JPH0415655A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance resistance of electrostatic characteristics against environmental conditions by incorporating specified resins in a binder resin. CONSTITUTION:The binder resins comprise the resins A and B, and the resin A is a copolymer comprising a main polymer chain comsisting of polymer components each represented by formulae IIa and IIb and polymer components each having a polar group, such as -COOH, and monofunctional macromonomers MA each having a polymerizable double bond group represented by formula I and combined with the only one terminal of said polymer chain, and a monomer represented by formula II. The resin B is a graft copolymer comprising the C block comprising polymer components each having an acidic group, such as PO3 H2 group and a cyclic acid anhydride, and the D block comprising polymer components each represented by formula III and monofunctional macromonomers MB each having a double bond and combined with the terminal of the poymer chain of the D block. In formulae I, II, IIa, IIb, and III, each of X0, X1, X2, X3, and X4 is -COO- or the like; each of a1, a2, b1, b2, c1, c2, d1 and d2 is H or the like; each of Q1 and Q2 is an aromatic group; V is -CN or the like; and R21 is a hydrocarbon group, thus permitting the electrostatic characteristics to be maintained against environmental variations.

Description

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

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

As representative electrophotographic photoreceptors, there are photoreceptors having a photoconductive layer formed on a support and photoreceptors having an insulating layer on the surface, which are widely used. The photoreceptor, consisting of a support and at least one layer of photoconductive tN, is used for imaging by the most common electrophotographic processes, ie, charging, imagewise exposure and development, and optionally transfer.

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

The binder used to form the photoconductive layer of the electrophotographic photoreceptor has excellent film-forming properties and ability to disperse the photoconductive powder into the binder, and also has excellent properties as a base material for the formed recording layer. In addition, the photoconductive layer of the recording layer has excellent charging ability, low dark decay, large light decay, low pre-exposure fatigue, and changes in humidity during imaging. It is necessary to have various electrostatic properties such as the need to stably hold the image, 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 resins have many problems, particularly in chargeability, dark charge retention, electrostatic properties of photosensitivity, smoothness of the photoconductive layer, etc., and are not practically satisfactory.

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

Furthermore, in order to solve these problems ☆, a copolymer component containing an acidic group in the side chain of the polymer was used as a binder resin.
A low molecular weight resin containing 05 to 10% or a low molecular weight resin that binds acid to the end of the polymer main chain (t'1w1
o1 to 104), and furthermore, by using a comb-shaped polymer in which an acidic group is bonded to the end of the polymer main chain, the smoothness and electrostatic properties of the photoconductive layer are improved, and image quality without background smearing is obtained. JP-A-63-217354, JP-A-64-70761 and JP-A-2-6756, respectively.
It is stated in No. 3.

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.
No. 9690 ζ The technique of using a resin containing an acidic group in the side chain of the copolymer or bonding to the end of the main chain of the polymer together with a crosslinking agent is disclosed in JP-A-1-102573 and JP-A-2-874. Furthermore, the low molecular weight form of the resin (weight average molecular weight 103 to 104) is mixed with the high molecular weight form (weight average molecular weight 10
The technology used in combination with the above resins was disclosed in Japanese Patent Application Laid-open No. 64-5.
No. 64, No. 63-220149, No. 63-22014
No. 0, JP-A-1-280761Σ, JP-A-1-116643
JP-A No. 1-211766 and JP-A No. 2-34859 disclose a technique of using such a low molecular weight material in combination with a heat-curable and/or photo-curable resin. Techniques to be used in combination are disclosed in Japanese Patent Application Laid-Open No. 53064/1999, Japanese Patent Application No. 56558/1983, and Japanese Patent Application No. 254786/1986, respectively.

These technologies allow the use of resins containing acidic groups in side chains or terminals to achieve sufficient film strength and increase mechanical strength without impairing the properties listed in 1F. It is stated that

(Problem to be solved by the invention) However, even when these resins are used, the environment is high temperature and
It has been found that it is still insufficient to maintain stable performance when the temperature fluctuates significantly from high temperature to low temperature. 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/10
If the difference is large, the gradation of the copied image will be soft, and furthermore, it will be difficult to reduce the residual potential after exposure, and the capri of the copied image will become noticeable.Also, even if printed as an offset master, This has resulted in serious problems such as traces of pasted originals appearing 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 c
An object of the present invention is to provide a PC electrophotographic photoreceptor.

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

Another object of the present invention is to provide an original plate for electrophotographic planographic printing.
It has excellent electrostatic properties (particularly dark charge retention and photosensitivity), reproduces copied images that are faithful to the original, and does not cause not only uniform background smudges on the entire surface of printed matter but also dotted smudges. ,
Another object of the present invention is to provide a lithographic printing original plate that has excellent rigidity and does not leave any pasting marks.

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

Binder resin [A]; at least one of the polymer components represented by the following general formulas (Ila) and (I[b), and -COOH group, PO,
H, group, -PO3H2 group, -OH group and c in formula (1),
X (1 is -COO--0CO--CHzOCO-1-C
HxCOO-1-O--SO□--CO-1-CONH
At least one group selected from COOH (representing a hydrogen group)
At least one of the polymer components containing two polar groups
A monofunctional macromonomer (MA) with a weight average molecular weight of 2X10' or less, which is formed by bonding a polymerizable double bond group represented by the following general formula (1) only to one end of a polymer main chain containing each species. and a monomer represented by the following general formula (I[[), having a weight average molecular weight of 1. OXIO'
~2. Copolymer of OXIO'.

General formula (1,) a+ at CIl Fog C (represents a hydrogen chloride group).

al and a2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -CO
Represents -Coo-Zl via O4+ or a hydrocarbon (Zl represents a hydrogen atom or a hydrocarbon group which may be substituted). ] General formula (Ila) b+ bt -f-CH-C-juice- X, -Q.

General formula (II b) a- (2 In (IIa) or (IIb), x1 represents the same content as Xo in 2 (1). Ω is an aliphatic group having 1 to 18 carbon atoms or Represents an aromatic group having 6 to 12 carbon atoms.

bl and b2 may be the same or different from each other, and are expressed by the formula (
81 in 1) represents the same content as a2.

Y represents a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, or -COOZz (Zz represents an alkyl group, an aralkyl group, or an aryl group). ]General Noshiro DI)
c-c- C1l=C z Qz [In formula (I[l), x2 is (o X o
Q2 represents the same content as Q in formula (I[a)]. cl and C2 may be the same or different, and represent the same content as al and a2 in formula (1). ) Binder resin [B]: at least a polymer component containing at least one acidic group selected from PO, 82 groups, -COOH groups, -5o, I (groups), phenolic and cyclic acid anhydride-containing groups. Polymerized at the end of the polymer main chain of the B block of an A-B block copolymer composed of an A block containing one type of polymer component and a B block containing at least a polymer component represented by the following general formula (■). A monofunctional macromonomer with a weight average molecular weight of 1 x 103 to 2 x 104 (
A graft type copolymer having a weight average molecular weight of 3X10' to 1X10' and containing at least one type of copolymerization component MB).

General formula (IV) d, d.

+CH-C)- 4Rz c In formula (IV), d and m each represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group. x4 is COO
--0CO-, (CH塘;0CO-, GAHη4C00C
1,,1, represents an integer from 1 to 3), -〇Rz3
Rzx so, --GO-1-CON--5O2N-1-CON
HCOO represents a hydrogen atom or a hydrocarbon group).

L+ represents a hydrocarbon group. However, when x4 represents -◎, R2I represents a hydrogen atom or a hydrocarbon group.

] That is, the binder resin provided in the present invention is a low molecular weight graft type copolymer containing at least a -functional macromonomer (1'lA) and a monomer represented by the general formula (I [[)]. combined CA) and A containing the above specific acidic group-containing component
Monofunctionality formed by bonding a polymerizable double bond group to the polymer main chain end of the B block of an AB type copolymer of the block and the B block containing the polymer component represented by the above formula (IV) It is composed of at least a high molecular weight resin (B) consisting of a graft copolymer containing at least one macromonomer (MB) as a copolymerization component.

The graft copolymer used in the resin [A) of the present invention has one or more polar groups selected from -POsHz group, -SO, H1]H) at one end of the polymer main chain. (Hereinafter, this resin CA'J will be referred to as resin [
(Sometimes referred to as A'1).

Furthermore, as the high molecular weight resin CB], a graft type copolymer containing at least one of the above macromonomers (-B) and a polymer component represented by the following general formula (V) is used. Preferably, it is a combination.

General formula (V) dco d4 1+CH-CtoXS R2! [In formula (V), d5, d4, X, and R2Z are the formula (TV
) respectively represent the same contents as d3, d2, X4 and R2+. ] The conventionally known acidic group-containing binder resins as mentioned above are mainly used for off-cent masters, and their molecular weights are large (for example, 5.
X10' or more), and these copolymers were random copolymers, and the acidic group-containing copolymer components were randomly present in the polymer main chain.

On the other hand, the resin [A] used in the binder resin of the present invention
is a graft copolymer, and is a copolymer in which the polar groups contained in the resin are not randomly present in the main chain of the polymer, but are contained in the graft portion of the polymer.

Therefore, the portion of the polar group present at a specific position away from the main chain of the polymer adsorbs to the stoichiometric defects of the inorganic photoconductor, and the main chain portion of the polymer covers the surface of the photoconductor. It is estimated that the coating is loose and sufficient. Due to that,
It compensates for traps in the photoconductor and improves humidity characteristics, while ensuring sufficient dispersion of the photoconductor, suppressing agglomeration, and being stable even when the environment changes significantly from high temperature/high temperature to low temperature/low humidity. It was found that high performance electrophotographic properties were maintained. And resin [B] is resin [A
The resin [A] can provide sufficient mechanical strength to the photoconductive layer, which is insufficient when using the resin [A] alone, without impairing the high performance of the electrophotographic properties described above. This is particularly effective when using a scanning exposure method using a semiconductor laser.

