JPH06175379A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To always maintain stable electrostatic characteristics and to obtain sharp and good picture images by using a binder resin containing a specified resin [A] and specified resins [B1] and [B2]. CONSTITUTION:The binder resin contains a resin [A] and resin [B1], [B2]. The resin [A] is a grafted copolymer having 1X10<3>-2X10<4> weight average mol.wt. and containing macromonomers as a polymer component having 1X10<3>-1.5X10<4> weight average mol.wt. expressed by formulae I, II, etc. In formulae I, II, f<1>, f<2> are hydrogen atoms, halogen atoms, etc., X<1> is a single bond, -COO-, etc., Y<1> is a group to connect X<1> and -COO-, Z<1> and Z<2> are bivalent aliphatic groups, and R<31> is hydrogen atom, etc. Each of resin [B1] and [B2] is a specified star polymer different from each other containing a polymer component expressed by formula III. The resin [B1] or [B2] contains a specified polymer component having a specified polar group by 0.001-10wt.% and the polymer component expressed by formula III by >=30wt.%. In formula III, b<1>, b<2> are hydrogen atoms, etc., and R<4> is a hydrocarbon group.

Description

Detailed Description of the Invention

[0001]

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

[0002]

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

Photoreceptors 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 offset original plate 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 these resins or combinations of resins are used, they are still insufficient in maintaining stable performance when the environment changes significantly from high temperature / high humidity to low temperature / low humidity. I knew it was. The scanning exposure method that uses a semiconductor laser beam has a longer exposure time than the conventional simultaneous full-exposure method that uses visible light, and also has a limited exposure intensity, so electrostatic characteristics, especially dark charge retention characteristics, are used. , For light sensitivity,
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. It has become noticeable.
Further, when it is used as a lithographic printing original plate, there arises a problem that a printed document has a trace of being stuck on a printed matter.

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. 1 of the present invention
One purpose is to provide an electrophotographic photosensitive member having a clear and high-quality image, which constantly maintains good electrostatic characteristics even when the environment during copy image formation changes such as low temperature and low humidity or high temperature and high humidity. It is to be.

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. Still another object of the present invention is to provide an electrophotographic photosensitive member effective for a scanning exposure system using a semiconductor laser beam. Still another object of the present invention is to reproduce a copy image which is excellent in electrostatic characteristics (especially dark charge retention and photosensitivity) and which is faithful to an original image (especially high-definition continuous tone image), and It is an object of the present invention to provide an electrophotographic lithographic printing plate precursor that 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 ₁ ] and [B ₂ ] 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 ₁ ] having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ ,
_{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 star-type polymer in which at least three AB block polymer chains each having an A block contained therein and a B block containing a polymer component represented by the following general formula (IV) are bonded in an organic molecule. A polymer containing 0.01 to 10% by weight of the polymer component having the polar group and 30% by weight or more of the polymer component represented by the general formula (IV).

[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. Resin [B ₂ ] having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ and having at least three polymer chains containing the polymer component represented by the general formula (IV) bound to the organic molecule. At least one selected from the specific polar groups represented by the resin [B ₁ ] at the end of the opposite main chain bonded to the organic molecule of the polymer chain. The polymer component having a polar group is bound to the polymer component having a polar group of 0.
A polymer containing 0 to 10% by weight and containing 30% by weight or more of the polymer component represented by the general formula (IV).

That is, the binder resin of the present invention has the general formula (I
a), (Ib), (IIa), (IIb) and at least one of the resins [A] which is a graft copolymer containing a macromonomer (M) represented by (III) as a copolymerization component. One type and a resin [B ₁ ] which is a star-type polymer in which three or more AB block polymer chains are bonded in an organic molecule and a polymer component represented by the above general formula (IV) are contained and specified at the end. Resins [B ₂ ] (resins [B ₁ ] and [B ₂ ]), which are star-type polymers in which three or more polymer chains having polar groups bonded in an organic molecule are collectively referred to as resin [B] And at least one of the above).

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 medium to high molecular weight resin to be used in combination with the low molecular weight resin [A] which is the graft copolymer of the present invention, a polar group according to the present invention is added to one end and / or a block of the polymer chain. It has been found that the above problems can be effectively solved by using the resin [B] which is a star-type polymer contained in the form.

This is due to the synergistic effect of the binder resins [A] and [B] of the present invention, the photoconductive particles are present in a state in which they are sufficiently dispersed and not condensed, and further, the spectral sensitizing dye and the chemical sensitizing dye are present. At a high performance level, the sensitizer is sufficiently adsorbed on the surface of the photoconductor particles, and the binder resin is sufficiently adsorbed on the extra active sites on the surface of the photoconductor to compensate for traps. It is estimated that the electrostatic characteristics can be stably maintained.

That is, the low molecular weight resin [A], which is the graft copolymer of the present invention, is sufficiently adsorbed to the photoconductor particles to uniformly disperse the particles, and the polymer chain is short. It has important effects such as suppressing aggregation and preventing adsorption of the spectral sensitizing dye. Further, by using the resin [B] of the present invention, which is a star-type polymer having at least three polymer chains containing a specific component in the same molecule, the mechanical strength of the photoconductive layer is significantly improved. To do.
This is because the polar group-containing component of the resin interacts weakly with the photoconductor particles as compared with the resin [A], and the polymer chains of this resin are entangled between the polymer chains due to the star-shaped regulation. It is thought that this is due to the effects.

Furthermore, the electrostatic characteristics are improved as compared with the case where a known medium to high molecular weight resin is used in combination. It is considered that this is because the polar group-containing portion that interacts with the photoconductor particles has a polarity, and thus has a function of suppressing adsorption and exclusion of the spectral sensitizing dye. From these facts, the details are not clear, but when the photoconductive particles, the spectral sensitizing dye, the resin [A] and the resin [B] coexist, these are the same as the photoconductive particles of the spectral sensitizing dye. It is presumed that it was possible to appropriately participate in the suppression of adsorption and alienation or the electrophotographic interaction, and to bring about the effect of improving the strength of the photoconductive layer.

This effect is particularly remarkable with a polymethine dye or a phthalocyanine pigment which is particularly effective as a spectral sensitizing dye for near infrared to infrared. Furthermore, 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 pick-up property and remarkably good water retention. That is, the photoconductor of the present invention on which a copied image is formed through an electrophotographic process is desensitized by chemically treating the non-image portion with a conventionally known desensitizing treatment liquid to obtain a printing plate, which is printed by offset printing. When it is done, it shows excellent performance.

