JPH02135456A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic sensitive body capable of holding stably superior electrostatic characteristics against variation of environmental conditions in the stage of forming copy picture by incorporating a specified resin and another resin having a specified crosslinked structure into a binder resin constituting a photoconductive layer. CONSTITUTION:In an electrophotographic sensitive body prepd. from an inorganic photoconductive material and a binder resin, the binder resin contains at least one kind of resins A and at least one kind of resins B. The resin A has 1X10<3>-2X10<4> weight average mol.wt. contg. >=30wt.% at least one kind of recurrent units expressed by the formula I or II as a component of the polymer wherein at least one substituent selected from -PO3H2 group, -SO3H group, -COOH group is bonded to only one terminal of the polymer chain. The resin B has >=5X10<4> weight average mol.wt. and a crosslinked structure contg. a recurrent unit expressed by the formula III as the component of the polymer.

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 and moisture resistance.

In particular, it relates to a CPC photoreceptor with excellent performance.

(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, consisting of a support and at least one photoconductive layer, are used for imaging by most common electrophotographic processes, ie, charging, imagewise exposure and development, and optionally transfer.

Furthermore, the method of using an electrophotographic photoreceptor as an offset master plate for direct plate making is widely used (in practical use).In recent years in particular, direct electrophotographic plates have been used to produce high-quality printed matter with a print count of several hundred to several dozen sheets. This is becoming an important printing method.

The binder used to form the photoconductive layer of the electrophotographic photoreceptor has excellent film-forming properties and the ability to disperse photoconductive powder into the binder, and also has excellent properties in the formation of the formed recording layer. It has good adhesion to the substrate, and the photoconductive layer of the recording layer has excellent charging ability, low dark decay, large light decay, and little pre-exposure fatigue. It is necessary to have various electrostatic properties such as stable properties 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), alkyd resin, maleic acid resin, polyamide (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. 3541216), acrylic acid ester copolymer (e.g. Japanese Patent Publication No. 35-11219, Japanese Patent Publication No. 36-85)
No. 10, Japanese Patent Publication No. 41-13946, etc.) are known.

However, electrophotographic light-sensitive materials using these resins lack 1) affinity with photoconductive powder, resulting in poor dispersibility of the coating solution. 2) Low chargeability of the photoconductive layer, 3
) The quality of the image area of the copied image (especially halftone reproducibility and resolution) is poor; 4) The environment at which the copied image was created (e.g. high temperature,
The problem was that the image quality was easily affected by low temperatures (low temperature, low humidity, etc.).

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 nitro group in an aromatic ring or a furan ring, or a dicarboxylic acid anhydride. Japanese Patent Publication No. 42-6878 and Japanese Patent Publication No. 45-3073 disclose a method of further combining materials to coexist in a photoconductive layer. However, even the photosensitive materials improved by these methods do not have sufficient electrostatic properties, and none particularly have excellent light attenuation properties. 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 produced by this method have a remarkable whiteness. This causes deterioration in the quality of the recording medium, and in some cases causes deterioration in the dark decay of the photosensitive material, resulting in the problem that a sufficient copy image cannot be obtained.

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 distribution of 103 to 104;
A technique has been described for improving electrostatic properties (particularly repeatability as an RPC pentamer), moisture resistance, etc. by using together components having a distribution of ~2X105.

Furthermore, research is being carried out on lithographic printing original plates using electrophotographic photoreceptors, and a binder resin for the photoconductive layer that has both the electrostatic properties of an electrophotographic photoreceptor and the printing properties of a printing original plate has been developed. For example, in Japanese Patent Publication No. 50-31011, a (meth)acrylate monomer and other monomers are copolymerized in the presence of fumaric acid, Mwl, 8 to 10
10' and a TglO~80°C resin and a copolymer consisting of a (meth)acrylate monomer and a monomer other than fumaric acid, and JP-A-53-54
In No. 027, a terpolymer containing a (meth)acrylic acid ester having a substituent having a carboxylic acid group separated from an ester bond by at least 7 atoms is used; No. 57-202544 uses a quaternary or quinary copolymer containing acrylic acid and hydroxyethyl (meth)acrylate, and JP-A-58-68046 uses an alkyl group having 6 to 12 carbon atoms as a substituent. It is described that a terpolymer containing a (meth)acrylic acid ester and a carboxylic acid-containing vinyl monomer is effective in improving the fat resistance of the photoconductive layer.

However, even if the resin is said to be effective in the above-mentioned electrostatic properties and moisture resistance properties, when actually evaluated, it is found that the electrostatic properties such as chargeability, dark charge retention, photosensitivity, photoconductive layer, etc. There are problems with the smoothness, etc., and it is 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 planographic printing, when actually evaluated, there were problems with the above-mentioned electrostatic properties, scumming of printed matter, moisture resistance properties, etc.

Furthermore, in order to solve these problems, 0.05 to 10% by weight of a copolymer component containing acidic groups was added as a binder resin.
By using a low molecular weight resin (MwlO'~104), the smoothness and electrostatic properties of the photoconductive layer can be improved, and in addition, it is possible to obtain both awards without background smearing.
No. 217354 further discloses that by using such a low molecular weight resin in combination with a high molecular weight resin (MwlO' or higher), the film strength of the photoconductive layer can be made sufficient without impeding the above characteristics, and the printing durability can be improved. Japanese Patent Application No. 63-49817, JP-A No. 63220148 and 63-220149
listed in the number.

(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 changes such as low temperature and low humidity or high temperature and high humidity. It is to provide.

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.

(Means for Solving the Problems) The above-mentioned problems provide an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material and a binder resin.
It has been found that the problem can be solved by an electrophotographic photoreceptor characterized in that the binder resin contains at least one of the following resins [A] and at least one of the following resins [B].

Resin [A] A polymer having a weight average molecular weight of 1 x 103 to 2 x 104 and containing at least 30% by weight of at least one repeating unit represented by the following formula (1) or formula (II) as a polymerization component. Yes, and one terminal of the polymer main chain has 2 (7) Mi PO
, 82 groups, -3O3H groups, -Coo) I groups, P-OH groups, (R is a hydrocarbon group having 1 to 10 carbon atoms or -OR'
(R' represents a hydrocarbon group having 1 to 10 carbon atoms)
, a -SO group, an acidic group of a phenolic oH group, and a cyclic acid anhydride-containing group.

