JPH05297603A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To maintain stable and good electrostatic characteristics and to obtain good quality of images even when the environment for formation of copy images changes, by incorporating a specified resin A and a resin B as a binder resin. CONSTITUTION:The binder resin contains at least each one kind of resin A and resin B. The resin A is graft copolymers having 1X10<3>-2X10<4> weight average mol.wt. containing macromonomers expressed by formula I or the like having 1X10<3>-1.5X10<4> weight average mol.wt. as the polymer component. In formula I, f<1> and f<2> are hydrogen atoms, halogen atoms, etc., X is a single bond,-COO-, etc., Y<1> is a group which connects X<1> and -COO-, Z<1> and Z<2> are bivalent aliphatic groups or bivalent aromatic groups, and R<31> is a hydrogen atom or hydrocarbon group. The resin B has 2X10<4>-1X10<6> weight average mol.wt. and consists of a block comprising polymer components containing polar groups and a block containing polymer components expressed by formula II. In formula II, b<1> and b<2> are hydrogen atoms, halogen atoms, etc., and R<4> is a hydrocarbon group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor,
More specifically, it relates to an electrophotographic photoreceptor having excellent electrostatic characteristics and moisture resistance.

[0002]

2. Description of the Related Art Electrophotographic photoreceptors have various structures in order to obtain predetermined characteristics or depending on the type of electrophotographic process applied. Typical electrophotographic photoconductors are a photoconductor having a photoconductive layer formed on a support and a photoconductor having an insulating layer on the surface thereof, which are widely used.

Photoreceptors comprising a support and at least one photoconductive layer are used in the most common electrophotographic processes, ie, charging, imagewise exposure and development, and optionally, image formation by transfer.

Further, a method of using an electrophotographic photosensitive member as an offset original plate for direct plate making is widely used. In recent years, in particular, direct electrophotographic lithographic printing plates have become important as a method of printing high-quality printed matter with a printing number of several hundreds to several thousands. In such a situation, the binder resin used to form the photoconductive layer of the electrophotographic photosensitive member has excellent film-forming property of itself and dispersibility in the binder resin of the photoconductive powder, The formed recording layer has good adhesion to the substrate, and the photoconductive layer of the recording layer has excellent charging ability, small dark decay, large light decay, little pre-exposure fatigue, and shooting It is necessary to have various electrostatic characteristics such as that these characteristics need to be stably maintained due to changes in humidity with time, and excellent image pickup properties.

Further, research on a lithographic printing plate precursor using an electrophotographic photosensitive member has been earnestly conducted, and a photoconductive layer for a photoconductive layer having both electrostatic properties as an electrophotographic photosensitive member and printing properties as a printing original plate has been made. Binder resin is required. Inorganic photoconductive material,
It has been found that, in the photoconductive layer containing at least the spectral sensitizing dye and the binder resin, not only the smoothness but also the electrostatic properties are greatly affected by the chemical structure of the binder resin. Especially in the electrostatic characteristics, the charge retention ratio in the dark (D.R.
R. ) And light sensitivity are greatly affected.

On the other hand, various techniques for improving smoothness and electrostatic properties have been studied by using a resin having a relatively low molecular weight (about 10 ³ to 10 ⁴ ) containing an acidic group as a binder resin. ing. For example, JP-A-63-217354 discloses a resin in which an acidic group-containing polymerization component is randomly present in the polymer main chain, and JP-A No. 64-70761 is a resin in which an acidic group is bonded to one end of the polymer main chain. Resin, JP-A-2-67563
No. 2, No. 2365651, No. 2-238458, No. 2-236562, No. 2-247656, and the like, a resin or an acidic group formed by bonding an acidic group to the main chain end of the graft-type copolymer. Resins contained in the graft portion of the graft type copolymer, AB type block copolymers containing an acidic group in a block, 3-2181648, and 3-21416.
No. 5 describes a graft type copolymer in which an AB type block copolymer is contained in a graft portion, and No. 3-219253 describes a resin partially having a crosslinked structure.
These are such that the low molecular weight resin has an effect of sufficiently dispersing the photoconductor and suppressing the aggregation of the photoconductors, and the adsorption of the photoconductor and the spectral sensitizing dye is not excluded from the inorganic substance. It is presumed that this is due to the fact that the photoconductor is sufficiently adsorbed to the stoichiometric defects and the surface of the photoconductor is covered gently and sufficiently.

Further, in order to make the mechanical strength of the photoconductive layer sufficient by using only these low molecular weight resins,
Various techniques of using other resins of medium to high molecular weight in combination have been studied. For example, JP-A-2-68561 and JP-A-2-681
Nos. 562 and 2-69759 include thermosetting resins that form a crosslinked structure between polymers, a resin partially having a crosslinked structure, and an acidic group bonded to the end of the main chain of the graft copolymer. Resins are listed.

Further, recently, a relatively stable performance is maintained even when the environment fluctuates remarkably, and it is relatively high even when the environment changes or a scanning exposure method using a semiconductor laser is used. Techniques for maintaining performance are being studied. For example, JP-A-3-29954 and 3-
77954, 3-92861, 3-53257.
JP-A No. 3-206464 and the like, a resin in which an acidic group having a medium to high molecular weight is bonded to the end of the graft portion of the graft copolymer, a resin containing an acidic group in the graft portion of the graft copolymer, AB It is described that a graft type copolymer containing a block type copolymer in the graft portion is used. Furthermore, JP-A-2-304451 and 3-
No. 100657, No. 3-186852, No. 3-221
No. 961, No. 3-223762, No. 4-14050
According to Nos. 4-14051, 4-15654 and the like, a low molecular weight graft copolymer containing the above various acidic groups and a medium to high molecular weight graft copolymer or a medium to high molecular weight graft copolymer. When a part of the resin having a cross-linking structure is used in combination, or when a part of the low-molecular weight resin having a cross-linking structure is used in combination with the above-mentioned various medium to high molecular weight graft type copolymers. Have been described.

[0009]

However, even if various low molecular weight resins containing these acidic groups, and further various medium to high molecular weight resins are used in combination with these resins, the environment is high and high temperature. It has been found that it is still insufficient to maintain stable performance when the humidity significantly changes from low temperature to low humidity. The scanning exposure method that uses a semiconductor laser beam has a longer exposure time than the conventional simultaneous full-exposure method that uses visible light, and also has a limited exposure intensity, so electrostatic characteristics, especially dark charge retention characteristics, are used. In terms of photosensitivity, higher performance is required.

In particular, in the electrophotographic lithographic printing plate precursor, when a scanning exposure method using a semiconductor laser beam was adopted, when actually tested with a conventional photoreceptor, the above electrostatic characteristics were found to be sufficient. This is not satisfactory, and especially the difference between E _1/2 and E _1/10 is large and the gradation of the copied image becomes soft, and it becomes difficult to reduce the residual potential after exposure, causing fog in the copied image. Became noticeable, and again
Even when printing as an offset master, a problem such as a print original sticking mark on the printed matter appeared.

Further, in recent years, it has been desired to realize a technique for faithfully reproducing not only a copy image of an image composed of line drawings and halftone dots but also a high-definition image composed of continuous gradations by using a liquid developer. However, the above-mentioned known technology has not been able to sufficiently satisfy these demands.

In the conventionally known technique, the medium to high molecular weight resin used in combination with the low molecular weight resin may lower the electrostatic properties of the low molecular weight resin which have been improved in performance. The electrophotographic photosensitive member having a photoconductive layer used in combination with these known resins as described above has high reproducibility of reproduced images of high definition images (especially continuous tone images) or low output. It was clarified that a problem can occur with respect to the imaging property of the scanning exposure method using laser light.

The present invention is to improve the problems of the above-described conventionally known electrophotographic photoreceptors. An object of the present invention is to provide an electrophotographic photosensitive member having a clear and high-quality image which constantly maintains good electrostatic characteristics even when the environment for forming a copied image changes such as low temperature and low humidity or high temperature and high humidity. Is to provide.

Another object of the present invention is to provide a CPC electrophotographic photosensitive member which is excellent in electrostatic characteristics and has little environmental dependence. Another object of the present invention is to provide an electrophotographic photosensitive member effective for a scanning exposure system using a semiconductor laser beam. A further object of the present invention is as an electrophotographic lithographic printing original plate, which is excellent in electrostatic properties (particularly dark charge retention and photosensitivity) and has an original image (particularly a high-definition continuous tone image).
Reproduces a copy image that is faithful to, and does not generate spot stains as well as uniform stains on the entire printed matter.
Another object is to provide a lithographic printing original plate having excellent printing durability.

[0015]

The above object is to provide an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye and a binder resin, wherein the binder resin is ] And at least one resin [B] described below are contained in the electrophotographic photosensitive member.

Resin [A] Weight average molecular weight represented by the following general formulas (Ia), (Ib), (IIa), (IIb) and (III): 1 × 10 ^{3 to} 1.5
At least one of × 10 ⁴ macromonomers (M)
A graft-type copolymer having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ containing at least one as a polymer component.

[0017]

[Chemical 9]

[0018]

[Chemical 10]

[0019]

[Chemical 11]

[0020]

[Chemical 12]

[0021]

[Chemical 13]

{Formulas (Ia), (Ib), (IIa), (II
In b) and (III), [] represents a repeating unit. f
¹ and f ² may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, —COO—T ¹ or a hydrocarbon group having 1 to 8 carbon atoms. Represents -COO-T ¹ (T ¹ represents a hydrocarbon group having 1 to 18 carbon atoms). X ¹ , X ² and X ³ are a single bond or —COO—, —OCO—, — (CH ₂ ) _a —.
_{COO -, - (CH 2)} b -OCO- (a, b is 1 to 3
Represents an ^{integer), - CON (k 1)} - [k ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms], -CON
HCONH -, - CONHCOO -, - O -, - C 6 H
₄ - or -SO ₂ - represents a. Y ¹ is X ¹ and -COO-
Represents a group connecting with. Z ¹ and Z ² may be the same or different from each other, and each is a divalent aliphatic group, a divalent aromatic group [in the bond of each divalent organic residue, —O—, —S
^{-, - N (k 2)} -, - SO 2 -, - COO -, - OC
O-, -CONHCO-, -NHCONH-, -CON
^{(K 2) -, - SO} 2 N (k 2) - and -S _i (k ^{2)
(K 3) - (k 2} , k 3 denote the same contents as the k ¹⁾ organic residue constituted by a combination of at least one linking group may be interposed] or those residues selected from Represents. R ³¹ represents a hydrogen atom or a hydrocarbon group. Z ³ represents a divalent aliphatic group. Y ² is X ² and V ¹
Represents a group connecting with. V ¹ was -CH ₂ -, - O-, or an -NH-. R ³² and R ³³ represent a hydrogen atom, a hydrocarbon group or a —COR ³⁴ group (R ³⁴ represents a hydrocarbon group). Y ³ represents a group connecting X ³ -O- with an. In formula (III), [] represents a repeating unit. α represents an integer of 1 to 3. When α is 2 or more, W in [] represents a group different from at least W in the adjacent []. W
Is -CH (α ¹ ) -CH (α ² )-or-(C
H ₂ ) ₄ — (α ¹ and α ² may be the same or different from each other and each represents a hydrogen atom or an alkyl group). }

Resin [B] having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ , and -P
O ₃ H ₂ group, -SO ₃ H group, -COOH group, -P (= O)
(OH) R ¹ [R ¹ represents a hydrocarbon group or —OR ² (R ² represents a hydrocarbon group) group] group and at least one polar group selected from cyclic acid anhydride-containing groups A composed of an A block containing at least one polymer component containing a and a B block containing at least a polymer component represented by the following general formula (IV)
B block copolymer.

[0024]

[Chemical 14]

[In the formula (IV), b ¹ and b ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ⁴ represents a hydrocarbon group. ]

That is, the binder resin of the present invention has the general formula (I
a), (Ib), (IIa), (IIb) and (III), a low molecular weight resin [A] which is a graft copolymer containing at least one macromonomer (M) as a copolymerization component. And an AB block copolymer (resin [B]) of an A block containing a specific polar group-containing component and a B block containing a polymer component represented by the general formula (IV).

Further, as a result of various studies, as described above, in the known technique in which a low molecular weight polar group-containing resin is used in combination with a medium to high molecular weight resin, the above-mentioned low molecular weight resin is used depending on the medium to high molecular weight resin used in combination. It has been found that the electrostatic characteristics, which have been enhanced by the resin, may deteriorate. It is also more important than expected that these medium to high molecular weight resins interact more appropriately with the interaction between the photoconductor, the spectral sensitizing dye, and the low molecular weight resin in the photoconductive layer. It has become clear that this is the cause.

As a result of repeated studies, a low molecular weight resin [A], which is a graft copolymer using a polyester macromonomer or a polyether macromonomer in the graft portion, and a high molecular weight resin containing a polar group in a block are used. It has been found that the above problem can be effectively solved by using the resin [B] which is an AB block copolymer in combination.

This is due to the synergistic effect of the binder resins [A] and [B] of the present invention, in which the photoconductive particles are present in a state in which they are sufficiently dispersed and not condensed, and the spectral sensitizing dye is photoconductive. It is presumed that this is due to the fact that it is sufficiently adsorbed on the surface of the body particles and that the binder resin sufficiently adsorbs the extra active sites on the surface of the photoconductor to compensate the traps.

That is, the low molecular weight resin [A] is sufficiently adsorbed on the photoconductor particles to uniformly disperse the particles, and the polymer chain is very short to suppress aggregation.
A medium to high molecular weight AB block copolymer having a block A containing a specific polar group and a block B not containing it, which has important functions such as preventing adsorption of a spectral sensitizing dye. The use of the coalesced material works better and the mechanical strength of the photoconductive layer is sufficiently maintained. This is because the block A portion of the resin [B] has a weaker interaction than the photoconductor particles and the resin [A], and the entanglement effect between polymer chains of the block B portion of the resin [B]. It is thought to be due to.

Furthermore, in addition to the above characteristics of the resin [A] itself, it has the effect of improving the electrostatic characteristics as compared with the known medium to high molecular weight resins used in combination. It is considered that since the block A portion of the resin [B] having an interaction has a polar group, it has a function of suppressing adsorption and exclusion of the spectral sensitizing dye.

This effect is particularly remarkable with polymethine dyes or phthalocyanine pigments which are particularly effective as dyes for spectral sensitization from near infrared to infrared light. On the other hand, when the electrophotographic photoreceptor of the present invention using photoconductive zinc oxide as the photoconductor is used as a conventionally known direct printing plate, it exhibits excellent image pick-up property and remarkably good water retention.

That is, the photoconductor of the present invention, on which a copied image is formed through an electrophotographic process, is desensitized by chemically treating the non-image area with a conventionally known desensitizing treatment liquid to prepare a printing original plate. Shows excellent performance as an original plate for printing when printed by offset printing.

When the photosensitizer of the present invention is desensitized, the non-image area is sufficiently hydrophilized and the water retention property is improved, resulting in a dramatic increase in the number of printed sheets. This is because the zinc oxide particles are uniformly dispersed and the presence state of the binder resin present on the surface of the zinc oxide particles is appropriate and the desensitizing reaction with the desensitizing treatment liquid is not alienated and quickly. It is considered that this is due to effective progress.

Further, the binder resin [A] contains --PO ₃ H ₂ groups, --SO ₃ H groups, --OH only at one end of the polymer main chain.
Group, -COOH group, -P (= O) (OH) R ¹ (R ¹ represents the same as described above), cyclic acid anhydride-containing group, -S
It is preferable that the polymer is a polymer formed by bonding at least one polar group selected from H group, -CONH ₂ group and -SO ₂ NH ₂ group (hereinafter, this low molecular weight compound is particularly referred to as resin [A ']). ..

