JPH06161120A - Photosensitive body for electrophotography - Google Patents

Abstract

PURPOSE:To maintain always stable and excellent electrostatic characteristics and provide a clear and excellent image, by forming a binding resin of specific two kinds of resins contained. CONSTITUTION:A binding resin is constituted by containing a resin (A) and a resin (B). The resin (A) is graft copolymer of a weight-average molecular weight of 1X10<3> to 10X10<4> containing macro monomer of a weight-average molecular weight of 1X10<3> to 1.5X10<4> for a polymer component expressed by formula I and the like, The resin (B) is AB block copolymer which has a weight-average molecular weight of 2X10<4> to 1X10<6> and is constituted of A-block containing a polymer component having a polar group such as -PO3H2 ad B-block containing a polymer component expressed by formula II, where in formulae I and II, f<1>, f<2> represent hydrogen atoms, X<1> -COO-and the like, Y<1>, a group for linking X<1> to -COO-, Z<1>, Z<2>, bivalent aliphatic group and the like, R<31>, hydrocarbon radical and the like b<1>, b<2>, cyano radical and the like ad R<4>, hydrocarbon radical.

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

Further, a method of using an electrophotographic photosensitive member as an original plate for offset lithographic printing for direct plate making is widely used. Particularly in recent years, the direct electrophotographic lithographic printing plate has become important as a method for printing high-quality printed matter by printing several hundred to several thousand sheets. Under such circumstances, the binder resin used for forming the photoconductive layer of the electrophotographic photosensitive member is excellent in film-forming property of itself and the ability to disperse the photoconductive particles in the binder resin, and at the same time, is formed. Adhesion of the recording layer to the substrate is good, and the photoconductive layer of the recording layer has excellent charging ability, small dark decay, large light decay, little pre-exposure fatigue, and at the time of shooting. It is necessary to have various electrostatic characteristics such as being required to stably hold these characteristics due to changes in the humidity of the above, 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. It has been found that in the photoconductive layer containing at least the inorganic photoconductor, 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 dark charge retention rate (DRR)
The light sensitivity is greatly affected.

Japanese Unexamined Patent Publication Nos. 2-236561 and 2-238.
Nos. 458 and 2-236562 disclose a technique for improving the smoothness and electrostatic properties of a photoconductive layer by using a graft copolymer in which a graft portion is a polyester macromonomer or a polyether macromonomer. There is. Further, a technique for improving the mechanical strength of the photoconductive layer by using a low molecular weight resin containing these acidic groups and a medium to high molecular weight resin in combination is disclosed in JP-A-2-266358 and 2-272558.
No. 2, No. 2-272559, No. 2-297558, No. 2-304450, No. 2-304452, and No. 2-3.
08165, 2-308166, 2-3081
No. 67, No. 3-186852, No. 3-214164.
No. 3, No. 3-186853, No. 3-259151, No. 3-186854, No. 3-259153, and No. 3-1.
88454, 4-20699, 4-20970
No. 4, No. 4-14050, No. 4-15654, No. 4-
No. 14051 and the like.

[0007]

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 using a semiconductor laser beam has a longer exposure time than the conventional simultaneous full-time exposure method using visible light and has a limitation in the exposure intensity. Therefore, electrostatic characteristics, especially dark charge retention In terms of photosensitivity, higher performance is required.

Particularly, in the electrophotographic lithographic printing plate precursor, when a scanning exposure method using a semiconductor laser beam is adopted, when actually tested with a conventional photoconductor, the above electrostatic characteristics are sufficiently obtained. This is not satisfactory, and especially the difference between E _1/2 and E _1/10 is large, 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 printed as a lithographic printing original plate, problems such as a trace of a printed original sticking to 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 performance of the low molecular weight resin, which has been improved in performance. The electrophotographic photosensitive member having a photoconductive layer used in combination with these known resins as described above is capable of reproducing the faithful reproduction of a high-definition image (especially continuous tone image) as described above or a 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 intended 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 plate precursor, excellent in electrostatic properties (particularly dark charge retention and photosensitivity) and faithful to original images (particularly high-definition continuous tone images). An object of the present invention is to provide a lithographic printing plate precursor that reproduces an image, does not cause spot stains as well as uniform stains on the entire surface of a printed matter, and has excellent printing durability.

[0013]

The above object is to provide an electrophotographic photosensitive member having a photoconductive layer containing at least an inorganic photoconductor, a spectral sensitizing dye and a binder resin, wherein the binder resin is ] And at least one of the following resins [B] are included 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)
1 as a polymer component
^{3 to} 2 × 10 ⁴ graft type copolymer.

[0015]

[Chemical 9]

[0016]

[Chemical 10]

[0017]

[Chemical 11]

[0018]

[Chemical 12]

[0019]

[Chemical 13]

{Formulas (Ia), (Ib), (IIa), (II
In b) and (III), 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 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
It represents an integer ^{3), - CON (k 1)} - [k ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms], -CO
NHCONH -, - CONHCOO -, - O -, - C 6
Represents H ₄ — or —SO ₂ —. Y ¹ is X ¹ and -COO
It represents a group connecting-and. 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] has a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ , and
_{O 3 H 2, -COOH, -SO} 3 H, -P (= O) (O
H) R ¹ [R ¹ represents a hydrocarbon group or —OR ² (R ² represents a hydrocarbon group)] and a polymer component having at least one polar group selected from cyclic acid anhydride groups. A composed of an A block contained and a B block containing at least a polymer component represented by the following general formula (IV)
It is composed of a B block copolymer, and in the A block, at least one polar group selected from the above specific polar groups is bonded to the end of the polymer main chain on the side opposite to the B block. resin.

[0022]

[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 of an A block containing the specific polar group-containing component and a B block containing the polymer component represented by the general formula (IV). It is composed of at least a medium to high molecular weight resin [B] in which the above-mentioned specific polar group is bonded to the terminal of the polymer main chain on the side.

As a result of various studies, as described above, in the known technique of using a low molecular weight polar group-containing resin 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 was found that the high performance electrostatic characteristics may be deteriorated. And among these
It is also clear that it is more important than expected that the high molecular weight resin makes the interaction between the photoconductor, the spectral sensitizing dye and the low molecular weight resin in the photoconductive layer more appropriate. It's coming.

As a result of repeated studies, a low molecular weight resin [A], which is a graft type copolymer using a polyester macromonomer or a polyether macromonomer in the graft portion, and a polar group according to the present invention are added to the polymer main chain. The above problem is effectively solved by using the resin [B] which is an AB block copolymer contained in one end and in the A block and having the A block and the B block containing no polar group. It has been found that

This is due to the synergistic effect of the binder resins [A] and [B] of the present invention, in which the photoconductor particles are sufficiently dispersed and not condensed, and the spectral sensitizing dye is used as the photoconductive dye. It is presumed that this is due to the fact that the particles are sufficiently adsorbed on the surface of the body particles and that the binder resin sufficiently adsorbs 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.
It has an important effect such as preventing adsorption of the spectral sensitizing dye. In addition, the resin [B] of the present invention, which contains a specific polar group at one end of the polymer main chain and in the A block, and which is composed of a B block not containing it, has a medium to high molecular weight. By using the AB block copolymer, the electrostatic properties are improved and the mechanical strength of the photoconductive layer is significantly improved. This is because a specific polar group bonded to one end of the main chain of the resin [B] is selectively adsorbed on the photoconductor particles,
Moreover, since the A block portion has a polar state and exists on the surface of the photoconductor particles and in the vicinity thereof, it is easy to adsorb the spectral sensitizing dye, and further the chemical sensitizer to the photoconductor particles. It is presumed that this is due to the formation of the state.