When the photosensitizer of the present invention is desensitized, the non-image areas are sufficiently hydrophilized and the water retention is improved, so that the number of printed sheets is dramatically improved. 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] used as the binder resin for the photoconductive layer of the electrophotographic photosensitive member of the present invention will be described in more detail below. The resin [A] has the general formula (Ia) or (I
b), (IIa), (IIb) and (III) containing at least one of the macromonomers (M) having a weight average molecular weight of 1 × 10 ^{3 to} 1.5 × 10 ⁴ as a polymer component. It is a thing. The resin [A] may contain two or more kinds of these macromonomers, and in particular, those represented by the general formula (I
a) and / or (Ib) the macromonomer (M
-1) containing at least one resin [A-1], and containing at least one macromonomer (M-2) represented by the general formula (IIa) and / or (IIb) [A-2].
And a macromonomer represented by the general formula (III) (M-
Resin [A-3] containing at least one of 3) 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 are changed 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 a 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.

In [] in the general formulas (Ia) and (Ib), the weight average molecular weight of the macromonomer (M-1) of the formula (Ia) and / or (Ib) is 1 × 10 ³ to 1.
It represents a repeating unit sufficient to give 5 × 10 ⁴ .

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, ^one of f ¹ and 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 connecting X ¹ and --COO--, and represents a single bond or a connecting group. Specifically, -C a group linked ^{(e 1) (e 2)} -, - C 6 H 10
_{-, - C 6 H 4 -} , - C (e 3) = C (e 4) -, - C
OO -, - OCO -, - O -, - S -, - SO 2 -, -
^{N (e 5) -, -} CON (e 6) -, - SO 2 N
^{(E 7) -, - 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 represent a divalent organic residue, and are --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.

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

[0050]

[Chemical 15]

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

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

[0056]

[Chemical 16]

[0057]

[Chemical 17]

[0058]

[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.

[0060]

[Chemical 19]

[0061]

[Chemical 20]

[0062]

[Chemical 21]

[0063]

[Chemical formula 22]

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

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

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 synthesizing 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.

[0069]

[Chemical formula 23]

[0070]

[Chemical formula 24]

[0071]

[Chemical 25]

[0072]

[Chemical formula 26]

[0073]

[Chemical 27]

[0074]

[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 used 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.

[0079]

[Chemical 29]

[0080]

[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 a carboxyl group at one end of a polyester oligomer, a reaction of esterifying a carboxylic acid or an acid amidation of a carboxylic acid in a conventionally known low molecular weight compound is used. Things can be combined. That is, 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.

[0084]

[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.

[0087]

[Chemical 32]

[0088]

[Chemical 33]

[0089]

[Chemical 34]

[0090]

[Chemical 35]

[0091]

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

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 contents as the aliphatic group having i ¹ and i ² can be mentioned), and the number of carbon atoms. 6 to 12 aromatic groups (eg, phenyl group, tolyl group, xylyl group, methoxyphenyl group, chlorophenyl group, naphthyl group, etc.)
Alternatively, it represents a —OR ⁵³ group (R ⁵³ represents a hydrocarbon group, and specifically includes an aliphatic group and an aromatic group for i ³ and i ⁴ ).

In addition to a hydrogen atom, k ⁵ is preferably a hydrocarbon group which may be substituted and has 1 to 18 carbon atoms (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).

[0097] 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).

[0098]

[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.

[0100]

[Chemical 38]

[0101]

[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.

[0104]

[Chemical 40]

[0105]

[Chemical 41]

[0106]

[Chemical 42]

Resin used in 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], a monomer represented by the above general formula (IV) is preferable as a component copolymerizable with the macromonomer (M).

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

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

Further, R ⁴ preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. During the polymer _{backbone, -PO 3 H 2, -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]).

[0113]

[Chemical 43]

[0114]

[Chemical 44]

[In Formulas (IVa) and (IVb), A ³ and A
⁴ 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 ³ and B ⁴ respectively bond -COO- and the 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 due to the effect of the planar benzene ring or naphthalene ring having a substituent at the ortho position, which is the ester component of methacrylate, the zinc oxide interface in the film is It is considered that the arrangement of these polymer molecular chains in 1 is appropriately performed.

In formula (IVa), preferred A ³ and A
⁴ , 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 ³ and B ⁴ are each a single bond connecting —COO— and the 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.

[0120]

[Chemical formula 45]

[0121]

[Chemical formula 46]

[0122]

[Chemical 47]

[0123]

[Chemical 48]

[0124]

[Chemical 49]

20% by weight to 99.5% by weight of the copolymer containing 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.

[0128]

[Chemical 50]

A 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, and thiophene-ring.
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, the P. 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. The resin [B] used as the binder resin of the photoconductive layer of the electrophotographic photosensitive member of the present invention will be described in more detail below. The resin [B] of the present invention comprises a polymer component having a specific polar group and a polymer component corresponding to the repeating unit represented by the general formula (IV) in a specific embodiment in the same molecule. It is a star-type polymer having at least three.

First, as the resin [B ₁ ], the specific polar group-containing component and the component represented by the general formula (IV) are present as a block in the polymer chain. The resin [B ₁ ] is composed of an A block containing a polymer component having a specific polar group and a B block containing a polymer component represented by the general formula [IV]. It is a star-type polymer in which at least three are bonded. The B block does not contain the particular polar group contained in the A block. In this case, the A block and the B block may be arranged in any order in the polymer chain. The resin [B ₁ ] is schematically shown below.

[0138]

[Chemical 51]

[Wherein X represents an organic molecule, and (A)
Represents the A block, (B) represents the B block,
(A) - then (B) represents a polymer chain], the resin [B _2], the specific polar group is bonded to the terminal of the main chain of the opposite binding organic molecules of the polymer chain . Such a resin [B ₂ ] is a star-type polymer in which at least three polymer chains containing the polymer component represented by the general formula (IV) are bound in an organic molecule, and the polymer chain Is a star-type polymer in which a specific polar group is bonded to the end of the opposite main chain bonded to the organic molecule. Such resin [B ₂ ]
Is schematically shown below.