The resin [A] of the present invention will be described below. The resin [A] has general formulas (Ia), (Ib), (II
a), (IIb) and (III) weight average molecular weight 1
It contains at least one of the macromonomers (M) of × 10 ^{3 to} 1.5 × 10 ⁴ as a polymer component. The resin [A] may contain two or more kinds of these macromonomers, and in particular, the compound represented by the general formula (Ia)
And / or the macromonomer represented by (Ib) (M-
1) at least one resin [A-1], at least one macromonomer (M-2) represented by the general formula (IIa) and / or (IIb) [A-2], and Macromonomer (M-3) represented by formula (III)
Resin [A-3] containing at least one is preferable.

The weight average molecular weight of the resin [A] is 1 × 10 ^3.
˜2 × 10 ⁴ , preferably 3 × 10 ³ to 1 × 10 ⁴ . When the molecular weight of the resin [A] is less than 1 × 10 ³ , the film-forming ability is lowered and sufficient film strength cannot be maintained. On the other hand, when the molecular weight of the resin [A] is more than 2 × 10 ⁴ , the resin of the present invention is particularly preferable. Electrophotographic characteristics of photoreceptors using near-infrared to infrared spectral sensitizing dyes under severe conditions of high temperature / high humidity, low temperature / low humidity (especially initial potential / dark decay retention rate and photosensitivity)
Of the present invention is somewhat increased, and the effect of the present invention that a stable copy image is obtained is diminished.

The ratio of the macromonomer (M) in the polymer of the resin [A] of the present invention is 0.5 to 0.5.
It is preferably 80% by weight. In particular, the general formula (I
Macromonomers (M-1) represented by a) and (Ib)
When R ³¹ is a hydrogen atom, its proportion is
It is preferably 0.5 to 30% by weight. In addition, the macromonomers (M of the general formulas (IIa) and (IIb) (M
-2), the abundance ratio is preferably 1 to 40% by weight, and the abundance ratio is 1 to 8 in the macromonomer (M-3) represented by the general formula (III).
It is preferably 0% by weight, particularly 5 to 50% by weight.

When the content of the macromonomer in the binder resin [A] is less than 0.5% by weight, the electrophotographic characteristics (especially dark decay rate and photosensitivity) are deteriorated, and the electrophotographic characteristics are fluctuated under environmental conditions. In particular, it becomes large when combined with a near infrared to infrared spectral sensitizing dye. It is considered that this is because the macromonomer which becomes the graft portion becomes fine, resulting in almost the same composition as the conventional homopolymer or random copolymer.

On the other hand, when the content of the macromonomer exceeds 80%, the copolymerizability between the monomer corresponding to the other copolymerization component and the macromonomer according to the present invention becomes insufficient, and even when it is used as a binder resin. Sufficient electrophotographic characteristics cannot be obtained. Further, when R ³¹ in the general formulas (Ia) and (Ib) of the macromonomer (M-1) is a hydrogen atom, if the macromonomer exceeds 30% by weight, the dispersibility is lowered and the film smoothness is deteriorated. However, the image quality of the copied image deteriorates and the background stain of the printed matter increases when it is used as an offset master. This is because the macromonomer contains -C.
It is considered that this is because the number of OOH groups increases and the dispersibility strongly interacts with the inorganic photoconductor, causing aggregation of the inorganic photoconductor.

The glass transition point of the resin [A] is preferably -40 ° C to 120 ° C, more preferably -30 ° C to 90 ° C.
℃. The content of the binding component in the resin [A ′] containing the specific polar group is 0.1 to 15% by weight, preferably 0.5 to 100 parts by weight of the resin [A ′].
10 to 10% by weight. Particularly, the abundance in the resins [A′-1] and [A′-3] is such that the resin [A ′] 100
It is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on parts by weight.

The content of polar group in the resin [A '] is 0.
If it is less than 1% by weight, the effect of improving the film strength of the photoconductive layer becomes small. On the other hand, if it exceeds 15% by weight, the dispersion of the inorganic photoconductor will agglomerate. The resin [A] of the present invention has a weight average molecular weight of 1.0 × 10 ^{3 to} 1.5 × 1.
It is a graft copolymer having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ^{4 and} containing 0 ⁴ macromonomer (M) as a copolymerization component, and further preferably a polymer main component of the graft copolymer. -PO ₃ H ₂ group at the chain ends, -SO ₃ H
Group, -COOH group, -OH group, -P (= O) (OH) R
¹ group (R ¹ has the same meaning as described above, and will be described in detail later.) Cyclic acid anhydride-containing group, -SH group, -CONH
It is a resin formed by bonding at least one polar group selected from _two groups and a —SO ₂ NH ₂ group (resin [A ′]).

The polymerizable double bond group, which serves as a copolymerization component of the resin [A-1], is bonded to one terminal and the R ³¹ group representing a hydrogen atom or a hydrocarbon group is bonded to the other terminal. Macromonomer having polyester structure (M-
1) will be described more specifically. General formula (Ia)
In and (Ib), the inside of [] is represented by the formula (Ia) and / or
Alternatively, it represents a repeating unit sufficient to make the weight average molecular weight of the macromonomer (M-1) of (Ib) 1 × 10 ^{3 to} 1.5 × 10 ⁴ .

The macromonomer of the general formula (Ia) (M-
In 1), preferably, f ¹ and f ² may be the same or different from each other, and each is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom), a cyano group, an alkyl group having 1 to 3 carbon atoms. Group (for example, methyl group, ethyl group, propyl group, etc.), -COOT ¹ or -CH ₂ CO
OT ¹ {T ¹ is an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group,
Hexyl group, octyl group, etc.), aralkyl group having 7 to 9 carbon atoms (eg benzyl group, phenethyl group, 3-phenylpropyl group etc.) or optionally substituted phenyl group (eg phenyl group, tolyl group, xylyl group, Represents a methoxyphenyl group).

More preferably, ^one of f ¹ and f ² represents a hydrogen atom. X ¹ is preferably
-COO -, - OCO -, - CH 2 COO -, - CH 2
OCO-, -CONH-, -CONHCONH-, -C
ONHCOO- or _{-C 6 H 4 -, - CON} (k 1) -
Represents. X ¹ is -C ₆ H ₄ - may represent a benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group,
Chloromethyl group, methoxymethyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) and the like.

K ¹ is a hydrogen atom or a carbon number of 1 to 1.
2 hydrocarbon groups (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-cyanoethyl group, benzyl group, And a methylbenzyl group, a chlorobenzyl group, a methoxybenzyl group, a phenethyl group, a phenyl group, a tolyl group, a chlorophenyl group, a methoxyphenyl group, a butylphenyl group and the like).

Y ¹ represents a group connecting X ¹ and --COO--, and represents a single bond or a connecting group. Specifically, -C a group linked ^{(e 1) (e 2)} -, - C 6 H 10
_{-, - C 6 H 4 -} , - C (e 3) = C (e 4) -, - C
OO -, - OCO -, - O -, - S -, - SO 2 -, -
^{N (e 5) -, -} CON (e 6) -, - SO 2 N
(E ⁷ )-represents a linking group formed by a linking group selected from -NHCOO-, -NHCONH-, and -CO-, or a combination of these linking groups {here, e ¹
To e ⁴ may be the same or different, and each is a hydrogen atom, a halogen atom (preferably, for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or a hydrocarbon group having 1 to 7 carbon atoms (preferably, for example, methyl group). Group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-methoxyethyl group,
2-methoxycarbonylethyl group, a benzyl group, methoxybenzyl group, a phenyl group, methoxyphenyl group, a methoxycarbonylphenyl group and the like), e ⁵ to e ⁷ represents the same as the contents of the above-described k ^1}.

Z ¹ and Z ^{2, which} may be the same or different, each represents a divalent organic residue, --O--, --S--,
^{-N (k 2) -, -} SO -, - SO 2 -, - COO-,
-OCO-, -CONHCO-, -NHCONH-,-
^{CON (k 2) -, -} SO 2 N (k 2) - and -Si
(K ² ) (k ³ )-, which may have a bonding group selected from them, a divalent aliphatic group or a divalent aromatic group, or a combination of these divalent residues. Represents an organic residue. Here, k ² and k ³ have the same contents as k ¹ , respectively.

Examples of the divalent aliphatic group include the following compounds:
The ones are listed.

[0050]

[Chemical 15]

[In the formula, e ⁸ and e ⁹ may be the same or different from each other and each is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like) or a carbon number of 1 to 1.
2 represents an alkyl group (eg, methyl group, ethyl group, propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.). Q is -O -, - S- or -NR ³⁶ - represents, R ³⁶
Is an alkyl group having 1 to 4 carbon atoms, -CH ₂ Cl or -CH
₂ represents Br}.

The divalent aromatic group includes, for example, a benzene ring group, a naphthalene ring group and a 5- or 6-membered heterocyclic group (as a hetero atom constituting the hetero ring, selected from an oxygen atom, a sulfur atom and a nitrogen atom). Containing at least one hetero atom). These aromatic groups may have a substituent, for example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group). , A butyl group, a hexyl group, an octyl group, etc.) and an alkoxy group having 1 to 6 carbon atoms (eg, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.) can be mentioned as examples of the substituent.

Examples of the heterocyclic group include furan ring, thiophene ring, pyridine ring, pyrazine ring, piperazine ring, tetrahydrofuran ring, pyrrole ring, tetrahydropyran ring, 1,3-oxazoline ring and the like. R ³¹ preferably represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and specific examples of the hydrocarbon group are the same as those mentioned above for f ¹ and f ² .

Z ³ represents a divalent aliphatic residue, specifically,-(CH ₂ ) _m 1-(m 1 is an integer of 2 to 18),-
CH ₂ -C (g ¹ ) (g ² )-(g ¹ and g ² are each a hydrogen atom or a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, and the like, having 1 to 1 carbon atoms.
Represents 12 alkyl groups. However, neither g ¹ nor g ² represents a hydrogen atom), —CH (g ³ ) —
(CH ₂ ) _{m 2-} (g ³ is an alkyl group having 1 to 12 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group,
Hexyl group, octyl group, etc., and m 2 is 2 to 18
Represents the integer) and the like.

CH (f ¹ ) = C in the macromonomer (M-1) in the general formula (Ia) or the general formula (Ib).
Specific examples of the portion represented by (f ² ) -X ¹ -Y ^1- include the following, but are not limited to these. However, in each of the following examples, Q ¹ is -H,-
_{CH 3, -CH 2 COOCH 3,} -Cl, -Br or -
Represents CN, Q ² represents —H or —CH ₃ , and n represents 2 to
12 represents an integer of 12, and m represents an integer of 1 to 12.

[0056]

[Chemical 16]

[0057]

[Chemical 17]

[0058]

[Chemical 18]

[0059]

[Chemical 19]

[0060]

[Chemical 20]

Specific examples of Z ¹ and Z ² include the following organic residues, but the present invention is not limited thereto. However, in each of the following examples, R ⁴¹ is an alkyl group having 1 to 4 carbon atoms, —CH ₂ Cl or —CH ₂
Represents Br, R ⁴² represents an alkyl group having 1 to 8 carbon atoms, — (C
^{_{H 2) m3 -OR 41 (R}} 41 represents the above meaning, m3 represents an integer of 2~8), - CH ₂ Cl or -CH ₂ B
r, R ⁴³ represents —H or —CH ₃ , R ⁴⁴ represents an alkyl group having 1 to 4 carbon atoms, Q represents —O—, —S— or —NR ⁴¹ — (R ⁴¹ represents the above. Represents an integer), p represents an integer of 1 to 26, q represents an integer of 0 or 1 to 4, r represents an integer of 1 to 10, and j represents an integer of 0 or 1 to 4. , K represents an integer of 2 to 6.

[0062]

[Chemical 21]

[0063]

[Chemical formula 22]

[0064]

[Chemical formula 23]

[0065]

[Chemical formula 24]

[0066]

[Chemical 25]

The macromonomer (M-1) represented by the general formula (Ia) is used as a diol and a dicarboxylic acid as exemplified in "Polymer Data Handbook [Basic Edition]" (published in 1986) edited by The Society of Polymer Science, Japan. Weight average molecular weight 1 × 10 ^{3 to} 1.5 × 10 ⁴ synthesized by polycondensation reaction with acid, dicarboxylic acid anhydride or dicarboxylic acid ester
It can be easily produced by a method of introducing a polymerizable double bond group by a polymer reaction only in the hydroxyl group at one end of the polyester oligomer.

The polyester is synthesized by a conventionally known polycondensation reaction. Specifically, specifically, Eiichiro Takiyama "Polyester Resin Handbook", Nikkan Kogyo Shimbun (1
986), "Polycondensation and Polyaddition" edited by The Society of Polymer Science, Kyoritsu Shuppan (1980), I.S. Goodman "Ency
Clopedia of Polymer Science
ce and Engineering Vol 1
2 "p1. John Wiley & Sons (1
1985) and the like.

The method of introducing the polymerizable dipolymerizable group only into the hydroxyl group at one end of the polyester oligomer is to use the reaction of esterifying an alcohol or urethane of an alcohol in a conventionally known low molecular weight compound. Can be synthesized. That is, a method of synthesizing a macromonomer by esterification by reaction with a carboxylic acid containing a polymerizable double bond group in the molecule, a carboxylic acid ester, a carboxylic acid halide or a carboxylic acid anhydride, or in the molecule This can be achieved by a method of urethanization by reaction with a monoisocyanate containing a polymerizable double bond group to synthesize a macromonomer. Specifically, the Chemical Society of Japan, “New Experimental Chemistry Course 14 , Synthesis and Reactions of Organic Compounds [II]”, Chapter 5, Maruzen Co., Ltd. (1977).
Annually), "Synthesis and Reactions of Organic Compounds [III], No. 1
It can be synthesized using the method described in detail on page 652, Maruzen Co., Ltd. (published in 1978) and the like.

The macromonomer (M-1) represented by the general formula (Ib) is obtained by synthesizing a polyester oligomer by a self-polycondensation reaction of a carboxylic acid containing a hydroxyl group in the molecule, A method for synthesizing a macromonomer by a polymer reaction similar to the monomer synthesis can be produced by a method for synthesizing by a living polymerization reaction of a carboxylic acid having a polymerizable double bond group and a lactone. Specifically, T.W. Yasuda, T .; A
ida and S. Inoue, J .; Macrom
ol. Sci. Chem. , A, 21 , 1035
(1984), T.S. Yasuda, T .; Aida
and S. Inoue, Macromolecule
es, 17 , 2217 (1984), S.S. Sosn
owski, S .; Stomkowski and S.
Penczek, Makromol. Chem.
188 , 1347 (1987), Y. Gnanou
and P.D. Rempp. , Makromol. Ch
em. 188 , 2267 (1987), T.S. Shio
ta and Y. Goto, J .; Appl. Pol
ym. Sci. , 11 , 753 (1967) and the like.

The formula (I
a) or a macromonomer represented by (Ib) (M-
A specific example of 1) is shown below. However, in each of the following examples, the weight average molecular weight of the macromonomer is 1 × 1 in [].
The repeating unit is sufficient to make it 0 ^{3 to} 1.5 × 10 ⁴ , Q ¹ has the same contents as described above, and Q ³ is -H or-.
Indicates CH _3, R ⁴⁵ and R ⁴⁶ represent each -CH ₃ or -C ₂ H ₅ may be the same or different, R ⁴⁷ and R ⁴⁸ each -Cl may be the same or different, -Br, - CH ₂ C
l or indicates -CH ₂ Br, s is an integer of 1 to 25, t is an integer of 2 to 12, u represents an integer of 2 to 12, x is an integer of 2 to 4, y Represents an integer of 2 to 6, and z represents an integer of 1 to 4.

