JPH0430169A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance printing resistance by using a binder resin comprising at least 2 kinds of specified resins. CONSTITUTION:One of the binder resins is an A-B block copolymer having a weight average molecular weight of 1X10<3> - 2X10<4> and comprising A blocks each composed of at least one kind of repeating unit having an acid group, such as -PO3H2, -COOH, and cyclic acid anhydrides, and B blocks each composed of at least one kind of repeating unit represented by formula I, thus permitting superior printing resistance to be obtained. In formula I, R1 is a hydrocarbon group. The copolymer has a weight average molecular weight of 3X10<4> - 1X10<6> and one of polyester type macromonomers (MB) each represented by formulae II and III as a repeating unit and having a weight average molecular weight of 1X10<3> - 1.5X10<4>. In formulae II and III, each of f1 and f2 is independently H, halogen, cyano, or a hydrocarbon group.

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 CPCG light body 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.

Typical electrophotographic photoreceptors include photoreceptors with a photoconductive layer formed on a support and photoreceptors with an insulating layer on the surface.
A photoreceptor consisting of two photoconductive layers can be produced by the most common electrophotographic processes, namely charging, image exposure and development.
Furthermore, it is used for image formation by transfer, if necessary.

Furthermore, a method of using an electrophotographic photoreceptor as an offset original plate for direct plate making is widely used. Particularly in recent years, direct electrophotographic lithography has become important as a method for printing high-quality printed matter with a print count of several hundred to several dozen sheets.

The binder resin used to form the photoconductive layer of the electrophotographic photoreceptor has excellent film-forming properties itself and ability to disperse photoconductive powder into the binder resin. The photoconductive layer of the recording layer has good adhesion to the substrate, and the photoconductive layer of the recording layer has excellent charging ability, and has low dark decay (high light decay, little pre-exposure fatigue, and can withstand changes in humidity during photographing. Therefore, it is necessary to have various electrostatic properties such as the need to stably maintain these properties and excellent imaging performance.

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. is necessary.

However, conventionally known binder resins have many problems, particularly in electrostatic properties such as chargeability, dark charge retention, photosensitivity, and smoothness of the photoconductive layer.

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 in an amount of 0.05 to 1.
A low molecular weight resin containing 0% by weight or a low molecular weight resin that binds an acidic group to the end of the polymer main chain (FrwlO'~1
04), the smoothness and electrostatic properties of the photoconductive layer are improved, and image quality without background smear is obtained, as disclosed in JP-A-63217-354 and JP-A-64-7, respectively.
No. 0761 and JP-A No. 267563.

In addition, as a binder resin, a resin containing a polymeric component containing an acidic group in the side chain of the copolymer, or bonded to the end of the main chain of the polymer, and containing a thermally and/or photocurable functional group. The technique using this is disclosed in Japanese Patent Application Laid-open No. 1-100554 and Japanese Patent Application No. 1983-3.
9690, and JP-A-1-102573 and JP-A-2-874 disclose a technique in which a resin containing an acidic group in the side chain of the copolymer or bonded to the end of the main chain of the polymer is used in combination with a crosslinking side. Furthermore, the low molecular weight substance (weight average molecular weight 103 to 104) of the resin is converted into a high molecular weight substance (weight average molecular weight 1O4).
The technology used in combination with the above resins was disclosed in Japanese Patent Application Laid-open No. 64-56.
No. 4, No. 63-220149, No. 6'3-22014
No. 8, JP-A No. 1-280761, JP-A No. 1-116643
JP-A No. 1-211766 and JP-A No. 2-34859 disclose a technique for using such a low molecular weight material in combination with a heat-curable and/or photo-curable resin. Techniques used in combination with this are disclosed in Japanese Patent Application Laid-open No. 2-53064, Japanese Patent Application No. 2-56558, and Japanese Patent Application No. 63254786, respectively. With these techniques, the film strength of the photoconductive layer can be made sufficient and the mechanical strength can be increased without impairing the above-mentioned properties due to the use of a resin containing an acidic group in the side chain or terminal. Are listed.

(Problem B that the invention attempts to solve) However, even if 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 El/l.

The large difference between the gradation and the gradation of the copied image becomes soft, and furthermore, it becomes difficult to reduce the residual potential after exposure, resulting in noticeable fogging of the copied image.Also, even when printed as an offset master, This has resulted in serious problems such as the appearance of pasted marks from printed manuscripts on 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 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.

A further object of the present invention is to use an electrophotographic lithographic printing original plate that has excellent electrostatic properties (particularly dark charge retention and photosensitivity), reproduces a copy image that is faithful to the original image, and is capable of reproducing the entire surface of a printed matter. It is an object of the present invention to provide a lithographic printing original plate which does not generate not only such background stains but also dotted background stains and which has excellent rigidity resistance.

(Means for Solving Problem !II) The above object is to provide an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor and a binder resin, wherein the binder resin is a resin [A] shown below. ] and at least one resin [B].

Resin [A]; has an average molecular weight of 1x103 to 2XlO', ・PO,
At least one polymer containing at least one acidic group selected from H, a -COOH group, a -SOH group, a phenolic group (R' is a hydrocarbon group), and a cyclic acid anhydride-containing group. A block consisting of components and B containing at least a polymer component represented by the following general formula (1)
A resin comprising an AB block copolymer composed of blocks.

General formula (ri) Coo-R.

(In formula (1), R+ represents a hydrocarbon group.) Binder resin [B]: Represented by the following general formulas (I[la) and (I[[b)], weight average molecular weight 1 x 103 A copolymer having a weight average molecular weight of 3X10' to 1X10'' and containing at least one polyester-type macromolecule of 1.5 XIO' as at least a polymer component.

General formula (Illa) H-C At -at -coo +n+-oco-nt-co
o-)-R61 General formula (I[lb) O-C At B! COO+D3 COO+Riz formula [
In 1[1al and [[lb], the characters in brackets represent repeating units.

f and f2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -Coo-T, or a hydrocarbon group having 1 to 8 carbon atoms. -C00-Tz (T+ and T2 each represent a hydrocarbon group having 1 to 18 carbon atoms).

^, is a single bond or -coo--oc.

+CH2CH2low C00-1+z-0CO-(u
+ + u z represents an integer from 1 to 3), -CON
-(d represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms), or -SO,-.

B1 represents a group connecting At and -000-.

D and D2 may be the same or different, and each represents a divalent aliphatic group or a divalent aromatic group (each 2 (d□ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms). ),
Sow COO0CO-CONHCO -NHCONH- CON Cds represents the same content as d2), SOJ (da is the same as d2, but d may include one bonding group), or a combination of these residues. represents an organic residue.

R1- represents a hydrogen atom or a hydrocarbon group.

fl, f6, A2, B2 and Rat in the general formula (nib) are respectively fl, f2,
Represents the same content as A3, B, and Re.

D represents a divalent aliphatic residue.

The binder resin used in the present invention is an AB block copolymer (A) of an A block containing the above-mentioned specific acidic group-containing component and a B block containing the polymer component represented by the above formula (1). and the above general formulas (I[Ia) and (I[lb)
Resin CB of a high molecular weight graft copolymer containing at least one kind of macromonomer (MB) represented by
).

Furthermore, as the low molecular weight resin [A], the following general formula (
Ia) and general formula (Ib) having a specific substituent containing a benzene ring or an unsubstituted naphthalene ring having a specific substituent at the 2-position and/or the 2-position and the 6-position Resin containing a methacrylate component and an acidic group component [
A] (hereinafter, this low-molecular-weight substance is particularly referred to as resin [A']) is preferable.

General formula (Ia) Hs t General formula (I b) Hs [In formula (Ia) or (Ib), XI and X2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, Bromine atom, -COZt or -CC00L (
Each z represents a hydrocarbon group having 1 to 10 carbon atoms. However, both xl and x2 do not represent hydrogen atoms.

Ll and L2 each represent a single bond or a linking group having 1 to 4 linking atoms that connects -COO- to the benzene ring. ] The resin (A) used in the present invention is an AB block copolymer, where the A block is composed of at least one polymeric component containing at least one kind selected from the above-mentioned specific acidic groups, and the B block comprises a polymer component containing at least one methacrylate component represented by formula (1), and has a weight average molecular weight of lX
It is characterized by IO3 to 2×104.

Among the acidic group-containing binder resins known to improve the smoothness and electrostatic properties of the photoconductive layer, those using low molecular weight polymers have acidic group-containing polymeric components randomly present in the polymer main chain. or resins with an acidic group bonded only to one end of the polymer main chain.

On the other hand, the resin [A] used in the binder resin of the present invention
The acidic groups contained in the resin are not randomly present in the polymer main chain or bonded only to the ends of the polymer main chain, but are present in blocks in the polymer main chain. This is a more specific copolymer.

In the copolymer according to the present invention, the region of acidic groups unevenly distributed on one side of the main chain of the polymer sufficiently adsorbs to the stoichiometric defects of the inorganic photoconductor, and
It is presumed that the other block portions constituting the polymer main chain loosely and sufficiently cover the surface of the photoconductor. Due to its mechanism of action, the copolymer according to the present invention has a sufficient adsorption area even if the stoichiometric defect portion of the inorganic photoconductor changes, so that the inorganic photoconductor and resin (A It is inferred that the interaction with It has been found that the conductor is sufficiently dispersed and agglomeration is suppressed.

Resin [B] does not impede the high performance of electrophotographic properties due to the use of resin (A), and provides sufficient mechanical strength to the photoconductive layer, which is insufficient with resin (A) alone. It has been found that sufficiently good imaging performance can be obtained even when the environment changes as described above or when a low-output laser beam is used.