That is, as the binder resin of the inorganic photoconductor, resin [A] and resin (B) are each selected based on the weight average molecular weight of the resin, the structure of the graft part, and the content of polar groups specifically contained in the resin. By specifying the properties, it is possible to change the strength of the interaction between the inorganic photoconductor and the resin, and also change the ease of interaction between the polymer molecular chains of the resin (Al and resin [B]). As a result, the resin [A], which has a low molecular weight, contains many polar groups, and has stronger interactions, is selectively and appropriately adsorbed to the inorganic photoconductor, and the macromonomer (MA) of the resin [A]
component (graft part) and monomer component of formula (III) (
The molecular chain of the main chain portion) sufficiently interacts with the molecular chain of the component of the main chain portion of the resin [B], and furthermore, the macromonomer (
The molecular chains of the MB) component (graft portion) sufficiently interact with each other and exhibit a so-called anchor effect. As a result, it is presumed that the electrophotographic properties are significantly improved mainly due to the action of the resin [A], and the mechanical strength of the photoconductive layer is further improved due to the action of the resin [B]. In the resin (B), it is presumed that the acidic group bonded to a specific position on the polymer main chain interacts gently with the inorganic photoconductor to the extent that the electrophotographic properties are not adversely affected.

Further, in the present invention, the surface of the photoconductive layer has smoothness. When a photoreceptor with a rough photoconductive layer surface is used as an electrophotographic lithographic printing original plate, the dispersion state of the zinc oxide particles that are the photoconductor and the binder resin is not appropriate, and aggregates may be present. Because a photoconductive layer is formed, even if 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, and as a result, the printed matter deteriorates. Background stains occur in non-image areas.

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

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

The spectral 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 binder 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.

Even when only the low molecular weight resin [A] in the present invention is used as the binder resin, the photoconductor and the binder resin can sufficiently adsorb and coat the particle surface, which improves the smoothness of the photoconductive layer. It has good electrostatic properties, 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, can be 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 has sufficient strength, making it possible to print a minimum of 7,000 sheets even under harsh printing conditions (for example, when printing pressure is high with a large printing press).

Furthermore, the film strength is also improved, and rigidity resistance is improved.

In resin [A], the weight average molecular weight of the graft copolymer is 1XIO3 to 2X10', preferably 3X10'
~1×104, the proportion of copolymerized components of the macromonomer (MA) is 1 to 80% by weight, preferably 5 to 70% by weight, when a polar group is bonded to the end of the copolymer main chain. The proportion of polar groups in the copolymer is 0.5 to
15% by weight, preferably 1 to 10% by weight. Also,
The glass transition point of the resin [A] is preferably -20°C to 1
The temperature is more preferably -10°C to 90°C than 20°C.

Furthermore, if the molecular weight of the resin [A] is smaller than 1X10', the film forming ability will decrease and sufficient film strength cannot be maintained, and if the molecular weight is larger than 2X10', even the resin of the present invention has electrophotographic properties (especially Initial potential, dark decay retention rate) are deteriorated, which is undesirable. Particularly in the case of such high molecular weight materials, if the polar group content exceeds 3% by weight, the electrophotographic characteristics deteriorate significantly, and when used as an offset master. Ground stains become noticeable.

If the content of any polar group (any polar group at the end of the main chain) 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; When the group content is more than 15% by weight, the dispersibility decreases, film smoothness and high-temperature electrophotographic properties decrease, and furthermore, background smearing increases when used as an offset master.

The -functional macromonomer (1'lA
) will be explained in more detail. -Functional macromonomer (MA) specifies that the polymerizable double bond group represented by general formula (1) is at least one of the polymer components represented by general formulas (na) and (nb). polar group (-CO
OH group, -POJz group, -3O, H group, and at least one of υH group, which is bonded to only one end of the polymer main chain, and has a weight average molecular weight of 2×10
'It is the following.

In general formula (1), (I[a) and (Ilb), a
3, azsXo, bl, b! , X3, Q, and V each have the indicated number of carbon atoms (as an unsubstituted hydrocarbon group), but these hydrocarbon groups may have a substituent.

General formula (1) Niite, X, -coo-1-OC
O-1CH,0CO-2-cozcoo-1-o--s
o□--CO-2CONIICOO--CONHCON
B-1-CONH5OtP is a hydrogen atom, and preferable hydrocarbon groups include 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, Hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-
cyanethyl group, 2-methoxycarbonylethyl group, 2
-methoxyethyl group, 3-bromopropyl group, etc.), an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example,
2-methyl-1-propenyl group, 2-butenyl group, 2-
Pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4
methyl-2-hexenyl group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group) , bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxyhensyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic groups having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2 -cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or carbon number 6 or more
12 optionally substituted aromatic groups (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxy phenyl group, decyloxyphenyl group,
Chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc. ) can be given.

When xo represents -〇, the benzene ring may have a substituent. Examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an alkyl group (for example, a methyl group, an ethyl group, a propyl group, Butyl group, chloromethyl group,
methoxymethyl group, etc.), alkoxy groups (eg, methoxy group, ethoxy group, propioxy group, butoxy group, etc.), and the like.

al and a may be the same or different from each other,
Preferably a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), -coo-z , or C00Z via hydrocarbon
+ (Z+ is preferably a hydrogen atom or a carbon number of 1 to 18
represents an alkyl group, alkenyl group, aralkyl group, alicyclic group, or aryl group, which may be substituted, and specifically represents the same content as explained for P above) .

Examples of the hydrocarbon in the -Coo-Z group via the hydrocarbon include a methylene group, an ethylene group, a propylene group, and the like.

More preferably, in general formula (1), Xo is COO
OCOCHzOCOCHzCOO--0--CONHC
OO--CON) ICONB--CONH may be the same or different, and each hydrogen atom, methyl group, -cooz
, or -CHtCOOZ+ (Z+ is more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group)
represents, ) represents. Even more preferably al, a
In 2, either one represents a hydrogen atom.

That is, specific examples of the polymerizable double bond group represented by 2N) include C11tCOOCH2cazcoou.

In the general formula (na) or (IIb), X represents the same content as xo in 2 (1). b2 and b2 may be the same or different from each other, and a5 and a2 in formula (1)
represents the same content as .

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

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,
Dodecyl group, tridecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2
~Hydroquinlethyl group, 2~methoxyethyl group, 2-
Ethoxyethyl group, 2-cyanoethyl group, 3-chloropropyl group, 2-()rimethoxysilyl)ethyl group, 2-
Tetrahydrofuryl group, 2-thienylethyl group, 2-N
, ~dimethylaminoethyl group, 2-N,N diethylaminoethyl group, etc.), fluoroalkyl group having 5 to 8 carbon atoms (e.g. cycloheptyl group, cyclohexyl group, cyclooctyl group, etc.), fluoroalkyl group having 7 to 12 carbon atoms Aralkyl groups that may be substituted (e.g., hensyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromohensyl group, dichlorohensyl group, methylbenzyl group, chloro- Methyl-benzyl group, dimethylbenzyl group, trimethylbenzyl group,
aliphatic groups such as methoxybenzyl groups, etc., and furthermore, carbon atoms of 6 or more.
12 optionally substituted aryl groups (e.g., phenyl group, tolyl group, xylyl group, chlorophenyl group, bromophenyl group, dichlorophenyl group, chloro-methyl-phenyl group, methoxyphenyl group, methoxycarbonylphenyl group, naphthyl group, Examples include aromatic groups such as chloronaphthyl group, etc.).

In formula (Ila), preferably X is -COOOC
O---CH, C0(1--co, oco-1-〇-G
O--CON)ICOO--CON)ICONH--
-CONHb3, preferable examples of b2 include the above-mentioned als
Represents the same content as at.

General formula (n b) Nioiite, V bar CN, -CONH
Bifurcated atoms (e.g. chlorine atom, bromine atom, etc.), hydrocarbon groups (e.g. methyl group, ethyl group, propyl group, butyl group, chloromethyl group, phenyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, (propioxy group, butoxy group, etc.) or -COOZz (Zz preferably represents an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryl group).

The macromonomer (MA) may contain two or more types of polymer components represented by formulas (IIa) and/or (■b). When Q is an aliphatic group, the aliphatic group having 6 to 12 carbon atoms is preferably used in an amount not exceeding 20% by weight of the total polymer component in the macromonomer (MA).

Furthermore, when 1 in general formula (Ila) is -COO-, the polymer component represented by 2 (Ila) is at least 301% by weight of all the polymer components in the macromonomer (MA). Preferably, it is contained.

Generally speaking, in the macromonomer (MA), the formula (IIa
) and/or (I[b), which is copolymerized as a further component with the copolymer component denoted by
group, -POJ, group, -SO,H4, -OH group, -P-1
As the component containing H (+, group), any vinyl compound containing the polar group that can be copolymerized with the macromonomer (MA) can be used. For example, it is described in Kobunshi Data "Kobunshi Data Handbook [edited by Kifl1]" Baifukan (published in 1986). in particular,
Acrylic acid, α and/or β substituted acrylic # (e.g. α
-acetoxy form, α-acetoxy7methyl form, α(2-amino)methyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylinyl form, α-cyano form, β-
chloro form, β-bromo form, β-fluoro form, β-menxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides,
Crotonic acid, 2-alkenyl carboxyne tII (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, vinylphosphonic acid, dicarboxylic acids, vinyl or allyl groups of alcohols and half-ester derivatives of these carboxylic acids or sulfonic acids, ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing the polar group in the substituent of amide derivatives.

k represents an integer of 2 to 5, h represents an integer of 1 to 4, and i represents an integer of 1 to 12.

Examples of H 2 include the same hydrocarbon groups as mentioned above for Ω in formula (I[a)]. Examples of the ON group include vinyl group- or allyl group-containing alcohols (for example, allyl alcohol, ester substituents such as methacrylic acid ester, acrylamide, etc., compounds containing an -OH group in the N-substituent, etc.), hydroxyphenol, or hydroxyl group. Examples include methacrylic acid esters or amides containing a phenyl group as a substituent.

For example, the following monomers are shown as examples,
The scope of the present invention is not limited thereto.