[In the formula, Xl and x2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, ~coy, or -COOY2 (Yl and Y2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, (represents a hydrocarbon group). However, both Xl and x2 do not represent hydrogen atoms.

- and W2 each represent a direct bond or a linking group having 1 to 4 linked atoms that connects -COO- to the benzene ring. ] Resin [B] has a weight average molecular weight of 5X10' or more, and has the following formula (
A resin containing at least a repeating unit represented by III) as a polymer component and having a crosslinked structure.

General formula (II[) a, a.

[In the formula, T is CH2COO ■ is carbon number 1 al and a2 are each hydrogen atom, COOOOCOCHzOco- Represents 〇- or -3O□-.

~22 hydrocarbon groups.

-COO-Z (Z is the number of carbon atoms 1-1
8) represents a hydrocarbon group. ] Furthermore, the resin [B] further contains -P(ht(z, 5O311, -C
OOII, -0R1-S)l.

(b+, b2 may be the same or different and represent a hydrogen atom or a hydrocarbon group) It is preferable that the resin is formed by bonding at least one polar group, and furthermore, the resin [B] is It is more preferable that the resin does not contain a repeating unit containing an acidic group or a cyclic acid anhydride-containing group represented by resin [A] as a polymer component.

That is, the binder resin used in the present invention contains a methacrylate polymerization component having a specific substituent, and further contains an acidic group and/or a cyclic acid anhydride-containing group (hereinafter referred to herein as a cyclic acid anhydride-containing group) at the end of the main chain of the polymer. Among them, unless otherwise specified, the term acidic group includes a cyclic acid anhydride-containing group) [A], a low molecular weight resin [A], and a high molecular weight resin [A], which is at least partially crosslinked. B]. resin〔
B] is preferably a resin in which a specific polar group is bonded only to at least one end of the polymer main chain (hereinafter referred to as resin [B']).
), more preferably resin [A
The side chain of the polymer does not contain the acidic group shown in ].

In the present invention, the acidic group-terminated resin [A] containing a methacrylate copolymerization component having a specific substituent has an acidic group bonded to the end of the polymer main chain in the resin that has a stoichiometry of the inorganic photoconductor. Because it adsorbs to the defects of the photoconductor and has a low molecular weight, it improves the coverage of the surface of the photoconductor, compensating for the trap of the photoconductor and dramatically improving the humidity characteristics. It was found that the particles were sufficiently dispersed, agglomeration was suppressed, and stable, high-performance electrophotographic properties were maintained even when the environment varied significantly from high temperature and high temperature to low temperature and low humidity. Resin [B] does not impede the above-mentioned high performance electrophotographic properties due to the use of resin [A], and has sufficient mechanical strength of the photoconductive layer, which is insufficient with resin [A] alone. It is something to tighten.

The resin [B] of the present invention is appropriately crosslinked, and furthermore, the resin [B]
B'] is a copolymer with a polar group bonded only to one end of the main chain, so interactions between polymer chains and weak interactions between polar groups and photoconductive particles act synergistically. Therefore, it is considered that the film achieves both extremely excellent performance in terms of electrophotographic properties and film strength. This is particularly effective when using a scanning exposure method using a semiconductor laser.

On the other hand, if resin [B] contains acidic groups similar to those shown in resin [A], the dispersion of the photoconductor is destroyed, and aggregates or precipitates are formed, or even a coating film is formed. However, it is not preferable because the electrostatic properties of the obtained photoconductor are significantly deteriorated, the smoothness of the surface of the photoconductor becomes rough, and the strength against mechanical abrasion is deteriorated.

Furthermore, even when only the low molecular weight resin [A] in the present invention is used as the binder resin, the photoconductor and the binder resin can sufficiently adsorb and coat the particle surface, resulting in a smooth photoconductive layer. Although it is possible to obtain image quality that is good in terms of electrostatic properties and electrostatic properties, is free from background smearing, and is less dependent on the environment, the film strength is still insufficient and satisfactory results cannot be obtained in terms of durability.

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

In the resin [A], the weight average molecular weight is lXl0''~2
×104, preferably 3X10′ to 1×104, formula (I
) or the repeating unit of formula (n) (hereinafter sometimes referred to as (i)), the proportion of the polymer component or copolymer component (hereinafter sometimes referred to as (i)) is 30% by weight or more, preferably 50 to 97% by weight, and the polymer is mainly The proportion of the acidic group bonded to the end of the chain in the resin [A] is 0.5 to 15% by weight, preferably 1 to 10% by weight.
Weight%. Further, the glass transition point of the resin [A) is preferably -10°C to 100°C, more preferably -15°C.
C to 80°C.

When the molecular weight of the resin [A] is smaller than 1X10', the film forming ability decreases and sufficient film strength cannot be maintained.

On the other hand, if the molecular weight is greater than 2×10 4 , electrophotographic properties (especially initial potential and dark decay retention) deteriorate, which is not preferable. Particularly in the case of such a high molecular weight material, if the content of acidic groups exceeds 3%, the electrophotographic properties deteriorate significantly, and when used as an offset master, background smudge becomes noticeable.

If the acidic group content in the 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 content of acidic groups is more than 15% by weight, the dispersibility decreases, the film smoothness and the high-temperature electrophotographic properties decrease, and furthermore, background smearing increases when used as an offset or 7-tooth master.

The resin [A] of the present invention contains a repeating unit represented by formula (1) or formula (II) as a polymerization component (or copolymerization component), and further has an acidic group bonded to the terminal of the polymer main chain. Become. Two or more types of each repeating unit represented by formula (1) or formula (II) may be contained in resin [A].

2N), preferable X and x2 include hydrogen, chlorine, and bromine atoms, respectively, and preferable 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., benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group,
dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-methyl-benzyl group, etc.) and aryl groups (e.g. phenyl group, tolyl group,
silyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group, etc.), and -C
OY, and -COOYz (preferred Yl and v2
Examples of the hydrocarbon group include those described above as the preferred hydrocarbon group. However, ×
Both 1 and X2 do not represent hydrogen atoms.