[0072]

[Chemical formula 26]

[0073]

[Chemical 27]

[0074]

[Chemical 28]

[0075]

[Chemical 29]

[0076]

[Chemical 30]

[0077]

[Chemical 31]

A polymerizable double bond group is provided at one end and a hydrogen atom is provided at the other end, which is provided as a copolymerization component of the graft copolymer resin used in the resin [A-2] of the present invention.
R ³² each representing a hydrocarbon group or a —COR ³⁴ group (R ³⁴ represents a hydrocarbon group) was bonded. The macromonomer (M-2) having a polyester structure will be described more specifically.

In the general formulas (IIa) and (IIb),
In [], the weight average molecular weight of the macromonomer of the formula (IIa) and / or (IIb) is 1 × 10 ^{3 to} 1.5 × 10 ^4.
Represents a repeating unit sufficient to General formula (II
a) and / or (IIb) the macromonomer (M
In -2), f ¹ , f ² , Z ¹ , Z ² and Z ³ are as described above. X ² has the same contents as X ¹ .

Further, Y ² represents a group connecting X ² and V ^1, and specifically has the same contents as Y ¹ . V
¹ -CH ₂ -, - O- or represent -NH-. R ³² represents a hydrogen atom, a hydrocarbon group or —COR ³⁴ . As the hydrocarbon group, an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group) , 2-methoxyethyl group, 3-methoxyethyl group, 2-cyanoethyl group,
2-ethoxyethyl group, etc.), an aralkyl group having 7 to 9 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group, chlorobenzyl group) Etc.), an alicyclic group having 5 to 8 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, etc.), an optionally substituted aromatic group having 6 to 12 carbon atoms (for example, a phenyl group, a tolyl group,
Xylyl group, naphthyl group, chlorophenyl group, bromophenyl group, alkoxyphenyl group (as alkyl group, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, etc.) , Acetoxyphenyl group, methyl-chloro-phenyl group, propylphenyl group, butylphenyl group, decylphenyl group, etc.) and the like.

R ³⁴ in the —COR ³⁴ group represents a hydrocarbon group, and specifically has the same content as the hydrocarbon group for R ³² . CH (f ¹ ) ═C in macromonomer (M-2) in general formula (IIa) and general formula (IIb)
^{(F 2) -X 2 -Y 2} -V 1 - ones of each following specific examples of moieties represented by including without being limited thereto. However, in each of the following examples, Q ¹ and Q ² have the same contents as described above, and X is —Cl or —B.
r, n is an integer of 2 to 12, and z is an integer of 1 to 4.

[0082]

[Chemical 32]

[0083]

[Chemical 33]

[0084]

[Chemical 34]

[0085]

[Chemical 35]

Specific examples of Z ¹ and Z ² in the macromonomer (M-2) include the macromonomer (M
The same as those mentioned in -1) can be mentioned. The macromonomer represented by the general formula (IIa) (M-
2) is exemplified in "Polymer Data Handbook [Basic]" edited by The Society of Polymer Science, Japan (1986), Baifukan, etc.
Polyester oligomer having a weight average molecular weight of 1 × 10 ^{3 to} 1.5 × 10 ⁴ synthesized by a polycondensation reaction of a diol and a dicarboxylic acid, a dicarboxylic acid anhydride or a dicarboxylic acid ester, only at a carboxyl group at one end It can be easily produced by a method of introducing a polymerizable double bond group by a polymer reaction.

The polyester is synthesized by a conventionally known polycondensation reaction. Specifically, specifically, Eiichiro Takiyama “Polyester Resin Handbook”, Nikkan Kogyo Shimbun (1
986), "Polycondensation and Polyaddition" edited by The Society of Polymer Science, Kyoritsu Shuppan (1980), I.S. Goodman "Ency
Clopedia of Polymer Science
ce and Engineering Vol 1
2 ”p1. John Wiley & Sons
(Published in 1985) and the like.

As a method for introducing a polymerizable double bond group only to a carboxyl group at one end of a polyester oligomer, a reaction of esterifying a carboxylic acid or an acid amidation of a carboxylic acid in a conventionally known low molecular weight compound is used. Things can be combined. That is, the functional group containing a polymerizable double bond group in the molecule and chemically reacting with the carboxyl group includes, for example, —OH group, halogen compounds (chloride, bromide, iodide), —NH ₂ , —COO.
R ⁵¹ (R ⁵¹ is a methyl group, a trifluoromethyl group, 2,
The macromonomer is synthesized by polymer-reacting a polyester oligomer with a compound containing a compound represented by the following Chemical Formula 36 together with a 2,2-trifluoroethyl group).

[0089]

[Chemical 36]

Specifically, edited by The Chemical Society of Japan, "New Experimental Chemistry Course 14 , Synthesis and Reaction of Organic Compounds [II]", Chapter 5, Maruzen Co., Ltd. (Published in 1977), Yoshio Iwakura, Keisuke Kurita. ,
“Reactive polymer” can be synthesized by the method described in Kodansha (published in 1977) and the like. The macromonomer represented by the general formula (IIb) is obtained by synthesizing a polyester oligomer by a self-polycondensation reaction of a carboxylic acid having a hydroxyl group in the molecule, and then performing a macromolecular reaction similar to the macromonomer synthesis of the general formula (IIa). Can be produced by a method of synthesizing a macromonomer.

Further, specific examples of the macromonomer (M-2) represented by the formula (IIa) or (IIb) are shown below. However, the scope of the present invention is not limited to these. However, in each of the following examples, [] indicates a repeating unit sufficient to make the weight average molecular weight of the macromonomer (M-2) 1 × 10 ^{3 to} 1.5 × 10 ^4, and Q ³ is —H or Represents —CH ₃ , R ⁴⁵ and R ⁴⁶ may be the same or different, and each is —CH ₃ or —
Shows the C ₂ H _5, R ⁴⁹ is _{-CH 3, -C 2 H 5,} -C 3
Indicates H ₇ or -C ₄ H _9, Y represents a -Cl or -Br, W ₁₀ represents -O- or -S-, s1 is an integer of 2 to 12, t1 is 1 to 25 Indicates an integer, u is 2-1
2 is an integer, t2 is an integer of 2 to 16, and t3 is 1 to
4 represents an integer of 4 and t4 represents 0.1 or 2.

[0092]

[Chemical 37]

[0093]

[Chemical 38]

[0094]

[Chemical Formula 39]

[0095]

[Chemical 40]

[0096]

[Chemical 41]

In the macromonomer (M-3) represented by the general formula (III), f ¹ and f ² are as described above, and X ³ has the same contents as X ¹ and X ² .
Y ³ represents a group connecting X ³ and —O—, and represents a single bond or a divalent linking group which may have a hetero atom (as a hetero atom, an oxygen atom, a sulfur atom, a silicon atom, a nitrogen atom, or the like). Indicates).

For example, -C (i ¹ ) (i ² )-, -C ₆ H
_{10 -, - C 6 H 4} -, - (CH = CH) -, - O -, -
^{S -, - N (k 5} ) -, - COO -, - CONH -, -
_{SO 2 -, - Si (i} 3) (i 4) -, - SO 2 NH
-, -NHCOO-, -NHCONH-, etc. are composed of a single or a combination of bonding units (provided that i ¹ and i ² may be the same or different and each is a hydrogen atom,
Halogen atom (for example, chlorine atom, bromine atom), hydroxyl group, cyano group, aliphatic group having 1 to 12 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, Dodecyl group, benzyl group, phenethyl group, 2-chloroethyl group, 2-cyanoethyl group, etc.).

I ³ and i ⁴ may be the same or different, and are an aliphatic group having 1 to 12 carbon atoms (specifically, the same contents as the aliphatic group having i ¹ and i ² can be mentioned), and the number of carbon atoms. 6-12 aromatic groups (eg phenyl, tolyl, xylyl, methoxyphenyl, chlorophenyl, naphthyl, etc.)
Alternatively, it represents a —OR ⁵³ group (R ⁵³ represents a hydrocarbon group, and specifically includes an aliphatic group and an aromatic group for i ³ and i ⁴ ). In addition to hydrogen atom, k ⁵ is preferably a hydrocarbon group having 1 to 18 carbon atoms which may be substituted (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group). Group, decyl 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.), carbon number 4 to 1
8 optionally substituted alkenyl groups (eg, 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.), and optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-
Naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), alicyclic group having 5 to 8 carbon atoms which may be substituted ( For example, a cyclohexyl group, a 2-cyclohexylethyl group,
2-cyclopentylethyl group) or a carbon number of 6 to 1
2 optionally substituted aromatic groups (eg, phenyl groups,
Naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl Group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group and the like).

[0100] W is ^{-CH (α 1) -CH (α} 2) - or - (CH _{2) 4} - {However represent, alpha ^1, alpha ^2, which may be the same or different, a hydrogen atom or a carbon atoms 1-8 alkyl groups (eg, methyl, ethyl, propyl,
Butyl group, hexyl group, octyl group, etc.)}.
[] Represents a repeating unit, and [alpha] represents an integer of 1 to 3. However, when α is 2 or more, W in [] represents a group different from at least W in adjacent [], and for example, the following combinations are possible (in each of the following examples, W ¹ , W ² and W ³ each represent a different group and represent the same contents as W).

[0101]

[Chemical 42]

[In the formula, R³³Is the R³²Table similar to
Forget CH of macromonomer in general formula (III)
(F¹) = C (f²) -X³-Y³-Represented by
Specific examples include, but are not limited to:
It is not something that will be done. In each of the following examples, f¹¹
Is -H, -CH₃, -CH ₂COOCH₃, -Cl,-
Represents Br or -CN, f¹²Is -H or -CH₃The table
Where n1 is an integer of 1 or 2 and n2 is an integer of 2-12.
Represents a number, and n3 represents an integer of 3 or 4.

[0103]

[Chemical 43]

[0104]

[Chemical 44]

[0105]

[Chemical 45]

The polyether type macromonomer (M-3) represented by the general formula (III) can be produced by a conventionally known synthesis method. That is, it can be obtained by a method of synthesizing by cationic polymerization of carboxylic acids or alcohols with epoxysides or tetrahydrofuran. Specifically, P. F. Remp and E. F
ranta, Adv: Polym. Sci. 58,3
(1984), R.S. Asami, M .; Takak
i, K. Kita and E. Asakura,
Makromol. Chem. 186 , 685 (198
5), R.A. Asami and M.D. Takaki,
Makromol. Chem. Suppl. , 1
2 , 163 (1985), p. Rempp, P.P. L
utz, P.P. Masson and E. Frant
a, Makromol. Chem. , Suppl.
No. 8 , 3 (1984), Takuzo Aida, Shohei Inoue, Journal of Organic Synthesis Society, 43 , 300 (1985) and the like.

Specific examples of the macromonomer (M-3) represented by the general formula (III) used in the present invention are shown below, but the scope of the present invention is not limited thereto. Further, in each example, f ¹¹ , f ¹² , n1, n2 and n3 have the same contents as described above.

[0108]

[Chemical 46]

[0109]

[Chemical 47]

[0110]

[Chemical 48]

Resin used for the binder resin of the present invention [A]
Is the above general formula (Ia), (Ib), (IIa),
It is a graft copolymer containing at least one macromonomer selected from (IIb) and (III) as at least a copolymerization component, and the other copolymerization component satisfies the above-mentioned physical properties of the binder resin, and Any monomer may be used as long as it can be radically copolymerized with the macromonomer.

In this resin [A], the monomer represented by the above general formula (IV) is preferable as a component to be copolymerized with the macromonomer (M).

In the formula (IV), b ¹ and b ² are each a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom),
It represents a cyano group or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.) and the like.

R ⁴ represents a hydrocarbon group, specifically an alkyl group, an aralkyl group or an aromatic group, preferably an aralkyl group or an aromatic group which is a hydrocarbon group containing a benzene ring or a naphthalene ring. is there.

Further, R ⁴ preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. During the polymer backbone, -PO ₃ H ₂ group, -SO ₃ H group, -COOH
Group, -OH group, -SH group and -P (= O) (OH) R ¹
Those which do not contain a copolymerization component containing a polar group of the group are preferred, and therefore, examples of the substituent include a substituent other than the polar group contained in the polymer component containing the polar group in the resin [A]. For example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), —OZ
^{6, -COOZ 6, -OCOZ 6 (} Z 6 is 1 to 2 carbon atoms
2 represents an alkyl group, such as a methyl group, an ethyl group,
Propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group and the like). The preferred hydrocarbon group is an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group,
Dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), C4-18 An optionally substituted alkenyl group (eg, 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 group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-
Naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), alicyclic group having 5 to 8 carbon atoms which may be substituted ( For example, a cyclohexyl group, a 2-cyclohexylethyl group,
2-cyclopentylethyl group) or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group,
Butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl Group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group,
Propioamidophenyl group, dodecyloylamidophenyl group, etc.) and the like.

In the repeating unit of the general formula (IV) which is a component having such a substituent R ⁴ , more preferably at the 2-position represented by the general formula (IVa) and / or the general formula (IVb), And / or containing a benzene ring or a naphthalene ring having a specific substituent at the 2- and 6-positions,
A methacrylate component having a specific substituent is preferred (hereinafter, this low molecular weight product is particularly referred to as resin [AA]).

[0117]

[Chemical 49]

[0118]

[Chemical 50]

[In the formulas (IVa) and (IVb), A ¹ and A
² are each independently a hydrogen atom and a carbon number of 1 to 10
Hydrocarbon group, halogen atom (for example, chlorine atom, bromine atom), cyano group, —COZ ¹⁰ or —COOZ ¹⁰ (Z ¹⁰
Represents a hydrocarbon group having 1 to 10 carbon atoms). B ¹ and B ² respectively bond —COO— and a benzene ring,
It represents a single bond or a connecting group having 1 to 4 connecting atoms. ] When the above-mentioned specific resin [AA] is used, the electrophotographic characteristics (particularly V ₁₀ , DRR, E) are further improved as compared with the case of the resin [A].
_1/10 ) improvement can be achieved.

The reason for this is not clear, but one reason is that, due to the effect of a planar benzene ring or naphthalene ring having a substituent at the ortho position, which is an ester component of methacrylate, the zinc oxide interface in the film is It is thought that this is due to the proper arrangement of these polymer molecular chains in.

In formula (IVa), preferred A ¹ and A
² independently of each other, in addition to a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom) and a cyano group,
As the hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, aralkyl group having 7 to 9 carbon atoms (eg, benzyl group, phenethyl group). , 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloromethylbenzyl group) and aryl groups (for example, phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and -COZ ¹⁰ and -COOZ ¹⁰ (preferably Z
Examples of ¹⁰ include those described as the above-mentioned preferred hydrocarbon group having 1 to 10 carbon atoms).

In the formulas (IVa) and (IVb), B ¹ and B ² are each a single bond connecting —COO— and a benzene ring or — (CH ₂ ) _e — (e represents an integer of 1 to 3). ,-
_{CH 2 OCO -, - CH 2} CH 2 OCO -, - (CH 2
O) _f - _(f is an integer of 1 or _2), - CH 2 CH
A connecting group having 1 to 4 connecting atoms such as ₂ O- and the like, more preferably, a single bond or a connecting group having 1 to 2 connecting atoms can be mentioned.

