (IIIb)
_2 and R_3_2 are each c in general formula (IIIa)
It represents the same content as _1, c_2, X_1, Y_1 and R_3_1. W_3 represents a divalent aliphatic residue. (2) In the resin [A], as a copolymer component represented by the general formula (I), the following general formulas (IIa) and (IIb) are used.
The electrophotographic photoreceptor according to claim 1, characterized in that it contains at least one of the following aryl group-containing methacrylate components. General formula (IIa) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIb) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ In formulas [IIa] and [IIb], A_1 and A_2 are each hydrogen atoms independently of each other. , a hydrocarbon group having 1 to 10 carbon atoms,
Chlorine atom, bromine atom, -COD_1 and -COOD_2
(D_1 and D_2 each represent a hydrocarbon group having 1 to 10 carbon atoms). However, A_1 and A_2 do not both represent hydrogen atoms. B_1 and B_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 [B] has =PO_3H_2 groups, -SO_
At least one acidic group selected from 3H group, -COOH group, -OH group, ▲mathematical formula, chemical formula, table, etc.▼ (R_0 represents the same content as R), and cyclic acid anhydride-containing group. Claim (1) or (1) which is a resin bonded to the terminal of the polymer main chain portion of the copolymer.
2) The electrophotographic photoreceptor described above.