In formula (1), Kai is a direct bond connecting -COO- and a benzene ring, or -←CH2-h- (n represents an integer of 1 to 3), CIIzCIIzOCO-CII
zO廿(m represents an integer of 1 or 2), CIl□CH
Represents a linking group having 1 to 4 linking atoms, such as 20-.

Wz in formula (II) represents the same content as .

Formula (1) or (II) used in the resin [A] of the present invention
) Specific examples of the repeating unit (i) are listed below. However, the scope of the present invention is not limited thereto.

205 death! C1l.

■3 Shirishi+13 OR' includes P-OH group and cyclic acid anhydride-containing group. can.

Further, among the acidic groups bonded to the terminals of the polymer main chain in the resin [A] of the present invention, preferred acidic groups include -
P03H2 group, -5 (hl+ group, -COOI+ group, I<(R' represents a hydrocarbon group), and R and R' are preferably an aliphatic group having 1 to 22 carbon atoms (for example, a methyl group, Ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 2
-chloroethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, allyl group, crotonyl group, futhynyl group,
cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group, etc.), or an optionally substituted aryl group (for example, 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.).

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, cyclopencune-1,2-dicarboxylic anhydride ring, and cyclohexane-1,2-dicarboxylic anhydride ring. These rings include, for example, chlorine atom, bromine atom, etc. may be substituted with a halogen 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 propyl group or a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (for example, a methoxy group, an ethoxy group, etc.).

The polymer of the present invention has at least the above formula (1) or (n)
The acidic group may be synthesized by bonding the acidic group to the end of the main chain of the polymer consisting of the polymerization component.

Specifically, a method using a polymerization initiator containing the acidic group or a functional group that can be converted later into the acidic group, or a method using a polymerization initiator containing the acidic group or a functional group that can be converted later into the acidic group. It can be produced by a method using a chain transfer agent, a method using a combination of the above two, and a method in which the functional group is introduced by utilizing a termination reaction in an anionic polymerization method.

For example, P, Dreyfu3s, R,P, Gui
rk, Encycle.

Polym, Sci, Eng, 7. 55
H1987), V. Percec.

Appl, Polym, Sci, 285
95 (1985), P. F. Rempp.

E, Franta, Adv, Polym,
Sci, 58. H1984), Y.

Yamashita, J., Appl, Po.
lym, Sci, Appl, Polym.

Symp, 36. 193 (1981), R.A.
sami, M., and Takaki.

Makromol, 5upp1.12 163 (19
It can be produced by the synthetic method of the founding citation such as 85).

Furthermore, the resin [A] of the present invention contains a monomer corresponding to the repeating unit of general formula (I) or (If) described above,
Other monomers other than these may be contained as copolymerization components.

For example, α-olefins, vinyl alkanoates or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylic esters, methacrylic esters, acrylamides, methacrylamides, styrenes, heterocyclic vinyls (e.g. Vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidacillin, vinylpyrazole, vinyldioxane, vinylquinoline, vinylthiazole,
vinyloxazine, etc.).

On the other hand, the resin [B] is a polymer containing at least one type of repeating unit represented by the formula (III), and a resin having a weight average molecular weight of 5×10' or more with a part of the polymer crosslinked, and more Preferably weight average molecular weight 8XIO
'~6X10'.

The glass transition point of the resin (B) is preferably 0°C to 120°C.
℃ range, more preferably 10°C to 95°C.

When the weight average molecular weight of the resin [B] is less than 5×10′, the film strength becomes insufficient. Furthermore, if the weight average molecular weight of the resin [B] exceeds the above-mentioned preferred upper limit, it is not preferable because it has almost no solubility in organic solvents and becomes practically unusable.

The resin [B] of the present invention satisfies the physical properties described above, has a part of the polymer crosslinked, and further contains a polymer component selected from repeating units represented by the -e formula (II [)]. , as a homopolymer component or as a copolymer component with another monomer that can be copolymerized with the monomer corresponding to the repeating unit represented by general formula (III). be.

In the repeating unit represented by the general formula (I[[), the hydrocarbon group may be substituted.

- In the formula (I[[), T is preferably -COOO
COCHZOCO--C02COO- or -0-, more preferably -COOCH2C00- or 0-.

(2) preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. The substituent may be any substituent other than the polar group bonded to one end of the main chain of the polymer, such as a halogen atom (e.g., a fluorine atom,
chlorine atom, bromine atom, etc.), 0-■3, Coo-Vz,
-oco-v3, (v, ~v:l has 6 to 22 carbon atoms
represents an alkyl group such as a hexyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, an octadecyl group, and the like. Preferred hydrocarbon groups include optionally substituted alkyl groups having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group,
Butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanethyl group, 2-methoxycarbonylethyl group, 2 -methoxyethyl group, 3-bromopropyl group, etc.), carbon number 4
-18 optionally substituted alkenyl 75C e.g.
2-methyl-1-propenyl group, 2-butenyl group, 2-
Pentenyl group, 3-methyl-2-pentenyl! , 1-pentenyl L 1-hexenyl group, 2-hexenyl group,
4-methyl-2hexenyl group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chloro benzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic groups having 5 to 8 carbon atoms (for example, cyclohexyl group, 2-cyclohexylethyl group, 2cyclopentylethyl group, etc.) or carbon number 6-
12 optionally substituted aromatic groups (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxy Phenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group , dobcyroylamidophenyl group, etc.).

al and a2 may be the same or different, and are preferably a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms, -coo-z or -C112COO-Z (Z preferably represents an aliphatic group having 1 to 22 carbon atoms). More preferably, all and az may be the same or different, and are 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-z or -C02COO-Z (Z more preferably represents an alkyl group or alkenyl group having 1 to 18 carbon atoms, such as a methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group) , dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, etc., and these alkyl groups and alkenyl groups have the same substituents as shown in (1) above. ).

In resin [B], a commonly known method can be used to introduce a crosslinked structure into the polymer. That is, there are two methods: a method in which a polyfunctional monomer is coexisting in the polymerization reaction of monomers, and a method in which a functional group that promotes a crosslinking reaction is contained in the polymer and crosslinked by a polymer reaction.