[0140]

[Chemical 52]

[Where X represents an organic molecule, and [Polym
er] represents a polymer chain, (A) represents an A block, (B) represents a B block, and (A)-(B) represents a polymer chain. W represents a specific polar group. 〕In particular,
As shown in the above (B-4), the resin [B] in which the polymer chain is composed of the B block and the A block and the specific polar group is bonded to the end of the A block gives the better electrostatic property. preferable.

In the star polymer, the polymer chains having three or more molecules bonded to the organic molecule may be structurally identical or different, and the polymer chains have the same length. Or may be different.

In the star polymer of the resin [B], the upper limit of the number of polymer chains bonded to the organic molecule is at most 15,
Usually, it is about 10. The resin [B] contains a polymer component having a specific polar group in an amount of 0.01 to 1 based on the resin [B].
0% by weight and 30% of the polymer component represented by the general formula (IV)
It is characterized by containing at least wt%.

The polar group-containing component in the resin [B] is 0.
If the amount is less than 01% by weight, the initial potential is low and a sufficient image density cannot be obtained. On the other hand, if the amount of the polar group-containing component is more than 10% by weight, the dispersibility of the photoconductor particles is lowered and the film smoothness is reduced. And the electrophotographic characteristics are deteriorated under high temperature and high humidity conditions, and further, when used as an offset master, scumming is increased, which is not preferable. The amount of the polar group-containing component in the resin [B] is preferably 0.05 to 8% by weight.

In the resin [B], the total amount of the specific polar group-containing polymer component contained in the polymer is the total amount of the specific polar group-containing polymer component contained in the resin [A]. On the other hand, it is preferably 10% by weight to 50% by weight. The total amount of the resin [B] is 1 of that of the resin [A].
If it is less than 0% by weight, electrophotographic properties (especially dark charge retention rate, photosensitivity) and film strength tend to be lowered. Also,
If it exceeds 50% by weight, the uniformity of the dispersion of the photoconductor particles may be insufficient and the electrophotographic characteristics may be deteriorated, or the water retention property of the offset master plate may be deteriorated.

The content of the polymer component represented by the general formula (IV) in the resin [B] is preferably 50% by weight or more. The weight average molecular weight of the resin [B] is 2 × 10 ⁴ to 1 × 1.
0 ⁶ , preferably 3 × 10 ^{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 sufficient film strength cannot be maintained, and the molecular weight is 1 ×.
When it is larger than 10 ^6, the effect of the resin [B] of the present invention is reduced, and the electrophotographic characteristics are not so different from those of the conventionally known resin.

The glass transition point of the resin [B] is from -10 ° C to
It is preferably in the range of 100 ° C., more preferably 0.
C to 90C.

Next, the polymer component having a specific polar group in the resin [B] will be described. Here, the polymer component having a specific polar group includes those present in the polymer chain and those present at one end of the polymer chain. The polar group in the polar group-containing polymer component is, as described above, -PO.
₃ H ₂ , -SO ₃ H, -COOH, -P (= O) (O
H) those selected from R ¹ and cyclic acid anhydride groups.
Specific examples of the —P (═O) (OH) R ¹ group and the cyclic acid anhydride group include those described for the resin [A].

In the resin [B], when the polar group is present in the polymer chain of the polymer chain or at the terminal, the polar group may be directly bonded to the polymer chain or may be bonded via a linking group. May be. Examples of the linking group include the same as the linking group in the case where the polar group in the resin [A] is bonded to the polymer main chain terminal.

The polymer component containing such a polar group is copolymerized with a monomer corresponding to the repeating unit represented by the general formula (IV) [including general formulas (IVa) and (IVb)]. Any one can be used as long as it is derived from the obtained vinyl compound containing the polar group. The vinyl compound is described, for example, in "Polymer Data Handbook [Basic Edition]", edited by Japan Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) ethyl form, α-chloro form, α-bromo form, α -Fluoro compound, α-tributylsilyl compound, α-cyano compound, β-chloro compound, β-bromo compound, α
-Chloro-β-methoxy form, α, β-dichloro form, etc.),
Methacrylic acid, itaconic acid, itaconic acid half-esters,
Itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (eg 2-pentenoic acid, 2-methyl-2-
Hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid,
Maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, half-ester derivative of vinyl group or allyl group of dicarboxylic acids, and these carboxylic acids or sulfones Examples thereof include compounds having the polar group in the substituent of the acid ester or amide derivative.

Examples of the polar group-containing polymer component of this type are shown below. Here, h ¹ is H or CH ₃
, H ² represents H, CH ₃ or CH ₂ COOCH ₃ , R ₁₄ represents an alkyl group having 1 to 4 carbon atoms, and R ₁₅ represents an alkyl group having 1 to 6 carbon atoms, a benzyl group or a phenyl group. , C is an integer of 1 to 3, d is an integer of 2 to 11, e1 is an integer of 1 to 11, e2 is an integer of 2 to 4, and g is an integer of 2 to 10. Show.

[0152]

[Chemical 53]

[0153]

[Chemical 54]

[0154]

[Chemical 55]

[0155]

[Chemical 56]

[0156]

[Chemical 57]

[0157]

[Chemical 58]

Further, the compound represented by the general formula (I
The details of the polymer component represented by V) are as described in the above resin [A]. The resin [B] may contain a polymer component other than the above-mentioned polymer component, and examples of such a polymer component include a polymer component corresponding to the repeating unit of the following general formula (V).

[0159]

[Chemical 59]

In the general formula (V), V ¹⁰ is -COO-,-
_{OCO -, - (CH 2)} a1 OCO -, - (CH 2) a1 C
OO- (a1 represents an integer of 1 to 3), -O-, -S.
_{O 2 -, - CO -,} - CON (Z 11) -, - SO 2 N
^{(Z 11) -, - CONHCOO} -, - CONHCONH
- or -C ₆ H ₄ - represents a. Here, Z ¹¹ is not only a hydrogen atom but also a preferable hydrocarbon group having 1 to 22 carbon atoms.
Optionally substituted alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2 -Bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), 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-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), Aralkyl groups which may be substituted and have 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 (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, etc.).

R ⁵ represents a hydrocarbon group, and is preferably the same as those listed as the preferable hydrocarbon group for Z ¹¹ . V ¹⁰ is -C ₆ H ₄ - may represent, R ⁵ represents another hydrogen atom of the hydrocarbon, further benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group, Ethoxy group, propioxy group, butoxy group, etc.) and the like.