Formula (IV) used in the resin [A] of the present invention
Specific examples of the repeating unit represented by a) or (IVb) are shown below. However, the scope of the present invention is not limited to this.

[0124]

[Chemical 51]

[0125]

[Chemical 52]

[0126]

[Chemical 53]

[0127]

[Chemical 54]

[0128]

[Chemical 55]

The monomer represented by the general formula (IV) is contained as a copolymer in an amount of 20% by weight to 99.5% by weight in the copolymer. Further, the component copolymerizable with the macromonomer (M) in the graft copolymer of the present invention may be a monomer other than the general formula (IV), (IVa) or (IVb), For example, in addition to methacrylic acid esters, acrylic acid esters, and crotonic acid esters having a substituent other than those described in the general formula (IV), α-olefins, vinyl carboxylates or allyl acid esters (for example, carboxylic acid As, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (eg, dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides , Styrenes (eg styrene, vinyltoluene, chlorostyrene, hydroxystyrene , N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene,
Methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinylsulfone-containing compounds, vinylketone-containing compounds, heterocyclic vinyls (eg vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene,
Vinyl imidazoline, vinyl pyrazole, vinyl dioxane, vinyl quinoline, vinyl tetrazole, vinyl oxazine and the like). As a preferable example, vinyl alkanoate having 1 to 3 carbon atoms or allyl ester,
Examples thereof include acrylonitrile, methacrylonitrile, styrene and styrene derivatives (for example, vinyltoluene, butylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, ethoxystyrene, etc.).

It is preferable that these other monomers do not exceed 30% by weight in the copolymer of the resin [A]. Further, the resin [A] of the present invention is preferably a resin in which the polar group is bonded to one end of the polymer main chain (resin [A ']), specific contents of the combined by polar groups, -PO ₃ H ₂ group, -S
O ₃ H group, -OH group, -COOH group, -P (= O) (O
H) R ¹ group, cyclic acid anhydride-containing group, -SH group, -CON
H ₂ group, -SO ₂ NH ₂ group can be mentioned.

Here, -P (= O) (OH) R ¹ represents a group represented by the following chemical formula 56, R ¹ represents a hydrocarbon group or an OR ² group (R ² represents a hydrocarbon group). , R ¹
And R ² is preferably an aliphatic group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 2-chloroethyl group, 2-methoxyethyl group,
3-ethoxypropyl group, allyl group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group, etc.) or substituted Aryl groups which may be substituted (for example, phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl Group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.) and the like.

[0132]

[Chemical 56]

Further, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and the cyclic acid anhydride to be contained includes an aliphatic dicarboxylic acid anhydride and an aromatic dicarboxylic acid anhydride. Things can be mentioned. Examples of the aliphatic dicarboxylic acid anhydride include succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-
1,2-dicarboxylic acid anhydride ring, cyclohexane-1,
2-dicarboxylic acid anhydride ring, cyclohexene-1,2-
Dicarboxylic acid anhydride ring, 2,3-bicyclo [2.2.
2] Octanedicarboxylic acid anhydride rings and the like, and these rings are substituted with, for example, halogen atoms such as chlorine atom and bromine atom, alkyl groups such as methyl group, ethyl group, butyl group and hexyl group. Good.

Examples of aromatic dicarboxylic acid anhydrides include phthalic anhydride ring, naphthalene-dicarboxylic acid anhydride ring, pyridine-dicarboxylic acid anhydride ring, thiophene-
Dicarboxylic acid anhydride ring and the like, these rings, for example, a chlorine atom, a halogen atom such as a bromine atom, a methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group,
A hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (such as a methoxy group and an ethoxy group as the alkoxy group) may be substituted.

In the polar group bonded to one end of the polymer main chain in the resin [A], a preferable polar group is -P.
O ₃ H ₂ group, -SO ₃ H group, -COOH group, -P (=
Examples thereof include O) (OH) R ¹ groups and cyclic acid anhydride-containing groups. These polar groups may be directly bonded to the ends of the polymer main chain or may be bonded via a linking group. The linking, may be any binding group, for example, if specifically ^{mentioned, -C (d 1) (d} 2) -
(D ¹ and d ² may be the same or different and each is a hydrogen atom, a halogen atom (chlorine atom, bromine atom, etc.), -OH.
Group, cyano group, alkyl group (methyl group, ethyl group, 2-
Chloroethyl group, 2-hydroxyethyl group, propyl group, butyl group, hexyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), phenyl group, etc.),-
^{CH (d 3) = CH (} d 4) - (d 3, d 4 is d ^1, d
Represents a ² same content _{as), - C 6 H 10 -} , - C 6 H 4
-, - O -, - S -, - N (d 5) - {d 5 represents a hydrogen atom, or a hydrocarbon represents a group (carbonization Specific examples of hydrogen a hydrocarbon group having 1 to 12 carbon atoms ( For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, 2-methoxyethyl group, 2
-Chloroethyl group, 2-cyanoethyl group, benzyl group,
(Methylbenzyl group, chlorobenzyl group, methoxybenzyl group, phenethyl group, phenyl group, tolyl group, chlorophenyl group, methoxyphenyl group, butylphenyl group, etc.)
)}, -CO-, -COO-, -OCO
^{-, - CON (d 5)} -, - SO 2 N (d 5) -, - S
_{O 2 -, - NHCONH -,} - NHCOO -, - NHS
_{O 2 -, - CONHCOO -,} - CONHCONH-,
Heterocycle (any 5- to 6-membered ring containing at least one kind of O, S, N or the like as a hetero atom or a condensed ring thereof: for example, a thiophene ring, a pyridine ring, a furan ring, an imidazole ring, piperidine ring, morpholine ring and the like) or ^{-Si (d 6) (d 7} ) -
{D ⁶ and d ⁷ may be the same or different and each represents a hydrocarbon group or -Od ⁸ (d ⁸ is a hydrocarbon group). Examples of these hydrocarbon groups include the same ones as those mentioned for d ⁵ ) or the like, or a linking group constituted by a combination of these.

In the resin [A], the polar group is bonded to one end of the polymer main chain by reacting various reagents with the end of the living polymer obtained by conventionally known anionic polymerization or cationic polymerization. (Method by ionic polymerization method), radical polymerization using a polymerization initiator and / or chain transfer agent containing a specific polar group in the molecule (method by radical polymerization method), or ionic polymerization method as described above or Such as a method of converting a polymer containing a reactive group (for example, an amino group, a halogen atom, an epoxy group, an acid halide group, etc.) having a terminal obtained by a radical polymerization method into a specific polar group of the present invention by a polymer reaction. It can be easily produced by a synthetic method.

Specifically, P.I. Dreyfuss,
R. P. Quirk, Encycl, Polym.
Sci. Eng. , 7 , 551 (1987), Yoshiki Nakajo, Yuya Yamashita "Dyes and Pharmaceuticals", 30 , 232 (198).
5), Akira Ueda, Susumu Nagai "Science and Industry" 60 , 57 (19)
86) etc. and the methods described in the references cited therein and the like.

Specifically, the chain transfer agent used is
For example, a mercapto compound containing the polar group or the reactive group (that is, a group capable of being induced to the polar group) (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid,
2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3-
[N (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropane Sulfonic acid, 4-mercaptobutane sulfonic acid, 2-mercaptoethanol, 1-mercapto-2-
Propanol, 3-mercapto-2-butanol, mercaptophenol-2-mercaptoethylamine, 2-
Mercaptoimidazole, 2-mercapto-3-pyridinol, 4- (2-mercaptoethyloxycarbonyl) phthalic anhydride, 2-mercaptoethylphosphonoic acid, 2-mercaptoethylphosphonoic acid monomethyl ester, etc.) or the above polar group Alternatively, an iodinated alkyl compound having a substituent (for example, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.) can be mentioned. Preferred are mercapto compounds.

Specific examples of the polymerization initiator containing the polar group or the specific reactive group include 4,4'-azobis (4-cyanovaleric acid) and 4,4'-azobis (4-
Cyanovaleric acid chloride), 2,2′-azobis (2-
Cyanopropanol), 2,2'-azobis (2-cyanopentanol), 2,2'-azobis [2-methyl-
N- (2-hydroxyethyl) -propioamide],
2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propioamide}, 2,2'-azobis {2- [1- (2-hydroxyethyl)] -2-Imidazolin-2-yl) propane}, 2,2'-azobis [2- (2imidazoline-
2-yl) propane], 2,2'-azobis [2-
(4,5,6,7-tetrahydro-1H-1,3-diazopin-2-yl) propane] and the like.

The amount of the polymerization initiator and / or the chain transfer agent used is 0.1 to 10% by weight, preferably 0.3 to 5% by weight, based on all the monomers. Next, the resin [B] of the present invention will be described. The resin [B] is an AB block copolymer, and the specific polar group in the block copolymer [B] means —PO ₃ H ₂ group, —SO ₃ H group, and —COO.
H group, —P (═O) (OH) R ¹ (R ¹ has the same meaning as above) group and cyclic acid anhydride-containing group, and the amount of the polymer component of the polar group-containing component is Polymer resin [B] 100
The content is preferably 0.1 to 5 parts by weight, and more preferably 0.2 to 3 parts by weight per part by weight.

When the content of the polar group in the binder resin [B] is less than 0.1% by weight, the initial potential is low and a sufficient image density cannot be obtained, and the content of the polar group is 5% by weight.
If the amount is larger than the above range, the dispersibility is lowered, the film smoothness and the high temperature and high humidity of the electrophotographic characteristic are lowered, and further, the background stain is increased when used as an offset master, which is not preferable.

The weight average molecular weight of the copolymer [B] is 2 × 1.
0 ⁴ to 1 × 10 ⁶ , preferably 3 × 10 ^{4 to} 5 × 10 ^5.
Is. When the molecular weight of the resin [B] is less than 2 × 10 ⁴ , the film forming ability is lowered and sufficient film strength cannot be maintained, and when the molecular weight is more than 1 × 10 ⁶ , the effect of the resin [B] of the present invention is obtained. The amount is reduced, and the electronic characteristics are the same as those of conventionally known resins.

The glass transition point of the resin [B] is −10 ° C.
The temperature is preferably in the range of -100 to 100 ° C, more preferably 0 to 90 ° C. Specific examples of the specific polar group contained in the A block of the AB block copolymer (resin [B]) of the present invention are the same as the specific polar groups of the resin [A] described above.

The "polymer component containing a specific polar group" constituting the A block of the resin [B] is, for example, B
Any vinyl-based compound containing the polar group, which is copolymerized with the corresponding vinyl-based compound such as the methacrylate component represented by the general formula (IV), which constitutes the block, can be used.

For example, it is described in "Polymer Data Handbook [Basic Edition]" edited by Japan Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α and / or β
Substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) methyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form Body, β-chloro form, β-bromo form,
α-chloro-β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half-esters, itaconic acid half-amides, crotonic acid, 2-alkenylcarboxylic acids (eg 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 Examples thereof include vinyl ester- or aryl group-half ester derivatives, and ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing the polar group in the substituents of amide derivatives.

The following can be mentioned as specific examples of these compounds. However, in each of the following examples, p
¹ is _{-H, -CH 3, -Cl, -Br} , -CN, -CH
₂ COOCH ₃ or —CH ₂ COOH is shown, and p ² is —
H or indicates -CH _3, y1 represents an integer of 2 to 18,
y2 shows the integer of 1-12, y3 shows the integer of 1-4.

[0147]

[Chemical 57]

[0148]

[Chemical 58]

[0149]

[Chemical 59]

[0150]

[Chemical 60]

[0151]

[Chemical formula 61]

[0152]

[Chemical formula 62]

Two or more kinds of the polymerization component containing the specific polar group as described above may be contained in the A block,
In that case, the two or more kinds of polar group-containing components may be contained in the A block in any mode of random copolymerization or block copolymerization.

Further, a polymer component other than the above polar group-containing polymer component may be contained in the block A, and such a polymer component preferably corresponds to the repeating unit of the general formula (IV). Polymer components may be mentioned.

Further, as a polymer component which can be contained in the A block together with the polymer component represented by the formula (IV), it corresponds to another repeating unit copolymerizable with the polymer component represented by the formula (IV). Examples thereof include acrylonitrile, methacrylonitrile, and heterocyclic vinyls (eg, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.). These other monomers are used within a range not exceeding 20 parts by weight based on 100 parts by weight of the total polymer component of the A block.

Next, the polymerization component constituting the B block component in the AB block copolymer [B] will be described in detail. The B block component contains at least a polymer component represented by the repeating unit represented by the general formula (IV), and the component represented by the formula (IV) is preferably 30 to 100% by weight in the B block component, More preferably 50
˜100% by weight.

The specific contents of the component of the general formula (IV) are the same as those described for the resin [A].
Other polymer components that can be contained include components represented by the following general formula (V).

[0158]

[Chemical 63]

[In the formula (V), a ¹ and a ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. V ¹⁰ is -COO -, - OCO -, - (CH 2) X1 O
_{CO -, - (CH 2)} X1 COO-, (x1 represents an integer of 1~3.) - O -, - SO 2 -, - CO -, - CON
^{(Z 11) -, - SO} 2 N (Z 11) -, - CONHCOO
-, - CONHCONH- or -C ₆ H ₄ - are expressed (here Z ¹¹ represents a hydrogen atom or a hydrocarbon group). R
⁶⁰ represents a hydrocarbon group. However, when V ¹⁰ represents —C ₆ H ₄ —, R ⁶⁰ represents a hydrogen atom or a hydrocarbon group. ] In the general formula (V), V ¹⁰ is -COO-, -OCO.
_{-, - (CH 2) X1} OCO -, - (CH 2) X1 COO-
(X1 represents an integer of 1 to 3), -O-, -SO.
_{2 -, - CO -, -} CON (Z 11) -, - SO 2 N (Z
^{11) -, - CONHCOO -,} - CONHCONH or -C ₆ H ₄ - represents a. Here, Z ¹¹ is not only a hydrogen atom but also a preferable hydrocarbon group is an alkyl group having 1 to 18 carbon atoms which may be substituted (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group). Base,
Octyl group, decyl 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.), which may be substituted with 4 to 18 carbon atoms. Alkenyl group (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), carbon number 7
To 12 optionally substituted aralkyl groups (eg, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group) , A methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, etc.) or Optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group, tolyl group, xylyl group,
Propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group,
Bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.).

R ⁶⁰ represents a hydrocarbon group, preferably the same as those listed as the preferable hydrocarbon group for Z ¹¹ . V ¹⁰ is -C ₆ H ₄ - may represent, R ⁶⁰ represents other hydrogen atoms of the hydrocarbon, further benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group, Ethoxy group, propioxy group, butoxy group, etc.) and the like.

A ¹ and a ² may be the same or different from each other, preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a cyano group, a carbon number of 1 to 4
An alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), -COOZ ¹² or COOZ ¹² (Z ¹² is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, Represents an aralkyl group, an alicyclic group or an aryl group, which may be substituted,
Specifically, it represents the same contents as those described for Z ¹¹ ). COOZ via the above hydrocarbons
Examples of the hydrocarbon in the ¹² group include a methylene group, an ethylene group, a propylene group and the like.

More preferably, in the general formula (V),
V ¹⁰ is -COO -, - OCO -, - CH 2 OCO -, -
_{CH 2 COO -, - O -} , - CONH -, - SO 2 NH
- or -C ₆ H ₄ - represents, a ¹ and a ^2, which may be the same or different, a hydrogen atom, a methyl group, -COO
Z ¹² or —CH ₂ COOZ ¹² {Z ¹² is more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.)
Represents}. Even more preferably, a ¹ and a
^{In 2} , one of them represents a hydrogen atom.