The resin [B] of the present invention has a simple manufacturing method (for example, it requires a long reaction time, the reaction is not quantitative, and there are few problems such as contamination of impurities due to the use of reaction accelerators, etc.). , a functional group that undergoes a self-crosslinking reaction: C0NH
Cross-linking reactions using CH20R+1 (RO represents a hydrogen atom or an alkyl group) or polymerization are effective.

In the case of a polymerization-reactive group, the polymerizable functional group is preferably 2
Preferred is a method in which polymer chains are bridged by polymerizing a monomer having 1 or more monomers with the monomer of formula (I) described above.

Specifically, as the aggregating functional group, CI (2=C11I C1h=CH-Ctl□-0-C-1CH□=CH-N
lIC0-CI□=CII-CHz-NHCO-1C1
h-CH-3O□-1CIl□=Cl-COCl1□=
Cll-0-1CH2=CH-3-, etc., but monomers having two or more of the above polymerizable functional groups may contain two or more of the same or different polymerizable functional groups. It is sufficient if the monomer has at least one of these.

Specific examples of monomers having two or more polymerizable functional groups include styrene derivatives such as divinylbenzene and trivinylbenzene; polyhydric alcohols (e.g. ethylene Glycol, diethylene glycol, triethylene glycol, polyethylene glycol #200, #400, 600.1.3-
methacrylic acid of polyhydroxyphenols (e.g. hydroquinone, resorcinol, catechol and their derivatives); Acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers: vinyl esters of dibasic acids (e.g. malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) , allyl esters,
Vinylamides or allylamides: polyamines (e.g. ethylenediamine, 1,3-propylenediamine,
, 4-butylene diamine, etc.) and a vinyl group-containing carboxylic acid (for example, methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

In addition, monomers having different polymerizable functional groups include, for example, carboxylic acids containing vinyl groups [e.g., methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpropionic acid, acryloylpropionic acid, itaconyloyl acetic acid, itaco Niloylpropionic acid, reactants of carboxylic acid anhydride and alcohol or amine (e.g. allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.)) Containing ester derivatives or amide derivatives (e.g. vinyl methacrylate, vinyl acrylate,
Vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate,
Vinyl methacryloylpropionate, allyl methacryloylpropionate, vinyloxycarbonylmethyl methacrylate, vinyloxycarbonylmethyloxycarbonyl ethylene ester acrylate, N-allylacrylamide, N-allylmethacrylamide, N-allylitaconamide, methacryloylpropionic acid allylamide, etc.) or amino alcohols (e.g., aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and a condensate of a vinyl group-containing carboxylic acid. .

In the present invention, the partially crosslinked resin of the present invention (BE More preferably, the monomer is 15% by weight or less in the case of a resin synthesized by a method of introducing a polar group at the terminal with a chain transfer agent described below, and 5% by weight in other cases. % or less.

On the other hand, if the resin [B] does not contain a terminal polar group (not the resin [B'] described below), a resin containing a crosslinkable functional group that causes a curing reaction with heat and/or light may be used. A crosslinked structure may be formed in [B].

The functional group may be any functional group as long as it can cause a chemical reaction between molecules and form a chemical bond. That is, it is possible to use 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, a functional group H having a dissociable hydrogen atom (R1 is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group,
propyl group, butyl group, hexyl group, etc.), carbon number 7-1
1 aralkyl group (e.g. benzyl group, phenethyl group,
methylbenzyl group, chlorobenzyl group, methoxybenzyl group, etc.) or an aryl group having 6 to 12 carbon atoms (e.g., phenyl group, tolyl group, xylyl group, mesitylene group, chlorophenyl group, ethylphenyl group, methoxyphenyl group, naphthyl group, etc.) ) or -OR, a group (R2 represents the same content as the above hydrocarbon group indicated by R))
, -O1+ group, -SR group, -NHR, group (R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, butyl group)] or -CONHCH20R, (R4 is 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, a hexyl group, etc.) ) or a polymerizable double bond group.

Specific examples of the polymerizable double bond group include those mentioned above as specific examples of the polymerizable functional group.

Furthermore, for example, Tsuyoshi Endo, “Refinement of Thermosetting Polymers J.
(C, M, C Aji, 1986), Yuji Harasaki, “Latest Binder Technology Handbook” Chapter 1I-1 (General Technology Center, 1985), Otsu Accompanying “Synthesis of Acrylic Resin.
"Design and New Application Development" (Chubu Business Development Center Publishing Department,
(published in 1985), Eizo Omori “Functional Acrylic Resin”
(Technosystem, published in 1985) Hideo Inui, Gentabe Nagamatsu,
"Photosensitive Polymer" (Kodansha, 1977), Takahiro Tsunoda, "New Photosensitive Resin" (Printing Society Publishing Department, 1981)
Annual), G, E, Green and, B, P.

5tar R, J, Macro, Sci Revs M
acro, Chem,, C21(2)+187~27
3 (1981-82), C.G., Roffey, r.
Photopolymerization of 5u
rface Coatings” (A, WileyT
(Published in 1982)
Functional groups, compounds, etc. cited in the reviews of et al. can be used.

These crosslinkable functional groups may be contained in one copolymer component, or may be contained in separate copolymer components to carry out the crosslinking reaction.

Specific monomers corresponding to the copolymer component containing these crosslinkable functional groups include, for example, -a formula (I
Examples include vinyl compounds containing the functional group that can be copolymerized with the monomer [[).

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, α, β-dichloro, 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, 4-ethyl-2
- octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinyl benzene carboxylic acid, vinyl benzene sulfonic acid, vinyl sulfonic acid, vinyl phosphoric acid, half ester derivatives of vinyl or allyl groups of dicarboxylic acids, and ester derivatives of these carboxylic acids or sulfonic acids, compounds containing the crosslinkable functional group in the substituent of amide derivatives, and the like.

The proportion of the above-mentioned "copolymer component containing a crosslinkable functional group" in the resin [B] of the present invention is preferably 1 to 1.
It is 80% by weight, more preferably 5 to 50% by weight.