This is achieved by specifying the weight average molecular weight of the resin (A) and resin CB) as the binder resin of the inorganic photoconductor, as well as the content and bonding position of acidic groups in the resin. This is presumed to be due to the ability to appropriately change the strength of the interaction between the conductor and the resin. That is, the resin (A) with stronger interaction is selectively and appropriately adsorbed to the inorganic photoconductor, while the resin (A) with weaker interaction than resin (A) is selectively and appropriately adsorbed to the inorganic photoconductor.
In B], it is presumed that by interacting gently with the inorganic photoconductor to the extent that the electrophotographic properties are not inhibited, both the electrophotographic properties and the mechanical strength can be significantly improved as described above. When resin [A'] is used, the electrophotographic properties (
In particular, improvements in (1°, D, R, R, El/10) can be achieved.

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

Further, in the present invention, the surface of the photoconductive layer has smoothness. On the other hand, when a photoreceptor with a rough surface of the photoconductive layer is used as an electrophotographic lithographic printing original plate, the dispersion state of the zinc oxide particles that are the photoconductor and the binder resin is not appropriate, resulting in the presence of aggregates. Since a photoconductive layer is formed in the dry state, even if desensitization treatment is performed using a desensitization treatment liquid, the non-image areas cannot be made uniformly and sufficiently hydrophilic, causing printing ink to adhere during printing, resulting in Background stains occur in non-image areas of printed matter.

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

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 be sufficiently adsorbed and coat the particle surface, which improves the smoothness of the photoconductive layer. It has good electrostatic properties, provides image quality without background smearing, and has sufficient film strength for use as a CPC photoreceptor or as an offset original plate for printing several tens of sheets. However, by coexisting resin [B] as in the present invention, the mechanical strength of the photoconductive layer, which is still insufficient with resin [A] alone, is further improved without alienating the function of resin [A]. I was able to do it. Therefore, the photoreceptor of the present invention has excellent electrostatic properties even when environmental conditions vary, and
The film strength is also sufficient, making it possible to print more than 10,000 sheets even under harsh printing conditions (for example, when printing pressure is high with a large printing machine).

Furthermore, the high molecular weight resin [B] contains the above macromonomer (
MB), and at least one polar group selected from -PO2H1 group, SOJ group, H2 group) and a cyclic dicarboxylic anhydride-containing group is bonded to the end of the polymer main chain. A graft type copolymer consisting of
B']) is preferable.

In particular, the general formula (I[Ia) and/or (I[
In the macromonomer MB of lb), R61 or R1
When represents a hydrocarbon group, it is particularly preferable to use a resin in which the polar group is bonded to the main chain of the polymer.

When resin [B'] is used, electrostatic properties, especially [1,R.

R1 and El/I11 are better, and the excellent properties achieved by using resin (A) are not affected at all, and the effect hardly changes even under environmental changes such as high temperature, high temperature, low temperature, low humidity, etc. Very preferable. Furthermore, the film strength is also improved, and rigidity resistance is improved.

The spectral sensitizing dye, which is normally used to maintain photosensitivity in the visible to infrared light range, fully functions its spectral sensitizing action when adsorbed to the photoconductor. It is assumed that the polymer-containing binding resin interacts appropriately with the photoconductor without inhibiting adsorption of the spectral sensitizing dye. This effect was particularly remarkable with cyanine dyes or phthalocyanine pigments, which are particularly effective as dyes for spectral sensitization of near-infrared to infrared light.

The amount of the specific acidic group-containing component in the block copolymer (A) is preferably 0.5 to 20 parts by weight, more preferably 3 to 1 part by weight per 100 parts by weight of the copolymer (A).
It is contained in a proportion of 5 parts by weight.

The amount of the methacrylate component represented by formula (1) in the block portion (B block) containing the methacrylate component represented by general formula (1) is preferably 30% to 100% by weight, more preferably 30% to 100% by weight based on the total weight of the block. is 5
It is 0 to 100% by weight. The weight average molecular weight of the copolymer (A) is 1X10" to 2x104, preferably 3x103
~1×103.

When the molecular weight of the resin (A) is smaller than 1 x 103, the film forming ability is reduced and sufficient film strength cannot be maintained, and when the molecular weight is larger than 2 x 104, the effect of the resin (A) of the present invention is reduced. However, the electronic properties are comparable to those of conventionally known resins.

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

The glass transition point of the resin (A) is -10°C to 100°C
The temperature range is preferably 5°C to 85°C, more preferably 5°C to 85°C.
It is °C.

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

As acidic groups, -POJz group, -COOH group, -5O
, H group, -OR' group (R' is a hydrocarbon group) and a cyclic acid anhydride-containing group, preferably -C0
OH group, -5O3H group, phenolic OH group, and group (
R' represents a hydrocarbon group), and R and R' preferably represent an aliphatic group having 1 to 22 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group). group, dodecyl group, octadecyl group, 2-
Chloroethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, allyl group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylhensyl group, chlorobenzyl group, fluorohensyl group, methoxy Hensyl group, etc.), or an optionally substituted aryl group (e.g., phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, (dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.).

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

In addition, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride include aliphatic 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, cyclopentane-1,2-dicarboxylic anhydride ring, and cyclohexane-1,2-dicarboxylic acid anhydride ring. Examples include anhydride ring, cyclohexene-1,2-dicarboxylic anhydride ring, 2,3-bicycloC2,2,2)octanedicarboxylic anhydride ring, and these rings include, for example, chlorine atom, bromine atom halogen atoms such as, alkyl groups such as methyl group, ethyl group, butyl group, hexyl group, etc. may be substituted.

Examples of aromatic dicarboxylic anhydrides include phthalic anhydride rings, naphthalene-dicarboxylic anhydride rings, pyridine-dicarboxylic anhydride rings, thiophene-dicarboxylic anhydride rings, etc. For example, 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.).

Examples of the above-mentioned "polymer component containing a specific acidic group" include the polymer component constituting the B block component in the resin (A) of the present invention, that is, the methacrylate component represented by general formula (1), etc. Any vinyl compound containing the acidic group can be used as long as it copolymerizes with a corresponding vinyl compound such as.

For example, see the Polymer Data Handbook [Polymer Data Handbook]
Vinyl compounds described in Baifukan (1986), etc., can be used. Specifically, vinyl compounds described in acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy compound, 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 form, α
.

β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids If (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, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphoric acid Examples include half-ester derivatives of vinyl or allyl groups of acids and dicarboxylic acids, and ester derivatives and amide derivatives of these carboxylic acids or sulfonic acids, and compounds containing the acidic group in a substituent thereof.

Specific examples of these compounds include the following. However, on each side below, a is -H, -C
)13, -CI, -Br, -CN-1-C) IZC
represents OOCH3 or -CH,C0OH, b represents 1 or -CH, n represents an integer of 2 to 18, m represents 1 to
It represents an integer of 12, and l represents an integer of 1 to 4.

(a-1) OOH ool (a-3) (a-4) CH2=C Coo(CHz)ncOOII (a-5) OH2 C0NH((Jlz)ncOOH (a-6) TeC00(CHz)noco(CHt )scOOH(a-
7) 〒 (a-8) 〒 CONH(CHz)nOcO(CHz)scOOH(a
-9) r (a C0NIC0NH(CHz) ncOOH(a-11) 0NHCH C1,C00H (a (a COO(CHz)mNHcO(CHzCoo(CHz)
may be the same or different) (a CHz=CHCHzOCO(C)It)IIcOOH(
a C1h=CH+CH-rCOOH (a C00CHzCHCHz00C(CHz)■C00H(
a CH2=c Coo(CHz)nocOH H 0OH (a (a-20) (a-21) (a-22) (a-23) (a-24) (a-25) H H (a-26) (a-27) (a-29) H (a-30) (a-31) (a-35) C1,=C C0N(CHzCHzCOOll)z (a-37) C00(CHz)1cON(CHzCHiCOOH)z
(a-38) SO,H (a-39) (a-40) OOH (a-45) Even if two or more types of polymerization components containing the above-mentioned specific acidic groups are contained in the A block, In that case, the two or more acidic group-containing components may be contained in the A block in either random copolymerization or block copolymerization.

Further, a component not containing the acidic group may be included in the A block, and examples of the component include a component represented by the general formula (1) or the general formula (I[) described below. The content of such acidic group-free components is preferably 0 to 50% by weight, more preferably 0 to 20% by weight in A block, and most preferably, such acidic group-free components are not included in A block. .

Next, the polymer components constituting the B block component in the AB block copolymer ('A) will be explained in detail.

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

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

R1 preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. The substituent may be any substituent other than the acidic group contained in the polymerization component constituting the A block of the AB block copolymer,
For example, halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.) -〇-Z, , -Coo-Zl, -0CO
-Z, , (Z represents an alkyl group having 1 to 22 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group etc.). A preferable hydrocarbon group has 1 to 1 carbon atoms.
18 optionally substituted alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2chloroethyl group, 2 -bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), optionally substituted alkenyl groups having 4 to 18 carbon atoms (e.g., 2-methyl- 1-propenyl group, 2-
butenyl group, 2-pentenyl group, 3-methyl 2-pentenyl group, l-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), carbon number 7 to 12 an optionally substituted aralkyl group (for example,
benzyl group, phenethyl group, 3-phenylpropyl group,
Naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.) 1, substituted with 5 to B carbon atoms alicyclic groups (e.g. cyclohexyl group, 2-
cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (
For example, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, Dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group,
acetamidophenyl group, propioamidophenyl group,
dobcyroylamide phenyl group, etc.).

In the hydrocarbon group R, when R1 is an aliphatic group, it is preferable that the component represented by formula (1) contains 60% by weight or more of a hydrocarbon group having 1 to 5 carbon atoms.