Other polymer components that can be contained in the B block of the resin [B] include components that may be contained in addition to the general formula (IV) shown in the block A. However, the block B is characterized by not containing the specific polar group-containing component contained in the block A.

The AB block copolymer [B] of the present invention is
It can be produced by a conventionally known polymerization reaction method.
Specifically, in the monomer corresponding to the polymer component containing the specific polar group, the polar group is preliminarily protected as a functional group, and an organometallic compound (eg, alkyllithium, lithium diisopropylamide, alkylmagnesium) is used. After synthesizing an AB block copolymer by a known so-called living polymerization reaction such as an ionic polymerization reaction with a halide or the like) or a hydrogen iodide / iodine system, a photopolymerization reaction using a porphyrin metal complex as a catalyst, or a group transfer polymerization reaction A method of forming a polar group by performing a deprotection reaction on a functional group having a protected polar group by a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction, a photodecomposition reaction, or the like. One example thereof is shown in the following reaction scheme (1).

[0165]

[Chemical 64]

These are, for example, P.M. Lutz, P.M. M
asson et al, Polym. Bull. 1
2 . , 79 (1984), B.I. C. Anderson,
G. D. Andrews et al, Macromol
ecules, 14 , 1601 (1981), K .; Ha
tada, K .; Ute. et al, Polym. J. 1
7 , 977 (1985), 18 , 1037 (198)
6), Koichi Right Hand, Koichi Hatada, Polymer Processing, 36 , 366
(1987), Toshinobu Higashimura, Mitsuo Sawamoto, Transactions on Polymers, 4
6 , 189 (1989), M.S. Kuroki, T .; Ai
da, J. Am. Chem. Soc. 109 , 4737
(1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 4.
3 , 300 (1985), D.I. Y. Sogah, W.C.
R. Hertletal. Macromolecule
It can be easily synthesized according to the synthetic method described in Les, 20 , 1473 (1987) and the like.

Further, the AB block copolymer [B] uses a monomer in which the polar group is not protected and uses a compound containing a dithiocarbamate group and / or a compound containing a xanthate group as an initiator. Alternatively, it can be synthesized by performing a polymerization reaction under irradiation with light. For example, Takayuki Otsu, Polymer, 37 , 248 (1988), Shunichi Hinomori, Ryuichi Otsu,
Polym. Rep. Jap. 37 . 3508 (198
8), JP-A 64-111, and JP-A 64-26619.
No., Nobuyuki Higashi, Polymer Preprints,
Japan, 36 , (6), 1511 (1987),
M. Niwa, N.N. Higashi, et al. M
acromol. Sci. Chem. A24 (5), 5
67 (1987) and the like.

Regarding protection of a specific polar group with a protective group and elimination of the protective group (deprotection reaction) of the present invention,
This can be easily performed by utilizing the conventionally known knowledge.
For example, various descriptions are given in the above cited document, and further,
Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer" published by Kodansha Ltd. (1977), T.S. W. Greene, "Prote
ctive Groups in Organic S
"Thensis", John Wiley & So
ns (1981), J. F. W. McOmie, "P
Protective Groups in Organ
ic Chemistry "Plenum Pres
s, (1973) and the like, which are described in detail in the review article, can be appropriately selected and performed.

Further, the block A is equivalent to synthesizing an azobis compound (that is, a high molecular weight azobis initiator) containing any part of the block B and using this as an initiator to form the other block. A method of synthesizing the above-mentioned monomers by radical polymerization reaction can also be used.

Specifically, it should be synthesized by the method described in Akira Ueda, Susumu Nagai, Kobunshi Shinbun, 44 , 469 (1987), Akira Ueda, Osaka City Institute of Industrial Research, 84 (1989), etc. You can

When synthesizing using this reaction, the weight average molecular weight of the polymer azobis initiator is 2 × because of the ease of synthesis of the polymer azobis initiator and the regularity of the polymerization reaction of blocking. It is preferably 10 ⁴ or less. On the other hand, in the resin [B] of the present invention, it is preferable that the block B has a longer polymer chain than the block A.

From the above, when synthesizing by this reaction,
A method using a block A-containing polymer initiator is preferable. For example, the reaction can be carried out according to the reaction scheme (2) shown below.

[0173]

[Chemical 65]

As the binder resin used for the photoconductive layer of the present invention, the above-mentioned known resins for inorganic photoconductors may be used in combination in addition to the resins [A] and [B] of the present invention.
However, the proportion of these other resins used is the total amount of the binder resin 10
A range not exceeding 30% by weight in 0 part by weight is preferable. If this ratio is exceeded, the effect of the present invention will be significantly reduced.

Typical other resins that can be used in combination are, for example, vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer, methacrylate copolymer, acrylate copolymer. , Vinyl acetate copolymer, polyvinyl butyral, alkyd resin, silicone resin, epoxy resin, epoxy ester resin, polyester resin and the like.

Specifically, Ryuji Shibata, Jiro Ishiwata, "Polymer," Vol. 17, p. 278 (1968), Harumi Miyamoto.
Hidehiko Takei "Imaging" 1973 (No.8) 9th
Pp. Koichi Nakamura, "Practical Technology of Binders for Insulating Materials," Chapter 10, C.I. H. C. Published (1985), D.M. D.
Tatt, S. C. Heidecker, Tappi,
49 (No. 10), 439 (1966), E.I. S. B
Altazzi, R.A. G. Blanklotte et
al, Photo. Sci. Eng. 16 (No.
5), 354 (1972), Nguyen Chan Kay, Isamu Shimizu, Eiichi Inoue, The Institute of Electrophotography 18 (No. 2),
28 (1980), JP-B-50-31011, JP-A-53-54027, JP-A-54-20735, and JP-A-57-57.
The resins disclosed in JP-A-202544 and JP-A-58-68046 are cited.

The total amount of the binder resin used in the photoconductive layer of the present invention is 1 with respect to 100 parts by weight of the inorganic photoconductor.
The amount is preferably 0 to 100 parts by weight, more preferably 15 to 50 parts by weight. The ratio of the amounts of the resin [A] and the resin [B] used in the present invention varies depending on the kind, particle size and surface condition of the inorganic photoconductive material used, but generally the ratio of the resin [A] and the resin [B] used. Is 5-6
0 to 95-40 (weight ratio), preferably 10-4
It is 0 to 90 to 60 (weight ratio).

If the total amount ratio of the binder resin is 10 parts by weight or less, the film strength of the photoconductive layer cannot be maintained. On the other hand, when the amount is 100 parts by weight or more, the electrostatic characteristics are deteriorated and the copy image is deteriorated in the actual image pickup property.

Further, when the weight ratio of the resin [A] to the resin [A] and the resin [B] of the present invention is 0.05 or less, the effect of improving the electrostatic characteristics is diminished. On the other hand, 0.6
If the above is the case, the film strength of the photoconductive layer cannot be sufficiently maintained (particularly as an electrophotographic lithographic printing plate precursor).

Examples of the inorganic photoconductive material used in the present invention include zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide and lead sulfide.

The spectral sensitizing dye used in the present invention includes
If necessary, various dyes are used alone or in combination. For example, Harumi Miyamoto, Hidehiko Takei, Imaging 1973 (N
o. 8) Page 12, C.I. J. Young et al., RCA R
view 15 , 469 (1054), Kouhei Kiyota,
IEICE Transactions J63 - C (No. 2 ), 97
(1980), Yuji Harasaki et al., Industrial Science Magazines 66 78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35 ,
Carbon dioxide dyes, diphenylmethane dyes, triphenylmethane dyes, such as 208 (1972)
Examples thereof include xanthene dyes, phthalein dyes, polymethine dyes (eg, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain a metal), and the like.

More specifically, as those mainly containing carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes, Japanese Patent Publication No. 51-45.
No. 2, JP-A Nos. 50-90334 and 50-11422.
No. 7, No. 53-39130, No. 53-82353,
US Pat. Nos. 3,052,540 and 4,054,45
No. 0, those described in JP-A-57-16456, and the like.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include F.I. M. Harmmer "The Cyani
neDyes and Related Compou
The dyes described in "nd" and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384 and 3,11.
0,591, 3,121,008, 3,12
5,447, 3,128,179 and 3,13
2,942, 3,622,317, British Patents 1,226,892, 1,309,274, 1,405,898, Japanese Patent Publication Nos. 48-7814, 5
Examples thereof include dyes described in No. 5-18892.

Further, as a polymethine dye for spectrally sensitizing a near-infrared region to an infrared region having a long wavelength of 700 nm or more, JP-A No. 4/1992 has been proposed.
No. 7-840, No. 47-44180, and Japanese Patent Publication No. 51-4
1061, JP-A-49-5034, and JP-A-49-451.
No. 22, No. 57-46245, No. 56-35141.
No. 57-157254, No. 61-26044,
No. 61-27551, U.S. Pat. No. 3,619,154.
No. 4,175,956, "Research D
isclosure ", 1982, 216, 117-
Examples thereof include those described on page 118. The photoconductor of the present invention is excellent in that its performance does not easily change depending on the sensitizing dye even when various sensitizing dyes are used in combination. Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers such as chemical sensitizers can be used in combination. For example,
Review Article: Imaging 1973 (No. 8) No. 1
Electron-accepting compounds (for example, halogen, benzoquinone, chloranil, acid anhydride organic carboxylic acid, etc.) in the review article on page 2, etc., Hiroshi Komon, et al., "Development and practical application of bacterial photoconductive materials and photoconductors" Chapters 4 to 6 • Polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, and the like, which are the reference examples of the Japanese Science Information Publishing Co., Ltd. (1986).

The addition amount of these various additives is not particularly limited, but usually 0.0 to 100 parts by weight of the photoconductor.
001 to 2.0 parts by weight. The photoconductive layer has a thickness of 1 to 1.
00μ, particularly 10 to 50μ is suitable.

When the photoconductive layer is used as the charge generation layer of the laminated type photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is 0.01 to 1 μm, particularly 0.05 to 0. 5
μ is preferred.

In some cases, an insulating layer may be additionally provided for the purpose of protecting the photoreceptor and improving durability and dark decay characteristics.
At this time, the insulating layer is set to be relatively thin, and the insulating layer provided when the photoconductor is used in a specific electrophotographic process is set to be relatively thick.

In the latter case, the insulating layer has a thickness of 5 to 70.
μ, particularly 10 to 50 μ. Examples of the charge transport material of the laminated type photoreceptor include polyvinyl carbazole, oxazole dyes, pyrazoline dyes, triphenylmethane dyes and the like. The thickness of the charge transport layer is 5 to 4
0 μ, particularly 10 to 30 μ is preferable.

Typical resins used for forming the insulating layer or the charge transport layer are polystyrene resin, polyester resin, cellulose resin, polyether resin,
Vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl chloride copolymer resin, polyacrylic resin, polyolefin resin, urethane resin, polyester resin, epoxy resin, melamine resin, silicone resin thermoplastic resin and effective resin are appropriately used. .

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably conductive, and as the conductive support, just as in the conventional case, for example, metal, paper, plastic sheet or the like is basically impregnated with a low resistance substance. Conductive treated by, for example, a basic back surface (surface opposite to the surface on which the photosensitive layer is provided) to have conductivity, and at least one layer coated for the purpose of preventing curling,
Paper having a water-resistant adhesive layer provided on the surface of the support, one having at least one precoat layer provided on the surface layer of the support as required, and a substrate made of electroconductive plastic such as Al vapor-deposited into paper. Those laminated to can be used.

Specifically, as examples of the conductive substrate or the conductive material, Yukio Sakamoto, Electrophotography, 14 (No.
1), P2-11 (1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry", Polymer Publishing (1975), M.M. F. Hoo
ver., J. Macromol. Sci. Chem. A
-4 (6), 1327 to 1417 (1970) and the like are used.

To prepare a printed matter using the electrophotographic printing original plate using the electrophotographic photosensitive member of the present invention, after forming a copy image on the electrophotographic original plate having the above-mentioned constitution by a conventional method, a non-image area is formed. It is created by desensitizing treatment.

As a desensitizing method for zinc oxide, any of conventionally known processing liquids can be used. For example,
Using a ferrocyan compound as the main agent for desensitization,
JP-A-62-239158, JP-A-62-292492
No. 63-99993, No. 63-9994, Japanese Examined Patent Publication No. 40-7334, No. 45-33683, and JP-A No.
7-107889, Japanese Examined Patent Publication No. 46-21244, 4
4-9045, 47-32681, 55-93.
No. 15, JP-A No. 52-101102, and the like.

However, the following processing solutions are preferable from the viewpoint of the safety of the processing solutions. For example, JP-B-43-28408, JP-B-45-24609, JP-A-51-103501, JP-A-54-10003, JP-A-53-83805, and JP-A-53-53, which use a phytic acid compound as a main agent.
83806, 53-127002, 54-44.
901, 56-2189, 57-2796,
Nos. 57-20394 and 59-20729, and Japanese Patent Publications No. 38-9665 and 39-39, wherein a water-soluble polymer capable of forming a metal chelate is used as a main agent.
No. 22263, No. 40-763, No. 43-28404.
No. 47-29642, JP-A-52-126302
No. 52-134501, No. 53-49506,
JP-A-53-104301 and JP-B-55-153, which are described in JP-A-53-59502 and JP-A-53-104302, and which use a metal complex compound as a main agent.
No. 13, No. 54-41924, etc.,
Alternatively, using inorganic and organic acid compounds as the main agent,
Examples include those described in JP-B-39-13702, JP-B-40-10308, JP-B-46-26124, JP-A-51-118501 and JP-A-56-111695.

The electrophotographic photosensitive member of the present invention can be used in applications utilizing any conventionally known electrophotographic process. That is, the photoconductor of the present invention can be used for both PPC and CPC recording systems, and
As the developer, any combination of a dry developer and a liquid developer can be used.

In particular, since it is possible to form a copy image of a high-definition original faithfully, the effect of the present invention is more exerted when used in combination with a liquid developer. Also, by combining with a color developer, not only black and white copy images,
It can also be applied to color reproduction images (for example, Kuro Takizawa, “Photo Industry” 33 , 34 (1975), Masayasu Anzai, “Technical Research Report of the Institute of Electronics and Communication Engineers” 77 , 17 (19).
1977) etc.).

Further, it is also effective in a system used for other purposes using the electrophotographic process in recent years. For example, the photoconductor of the present invention using photoconductive zinc oxide as a photoconductor is used as an offset lithographic printing plate precursor and is made of photoconductive zinc oxide or photoconductive titanium oxide which is pollution-free and has a good whiteness. The photoconductor can be used as an underprinting material used in an offset printing process, a color group, or the like.

[0198]

EXAMPLES Examples of the present invention will be illustrated below, but the contents of the present invention are not limited thereto. (Synthesis Example of Resin [A-1]) Macromonomer Synthesis Example 101: MA-101 1,4-butanediol 90.1 g, succinic anhydride 10
A mixture of 5.1 g, 1.6 g of p-toluenesulfonic acid monohydrate and 200 g of toluene was added to Dean-StarR.
4 under reflux with stirring in a flask equipped with a reflux device.
Heated for hours. The amount of water distilled off azeotropically with the toluene solvent was 17.5 g.