When producing such a resin, a reaction accelerator may be added as necessary to promote the crosslinking reaction. Examples include acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), peroxides, azobis compounds, crosslinking agents, sensitizers, photopolymerizable monomers, and the like. Specifically, the crosslinking agent is described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (
(1981) etc. can be used. For example, commonly used crosslinking agents such as organic silanes, polyurethanes, and polyisocyanates, and curing agents such as epoxy resins and melamine resins can be used.

When containing a photocrosslinking-reactive functional group, the compounds cited in the above-mentioned review of photosensitive resins can be used.

In addition, the resin [B] includes a monomer corresponding to the repeating unit represented by the general formula (III) described above and the polyfunctional monomer described above, as well as other monomers other than these (for example, the resin [A ) may be contained as a copolymerization component.

As described above, the resin [B] of the present invention is characterized by having a crosslinked structure in at least a part of the polymer, and further contains an inorganic photoconductor and the binder resin for forming a photoconductive layer. It needs to be soluble in the organic solvent used to prepare the dispersion. Specifically, it is sufficient that at least 5 parts by weight of the resin [B] can be dissolved in, for example, 100 parts by weight of the toluene solvent at a temperature of 25°C. Solvents for these applications include halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, methylchloroform, trichlene, methanol, ethanol,
Alcohols such as propatool and butanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethers such as tetrahydrofuran and dioxane, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and methyl propionate, ethylene glycol monomethyl Examples include ether, glycol ethers such as 2-methoxyethyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and tetralobenzene, and these may be used alone or in combination.

Furthermore, as a preferable embodiment of the resin [B), general 2 ([[
) is a polymer containing a small number of repeating units (both of which are one type), is partially crosslinked, and has PO31 (Z group, -503H group, -COOI+) only at one end of at least one main chain. group, -01l group, -311 group, which is the same as the above R), a cyclic acid anhydride-containing group (specifically, the same content as described in resin [A]), A weight average molecule of 15X10' formed by bonding at least one polar group selected from groups (b, b2 may be the same or different and represent a hydrogen atom or a hydrocarbon group)
or more, preferably a weight average molecular size of 8×104 to 6×1
Polymer No. 05 (hereinafter referred to as resin [B']) can be mentioned.

The glass transition point of the resin [B'] is preferably O''C~12
The range is 0°C, more preferably 10°C to 95°C. Specific examples of b and b2 include hydrogen atoms as well as optionally substituted aliphatic groups having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, 2-cyanoethyl group). group, 2 chloroethyl group, 2
-ethoxycarbonylethyl group, benzyl group, phenethyl group, chlorohensyl group, etc.), optionally substituted aryl group (e.g. phenyl group, tolyl group, xylyl group,
chlorophenyl group, bromophenyl group, methoxycarbonylphenyl group, cyanophenyl group, etc.).

Further, preferable terminal polar groups are -PO, H□ group, C00
11 groups, -5031+ groups, -〇11 groups, -311 groups, -
P-0110R" group, -CONl!2 group and -SO□Nl+□ group.

The specific polar group bonded to only one end of the polymer main chain has a chemical structure in which it is bonded directly to one end of the polymer main chain or via an arbitrary linking group.

Bonding groups include carbon-carbon bonds (-double bonds or double bonds), carbon-heteroatom bonds (heteroatoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), and heteroatoms-heteroatoms. Atom atoms, halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, etc.), cyano groups, hydroxyl groups, alkyl groups (e.g., methyl groups, ethyl groups,
propyl group, etc.], -+Cll=C11+-1
-C-1-N-1-COO-1-SO2-1-CONR
11R13 [Here, RI3 is a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group,
pentyl group, hexyl group, benzyl group, phenethyl group,
phenyl group, tolyl group, etc.) or OR+4 (R14 is
(represents the same content as the hydrocarbon group of RI3)], etc.

The resin [B] of the present invention, in which a specific polar group is bonded to at least one end of the polymer main chain, can be obtained by attaching various reagents to the ends of living polymers obtained by conventionally known anionic or cationic polymerization. A method of reacting (a method using an ionic polymerization method), a method of radical polymerization using a polymerization initiator and/or a chain transfer agent containing a specific polar group in the molecule (a method using a radical polymerization method), or an ion method as described above. It can be easily produced by a synthetic method such as a method in which a polymer containing a reactive group at the end obtained by a polymerization method or a radical polymerization method is converted into the specific polar group of the present invention by a polymer reaction.

Specifically, r', Dreyfuss, R, P, Qu
irk, Encycl.

Polym, Sci, Eng, -e: 551 (198
7) Yoshiki Nakajo, Yuya Yamashita “Dye and Medicine”, Kari, 23
2 (1985), Akira Ueda, Susumu Nagai, “Science and Industry”, Utsubo,
57 (1986) and the literature cited therein.

Specifically, the polymer of the resin [B'] used in the present invention includes - a monomer corresponding to the repeating unit represented by the formula (II), a polyfunctional monomer for forming the above-mentioned crosslinked structure, A method in which a mixture of a chain transfer agent containing a polymer and a polar group to be bonded to one end is polymerized using a polymerization initiator (for example, an azobis compound, a peroxide, etc.), or a method in which the chain transfer agent is polymerized without using the above-mentioned chain transfer agent. A method of polymerization using a polymerization initiator containing a polar group, or a method of using a compound containing the polar group as both a chain transfer agent and a polymerization initiator,
Furthermore, in the above three methods, as a substituent of the chain transfer agent or polymerization initiator, an amino group, a halogen atom,
It can be produced using a method in which a polar group is introduced by performing a polymerization reaction using a compound containing an epoxy group, an acid halide group, etc., and then reacting with these functional groups in a polymer reaction. Examples of the chain transfer agent used include mercapto compounds containing the polar group or a substituent that can be derived from the polar group (e.g., thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid,
-Mercaptopropionic acid, 3-mercaptobutyric acid, N-
(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-[N(2-mercaptoethyl)carbamoyl]propionic acid, 3-(N-(2-mercaptoethyl)aminocopropionic acid, N-(3mercaptoethyl)aminocopropionic acid, propionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-
Mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1゜2-propanediol, ■-
Mercapto 2-propertool, 3-mercapto-2-
butanol, mercaptotraenol (2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-viridinol, etc.), or iodized alkyl compounds containing the above polar groups or substituents (for example, iodoacetic acid, iodopropionic acid, diiodoethanol, 2-
iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferred are mercapto compounds.