Furthermore, in the resin (A), some or all of the repeating units represented by the general formula (1) constituting the B block component are repeating units represented by the following general formula (Ia) and/or (Ib). It is preferred that there be at least one repeating unit selected from the following -1 formulas (1a) and (Ib) in the B block component, and therefore one repeating unit in the other block.
It is preferably contained in an amount of 0% by weight or more, particularly 50 to 100% by weight.

-1 Formula (Ia) CH3 λ General Formula (I b) l13 [In Formula (Ia) or (Ib), X and X each independently represent a hydrogen atom or a hydrocarbon having 1 to 10 carbon atoms; group, chlorine atom, bromine atom -COZz or -cooz, z(
2g each represents a hydrocarbon group having 1 to 10 carbon atoms), provided that X and X2 do not both represent a hydrogen atom.

Ll and L2 each represent a single bond or a linking group having 1 to 4 linking atoms that connects -COO- to the benzene ring. ] By incorporating the repeating unit represented by the formula (I a) and/or (I b) into the B block that does not contain an acidic group, electrophotographic properties (specially V1O, D
, R, R, El/10 ) can be achieved.

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

In formula (Ia), preferred x1 and xi are hydrogen, chlorine, and bromine, respectively, and preferred hydrocarbon groups include alkyl groups having 1 to 4 carbon atoms (e.g., methyl, ethyl, propyl). , butyl group, etc.),
Aralkyl groups having 7 to 9 carbon atoms (e.g. benzyl group, phenethyl group, 3-phenylpropyl group, chlorohensyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-methyl-benzyl group, etc.); Aryl groups (e.g. phenyl group, tolyl group, silyl group, bromophenyl group, methoxyphenyl group,
chlorophenyl group, dichlorophenyl group, etc.), and -
COZz and -COOh (preferred examples of Z2 include those described above as preferred hydrocarbon groups). However, both xl and Xt do not represent hydrogen atoms.

In formula (Ia), Ll is a direct bond or 100H! that connects -COO- and the benzene ring. +-rr-(nl
represents an integer from 1 to 3), CHgCHg0CO-1
(C) 120), □ (n□ represents an integer of 1 or 2)
, CHgCHzO, etc. represents a linking group having 1 to 4 linking atoms.

They represent the same content as ``shi'' and ``shi'' in formula (lb).

Specific examples of the repeating unit represented by formula (Ia) or (Ib) that are preferably used in the B block of the resin (A) of the present invention are listed below.

but, Book The scope of the invention is It is not limited to these.

(b CH3 (b CH3 (b CH.

(b-4) CH.

Shi4Hq (b-5) (b (b-8) CH3 CH.

(b death! (b (b (b-15) CH.

l3 C.B.

(b (b (b (b CH3 CI(.

C.I. CH3 CH1 (b (b-22) (b-23) <b-24) CH3 CH8 r Shil CH3 (b-26) (b-28) CH3 CH3 lr ShiH3 (b-29) CH.

(b-30) CH.

1+CHt C→- (b-31) CH3 (b-32) Hs (b CH3 (b-34) CH3 (b CH.

(b-36) CH.

(b-37) (b (b (b-40) H3 C.I.

H3 In the B block constituted separately from the A block consisting of the polymerization component containing the specific acidic group, the repeating unit represented by the formula (I) (preferably (Ia) or (Ib) 1) is Two or more types of polymerization components may be contained, and may further contain other polymerization components other than these.When two or more types of polymerization components are contained in the B block that does not contain an acidic group, the AB The block copolymerization component may be contained in the B block in either random copolymerization or block copolymerization, but it is preferably contained randomly.

Other polymeric components that can be contained in the B block together with the polymeric components selected from the repeating units represented by the above formulas (1), (Ia) and/or (Ib) are components that copolymerize with these components. Either is fine.

For example, a repeating unit represented by the following formula-1 (II) can be mentioned.

General formula (n) a, aZ −←CH−C→− -R2 [In formula (It), T is -COO -OCO-.

+CHr-)-, +OC0''++112 each represent an integer from 1 to 2, and R
1 represents the same content as R1 in formula (1), Rf
fi represents the same content as R in formula (+).

a and R2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -Coo-Z3, or a hydrocarbon group having 1 to 8 carbon atoms. More preferably a
l+ ax may be the same or different from each other (, hydrogen atom, alkyl group having 1 to 3 carbon atoms (e.g., methyl group, ethyl group, propyl group, etc.), Coo-Z3 or -CHzC
OO-Zs (Z3 more preferably represents an alkyl group or alkenyl group having 1 to 18 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dotecyl group, tridecyl group) group, tetradecyl group, hexadecyl group, octadecyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, etc., and these alkyl groups and alkenyl groups are
may have the same substituents as shown in ).

As monomers constituting repeating units other than these, styrene I! (e.g. styrene, vinyltoluene, chlorostyrene, bromostyrene, dichlorostyrene, vinylphenol, methoxystyrene, chloromethylstyrene, methoxymethylstyrene, acetoxystyrene,
methoxycarbonylstyrene, methylcarbamoylstyrene, etc.), acrylonitrile, methacrylonitrile,
Acrolein, methacrolein, vinyl group-containing heterocyclic compounds (e.g. N-vinylpyrrolidone, vinylpyridine,
Examples include vinylimidazole, vinylthiophene, etc.) acrylamide, methacrylamide, etc., but other copolymerizable components are not limited thereto.

The AB block copolymer (A) of the present invention can be produced by a conventionally known polymerization reaction method.

Specifically, in the monomer corresponding to the polymer component containing the specific acidic group, the acidic group is previously protected as a functional group, and an organometallic compound (for example, alkyl lithiums, lithium diisopropylamide, alkyl magnesium After synthesizing an AB block copolymer using known so-called living polymerization reactions such as halides, etc.) or ionic polymerization reactions using hydrogen iodide/iodine systems, photopolymerization reactions using porphyrin metal complexes as catalysts, or group transfer polymerization reactions. Examples include a method in which a functional group with a protected acidic group is deprotected by a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction, a photolysis reaction, etc. to form an acidic group. One example is shown in reaction scheme (1) below.

For example, P, Lutz+ P, Masson et
al, Polym, Bull.

12,,79 (1984), B, C,^nder
son, G, D, ^ndrewsetal, M
acromolecules, 14+ 1601
(1981), K.

Hatada, K., Ute, etal, P.
olym, J, 17.977 (1985) lfi
, 1037 (1986), Hiroshi Miguchi-1 Ko Hatada-
1 Polymer Processing, Co., 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymer Papers, Kawa, 189 (1989)
), M, Kuroki, ? .

^ida, J, As, Chew, So
c, 1flf% 4737 (1987),
Takuzo Aida, Shohei Inoue, Organic Synthetic Chemistry, Mura, 300 (
1985), D, Y, Sogah, L R, He
rtler etal, Macromolecule
s.

, fi, 1473 (1987).

Furthermore, the AB block copolymer (A) can also be synthesized by a photoiniferter polymerization method using a monomer with its acidic group left unprotected and a dithiocarbament compound as an initiator. accompanying, polymer, nail, 24
B (1988), Shun Himori-Ryuichi Otsu, Polym.
Rep, Jap, iL, 350B (1988
), JP-A-64-111, JP-A-64-26619, and the like.

Further, the protecting group that protects the specific acidic group of the present invention and the removal (deprotection reaction) of the protecting group can be easily carried out using conventionally known knowledge. For example, it is variously described in the cited documents mentioned above, and furthermore, Yoshiyu Iwakura,
Keisuke Kurita, “Reactive Polymer” Published by Kodansha (1977)
, T.W., GreenerProtective
Groups in Organic 5ynthe
sis” John Wiley & 5ons (
(1981), J., F., W., McOmie'P.
Protective Groups in Organ
ic ChemistryJPlenum Pres
The method described in detail in reviews such as s+ (1973) can be appropriately selected and carried out.

In the resin (A), the amount of the polymer component containing the specific acidic group in the AB block copolymer is 0.5 to 20% by weight based on 100 parts by weight of the resin (A), preferably It is 3 to 15% by weight. The weight average molecular weight of the resin (A) is preferably 3 x 10'' to 1 x 103.

On the other hand, the weight average molecular weight of resin CB) is 3X10' to IX1
0', preferably 5X10' to 5X10'.

-1 The abundance ratio of the macromonomer represented by formula (I [[a) and/or (Illb) in the polymer] is 0.5
It is preferable that it is ~80% by weight, especially -1 formula (I[
In 1a) and (I[lb), in the case of a macromonomer in which R61 or Rb2 is a hydrogen atom, the proportion thereof is preferably 0.5 to 30% by weight.

The glass transition point of resin CB) is preferably 0°C to 110°C.
℃, more preferably 20'' to 90℃.

Furthermore, if the molecular weight of the binder resin [B] is smaller than 3X10', the film strength cannot be maintained sufficiently, while if the molecular weight is larger than 106, the dispersibility decreases and the film smoothness deteriorates, resulting in poor quality of the copied image. The image quality (particularly the reproducibility of fine lines and characters deteriorates) deteriorates, and furthermore, when used as an offset master, background stains become significant.

Macro 7mer content in binder resin CB) is 0.5
If it is less than % by weight, the electrophotographic properties (especially dark decay law, photosensitivity) will deteriorate, 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 the macromonomer that forms the graft portion is small, resulting in a composition that is almost the same as that of conventional homopolymers or random copolymers.

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

Furthermore, when R1 or R in Formulas -1 (I[la) and (Illb) is a hydrogen atom, the macromonomer is 3
If it exceeds 0% by weight, the dispersibility decreases, the film smoothness deteriorates, the image quality of the copied image deteriorates, and the background smudge of the printed matter increases when used as an offset master. This is thought to be because the macromonomer contains more --COOH groups, which strengthens the interaction with the inorganic photoconductor due to its dispersibility, causing aggregation of the inorganic photoconductor.