That is, the mutual effect between the resin [A] and the polar group bonded to the terminal of the resin [B] and the A block, and the A block portion of the resin [B] of the present invention is the photoconductive particles and the resin [A]. ], The active site of the photoconductor particles is sufficiently trapped to stabilize the electrostatic characteristics, and the adsorption of various sensitizers to the photoconductor surface is not excluded. It is considered that the electrostatic properties can be maintained at a high level by forming the state.

Furthermore, the portions of the B block not containing a specific polar group in the resin [A] and the resin [B] produce a sufficient entanglement effect between the polymer chains, and as a result, the photoconductive layer of the photoconductive layer is formed. It is estimated that the mechanical strength is improved. In other words, as the binder resin of the present invention, a resin [A], which is a graft copolymer using a polyester macromonomer or a polyether macromonomer in the graft portion, and a polar group are added to one end of the polymer main chain and A AB contained in a block and having the A block and a B block containing no polar group
By further specifying the weight average molecular weight of the resin [B], which is a block copolymer, and the content of polar groups in the resin, the strength of the interaction between the inorganic photoconductor and the resin can be appropriately adjusted. It is presumed that it was possible to change to. That is, the resin [A] having a stronger interaction is selectively and appropriately adsorbed on the inorganic photoconductor, while the resin [B] having a high molecular weight is
Interactions between polymer chains, and weak interactions between polar groups at the ends of the blocks and main chain and photoconductive particles, etc. synergize to achieve remarkably excellent performance in electrophotographic characteristics and film strength. It is thought that it is doing.

This effect is particularly remarkable with a polymethine dye or a phthalocyanine-based pigment which is particularly effective as a dye for spectral sensitization from near infrared to infrared light. Further, when the electrophotographic photosensitive member of the present invention using photoconductive zinc oxide as a photoconductor is used as a conventionally known original plate for direct printing, it exhibits excellent image pickup property and remarkably good water retention. That is,
The photoconductor of the present invention, on which a copied image was formed through an electrophotographic process, was desensitized to a non-image portion by a chemical treatment with a conventionally known desensitizing treatment liquid to prepare a printing original plate, which was printed by offset lithographic printing. It sometimes shows excellent performance.

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. It is considered that this is because the chemical reaction of zinc oxide, which acts to modify the hydrophilic surface by the desensitizing treatment, is in a state where it can easily and in large quantities proceed. That is, each of the resin [A] and the resin [B] used as the binder resin disperse the zinc oxide particles uniformly and sufficiently, and the surface of the zinc oxide particles and the vicinity of the surface rapidly interact with the desensitizing treatment aqueous solution. It is presumed that it forms a state that acts and causes a reaction.

Further, the binder resin [A] contains --PO ₃ H ₂ , --SO ₃ H, --OH and --C only on one end of the polymer main chain.
OOH, -P (= O) (OH) R ¹ (R ¹ has the same meaning as described above), cyclic acid anhydride group, -SH, -CONH
_It is preferably a copolymer having at least one polar group selected from ₂ and —SO ₂ NH ₂ (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, but in particular, a resin containing at least one kind of macromonomer (M-1) represented by the general formula (Ia) and / or (Ib). [A-1], macromonomer (M-2) represented by formula (IIa) and / or (IIb)
[A-2] containing at least one of
A resin [A-3] containing at least one macromonomer (M-3) represented by (III) 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 . If 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, if the molecular weight is more than 2 × 10 ⁴ , the resin of the present invention is Electrophotographic characteristics of photoconductors using near-infrared to infrared spectral sensitizing dyes under severe conditions of high temperature / high humidity, low temperature / low humidity (especially initial potential / dark charge 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 proportion of the macromonomer (M) in the resin [A] of the present invention in the copolymer is 0.5.
It is preferably about 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 charge retention rate and photosensitivity) are deteriorated, and the electrophotographic characteristics change under environmental conditions. Especially 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 of the monomer corresponding to the other polymer component and the macromonomer according to the present invention becomes insufficient, and even when it is used as the binder resin. Sufficient electrophotographic characteristics cannot be obtained. Further, when R ³¹ in the general formulas (Ia) and (Ib) in the macromonomer (M-1) is a hydrogen atom and the content of the macromonomer exceeds 30% by weight, the dispersibility of the photoconductor particles is deteriorated. However, the film smoothness is inferior, the copy image is deteriorated, and the background stain of the printed matter increases when it is used as an offset lithographic printing plate precursor. It is considered that this is because the number of —COOH groups contained in the macromonomer increases, the interaction with the inorganic photoconductor becomes strong, and aggregation of the inorganic photoconductor is caused.

The glass transition point of the resin [A] is preferably -40 ° C to 120 ° C, more preferably -30 ° C to 90 ° C.
℃. The resin [A] of the present invention has a weight average molecular weight of 1.
Weight average molecular weight of 1 × 10 ³ containing 0 × 10 ^{3 to} 1.5 × 10 ⁴ macromonomer (M) as a polymer component
To 2 × 10 ⁴ graft type copolymers, preferably —PO ₃ H ₂ , —SO ₃ H, —COOH, —OH at one end of the polymer main chain of the graft type copolymer. ,-
P (= O) (OH) R ¹ (R ¹ has the same meaning as described above, and will be described in detail later.), Cyclic acid anhydride group, -S
A resin formed by bonding at least one polar group selected from H, —CONH ₂ and —SO ₂ NH ₂ (resin [A ′]).

The amount of the specific polar group bonded to one end of the polymer main chain in the resin [A '] is determined by the resin [A'].
It is 0.1 to 15% by weight, preferably 0.5 to 10% by weight, per 100 parts by weight. In particular, the resin [A'-
1] and [A′-3] are preferably present in an amount of 0.1 to 10% by weight, and more preferably 0.5 to 5% by weight, based on 100 parts by weight of the resin [A ′].

The resin [A '] has a polar group content of 0.
If it is less than 1% by weight, the effect of improving the film strength of the photoconductive layer becomes small. Further, if the amount exceeds 15% by weight, aggregation of the dispersion of the inorganic photoconductor will occur.

The polymerizable double bond group, which serves as a polymer 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. First, general formulas (Ia) and (Ib) will be described. General formula (I
The values in [] in a) and (Ib) are sufficient to make the weight average molecular weight of the macromonomer (M-1) of the formula (Ia) and / or (Ib) 1 × 10 ^{3 to} 1.5 × 10 ^4. What
Represents a repeating unit.

In the general formula (Ia) or (Ib),
Preferably, f ¹ and f ² may be the same as 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, or a carbon number of 1 to 3.
An alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), —COOT ¹ or —CH ₂ COOT ¹ {T ¹ is an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an 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 A phenyl group, a tolyl group, a xylyl group, a methoxyphenyl group, etc.). More preferably, either f ¹ or f ² represents a hydrogen atom.

X ¹ is preferably --COO--, --OC.
_{O -, - CH 2 COO -} , - CH 2 OCO -, - CON
H -, - CONHCONH -, - CONHCOO- or _{-C 6 H 4 -, - CON} (k 1) - represents a. X ¹ is-
When representing C ₆ H ₄ —, the 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.

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 for connecting X ¹ and --COO--, and represents a single bond or a group for connecting. 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) -, - NHCOO} -, - NHCONH-, and a linking group represented {here formed by linking groups or combinations of these linking groups selected from -CO-, 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 or the like) or a hydrocarbon group having 1 to 7 carbon atoms (preferably, for example, methyl). Group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-methoxyethyl group,
2-methoxycarbonylethyl group, 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 may be the same as or different from each other and each represents a divalent organic residue, such as --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 be interposed with a linking group selected from divalent aliphatic groups or divalent aromatic groups, 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. As the divalent aliphatic group, for example, the following chemical formula 1
5 are mentioned.

[0048]

[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}.

Examples of the divalent aromatic group include 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 (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.) can be given 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 m2 is 2 to 18
Represents the integer) and the like.