These chain transfer agents or polymerization initiators are each used in an amount of 0.5 to 15 parts by weight based on 100 parts by weight of the total monomers,
Preferably it is 1 to 10 parts by weight.

In the present invention, resin [A] and resin [B] M according to the present invention
In addition to B'), other resins can also be used in combination. Examples of such resins include alkyd resins,
Examples include polybutyral resin, polyolefins, ethylene-vinyl acetate copolymer, styrene resin, styrene-butadiene resin, 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 ratio of the amounts of resin [A] 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 5-80:95-20 (weight ratio), preferably 15-60:85-40 (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 photoconductive couple.

In the present invention, various dyes can be used in combination as spectral sensitizers, if necessary. For example, Harumi Miyamoto, Hidehiko Takei, Imaging 1973 (No. 8) p. 12, C
, J. Young et al., RCA Review 15 4
69 (1954), 'Wataru Kiyota, Journal of the Institute of Electrical Communication J 63-C (No, 2), 97 (1980), Yuji Harasaki et al., Journal of Industrial Science 6678 and 188 (1963)
, Tadaaki Tani, Journal of the Photographic Society of Japan, 208 (1972), etc., carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthine dyes, phthalein dyes, polymethine dyes (e.g., oxonol dyes, merocyanine dyes) , cyanine dye, logocyanine dye, styryl dye, etc.), phthalocyanine dye (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
, Hammer rThe Cyanine Dy
es and Related Compounds”
It is possible to use the pigments described in et al., and more specifically,
U.S. Patent No. 3,047,384, U.S. Patent No. 3,11
No. 0,591, U.S. Patent No. 3,121,008, U.S. Patent No. 3.125.447, U.S. Patent No. 3.128.
No. 179, U.S. Patent No. 3,132,942, U.S. Patent No. 3,622,317, British Patent No. 1.226.89
No. 2, British Patent Tube No. 1,309,274, British Patent Tube No. 1
．． Examples include dyes described in Japanese Patent Publication No. 405.898, 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 5746245, JP 56-35141, JP 57- No. 157254, JP-A-61-2604
No. 4, Japanese Patent Application Publication 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 additives for electrophotographic photosensitive layers such as chemical sensitizers can be used in combination. For example, the above review: Imaging 1
973 (No. 8), p. 12 of the review, etc., cite electron-accepting compounds (e.g., halogens, penduquinone, chloranil, acid anhydrides, organic carboxylic acids, etc.), Hiroshi Komon et al., "Recent photoconductive materials and photosensitive materials. Examples include polyarylalkane compounds, hindered phenol compounds, and P-phenylenediamine compounds cited in the review of Nihon Kagaku Information (I Unpublished Division (1986)) .

The amount of these various additives added is 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 laminated type photoreceptor consisting of a charge generation layer and a charge transport layer, the thickness of the charge generation layer is 0.01 to 1μ, particularly 0.05 to 0.5μ. suitable.

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 copolymer resin, and polyvinyl chloride copolymer resin. Thermoplastic resins and curable resins such as acrylic resins, polyolefin resins, urethane 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, a base material such as metal, paper, or plastic sheet impregnated with a low-resistance substance is used in the same manner as in the past. 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 surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and also to prevent curling, and those that have been coated with at least one layer for the purpose of preventing curling, etc. A water-resistant adhesive layer is provided on the surface of the body, and at least one precoat layer is provided on the surface layer of the support as required! A material made by laminating electrically conductive plastic onto paper or the like can be used.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, electronic photography, 14 (No, 1), P2-11 (
1975), Hiroyuki Moriga, “Introductory Chemistry of Special Papers” Kobunshi Publishing (1975), M.F., Hoover, J.Ma.
cromol, Sci, Chem.

A-4(6), pp. 1327-1417 (1970)
Use those listed in etc.

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

A: After heating a mixed solution of 95 g of A-12-chloro-6-methylphenyl methacrylate, 150 g of toluene, and 50 g of isopropanol to a temperature of 80°C under a nitrogen stream, 4.4'-azobis (4-cyanovaleric acid) (hereinafter abbreviated as A, B, C, V,
5 g of the solution was added and reacted for 10 hours.

The weight average molecular weight of the obtained copolymer (A-1) was 6.5
00, the glass transition temperature was 40″C.

Structure of resin (A-1) table CH, CH.

HOO(,-CH2CH,-C-+CH!-C-±-C
N Coo-R The copolymers shown in Table 1 were produced under the same conditions as in Production Example I of Resin [A].

The weight average molecular weight of each of the obtained resins (A-2) to (A-23) was 6,000 to 8,000.

A mixed solution of 50 g of 2.6-dichlorophenyl methacrylate 9-propatur was heated to a temperature of 65°C under a nitrogen stream, and then 0.8 g of azobisisobutyronitrile was added and reacted for 8 hours. The weight average molecular weight of the obtained copolymer (A-24) was 7800, and the glass transition point was 36°C.

Structure of Resin (A-24) Each copolymer was produced under the same conditions as in Production Example 24, except that the thioglycolic acid used in Production Example 24 of Resin [A] was replaced with the compound shown in Table 2. Synthesized.

Table-2 C11.

B-1: After heating a mixed solution of 100 g of B-1 ethyl methacrylate, 1.0 g of ethylene glycol dimethacrylate and 200 g of toluene to a temperature of 75°C under a nitrogen stream, 1.0 g of abbisisobutyronitrile was added. The mixture was added and reacted for 10 hours. The weight average molecular weight of the obtained copolymer CB-1) was 4.2×10
It was 4.

With the monomer under the same polymerization conditions as in Production Example 1 of Resin [B],
Resin [B] was crosslinked using the compounds shown in Table 3 below.
was manufactured.