Here, on each side below, a is -H1-CH3, -
CI, -Br, -CN, -CHxCOOCHs or -Clzcoon, b represents -H or -CH5, j represents an integer from 2 to 18 (A-2) CH= CH OOH CONHC) I CHI Cool ( ( A-13) CL=CH CI(!0CO(CHri, C00H (A-17) CJl, =C CH COOCHzCHCHzooC(CHz) IC0OH
CH2=C COO(CHz) jOCOCH= CHC00H(A
-19) (A-24) 0 ■ (A-25) CHf=C Coo (CHz) J O-P-C, H5 CH (A-26) CH (＾-27) (A-20) (A- 30) (A-31) (A-43) CHs CH= tut Coo (CHi) JOH (A-46) (A-38) (A-40) (A-41) (A-47) (A-48 ) coz=c C)1.01( 0NHCH C11,OH (8-52) (A-53) (A-56) CL=C C0NHCOO(CL) ,OH OH CH,=C C00(C)1f)icOO (clf, 01) The amount contained as the copolymer component containing the polar group in the total polymer components in the macromonomer (MA) is preferably 0.5 to 100 parts by weight per 100 parts by weight of the total polymer components. It is 50 parts by weight, more preferably 1 to 40 parts by weight.

When the monofunctional macromonomer composed of these polar group-containing random copolymers is contained in the resin [A] as a copolymerization component, the polar groups contained in all the graft parts in the resin [A] It is preferable that the total amount of the components is 0.1 to 10 parts by weight per 100 parts by weight of all polymer components in the resin [A].

More preferably -COOHP! E, -5(hH group and -Poll(.

When containing an acidic group selected from the group, the resin CAJ
Among them, the total amount present in the graft portion is 0.1 to 5% by weight.

The polymer component in the macromonomer (MA) may include other polymer components other than these, for example, monomers corresponding to other repeating units that can be polymerized include acrylonitrile, methacrylonitrile, acrylamides,
Methacrylamides, styrene and its derivatives (e.g. vinyltoluene, chlorostyrene, dichlorostyrene,
Bromostyrene, hydroxymethylstyrene, N, N-
dimethylaminomethylstyrene, etc.), heterocyclic vinyls (
Examples include vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylvirasol, vinyldioxane, vinyloxazine, etc.).

When these other monomers are contained, it is preferably 1 to 20 parts by weight per 100 parts by weight of the total polymer component of the macromonomer (MA).

The macromonomer provided in the present invention is a random polymer main chain consisting of at least a repeating unit represented by the general formula (Ila) and/or (IIb) and a repeating unit containing a specific polar group, as described above. has a chemical structure in which a polymerizable double bond group represented by general formula (1) is directly bonded to only one end of the bonding group or bonded to one end thereof by an arbitrary linking group. 2 (I) component and formula (Ila
) or (Ilb) component or a polar group-containing component, carbon-carbon bonds (-multiple bonds or double bonds), carbon-heteroatom bonds (heteroatoms include, for example, oxygen atoms, (sulfur atom, nitrogen atom, silicon atom, etc.), and any combination of atomic groups of heteroatom-heteroatom bonds.

[R1□, R1, is a hydrogen atom, a halogen atom (for example,
fluorine atom, chlorine atom, bromine atom, etc.), hydroxol group, alkyl group (e.g. methyl group, ethyl group,
a hydrogen atom, a hydrogen atom, a hydrocarbon group having the same content as Q in the above formula (I[a)], )■4 R14 A single element selected from atomic groups such as represents a linking group or two or more linking groups composed of an arbitrary combination.

The weight average molecular weight of the macromonomer (MA) is 2X10'
Exceeding this is not preferable because the copolymerizability with the monomer decreases. On the other hand, if the weight average molecular weight is too small, the effect of improving the electrophotographic properties of the photosensitive layer will be small;
It is preferable that it is 0' or more.

The macromonomer (MA) used in the present invention can be produced by conventionally known synthetic methods. in particular,
Terminals obtained by radical polymerization using a polymerization initiator and/or chain transfer agent containing a reactive group such as a carboxyl group, a carboxyhalide group, a hydroxyl group, an amino group, a halogen atom, or an epoxy group in the molecule. It is synthesized by a method such as a radical polymerization method in which a reactive group-bonded oligomer is reacted with various reagents to form a macromonomer.

Specifically, P, Dreyfuss & R, P, Qu
irk, Encycl.

PolytSci, [ing,,l, 551 (19
87), P, F, Re+*pp.

E, Franta SAdu, Polym, Sci.
58.1 (1984), Yuji Yogami, Chemical Industry, details, 5
6 (1987), Yuya Yamashita, Polymer, ■, 988 (19
82), Yobe Kobayashi, Polymers, Dishes, Hiroshi Ito-1 Polymer Processing, ■, 262 (1986), Yobe Higashi, Takashi Tsuda, Functional Materials, Tangon No. 10.5, etc. review and references thereto. It can be synthesized according to methods described in literature, patents, etc.

However, since the macromonomer (MA) of the present invention contains the polar group as a constituent of its repeating unit, it is synthesized with the following considerations in mind, for example.

One method is, for example, as shown in reaction formula (1), using a monomer containing the acidic group in the form of a protected functional group, and carrying out radical polymerization and terminal reactive group formation using the above method. This is to be introduced.

Reaction formula (1) Protecting group for nee C0OH; e.g. -C(C6H5)
3. The polar groups randomly contained in the macromonomer (MA) provided in the present invention (S (hH group, -POJz group, hydrolysis H deprotection reaction (e.g. hydrolysis reaction, hydrolysis reaction, Oxidative decomposition reactions, etc.) can be carried out by conventionally known methods.Specifically, J, F.

W. McOmie, “Protective
Gvoups in Organic Chem
istry, Plenus Press (197
3 years), T., W., Greene.

”Protective Gvoups in Org
anic 5ynthesis"John Wiley
& 5ous (1981), Ryohei Oda's "Polymer Fine Chemicals" Kodansha (1976), Yoshiyu Iwakura,
Keisuke Kurita "Reactive Polymer" Kodansha (1977), G.
Berner et al s J, Radiat.
ion Curing, 1986, No. IO, P.
lo, JP-A-62-212669, JP-A-6228
No. 6064, JP-A-62-210475, JP-A-62
It can be synthesized using the methods described in Japanese Patent Application No. 195684, Japanese Patent Application Laid-open No. 62-258476, Japanese Patent Application Publication No. 63-260439, Japanese Patent Application No. 62-220510, Japanese Patent Application No. 62-226692, etc.

As another method, for example, as shown in reaction formula (n), after synthesizing an oligomer as described above, a "specific reactive group" bonded to one end of the oligomer and a This is a synthesis method that takes advantage of the difference in reactivity with the polar group and reacts it with a reagent containing a polymerizable double bonding group that reacts only with "specific reactivity."

Reaction formula (n) CH.

Table A shows specific examples of combinations of specific functional groups in Keyaki shown in Reaction Formula (n) as follows. However, the present invention is not limited thereto, and the important thing is that macromonomerization can be achieved without protecting the polar groups in the oligomer by utilizing the reaction selectivity in ordinary organic chemical reactions. It would be good if it were done.

Part 8 C00Q, C00CII co,
As the chain transfer side that can be used in the onC section, for example, the polar group or a mercapto compound containing a substituent that can be later induced into the polar group (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid) ,3
-Mercaptopro and onic acid, 3-mercaptoacetic acid, N-
(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-(N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-(N-(2-mercaptoethyl)amine)propionic acid, N(3-mercapto propionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptobutanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propatol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mecarbutoimidazole, 2-mercapto-3-
pyridinol, etc.) or disulfide compounds which are oxidized products of these mercapto compounds, or iodized alkyl compounds containing the above polar groups or substituents (e.g. iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, -iodopropanesulfonic acid, etc.). Preferred are mercapto compounds.

Specific reactive group-containing polymerization initiators that can be used include, for example, 2.2'-azobis(2-cyatuburobanol), 2.2'-azobis(2-cyanobentanol), 4.4 '-Azobis (4-Shiano Valerian MI)
, 4.4'-azobis(4-cyanovaleric acid chloride)
, 2,2'-azobis[2-(5-methyl-2-imidapurin-2-yl)propane], 2,2'-azobis(
2-(2-imidacillin-2-yl)propane), 2.
2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane], 2'-azobis(2-(1-(2-hydroxyethyl)-2-imidacylin-2 -yl]propane), 2,2'-azobis[
2-methyl-N-(2-hydroxyethyl)-propionamide] or derivatives thereof.

The amount of these chain transfer agents or polymerization initiators is 0.1 to 15% by weight, preferably 0.5 to 10% by weight, based on 100 parts by weight of the total monomers.

Specific examples of the macromonomer (MA) of the present invention include the following compounds. However, the scope of the present invention is not limited to these. In addition, on each side below, b represents -H or CH3, and d represents -
H1~CH, or -CHzCOOCHr, R is -
C,,)ILy++I (n represents an integer from 1 to 18)
, -Br, -CH5, -COC)13 or -COOC
H3), Gen, -CN, -0COCHs,
-CONHz or -cans, 112 is -CI,
-Br, -CN or -○CHz, e is 2 to 1
represents an integer of 8, f represents an integer of 2 to 12, and g represents an integer of 2 to 12.
Indicates an integer of 4.

(MA-1) (MA-5) (MA-2) (MA-6) H (MA-3) (MA-7) (MA-4) (MA-9) (MA (Mon A (A) MA (MA 0OR COO(CHz) -08 H (MA-14) (MA-15) (A-19) (MA-22) Rate Coo(CH toco(CH2), COOH(MA
-23) b (MA-26) (MA-24) (MA-25) Umbrella-Coo (CH, 0) f On the other hand, the monomer copolymerized with the macromonomer (MA) described above has the general formula (I [Indicated by parentheses. In formula (I[l), CI and Ct may be the same or different from each other and represent the same content as 81 and a2 in formula (1), and X2 is represented by formula (
xl in I[a) and Q2 each represent the same content as 01 in formula (I[a)].

In the resin of the present invention, the composition ratio of the copolymerization component having a macromonomer (MA) as a repeating unit and the copolymerization component having a repeating unit of a monomer represented by formula -1 (I[l) is preferably The weight composition ratio is 5-70/95-30, more preferably 10-60/90-40.

Further, it is preferable that the main chain of the polymer does not contain a copolymer component containing polar groups such as -POsH* group, -5O3H group, -COOHM, and -PO3R1 group.