Next, a mixed solution of 17.2 g of acrylic acid and 150 g of toluene and 1.0 part of t-butylhydroquinone.
After adding g to the above reaction product, the mixture was reacted for 4 hours under reflux with further stirring. After cooling to room temperature, it was reprecipitated in 2 liters of methanol, and the precipitated solid was collected by filtration and dried under reduced pressure.
The yield was 135 g, and the obtained macromonomer (MA-
101) The weight average molecular weight was 6.8 × 10 ³ .

[0200]

[Chemical 66]

Macromonomer Synthesis Example 102: MA-1
02 120 g of 1,6-hexanediol, glutaric anhydride 1
14.1 g, p-toluenesulfonic acid monohydrate 3.0 g
And a mixture of 250 g of toluene were reacted under the same conditions as in Macromonomer Synthesis Example 101. The amount of water distilled off azeotropically was 17.5 g.

After cooling to room temperature, the product was reprecipitated in 2 liters of n-hexane, the liquid was decanted, collected, and dried under reduced pressure. When the reaction product was dissolved in toluene and the carboxyl group content was measured by a method of neutralization titration with 0.1N potassium hydroxide methanol solution, it was 500 μmol /
gr. Became.

100 g of the above solid and 8.6 methacrylic acid
A mixture of g, 1.0 g of t-butylhydroquinone and 200 g of methylene chloride was dissolved under stirring at room temperature. Dicyclohexylcarbodiimide (D.C.C) 20.3
g, 4- (N, N-dimethyl) aminopyridine 0.5 g
And a mixed solution of 100 g of methylene chloride were titrated to the above mixture under stirring for 1 hour. Further, the mixture was stirred as it was for 4 hours.

D. C. As the C solution was dropped, insoluble crystals were precipitated. The reaction mixture was filtered through a 200-mesh nylon cloth to remove insoluble materials. The filtrate was reprecipitated in 2 liters of hexane, and the powder was collected by filtration. 50 parts of acetone
After adding 0 ml and stirring for 1 hour, the insoluble matter was naturally filtered using a filter paper. After concentrating the filtrate under reduced pressure until the total volume becomes 1/2, add this solution to 1 liter of ether and add 1
Stir for hours. The precipitated solid matter was collected by filtration and dried under reduced pressure.

The macromonomer (M
The weight average molecular weight of A-102) was 8.2 × 10 ³ .

[0206]

[Chemical 67]

Macromonomer Synthesis Example 103: MA-1
03 12-hydroxystearic acid 500g, outside temperature 150
The mixture was stirred in an oil bath at 0 ° C. under reduced pressure of 10 to 15 mmHg for 10 hours while distilling off the produced water. The carboxyl group content of the obtained liquid was 600 μmol / gr.
100 g of the above liquid, 18.5 g of methacrylic anhydride,
A mixed solution of 1.5 g of t-butylhydroquinone and 200 g of tetrahydrofuran was stirred at a temperature of 40 to 45 ° C for 6 hours. The reaction mixture was added to 1 liter of water with stirring.
The mixture was added dropwise over time, and the mixture was further stirred for 1 hour. Let it stand and take out the sedimented liquid by decantation.
g, and reprecipitated in 1 liter of methanol. The precipitated liquid material was taken out by decantation and dried under reduced pressure.

With a yield of 62 g, the macromonomer (MA-10
The weight average molecular weight of 3) was 6.7 × 10 ³ .

[0209]

[Chemical 68]

Macromonomer Synthesis Example 104: MA-1
04 S. Penczek et al. Makromo
l. Chem. According to the synthetic method described in 188.1347 (1987), the macromonomer having the following structure (MA-1
04) was synthesized.

[0211]

[Chemical 69]

Macromonomer Synthesis Example 105: MA-1
05 Macromonomer (MA-104) 50g, Methanol 3
g, t-butyl hydroquinone 0.5 g, and methylene chloride 150 g in a mixed solution. C. C. 6 g, 4-N,
A mixed solution of 0.1 g of N-dimethylaminopyridine and 10 g of methylene chloride was added dropwise with stirring at a temperature of 20 to 25 ° C for 30 minutes, and the mixture was further stirred for 4 hours. 5 g of formic acid was added to this reaction mixture and the mixture was stirred for 1 hour, and then the precipitated insoluble matter was filtered off. The filtrate was reprecipitated in 1 liter of methanol, the solvent was removed by decantation, and the precipitate was collected and dried under reduced pressure. The obtained viscous product had a yield of 28 g and Mw of 7.5 × 10 ³ .

[0213]

[Chemical 70]

Resin [A] Synthesis Example 101: [A-101] 85 g of ethyl methacrylate, 15 g of the compound (MA-101) of Synthesis Example 101 of macromonomer and toluene 2
00 g of the mixture was warmed to a temperature of 85 ° C. under a stream of nitrogen.
2,2'-azobis (valeronitrile) (abbreviation AI
V. N. ) 6 g was added and stirred for 3 hours. Furthermore, A. I.
V. N. 1 g was added for 3 hours, and then A. I. V.
N. 0.8 g was added and stirred for 4 hours. The Mw of the obtained copolymer was 8.0 × 10 ³ .

[0215]

[Chemical 71]

Synthesis Example of Resin [A] 102: [A-10
2] 95 g of benzyl methacrylate, 5 g of the compound of Synthesis Example 104 of macromonomer (MA-104), and toluene 15
A mixture of 0 g and 50 g of ethanol was heated to a temperature of 80 ° C. under a nitrogen stream. 5 g of 4,4′-azobis (2-cyanovaleric acid) (abbreviation: ACV) was added, and the mixture was stirred for 4 hours. Next, A. C. V. 1 g was added for 3 hours, and then A. C. V. 0.5 g was added and stirred for 3 hours. The weight average molecular weight of the obtained copolymer was 8.5 × 10 ³ .

[0217]

[Chemical 72]

Synthesis Examples 103 to 113 of Resin [A]: [A
-103] to [A-113] The same polymerization method as in Synthesis Example 101 of Resin [A] was carried out, and the following table-
Each resin A was synthesized.

[0219]

[Table 1]

[0220]

[Table 2]

[0221]

[Table 3]

Synthesis Example 114 of Resin [A] of the Present Invention: [A
-114] benzyl methacrylate 95 g, macromonomer [MA
-102] 5 g, thiomalic acid 2.5 g, toluene 15
A mixture of 0 g and 50 g of ethanol was heated to a temperature of 75 ° C. under a nitrogen stream. 0.8 g of 2,2'-azobisisobutyronitrile (abbreviation AIBN) was added and reacted for 4 hours. I. B. N. Add 0.5g for 3 hours,
Furthermore, A. I. B. N. 0.5 g was added and reacted for 3 hours.

The Mw of the obtained copolymer was 7.5 × 10 ^3.
Met.

[0224]

[Chemical formula 73]

Synthesis Examples 115-123 of Resin [A]: [A
-115] to [A-123] In Synthesis Example 114 of Resin [A], the following mercapto compound was used as a chain transfer agent, and Resin [A] of Table-B was produced under the same polymerization conditions.

[0226]

[Table 4]

[0227]

[Table 5]

Synthesis Examples 124 to 131 of Resin [A]: [A
-124] to [A-131] In Synthesis Example 102 of Resin [A], as the azobis compound, A.I. C. V. Instead of the other azobis compound, a resin [A] shown in Table-C was produced under similar polymerization conditions. Mw of each resin [A] is 8 × 10 ^{3 to} 1.5 × 10
^{Was 4} .

[0229]

[Table 6]

[0230]

[Table 7]

Synthesis Examples 132 to 141: [A of Resin [A]
-132] to [A-141] Each resin [A] shown in Table D below was synthesized under the same polymerization conditions as in Synthesis Example 101 of Resin [A]. The Mw of the obtained copolymer was 7.5 × 10 ^{3 to} 9.5 × 10 ³ .

[0232]

[Table 8]

[0233]

[Table 9]

Synthesis Example 142 of Resin [A]: [A-14
2] 80 g of benzyl methacrylate, 20 g of the compound (MA-105) of Synthesis Example 105 of macromonomer, toluene 2
00 g of the mixture was reacted under the same polymerization conditions as in Synthesis Example 102 for resin [A] to synthesize resin [A-142]. The weight average molecular weight of the obtained copolymer was 9.5 × 10 ³ .

[0235]

[Chemical 74]

(Synthesis Example of Resin [A-2]) Macromonomer Synthesis Example 201: MA-201 1,4-butanediol 90.1 g, succinic anhydride 10
A mixture of 5.1 g, 1.6 g of p-toluenesulfonic acid monohydrate and 200 g of toluene was added to Dean-StarR.
Under reflux with stirring in a flask equipped with a reflux device,
Heated for 4 hours. The amount of water distilled off azeotropically with the toluene solvent was 17.5 g.

Then, after adding a mixed solution of 21.2 g of 2-hydroxyethyl methacrylate and 150 g of toluene and 1.0 g of t-butylhydroquinone to the above reaction product,
Dicyclohexylcarbodiimide (D.C.C.) 3
A mixed solution of 3.5 g, 1.0 g of 4- (N, N-dimethylamino) pyridine and 100 g of methylene chloride was added dropwise to the above mixture under stirring for 1 hour. Furthermore, 4 as it is
Stir for hours.

The reaction mixture was passed through a nylon cloth of 200 mesh to remove insoluble matter by filtration. The filtrate was reprecipitated in 3 liters of methanol, and the powder was collected by filtration. This was dissolved in 200 g of methylene chloride and reprecipitated again in 3 liters of methanol. The powder was collected by filtration and dried under reduced pressure to obtain 103% of macromonomer having a weight average molecular weight (hereinafter Mw) of 6.3 × 10 ^3.
g was obtained.

[0239]

[Chemical 75]

Macromonomer Synthesis Example 202: MA-2
02 120 g of 1,6-hexanediol, glutaric anhydride 1
14.1 g, p-toluenesulfonic acid monohydrate 3.0 g
And a mixture of 250 g of toluene were reacted under the same conditions as in Synthesis Example 1. The amount of water distilled off azeotropically was 17.5 g. After cooling to room temperature, the product was reprecipitated in 2 liters of n-hexane, the liquid was decanted, collected, and dried under reduced pressure. The reaction product was dissolved in toluene and neutralized and titrated with a 0.1N potassium hydroxide methanol solution to measure the carboxyl group content, which was 500 μmol / gr. 100 g of the above solid, glycidyl methacrylate 10.7
A mixture of g, 1.0 g of t-butylhydroquinone, 1.0 g of N, N′-dimethyldodecylamine and 200 g of xylene was stirred at a temperature of 140 ° C. for 5 hours.

After cooling, the reaction solution was reprecipitated in 3 liters of n-hexane, the liquid was decanted, collected, and dried under reduced pressure. This macromonomer was titrated by the above-mentioned neutralization titration method to measure the residual carboxyl group content.
It became μmol / gr and the reaction rate was 99.8%.
The yield of the obtained macromonomer was 63 g, and the weight average molecular weight was 7.6 × 10 ³ .

[0242]

[Chemical 76]

Macromonomer Synthesis Example 203: MA-2
03 To a mixture of 100 g of the polyester oligomer obtained in Synthesis Example 202 of macromonomer, 200 g of methylene chloride and 1 cc of dimethylformamide, 15 g of thionyl chloride was added dropwise with stirring at a temperature of 25 to 30 ° C. After completion of dropping, the mixture was stirred for 2 hours as it was. Next, methylene chloride and excess thionyl chloride were distilled off under reduced pressure by an aspirator, and then 200 g of tetrahydrofuran and 11.9 of pyridine were added to the residue.
g and added to dissolve, 8.7 g of allyl alcohol at a temperature of 2
It was added dropwise with stirring at 5 to 30 ° C. After dropping, just as it is,
After stirring for 3 hours, the reaction mixture was poured into 1 liter of water and stirred for 1 hour. After standing, the precipitated liquid substance was separated by decanting. 1 liter of water was added to this liquid material, the mixture was stirred again for 30 minutes, and allowed to stand, and the liquid material precipitated was collected by decanting. This operation was repeated until the supernatant solution became neutral. Next, 500 ml of diethyl ether was added to this liquid substance, and the mixture was stirred to be solidified.

The solid matter was collected by filtration and dried under reduced pressure to obtain 59 g of a macromonomer having a weight average molecular weight of 7.7 × 10 ³ .

[0245]

[Chemical 77]

Macromonomer Synthesis Example 204: MA-2
04 12-hydroxystearic acid 500g, outside temperature 150
The mixture was stirred in an oil bath at 0 ° C. for 10 hours while distilling off water produced under reduced pressure of 10 to 15 mmHg. The carboxyl group content of the obtained liquid was 600 μmol / gr.
24.8 g of dicyclohexylcarbodiimide (D.C.C.), 4- (N,) in a mixed solution of 100 g of the above liquid, 13.9 g of 2-hydroxyethyl acrylate, 1.5 g of t-butylhydroquinone and 200 g of methylene chloride.
A mixed solution of 0.8 g of N-dimethyl) aminopyridine and 100 g of methylene chloride was added dropwise to the above mixture at room temperature under stirring for 1 hour. Furthermore, the mixture was stirred as it was for 4 hours.
The reaction mixture was filtered through a 200-mesh nylon cloth to remove insoluble materials.

The filtrate was concentrated under reduced pressure, 300 g of n-hexane was added to the residue and the mixture was stirred, and the insoluble material was filtered off with a filter paper. After the filtrate was concentrated, 100 g of tetrahydrofuran was added to the residue to dissolve it. This mixture was reprecipitated in 1 liter of methanol, and the precipitated liquid material was dispersed by decanting. After drying under reduced pressure, the yield was 60 g and the weight average molecular weight was 6.7 ×.
10 ³ macromonomers were obtained.

[0248]

[Chemical 78]

Resin [A] Synthesis Example 201: [A-201] A mixture of 80 g of benzyl methacrylate, 20 g of the compound (MA-201) of Synthesis Example 201 of macromonomer, 150 g of toluene and 50 g of ethanol under a nitrogen stream at a temperature of 80 ° C. Warmed to. 6 g of 4,4′-azobis (4-cyanovaleric acid) (abbreviation ACV) was added and stirred for 4 hours. Furthermore, A. C. V. Add 1.0 g for 2 hours, then add A. C. V. 1.0 g was added and stirred for 3 hours. The weight average molecular weight of the obtained copolymer was 8.8 × 10 ³ .

[0250]

[Chemical 79]

Synthesis Examples 202 to 217 of Resin [A]: [A
-202] to [A-217] The following table shows the same polymerization method as in Synthesis Example 201 of Resin [A].
Each resin [A] of E was synthesized. The weight average molecular weight of each resin was 8.0 × 10 ^{3 to} 9.5 × 10 ³ .

[0252]

[Table 10]

[0253]

[Table 11]

[0254]

[Table 12]

[0255]

[Table 13]

Synthesis Example 218 of Resin [A]: [A-21
8] A mixed solution of 80 g of benzyl methacrylate, 20 g of a macromonomer (MA-205) having the following structure, 3 g of thioglycolic acid and 200 g of toluene under a nitrogen stream at a temperature of 75.
Warmed to ° C. A. I. B. N. 0.8 g was added and stirred for 4 hours. Furthermore, A. I. B. N. 0.5 g was added for 4 hours, and A. I. B. N. 0.3 g was added and stirred for 5 hours. The weight average molecular weight of the obtained copolymer is 8.0 × 1.
It was 0 ³ .