B's tq: B-19 methyl methacrylate 99g 1 ethylene glycol dimethacrylate Ig, toluene 150g and methanol 50g
After heating the mixed solution to a temperature of 70''C under a nitrogen stream,
4,4゛-azobis(4-cyanopencunic acid) 1.0g
was added and reacted for 8 hours.

h of the obtained copolymer was 1.0×105.

In Production Example 19 of the above resin [B], the polymerization initiator:
Resin [B] was produced under the same conditions as in Production Example 19 using the compounds shown in Table 4 below in place of 4,4'-azobis(4-cyanopenconic acid). h of each resin is 1.0X
It was 105-3X10'.

B-24: B-24 ethyl methacrylate) 99g, thioglycolic acid 1.0g
A mixed solution of 2.0 g of divinylbenzene and 200 g of toluene was heated to a temperature of 80° C. with stirring under a nitrogen stream. 2. Add 0.8 g of 2゛-azobis(cyclohexane-1 carbonitrile) (abbreviation A, C, H, N,) and add 4
React for 2 hours, then add 0.4g of A, C, H, N for 2 hours, then add 0.2g of A, C, H, N,
Time reacted.

h of the obtained polymer was 1.2×105.

Production Example 24 of Resin [B] except that the polyfunctional monomer or oligomer shown in Table 5 below was used instead of 2.0 g of divinylbenzene, which is a crosslinking polyfunctional monomer. Resin [B] was produced in the same manner as above.

B 138-45: B-38) Methyl methacrylate 39g, ethyl methacrylate 60
After heating a mixed solution of 1.0 g of the mercapto compound shown in Table 6 below, 2 g of ethylene glycol dimethacrylate, 150 g of toluene, and 50 g of methanol to a temperature of 70°C under a nitrogen stream, 2,2'-azobis(iso Butyronitrile) 0.8g was added and reacted for 4 hours, and then 2,2
0.4 g of ゛-azobis(isobutyronitrile) was added and reacted for 4 hours.

h of each obtained polymer is 9.5 x 10' to 2 x 10
It was 5.

Table 6 Examples 1 to 2 and Comparative Examples A to E Example 1 6 g of the resin (A-1) manufactured in Production Example 1 of Resin [A] (
Resin CB-1) produced in Production Example 1 of Resin [B] 34 g (as solid content), Zinc oxide 20
0g, hebutamethine cyanine dye [A] with the following structure: 0.
02g, phthalic anhydride 0.05g and toluene 300g
g of the mixture was dispersed in a ball mill for 2 hours to prepare a photosensitive layer-forming product, which was coated on electrically conductive treated paper with a wire bar so that the dry adhesion amount was 18 g/rrf.
Dry at 10°C for 1 minute, then dry at 20°C 65% in the dark.
An electrophotographic light-sensitive material was produced by leaving it for 24 hours under RH conditions.

Dye [A] Example 2 In Example 1, instead of 34 g of resin (B-1),
An electrophotographic light-sensitive material was prepared in the same manner as in Example 1, except that 34 g (solid content) of resin (B-24) was used.

Comparative Example A In Example 1, 6 g of resin (A-1) and resin CB-1
An electrophotographic material was prepared in the same manner as in Example 1, except that 40 g of resin 1'A-1) was used instead of 134 g.

Comparative Example B In Comparative Example A, instead of 40 g of resin (A-1), [ethyl methacrylate/acrylic acid (9515) weight ratio] copolymer (Mw: 7.500) (R-1)
An electrophotographic light-sensitive material was prepared in the same manner as in Comparative Example A, except that 40 g of the sample was used.

Comparative Example C In Comparative Example A, resin (instead of A-1340g,
[Ethyl methacrylate/acrylic acid (98°5/1.
5) Weight ratio) Copolymer (Mw 45,000): (
R-2) An electrophotographic light-sensitive material was produced in the same manner as Comparative Example A except that 40 g was used.

Comparative Example An electrophotographic light-sensitive material was prepared in the same manner as in Example 1, except that 6 g of resin (A-1) was replaced with 116 g of resin (R-1).

Comparative Example E An electrophotographic light-sensitive material was prepared in the same manner as in Example 1 except that resin (R-136g was used instead of resin (A-136g) in Example 2.

The film properties (surface smoothness), electrostatic properties, imaging performance, and imaging performance of these photosensitive materials under environmental conditions of 30'C180%R11 were investigated. Furthermore, when these photosensitive materials are used as original plates for offset masters, the desensitization of photoconductivity (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 7.

The implementation aspects of the evaluation items listed in Table-7 are as follows.

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

Note 2) Mechanical strength of photoconductive layer: The surface of the obtained photosensitive material was measured with emery paper (!11000) using a Hayton-14 type surface test material (manufactured by Shinrai Kagaku ■) at a load of 50 g/cffl. Repeatedly probe 1000 times to remove wear particles from the photosensitive layer. The remaining film rate (χ) was determined from JIi and was taken as the mechanical strength.

Note 3) Electrostatic characteristics: Temperature 20°C 165%l? In a dark room at I+, each photosensitive material was analyzed using a paper analyzer (Paper Analyzer 5P-428 model manufactured by Kawaguchi Electric).
After causing corona discharge for 20 seconds, it was left to stand for 10 seconds, and the surface potential LO at this time was measured. Then 9 in the dark
Potential V after standing still for 0 seconds. . is measured, and the retention of the potential after dark decaying for 90 seconds, that is, the dark decay retention rate (D
RR(χ)], (V+oo/Lo) xlOO(χ
).

Further, after the surface of the photoconductive layer was charged to -400 V by corona discharge, the surface of the photoconductive layer was irradiated with gallium-°aluminum-arsenide semiconductor laser (oscillation wavelength: 830 nm) light, so that the surface potential (V+) became 1. Find the time it takes to attenuate to /10, and from this calculate the exposure IE+/+o(erg/c+f
Calculate l).

The environmental conditions at the time of measurement were 20°C, 165%RH (1) and 3.
The test was carried out at 0°C and 180% RH (II).