Further, the resin [A] of the present invention may contain monomers other than these as further copolymerization components together with the above-mentioned macromonomer (MA) and the monomer of general formula (III).

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

However, the amount of these other monomers other than the macromonomer (MA) and the monomer of formula (III) is 20% by weight in the copolymer.
It never exceeds.

In the graft copolymer of the present invention, the macromonomer (
When the copolymerization component corresponding to MA) is 1% by weight or less,
If the amount exceeds 80% by weight, the copolymerization with the polymer of general formula (III) will not proceed sufficiently, resulting in a non-desired graft copolymer. This is not preferable because a polymer consisting only of the monomer of general formula (m) or other monomers is formed. Furthermore, when these resins are used for dispersion, aggregation with the photoconductor occurs.

Furthermore, the resin [A] contains a -PChHz group, - 3o31 (group, and -
It may also be a copolymer (resin (A')) formed by bonding at least one type of acid pole group selected from COOH groups, -OH groups, and -P-R groups. Also copolymer [A]
and [A'] may be used together, where L.

It represents the content of H as in the above-mentioned OH group, -P-R, group in the gold component. Further, the polar group has a chemical structure in which it is directly bonded to one end of the polymer main chain or bonded via an arbitrary linking group.

Bonding groups include carbon-carbon bonds (-double bonds or double bonds), carbon-hetero atom bonds (hetero atoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), and hetero atoms-hetero atoms. 11m is composed of any combination of atomic groups of atomic bonds. For example, +C→-1-(CH=CH→, R1
Shizuku-C---N ---COO--5o□ --CON
−R2゜
Rz.

(Ls-Rz. each has the same contents as +1+z to R14), etc., is a linking group composed of a single atomic group or a combination of two or more.

In the resin [A] used in the present invention, in order to synthesize the resin [A'] in which the polar group is bonded to the terminal of the polymer main chain, at least the macromonomer (MA) described above and the general formula ( This can be achieved by concurrently using a polymerization initiator or chain transfer agent containing the polar group or a specific reactive group that can be derived therefrom in the molecule during the polymerization reaction with the monomer represented by I[l).

Specifically, it can be obtained in the same manner as the method for oligomers bonded with a reactive group at one end as described above in the synthesis of macromonomers.

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

On the other hand, in resin (B), the weight average molecular weight is 3 x 104 ~
I XIO', preferably 5X10' to 5X10'.

The proportion of the monofunctional macromonomer comprising the A-B type bronc copolymer component in the polymer is preferably as follows:
The content is 1 to 60% by weight, more preferably 5 to 50% by weight. Furthermore, the proportion of the polymer component represented by general formula (V) is preferably 40 to 99% by weight, more preferably 50 to 95% by weight.

The glass transition point of the resin [B] is preferably O″C~11
The temperature is more preferably 20°C to 90°C than 0°C.

If the molecular weight of the binder resin [B] is smaller than 3 x 10', the film strength cannot be maintained sufficiently, while if the molecular weight is larger than 1 x 106, the dispersibility decreases, the film smoothness deteriorates, and the quality of the copied image deteriorates. The image quality (particularly the reproducibility of fine lines and characters deteriorates) deteriorates, and furthermore, when used as an offset master, background stains become significant.

Furthermore, if the macromonomer content in the binder resin [B] is less than 1% by weight, the electrophotographic properties (especially dark decay rate, photosensitivity) will decrease, and the electrophotographic properties will fluctuate under environmental conditions, especially near infrared. ~In combination with an infrared spectral sensitizing dye,
growing. This is thought to be due to the fact that the amount of the macromonomer that becomes 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, when the macromonomer content exceeds 60% by weight,
The copolymerizability of the macromonomer according to the present invention with monomers corresponding to other copolymerization components is insufficient, and sufficient electrophotographic properties cannot be obtained even when used as a binder resin.

Next, preferred embodiments of the resin [B] will be described below.

The monofunctional macromonomer (?lB) used in the resin [B] of the present invention will be explained in more detail.

The acidic groups contained in the components constituting the A-block of the macromonomer (MB) include -po3n, group, -C
OOH group, -5osn, phenolic OH group, -P-
Examples include an OH group (R represents the same content as R) or a ring R4 acid anhydride-containing group, preferably a -COOH group, a -5OsH group, a phenolic OH group, or a -P-OH group.
It is the basis.

In the case of R1-P-OH group, specifically, the same content as explained for resin [A] is expressed.

Furthermore, specific examples of the polymerization component containing the above-mentioned specific acidic group include those similar to those of the above-mentioned resin [A].

Examples of the phenolic OH group include methacrylic 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, silocpentane-1,2-dicarboxylic anhydride ring, and siloxhexane-1,2-dicarboxylic anhydride ring. monocycle, soloxhexene-1,2-dicarboxylic acid anhydride ring, 2,3-bicycloC2,2゜2]octanedicarboxylic acid anhydride ring, and the like. Atom, alkyl group 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.).

Two or more types of polymerization components containing specific acidic groups as described above may be contained in the block, and in this case, the two or more types of acidic group-containing components are randomly copolymerized or block copolymerized in the block. It may be contained in any mode of polymerization.

In addition, a component not containing the acidic group may be included in the A block, and examples of the component include the general formula (I
Examples include components represented by V).

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

Next, the polymerization components constituting the B block component in the monofunctional macromonomer of the graft copolymer will be explained in detail.

In the present invention, at least a repeating unit represented by the general formula (IV) is included as a component constituting the B-block.

In the general formula (TV), X is -coo-, -oc.

'(CH2舅-oco-1CCH2aroundCOO-(Zego J
, represents an integer from 1 to 3), -O--SO□--〇〇-13R23 CON--5ozs-1-CON)ICOO-, (:0
N)IcOII)l- or Here, RZ3 is a hydrogen atom, and preferable hydrocarbon groups include an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group) group, heptyl group, hexyl group, octyl group, dedyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group , 3-bromopropyl group, etc.), optionally substituted alkenyl groups having 4 to 18 carbon atoms (e.g., 2-methyl-1-propenyl group, 2-butenyl L2-pentenyl group, 3-methyl-2-pentenyl group) , ■-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl &, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group) , 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorohensyl group, fromohensyl group, methylhensyl group, ethylhensyl group, methoxybenzyl group, dimethylhensyl group,
dimethoxyhensyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2cyclohexylethyl group, 2-cyclopentylethyl group, etc.), or a substituted alicyclic group having 6 to 12 carbon atoms. Aromatic groups (e.g. phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxy Phenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobusylylamide phenyl group, etc.).

R2+ represents a hydrocarbon group, and preferred specific examples thereof are the same as those explained for Ruff,
R11 represents a hydrogen atom or a hydrocarbon group.

It may have. Examples of substituents include halogen atoms (e.g., chlorine atom, bromine atom, etc.), alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, propioxy group, butoxy group, etc.).

d and d2 may be the same or different from each other,
Preferably a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), -COO-R24 or -COO via hydrocarbon
-Rza (Rza represents a hydrogen atom or an alkyl group, alkenyl group, aralkyl group, alicyclic group, or aryl group having 1 to 1 carbon atoms, which may be substituted, specifically, the above-mentioned represents the same content as that described for R23).

Examples of the hydrocarbon in 1COO-Rza via the hydrocarbon include a methylene group, an ethylene group, a propylene group, and the like.

More preferably, in the general formula (rV), x4 is CO
O--0CO--CHzOCO-1-CHzCOO-1
-〇 May be the same or different from each other, hydrogen atom, methyl group, -COORza or -CHzCOORza (Rz
a is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, hex
) represents (L/group, etc.), and even more preferably, one of dis dz represents a hydrogen atom.

In the B block constituted separately from the A block consisting of a polymerization component containing the above-mentioned specific acidic group, the above-mentioned formula (
Two or more types of repeating units represented by IV) may be contained, and furthermore, other polymeric components other than these may be contained. When two or more types of polymerization components are contained in the B block that does not contain an acidic group, the copolymerization components are contained in either random copolymerization or block copolymerization in the B block. However, it is preferable that they be included randomly.

Other polymeric components that may be contained in other blocks together with the polymeric component selected from the repeating units represented by formula (IV) described above may be any component that copolymerizes with these components.

As a polymer component contained in the 11B-block, examples of monomers corresponding to other repeating units that can be copolymerized with the polymer component represented by formula (TV) include acrylonitrile, methacryl b-nitrile, and heterocyclic vinyl. II (
Examples include vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.). These other monomers make up the total polymer component 10 of the B-block.
It is used in an amount not exceeding 20 parts by weight out of 0 parts by weight. Further, it is preferable that the B block does not contain a polymer component containing a polar group, which is a constituent component of the A-block.

Next, in the macromonomer (MB) of the present invention, the A-block consisting of the polar group-containing component described above and the B-block consisting of the polymer component represented by general formula (IV) are connected in an A-B type. Also, the polymerizable double bond group connected to the other end of the B-block connected to the A-block will be explained.

Specifically, a polymerizable double bond group represented by the following general formula (Vl) may be mentioned.

General formula (Vl) In formula (Vl), X represents the same content as x4 in formula (IV).

dl and d may be different from each other and represent the same content as dls dz in formula (IV).

That is, more specifically, the polymerizable double bond group represented by the general formula (Vl) is cnz=co-c-.

0=C-O- O=C-O I-C X, - Examples include CH8.CIlCIIzhO-C-.

The macromonomer (MB) provided in the present invention has a polymerizable double bond group represented by the general formula (Vl) directly bonded to one end of the B-block as described above, or
It has a chemical structure bonded with an arbitrary linking group. Linking groups include carbon-carbon bonds (-double bonds or double bonds), carbon-heteroatom bonds (heteroatoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), heteroatoms - It is composed of any combination of atomic groups of heteroatom bonds.

ZS, specifically, a simple bond or -tC [R23
, zh R1 & represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (e.g., a methyl group, an ethyl group, a propyl group, etc.), - (CIl, CH)-1R1? -COO--C--5Oz-2-CON-1-sotN
-1-NHCOORt, R intention.

A single linkage selected from an atomic group such as 1tt NHCONH-1-5i- (Rzt and Rzs each represent a hydrogen atom, a hydrocarbon group, etc. representing the same content as llz+ in the formula (R/)) Represents a linking group composed of a group or an arbitrary combination.