[0257]

[Chemical 80]

[0258]

[Chemical 81]

Synthesis Examples 219 to 227 of Resin [A]: [A
-219] to [A-227] Under the same polymerization conditions as in Synthesis Example 218 of Resin [A], the respective monomers and the mercapto compound were replaced and reacted, and the following table-
Each resin of F was synthesized. The weight average molecular weight of each obtained resin was in the range of 7.0 × 10 ^{3 to} 1.5 × 10 ⁴ .

[0260]

[Table 14]

[0261]

[Table 15]

(Synthesis Example of Resin [A-3]) Synthesis Example 301 of Resin [A]: [A-301] 80 g of benzyl methacrylate, 20 g of macromonomer (MA-301) having the following structure, 150 g of toluene and 50 g of ethanol. The mixture was warmed to a temperature of 80 ° C. under a stream of nitrogen. A. C. V. 7 g was added and stirred for 4 hours. Furthermore, A. C. V. 1.0 g was added for 4 hours, and then A.
I. B. N. 0.2 g was added and stirred for 3 hours. The Mw of the obtained copolymer was 9.3 × 10 ³ .

[0263]

[Chemical formula 82]

[0264]

[Chemical 83]

Synthesis Examples 302 to 307 of Resin [A]: [A
-302] to [A-307] In Synthesis Example 301 of Resin [A], the reaction was performed in the same manner as in Synthesis Example 301 except that the macromonomer (MA-301) was replaced with the macromonomer shown in the table below. The resins [A] shown in Table-G were each synthesized. The Mw of the obtained copolymer was 9.0 × 10 ^{3 to} 1.2 × 10 ⁴ .

[0266]

[Table 16]

[0267]

[Table 17]

Synthesis Example 308 of Resin [A]: [A-30
8] A mixed solution of 75 g of 2-chlorophenyl methacrylate, 25 g of macromonomer (MA-303), 3 g of thioglycolic acid and 200 g of toluene was heated at a temperature of 70 under a nitrogen stream.
Warmed to ° C. A. I. B. N. 1.0 g was added and the reaction was carried out for 4 hours. I. B. N. 0.5 g was added for 3 hours, and then A. I. B. N. 0.3 g was added and the temperature was raised to 80 ° C. to react for 4 hours.

The Mw of the obtained copolymer was 8.2 × 10 ^4.
Met.

[0270]

[Chemical 84]

Synthesis Examples 309 to 316 of Resin [A]: [A
-309] to [A-316] In Synthesis Example 308 of Resin [A], methacrylate,
Each resin [A] was synthesized by the same polymerization method, except that the macromonomer (MA) and the mercapto compound were replaced with the compounds corresponding to the structures shown in Table H below. The Mw of each resin [A] is 7.
It was in the range of 0 × 10 ^{3 to} 9 × 10 ³ .

[0272]

[Table 18]

[0273]

[Table 19]

[Synthesis of Resin [B]] Synthesis Example 1 of Resin [B] 1: [B-1] A mixed solution of 100 g of methyl methacrylate and 200 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream to give -2.
Cooled to 0 ° C. 0.8 g of 1,1-diphenylbutyllithium was added and reacted for 12 hours. Furthermore, to this mixed solution, a mixed solution of 60 g of methyl acrylate, 6 g of triphenylmethyl methacrylate and 5 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream and added, and the reaction was continued for 8 hours. The mixture was brought to 0 ° C. and then methanol 10
ml was added and reacted for 30 minutes to terminate the polymerization. The temperature of the obtained polymer solution was set to 30 ° C. under stirring, and
3% of hydrogen chloride ethanol solution was added and stirred for 1 hour. Then, the solvent was distilled off from the reaction mixture under reduced pressure until the total amount was halved, followed by reprecipitation in 1 liter of petroleum ether.

The Mw of the polymer obtained by collecting the precipitate and drying it under reduced pressure was 7.3 × 10 ⁴ , and the yield was 72 g.

[0276]

[Chemical 85]

Synthesis Example 2 of Resin [B]: [B-2] 70 g of methyl methacrylate and 30 g of methyl acrylate
A mixed solution of g, 0.5 g of (tetraphenylporphinato) aluminum methyl and 60 g of methylene chloride was heated to a temperature of 30 ° C. under a nitrogen stream. This was irradiated with light of 300 W-xenon lamp through a glass filter from a distance of 25 cm and reacted for 12 hours. Further to this mixture
After adding 60 g of methyl acrylate and 3.2 g of benzyl methacrylate and similarly irradiating with light for 8 hours, 3 g of methanol was added to this reaction mixture and stirred for 30 minutes to stop the reaction. Next, Pd-C was added to this reaction mixture, and a catalytic reduction reaction was carried out at a temperature of 25 ° C for 1 hour.

After filtering off the insoluble matter, petroleum ether 500 m
The precipitate was collected and dried. The yield of the obtained polymer was 118 g, and the Mw was 8 × 10 ⁴ .

[0279]

[Chemical formula 86]

Synthesis Example 3 of Resin [B]: [B-3] A mixed solution of 100 g of ethyl methacrylate and 200 g of toluene was thoroughly degassed under a nitrogen stream and cooled to 0 ° C.
Next, 2.5 g of 1,1-diphenyl-3-methylpentyllithium was added, and the mixture was stirred for 6 hours. Further, 60 g of methyl methacrylate and 4.6 g of 4-vinylphenyloxytrimethylsilane were added to this mixture, and the mixture was stirred for 6 hours.
3 g of methanol was added and stirred for 30 minutes.

Next, 10 g of a 30% hydrogen chloride ethanol solution was added to this reaction mixture, and the mixture was stirred at 25 ° C. for 1 hour, then reprecipitated in 1 liter of methanol and the collected precipitate was washed twice with 300 ml of methanol and dried. . The obtained polymer had a yield of 121 g and an Mw of 6.5 × 10 ⁴ .

[0282]

[Chemical 87]

Synthesis Example 4 of resin [B]: [B-4] A mixture of 67 g of methyl methacrylate and 4.8 g of benzyl N, N-diethyldithiocarbamate was sealed in a container under a nitrogen stream and heated to a temperature of 50 g. did. For this, 40
Photopolymerization was performed by irradiating with a 0 W high pressure mercury lamp from a distance of 10 cm through a glass filter for 6 hours.

To this was added 32 g of methyl acrylate, 1 g of acrylic acid and 180 g of methyl ethyl ketone, the atmosphere was replaced with nitrogen, and light irradiation was carried out again for 10 hours. The obtained reaction product was reprecipitated in 1 liter of methanol, collected, and dried. The obtained polymer had a yield of 73 g and an Mw of 4.8 × 10 ⁴ .

[0285]

[Chemical 88]

Synthesis Example 5 of Resin [B]: [B-5] Methyl methacrylate 50 g, ethyl methacrylate 2
A mixture of 5 g and 1.0 g of benzylisopulzanate was sealed in a container under a nitrogen stream and heated to a temperature of 50 ° C. This was irradiated with light from a high-pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 6 hours for photopolymerization.

This polymer was concentrated with tetrahydrofuran to a concentration of 4
A 0% solution was prepared, 22 g of methyl acrylate was added thereto, the atmosphere was replaced with nitrogen, and light irradiation was carried out again for 10 hours. Next, 3 g of 2- (2'-carboxyethyl) carbonyloxyethyl methacrylate was added to this mixture, and the atmosphere was replaced with nitrogen again to give 8
Irradiated for hours.

The obtained reaction product was reprecipitated in 2 liters of methanol, and the collected powder was dried. The obtained polymer had a yield of 63 g and Mw of 6 × 10 ⁴ .

[0289]

[Chemical 89]

Synthesis Example 6 of Resin [B]: [B-6] Ethyl acrylate 97 g, methacrylic acid 3 g, 2-mercaptoethanol 2 g and tetrahydrofuran 200.
The mixed solution of g was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. To this, 1.0 g of 2,2'-azobisisovaleronitrile (AIVN) was added and reacted for 4 hours,
Furthermore, A. I. V. N. 0.5 g was added and reacted for 4 hours.

After bringing the reaction mixture to a temperature of 20 ° C.,
8.6 g of 4,4'-azobis (cyanovaleric acid), 12 g of dicyclohexyldicarbodiimide, 0.2 g of 4- (N, N-dimethyl) pyridyl and tetrahydrofuran 30
The mixed solution of g was added dropwise over 1 hour. After stirring for another 2 hours as it was, 5 g of 85% formic acid aqueous solution was added and further stirred for 30 minutes. Next, the precipitated crystals are filtered off, and the filtrate is heated to a temperature of 2
The solvent was distilled off under reduced pressure at 5 ° C. The Mw of the obtained polymer (polymer initiator) having the following structure was 6.3 × 10 ³ .

[0292]

[Chemical 90]

A mixture solution of 70 g of methyl methacrylate and 170 g of toluene was stirred at a temperature of 70 while stirring under a nitrogen stream.
Warmed to ° C. Add 30 g of the above polymer to 3 parts of toluene.
The solution dissolved in 0 g was preliminarily crushed and replaced with nitrogen, and then added and reacted for 8 hours. The obtained polymer was reprecipitated in 2 liters of methanol, and the collected powder was dried. The yield of the obtained polymer was 72 g, and the Mw was ⁴ × 10 ⁴ .

[0294]

[Chemical Formula 91]

Synthesis Examples 7 to 16 of Resin [B]: [B-7]
~ [B-16] In the same reaction method as in Synthesis Example 3 of Resin [B], the following Table-I is used.
The resin [B] shown in was synthesized. Mw of the obtained copolymer
Was in the range of 5 × 10 ^{4 to} 9 × 10 ⁴ .

[0296]

[Table 20]

[0297]

[Table 21]

[0298]

[Table 22]

Synthesis Examples 17 to 23 of Resin [B]: [B-1
7] to [B-23] In the same reaction method as in Synthesis Example 4 of Resin [B], the following Table-J is used.
The resin [B] shown in was synthesized. Mw of the obtained copolymer
Was in the range of 4 × 10 ⁴ to 8 × 10 ⁴ .

[0300]

[Table 23]

[0301]

[Table 24]

Example 1 and Comparative Example 1 Resin [A-102] 6 g (as solid content), resin [B
-1] 34 g (as solid content), photoconductive zinc oxide 2
00g, 0.018g of cyanine dye [I] having the following structure,
A mixture of 0.10 g of phthalic anhydride and 300 g of toluene was placed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to rotate at a rotation speed of 6 ×.
A photosensitive layer-formed product was prepared by dispersing at 10 ³ rpm for 10 minutes, and a dry adhesion amount of 22 g / m 2 was applied to a conductive-treated paper.
Apply with a wire bar so that it becomes ^2, and 10 at 110 ℃
An electrophotographic light-sensitive material was prepared by drying for one second and then leaving it in the dark at 20 ° C. and 65% RH for 24 hours.

[0303]

[Chemical Formula 92]

Comparative Example 1: In Example 1, the resin [B-
1] 34 g of resin [R-1] having the following structure instead of 34 g
An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that was used.

[0305]

[Chemical formula 93]

With respect to these photosensitive materials, electrostatic characteristics, image pick-up property and environmental conditions (20 ° C., 65% RH), (30 ° C.,
The image pick-up property at 80% RH) and (15 ° C., 30% RH) was examined. The above results are shown in Table-K.

[0307]

[Table 25]

Embodiments of the evaluation items shown in Table-K are as follows. Note 1) Electrostatic characteristics: In a dark room at a temperature of 20 ° C and 65% RH,
-6k using a paper analyzer (Paper Analyzer SP-428 manufactured by Kawaguchi Electric Co., Ltd.) for each light-sensitive material
After corona discharge was performed for 20 seconds at V, the surface potential V ₁₀ at this time was measured after standing for 10 seconds. Then, the potential V ₁₀₀ after standing still in the dark for 90 seconds was measured, and the potential retention after dark decay for 90 seconds, that is, the dark decay retention rate [DRR (%)] was calculated as (V ₁₀₀ / V ₁₀ ) × 100 (%).

Further, the surface of the photoconductive layer was -40 by corona discharge.
After being charged to 0 V, the surface of the photoconductive layer was gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm).
The time until the surface potential (V ₁₀ ) is attenuated to 1/10 by irradiation with light is obtained. From this, the exposure amount E _1/10 (erg / cm
² ) is calculated. Environmental conditions at the time of measurement are 20 ° C and 65%
RH (I), 30 ° C, 80% RH (II) and 15 ° C, 3
Performed at 0% RH (III). Note 2) Imaging property: After leaving each light-sensitive material for 1 day under the following environmental conditions, each light-sensitive material is charged at −6 kV, and a 2.8 mW output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm) is used as a light source. With a pitch of 25 μm on the surface of the photosensitive material under an irradiation amount of 64 erg / cm ^2.
After speed exposure with a scanning speed of 300 m / sec, ELP-T (manufactured by Fuji Photo Film Co., Ltd.) was used as a liquid developer and developed, and then rinsed with a solvent of isoparaffin Isopar G (manufactured by Esso Chemical Co., Ltd.). The copied image (fog, image quality) obtained by fixing after washing was visually evaluated.

Environmental conditions at the time of imaging are 20 ° C. and 65% RH
(I), 30 ° C 80% RH (II) and 15 ° C, 30% R
Performed with H (III). As shown in Table K, the light-sensitive material of the present invention had good electrostatic characteristics even when environmental conditions changed, and the actual copied image was free of background fog and the copied image quality was clear.
On the other hand, Comparative Example 1 showed good image pick-up under normal temperature and normal humidity (I) conditions, but under high temperature and high humidity (II) conditions, it did not necessarily correspond to electrostatic characteristics, but The unevenness occurs in the intermediate density of the continuous tone part of the copy original which is a fine copy image. In addition, blurring of fine characters (especially Mincho type Kanji) occurred in some cases, resulting in a decrease in resolution.

Further, under the condition of low temperature and low humidity (III), minute uneven white spots were randomly generated in the solid image portion. From the above, an electrophotographic photoreceptor satisfying electrostatic characteristics and image pick-up properties (especially high-definition images) can be obtained only when the resin of the present invention is used, and particularly, a semiconductor laser light scanning exposure type photoreceptor system. It became clear that Example 2 and Comparative Example 2 5 g of resin [A-204] (as solid content), resin [B
-2] 35 g (as solid content), photoconductive zinc oxide 2
00g, 0.020g of methine dye (II) having the following structure, N
-Hydroxymaleinimide 0.20 g and toluene 3
An electrophotographic light-sensitive material was produced by operating 00 g of the mixture in the same manner as in Example 1.

[0312]

[Chemical 94]

Comparative Example 2: In Example 2, the resin [B-
2] An electrophotographic photosensitive material was produced in the same manner as in Example 2 except that 35 g of the resin [R-1] was used instead of 35 g. The film properties (smoothness of the surface) of each photosensitive material, the mechanical strength of the photoconductive layer, the electrostatic characteristics, the imaging properties and the environmental conditions are 20 ° C, 65% RH (I), 30 ° C, 80% RH (II).
The electrostatic characteristics and the image pick-up property at 15 ° C. and 30% RH (III) were examined. Furthermore, the printability when used as an original plate for electrophotographic lithographic printing was examined.