B ³ and b ⁴ may be the same as or different from each other, and examples thereof include the same ones as b ¹ and b ^{2 in} the general formula (IV). More preferably, in the general formula (V), V ¹⁰ is —COO—, —OCO—, —CH ₂ OCO.
_{-, - CH 2 COO -,} - O -, - CONH -, - SO
₂ NH- or -C ₆ H ₄ - represents, b ³ and b ⁴ may be the same or different, a hydrogen atom, a methyl group, -
COOZ ¹² or —CH ₂ COOZ ¹² (Z ¹² more preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.)}. Even more preferably, one of b ³ and b ⁴ represents a hydrogen atom.

Further, in addition to the polymer component corresponding to the general formula (V), as a polymer component which can be contained in the resin [B],
Monomers corresponding to other repeating units copolymerizable with the polymer component of the general formula (V), such as acrylonitrile, methacrylonitrile, and heterocyclic vinyls (for example, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, Vinylpyrazole, vinyldioxane, vinyloxazine, etc.) and the like. It is preferable that these other monomers are used within a range not exceeding 20 parts by weight based on 100 parts by weight of the resin [B].

In the resin [B] according to the present invention, as an organic molecule having three or more polymer chains bonded, its molecular weight is 1
If it is 000 or less, it is not particularly limited. For example, the following trivalent or higher hydrocarbon residue may be mentioned.

[0165]

[Chemical 60]

(Here, () represents a repeating unit.
r ^{1 to} r ⁴ represent a hydrogen atom or a hydrocarbon group. Where r
^At least one of ¹ and r ² or r ³ and r ⁴ is linked to the polymer chain. ) These organic residues consist structure alone or in any combination thereof, in the case of combinations, -O -, - S -, - N (r 7) -, - CO -, -
CS -, - COO -, - CON (r 7) -, - SO
_{2 -, - SO 2 N (} r 7) - ( wherein r ⁷ represents a hydrogen atom or a hydrocarbon), - NHCOO -, - NHCONH
-, An oxygen atom, a sulfur atom, a heterocyclic group containing a hetero atom such as a nitrogen atom (for example, a thiophene ring, a pyridine ring, a pyran ring, an imidazole ring, a benzimidazole ring, a furan ring, a piperidine ring, a pyrazine ring, a pyrrole ring, A piperazine ring, etc.) and the like.

Examples of the organic molecule to which another polymer chain is bound include those formed by a combination of the following chemical formula 61 and the above-mentioned binding unit. However, specific examples of the organic molecule according to the present invention are not limited to these.

[0168]

[Chemical formula 61]

The star polymer of the present invention can be synthesized by utilizing a conventionally known method for synthesizing a star polymer of a monomer containing a polar group and having a polymerizable double bond group.
For example, one of them is a polymerization reaction using a carbanion as an initiator. Specifically, M. Morton,
T. E. Helminiak et al. Poly
m. Sci. 57 , 471 (1962), B.I. Gor
don III, M.D. Blumenthal, J. et al. E. L
oftus, et al, Polym. Bull. , 1
1 , 349 (1984), R.I. B. Bates, W.C.
A. Beavers, et al. Org. Che
m. 44 , 3800 (1979).

However, when this reaction is used, the specific polar group of the present invention is used as a protected functional group to polymerize, and then the protection is eliminated. The protection of the specific polar group of the invention with a protecting group and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing the conventionally known knowledge. For example, various references are given in the above cited document, and further, Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer" Kodansha Co., Ltd. (1977), T.S. W. Green
ne, "Protective Groups in
"Organic Synthesis", John
Wiley & Sons (1981), J. Am. F.
W. McOmie, "Protective Grou
ps in Organic Chemistry "Pl
The method described in detail in the review article such as enum Press, (1973) can be appropriately selected and performed.

As another method, the monomer of the present invention in which a specific polar group is not protected is used, and a compound containing a dithiocarbamate group and / or a compound containing a xanthate group is used as an initiator for irradiation with light. It can also be synthesized by performing a polymerization reaction below. For example, Takayuki Otsu, Polymer, 3
7 , 248 (1988), Shunichi Hinomori, Ryuichi Otsu, Pol
ym. Rep. Jap. 37 . 3508 (1988),
JP-A-64-111, JP-A-64-26619, Nobuyuki Higashi, Polymer Preprints, Japan
an, 36 , (6), 1511 (1987), M.A. Ni
wa, N.W. Higashi, et al. Macro
mol. Sci. Chem. A24 (5), 567 (1
987) and the like.

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 0.60 / 0.95-0.40,
More preferably 0.10 to 0.40 / 0.90 to 0.6
It is 0. If the weight ratio of the resin [A] to the resin [A] and the resin [B] is less than 0.05, the effect of improving the electrostatic properties is diminished. On the other hand, when it exceeds 0.60, the film strength of the photoconductive layer cannot be sufficiently maintained (particularly as an electrophotographic lithographic printing plate precursor).

Two or more kinds of resin [A] and resin [B] may be used in the photoconductive layer, and it is important that the proportion of resin [A] and resin [B] as described above is used. Is to be used in. 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, known resins for inorganic photoconductors can be used in combination. However, the ratio of these other resins used is 100% of all binder resins.
A range not exceeding 30 parts by weight is preferable. If this ratio is exceeded, the effect of the present invention will be significantly reduced.
As other resins that can be used in combination, for example, typical ones are vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer, methacrylate copolymer, acrylate copolymer, vinyl acetate. Copolymer, polyvinyl butyral, alkyd resin, silicone resin, epoxy resin, epoxy ester resin,
There are polyester resins 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 described in No. 202544, No. 58-68046 and the like can be mentioned.