The weight average molecular weight of macromonomer (MB) is 2 x 104
If it exceeds l
It is preferable that it is l0' or more.

The macromonomer (MB) of the present invention can be produced by a conventionally known synthesis method.6 For example, in a monomer corresponding to the specific acidic group-containing polymer component,
The acidic group is preprotected as a functional group, and an ionic polymerization reaction with an organometallic compound (for example, alkyl lithiums, lithium diisoproamides, alkyl magnesium halides, etc.) or a hydrogen iodide/iodine system, or a porphyrin metal complex is performed. After synthesizing an A-B bronc copolymer using a known so-called living polymerization reaction such as a photopolymerization reaction using a catalyst or a group transfer polymerization reaction, various reagents are reacted at the ends of this living polymer to form a polymerizable double polymer. Introducing a bonding group.

Thereafter, the functional group with the protected acidic group is deprotected by hydrolysis reaction, hydrogenolysis reaction, oxidative decomposition reaction, photolysis reaction, etc. to form an acidic group. One example is shown in reaction scheme (1) below.

For example, P. Lutz, P. Masson et a.
Polym, BullLl+ 79 (1984
)+ B, C, Andersor++ G, D, And
rews etal, Macromolecules
+ 14.1601 (1981), K. Hatada
K, Ute, et al., Polym, J., 1
7.977 (1985), 181037 (198
6), Hiroshi Miji-1 Ko Hatada-1 Polymer processing, plate, 3
66 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymer Papers, 46.189 (1989), M, Kuroki
, T., Aida, J. Am.

Chem, Sic, 109.4737 (1987)
, Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, Tsumu, 300 (
(1985), D. Y., Sogoh W., and R. Hertl.
er et al+ Macromolecules+
20+ 1473 (1987), etc., living polymers can be easily synthesized. Moreover, as a method for introducing a polymerizable double bond group to the terminal of the living polymer, the macromonomer of the present invention can be easily obtained by following a conventionally known synthesis method of macromonomer method.

Specifically, P, Dreyfuss & R, P, Qu
irk+ encycle.

Poplym, Sci, Eng,, 7, 5
51 (1987), P.F. Rempp.

E. Franta Adu, Polym.
Sci, 58. 1 (1984), V.

Percec, Appl, Po1yv+, Sc
i, 2fJ51.95 (1984), R.

Asami, M., TakaRi, Makvam
ol, Chew, 5upp1. 12163
(1985), P. Rempp, et al., Mak.
vamol, Chew.

5upp1.8, 3 (1984), Yuji Yogami, Kagaku Kogyo, Kyou56 (1987), Yuya Yamashita, Polymer,
3L 988 (1982) Shibe Kobayashi, Kobunshi, Co., Ltd.
625 (1981), Toshinobu Higashimura, Japan Adhesive Association Journal 1
8.536 (1982), Hiroshi Ito-1 Polymer Processing, Peeling, 262 (1986), Takashi Higashi, Takashi Tsuda, Functional Materials, 1987 110.5, etc. Reviews and examples of literature and patents, etc. It can be synthesized according to the method of

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, there are various descriptions in the above-mentioned cited documents, and furthermore, Giyu Iwakura, Keisuke Kurita, "Reactive Polymer" ■ Kodansha (1977), TJ, Greene'Protective G
roups in Organic 5ynthesi
sJJohn Wiley & 5ons (1981
), J., F., W., McOmie.

rProtective Groups in Org
anic Organic Chesistry”, P
This can be carried out by appropriately selecting a method described in detail in a review article such as Lenu++ Press, (1973).

As another method for synthesizing the AB type block copolymer (A), it can also be synthesized by a photoiniferter polymerization method using a dithiocarbament compound as an initiator. For example,
Takayuki Otsu, Polymer, 37.248 (1988), After Inspection-1 Takashi Otsu-1 Polym, Rep, Jap.

Gong, 3508 (1988), Japanese Patent Publication No. 1983-111
It was synthesized according to the synthesis method described in JP-A-6426619, etc.

The macromonomer of the present invention can be obtained using the macromonomer synthesis method described above.

The macromonomer (MB) of the present invention can be specifically exemplified by the following compounds. However, the scope of the present invention is not limited to these.

On each side below, Qo, Q! and Q, are each -Hl
-CHs or -CHzCOOCHs, Q4 is -H
or -CH3, R31 is -C*Hxa++ (n
represents an integer from 1 to 18), -(CHzhCJs (m
represents an integer of 1 to 3), R3Z represents CQH2Q4 (q represents an integer of 1 to 8)
or (CI(z)-CJs, where T is OH.

COOH O3H I P-OH or P-OCH3 is shown and T2 is OH OH COOH.

5ChH.

P-OH again OH teeth Indicates P-OCH3, ``to 2・denotes an integer of 12, OH represents an integer from 2 to 6.

(gate B (-B-2) COOIh+ 0OH (-B-3) COOR.

Cool( (MB Hz 0OR3 COOH (MB-8) (MB-9) (MB-4) mouth.

(MB-5) (Gate B-6) (MB (-B (gate B C1l.

0OR31 Cool T.

0OR31 Coo(CH,)-i-COOH COOR1+ Coo(CH2 and IT2 (MB-13) (MB-14) COOR31 COOR (MB CI'13 (?fB-16) Copolymerizes with the above-mentioned macromonomer (MB) The monomers are preferably those represented by general formula (V).

In formula (V), dl, d4, X, and Lx are represented by formula (I
V) dl, dl, X4 and I? Each represents the same content as z+. Particularly preferably, d represents a hydrogen atom, d4 represents methyl, and X represents -coo-.

In the resin (B) of the present invention, the A pronk/B block ratio is preferably 1 to 30/99 to 70 (weight ratio), and the amount of the acidic group-containing component in the resin (B) is 0. .1 to 20% by weight, particularly preferably 0.5 to 10% by weight, and a copolymerization component having macromonomer (MB) as a repeating unit and a monomer represented by general formula (V). The composition ratio of the copolymer components used as repeating units is preferably 1 to 60/99 to 40 (weight composition ratio), more preferably 5 to 50/95 to 50 (weight composition ratio).

In addition, the main chain of the polymer contains -POsHz groups, -5o,! f
group, COOR group, -OR group, -5H group and -POJaH
Those containing no copolymerization component containing a polar group are preferred.

Binder resins [A] and [B] of the present invention can be produced by copolymerizing corresponding monofunctional polymerizable compounds in desired proportions. As the polymerization method, it can be produced by using known methods such as solution polymerization, suspension polymerization, precipitation polymerization, and emulsion polymerization. For example, in solution polymerization, a copolymer solution can be obtained by adding monomers at a predetermined ratio in a solvent such as benzene or toluene, and polymerizing with an azobis compound, a peroxide compound, or a radical polymerization initiator. A desired copolymer can be obtained by drying it or adding it to a poor solvent. In suspension polymerization, monomers are suspended in the presence of a dispersant such as polyvinyl alcohol or polyvinylpyrrolidone, and copolymerized in the presence of a radical polymerization initiator to obtain a copolymer.

Furthermore, in the binder resin of the present invention, synthesis of the low molecular weight resin [A] and the high molecular weight resin [B], which is a preferred embodiment, can be carried out using the type of initiator (
(the half-life differs depending on the temperature), the amount of initiator, the polymerization initiation temperature, or the combined use of a chain transfer agent can be easily adjusted.

As the binder resin of the photoconductive layer of the present invention, binder resins of the present invention and those conventionally used as binder resins for electrophotography can also be used in combination. For example, Harumi Miyahara, Hidehiko Takei, [Imaging J1978 N1
18 9-12, Ryuji Kurita, Tsugube Ishiwatari, “Polymer J,
17.278-284 (1968) and other review articles cited.

Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and its derivatives, Polymers and copolymers, butadiene-styrene copolymers, isoprene-styrene copolymers, butadiene-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile copolymers, alkyl vinyl ether copolymers, acrylics Acid ester polymers and copolymers, methacrylic ester polymers and copolymers, styrene-acrylic ester copolymers, styrene-methacrylic ester copolymers,
Itaconic acid diester polymers and copolymers, maleic anhydride copolymers, acrylamide copolymers, methacrylamide copolymers, hydroxyl-modified silicone resins, polycarbonate resins, ketone resins, amide resins, hydroxyl- and carboxyl-modified polyester resins, Butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylate ester copolymer, cyclized rubber-acrylate ester copolymer, copolymer containing a heterocycle containing no nitrogen atom (for example, furan as a heterocycle) ring, tetrahydrofuran ring,
(thiophene ring, dioxane ring, dioxolane ring, lactone ring, benzofuran ring, benzothiophene ring, 13-dioxetane ring, etc.), epoxy resins, and the like.

However, it is preferable to use these resins in an amount not exceeding 30% by weight of the total binder resin amount.

The ratio of resin [A] and [B] to be used is not particularly limited, but the resin [A]/[B) ratio is 5 to 50/95 to 50, particularly 10 to 40/90 to 60 (weight ratio). It is preferable.

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

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

In the present invention, various dyes can be used in combination as spectral sensitizers, if necessary. For example, Harumi Miyamoto, Hidehiko Takei, Imaging 1973 (Nct8) p. 12, C
, J. Young et al., RCA Review 15 4
69 (1954).

Wataru Kiyota, Institute of Electrical Communication Engineers paper 1, Kokudo (隘2) 97
(1980), Yuji Harasaki et al., Industrial Chemistry Journal 78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan, 2.
08 (1972), carbonium dyes, diphenylmethane dyes, triphenylmethane dyes,
Examples include xanthine dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain metal), and the like.

More specifically, examples using mainly carbonium dyes, triphenylmethane dyes, xanthine dyes, and phthalein dyes include Japanese Patent Publication No. 51452 and Japanese Patent Publication No. 5
0-90334, JP 50-114227, JP 53-39130, JP 5382353, 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 rhodacyanine dyes include F, M
,Harmmar rThe Cyanine Dye
s andRelated Compour+ds J
It is possible to use the pigments described in et al., and more specifically,
U.S. Patent No. 3,047,384, U.S. Patent No. 3.11
No. 0,591, U.S. Patent No. 3,121.008, U.S. Patent No. 3,125,447, U.S. Patent No. 3.128,
No. 179, U.S. Patent No. 3,132,942, U.S. Patent No. 3,622,317, British Patent No. 1,226,89
No. 2, British Patent No. 1,309,274, British Patent No. 1
, No. 405,898, Japanese Patent Publication No. 48-7814, Japanese Patent Publication No. 55-18892, and the like.