Note 4) Image quality: After leaving each photosensitive material for one day and night under the following environmental conditions, each photosensitive material was charged at -6 KV, and a gallium-aluminum-arsenide semiconductor laser (oscillation wavelength 830 nm) with an output of 2.81 was used as a light source. 64er on the surface of the photosensitive material using
After exposure under an irradiation dose of g/ctA at a pitch of 25 μm and a scanning speed of 300 m/sec, the image was developed and fixed using ELP-T (manufactured by Fuji Photo Film ■) as a liquid developer. The copied images (fogging, image quality) were visually evaluated. The environmental conditions during imaging were 20°C, 65% RH (1) and 30°C, 80% RH (I
I).

Note 5) Contact angle with water; After passing each photosensitive material once through an etching processor using a desensitizing liquid ELP-E (manufactured by Fuji Photo Film) to desensitize the photoconductive layer surface, Distilled water 2
A μl water droplet is placed on it, and the contact angle with the water formed is measured using a goniometer.

Note 6) Printing durability After making the plate in the same manner as for imageability in Note 3) above,
) under the same conditions as the offset printing machine (Oliver 5 manufactured by Sakurai Seisakusho) and used as an offset master.
This indicates the number of sheets that can be printed using high-quality paper (type 2) as printing paper without causing background stains in the non-image areas of printed matter or problems with image quality in the image areas (the higher the number of sheets printed, the better the rigidity resistance). ).

As shown in Table 7, 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 20 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 A using only the resin [A] of the present invention had extremely good electrostatic properties, but when printed using it as an offset master original, the image quality of the printed matter deteriorated after 3000 sheets.

In addition, in Comparative Example B, R and R decreased after 90 seconds of adhesion, and El
/l.

has also grown larger.

Furthermore, in Comparative Example C, in which the weight average molecular weight was increased using a copolymer having the same chemical structure as the resin of Comparative Example B, the electrostatic properties were significantly deteriorated. This is presumed to be due to an increase in the molecular weight of the binder resin, which causes adsorption to the photoconductor particles and aggregation between the particles, resulting in an adverse effect.

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 3 to 26 In Example 1, resin (A-1) and resin (B-1)
Each electrophotographic light-sensitive material was produced in the same manner as in Example 1, except that each resin (A) and each resin [B] shown in Table 8 below were used instead.

Examples 27 to 45 As a binder resin, resin [A] 6.5 shown in Table 9 below
g and resin [B] 33.5 g, zinc oxide 200 g, rose bengal 0.05 g, tetrabromophenol blue 0.03 g, uranine 0.02 g, phthalic anhydride 0.01 g and toluene 240 g in a ball mill. Dispersed for 2 hours. Apply this to conductive treated paper with a wire bar so that the dry adhesion is 118 g/n (1
Heated at 10°C for 30 seconds. Then 20°C 165%
An electrophotographic light-sensitive material was prepared by leaving it for 24 hours under RH conditions.

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

Further, when this was printed using as an original plate for an offset master, prints with clear image quality were obtained even at the number of prints shown in Table 9.

However, El/10 in electrostatic properties is determined by charging the surface of the photoconductive layer to -400V by corona discharge, then irradiating the surface of the photoconductive layer with visible light at an illuminance of 2.0 lux, and increasing the surface potential (V+O ) attenuates to 1710, and from this the exposure It E + y +. (looks/seconds) was calculated.

In addition, for plate making of photosensitive materials, fully automatic plate making 1ELP404V (
A toner image was formed using ELP-T (manufactured by Fuji Photo Film ■) as a toner.

(3 others)

Claims (3)

[Claims] (1) In an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material and a binder resin, the binder resin includes at least one of the following resins [A] and the following resin [B].
An electrophotographic photoreceptor comprising at least one of the following. Resin [A] has a weight average molecular weight of 1 x 10^3 to 2 x 10^4,
A polymer containing 30% by weight or more of at least one repeating unit represented by the following formula (I) or formula (II) as a polymerization component, and containing -PO only at one end of the polymer main chain.
_3H_2 group, -SO_3H group, -COOH group, ▲Mathematical formula, chemical formula, table, etc.▼ group, {R has 1 to 10 carbon atoms
or -OR'(R' represents a hydrocarbon group having 1 to 10 carbon atoms)}, -SH group, acidic group of phenolic OH group, and cyclic acid anhydride-containing group. A resin formed by bonding one substituent. Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X_1 and Hydrocarbon group, chlorine atom, bromine atom, -COY_1 or -COOY_2 (Y_1 and Y
_2 each represents a hydrocarbon group having 1 to 10 carbon atoms. However, both X_1 and X_2 do not represent hydrogen atoms. W_1 and W_2 each represent a direct bond or a connecting group having 1 to 4 connected atoms that connects -COO- and the benzene ring. ] Resin [B] A resin having a weight average molecular weight of 5×10^4 or more, containing at least a repeating unit represented by the following general formula [III] as a polymer component, and having a crosslinked structure. General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, T is -COO-, -OCO-, -CH_2OC
Represents O-, -CH_2COO-, -O- or -SO_2-. V represents a hydrocarbon group having 1 to 22 carbon atoms. a_1 and a_2 may be the same or different from each other,
Each hydrogen atom, halogen atom, cyano group, carbon number 1-8
represents a hydrocarbon group, -COO-Z, or -COO-Z via a hydrocarbon group having 1 to 8 carbon atoms (Z represents a hydrocarbon group having 1 to 18 carbon atoms). ] (2) Resin [B] is further provided with -PO_3H_2, -SO_3H, - only at one end of at least one polymer main chain.
COOH, -OH, -SH, ▲Mathematical formulas, chemical formulas, tables, etc.▼ (R'' indicates a hydrocarbon group), cyclic acid anhydride, -CHO, -CONH_2,
A resin formed by bonding at least one polar group selected from -SO_2NH_2 and ▲Mathematical formulas, chemical formulas, tables, etc.▼ (b_1 and b_2 may be the same or different and each represents a hydrogen atom or a hydrocarbon group) A claim that is (
1) The electrophotographic photoreceptor described above. (3) Claim (1) or (2) wherein the resin [B] is a resin that does not contain, as a polymer component, a repeating unit containing an acidic group or a cyclic acid anhydride-containing group as shown in the resin [A].
The electrophotographic photoreceptor described above.