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

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. As the spectral sensitizing dye used in the present invention, various dyes can be used alone or in combination as required. For example, Miyamoto Harumi, Takei Hidehiko, Imaging 1973 (No. 8) No. 1
Page 2, C.I. J. Young et al., RCA Review 1
5 , p. 469 (1954), Kouhei Kiyota et al., IEICE Transactions J63-C (No. 2), p. 97 (198).
0), Yuji Harasaki et al., Industrial Science Magazine 66 78 and 18
Page 8 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35 , 2
Carbon dioxide dyes, diphenylmethane dyes, triphenylmethane dyes, which are cited in the review articles such as page 08 (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, carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes are described in JP-B-51-452 and JP-A-50-.
90334, 50-114227, 53-39.
130, No. 53-82353, US Pat. No. 3,053.
2,540, 4,054,450, JP-A-57-
Examples thereof include those described in No. 16456.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include F.I. M. Hamer "The Cyanine
Dyes and Related Compound
The dyes described in "ds" 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 near infrared to infrared light region of 700 nm or more, JP-A-47-84
No. 0, No. 47-44180, Japanese Patent Publication No. 51-41061
JP-A-49-5034, JP-A-49-45122,
57-46245, 56-35141 and 57.
-157254, 61-26044, 61-2
7551, U.S. Pat. Nos. 3,619,154 and 4,
175,956, "Research Disclo
"Sure", 1982, 216, pages 117 to 118, and the like. The electrophotographic photoreceptor of the present invention is excellent in that its performance is unlikely to 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,
Review Article: Imaging 1973 (No. 8) No. 1
Electron-accepting compounds (eg halogen, benzoquinone, chloranil, organic carboxylic acid anhydrides, etc.) in the review article on page 2 etc., Hiroshi Komon, et al., "Recent Developments and Commercialization of Photoconductive Materials and Photoconductors" Chapter 4 to Chapter 6 ・ Polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds and the like, which are cited as reference articles of the Japanese Scientific Information Co., Ltd. Publishing Department (1986).

The addition amount of these various additives is not particularly limited, but usually 0.0 to 100 parts by weight of the photoconductor.
001 to 2.0 parts by weight. The photoconductive layer has a thickness of 1 to 1.
00 μm, particularly 10 to 50 μm is suitable. Further, 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 0.0
1 to 1 μm, particularly 0.05 to 0.5 μm is suitable.

In some cases, an insulating layer may be additionally provided for the purpose of protecting the photoreceptor and improving durability and dark charge characteristics.
At this time, the insulating layer is set to be relatively thin, and the insulating layer provided when the photoconductor is used in a specific electrophotographic process is set to be relatively thick. In the latter case, the thickness of the insulating layer is 5
˜70 μm, especially 10 to 50 μm.

Examples of the charge transport material for the laminated type photoreceptor include polyvinyl carbazole, oxazole dyes, pyrazoline dyes, triphenylmethane dyes and the like. The thickness of the charge transport layer is 5 to 40 μm, particularly 10 to 30 μm.
m is preferred. 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, Thermoplastic resins and curable resins such as polyacrylic resins, polyolefin resins, urethane resins, polyester resins, epoxy resins, melamine resins, and silicone resins are appropriately used.

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably conductive, and as the conductive support, just as in the conventional case, for example, metal, paper, plastic sheet or the like is basically impregnated with a low resistance substance. Conductive treated by, for example, 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,
A substrate having a water-resistant adhesive layer provided on the surface of the support, a substrate having at least one or more precoat layers provided on the surface layer of the support, and a substrate made of aluminum or the like on which electroconductive plastic is deposited on paper. Those laminated to can be used. Specifically, as examples of the conductive substrate or the conductive material, Yukio Sakamoto, Electrophotography, 14 (No.
1), P2-11 (1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry", Polymer Publishing (1975), M.M. F. Hoo
ver., J. Macromol. Sci. Chem. A
-4 (6), 1327 to 1417 (1970) and the like are used.

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
Either a dry developer or a liquid developer can be used as the developer.

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 it is 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 copy images. For example, Kuro Takizawa, "Photo Industry" 33 , 34 (1975), Masayasu Anzai, "Technical Research Report of the Institute of Electronics and Communication Engineers" 77 , 17 (19)
1977) and the like.

Furthermore, it can be effectively used in other systems using the electrophotographic process in recent years. For example, the photoreceptor of the present invention using photoconductive zinc oxide as the photoconductor,
A photoconductor using photoconductive zinc oxide or photoconductive titanium oxide, which is a pollution-free original plate and is pollution-free and has good whiteness, is used as an underprinting recording material or a color group used in the offset printing process. Can be used.

[0187]

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 .

[0189]

[Chemical formula 62]

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

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

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

[0195]

[Chemical formula 63]

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 .

[0198]

[Chemical 64]

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.

[0200]

[Chemical 65]

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 .

[0202]

[Chemical formula 66]

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 .

[0204]

[Chemical formula 67]

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 .

[0206]

[Chemical 68]

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.

[0208]

[Table 1]

[0209]

[Table 2]

[0210]

[Table 3]

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

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

[0213]

[Chemical 69]

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.

[0215]

[Table 4]

[0216]

[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 .

[0218]

[Table 6]

[0219]

[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 .

[0221]

[Table 8]

[0222]

[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 .

[0224]

[Chemical 70]

(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.

[0228]

[Chemical 71]

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 .

[0231]

[Chemical 72]

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 .

[0234]

[Chemical formula 73]

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

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

[0237]

[Chemical 74]

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 .

[0239]

[Chemical 75]

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 .

[0241]

[Table 10]

[0242]

[Table 11]

[0243]

[Table 12]

[0244]

[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 .

[0246]

[Chemical 76]

[0247]

[Chemical 77]

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 .

[0249]

[Table 14]

[0250]

[Table 15]

(Synthesis example of resin [A-3]) Synthesis example of resin [A] 301: [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 .

[0252]

[Chemical 78]

[0253]

[Chemical 79]

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 .

[0255]

[Table 16]

[0256]

[Table 17]

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

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

[0259]

[Chemical 80]

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 .

[0261]

[Table 18]

[0262]

[Table 19]

[Synthesis of Resin [B]] Synthesis Example of Resin [B] 1: Resin [B-1] 74 g of methyl methacrylate and an initiator of the following structure [I
-1] 12.4 g of the mixture was heated at a temperature of 50 ° C under a nitrogen stream.
Warmed to. 10c of this solution with 400W high pressure mercury lamp
Photopolymerization was performed by irradiating with light from a distance of m through a glass filter for 5 hours.

Tetrahydrofuran 100 was added to this polymer.
g was added and dissolved, 25 g of methyl acrylate and 1.0 g of acrylic acid were further added, and then the mixture was heated again to a temperature of 50 ° C. under a nitrogen stream.

[0265]

[Chemical 81]

Then, in the same manner as above, after irradiating with light for 10 hours, the obtained reaction product was reprecipitated in 2 liters of methanol, and the precipitate was collected and dried to obtain a weight of 78 g. A polymer having an average molecular weight (Mw) of 6 × 10 ⁴ was obtained.