Specific examples of the moiety represented by CH (f ¹ ) ═C (f ² ) —X ¹ —Y ¹ — in the general formula (Ia) or the general formula (Ib) include the following. It is not limited to. However, in each of the following examples, Q ¹ is -H, -CH ₃ , -CH ₂ COOCH ₃ ,-.
Cl, showed -Br or -CN, Q ² is -H or -CH
₃ , n is an integer of 2 to 12, and m is an integer of 1 to 12.

[0054]

[Chemical 16]

[0055]

[Chemical 17]

[0056]

[Chemical 18]

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 ³ represents —O—, —S— or —NR ⁴¹ — (R ⁴¹ represents the above. Represents the meaning of), 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, j represents an integer of 0 or 1 to 4, and k represents an integer of 2 to 6. Indicates.

[0058]

[Chemical 19]

[0059]

[Chemical 20]

[0060]

[Chemical 21]

[0061]

[Chemical formula 22]

The macromonomer (M-1) represented by the general formula (Ia) is a diol and a dicarboxylic acid as exemplified in "Polymer Data Handbook [Basic Edition]" (published in 1986) by Baifukan, 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.

As a method of introducing a polymerizable double bond group only into the hydroxyl group at one end of the polyester oligomer, a reaction of esterifying an alcohol or a urethane of an alcohol in a conventionally known low molecular weight compound is used. Can be synthesized with. 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. (197).
7 years), "Synthesis and Reactions of Organic Compounds [III], p. 1652, Maruzen Co., Ltd. (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 having a hydroxyl group in the molecule, and then deriving the macromonomer of the general formula (Ia). A method for synthesizing a macromonomer by a polymer reaction similar to the monomer synthesis can be carried out 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 macromonomer (M) represented by the general formula (Ia) or (Ib) that can be used in the present invention is described below.
Specific examples of -1) are shown below. However, the scope of the present invention is not limited to these. However, in each of the following examples, [] represents a repeating unit sufficient to make the weight average molecular weight of the macromonomer 1 × 10 ^{3 to} 1.5 × 10 ^4, and Q ¹ represents the same contents as above. , Q ⁴ represents -H or -CH ₃ , R ⁴⁵ and R ⁴⁶ may be the same or different and each represents -CH ₃ or -C ₂ H ₅ , and R ⁴⁷ and R ⁴⁸ may be the same or different. -Cl, -Br,
Indicates -CH ₂ Cl or -CH ₂ Br, s is an integer of 1 to 25, t is an integer of 2 to 12, u is from 2 to 12
, X is an integer of 2 to 4, y is an integer of 2 to 6, and z is an integer of 1 to 4.

[0067]

[Chemical formula 23]

[0068]

[Chemical formula 24]

[0069]

[Chemical 25]

[0070]

[Chemical formula 26]

[0071]

[Chemical 27]

[0072]

[Chemical 28]

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

First, the general formulas (IIa) and (IIb) will be specifically described. In the general formulas (IIa) and (IIb), the weight average molecular weight of the macromonomer of the formula (IIa) and / or (IIb) is in the range of [] is 1 × 10 ^{3 to} 1.5 ×.
It represents a repeating unit sufficient to give 10 ⁴ . In the macromonomer (M-2) represented by the general formula (IIa) and / or (IIb), f ¹ , f ² , Z ¹ , Z ² and Z ³
Is 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.), aralkyl group having 7 to 9 carbon atoms and 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 in the general formula (IIa) and the general formula (IIb)
Specific examples of the moiety represented by (f ¹ ) = C (f ² ) -X ² —Y ² —V ¹ — include, but are not limited to, the following. However, in each of the following examples, Q ¹ and Q ² have the same contents as described above, and X is −
Cl or -Br is shown, n shows the integer of 2-12, z
Represents an integer of 1 to 4.

[0077]

[Chemical 29]

[0078]

[Chemical 30]

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 the carboxyl group at one end of the 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, as the functional group containing a polymerizable double bond group in the molecule and chemically reacting with the carboxyl group, 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 compound containing a compound such as 2,2-trifluoroethyl group) and a compound represented by the following Chemical formula 31, with a polyester oligomer.

[0082]

[Chemical 31]

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 (M-2) represented by the general formula (IIb) is obtained by synthesizing a polyester oligomer by a self-polycondensation reaction of carboxylic acids having a hydroxyl group in the molecule, and then synthesizing the general formula (IIa)
It can be produced by a method of synthesizing a macromonomer by a polymer reaction similar to that of the macromonomer synthesis.

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 ⁴ 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.

[0085]

[Chemical 32]

[0086]

[Chemical 33]

[0087]

[Chemical 34]

[0088]

[Chemical 35]

[0089]

[Chemical 36]

A polymerizable double bond group is provided at one end and a hydrogen atom or a hydrocarbon is provided at the other end, which is used as a polymer component of the graft copolymer used in the resin [A-3] of the present invention. The macromonomer (M-3) having a polyether structure in which R ³² each representing a group or —COR ³⁴ (R ³⁴ represents a hydrocarbon group) is bonded will be described more specifically. First, the general formula (III) will be specifically described. 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 content as X ¹ and X ² . Y ³ is X ³ and -O
Represents a group connecting-, and represents a single bond or a divalent linking group optionally having a hetero atom (as a hetero atom, an oxygen atom, a sulfur atom, a silicon atom, a nitrogen atom or the like is shown).

As Y ³ , 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-,
And the like, each consisting of a single or a combination of bonding units (provided that i ¹ and i ² may be the same or different, respectively, a hydrogen atom, a halogen atom (eg 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-
A cyanoethyl group). ). 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 content as the aliphatic group having i ¹ and i ² can be mentioned), and 6 to 12 carbon atoms. Aromatic groups (eg, phenyl groups,
A tolyl group, a xylyl group, a methoxyphenyl group, a chlorophenyl group, a naphthyl group or the like) or an —OR ⁵³ group (R ⁵³ represents a hydrocarbon group, and specifically, an aliphatic group or an aromatic group at i ³ and i ⁴ is Can be mentioned).

In addition to a 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). 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.), 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).

[0093] 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).

[0094]

[Chemical 37]

[In the formula, R ³³ represents the same content as R ³² described above. CH of Macromonomer in General Formula (III)
Specific examples of the portion represented by (f ¹ ) = C (f ² ) —X ³ —Y ³ — include the following examples, but the invention is not limited thereto. In each of the following examples, f ¹¹
It is _{-H, -CH 3, -CH 2 COOCH} 3, -Cl, -
Br or represents -CN, f ¹² represents -H or -CH _3, n1 represents an integer of 1 or 2, n2 represents an integer of 2 to 12, n3 represents an integer of 3 or 4.

[0096]

[Chemical 38]

[0097]

[Chemical Formula 39]

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,
Makvomol. Chem. 186 , 685 (198
5), R.A. Asami and M.D. Takaki,
Makvomol. Chem. Suppl. , 1
2 , 163 (1985), p. Rempp, P.P. L
utz, P.P. Masson and E. Frant
a, Makromol. Chem. , Suppl.
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.

[0100]

[Chemical 40]

[0101]

[Chemical 41]

[0102]

[Chemical 42]

Resin used for the binder resin of the present invention [A]
Is the above general formula (Ia), (Ib), (IIa),
(IIb) and (III) is a graft-type copolymer containing at least one macromonomer as a polymer component, and the other polymer 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 (for example, a chlorine atom,
Bromine atom), a cyano group, or an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, 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, -SO 3} H, -OH, -COO
H, -P (= O) (OH) R ¹ (R ¹ has the same meaning as described above), cyclic acid anhydride group, and polar groups such as -SH, -CONH ₂ and -SO ₂ NH _2. Those which do not contain a copolymerization component are preferable, and therefore, the substituent may be a substituent other than the polar group contained in the polar group-containing polymer component in the resin [A]. atom (e.g. fluorine atom, chlorine atom, bromine atom, ^{etc.), - OZ 6, -COOZ 6} , -OCOZ 6 (Z
⁶ represents an alkyl group having 1 to 22 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group,
Octyl group, decyl group, dodecyl group, hexadecyl group,
A substituent such as an octadecyl group). The preferred hydrocarbon group is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, 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., alkenyl group having 4 to 18 carbon atoms which may be substituted (for example, 2-methyl-1-propenyl group) , 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), 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) , Methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.) and alicyclic groups having 5 to 8 carbon atoms which may be substituted (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) 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 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 following general formula (IVa) and / or 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]).