Furthermore, as a polymethine dye that spectrally sensitizes the near-infrared to infrared light region with a long wavelength of 700 nm or more, JP-A-47840, JP-A-47-44180, and JP-B-Sho 51-41061 are used.
No., JP-A-49-5034, JP-A-49-45122
No., JP-A-5746245, JP-A-56-35141
No., JP-A-57-157254, JP-A-61-260
No. 44, JP-A No. 61-27551, U.S. Patent No. 3.6
No. 19.154, U.S. Pat. No. 4,175,956,'
Research Disclosure 1982
216, pp. 117-118. The photoreceptor of the present invention is excellent in that its performance does not easily vary depending on the sensitizing dye, even when various sensitizing dyes are used together. Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers, such as chemical sensitizers, can be used in combination.
Example (Floor 8) Electron-accepting compounds cited in the review, such as page 12 (
For example, halogens, benzoquinone, chloranil, acid anhydrides, organic carboxylic acids, etc.), Hiroshi Komon et al., "Recent Development and Practical Application of Photoconductive Materials and Photoreceptors" Chapters 4 to 6 2 Japanese Scientific Information ■ Examples include polyarylalkane compounds, hindered phenol compounds, and p-phenylenediamine compounds cited in the review published by Shuppan Department (1986).

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

The thickness of the photoconductive layer is between 1 and 100μ, in particular between 10 and 50μ.
is suitable.

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, birapurin dyes, triphenylmethane dyes, and the like.

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

Typical resins used to form the insulating layer or charge transport layer include polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl acetate copolymer resin, Thermoplastic resins and curable resins such as polyacrylic 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. Paper with a water-resistant adhesive layer on the surface of the body, paper with at least one precoat layer as required on the surface layer of the support, and paper with conductive plastic on which AI or the like is deposited. Laminated materials can be used.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, “Child Photography”, 14 (No. 1), 22-11
(1975), Hiroyuki Moriga, “Introductory Chemistry of Special Papers” Kobunshi Publishing (1975), M.F., Hoover.
J.

Macromol, Sci, ChelW, A-4
(6), pages 1327 to 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.

Production example 1 of macromonomer (?IA): 90 g of MM-1 ethyl methacrylate, 2-hydroxyethyl methacrylate-Hog, 5 g of thioglycol #I, and 20 g of toluene.
0g of the mixed solution was heated to a temperature of 75% while stirring under a nitrogen stream.
Warmed to ℃. 1.0 g of 2,2'-azobisisobutyronitrile (abbreviated as A, 1.B, N) was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N,N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to this reaction solution, and the temperature was increased to 100.
The mixture was stirred at 'C for 12 hours. After cooling, this reaction solution was
It was reprecipitated into hexane 21 to obtain 82 g of white powder. The weight average molecular weight of the polymer was 3.8 XIO'.

(MM-1) Production example 2 of CH yumacromonomer (MA): MM-2 A mixed solution of 90 g of butyl methacrylate, 10 g of methacrylic #, 4 g of 2-mercaptoethanol, and 200 g of tetrahydrofuran was heated to a temperature of 70°C under a nitrogen stream. did. A,
1.2 g of 1B and N were added and reacted for 8 hours.

Next, this reaction solution was cooled in a water bath to a temperature of 20°C, 10.2 g of triethylamine was added, and 14.5 g of methacrylic acid chloride was added dropwise with stirring at a temperature of 25°C or less. After the dropwise addition, the mixture was further stirred for 1 hour.

Thereafter, 0.5 g of t-butylhydroquinone was added and the mixture was heated to 60°C and stirred for 4 hours. After cooling, the mixture was added dropwise to 1 liter of water with stirring for about 10 minutes), stirred as it was for 1 hour, left to stand, and then the water was removed by decantation. After two more washes with water, 1 ml of tetrahydrofuran
00-, petroleum ether 2! It sank back inside. The precipitate was collected by decantation and dried under reduced pressure. The yield of the obtained viscous material was 65 g, and the weight average molecular weight was 5.6.
It was x 103.

(MM-2) COOC4H9C0OH Production Example 3 of Macromonomer (MA): MM-3 95 g of benzyl methacrylate 1 5 g of 2-phosphonoethyl methacrylate 1 A mixture of 4 g of 2-aminoethyl mercaptan and 200 g of tetrahydrofuran was heated at a temperature of 70'' with stirring under a nitrogen stream. It was heated to C.

A.1. B, N, 1.5g were added and reacted for 4 hours, and A, 1. 0.5 g of B and N were added and reacted for 4 hours. Next, this reaction solution was cooled to a temperature of 20°C, 10 g of acrylic anhydride was added, and the mixture was stirred at a temperature of 20 to 25°C for 1 hour.

Next, add 1.0 g of butylhytroquinone and bring to a temperature of 50.
Stir at ~60°C for 4 hours. After cooling, the reaction mixture was added dropwise to water 1β over about 10 minutes while stirring, and after stirring for 1 hour, it was allowed to stand, and the water was removed by decantation. After repeating the washing with water two more times, it was dissolved in 100 d of tetrahydrofuran and reprecipitated in 21 d of petroleum ether. The precipitate was collected by decantation and dried under reduced pressure.

The yield of the viscous material obtained was 70g, and the weight average molecular weight was 7.4.
It was XIO'.

(MM-3) Production example 4 of macromonomer (MA): 90 g of MM-42-chlorophenyl methacrylate, 10 g of the monomer of the following structure (1), 4 g of thioglycolic acid, and 200 g of toluene.
The mixed solution of g was heated to a temperature of 70°C under a nitrogen stream.

A.1. 1.5 g of B and N were added and reacted for 5 hours, and then A, 1. 0.5 g of B and N were added and reacted for 4 hours.

Next, 12.4 g of glycidyl methacrylate, )i, 1
1.0 g of 1-dimethyldodecylamine and 1.5 g of butylhydroquinone were added and reacted at a temperature of 110'C for 8 hours. After cooling, the reaction mixture was added to a solution of 3 g of p-)luenesulfonic acid and 1 O (lad!) of a 90 vol.
Stir for hours. The above mixture was reprecipitated in 2f of a mixed solution of water/ethanol ((1/3) volume ratio), and the precipitate was collected by decantation.The precipitate was dissolved in tetrahydrofuran 200111 and n-hexane 21. was reprecipitated to obtain 58 g of powder.The weight average molecular weight was 7.6 x 103.
Met.

Monomer (1) CH3 CII2=CCL COO5i-CatlJt) CH3 (MM-4) CH.

Production example 5 of macromonomer (MA): MM-52,6-
A mixed solution of 95 g of cyclophenyl methacrylate, 5 g of 3(2'-nitrohensyloxysulfonyl)propyl methacrylate, 150 g of toluene and 50 g of isopropyl alcohol was heated to a temperature of 80° C. under a nitrogen stream. 2.2'-azobis(2-Schiff/valeric acid) (abbreviation:
5.0 g of A, C, V,) was added and reacted for 5 hours, and further 1.0 g of A, C, V, was added and reacted for 4 hours. After cooling, methanol 2! The reaction product was reprecipitated in the solution, and the powder was collected by filtration and dried under reduced pressure.

The above powder 50g glycidyl methacrylate 14g 1N,
A mixture of 0.6 g of N-dimethyltosylamine, 1.0 g of t-butylhydroquinone, and 100 g of toluene was stirred at a temperature of 110°C for 10 hours. After cooling to room temperature 80
The mixture was irradiated with light for 1 hour under stirring using a W high-pressure mercury lamp. After that, the reaction mixture was mixed with methanol 1! The powder was collected by filtration and dried under reduced pressure. The yield was 34 g and the weight average molecular weight was 7.3XIO3.

(MM-5) CH.

Production example 1 of resin [A]: A-1 Phenyl methacrylate 75g 1 macromonomer (MA
) A mixed solution of 25 g of the compound (MM-2) of Synthesis Example 2 and 100 g of toluene was heated at a temperature of 100°C under a nitrogen stream.
It was heated to A.1. Add 6g of B, N, and react for 4 hours, and then add A, 1. 3 g of B and N were added and reacted for 3 hours. The weight average molecular weight of the obtained copolymer was 8.
It was 6×10″.

(A-1) Coo(Cut) Co5OsH Resin [A] Production Example 2: A-2 70 g of 2-chlorophenyl methacrylate, 30 g of the compound (MM-1) of Synthesis Example 1 of macromonomer (MA),
β-Mercaptopro, 3.0 g of onic acid and 15 toluene
0 g of the mixed solution was heated to a temperature of 80° C. under a nitrogen stream. A.1. B.

After adding 1.0 g of N and reacting for 4 hours, A.1. B, N
, 0.5g was added for 2 hours, and then A.1. B, N, 0
．． 3 g was added and reacted for 3 hours.

The weight average molecular weight of the obtained copolymer was 8.5×10′.

(A-2) Ta. The weight average molecular weight of the obtained copolymer was 8.5×10
'Met.

(A-3) Production example 3 of resin [A]: A-3 60 g of 2-chloro-6-methylphenyl methacrylate
, compound of synthesis example 4 of macromonomer (?IA): (M
M-4) 25 g, methyl acrylate 15 g,
100g toluene and 50g in-10-pyl alcohol
The mixed solution was heated to 80° C. under a nitrogen stream. A,
Add 5g of C, C, , react for 5 hours, and then add A, C, V, ,
1 g was added and reacted for 4 hours.Production Examples 4 to 13 of Resin [A]: A-4 to A-13 Production Examples of Resin [A) 1 In the same manner as in (A-1), the following table - Each resin [A) shown in 1 was manufactured. The weight average molecular weight of each resin [A] is 6. It ranged from OXIO' to 9X10'.