When the resin [B'] contains the specific polar group, the amount of the bonding component present is 0 per 1100 parts by weight of the resin CB'.
．． 1 to 10% by weight, preferably 0°5 to 5% by weight
It is.

If the polar group content is less than 0.1%, the effect of improving the film strength of the photoconductive layer will be reduced, and if it exceeds 10%, agglomeration of the inorganic conductor dispersion will occur.

The resin [B] of the present invention has the formula (I [[a) and/or the formula (
Weight average molecular weight represented by I[b) 1.0X10' to 1
．． Contains 5 x 10' macromonomer (MB) as a copolymerization component, weight average molecular weight 3 x 10' to 1 x 1
0h graft copolymer, preferably further including -PO3H at the end of the polymer main chain of the graft copolymer.

(R represents the same content as R) and a cyclic acid anhydride-containing group (both are high molecular weight resins [B'] formed by bonding one type of polar group).

As such polar groups, the same ones as those mentioned for the resin (A) can be mentioned. Regarding 0) 1 group, in addition to the phenolic OH group mentioned in the resin (A), vinyl group- or allyl group-containing alcohols (for example, allyl alcohol, methacrylic acid ester, ester substituent such as acrylamide, etc.), Examples include compounds containing an -OR group in the N-substituent.

The υH group is an aliphatic group having 1 to 18 carbon atoms or an aliphatic group having 6 to 18 carbon atoms.
Twelve aromatic groups may be mentioned. Specifically, an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tridecyl group, Hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-hydroxylethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-cyanoethyl group, 3-chloropropyl group, 2-
(trimethoxysilyl)ethyl group, 2-tetrahydrofuryl group, 2-thienylethyl group, 2-N.

N-dimethylaminoethyl group, 2-N,N-diethylaminoethyl group, etc.), cycloalkyl group having 5 to 8 carbon atoms (
For example, cycloheptyl group, cyclohexyl group, cyclooctyl group), optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group) aliphatic groups such as chlorobenzyl group, bromobenzyl group, dichlorobenzyl group, methylbenzyl group, chloro-methyl-benzyl group, dimethylbenzyl group, trimethylbenzyl group, methoxybenzyl group, etc.), and furthermore, an aliphatic group having 6 carbon atoms.
~12 optionally substituted aryl groups (e.g., phenyl group, tolyl group, xylyl group, chlorophenyl group, bromophenyl group, dichlorophenyl group, chloro-methyl-
Examples include aromatic groups such as phenyl group, methoxyphenyl group, methoxycarbonylphenyl group, naphthyl group, chloronaphthyl group, etc.

Regarding the macromonomer (MB) having a polyester structure and having 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], I will explain in detail.

In the general formulas (Illa) and (I[[b)], [] indicates the weight average molecular weight of the macromonomer (MB) of the formula (I[Ia) and/or (111b) from 1 x 103 to 1.5
Represents enough repeating units to make X 10'.

-1 In the macromonomer (MB) of formula (nla),
Preferably, f and b may be the same or different, and each represents a hydrogen atom, a halogen atom (for example, a chlorine atom,
bromine atom, fluorine atom), cyano group, alkyl group having 1 to 3 carbon atoms (e.g. methyl group, ethyl group, propyl group, etc.)
, -COOT, or -GHzCOOTx (1, and T are each an alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, etc.), carbon number 7-9 aralkyl group (e.g. benzyl group, phenethyl group, 3-phenylpropyl group, etc.) or optionally substituted phenyl group (e.g. phenyl group, tolyl group, xylyl group, methoxyphenyl group, etc.) .

More preferably, either fl or f2 represents a hydrogen atom.

A1 is preferably -COO-1-OCO-1-CH
, COO-2-co, oco-1-CONH-1-CO
NHCONH-1-CONHCOO- or dl is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-cyanoethyl group, benzyl group, methylbenzyl group, chlorobenzyl group, methoxybenzyl group, phenethyl group, phenyl group, tolyl group, chlorophenyl group, methoxyphenyl group, butylphenyl group etc.).

B represents a group connecting AI and -000-, represents a single bond or a connecting group, is formed by a connecting group specifically selected as the connecting group, or a combination of these connecting groups Represents a bonding group (where e and ~e4 may be the same or different, and include 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,
methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-methoxyethyl group, 2-methoxycarbonylethyl group, benzyl group, methoxybenzyl group, phenyl group, methoxyphenyl group, methoxycarbonylphenyl group) , and e, to e represent the same contents as the above dl).

D and D8 may be the same or different and each represents a divalent organic residue, -0- -S d -N--8O-1-5O□--COO--0CO--CO
NHCO-1 represents an organic residue composed of a divalent aliphatic group, a divalent aromatic group, or a combination of these divalent residues, which may have an open bonding group therebetween.

Here, d8 to d4 represent the same content as d.

Examples of divalent aliphatic groups include (e and e may be the same or different, each having a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.) or a carbon number of 1 ~12 alkyl groups (e.g. methyl group, ethyl group, propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.), Q is 10--S- or -NRis-, and R&3 represents an alkyl group having 1 to 4 carbon atoms, -CIICZ or -CHJr).

Examples of divalent aromatic groups include benzene ring groups, naphthalene ring groups, and 5- or 6-membered heterocyclic groups (hetero atoms constituting the heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom). (containing at least one kind of). These aromatic groups may have a substituent, such as a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (e.g. methyl group, ethyl group, propyl group). , butyl group, hexyl group, octyl group, etc.), and an alkoxy group having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) as examples of the substituent.

Examples of the heterocyclic group include furan ring, thiophene ring, pyridine ring, pyrazine ring, piperazine ring, tetrahydrofuran ring, pyrrole ring, tetrahydropyran ring, 1.3-
Examples include oxazoline rings.

R&l preferably represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and specific examples of the hydrocarbon group include fl, f2
The same examples as those mentioned above can be mentioned.

In the formula (I[lb), preferable fl, f4, A2,
B2 and E2 are the formula (I[[a) fls fz, A1,
Each represents the same contents as those described as preferable in B1 and R61.

0 represents a divalent aliphatic residue, specifically +CU
X→. (p+ is an integer of 2 to 18), represents an alkyl group such as a 1゛z group, an ethyl group, a propyl group,
Neither gl nor 82 represents a hydrogen atom)
, -cH+cuz→T'! (gs is an alkyl group having 1 to 8 carbon atoms (e.g. methyl group, ethyl group, propyl group,
butyl group, hexyl group, octyl group, etc.), and R2
represents an integer from 1 to 16).

Specific examples of the portions represented by in the macro numerals (MB) in the general formula (nla) and -1 formula (Dub) include, but are not limited to, the following.

However, in each of the following cases, Q is -H, -CH3, C
HxCOOCHs, -Ct, -Br or -CN;
Q2 represents -H or -CI(3, n represents an integer of 2 to 12, and m represents an integer of 1 to 12.

(Margin below) (B-1) Q+ CHl-C (B-2) CH.

CH-C (T4) CONH(CHg)-- (B-6) l1t-C C0NHCONtl(CHI), -(B-7) CH3 CHl=C C0NHCOO(CHri, - (B-8) QtomiCHl -C COO(CHz)-0CO(CHz)--(B-9) Q! CI low IC C0NH(C[(t)-0CO(CHz)--(B-1
0) (B-11) Q寞CHffi-C 0CO(Ch) -- (B-12) Q.

CH1=C C00(CHz)nOcOcH=cH-I CH1雛C11 CH,- (B-15) CHt猷CI CIbCHx- (B-16) CB, -CI Cut C00(CHx), 0CO
(CHt) --(B-17) Q! CHl-C C00(CHt), 5OINH(C1h), -(B-1
8) Q寞ut-c Coo(CHt) 5NHcOo(CHz) -(B-
19) Q.

CU, -C Coo(CIri3NH- (B-22) Q word C1l! -C C00CIItCHCHfOOC(CHl), -R (II-23) Cam-CB CHgOCO(CHt)--(B-2
6) Q2 (B-27) (B-28) l Specific examples of D and D2 include the following organic residues, but the present invention is not limited thereto, however, On each side below, Rh4 is an alkyl group having 1 to 4 carbon atoms, -CHICZ or -CHJ
r represents an alkyl group having 1 to 8 carbon atoms, →CHa
"0Rha (Rh4 represents the above meaning, l is 2~
represents an integer of 8), -CIICZ or -CHJr, Rh6 represents 1 or -CB, R&? represents an alkyl group having 1 to 4 carbon atoms, Q represents 10-2-3- or -HRha (Ro represents the above meaning), P represents an integer from 1 to 26, and q represents 0 or r represents an integer of 1 to 10, j represents 0 or an integer of 1 to 4, and k represents an integer of 2 to 6.

(D-1) →CH, →1- (D-2) -CH-CB- (D-3) -C-C- Rh4 (D-5) CH- Rh4 (D-8) CHz CCut Rh4 (Re , may be the same or different) (R6, may be the same or different) (1)-H) + C4hCHzOCHzCHz→Ti0CHzCHz
7-(D 10CHtCHiS CHzCHz±- (D +CHzCIbSCHgC1hOCHzCHz→7-(
D-23) CHtC-CCHt- (D-24) (D-25) (D-26) (D-27) (D-28) CHt CH=CHCHz- CHzOCHzClh- CHtCHzCHzOCHzCHzCHz-f-CH!
-)-i-3O□10C1h+CH2+-8-80CH
- "Macro 7-mer (MB) represented by the general formula (I [[a)]
The Polymer Science Society of Japan, ``Polymer Data Handbook
01) Synthesized by polycondensation reaction of diols and dicarboxylic acids, dicarboxylic acid anhydrides, or dicarboxylic acid esters, as exemplified by J (published in 1986) Baifukan et al., weight average molecular weight 1 x 103 to 1.5 x 101
It can be easily produced by a method of introducing a polymerizable double bond group through a polymer reaction only in the hydroxyl group at one end of the polyester oligomer.