[0108]

[Chemical 43]

[0109]

[Chemical 44]

[In the formulas (IVa) and (IVb), A ¹ and A
² are each independently a hydrogen atom and a carbon number of 1-10.
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 properties (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 the effect of a planar benzene ring or naphthalene ring having a substituent at the ortho position, which is an ester component of methacrylate, causes the zinc oxide interface in the film. It is considered that the arrangement of these polymer molecular chains in 1 is appropriately performed.

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 polymer component of the repeating unit represented by a) or (IVb) are shown below. However, the scope of the present invention is not limited to this.

[0115]

[Chemical formula 45]

[0116]

[Chemical formula 46]

[0117]

[Chemical 47]

[0118]

[Chemical 48]

[0119]

[Chemical 49]

20% by weight to 99.5% by weight in the copolymer, using the monomer represented by the general formula (IV) as a copolymer component.
contains. Furthermore, 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 containing 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 ']). the specific content of the polar group attached to a terminal, -PO ₃ H _{2,
-SO 3 H, -OH, -COOH,} -P (= O) (O
H) R ^1, a cyclic acid anhydride group, -SH, -CONH _2, -
SO ₂ NH ₂ and the like.

Here, -P (= O) (OH) R ¹ represents a group represented by the following chemical formula 50, 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.

[0123]

[Chemical 50]

Further, the cyclic acid anhydride group means at least 1
It is a group containing one cyclic acid anhydride, and examples of the cyclic acid anhydride contained therein include an aliphatic dicarboxylic acid anhydride and an aromatic dicarboxylic acid anhydride. Examples of the aliphatic dicarboxylic acid anhydride include a succinic anhydride ring, a glutaconic anhydride ring, a maleic anhydride ring, cyclopentane-1,
2-dicarboxylic acid anhydride ring, cyclohexane-1,2-
Examples thereof include a dicarboxylic acid anhydride ring, a cyclohexene-1,2-dicarboxylic acid anhydride ring, and 2,3-bicyclo [2.2.2] octanedicarboxylic acid anhydride ring, and these rings include, for example, a chlorine atom, A halogen atom such as a bromine atom, an alkyl group such as a methyl group, an ethyl group, a butyl group and a hexyl group may be substituted.

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, -SO 3 H} , -COOH, -P (= O) (O
H) R ¹ and a cyclic acid anhydride group can be mentioned. These polar groups may be directly bonded to one end of the polymer main chain or may be bonded via a linking group. The linking group may be any bondable group, and specifically, for example, —C (d ¹ ) (d ² )-[d ¹ and d ² may be the same or different and each is hydrogen. Atom, 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.], -C (d ³ ) = C (d
^{4) - (d 3, d} 4 represents the same content as ^{d 1, d 2), -} C 6 H 10 -, - C 6 H 4 -, - O -, - S-,
—N (d ⁵ )-{d ⁵ represents a hydrogen atom or a hydrocarbon group (specifically, a hydrocarbon group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a 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) -, - SO 2 -, - NHCON
H -, - NHCOO -, - NHSO 2 -, - CONHC
OO-, -CONHCONH-, heterocycle (a 5- or 6-membered ring containing at least one kind of O, S, N, etc. as a hetero atom, or a condensed ring thereof may be used: for example, thiophene ring, pyridine ring , A furan ring, an imidazole ring, a piperidine ring, a morpholine ring and the like) or —Si (d ⁶ ) (d ⁷ )-{d ⁶ and d ⁷ may be the same or different, and are a hydrocarbon group or —Od ⁸ (D ⁸ represents a hydrocarbon group). Examples of these hydrocarbon groups include the same connecting groups as those mentioned for d ⁵ ) and the like, or a connecting group composed of a combination thereof.

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), method of radical polymerization using polymerization initiator and / or chain transfer agent containing specific polar group in 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) at the 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 has a specific polar group bonded to one end of the polymer main chain on the opposite side to the B block of the A block, either directly or through a linking group. And that it is contained as a polymer component in the A block.

The amount of the specific polar group-containing polymer component in the AB block copolymer resin [B] is preferably 0.1 to 5% by weight per 100 parts by weight of the copolymer resin [B].
More preferably, the content is 0.2 to 3% by weight.
The amount of the polar group-containing polymer component in the binder resin [B] is 0.
If it is less than 1% by weight, the initial potential is low and a sufficient image density cannot be obtained, and the amount of the polar group-containing polymer component is 5%.
If it is more than wt%, the dispersibility of the photoconductor particles will decrease,
The film smoothness in high temperature and high humidity and the electrophotographic characteristics deteriorate,
Further, when it is used as an original plate for offset lithographic printing, scumming increases, which is not preferable.

In the resin [B], the total amount of the specific polar group-containing polymer component contained in all the copolymers is the same as the specific polar group-containing polymer component contained in the resin [A]. It is preferably 10% by weight to 50% by weight with respect to the total amount. When the total amount of the resin [B] is less than 10% by weight of that of the resin [A], electrophotographic characteristics (especially dark charge retention rate, photosensitivity) are significantly deteriorated, and film strength is also decreased. On the other hand, if it exceeds 50% by weight, the dispersion of the photoconductor particles becomes insufficient, the electrophotographic characteristics are deteriorated, and the water retention property is lowered as the offset lithographic printing original plate.

The weight average molecular weight of the AB block copolymer resin [B] is 2 × 10 ⁴ to 1 × 10 ⁶ , preferably 4 × 1.
It is 0 ^{4 to} 5 × 10 ⁵ .

When the molecular weight of the resin [B] is less than 2 × 10 ⁴ , the film forming ability is lowered and the sufficient film strength cannot be maintained.
On the other hand, when the molecular weight is more than 1 × 10 ^6, the effect of the resin [B] of the present invention is reduced, and the electrophotographic characteristics are comparable to those of the conventionally known resin. The glass transition point of the resin [B] is preferably in the range of -10 ° C to 100 ° C, more preferably 0 ° C to 90 ° C.

The specific polar group contained in the polymer of the resin [B] of the present invention and at one end of the polymer main chain is -P.
_{O 3 H 2, -COOH, -SO} 3 H, -P (= O) (O
H) R ¹ [R ¹ represents the same meaning as described above] and a cyclic acid anhydride group. Where -P (= O) (OH)
Specific examples of R ¹ and the cyclic acid anhydride group include resin [A]
The ones mentioned above are listed. In the resin [B], when the polar group is bonded to one end of the polymer main chain, the polar group may be directly bonded to one end of the polymer main chain or may be bonded via a linking group. You may. The linking group may be any group that bonds, but specifically,
—CR ¹⁴ R ¹⁵ — [wherein R ¹⁴ and R ¹⁵ 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.), a phenyl group, etc.], —CH (R ¹⁴ ) —CH (R ¹⁵ ) —, —C _{6
H 10 -, - C 6 H} 4 -, - O -, - S -, - N (R 16)
-[Wherein R ¹⁶ is a hydrogen atom or a hydrocarbon group (specifically, a hydrocarbon group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group. , Decyl group, dodecyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-cyanoethyl group,
Benzyl group, methylbenzyl group, phenethyl group, phenyl group, tolyl group, chlorophenyl group, methoxyphenyl group, butylphenyl group, etc.)}]-
CO -, - COO -, - OCO -, - CON (R 16)
_{-, - SO 2 N (R} 16) -, - SO 2 -, - NHCON
H -, - NHCOO -, - NHSO 2 -, - CONHC
OO-, -CONHCONH-, heterocycle (a 5- or 6-membered ring containing at least one kind of O, S, N or the like as a hetero atom or a condensed ring thereof may be used, and examples thereof include a thiophene ring, a pyridine ring, and a furan ring. , an imidazole ring, piperidine ring, morpholine ring and the like), or ^{_{-S i (R 17) (R}} 18) - [wherein R ^17, R ¹⁸ may be the same or different, each hydrocarbon radical or - OR ¹⁹
(Wherein R ¹⁹ represents a hydrocarbon group). Examples of these hydrocarbon groups include the same groups as those listed for R ¹⁶ ] or the like, or a linking group formed of a combination of two or more of these bonding groups.