Production examples 14 to 27 of resin [A]: A-14 to A-2
7 Production Example 2 of Resin [A] Each resin [A] shown in Table 2 below was produced in the same manner as in (A-2). The weight average molecular weight of each city [A] was in the range of 5 x 103 to 9 x 103. Synthesis example 1 of macromonomer (MB): (M-1) 10 g of triphenylmethyl methacrylate and 100 g of toluene
The mixed solution of g was thoroughly degassed under a nitrogen stream and heated to 20'
It was cooled to

1. Add 0.02g of 1-diphenylbutyllithium
Reacted for 0 hours.

Furthermore, a mixed solution of 90 g of ethyl methacrylate and 100 g of toluene was added to this mixed solution after sufficient degassing under a nitrogen stream, and the mixture was reacted for further 10 hours.

After this mixture was brought to 0°C, carbon dioxide gas was added at 60 d/gin.
The polymerization reaction was stopped by aerating at a flow rate of 30 minutes.

The resulting reaction solution was brought to a temperature of 25°C with stirring, and 2-
6 g of hydroxyethyl methacrylate was added, and a mixed solution of 10 g of dicyclohexylcarbodiimide, 0.2 g of 4N,N-dimethylaminopyridine, and 30 g of methylene chloride was added dropwise over 30 minutes, and the mixture was stirred for 3 hours.

After filtering out the precipitated insoluble matter, 10 d of 30% by weight hydrogen chloride/ethanol solution was added to this mixed solution and stirred for 1 hour.Next, the solvent was distilled off from the reaction mixture under reduced pressure until the total volume was reduced to half. After that, it was reprecipitated into 1 liter of petroleum ether.

The polymer obtained by collecting the precipitate and drying it under reduced pressure is -6
, 5 x 103, yield was 56 g.

(M-1) Hz Synthesis example 1 of macromonomer (MB) (M-2) 5 g of hensyl methacrylate, 0.01 g of aluminum methyl (tetraphenylporphinate) and 6 methylene chloride
0 g of the mixed solution was brought to a temperature of 30° C. under a nitrogen stream. This was irradiated with 300 W xenon lamp light from a distance of 25 cm through a glass filter, and reacted for 12 hours. After further adding 45 g of butyl methacrylate to this mixture and irradiating it with light for 8 hours, 5 g of 4-bromomethylstyrene was added to the reaction mixture and stirred for 30 minutes to stop the reaction.

Next, Pd-C was added to this reaction mixture, and a catalytic reduction reaction was carried out at a temperature of 25°C for 1 hour.

After filtering off the insoluble matter, it was reprecipitated in 500 d of petroleum ether, and the precipitate was collected and dried. The obtained polymer had a yield of 33
It was ~7X10' in g.

(M-2) Synthesis example 3 of macromonomer (MB): (M-3)4
A mixed solution of 20 g of -vinylphenyloxytrimethylsilane and 100 g of toluene was sufficiently degassed under a nitrogen stream and cooled to 0°C. 1. 0.1 g of l-diphenyl-3-methylpentyllithium was added and stirred for 6 hours. Further, a mixed solution of 80 g of 2-chloro 6-methylphenyl methacrylate and 100 g of ToJ renin was added to this mixture after sufficient degassing under a nitrogen stream, and the mixture was reacted for 8 hours. Ethylene oxide was bubbled through the reaction mixture at a flow rate of 30 d/min for 30 minutes with sufficient stirring, and the temperature was 15°C.
8 g of methacrylic acid chloride was added dropwise over 30 minutes, and the mixture was further stirred for 3 hours.

Next, 10 d of a 30% by weight hydrogen chloride ethanol solution was added to this reaction mixture, and after stirring at 25°C for 1 hour, it was reprecipitated in 11 petroleum ether, and the collected precipitate was washed twice with diethyl ether 300. and dried.

The obtained polymer had a yield of 55g? 1w 7.8XIO
'Met.

CH.

Synthesis example 4 of macromonomer (MB): (M-4) 15 g of triphenylmethyl acrylate and 100 g of toluene
The mixed solution of g was thoroughly degassed under a nitrogen stream and cooled to -20°C.

0.1 g of 5ec-butyllithium was added and reacted for 10 hours.

Next, add 85 g of styrene and 10 g of toluene to this mixed solution.
After sufficiently degassing under a nitrogen stream, 0 g of the mixed solution was added and reacted for 12 hours. After the mixture was cooled to 0°C, 8g of hensyl bromide was added and reacted for 1 hour, at a temperature of 25°C.
The reaction was continued for an additional 2 hours at C.

Add 1 part of a 30% hydrogen chloride-containing ethanol solution to this reaction mixture.
0m was added and stirred for 2 hours. After filtering off the insoluble matter, it was reprecipitated in 1 liter of n-hexane, and the precipitate was collected and dried under reduced pressure. The yield of the obtained polymer was 58g, Fiw4.5x1
It was 0+.

(M-4) CH2・C)! and heated to a temperature of 60''C.

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

Add to this 20 g of acrylic acid and 180 g of methyl ethyl ketone.
After adding g, the atmosphere was replaced with nitrogen and light was irradiated again for 10 hours.

To the resulting reaction mixture, 6 g of 2-isocyanatoethyl methacrylate was added dropwise at a temperature of 30°C over 1 hour, and the mixture was further stirred for 2 hours.

Next, the obtained reaction product was reprecipitated in 1.5 ml of hexane, collected, and dried. The obtained polymer was 68 g FIl, 16
, OXIO3.

(M-5) Synthesis Example 5 of Macro-Natsummer (MB): (M-5) A mixture of 80 g of phenyl methacrylate and 4.8 g of benzyl-N-hydroxylethyl-N-ethyl dithiocarboxylic acid was added under a nitrogen stream. Synthesis example 1 of resin [B] sealed in a container: l
:B-1) 80g of ethyl methacrylate, macromonomer resin (Bl
Synthesis Examples 10 to 20: [B-10) to [B20] Under the same polymerization conditions as in Synthesis Example 1 of resin [B], the following Table-4
A copolymer was synthesized. - of the obtained polymer are each 9
It was X10' to 2X105.

Examples 1 to 2 and Comparative Examples A to D Example 1 Resin CA] produced in Synthesis Example 8 of Resin CA-836g (
(as solid content), 34 g (as solid content) of resin (B-1) produced in Production Example 1 of resin [B], 20 g of zinc oxide
0 g, cyanine dye with the following structure (A10.018 g
, a mixture of 0.20 g of salicylic acid 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 amount of 25 g.
/ rd birch, apply with a wire bar, 110
Dry at °C for 30 seconds, then in the dark at 20 °C 65% R.
An electrophotographic light-sensitive material was produced by leaving it for 24 hours under H conditions.

Cyanine Dye [A] An electrophotographic light-sensitive material was prepared in the same manner as in Example 1, except that 6 g of cyanine dye [A] resin (A-3) was used.

Comparative Example A As a binder resin, 6 g of the following resin (R-1) and poly(ethyl methacrylate) (-1: 2.6X105):
Electrophotographic material A was produced in the same manner as in Example 1 except that 34 g of resin 7R-2) was used.

Resin (p-B Example 2 In Example 1, instead of 6 g of resin (A-8) w: 8
XIQ3C weight composition ratio] Comparative Example B Electrophotographic photosensitive material B was prepared in the same manner as in Example 1, except that 6 g of the following resin (R-3) and 34 g of the following resin (R-4) were used as the binder resin. Manufactured.

Resin [R 3] Wash) and printability (scumming, rigidity resistance, etc.) were investigated.

The above results are summarized in Table-5.

Mw: 6.5 × 103 Resin [R 4] Mw Near X10' Film properties (surface smoothness), film strength,
Electrostatic properties, imaging performance, and environmental conditions at 30°C, 380%RH
The electrostatic properties and imaging performance were investigated. Furthermore, when these photosensitive materials are used as original plates for offset masters, the photoconductive resistance to fat loss (contact angle with water of the photoconductive layer after desensitization treatment is shown in Table 5). The implementation of the evaluation items is as follows.

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

Note 2) Mechanical strength of the photoconductive layer: The surface of the photosensitive material obtained was tested with emery paper (11000) at a load of 60 g/ctl+ using Heyton-14 type surface test material (manufactured by Shinto Kagaku ■). The remaining film percentage (%) was determined from the weight loss of the irradiation layer after removing the abrasion powder and using the mechanical strength as the mechanical strength.

Note 3) Electrostatic properties: In a dark room at a temperature of 20°C and 265% RH, each photosensitive material was subjected to corona discharge at -6 kV for 20 seconds using a paper analyzer (Paper Analyzer S P-428 model manufactured by Kawaguchi Electric). After that, it was left to stand for 10 seconds, and the surface potential (■1°) at this time was measured. The potential VIQ was then left to stand in the dark for 180 seconds. The retention of potential after dark decaying for 180 seconds, that is, the dark decay retention rate (DRI?)
(χ) was calculated as (ν1../νI.)×100(%).

After the surface of the photoconductive layer is charged to -400 μm by corona discharge, it is irradiated with monochromatic light with a wavelength of 780 nm to increase the surface potential (
Find the time until V+O) attenuates to 1/lO, and calculate the exposure amount E l/It+ (erg/cffl)
Calculate.

Also, find the time until the surface potential (V+O) attenuates to 1/100, and calculate the exposure amount E l/loo (erg/
c%).

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

Next, it is charged with -5 kV and used as a light source with a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 7
80na+) on the surface of the photosensitive material.
After exposure at a pitch of 25n and a scanning speed of 330m/sec under an irradiation dose of g/cd, a copy obtained by developing and fixing using ELP-T (manufactured by Fuji Photo Film ■) as a liquid developer. Images (fogging, image quality) were visually evaluated.

Environmental conditions during imaging were 20°C, 65% RH, and 30'C80.
%RHH.

Note 5) Contact angle with water: Each photosensitive material was desensitized using a solution prepared by diluting ``fiELP-EX'' (manufactured by Fuji Photo Film) twice with distilled water. After the surface of the photoconductive layer was desensitized by passing through the photoconductive layer, a droplet of 2 μl of distilled water was placed thereon, and the contact angle with the water formed was measured using a goniometer.

Note 6) Rigidity Resistance Each photosensitive material is plate-made under the same conditions as Note 4) above to form a toner image, desensitized under the same conditions as Note 5) above, and this is used as an offset master to print 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 the image quality of the image areas (the higher the number of prints, the better the rigidity resistance). .