[0267]

[Chemical formula 82]

Synthesis Example 2 of Resin [B]: Resin [B-2] In Synthesis Example 1 of Resin [B-1], the initiator [I-1] is used.
Instead of 12.4 g, an initiator [I-2] 1 having the following structure
It operated on the same conditions as the synthesis example 1 except having used 6.0 g. The yield of the obtained polymer was 72 g, and the Mw was 6 × 10 ^4.
Met.

[0269]

[Chemical 83]

[0270]

[Chemical 84]

Synthesis Examples 3 to 9 of Resin [B]: Resin [B-
3] to [B-9] 65 g of methyl methacrylate and an initiator of the following Table-I
0.013 mol of the mixture was used as in Synthesis Example 1 of Resin [B].
The photopolymerization reaction was carried out in the same manner. Then add tetrahydr
Add 100 g of lofuran and dissolve, then add methyl acryl
Rate 30 g, N-vinylpyrrolidone 4 g and methacrylic acid
After the addition of 1 g of acid, photopolymerization and re-polymerization were carried out as in Synthesis Example 1.
Sinked. The Mw of the obtained polymer was 5 × 10. ^Four~ 8
× 10^FourWas in the range.

[0272]

[Table 20]

[0273]

[Table 21]

[0274]

[Table 22]

Synthesis Examples 10 to 15 of Resin [B]: Resin [B
-10] to [B-15] In Synthesis Example 1 of Resin [B], instead of methyl methacrylate, methyl acrylate and acrylic acid, each monomer corresponding to the polymer component shown in Table J below is used. Other than that, the same operation as in Synthesis Example 1 was performed to obtain each polymer. The Mw of the obtained polymer was in the range of 5 × 10 ^{4 to} 6 × 10 ⁴ .

[0276]

[Table 23]

[0277]

[Table 24]

Synthesis Examples 16 to 21 of Resin [B]: Resin [B
-16] to [B-21] 16.5 g of methyl acrylate, acrylonitrile 2.
5 g, 1.0 g of acrylic acid, 0.0 of the initiator of the following Table-K
A mixed solution of 072 mol and 20 g of tetrahydrofuran was irradiated with light in the same manner as in Synthesis Example 1 for 15 hours. Next, methyl methacrylate 60 was added to the reaction product.
g, 20 g of methyl acrylate and 80 g of tetrahydrofuran were added, and then a polymerization reaction and reprecipitation were carried out in the same manner as in Synthesis Example 1. The Mw of the obtained polymer was 5 × 10 ⁴ to 8
It was in the range of × 10 ⁴ .

[0279]

[Table 25]

[0280]

[Table 26]

Synthesis Examples 22 to 26 of Resin [B]: Resin [B
-22] to [B-26] A mixture of a monomer corresponding to the polymer component shown in Table L below and 14 g of the initiator [I-2] was heated to a temperature of 40 ° C under a nitrogen stream, and the following operation was performed. Was irradiated with light and polymerized for 5 hours in the same manner as in Example 1. After taking out the solid substance and dissolving it in 100 g of tetrahydrofuran, methyl acrylate 2
5 g and 1.5 g of acrylic acid were added, and the mixture was further heated to a temperature of 50 ° C. under a nitrogen stream and irradiated with light to polymerize in the same manner as above. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. The yield of each polymer is 65-
At 75 g, the Mw was in the range 5 × 10 ^{4 to} 7 × 10 ⁴ .

[0282]

[Table 27]

Synthesis Examples 27 to 33 of Resin [B]: Resin [B
-27] to [B-33] methyl methacrylate 56 g, methyl acrylate 24
After heating a mixture of g and 10 g of the initiator [I-3] having the following structure to a temperature of 40 ° C. under a nitrogen stream, the following operations were carried out in the same manner as in Synthesis Example 1 and polymerized by irradiation with light for 4 hours. After dissolving the solid substance in 100 g of tetrahydrofuran, each monomer corresponding to the polymer component in the following Table-M was added, and the mixture was further heated to a temperature of 50 ° C. under a nitrogen stream and irradiated with light in the same manner as above. Polymerized. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. The yield of each polymer is 65
The Mw was in the range of 4 × 10 ^{4 to} 7 × 10 ⁴ at ˜75 g.

[0284]

[Chemical 85]

[0285]

[Table 28]

[0286]

[Table 29]

Synthesis Example 101 of Resin [B]: Resin [B-1
01] 74 g of methyl methacrylate and an initiator of the following structure [I
-101] 12.4 g of the mixture was heated to a temperature of 5 under a nitrogen stream.
Warmed to 0 ° C. To this solution, use a 400W high-pressure mercury lamp.
Photopolymerization was carried out by irradiating light from a distance of 0 cm through a glass filter for 5 hours. Tetrahydrofuran 1 was added to this polymer.
Add 00g to dissolve, then 25g methyl acrylate
After adding 1.0 g of acrylic acid, the mixture was heated again to a temperature of 50 ° C. under a nitrogen stream.

[0288]

[Chemical 86]

Then, after irradiating with light for 10 hours in the same manner as above, the reaction product obtained was reprecipitated in 2 liters of methanol, and the precipitate was collected and dried to obtain a weight of 78 g. A polymer having an average molecular weight (Mw) of 6 × 10 ⁴ was obtained.

[0290]

[Chemical 87]

Synthesis Example 102 of Resin [B]: Resin [B-1
02] Methyl methacrylate 50.3 g, methyl acrylate 24.7 g, initiator [I-102] 8.0 g having the following structure
And a mixture of 75 g of tetrahydrofuran were heated to a temperature of 50 ° C. under a nitrogen stream. This solution was irradiated with light under the same conditions as in Synthesis Example 101 for 6 hours for photopolymerization.

[0292]

[Chemical 88]

Methyl methacrylate 23 was added to this polymer.
g, acrylonitrile (2.0 g) and tetrahydrofuran (25 g) were added, and the temperature was adjusted to 6
The mixture was heated to 0 ° C. and subjected to light irradiation for 12 hours to carry out photopolymerization in the same manner as above. The obtained reaction product was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried to give a yield of 75 g and a Mw.
1.2 × 10 ⁵ polymer was obtained.