Next, the polymer component constituting the A block of the resin [B] will be described. Examples of the polar group contained in the polymer chain of the A block of the resin [B] of the present invention include the same groups as those bonded to the ends of the main chain. The following can be mentioned as specific examples of the polymer component containing a specific polar group constituting the A block of the AB block copolymer (resin [B]) of the present invention. Where b
³ represents H or CH ₃ , b ⁴ represents H, CH ₃ or CH ₂
COOCH ₃ , R ⁷ represents an alkyl group having 1 to 4 carbon atoms, R ⁸ represents an alkyl group having 1 to 6 carbon atoms, a benzyl group or a phenyl group, e represents an integer of 1 to 3, g Represents an integer of 2 to 11, h represents an integer of 1 to 11, and x
Represents an integer of 2 to 4, and j represents an integer of 2 to 10.

[0139]

[Chemical 51]

[0140]

[Chemical 52]

[0141]

[Chemical 53]

[0142]

[Chemical 54]

[0143]

[Chemical 55]

[0144]

[Chemical 56]

Two or more kinds of the polymer component containing a 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 are contained in the A block. It may be contained in any form of random copolymerization or block copolymerization. Further, a polymer component other than the polar group-containing polymer component may be contained in the A block, and such a polymer component is preferably a polymer component corresponding to a repeating unit of the following general formula (V). Is mentioned.

[0146]

[Chemical 57]

[In the formula (V), V ² is -COO-, -OC.
_{O -, - (CH 2)} i OCO -, - (CH 2) i COO
-, - O -, - SO 2 -, - CON (R 22) -, - SO
₂ N (R ²² )-, -CO-, -CONHCOO-, -C
ONHCONH- or -C ₆ H ₄ - are presented (here,
i represents an integer of 1 to 3, and R ²² represents a hydrogen atom or a hydrocarbon). R ¹³ represents a hydrocarbon group. d ⁹ and d
¹⁰ may be the same as or different from each other, and have the general formula (I
The same contents as b ¹ and b ^{2 in} V) are shown. ]

Here, R ²² is not only a hydrogen atom, but also a preferable hydrocarbon group is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group). 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.), alkenyl group having 4 to 18 carbon atoms which may be substituted (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.), aralkyl group having 7 to 12 carbon atoms and which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group) , A bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), and an alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, a cyclohexyl group, 2- A cyclohexylethyl group, a 2-cyclopentylethyl group, etc.) 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, butoxyf Nyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarboxyphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group , Dodecylylamidophenyl group, etc.).

When V ² represents —C ₆ H ₄ —, the 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.

R ¹³ represents a hydrocarbon group, and a preferable hydrocarbon group is an optionally substituted alkyl group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group). , Hexyl group, octyl group,
Decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-
Methoxycarbonylethyl group, 2-methoxyethyl group,
3-bromopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms which may be substituted (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-perenyl group). Ntenyl 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 (eg, benzyl group, phenethyl group). Group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), carbon number 5 to 8 optionally substituted alicyclic groups (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc. 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, A propioamidophenyl group, a dodecyloylamidophenyl group, etc.).

More preferably, in the general formula (V),
V ² is -COO-, -OCO-, -CH ₂ OCO-,-.
_{CH 2 COO -, - O -} , - CONH -, - SO 2 NH
- or -C ₆ H ₄ - represents a.

Further, as a polymer component which can be contained in the A block together with the polymer component represented by the formula (V), it corresponds to another repeating unit copolymerizable with the polymer component represented by the formula (V). Monomers such as acrylonitrile, methacrylonitrile, and heterocyclic vinyls (for example, vinyl pyridine, vinyl imidazole, vinyl pyrrolidone, vinyl thiophene, vinyl pyrazole, vinyl dioxane, vinyl oxazine, etc.) and the like. 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 components constituting the B block component in the AB block copolymer resin [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, Preferably 50-
100% by weight is contained.

The specific contents of the component of the general formula (IV) are the same as those described for the resin [A]. Examples of the other polymer component that can be contained include the same components as those described as the component represented by the general formula (V) that can be contained in the A block or the other components. However, the B block is characterized by not containing the specific polar group-containing component contained in the A block.

AB block copolymer resin [B] of the present invention
Can be produced by a conventionally known polymerization reaction method. Specifically, in the monomer corresponding to the polymer component containing the specific polar group, the polar group is preliminarily protected as a functional group, and an organometallic compound (eg, alkyllithium, lithium diisopropylamide, alkylmagnesium) is used. Halides etc.) or ionic polymerization reaction with hydrogen iodide / iodine system, photopolymerization reaction using porphyrin metal complex as catalyst, group transfer polymerization reaction, or other known so-called living polymerization reaction to polymerize the AB block copolymer. After that, a specific polar group is directly introduced during the termination reaction, or a polar group is chemically bonded after introducing a functional group capable of binding the polar group, and then a functional group that protects the polar group in the polymer component is added. Hydrolysis reaction, hydrogenolysis reaction,
A method of forming a polar group by performing a deprotection reaction by an oxidative decomposition reaction, a photodecomposition reaction or the like can be mentioned. One example thereof is shown in the following reaction scheme (A).

[0156]

[Chemical 58]

These can be easily synthesized, for example, according to the synthetic method described in the literature and the like described in the synthetic method of the resin [A].

Further, an AB block copolymer resin [B]
Is light-irradiated using a monomer that does not protect the polar group, and a compound containing a disiocarbament group containing a specific polar group as a substituent and / or a compound containing a xanthate group as an initiator. It can also be synthesized by performing a polymerization reaction below. For example, it can be synthesized according to the synthetic method described in the literature described in the synthetic method of resin [A].

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,
The method described in detail in the review article described in the method of synthesizing resin [A] can be appropriately selected and performed.

On the other hand, in the resin [B] of the present invention, it is preferable that the B block has a longer polymer chain than the A block.

As the binder resin used for the photoconductive layer of the present invention, in addition to the resins [A] and [B] of the present invention, the above-mentioned known resins for inorganic photoconductors can be used in combination.
However, the proportion of these other resins used is the total amount of the binder resin 10
A range not exceeding 30 parts by weight in 0 parts 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 copolymers, styrene-butadiene copolymers, styrene-methacrylate copolymers, methacrylate copolymers, acrylate copolymers. , 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 Kae, Isamu Shimizu, Eiichi Inoue, The Electrophotographic Society of Japan 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. When 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 electrophotographic characteristics are deteriorated and the copied image is deteriorated even in the actual image pickup property.

The ratio of the resin [A] and the resin [B] used in the present invention is 0.05 to 0.05 by weight ratio of resin [A] / resin [B].
It is preferably 0.6 / 0.95 to 0.40, more preferably 0.10 to 0.50 / 0.90 to 0.50.
Is. If the weight ratio of the resin [A] to the resin [A] and the resin [B] used in the present invention is 0.05 or less, the effect of improving the electrophotographic characteristics is diminished. On the other hand, 0.
When it is 6 or more, the film strength of the photoconductive layer cannot be sufficiently maintained (particularly as an electrophotographic lithographic printing plate precursor). Two or more kinds of each of the resin [A] and the resin [B] provided for the photoconductive layer may be used, and what is important is to use the resin [A] and the resin [B] in the above proportions. Is to be done.