Polyester is synthesized by a conventionally known polycondensation reaction, but specifically, Eibe Takiyama, "Polyester Resin Handbook," Nikkan Kogyo Shimbunsha (published in 1986)
, “Reports of the Polymer Science Society of Japan: Polycondensation and Polyaddition” (Kyoritsu Shuppan, 1980)
Annual), 1. Goodman rEncyclop
edia of Polymer 5cienc
e and Engineering VOI 12
J pi, John Wiley L 5ons
(published in 1985) and others.

A method for introducing a polymerizable double group only into the hydroxyl group at one end of a polyester oligomer is to synthesize it by using a conventionally known reaction of esterifying an alcohol from a low-molecular compound or a reaction of converting an alcohol into a urethane. I can do it.

That is, a method in which a macromonomer is synthesized by esterification by reaction with carboxylic acids, carboxylic acid esters, carboxylic acid halides, or carboxylic acid anhydrides containing a polymerizable double bond group in the molecule; This can be achieved by a method in which a macromonomer is synthesized by reacting with a monoisocyanate containing a polymerizable double bond group to form a urethane.

Specifically, Nippon Kagaku Yoshin's ``New Experimental Chemistry Course ■''.

Synthesis and Reactions of Organic Compounds (II) J, Chapter 5, Maruzen ■,
(published in 197?), “Synthesis and Reaction of Organic Compounds [■
], p. 1652, Kuzen ■ (published in 1978).

Macromonomer (MB) represented by general formula (Illb)
is a method in which a polyester oligomer is synthesized by a self-polycondensation reaction of carboxylic acids containing hydroxyl groups in the molecule, and then a macromonomer is synthesized by a polymer reaction similar to the macromonomer synthesis of general formula (1 [a)]. , can be produced by a method of synthesis by living polymerization reaction of carboxylic acids containing a polymerizable double bond group and lactones. Specifically, T, Yasuda, T, Aida a
nd S, Inoue+ J, Macrosol, Sc.
i.

Chew, + A+ 11. 1035 (19
84L T, Yasuda, T, Aidan
d S, Inoue, Macromlecule
s+, ll+ 2217 (1984)+S,
Sosnowski, S., Stomkowski a.
nd S., Penczek, Makromol,
Che+s, 1dandan, 1347 (19B?
), Y, Gnanou and P, Re5pp,
, Makroaol, Chem, 18th, 2267
(19B?).

T, 5hiota and Y, Goto, J
, Appl, Polym, Sci,, ll.

753 (1967) and the like.

The formula (Ia) or (W
Specific examples of the macromonomer (MB) represented by b) are shown below. However, in each case below, the weight average molecular weight of the macromonomer is 1 x 103 to 1.5 XI
indicates a repeating unit sufficient to form O', Q+ indicates the same content as above, Q indicates -H or -cns, R
6, and may be the same or different and each represents -CH5 or -CJs, and R1゜ and R'l+ may be the same or different and each represents -CI, -Br, -CH, CI or CH
Jr, S represents an integer from 1 to 25, and t represents 2 to 12.
, U represents an integer from 2 to 12, and X represents an integer from 2 to 4.
, y represents an integer of 2 to 6, and 2 represents an integer of 1 to 4.

(Mu-1) Q.

(MB-2) (MB-3) (MB-4) (MB-5) (MB-6) C)I.

pot 3 (MB-9) Ql (MB-10) (MB-11) (Mu-12) Q.

(MB-13) Q.

(MB44) Q+ (MB-15) (MB-16) (MB-17) (MB-19) (MB-20) (MB-21) (MB-22) Q.

(MB-23) Q.

(MB-24) (MB-25) Q.

(MB-26) Resin CB used in the binder resin of the present invention is a graft copolymer containing at least one macromonomer selected from the general formulas (lla) and (IOb) as a copolymerization component. And other copolymerization components are:
Any monomer may be used as long as it satisfies the physical properties of the binder resin described above and can be radically copolymerized with the macromonomer.

Preferably, the copolymer contains 30% to 99.5% by weight of a monomer corresponding to the copolymerization component represented by the general formula (If) shown in the resin (A) as a copolymerization component.

Resin CB) may contain other copolymerization components other than the copolymerization component represented by general formula (It), and specifically corresponds to the other copolymerization components described for resin (A). Examples include each monomer.

The proportion of these other monomers as copolymer components is
It is preferable that the amount does not exceed at most 30% by weight, and more preferably 20% by weight or less in the total polymer components of resin [B].

The resin [B'] of the present invention, which has a specific polar group bonded only to one end of the polymer main chain, can be obtained by reacting various reagents at the end of a living polymer obtained by conventionally known anionic or cationic polymerization. method (ionic polymerization method), radical polymerization method using a polymerization initiator and/or chain transfer agent containing a specific polar group in the molecule (radical polymerization method), or the above ionic polymerization method Alternatively, a method in which 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 radical polymerization method is converted into the specific polar group of the present invention by a polymer reaction, etc. It can be easily produced by the following synthesis method.

Specifically, P, Dreyfuss, R9P,
QuirkEncycl, Po1y+n, Sci
, Eng, 7.551 (1987), Yoshiki Nakajo, Yuya Yamashita "Dye and Medicine", ■, 232 (1985)
, Akira Ueda, Susumu Nagai "Science and Industry" ■, 57 (1986
), etc., and the literature cited therein.

Specifically, the chain transfer agent used is, for example, a mercapto compound containing the polar group or the above-mentioned reactive group (i.e., a group that can be induced into the polar group) (e.g., thioglycolic acid, thiomalic acid, thiosalicylic acid). , 2-mercaptopropionic acid, 3-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-(3-mercaptopropionyl)alanine, 2
-Mercaptoethanesulfonic acid, 3mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanediol, 3-
Mercapto 2-butanol, mercaptophenol 2-
mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-viridinol, 4-(2mercaptoethyloxycarbonyl)phthalic anhydride, 2-mercaptoethylphosphonoic acid, 2mercaptoethylphosphonoic acid monomethyl ester, etc.), or the above Iodized alkyl compounds containing polar groups or substituents (e.g. iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanol,
iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferred are mercapto compounds.

Examples of the polymerization initiator containing the polar group or a specific reactive group include 4,4'-azobis(4-cyanovaleric acid), 4.4'-azobis(4-cyanovaleric acid), and 4.4'-azobis(4-cyanovaleric acid). chloride), 2.2'-azobis(2-cyatuburobanol), 2.2'-azobis(2cyanopentanol), 2.2'-azobis[2-methyl-N-(
2-hydroxyethyl)-propioamide), 2.2
'-azobis(2-methyl-N(1,1-bis(hydroxymethyl)-2-hydroxyethyl)propioamide), 2,2''-azobis(2-(1-(2-hydroxyethyl)-2-imidacyline) -2-yl]propane)
, 2,2'-azobis(2-(2imidacillin-2-
propane]2,2°-azobis[2-(4,5,
6,7-tetrahydro-18-1,3-diazopine-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, other resins may be used in combination with the resin (A) (including (A')) and resin [B] (also including [B')) according to the present invention. These resins include:
For example, alkyd resin, polybutyral resin, polyolefins, ethylene-vinyl acetate copolymer, styrene resin,
Examples include 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.

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, resin (A) and/or
Alternatively, in resin [B], a method of introducing a thermally and/or photocurable functional group into the main chain of the graft copolymer can be applied.

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 a heat-curable and/or photo-curable functional group can prevent the interaction between the binder resin and the zinc oxide particle surface without hindering the adsorption and coating of the binder resin. This has the effect of further improving the film strength.

When the resin (A) and/or [B] of the present invention contains the thermosetting functional group, a reaction accelerator may be added as necessary to promote the crosslinking reaction in the photosensitive layer. In the case of a reaction mode that forms a chemical bond between functional groups that may be added, for example, organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-)luenesulfonic acid, etc.), crosslinking agents, etc. Can be mentioned.

As a crosslinking agent, specifically, Shinzo Yamashita and Tosuke Kaneko ed.
Compounds described in "Crosslinking Agent Handbook" published by Taiseisha (1981) etc. can be used. For example, commonly used crosslinking agents such as organic silane, polyurethane, polyisocyanate, epoxy resin, melamine resin, etc. A curing agent or the like can be used.

In the case of a polymerizable reaction mode, a polymerization initiator (peroxide, azobis-based compound, etc., preferably an azobis-based polymerization initiator), a monomer containing a polyfunctional polymerizable group (for example, vinyl Methacrylate, allyl methacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, divinyl succinate, divinyl adipate, diallyl succinate,
2-methylvinyl methacrylate, divinylhenzen, etc.)
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 carried out by tightening the drying conditions during conventional photoreceptor production. For example, from 60°C to 1
The treatment can be carried out at 20° C. for 5 to 120 minutes, and when 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 (A) (including (A')) and resin [B] (including (B')) used in the present invention depends on the type, particle size, and surface condition of the inorganic photoconductive material used. Generally speaking, the ratio of resin (A) and resin [B] used is 5 to 5, although it varies depending on the
60:95-40 (weight ratio), preferably 10-40
The ratio is 40 to 90 to 60 (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 together as spectral sensitizers if necessary. For example, Harumi Miyamoto-Hidehiko Takei, Imaging, 19i (lb8) p. 12, C, J.
Young et al., RCA Review, ), 46
9 (1954).