Comparative Examples A and B using conventionally known resins as shown in Table 5
The mechanical strength of the photoconductive layer was insufficient. The electrostatic properties of these photoreceptors are D, l'1. R was somewhat unsatisfactory, and the fluctuations became even larger under high temperature and high humidity conditions. Also, the fluctuation of El/100 from E171° was too large.

As a result, when an image is captured by a scanning exposure method using a low-power semiconductor laser beam, the image capture performance deteriorates, especially under high temperature/high temperature conditions.

In other words, limitations on the amount of light irradiation due to a low-output light source or potential attenuation of unexposed areas (image areas) during the exposure time using the scanning exposure method may cause a decrease in the image quality of the actual copied image (for example, a decrease in D, fine lines). This resulted in blurring of letters, etc.). Furthermore, when the output of the semiconductor laser light becomes low and the amount of light irradiation is restricted, the residual potential after exposure becomes an important problem, and this appears in actual imaging performance as ground blur in non-image areas. This is the electrostatic characteristic E, 71°. The smaller this value is, the more preferable it is. Comparative example A-
D is still insufficient, and even in the copied image under the actual imaging conditions, the occurrence of ground force blur was observed.

However, all of the photosensitive materials of the present invention had good electrostatic properties and good imaging properties. Furthermore, the film strength of the photosensitive layer of the photosensitive material of the present invention was improved compared to Comparative Examples A and B.

Next, when the photoreceptor after plate making is used as an offset master original plate, desensitization with a desensitization treatment liquid is as follows:
In all cases, the contact with water in the non-image area, which was free of burrs, was as small as 10 degrees or less, and was sufficiently hydrophilized. However, when printing was performed under printing conditions equivalent to those of a large-scale printing press, Comparative Examples A and B used offset master master plates made under high temperature and high humidity conditions, and the resulting image deteriorated after plate making. Therefore, the defects were reflected in the print image quality of the printed matter, resulting in insufficient printing durability. - In the case of the strength wood invention, 8,000 prints with clear image quality without background stains can be produced regardless of the environmental conditions of plate making.
I got more than one.

In addition, in the photosensitive material of the present invention, Example 2 containing a polar group at the end of the main chain in the binder resin [A] has better electrostatic properties and imaging properties than Example 1, and furthermore, The printing durability as an off-cent master master plate has been further improved.

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

Examples 3 to 22 In Example 1, 6 g of resin [A-8] and resin (B-1
) 6g each of resin [A] shown in Table 6 below instead of 34g
, resin [B] were used in an amount of 34 g each, and cyanine dye [A] was used.
] Each photosensitive material was produced in the same manner as in Example 1, except that 0.018 g of cyanine dye [B] having the following structure was used instead of 0.018 g.

Cyanine dye [B] As shown in Table 6, excellent results were obtained in the present invention.

Further, when the resin [A) contains a terminal polar group, the electrostatic properties are further improved. In addition, as an offset master original plate, it showed a printing durability of 8,000 sheets or more in all the places where it was printed.

Examples 23 to 34 In Example 1, 5 g of resin (A8) and resin (B-1)
Instead of 34g, use 6g each of the resins (All) shown in Table 7 below.
, using 34 g each of resin (B), and cyanine dye [A]
Instead of 0.018 g, a methine dye with the following structure (
C) Each photosensitive material was produced in the same manner as in Example 1 except that 0.016 g was used.

Methine dye (C1 Table-7 Each characteristic was measured in the same manner as in Example 1.

Each of the photosensitive materials of the present invention has excellent chargeability, dark charge retention, and photosensitivity, and the actual reproduced images are also produced at high temperatures (30°C).
Even under the harsh conditions of 80% RH), clear images with no soil burr were obtained.

Examples 35 to 38 As a binder resin, resin [A] 6.5 shown in Table 8 below
g and resin (B) 33.5g, zinc oxide 200g,
A mixture of Rose Bengal o, osg, bromophenol blue 0.03 g, uranine 0.02 g, maleic anhydride 0.3 g and toluene 240 g was dispersed in a ball mill for 4 hours. This was applied to conductive treated paper using a wire bar at a dry adhesion weight of 20 g/i and heated to 110°C.
An electrophotographic material was produced by heating the material for 30 seconds at 0 and then leaving it for 24 hours under conditions of 20° C. and 65% RH.

Electrostatic properties are measured values under the conditions of (30°C, 80% RH).

The photosensitive material of the present invention has chargeability, dark charge retention,
It has excellent photosensitivity, and the actual copied images can be used even at high temperatures (30'
Even under the harsh conditions of C-80% 1it (20%), clear images were obtained with no occurrence of soil blurring.

Further, when this was printed using as an original plate of an offset master, printed matter with clear image quality was obtained even at the number of prints shown in Table 10.

However, El/□ in electrostatic properties. After the surface of the photoconductive layer is charged to -400 ν by corona radiation, the surface of the photoconductive layer is irradiated with visible light at an illuminance of 2.0 lux, and the surface potential (V, .) is attenuated to 1/10. Find the time until
From this, the exposure amount E1/1° (lux/second) was calculated.

In addition, plate making of photosensitive materials is carried out using a fully automatic plate making machine ELP404ν (
A toner image was formed using ELP-T (manufactured by Fuji Photo Film ■) as a toner.

Examples 39-46 In Example 35, resin (A-'1) 6.5.
g and the following table instead of 33.5 g of resin [B-1]-
10 each resin [A]6. Each electrophotographic light-sensitive material was produced in the same manner as in Example 35, except that 34 g of Resin (B) was used.

Table 10 (Effects of the Invention) According to the present invention, an electrophotographic photoreceptor having excellent electrostatic properties and mechanical strength can be obtained regardless of changes in environmental conditions.

In addition, as an offset master original plate, it was possible to print a large number of prints with clear images without background smudge (3 others).Each measurement was performed in the same manner as in Example 35.

All of the photosensitive materials of the present invention have excellent chargeability, dark charge retention, and light intensity, and the actual reproduced images can be used under high temperature and high humidity conditions (30
Even under the harsh conditions of ℃ and 80% R + (), it produced clear images without causing any soil blurring.Furthermore, when this was used as an original plate for an offset master, more than 8,000 sheets were printed in each case. was possible.

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. Binder resin [A]; at least one polymer component represented by the following general formulas (IIa) and (IIb), -COOH group, -PO_3
There are H_2 groups, -SO_3H groups, -OH groups, and ▲mathematical formulas, chemical formulas, tables, etc.▼{R_1 is a hydrocarbon group or -OR
_2 (R_2 represents a hydrocarbon group)} The following general formula is present only at one end of each polymer component containing at least one polymer component containing at least one polar group selected from _2 (R_2 represents a hydrocarbon group). A monofunctional macromonomer (MA) with a weight average molecular weight of 2×10^4 or less, which is formed by bonding a polymerizable double bond group represented by (I), and the following general formula (III
) A copolymer having a weight average molecular weight of 1.0 x 10^3 to 2.0 x 10^4 and consisting of at least the monomers represented by: General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In formula (I), X_0 is -COO-, -OCO-, -
CH_2OCO-, -CH_2COO-, -O-, -S
O_2-, -CO-, -CONHCOO-, -CONH
CONH-, -CONHSO_2-, ▲mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (here, R_1_1 represents a hydrogen atom or a hydrocarbon group). a_1 and a_2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -
COO-Z_1 or -COO-Z_1 via hydrocarbon
(Z_1 represents a hydrogen atom or a hydrocarbon group that may be substituted). ] General formula (IIa) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIb) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In formula (IIa) or (IIb), X_1 is the same as in formula (1) X
Represents the same content as _0. Q_1 is carbon number 1-18
represents an aliphatic group or an aromatic group having 6 to 12 carbon atoms. b_1 and b_2 may be the same or different from each other,
Represents the same content as a_1 and a_2 in formula (I). V represents -CN, -CONH_2 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and Y is a hydrogen atom, a halogen atom,
Hydrocarbon group, alkoxy group or -COOZ_2(Z_2
represents an alkyl group, an aralkyl group or an aryl group). ] General formula (III) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [In formula (III), Represents the same content. c_1 and c_2 may be the same or different, and represent the same contents as a_1 and a_2 in formula (I). [Binder resin [B]: -PO_3H_2 group, -COOH group, -SO_3H group,
A polymer component containing at least one acidic group selected from a phenolic OH group, a ▲ mathematical formula, a chemical formula, a table, etc. ▼ group (R_4 represents the same content as R_1), and a cyclic acid anhydride-containing group. At the end of the polymer main chain of the B block of an A/B block copolymer composed of an A block containing at least one kind and a B block containing at least a polymer component represented by the following general formula (IV), Weight average molecular weight 1 x 10^3 formed by bonding polymerizable double bond groups
A graft-type copolymer having a weight average molecular weight of 3 x 10^4 to 1 x 10^6 and comprising at least one copolymerization component of ~2 x 10^4 monofunctional macromonomer (MB). General formula (IV) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In formula (IV), d_1 and d_2 each represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group. X_4 is -COO-, -OCO-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (l_3 and l_4 represent integers from 1 to 3), -O-,
-SO_2, -CO-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CONH
COO-, -CONHCONH- or ▲ mathematical formula, chemical formula,
There are tables, etc., which represent ▼ (here, R_2_3 represents a hydrogen atom or a hydrocarbon group). R_2_1 represents a hydrocarbon group. However, if X_4 represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼, then R_2_1
represents a hydrogen atom or a hydrocarbon group. ] (2) The resin [A] further includes -PO_3H_2 groups, -S
At least one polar group selected from O_3H group, -COOH group, -OH group, and ▲ mathematical formula, chemical formula, table, etc. The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor is bonded to the terminal end of the chain. (3) In the resin [B], the macromonomer (MB
) as a monofunctional monomer constituting a copolymer with
The electrophotographic photoreceptor according to any one of claims (1) and (2), characterized in that it contains at least one monomer represented by the following general formula (V). General formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In formula (V), d_3, d_4, X_5 and R_2_2
are d_1, d_2, X_4 and R_2 in formula (IV)
Each represents the same content as _1. ]