The inorganic photoconductor used in the present invention includes:
Examples thereof 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 (1954), 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, those mainly containing carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes are disclosed in JP-B-51-45.
2, JP-A-50-90334 and JP-A-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 the near-infrared to infrared light region having a long wavelength of 700 nm or more, JP-A-4,
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 the performance thereof does not easily vary 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, the aforementioned review article: Imaging 1973 (No. 8) No. 12
Electron-accepting compounds (eg halogen, benzoquinone, chloranil, organic carboxylic acid anhydrides, etc.), Hiroshi Komon, et al., “Recent Developments and Practical Uses of Photoconductive Materials and Photoconductors” Chapters to Chapter 6 ・ Polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds and the like, which are the general references of the Japanese Scientific Information Co., Ltd. Publishing (1986).

The addition amount of these various additives is not particularly limited, but is usually 0.0001 to 2.0 parts by weight with respect to 100 parts by weight of the inorganic photoconductor. The thickness of the photoconductive layer is preferably 1 to 100 μm, particularly preferably 10 to 50 μm.

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 μm is preferable.

In some cases, an insulating layer may be additionally provided for the purpose of protecting the photoreceptor and improving durability and dark charge retention. 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 thickness of the insulating layer is 5 to 70 μm.
m, particularly 10 to 50 μm. Examples of the charge transport material for the laminated photoreceptor include polyvinyl carbazole, oxazole dyes, pyrazoline dyes, triphenylmethane dyes and the like. The thickness of the charge transport layer is 5 to
40 μm, particularly 10 to 30 μm is suitable.

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 acetate copolymer resin, polyacrylic resin, polyolefin resin, urethane resin, polyester resin, epoxy resin, melamine resin, silicone resin thermoplastic resin and curable resin are appropriately used. To be

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, the basic back surface (the 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, paper having at least one precoat layer provided on the surface layer of the support, if necessary, and electroconductive plastic substrate having Al vapor deposited thereon. Those laminated to can be used.

Concrete examples of the conductive substrate or the conductive material are 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.

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 IEICE 77 , 17 (197)”.
7 years) and the like).

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 lithographic printing process, a color group, or the like.

[0181]

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 1,9-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 g 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-1
The weight average molecular weight of 01) was 6.8 × 10 ³ .

[0183]

[Chemical 59]

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 Synthesis Example 101 of macromonomer. 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 a 0.1N potassium hydroxide methanol solution, it was 500 μmol /
gr. Became.

100 g of the above solid, 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 .

[0189]

[Chemical 60]

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 (THF) was added at a temperature of 40 to 45.
The mixture was stirred at 0 ° C for 6 hours. The reaction mixture in 1 liter of water,
The mixture was added dropwise with stirring for 1 hour and further stirred for 1 hour. Let stand and take out the sedimented liquid by decantation.
It was dissolved in 200 g of HF and reprecipitated in 1 liter of methanol. Remove the sedimented liquid by decantation,
It was 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 .

[0192]

[Chemical formula 61]

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.

[0194]

[Chemical formula 62]

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 .

[0196]

[Chemical formula 63]

Resin [A] Synthesis Example 101: [A-101] Ethyl methacrylate 85 g, macromonomer (MA-
101) A mixture of 15 g and 200 g of toluene was heated to a temperature of 85 ° C. under a nitrogen stream. 6 g of 2,2′-azobis (valeronitrile) (abbreviation AIVN) was added and 3
Stir for hours. In addition, 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 .

[0198]

[Chemical 64]

Synthesis Example of Resin [A] 102: [A-10
2] benzyl methacrylate 95g, macromonomer (MA
-104) 5 g, toluene 150 g and ethanol 50
g mixture was warmed to a temperature of 80 ° C. under a stream of nitrogen.
4,4'-azobis (2-cyanovaleric acid) (abbreviation: A.A.
C. V. ) 5 g was added and 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 .

[0200]

[Chemical 65]

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.

[0202]

[Table 1]

[0203]

[Table 2]

[0204]

[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 .

[0206]

[Chemical formula 66]

Synthesis Examples 115 to 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] shown in Table B below was produced under the same polymerization conditions.

[0208]

[Table 4]

[0209]

[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 the following Table-C was produced under the same polymerization conditions. Mw of each resin [A] is 8 × 10 ^{3 to} 1.5 ×
It was 10 ⁴ .

[0211]

[Table 6]

[0212]

[Table 7]

Synthesis Examples 132-141: [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 .

[0214]

[Table 8]

[0215]

[Table 9]

Synthesis Example 142 of Resin [A]: [A-14
2] 80 g of benzyl methacrylate, macromonomer (MA
A mixture of 20 g of -105) and 200 g of toluene 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 .

[0217]

[Chemical formula 67]

(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.

Next, 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 filtered through a 200-mesh nylon cloth to remove insoluble materials. 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.

[0221]

[Chemical 68]

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 .

[0224]

[Chemical 69]

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 still, the precipitated liquid material 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 .

[0227]

[Chemical 70]

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 matter 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.

[0230]

[Chemical 71]

Resin [A] Synthesis Example 201: [A-201] 80 g of benzyl methacrylate, macromonomer (MA
A mixture of 20 g of -201), 150 g of toluene and 50 g of ethanol was heated to a temperature of 80 ° C under a nitrogen stream.
4,4'-azobis (4-cyanovaleric acid) (abbreviation A.
C. V. ) 6 g 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 .

[0232]

[Chemical 72]

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 .

[0234]

[Table 10]

[0235]

[Table 11]

[0236]

[Table 12]

[0237]

[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 was heated at a temperature of 75 under a nitrogen stream.
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 .

[0239]

[Chemical formula 73]

[0240]

[Chemical 74]

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 .

[0242]

[Table 14]

[0243]

[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 .

[0245]

[Chemical 75]

[0246]

[Chemical 76]

Synthesis Examples 302 to 307 of Resin [A]: [A
-302] to [A-307] In Synthesis Example 301 of Resin [A], the following 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 following table. 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 .

[0248]

[Table 16]

[0249]

[Table 17]

Synthesis Example of Resin [A] 308: [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.

[0252]

[Chemical 77]

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 .

[0254]

[Table 18]

[0255]

[Table 19]

[Synthesis of Resin [B]] Synthesis Example 1 of Resin [B] 1: [B-1] 42.5 g of methyl acrylate, 2.5 g of acrylic acid,
2-Carboxyethyl N, N-diethyldithiocarbamate: [I-1] 7.6 g and tetrahydrofuran 50
The mixture of g was sealed in a container under a nitrogen stream and the temperature was 50 ° C.
Warmed to. To this, 10cm with 400W high pressure mercury lamp
Light was irradiated for 8 hours through a glass filter from a distance of 3 to photopolymerize.

The reaction product was reprecipitated in 500 ml of petroleum ether, and the precipitate was collected and dried. The yield of the obtained polymer was 41 g, and the Mw was 1.0 × 10 ⁴ . Further, a mixture of 10 g of the above-mentioned polymer (which serves as a polymer initiator), 65 g of methyl methacrylate, 25 g of methyl acrylate and 100 g of tetrahydrofuran was heated to 50 ° C. under a nitrogen stream. This is irradiated with light under the same conditions as above, and 1
Photopolymerized for 0 hours. The obtained mixture was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. The yield of the obtained block polymer was 85 g, and the Mw was 8.5 × 10 ⁴ .