Wataru Kiyota, Journal of the Institute of Electrical Communication Engineers 1fl2C (No, 2
).

97 (1980), Yuji Harasaki et al., Industrial Chemistry Magazine Tadashi
78 and 188 (1963), published by Tadaaki Tani, Journal of the Photographic Society of Japan.

Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthine dyes, phthalein dyes, polymethine dyes (e.g., oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.) cited in reviews such as 20B (1972), etc. , phthalocyanine dyes (which may contain metal), and the like.

More specifically, examples of carbonium dyes, triphenylmethane dyes, xanthine dyes, and phthalein dyes are disclosed in Japanese Patent Publication No. 51452 and Japanese Patent Application Laid-open 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
．． 450, JP-A-57-16456, and the like.

oxonol dye, merocyanine dye, cyanine dye,
Polymethine dyes such as logcyanine dyes include P, '
M, Hars+mar The Cyanine
Dyes and Related Compounds
J. et al., and more specifically, U.S. Pat. No. 3,047,384, U.S. Pat.
No. 110.591, U.S. Patent No. 3,121°008;
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. 1,226.
892, British Patent No. 1.309.274, British Patent No. 1,405.898, 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 ns 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 57457254, JP 61-2604
No. 4, JP-A No. 61-27551, U.S. Patent No. 3,61
No. 9,154, U.S. Pat. No. 4,175,956, rR
search Disclosure J 1982
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 aggravating agents, may be used in combination.
(Nf18) Electron-accepting compounds (e.g., halogens, benzoquinones, chloranil, acid anhydrides, organic carboxylic acids, etc.) cited in the review on page 12, etc. Hiroshi Komon et al., “Recent developments in photoconductive materials and photoreceptors. "Practical Application" Chapters 4 to 6 2 Nippon Kagaku Information Co., Ltd. Publishing Department (1986) References to Polyarylalkane Compounds and Hindered Phenol Compounds, p.
-phenylenediamine compounds and the like.

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 in a laminated 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. Those with a water-resistant adhesive layer on the surface of the body, those with at least one pre-coat layer provided as necessary on the surface layer of the support, and those with a conductive plastic base coated with At or the like vapor-deposited on paper. You can use the ones that have been prepared.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, Electrophotography, 14, (Nal), p2-11
(1975), Hiroyuki Moriga, “Introductory Chemistry of Special Papers”, Kobunshi Publishing (1975), M, F, Hoover,
J.

Macromol, Sci, Chem, A-
4(6), pp. 1327-1417 (1970
), etc. are used.

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

[Synthesis of resin (A)]

Synthesis Example 1 of Resin (A): (A-1) 95 g of ethyl methacrylate and 2 of tetrahydrofuran
00g of the mixed solution was thoroughly degassed under a nitrogen stream and heated to 20°C.
It was cooled to 1.1-diphenylbutyllithium 1.5
g was added and reacted for 12 hours. Further, a mixed solution of 5 g of triphenylmethyl methacrylate and 5 g of tetrahydrofuran was added to this mixed solution after being sufficiently degassed under a nitrogen stream, and the mixture was further reacted for 8 hours. After the mixture was cooled to 0° C., 10 ml of methanol was added and reacted for 30 minutes to terminate the polymerization. The obtained polymer solution was heated to a temperature of 30°C while stirring.
℃, and add 30% hydrogen chloride ethanol solution 3I11 to this.
was added and stirred for 1 hour.Next, the solvent was distilled off from the reaction mixture under reduced pressure until the total volume became half, and then reprecipitated into petroleum ether III.

The polymer obtained by collecting the precipitate and drying it under reduced pressure has a Pk
The yield was 70 g at 48.5 x 10'.

(A-1) (Weight ratio) b Indicates a niblock bond (Below *) Synthesis example 1 of resin (A) (A-23 46 g of n-butyl methacrylate, 0.5 g of aluminum methyl (tetraphenylporphinate) and A mixed solution of 60 g of methylene chloride was brought to a temperature of 30° C. under a nitrogen stream. This was irradiated with light from a 300 W xenon lamp from a distance of 25 c + w through a glass filter, and reacted for 12 hours. In addition, 4 g of benzyl methacrylate was added to this mixture. After 8 hours of light irradiation, 3 g of methanol was added to the reaction mixture and stirred for 30 minutes to stop the reaction.Next, Pd-C was added to the reaction mixture and the mixture was heated at 25"C for 1 hour. A catalytic reduction reaction was performed.

After filtering out insoluble matters, the mixture was reprecipitated in petroleum ether 5001d, and the precipitate was collected and dried. The obtained polymer had a yield of 33
g and PS119.3×10”.

(A-2) Shiri υshi 4n drops (n) Shiri υυn resin (A)
Synthesis Example 1 (A-3) 90 g of 2-chloro-6-methylphenyl methacrylate
A mixed solution of 200 g of toluene was thoroughly degassed under a nitrogen stream and cooled to 0°C.
- 2.5 g of methylpentyl lithium was added and stirred for 6 hours. Further, 10 g of 4-vinylphenyloxytrimethylsilane was added to this mixture and stirred for 6 hours, and then 3 g of methanol was added and stirred for 30 minutes.

Next, add 1 part of 30% hydrogen chloride ethanol solution to this reaction mixture.
After adding 0 g of petroleum ether and stirring at 25°C for 1 hour,
The precipitate reprecipitated and collected in 300 g of diethyl ether
Washed twice with m and dried. Obtained polymer C, yield 58
g i'Uw 7.8 X 10' i” Arata.

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

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

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

The obtained reaction product was reprecipitated in 1.5 ml of hexane, collected and dried. The resulting polymer was 68 g and ˜9.5×10 3 .

(A-4) Synthesis Examples 5 to 16 of Resin (A) Resin (A) shown in Table 1 below was synthesized in the same manner as in the synthesis example of Resin (A).

table CH.

~ of each resin (A) is 6X10' ~9.5X10' And Song.

(The following is a blank space) Synthesis Examples 19 to 23 of Resin (A) The following Table 2 was prepared in the same manner as in Synthesis Example [4] of Resin (A).
Resin (A) shown in was synthesized. Each resin is 8X10”
~1×103.

(Left below) Macromonomer synthesis example 1: M-1 90.1 g of 1,4-butanediol, 10 succinic anhydride
A mixture of 1.6 g of p-)luenesulfonic acid monohydrate and 200 g of toluene was added to a Dean-Star®
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 t-butylhydroquinone were added to the above reaction mixture, and the mixture was further reacted under reflux for 4 hours with stirring. After cooling to room temperature, it was reprecipitated into methanol 21, and the precipitated solid was collected by filtration and dried under reduced pressure.

The yield was 135 g, and the obtained macromonomer (M-1
) The weight average molecular weight was 6.8 XIO''.

(M-1) Cut-CH-Coo−CHz÷“OCO-(CH*tercOo)H Macromonomer synthesis example 2: M-2 1,6-hexanediol 120 g, geltanic anhydride 1
14.1 g,, P ) Luenesulfonic acid l hydrate 3.
A mixture of 0 g and 250 g of toluene was reacted under the same conditions as in Macromonomer Synthesis Example 1. The amount of water distilled off azeotropically was 17.5 g.

After cooling to room temperature, it was reprecipitated into n-hexane 21, and the liquid was collected after being decanted, and dried under reduced pressure.

The above reactive components were dissolved in toluene and 0. When the carboxyl group content was measured by neutralization titration with IN potassium hydroxide methanol solution, it was found to be 500μ o1/gr.
, φ 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.

Dicyclohexylcarbodiimide (D, C, C) 20.
3g.

A mixed solution of 0.5 g of 4-(N,N-dimethyl)aminopyridine 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.

As the solutions D, C, and C were added dropwise, insoluble crystals were precipitated from the reaction mixture, and the insoluble matter was filtered through a 200 mesh nylon cloth.

2 hexane for the filtrate! The powder was collected by filtration. After adding 500 ml of acetone and stirring for 1 hour, the undissolved soybean was filtered by gravity using a filter paper. After the filtrate was concentrated under reduced pressure until the total volume was 2, the solution was added to 1 liter of ether 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 (M-2) obtained in a yield of 53 g was 8.2×10 3 .

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

The carboxyl group content of the obtained liquid was 600 μmol.
/gr. 100g of the above liquid, methacrylic acid =
Water ts, sg, t-butylhydroquinone 1.
A mixed solution of 5 g and 200 g of tetrahydrofuran was stirred at a temperature of 40 to 45°C for 6 hours. Add 1 part water to the reaction mixture!
The solution was added dropwise to the solution over 1 hour while stirring, and the mixture was further stirred for 1 hour.

The precipitated liquid was taken out by decantation, dissolved in 200 g of THF, and reprecipitated in 1 liter of methanol. The precipitated liquid was taken out by decantation and dried under reduced pressure.

The yield was 162 g, and the weight average molecular weight of the macromonomer (M-3) was 6.7 XIO''.

(M-3) Macromonomer synthesis example 4: M-4 S, Penczek et al, Makro
mol, Chem, 188. 1347 (1987
), a macromonomer (M-4) having the following structure was synthesized.

Weight average molecular weight: ? , 3X10' Macromonomer synthesis example 5: M-5 Macro Nanatsuma (M-4) 50g, methanol 3g.

L-butylhydroquinone 0.5g and methylene chloride 1
To 50 g of mixed solution, D, C, C, 6 g, 4-N,
A mixed solution of 0.1 g of N-dimethylaminopyridine and 10 g of methylene chloride was stirred at a temperature of 20 to 25°C for 30 minutes.
The mixture was added dropwise over a period of minutes, and the mixture was further stirred for 4 hours. After adding 5 g of formic acid to this reaction mixture and stirring for 1 hour, the precipitated insoluble matter was filtered off. The filtrate was reprecipitated into 1 liter of methanol,
The solvent was removed by decantation, and the precipitate was collected and dried under reduced pressure. The obtained viscous substance has a yield of 28 g and a ~7.5
It was X 103.