[0294]

[Chemical 89]

Synthesis Examples of Resin [B] 103 to 110: Resins [B-103] to [B-110] A mixture of 65 g of methyl methacrylate and 0.008 mol of each of the initiators of the following Table-N was added to the resin [B]. Synthesis Example 101
A photopolymerization reaction was carried out in the same manner as in. Next, 100 g of tetrahydrofuran was added to and dissolved in this, and further, 32.2 g of methyl acrylate and 2.0 g of N-vinylpyrrolidone.
And 0.8 g of methacrylic acid were added, and then photopolymerization and reprecipitation were performed in the same manner as in Synthesis Example 101. M of the obtained polymer
The w was in the range of 8 × 10 ^{4 to} 1.0 × 10 ⁵ .

[0296]

[Table 30]

[0297]

[Table 31]

[0298]

[Table 32]

Synthesis Examples 111 to 116 of Resin [B]: Resins [B-111] to [B-116] In Synthesis Example 101 of resin [B], instead of methyl methacrylate, methyl acrylate and acrylic acid,
Each polymer was obtained by operating under the same conditions as in Synthesis Example 101 except that each monomer corresponding to the polymer component shown in Table 0 below was used. The Mw of the obtained polymer was 5 × 10 ^{4 to} 6 × 1.
It was in the range of 0 ⁴ .

[0300]

[Table 33]

[0301]

[Table 34]

Synthesis Examples 117 to 123 of Resin [B]: Resins [B-117] to [B-123] 63.6 g of methyl methacrylate, 31.4 g of methyl acrylate, 5 of 2-hydroxyethyl methacrylate.
g, a mixed solution of 1 × 10 ⁻³ mol of the initiator shown in Table P below and 100 g of tetrahydrofuran was irradiated with light for 8 hours in the same manner as in Synthesis Example 101. The obtained polymer was reprecipitated in 1.5 liter of methanol, and the precipitate was collected by filtration and dried to obtain 70 to 80 g of each polymer. M of the obtained polymer
The w was in the range of 8 × 10 ⁴ to 10 × 10 ⁴ .

[0303]

[Table 35]

[0304]

[Table 36]

[0305]

[Table 37]

Synthesis Examples 124 to 128 of Resin [B]: Resins [B-124] to [B-128] Monomers corresponding to the polymer components in the following Table-Q and the above initiator [I-102] 15 0.4 g of the mixture was heated to a temperature of 40 ° C. under a nitrogen stream, and the subsequent operations were carried out in the same manner as in Synthesis Example 101 to perform photopolymerization by irradiation with light for 5 hours. The solid was taken out and dissolved in 100 g of tetrahydrofuran, then 19.5 g of methyl acrylate and 0.5 g of acrylic acid were added, and the mixture was further heated to a temperature of 50 ° C. under a nitrogen stream and polymerized by irradiation with light in the same manner as above. . The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. The yield of each polymer is 65 to 75 g, and the Mw is 9 × 10 ⁴ to
The range was 1.2 × 10 ⁵ .

[0307]

[Table 38]

Synthesis Examples 129 to 135 of Resin [B]: Resins [B-129] to [B-135] 57 g of methyl methacrylate, 28 of methyl acrylate
After heating a mixture of g and 1.3 g of an initiator [I-118] having the following structure to a temperature of 40 ° C. under a nitrogen stream, the subsequent operations were performed in the same manner as in Synthesis Example 101, and light irradiation was performed to perform polymerization for 4 hours.

[0309]

[Chemical 90]

After dissolving the solid substance in 100 g of tetrahydrofuran, each monomer corresponding to the polymer component shown in the following Table-R was added, and the mixture was further heated to a temperature of 50 ° C. under a nitrogen stream and subjected to the same light irradiation as above. Irradiated and polymerized. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. The yield of each polymer is 70 to 80 g and the Mw is 9 × 10 ^4.
The range was up to 1.1 × 10 ⁵ .

[0311]

[Table 39]

[0312]

[Table 40]

Examples 1 and 2 and Comparative Example 1 Resin [A-109] 6 g (as solid content), resin [B
-3] (Example 1) or resin [B-104] (Example 2) 34 g (as solid content), photoconductive zinc oxide 200 g, methine dye [I] 0.01 having the following structure
8 g, thiosalicylic acid 0.18 g and toluene 300 g
The mixture was dispersed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at a rotation speed of 6 × 10 ³ rpm for 10 minutes to prepare a photosensitive layer-formed product, which was applied to a conductive-treated paper to give a dry adhesion amount of 2
Apply with a wire bar to achieve 5 g / m ² and
Dry at ℃ for 10 seconds, then in the dark at 20 ℃, 65% RH
An electrophotographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material) was produced by leaving it for 24 hours under the condition of.

[0314]

[Chemical Formula 91]

Comparative Example 1: In Example 1, the resin [B-
3] 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.

[0316]

[Chemical Formula 92]

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

[0318]

[Table 41]

Embodiments of the evaluation items shown in Table-S 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
(III) (15 ° C., 30% RH).

As shown in Table-S, 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 uneven white spots were randomly generated in the solid image area. 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 Examples 3 and 4 and Comparative Example 2 Resin [A-204] 6 g (as solid content), resin [B
-2] (Example 3) or resin [B-113] (Example 4) 36 g (as solid content), photoconductive zinc oxide 200 g, methine dye [II] 0.02 having the following structure:
A mixture of 0 g, N-hydroxymaleinimide 0.20 g and toluene 300 g was treated in the same manner as in Example 1 to prepare an electrophotographic light-sensitive material (however, the coating amount was 25
The wire bar was adjusted to be g / m ² and applied).

[0324]

[Chemical formula 93]

Comparative Example 2: In Example 3, the resin [B-
2] An electrophotographic photosensitive material was produced in the same manner as in Example 3, 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. The results are shown in Table-T below.

[0326]

[Table 42]

Embodiments of the evaluation items shown in Table-T 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-T, 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 original plate for offset lithographic printing, the water-retaining property of the lithographic 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]. Examples 5 and 6 and Comparative Example 3 Resin [A-304] 5 g (as solid content), resin [B
-23] (Example 5) or resin [B-116] (Example 6) 35 g (as solid content), photoconductive zinc oxide 200 g, methine dye [III] 0.02 having the following structure:
A mixture of 0 g, salicylic acid 0.10 g, phthalic anhydride 0.1 g and toluene 300 g was treated in the same manner as in Example 3 to prepare an electrophotographic photosensitive material.

[0331]

[Chemical 94]

Comparative Example 3: In Example 5, the resin [B-
23] An electrophotographic light-sensitive material was prepared in the same manner as in Example 3 except that 35 g of the following resin [R-2] was used instead of 35 g. The characteristics of each of the obtained light-sensitive materials were examined in the same manner as in Example 3, and the results are shown in Table-U.