[0258]

[Chemical 78]

Synthesis Example 2 of Resin [B-2]: [B-2] 67 g of methyl methacrylate and 33 g of methyl acrylate
g, benzyl N-ethyl-N- (2-carboxylethyldithiocarbamate: [I-2] 2.2 g and a mixed solution of 100 g of tetrahydrofuran under a nitrogen stream at a temperature of 50.
℃ was made. This was photopolymerized for 8 hours under the same light irradiation conditions as in Synthesis Example 1. The reaction mixture was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to obtain a polymer having a Mw of 8 × 10 ^{4 in} a yield of 85 g. A mixture of 85 g of the above polymer, 14 g of methyl methacrylate, 1 g of methacrylic acid and 150 g of tetrahydrofuran was heated to 50 ° C. under a nitrogen stream. This was photopolymerized for 16 hours under the same light irradiation conditions as in Synthesis Example 1. The reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to obtain a block copolymer having an Mw of 9.5 × 10 ^{4 in} a yield of 83 g.

[0260]

[Chemical 79]

Synthesis Example 3 of Resin [B]: [B-3] A mixed solution of 80 g of ethyl methacrylate and 200 g of toluene was sufficiently deaerated under a nitrogen stream and cooled to -20 ° C. Next, 2.0 g of 1,1-diphenyl-3-methylpentyllithium was added, and the mixture was stirred for 12 hours. Further, 19 g of methyl methacrylate and 1.5 g of 4-vinylphenylcarbonyloxytrimethylsilane were added to this mixture, and the mixture was reacted for 12 hours, then reacted in a carbon dioxide stream for 2 hours as it was, and further reacted at a temperature of 0 ° C. for 2 hours.

To this reaction mixture, 1 liter of a methanol solution containing 10 g of 30% hydrochloric acid was added dropwise with stirring for 30 minutes, and the mixture was stirred for 1 hour as it was. The precipitated powder was filtered off, washed with methanol and dried. A block copolymer having an Mw of 6.5 × 10 ⁴ was obtained with a yield of 75 g.

[0263]

[Chemical 80]

Synthesis Examples 4 to 13 of Resin [B]: [B-4]
~ [B-13] In the same reaction method as in Synthesis Example 2 of Resin [B], the following Table-I is used.
The resin [B] shown in was synthesized. Mw of each polymer obtained
Was in the range of 7 × 10 ^{4 to} 9 × 10 ⁴ .

[0265]

[Table 20]

[0266]

[Table 21]

[0267]

[Table 22]

Synthesis Examples 14 to 20 of Resin [B]: [B-1
4] to [B-20] In the synthesis example of the resin [B-1], the initiator [I-1]
Instead of 7.6 g, 4.2 x 1 of each initiator in Table-J below.
0 ^-3 other with moles, in the same manner as in Synthesis Example 1, it was synthesized the block copolymer. Mw of each copolymer is 8 × 10
It was in the range of ⁴ to 10 × 10 ⁴ .

[0269]

[Table 23]

Synthesis Examples 21 to 30 of Resin [B]: [B-2
1] to [B-30] Each polymer corresponding to the following Table-K was polymerized by a photopolymerization reaction in the same manner as in Synthesis Example [B-2].

[0271]

[Table 24]

[0272]

[Table 25]

Example 1 and Comparative Example 1 6 g (as solid content) of resin [A-107], resin [B
-1] 34 g (as solid content), photoconductive zinc oxide 2
00g, a mixture of 0.018 g of methine dye [I] having the following structure, 0.18 g of thiosalicylic acid and 300 g of toluene in a homogenizer (manufactured by Nippon Seiki Co., Ltd.), the rotation speed is 6 ×.
A photosensitive layer-formed product was prepared by dispersing at 10 ³ rpm for 10 minutes, and a dry adhesion amount of 18 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 (hereinafter, also simply referred to as a light-sensitive material) was produced by drying for one second and then leaving it in the dark at 20 ° C. and 65% RH for 24 hours.

[0274]

[Chemical 81]

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 photosensitive material was produced in the same manner as in Example 1 except that was used.

[0276]

[Chemical formula 82]

With respect to these photosensitive materials, the electrostatic property and the image pick-up property were examined. The results are shown in Table-L.

[0278]

[Table 26]

Embodiments of the evaluation items shown in Table-L are as follows. Note 1) Electrostatic characteristics: In a dark room at a temperature of 20 ° C and 65% RH,
-6 kV using a paper analyzer (Paper Analyzer SP-428 type manufactured by Kawaguchi Electric Co., Ltd.) for the photosensitive material
After corona discharge for 20 seconds, it was left for 10 seconds, and the surface potential V ₁₀ at this time was measured. Then 9 in the dark
The potential V ₁₀₀ after standing for 0 seconds was measured, and the potential retention after dark decay for 90 seconds, that is, the dark charge retention rate [D
RR (%)] was calculated by (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. The environmental conditions at the time of measurement are (I) (20
C, 65% R.C. H. ), (II) (30 ° C., 80% R.I.
H. ) And (III) (15 ° C., 30% RH). Note 2) Imaging property: After leaving the light-sensitive material under the following environmental conditions for one day and night, charge the light-sensitive material at −6 kV and use it as a light source.
Using a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm) with an output of 8 mW as a liquid developer after speed exposure with a pitch of 25 μm and a scanning speed of 300 m / sec under the irradiation amount of 64 erg / cm ² on the surface of the photosensitive material, ELP-T (Fuji Photo Film Co., Ltd.)
Developed image, washed with a rinse solution of isoparaffin Isopar G (manufactured by Esso Chemical Co., Ltd.) solvent, and then fixed. The copied image (fog, image quality of image) was visually evaluated. The environmental conditions at the time of imaging are (I) (20 ° C, 65%
R. H. ), (II) (30 ° C., 80% RH) and (I
II) (15 ° C., 30% RH).

As shown in Table-L, the light-sensitive material of the present invention is
Even if the environmental conditions changed, the electrostatic characteristics were good, and the actual copied image had no 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. Also, the deviation of fine characters (especially Mincho type Kanji)
In some cases, the resolution was lowered.

Further, under the condition of low temperature and low humidity (III), minute 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 6 g of resin [A-213] (as solid content), resin [B
-2] 36 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 photosensitive material was produced by operating 00 g of the mixture in the same manner as in Example 1. (However, the coating amount is 25 g / m ²
The wire bar was adjusted so that )

[0283]

[Chemical 83]

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 36 g of the resin [R-1] was used instead of 36 g. The film properties (smoothness of the surface) of each photosensitive material, the mechanical strength of the photoconductive layer, the electrostatic characteristics and the imaging property were examined. Furthermore, the printability when used as an original plate for electrophotographic lithographic printing was examined.

[0285]

[Table 27]

Embodiments of the evaluation items shown in Table-M are as follows. Note 3) Smoothness of surface layer: The photosensitive material was measured for its smoothness (sec / cc) using a Beck's smoothness tester (manufactured by Kumagai Riko Co., Ltd.) under an air volume of 1 cc. Note 4) Mechanical strength of photoconductive layer: Emery paper (# 1000) with a load of 75 g / cm ^{2 on} the surface of the photosensitive material using Haydon-14 type surface test material (manufactured by Shinto Chemical Co., Ltd.) The residual powder rate (%) was determined from the weight loss of the photosensitive layer by removing the abrasion powder after 1000 cycles of operation and determined as the mechanical strength. Note 5) Raw plate water retention: EPL-EX (Fuji Photo Film Co., Ltd.), a desensitizing treatment liquid for photosensitive materials (those that are not plate-making)
The solution obtained by diluting 7 times with distilled water was passed through an etching processor twice to desensitize the surface of the photoconductive layer, and then distilled water was used as fountain solution to prepare an offset printing machine (Hamada Co., Ltd.). 611XLA-II, manufactured by Printing Machinery Factory
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 image pickup property of Note 2) above, after plate making and forming a toner image, ELP-EX was used to pass through an etching processor twice to desensitize. This is used as an offset lithographic printing plate precursor and applied to an offset printing machine (Oliver 52 type manufactured by Sakurai Seisakusho Co., Ltd.) to show the number of prints that can be made without causing problems in the non-image area of the printed matter and the image quality of the image area. (The larger the number of printed sheets, the better the printing durability).