(M-5) CHl Resin of the present invention [B] Synthesis Example 1: A mixture of 85 g of [B-1] ethyl methacrylate), 15 g of the macromonomer compound (M-1) of Synthesis Example 1, and 200 g of toluene was heated with nitrogen. The mixture was heated to a temperature of 75° C. under air flow.

0.6 g of 11'-azobis(cyclohexane-1-carbonitrile) (abbreviated as A, B, C, C,) was added and stirred for 4 hours. Further, 0.3 g of A, B, C, and C were added for 3 hours, and then 0.2 g of A, B, C, and C were added and stirred for 4 hours. ~ of the obtained copolymer is 9. I x 10
'Met.

CB-1) CHff CH3 Synthesis Example 2 of the resin [B] of the present invention: [B-2] 95 g of benzyl methacrylate 1 5 g of the compound (M-4) of Synthesis Example 4 of the macromonomer, 200 g of toluene , and heated to a temperature of 75°C under a nitrogen stream. 4゜4゛-azobis(2-cyanovaleric acid) (abbreviation: A, C, V
, ) 0.6g was added and stirred for 4 hours. Next, A, C,
V, 0.3g was added for 3 hours, and then A, CJ, 0.
2 g was added and stirred for 3 hours. The weight average molecular weight of the obtained copolymer was 1.2 x 104.

(B-2) Synthesis examples 3 to 13 of resin [B] of the present invention: [B-3 to
[8-13] Each resin in Table 3 below was synthesized under the same polymerization conditions as in Synthesis Example 1 of Resin [B].

(Hereinafter, blank spaces) Synthesis Examples 14 to 23 of the resin [B] of the present invention: [B-14
1 to [B-23] In Synthesis Example 1 of Resin [B], using the following mercapto compound as a chain transfer agent and under the same polymerization conditions, Table-4
Resins CB) were produced.

(Hereinafter, blank space) Synthesis examples 24 to 31 of resin [B] of the present invention: [B-24
] ~ [B-311 In Synthesis Example 2 of Resin CB), A, C, and V were replaced with other azobis compounds, and the resins in Table 5 (B3 were each treated under the same polymerization conditions). Each resin [B] had ~8.OXIO'~2x104.

(Hereinafter, blank spaces) Synthesis examples 32 to 41 of resin [B] of the present invention: [B-32
] to [8-41] Each resin [B] in Table 6 below was synthesized under the same polymerization conditions as in Synthesis Example 1 of Resin [B].

~ of the obtained copolymer is 9. OXIO'~1.2 XI
It was O'.

(Blank below) Synthesis example of resin (B-423): [B-42] A mixture of 80 g of benzyl methacrylate, 20 g of the compound (M to 5) of macromonomer synthesis example 5, and 200 g of toluene was added to the resin (B-2). The reaction was carried out under the same polymerization conditions as in the synthesis example to synthesize resin (B-42). The weight average molecular weight of the obtained copolymer was 9.8×10′.

(B-42) (blank below) 1-2 A-B Resin (A-18) 6 g (as solid content), Resin (B-1) 34 g (as solid content), Cyanine dye with the following structure [1 ) A mixture of 0.018 g and 300 g of toluene was dispersed in a ball mill for 4 hours to prepare a photosensitive layer-forming product, and this was applied to conductive-treated paper with a dry adhesion weight of 25.
Apply with a wire bar so that g/rd is 110°
Dry for 30 seconds at C, then dry at 20"C 65% RH in the dark.
An electrophotographic light-sensitive material was produced by leaving it for 24 hours under the following conditions.

Cyanine dye (1) Example 2 The procedure was the same as in Example 1, except that 6 g of resin (A-5) (as solid content) was used instead of 6 g of resin (A-18). In this way, an electrophotographic photosensitive photographic material was produced.

An electrophotographic photosensitive material was prepared in the same manner as in Example 1, except that 6 g of resin (R-1) having the following structure was used instead of 6 g of resin [A-18] in Example 1. Created.

Comparative resin (R-1) CH3CH3 fw 6X10” (Random copolymer) This Jfd
Li: An electrophotographic light-sensitive material was prepared in the same manner as in Example 1, except that 6 g of resin (R-2) having the following structure was used instead of 6 g of resin (A-18).

(R-2) CH.

HOOC-CHz-3-(CHt-C)-CC00CH
x CJ sFr 8.0
RH) was investigated.

The above results are summarized in Table-7.

(Left space below) The implementation of the evaluation items shown in Table 7 is as follows.

Note 1) Electrostatic properties: In a dark room at a temperature of 20°C and 65% R11, corona discharge was applied to each photosensitive material using a paper analyzer (Paper Analyzer 5P-428 model manufactured by Kawaguchi 1TL! ■) for 20 seconds at -6 kV. After that, it was left to stand for 10 seconds, and the surface potential v1° at this time was measured. Then, the potential was v1° after being allowed to stand still in the dark for 90 seconds. The retention of the potential after dark decaying for 90 seconds, that is, the dark decay retention rate (DRR)
(χ)] was calculated as (V+*a/V+o)X100(%).

Further, after charging the surface of the photoconductive layer to -400 V by corona discharge, the surface of the photoconductive layer is irradiated with gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 7B0 nm) light,
The time required for the surface potential (V,.) to attenuate to 1/10 is determined, and the exposure amount E,/1° (erg/d) is calculated from this time. Similarly, find the time until the surface potential (V+) attenuates to 1/100, and calculate the exposure amount El/+6 from this.
Calculate °(6rg/cd). The environmental conditions at the time of measurement are:
20°C, 65% RH (1) and 30°C, 80% RH (It
).

Note 2) Imaging performance: 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-arsenic semiconductor laser (oscillation wavelength 780 nm) with a 2.8 mW output was used as a light source. ) on the surface of the photosensitive material.
Copied image obtained by developing and fixing using ELP-T (manufactured by Fuji Photo Film ■) as a liquid developer after exposure at a pitch of 254 and a scanning speed of 300 m/sec under an irradiation dose of erg/c1i (Kabri,
Image quality) was visually evaluated.

Environmental conditions during imaging were 20°C, 65% RH (1) and 30°C.
It was carried out at 80% RH (It).

As shown in Table 7, the photosensitive material of the present invention had good electrostatic properties, and the actual copied images had no ground force and the quality of the copied images was clear. On the other hand, in Comparative Examples A and B, the charging potential (V+O) decreased or the photosensitivity (El/I. and E1/1°.)
There is a decrease in image density (D,) even in actual copied images.
As a result, fine lines, letters, etc. became blurred, and the appearance of smudges occurred.

In particular, in the photoreceptor of the present invention and the photoreceptor of the comparative example, El/1
The 0° values are significantly different. E171°. The value is the non-image area (already exposed area) after exposure in actual imaging performance.
This shows how much potential remains in the image, and the smaller this value is, the less background smear will occur in the non-image area after development.

Specifically, it is necessary to make the residual potential below -10V, that is, how much exposure is required to actually make it below VR-10V?Scanning exposure using semiconductor laser light In this method, it is very important to reduce (1) to -1 Ov or less with a small exposure amount in terms of the design of the optical system of the copying machine (device cost, precision of the optical system optical path, etc.).

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

Furthermore, even when the resin of the present invention is used, the resin [A] containing a methacrylate component having a specific substituent
It has become clear that Example 2, consisting of the following, has better electrostatic properties than Example 1, and is especially advantageous for photoreceptor systems using laser beam scanning exposure methods for semiconductor devices.

Example 3 6.5 g (as solid content) of the resin (A-3) produced in the synthesis example, 33.5 g of the resin (B-3) having the following structure, 200 g of zinc oxide, and 0.0 g of the cyanine dye (If) having the following structure.
018g, phthalic anhydride 0.30g and toluene 300g
The mixture of g was dispersed in a ball mill for 4 hours. This was applied to electrically conductive treated paper using a wire bar so that the dry adhesion amount was 25 g/rd, and dried at 100°C for 30 seconds.

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

Cyanine dye (II) Film properties (surface smoothness), electrostatic properties, imaging properties, printability of this photosensitive material, and electrostatic properties, imaging properties, and printability when the environmental conditions are 30°C and 80% RH. I looked into it.

The implementation of the evaluation items shown in Table 8 is as follows.

Note 3) Smoothness of surface layer: The obtained photosensitive material was tested using a Beck smoothness tester (Kumagai Riko ■
The smoothness (
sec/cc) was measured.

Note 4) Contact angle with water: Each photosensitive material is exposed to light by passing it through an etching processor once using a solution prepared by diluting the desensitizing liquid EPL-EX (manufactured by Fuji Photo Film) twice with distilled water. After desensitizing the conductive layer surface, place 2.1 drops of distilled water on it,
The formed contact angle with water is measured with a goniometer.

Note 5) Printing durability: A toner image is formed by making a plate under the same conditions as the imaging performance in property 2) above, and is desensitized under the same conditions as property 4) above.
Use this as an offset master on an offset printing machine (
This indicates the number of sheets that can be printed without causing problems with background stains in the non-image areas of the printed matter and image quality in the image areas (the higher the number of prints, the better the rigidity resistance). .

As shown in Table 8, in the photosensitive material of the present invention, the smooth film of the photoconductive layer had good mechanical strength and electrostatic properties, and the actual copied images had no blurring and the quality of the copied images was clear. . This is presumed to be due to the photoconductor and the binder resin being sufficiently adsorbed and covering the particle surface. For the same reason, even when used as an offset master original, the desensitization treatment with the desensitization 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 it has been done. Even when the printed matter was actually printed and the background smear was observed, no background smudge was observed, and 9000 printed matter with clear image quality were obtained.