[0333]

[Chemical 95]

[0334]

[Table 43]

As shown in Table-U, 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 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, 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.

From the above, the resin [A] and the resin [B] of the present invention properly interact with the zinc oxide particles, and the desensitizing reaction by the desensitizing treatment liquid easily and easily proceeds. It shows that the state is formed and that the film strength is remarkably improved by the action of the resin [B]. Examples 7 to 38 In Example 5, the resin [A-304] and the resin [B-
23] instead of each resin [A] and each resin [B] shown in Table V below, the same operation as in Example 5 was carried out to produce each electrophotographic photosensitive member.

[0338]

[Table 44]

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 original plate and printed in the same manner as in Example 3, 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 39 to 41 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 dyes shown in Table W below.

[0341]

[Table 45]

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 of 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 42 and 43 and Comparative Example 4 Resin [A-202] (Example 42) or Resin [A-20
6] Any of 6.5 g of (Example 43), 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.

[0343]

[Chemical 96]

[0344]

[Chemical 97]

Comparative Example 4 In Example 42, 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 42. The characteristics of each light-sensitive material were examined in the same manner as in Example 1. The results are summarized in Table-X below.

[0346]

[Table 46]

In the above measurement, the electrostatic properties and the image pick-up properties were the same as in Example 1 except that the following operations were 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 mechanical strength of the photoconductive layer was good, but in Comparative Example 4, the mechanical strength was lower than these. The electrostatic properties showed good performance at room temperature and normal humidity (I), but especially at low temperature and low humidity (III).
Then, E _1/10 fell.

[0349] electrostatic properties of the light-sensitive material of the present invention is good, further, Example 43 using the resin (A) having a specific substituent is 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 desensitization treatment as offset lithographic printing plate precursors and printed, all of the present invention produced 10,000 copies of clear image quality with no background stain. However, in Comparative Example 4, the above-mentioned sticking mark was not removed even by the desensitizing treatment, and was generated from the printed matter printed out.

From the above, only the light-sensitive material of the present invention could give good characteristics. Examples 44 and 45 and Comparative Example 5 Resin [B-30] 3 in Examples 42 and 43
Electrophotographic photoreceptors of Examples 44 and 45 were produced in the same manner as in Example 39 and Example 40, except that 33.5 g of the resin [B-109] was used instead of 3.5 g.

Comparative Example 5 A light-sensitive material was prepared in the same manner as in Example 44 except that 33.5 g of the resin [R-1] was used instead of 33.5 g of the resin [B-109]. Was produced. The characteristics of each light-sensitive material were examined in the same manner as in Example 1. The results are summarized in Table-Y below.

[0353]

[Table 47]

All the above measurements were performed in the same manner as in Example 42. In each of the light-sensitive materials of the present invention, the mechanical strength of the photoconductive layer was good, but Comparative Example 5 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.
In (III), E _1/10 decreased.

[0355] electrostatic properties of the light-sensitive material of the present invention is good, further, the embodiment 45 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 5 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 desensitizing treatment as offset lithographic printing plate precursors and printed, all of the present invention produced 10,000 printed matters with clear image quality without scumming. However, in Comparative Example 5, the above-mentioned sticking mark was not removed even by the desensitizing treatment, and was generated from the printed matter. From the above, only the photosensitive material of the present invention,
Good characteristics could be given. Examples 46 and 47 5 g of resin [A-119] and 35 g of resin [B-25] (Example 46) or resin [B-132] (Example 47), 200 g of photoconductive zinc oxide, and 0 uranine. .0
A mixture of 2 g, rose bengal 0.04 g, bromphenol blue 0.03 g, phthalic anhydride 0.20 g and toluene 300 g was processed in the same manner as in Example 43 to prepare a light-sensitive material.

The light-sensitive material of the present invention was operated in the same manner as in Example 43 and examined for each performance. All were excellent in chargeability, dark charge retention rate and photosensitivity, and the actual copied image was high temperature and high 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 product was used as an offset lithographic printing plate precursor and printed, a printed matter having clear image quality was obtained even at 10,000 sheets. Examples 48 to 71 In Example 46, 5 g of resin [A-119] and 35 g of resin [B-132] were used instead of 5 g of resin [A-119] and 35 g of resin [B-132], and 35 g of resin [B] was used. Each light-sensitive material was prepared in the same manner as in Example 42.

[0359]

[Table 48]

The light-sensitive materials of the present invention are all excellent in chargeability, dark charge retention rate, and photosensitivity, and actually 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.

[0361]

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.

Claims (5)

[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 of resins [B ₁ ] and [B ₂ ]. 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 ₁ ] 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 star-type polymer in which at least three AB block polymer chains each having an A block contained therein and a B block containing a polymer component represented by the following general formula (IV) are bonded in an organic molecule. A polymer containing 0.01 to 10% by weight of the polymer component having the polar group and 30% by weight or more of the polymer component represented by the general formula (IV). [Chemical 6] [In the formula (IV), b ¹ and b ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ⁴ represents a hydrocarbon group. Resin [B ₂ ] having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ and having at least three polymer chains containing the polymer component represented by the general formula (IV) bound to the organic molecule. At least one selected from the specific polar groups represented by the resin [B ₁ ] at the end of the opposite main chain bonded to the organic molecule of the polymer chain. The polymer component having a polar group is bound to the polymer component having a polar group of 0.
A polymer containing 0 to 10% by weight and containing 30% by weight or more of the polymer component represented by the general formula (IV). 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 ³ and A ⁴ 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 ³
And B ⁴ 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 represents the same as the above), a cyclic acid anhydride group, -SH, -CONH ₂ and -SO ₂ NH _2. The electrophotographic photosensitive member according to claim 1 or 2, wherein the polar group is bonded. 4. The resin [B ₂ ], wherein the polymer chain is composed of a B block and an A block, and a specific polar group-containing component is present at the end of the main chain on the opposite side of the A block bonded to the B block. 4. The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is bonded. 5. In the resins [B ₁ ] and [B ₂ ] described above, the total amount of the specific polar group-containing polymer component contained in all the copolymers is specified in the resin [A]. The electrophotographic photoreceptor according to claim 1, wherein the content of the polar group-containing polymer component is 10% by weight to 50% by weight.