As shown in Table-M, 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 lithographic printing original plate, the desensitizing treatment with the desensitizing treatment liquid proceeds sufficiently, and even when the water retention under forced conditions is evaluated, it is sufficiently hydrophilized, and ink adhesion Was not recognized at all. 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 at the time of image pickup became severe, problems such as occurrence of unevenness in the high-definition continuous tone image portion or white spots and unevenness in the solid image portion occurred.

Further, as the offset lithographic printing plate precursor, 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 poor, and thus the image quality of the printed matter is naturally poor. The above is the fact that the resin [A] and the resin [B] of the present invention properly interact with the zinc oxide particles to form a state in which the desensitizing reaction by the desensitizing treatment liquid easily and easily proceeds. And that the film strength is remarkably improved by the action of the resin [B]. Example 3 and Comparative Example 3 Resin [A-314] 5 g (as solid content), Resin [B
-3] 35 g (as solid content), photoconductive zinc oxide 2
A mixture of 00 g, 0.020 g of methine dye [III] having the following structure, 0.10 g of salicylic acid, 0.10 g of phthalic anhydride and 300 g of toluene was treated in the same manner as in Example 2 to prepare an electrophotographic light-sensitive material.

[0290]

[Chemical 84]

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 following resin [R-2] 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-N.

[0292]

[Chemical 85]

[0293]

[Table 28]

As shown in Table-N, 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 photoconductive particles and the binder resin are sufficiently adsorbed and the particle surfaces are covered. For the same reason, even when used as an offset lithographic printing original plate, the desensitizing treatment with the desensitizing treatment liquid proceeds sufficiently, and even when the water retention under forced conditions is evaluated, it is sufficiently hydrophilized, and ink adhesion Was not recognized at all. 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 image capturing conditions 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, the water retention of the lithographic printing plate, which had been subjected to the desensitization treatment, was good as the offset lithographic printing plate. 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.

As described 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 that the film strength is remarkably improved by the action of the resin [B]. Examples 4 to 19 In Example 2, the resin [A-213] 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-O was used instead of 2].

[0297]

[Table 29]

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 lithographic printing plate precursor and printed in the same manner as in Example 2, at least 10,000 or more sheets could be printed. From the above, each of the light-sensitive materials of the present invention was good in all respects of the 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 methine dye [I] used in Example 1 was replaced with the dye shown in Table P below.

[0300]

[Table 30]

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 and high humidity (II) (30 ° C., 80% RH) and Even under severe environmental conditions of low temperature and low humidity (III) (15 ° C., 30% RH), a clear image with no background fog was provided. Examples 23 and 24 and Comparative Example 4 Resin [A-202] (Example 23) or Resin [A-20
6] Any of 6.5 g of (Example 24), resin [B-3
0] 33.5 g, photoconductive zinc oxide 200 g, uranine 0.02 g, methine dye [VII] 0.03 having the following structure
g, a mixture of 0.03 g of the methine dye [VIII] having the following structure, 0.18 g of p-hydroxybenzoic acid and 300 g of toluene in a homogenizer at a rotation speed of 6 × 10 ³ rpm and 5
The photosensitive layer-formed product was prepared by dispersing for a minute, and this was coated on 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. Next, each electrophotographic photosensitive member was prepared by leaving it in the dark at 20 ° C. and 65% RH for 24 hours.

[0302]

[Chemical 86]

[0303]

[Chemical 87]

Comparative Example 4 In Example 23, 33.5 g of the above resin [R-1] was used instead of 33.5 g of the resin [B-30],
A light-sensitive material was prepared in the same manner as in Example 23. The characteristics of each light-sensitive material were examined in the same manner as in Example 1. The results are summarized in Table-Q below.

[0305]

[Table 31]

In the above measurement, the electrostatic property and the image pickup property were the same as in Example 1 except that the following operation was performed. 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 the light-sensitive material for one day under the following environmental conditions, fully automatic plate-making machine EPL-404V (manufactured by Fuji Photo Film Co., Ltd.)
Then, the copied image (fog, image quality) obtained by plate making using EPL-T as a toner was visually evaluated. The environmental conditions at the time of imaging are (I) (20 ° C., 65% RH),
(II) (30 ° C., 80% RH) and (III) (15
C, 30% R.C. H. ) Was carried out. However, the original for copying (that is, the original copy) was prepared by cutting out and pasting other originals.

In each of the light-sensitive materials of the present invention, the photoconductive layer had good mechanical strength, 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.

[0308] 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 Became 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 at the time of 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 a desensitizing treatment as an offset lithographic printing original plate and printed, all of the present invention produced 10,000 printed matters with clear image quality without scumming. 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-119] and 35 g of resin [B-25],
Photoconductive zinc oxide 200g, uranine 0.02g, rose bengal 0.04g, bromphenol blue 0.0
A mixture of 3 g, 0.20 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.

The light-sensitive material of the present invention was operated in the same manner as in Example 24 and examined for each performance. All were excellent in chargeability, dark charge retention rate and photosensitivity, and actually copied images were high in temperature and humidity. (II) (30 ℃, 80% RH) and low temperature / low humidity (II)
Even under the severe condition of I) (15 ° C., 30% RH), a clear image without generation of background fog was provided.

Further, when this was used as an original plate for offset lithographic printing and printed, a printed matter having a clear image quality was obtained even at 10,000 sheets. Examples 26 to 49 In Example 25, 5 g of the resin [A] and 35 g of the resin [A-119] were used instead of 5 g of the resin [A-119] and 35 g of the resin [B-25]. Each light-sensitive material was prepared in the same manner as in Example 23.

[0313]

[Table 32]

All of the light-sensitive materials of the present invention are excellent in chargeability, dark charge retention rate, and photosensitivity, and actual copied images are high temperature / high humidity (II) (30 ° C., 80% RH) and low temperature ・Low humidity (II
Even under the severe condition of I) (15 ° C., 30% RH), a clear image without generation of background fog or fine line skip was obtained. Further, when printed as an offset lithographic printing original plate, a printed matter having clear image quality without generation of scumming was obtained even after printing 10,000 sheets.

[0315]

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

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03G 5/08 102 9223-2H 13/26

Claims (4)

[Claims] 1. An electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor, 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 photoreceptor 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)
1 as a polymer component
^{3 to} 2 × 10 ⁴ graft type copolymer. [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, -COOH, -SO} 3 H, -P (= O) (O
H) R ¹ [R ¹ represents a hydrocarbon group or —OR ² (R ² represents a hydrocarbon group)] and a polymer component having at least one polar group selected from cyclic acid anhydride groups. A composed of an A block contained and a B block containing at least a polymer component represented by the following general formula (IV)
It is composed of a B block copolymer, and in the A block, at least one polar group selected from the above specific polar groups is bonded to the end of the polymer main chain on the side opposite to the B block. resin. [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] contains --PO ₃ H ₂ , --SO ₃ H, --OH and --COO only at one end of the polymer main chain.
H, at least one selected from -P (= O) (OH) R ¹ (R ¹ has the same meaning as above), a cyclic acid anhydride group, -SH, -CONH ₂ and -SO ₂ NH ₂ . 3. The electrophotographic photosensitive member according to claim 1, which is formed by bonding a polar group. 4. In the resin [B], the total amount of the specific polar group-containing polymer component contained in all the copolymers is the specific polar group-containing polymer contained in the resin [A]. The electrophotographic photoreceptor according to claim 1, wherein the content is 10% by weight to 50% by weight based on the total amount of the components.