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

In Example 1, resin (A-18) and resin (B-1
) in place of each resin (A) and each resin [B] in Table 9 below.
] Each electrophotographic photoreceptor was produced in the same manner as in Example 1, except that

Electrostatic properties were measured in the same manner as in Example 1. Display the results -
9.

Measured values under conditions of surface electrostatic properties (30°C, %R11). Also, when used as an offset master master plate and printed in the same manner as in Example 1, 10,000 or more copies were printed in each case. was completed.

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.

Furthermore, it was found that the electrostatic properties were further improved by using resin (A').

The binder resin used in Example 1 was replaced with 6 g of resin (A) and 34 g of resin [B] in Table 1O below, and the following structure was used instead of 0.02 g of cyanine dye (1). The dye (I
I) An electrophotographic light-sensitive material was produced under the same conditions as in Example 1, except that the amount was changed to 0.019 g.

Dye (III) (C)Is) asOs'' Table All of the photosensitive materials of the present invention have chargeability, dark charge retention,
It has excellent light sensitivity, and the actual copied images can be used even in high temperature and high humidity conditions (30℃).
, 80% RH), it provided clear images without any distortion.

Furthermore, when this was used as an original plate for an offset master, more than 10,000 copies of clear image quality prints with no background blur were printed.

Resin (A-19) (Example 30) or Resin (A-21)
: 6.5 g of any of 1 (Example 31), resin (B-4
2) 33.5g, zinc oxide 200g, uranine 0.02
A mixture of 0.03 g of methine dye CD having the following structure, 0.03 g of methine dye [E] having the following structure, 0.18 g of p-hydroxybenzoic acid, and 300 g of toluene was dispersed in a ball mill for 3 hours to form a photosensitive layer. The formed product was prepared, and the dry adhesion amount was 25 g/r on conductive-treated paper.
Apply it with a wire bar so that it becomes rf, and
Each electrophotographic photoreceptor was prepared by drying for 0 seconds and then leaving it in a dark place under conditions of 20° C. and 65% RH for 24 hours.

Methine dye (D) Methine dye (E) The same procedure as in Example 30 was used except that 6.5 g of the resin (R-2) was used instead of 6.5 g of the resin (A-19). A photosensitive material was prepared.

In the same manner as in Example 1, the characteristics of each photosensitive material were investigated. The results are summarized in Table 11 below.

In the above measurements, the electrostatic properties and imaging properties were performed in the same manner as in Example 1, except that the following operations were followed.

Note 7) Method for measuring electrostatic properties E, 71° and El/+611 After the surface of the photoconductive layer was charged to -400 μ by corona discharge, the surface of the photoconductive layer was exposed to visible light at an illuminance of 2.0 lux. irradiated, the surface potential (ν1°) is 1/10 or E, /
,. . Find the time it takes for the light to attenuate, and from this calculate the exposure amount E
,/,. Or E171°. Calculate (looks/seconds).

Note 8) Imaging properties After leaving each photosensitive material for one day and night under the following environmental conditions, use a fully automatic plate making machine EPL-404V (manufactured by Fuji Photo Film ■).
A copy image (capri, image quality) obtained by plate making using EPL, T as a toner was visually evaluated. The environmental conditions during imaging were 20°C 65% R11 (1) and 30°C 80°C.
%R [1 (II). However, the manuscript for copying (ie, the draft manuscript) was created by cutting out and pasting other manuscripts.

No difference was observed in the smoothness and strength of the photoconductive layer among the photosensitive materials. However, in terms of electrostatic properties, Comparative Example C has a particularly high photosensitivity El/l. . The value of was large, and this was further exacerbated at high temperatures, resulting in deterioration. The electrostatic properties of the photosensitive material of the present invention are good, and Example 29 using the resin (A) having a specific substituent group is very good, especially E1/1°. The value of has become smaller.

When examining the actual imaging performance, in Comparative Example C, in addition to the original as a copy image, the frame of the cut out and pasted portion (that is, pasting trace) was observed as background stains in the non-image area.

However, in all cases of the present invention, clear images without background stains were obtained.

Furthermore, when these were desensitized and printed as offset printing original plates, 10,000 prints with clear image quality and no background smudge were obtained for all of the products of the present invention. However, in Comparative Example C, the above-mentioned pasting marks were not removed even with the desensitizing treatment and were generated from the printed matter.

From the above, only the photosensitive material of the present invention was able to provide good characteristics.

In Example 30, instead of 6.5 g of resin (A-19) and 5 g of resin (B-42333, the following table-
Each photosensitive material was produced in the same manner as in Example 30, except that 6.5 g of Resin (A) and 33.5 g of Resin CB of No. 12 were used.

Table 12 All of the photosensitive materials of the present invention have excellent chargeability, dark charge retention, and photosensitivity, and the actual reproduced images are produced at high temperatures (30°C, 18°C).
Even under the harsh conditions of 0% RH), clear images were produced without any occurrence of ground blur or fine line skipping.

Furthermore, when printed as an off-cent master original plate, clear prints with no background smearing were obtained even after printing 10,000 sheets.

Urasen [44 8 g of resin (A-24) and 2 resin [B2O] with the following structure
8g, zinc oxide 200g, uranine 0.02g, rose bengal 0.04g, bromophenol blue 0.
03 g, phthalic anhydride 0.40 g and toluene 3
00 g of the mixture was dispersed in a ball mill for 4 hours, then 3.5 g of 1,3-xylylene diisocyanate was added and further dispersed for 5 minutes.

The dry adhesion amount was 18g/rrf on conductive-treated paper.
It was applied with a wire bar and heated at 110°C for 30 seconds, then heated at 120°C for 2 hours. Each electrophotographic light-sensitive material was prepared by leaving it for 24 hours under H conditions.

Resin (A-24) 129.5 XIO' 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 in high temperature and high humidity conditions (30℃).
, 80% RH), it provided clear images with no soil blurring.

Furthermore, when this was used as an original plate for an offset master, prints with clear image quality were obtained even after printing 10,000 copies.

(Effects of the Invention) According to the present invention, an electrophotographic photoreceptor has excellent electrostatic properties (especially electrostatic properties under harsh conditions), has clear and high-quality images, and has excellent mechanical strength. can be obtained. It is particularly effective for scanning exposure methods using semiconductor laser light.

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

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 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,
-PO_3H_2 group, -COOH group, -SO_3H group,
At least one selected from phenolic OH group, ▲mathematical formula, chemical formula, table, etc.▼ group {R represents a hydrocarbon group or -OR' group (R' is a hydrocarbon group)}, and a cyclic acid anhydride-containing group. Contains an AB block copolymer consisting of an A block consisting of at least one polymer component containing one acidic group and a B block containing at least a polymer component represented by the following general formula (I). Made of resin. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In formula (I), R_1 represents a hydrocarbon group.) Binder resin [B]; General formula (IIIa) and general formula (IIIb) below At least one of the polyester macromonomers (MB) having a weight average molecular weight of 1 x 10^3 to 1.5 x 10^4 represented by
A copolymer having a weight average molecular weight of 3 x 10^4 to 1 x 10^6, which contains at least one of these as a polymer component. General formula (IIIa) General formula (IIIb) In formulas [IIIa] and [IIIb], the characters in brackets represent repeating units. f_1 and f_2 may be the same or different from each other,
Each hydrogen atom, halogen atom, cyano group, carbon number 1-8
hydrocarbon group, -COO-T_1 or -COO-T_2 (T_1 and T_
2 each represents a hydrocarbon group having 1 to 18 carbon atoms. A_1 is a single bond or -COO-, -OCO-, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (u_1, u_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-. B_1 represents a group connecting A_1 and -COO-. D_1 and D_2 may be the same or different from each other,
Each divalent aliphatic group, divalent aromatic group {-O-, -S-, ▲mathematical formula, chemical formula, table, etc. are present in the bond of each divalent organic residue▼(d_2 is a hydrogen atom or carbon number 1-12
represents a hydrocarbon group), -SO_2-, -COO-,
-OCO-, -CONHCO-, -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 ▲ Mathematical formulas, chemical formulas, tables, etc. There is at least one selected from ▼
} or a combination of these residues. R_6_1 represents a hydrogen atom or a hydrocarbon group. f_3, f_4, A_2, B in general formula (IIIb)
_2 and R_6_2 are each f in general formula (IIIa)
It represents the same content as _1, f_2, A_1, B_1 and R_6_1. D_3 represents a divalent aliphatic group. (2) A claim characterized in that the B block in the AB block copolymer contains 30% by weight or more of at least one repeating unit selected from the following general formulas (Ia) and (Ib): (1) The electrophotographic photoreceptor described above. General formula (I a) General formula (I b) [In formula (I a) or (I b), X_1 and X_2,
are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, -COZ_2 or -
COOZ_2 (Z_2 each represents a hydrocarbon group having 1 to 10 carbon atoms). However, both X_1 and X_2 do not represent hydrogen atoms. L_1 and L_2 each represent a single bond or a linking group having 1 to 4 linking atoms that connects -COO- to the benzene ring. ] (3) The resin [B] has -PO_3H_2 groups, -SO_
There are 3H groups, -COOH groups, -OH groups, ▲mathematical formulas, chemical formulas, tables, etc.▼ groups (R_0 represents the same content as R)
and at least one selected from cyclic acid anhydride-containing groups
The electrophotographic photoreceptor according to claim 1 or 2, which is a resin in which a polar group of a species is bonded to the end of the polymer main chain portion of the copolymer.