[0314]

[Table 26]

Embodiments of the evaluation items shown in Table-L are as follows. Note 3) Smoothness of surface layer: The photosensitive material obtained was measured using a Beck's smoothness tester (manufactured by Kumagai Riko Co., Ltd.) with an air capacity of 1 c.
The smoothness (sec / cc) was measured under the condition of c. Note 4) Mechanical strength of photoconductive layer: Emery paper (#) was applied to the surface of the obtained photosensitive material using Haydon-14 type surface test material (manufactured by Shinto Chemical Co., Ltd.) under a load of 75 g / cm ^2. 10
(00) was repeated 1000 times to remove the abrasion powder, and the residual film rate (%) was calculated from the weight reduction of the photosensitive layer and defined as the mechanical strength. Note 5) Raw plate water retention: Desensitizing solution EPL-EX (Fuji Photo Film Co., Ltd.)
Solution) was diluted 5 times with distilled water and passed through an etching processor twice to desensitize the surface of the photoconductive layer. Then, distilled water was used as fountain solution to prepare an offset printing machine (( ) Hamada Printing Machine Co., Ltd., 611XLA-II
After printing, the degree of background stain of the 50th printed material after printing was visually evaluated (corresponding to a forced condition for examining the degree of water retention of the desensitized original plate). Note 6) Printing durability: Under the same conditions as the above-mentioned Note 2) imaging property, after plate making and forming a toner image, it was passed through an etching processor twice using ELP-EX to be desensitized. The number of sheets that can be printed by using this as an offset master to an offset printing machine (Oliver 52 type, manufactured by Sakurai Seisakusho Co., Ltd.) without causing scumming in the non-image area of the printed matter and image quality of the image area (the number of printed sheets) The greater the number, the better the printing durability.)

As shown in Table-L, the light-sensitive material of the present invention comprises
The photoconductive layer has good smoothness, mechanical strength and electrostatic properties,
The actual copied image had no background fog and the copy quality was clear. It is presumed that this is because the photoconductor and the binder resin are sufficiently adsorbed and the particle surface is covered. For the same reason, even when used as an offset master original plate, the desensitizing treatment with the desensitizing treatment liquid proceeds sufficiently, and even if the water retention under the forced condition is evaluated, it is sufficiently hydrophilized, and the ink adhesion does not occur at all. I was not able to admit. Even when the print was actually printed and the print stain was observed, the print stain was not recognized at all, and 10,000 prints with clear image quality were obtained.

On the other hand, in Comparative Example 2, when the conditions during image pickup were severe, there were problems such as the occurrence of unevenness in the high-definition continuous tone image portion or the white spots and unevenness in the solid image portion.

Further, as the offset master original plate, the water retention of the lithographic printing plate which had been desensitized was good. However, in terms of actual printing durability, the image quality of the printed matter is
Naturally, it became defective. The above is
The resin [A] and the resin [B] of the present invention appropriately interact with the zinc oxide particles to form a state in which the desensitizing reaction by the desensitizing treatment liquid easily and easily proceeds. It shows that the film strength is remarkably improved by the action of the resin [B]. Example 3 and Comparative Example 3 Resin [A-315] 5 g (as solid content), Resin [B
-3] 35 g (as solid content), photoconductive zinc oxide 2
00 g, 0.020 g of methine dye (III) having the following structure, 0.21 g of salicylic acid and 300 g of toluene,
An electrophotographic photosensitive material was produced in the same manner as in Example 1.

[0319]

[Chemical 95]

Comparative Example 3: In Example 3, the resin [B-
3] An electrophotographic photosensitive material was produced in the same manner as in Example 2, except that 35 g of the resin [R-1] was used instead of 35 g. The characteristics of the obtained light-sensitive materials were examined in the same manner as in Example 2, and the results are shown in Table-M.

[0321]

[Table 27]

As shown in Table-M, the light-sensitive material of the present invention is
The photoconductive layer has good smoothness, mechanical strength and electrostatic properties,
The actual copied image had no background fog and the copy quality was clear. It is presumed that this is because the photoconductor and the binder resin are sufficiently adsorbed and the particle surface is covered. For the same reason, even when used as an offset master original plate, the desensitizing treatment with the desensitizing treatment liquid proceeds sufficiently, and even if the water retention under the forced condition is evaluated, it is sufficiently hydrophilized, and the ink adhesion does not occur at all. I was not able to admit. Even when the print was actually printed and the print stain was observed, the print stain was not recognized at all, and 10,000 prints with clear image quality were obtained.

On the other hand, in Comparative Example 3, when the conditions at the time of image pick-up became severe, there were problems such as the occurrence of unevenness in the high-definition continuous tone image portion or the white spots and unevenness in the solid image portion. Further, as the offset master original plate, the water-retaining property of the original plate which had been desensitized was good. However, in terms of actual printing durability, the image quality of the printed matter is poor, and thus the image quality of the printed matter is naturally poor.

From the above, the resin [A] and the resin [B] of the present invention properly interact with the zinc oxide particles, and the desensitizing reaction by the desensitizing treatment liquid easily and easily proceeds. It shows that the state is formed and the film strength is remarkably improved by the action of the resin [B]. Examples 4 to 19 In Example 2, the resin [A-204] and the resin [B-
Each electrophotographic photosensitive member was produced in the same manner as in Example 2 except that each resin [A] and each resin [B] in the following Table-N was used instead of 2]. In addition, electrostatic characteristics were measured in the same manner as in Example 2.

[0325]

[Table 28]

The electrostatic characteristics and the image pickup property of each light-sensitive material were measured in the same manner as in Example 1. All of the photosensitive materials have good electrostatic characteristics, and when the actual imaging properties of these photosensitive materials were examined, the reproducibility of fine lines and characters was good, there was no unevenness in the halftone, and there was no clear background fog. A duplicate image was obtained.

When used as an offset master original plate and printed in the same manner as in Example 2, at least 10,000 sheets or more could be printed. From the above, each of the light-sensitive materials of the present invention was good in all aspects of smoothness, film strength, electrostatic properties and printability of the photoconductive layer. Examples 20 to 22 Electrophotographic photosensitive materials were prepared under the same conditions as in Example 1 except that the cyanine dye [I] used in Example 1 was replaced with the dyes shown in Table 0 below.

[0328]

[Table 29]

The light-sensitive materials of the present invention are all excellent in chargeability, dark charge retention rate, and photosensitivity, and actually copied images have high temperature and high humidity (30 ° C., 80% RH) and low temperature and low humidity (15).
Even under severe conditions (° C., 30% RH), a clear image with no background fog was obtained. Examples 23 and 24 and Comparative Example 4 Resin [A-101] (Example 23) or Resin [A-20
5] (Example 24) 6.5 g, resin [B-2
3] 33.5 g, zinc oxide 200 g, uranine 0.02
g, 0.03 g of the methine dye [VII] having the structure shown below, 0.03 g of the methine dye [VIII] having the structure shown below, 0.18 g of p-hydroxybenzoic acid and 300 g of toluene, and a rotation speed of 6 × 10 ³ rpm in a homogenizer. For 5 minutes to prepare a photosensitive layer-formed product, which was applied to a conductive-treated paper with a wire bar so that the dry adhesion amount was 25 g / m ^2, and dried at 110 ° C. for 20 seconds. Then in the dark 20
Each electrophotographic photosensitive member was prepared by leaving it to stand at a temperature of 65 ° C. and 65% RH for 24 hours.

[0330]

[Chemical 96]

[0331]

[Chemical 97]

Comparative Example 4 In Example 23, 33.5 g of the resin [R-1] was used instead of 33.5 g of the resin [B-23],
A light-sensitive material was prepared in the same manner as in Example 23. Each characteristic of each light-sensitive material was examined in the same manner as in Example 1. The results are summarized in Table-P below.

[0333]

[Table 30]

In the above measurement, the same operation as in Example 1 was carried out except that the electrostatic property and the image pickup property were in accordance with the following operations. Note 7) Method for measuring E _1/10 of electrostatic characteristics After charging the surface of the photoconductive layer to −400 V by corona discharge, the surface of the photoconductive layer was irradiated with visible light having an illuminance of 2.0 lux to obtain the surface potential. The time until (V ₁₀ ) is attenuated to 1/10 is obtained, and the exposure amount E _1/10 (lux · second) is calculated from this. Note 8) Imaging property After leaving each light-sensitive material for 1 day under the following environmental conditions, fully automatic plate-making machine EPL-404V (Fuji Photo Film Co., Ltd.)
Manufactured by EPL-T as a toner, and a copy image (fog, image quality of the image) obtained by plate making was visually evaluated. Environmental conditions at the time of imaging are 20 ° C 65% RH (I), 30 ° C 8
Performed at 0% RH (II) and 15 ° C., 30% RH (III). However, the original for copying (that is, the original copy) was prepared by cutting out and pasting other originals.

In each of the photographic materials of the present invention, the mechanical strength of the photoconductive layer was good, but in Comparative Example 4, the mechanical strength was lower than these. The electrostatic properties showed good performance at room temperature and normal humidity (I), but especially at low temperature and low humidity (III).
Then, E _1/10 fell.

[0336] electrostatic properties of the light-sensitive material of the present invention is good, further, the embodiment 24 using the resin (A) having a specific substituent, very good, in particular the value of E _1/10 Has become smaller. As a result of examining the actual image pickup property, Comparative Example 4 shows that
In addition to the original as a copy image, the frame (that is, the trace of pasting) of the part cut out and stuck was recognized as the background stain of the non-image part. Furthermore, the environmental conditions during imaging are high temperature and high humidity (I
I), under low temperature and low humidity (III), the occurrence of unevenness in the halftone region of the continuous tone part of the copy image and the occurrence of minute unevenness of white spots in the solid image part were observed.

Further, when these were subjected to desensitization treatment as offset printing original plates and printed, all of the present invention produced 10,000 copies of clear image quality with no background stain.
However, in Comparative Example 4, the above-mentioned sticking mark was not removed even by the desensitizing treatment, and was generated from the printed matter printed out.

From the above, only the light-sensitive material of the present invention could give good characteristics. Example 25 5 g of resin [A-127] and 35 g of resin [B-22],
A mixture of 200 g of zinc oxide, 0.02 g of uranine, 0.04 g of rose bengal, 0.03 g of bromphenol blue, 0.40 g of phthalic anhydride and 300 g of toluene was treated in the same manner as in Example 24 to prepare a light-sensitive material. did.

The performance of the light-sensitive material of the present invention was examined in the same manner as in Example 24. As a result, all were excellent in chargeability, dark charge retention rate and photosensitivity. (30 ℃, 80% RH) and low temperature / low humidity (15 ℃, 30
% RH), a clear image with no background fog was obtained even under severe conditions.

Further, when this was used as an original plate of an offset master and printed, a printed matter of clear image quality was obtained even at 10,000 sheets. Examples 26 to 49 In Example 25, 5 g of resin [A] and 35 g of resin [B-22] were used instead of 5 g of resin [A-127] and 35 g of resin [B-22]. Each light-sensitive material was prepared in the same manner as in Example 23.

[0341]

[Table 31]

The light-sensitive materials of the present invention are all excellent in chargeability, dark charge retention rate and photosensitivity, and the actual copied images are high temperature / high humidity (30 ° C., 80% RH) and low temperature / low humidity (15 ° C., 30).
% RH), a clear image with no background fog or fine line skipping was provided even under severe conditions. Further, when printed as an offset master original plate, a printed matter having a clear image quality with no background stain was obtained even after printing 10,000 sheets.

[0343]

According to the present invention, an electrophotographic photoreceptor having a clear and high-quality image excellent in electrostatic characteristics (especially electrostatic characteristics under severe conditions) and further having excellent mechanical strength. Can be obtained. In particular, it is effective for a scanning exposure method using semiconductor laser light. Formula (Ia) or (I
By using the repeating unit containing the specific methacrylate component represented by b) in the resin of the present invention, the electrostatic characteristics are further improved.

Claims (3)

[Claims] 1. An electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye and a binder resin, wherein the binder resin is at least one of the following resins [A] and the following: An electrophotographic photosensitive member comprising at least one resin [B]. Resin [A] Weight average molecular weight represented by the following general formulas (Ia), (Ib), (IIa), (IIb) and (III) 1 × 10 ^{3 to} 1.5
At least one of × 10 ⁴ macromonomers (M)
A graft-type copolymer having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ containing at least one as a polymer component. [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] {Formulas (Ia), (Ib), (IIa), (IIb) and (II
In I), the inside of [] represents a repeating unit. f ¹ and f ²
May be the same or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms,
COO-T ¹ or —COO-T ¹ (T ¹ represents a hydrocarbon group having 1 to 18 carbon atoms) through a hydrocarbon group having 1 to 8 carbon atoms is represented. X ¹ , X ² and X ³ are a single bond or —COO—, —OCO—, — (CH ₂ ) _a —COO—,
_{- (CH 2) b -OCO- (} a, b represents an integer of ^{1~3), - CON (k 1} ) - [k ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms], -CONHCONH
-, - CONHCOO -, - O -, - C 6 H 4 - or -
Represents SO ₂ −. Y ¹ represents a group connecting X ¹ and -COO-. Z ¹ and Z ² may be the same as or different from each other, and each is a divalent aliphatic group, a divalent aromatic group [in the bond of each divalent organic residue, —O—, —S— , -N (k
_{^{2) -, - SO 2 -}} , - COO -, - OCO -, - CO
NHCO -, - NHCONH -, - CON (k 2) -,
-SO ^₂ N (k ₂₎ - and ^{_{-S i (k 2) (k}} 3) -
(K ² and k ³ have the same contents as k ¹ ) may be interposed] or an organic residue constituted by a combination of these residues. R ³¹ represents a hydrogen atom or a hydrocarbon group. Z ³ is 2
Represents a valent aliphatic group. Y ² represents a group connecting X ² and V ¹ . V ¹ is —CH ₂ —, —O—, or —NH—
Represents. R ³² and R ³³ are a hydrogen atom, a hydrocarbon group or-
It represents a COR ³⁴ group (R ³⁴ represents a hydrocarbon group). Y ³ represents a group connecting X ³ -O- with an. In formula (III), [] represents a repeating unit. α represents an integer of 1 to 3. When α is 2 or more, W in [] represents a group different from at least W in the adjacent []. W is -CH
^{(Α 1) -CH (α 2} ) - or - (CH _{2) 4} - a represents (alpha ¹ and alpha ^2, which may be the same or different,
Each represents a hydrogen atom or an alkyl group). } Resin [B] having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ , and -P
O ₃ H ₂ group, -SO ₃ H group, -COOH group, -P (= O)
(OH) R ¹ [R ¹ represents a hydrocarbon group or an —OR ² (R ² represents a hydrocarbon group) group] group and at least one polar group selected from cyclic acid anhydride-containing groups An AB block copolymer composed of an A block containing at least one polymer component containing a and a B block containing at least a polymer component represented by the following general formula (IV). [Chemical 6] [In the formula (IV), b ¹ and b ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ⁴ represents a hydrocarbon group. ] 2. The resin [A] as a copolymer component copolymerized with a macromonomer (M) is represented by the following general formula (IV
The electrophotographic photosensitive member according to claim 1, which contains at least one of a) and an aryl group-containing methacrylate component represented by the following general formula (IVb). [Chemical 7] [Chemical 8] [In formulas (IVa) and (IVb), A ¹ and A ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a cyano group, —COZ ¹⁰ or —COOZ ¹⁰ (Z
¹⁰ represents a hydrocarbon group having 1 to ¹⁰ carbon atoms), and B ¹
And B ² each represent a single bond or a connecting group having 1 to 4 connecting atoms for connecting —COO— and the benzene ring. ] 3. The resin [A] has a —PO ₃ H ₂ group, a —SO ₃ H group, a —OH group, a —OH group,
COOH group, -P (= O) (OH) R ¹ (R ¹ has the same meaning as above), cyclic acid anhydride-containing group, -SH group,
The electrophotographic photosensitive member according to claim 1 or 2, wherein at least one polar group selected from a —CONH ₂ group and a —SO ₂ NH ₂ group is bonded.