JP3112725B2 - Electrophotographic photoreceptor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor,
More specifically, the present invention relates to an electrophotographic photosensitive member having excellent electrostatic characteristics and moisture resistance.

[0002]

2. Description of the Related Art Electrophotographic photoreceptors have various configurations in order to obtain predetermined characteristics or according to the type of electrophotographic process to be applied. Representative electrophotographic photoreceptors include a photoreceptor having a photoconductive layer formed on a support and a photoreceptor having an insulating layer on the surface, and 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, image exposure and development, and, if necessary, transfer. Further, a method using an electrophotographic photosensitive member as an offset master for direct plate making has been widely used. In particular, in recent years, direct electrophotographic lithographic printing has become important as a method for printing high-quality printed matter with a print number of several hundreds to several thousands. Under these circumstances, the binder resin used to form the photoconductive layer of the electrophotographic photoreceptor has excellent film forming properties of itself and excellent dispersibility of the photoconductive powder in the binder resin.
The adhesion of the formed recording layer to the substrate is good, and the photoconductive layer of the recording layer has excellent charging ability, low dark decay, large light decay, low pre-exposure fatigue, and photography. It is necessary to have various electrostatic characteristics such as the necessity of maintaining these characteristics stably due to changes in humidity at the time, and excellent imaging properties.

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

On the other hand, Japanese Patent Application Laid-Open No. 63-217354 discloses
No. 64-70761, JP-A-2-67563,
2-236561, 2-238458, 2-
According to the techniques described in 236562 and 2-247656, an acidic group-containing polymerization component is a low molecular weight resin randomly present in a polymer main chain, and an acid group is bonded to one end of the polymer main chain. Low molecular weight resin or low molecular weight graft type copolymer resin having acidic group bonded to one end of polymer main chain, low molecular weight graft type copolymer containing acidic group in graft portion By using a resin or the like as a binder resin, smoothness and electrostatic characteristics can be improved. These include that the low molecular weight resin has an effect of sufficiently dispersing the photoconductor and suppressing aggregation between the photoconductors, and the inorganic material without alienating the adsorption between the photoconductor and the spectral sensitizing dye. This is presumed to be due to the fact that the photoconductor is sufficiently adsorbed to the stoichiometric defect and that the surface of the photoconductor is covered slowly and sufficiently.

[0006] Due to its action mechanism, even if the stoichiometric defect of the inorganic photoconductor fluctuates somewhat, it has a sufficient adsorption area, so that the inorganic photoconductor, the spectral sensitizing dye and the resin are relatively stable. It is inferred that the mutual interaction is maintained. In order to make the mechanical strength of the photoconductive layer insufficient with these low-molecular-weight resins alone, a technique of using other resins of medium to high molecular weight or a resin containing a curable group is used in combination. Technology for curing after film formation
No. 64, No. 63-220149, No. 63-22014
No. 8, JP-A-1-280761 and 1-111664.
Nos. 1-169455, 1-211766, 2-34859, 2-53064, 2-565
No. 58, No. 3-29954, No. 3-77954, No. 3-92961, No. 3-53257 and the like.

[0007]

However, even if these resins or combinations of resins are used, it is still insufficient to maintain stable performance when the environment fluctuates significantly from high temperature and high humidity to low temperature and low humidity. I found it to be. The scanning exposure method using a semiconductor laser beam has a longer exposure time and a limited exposure intensity than the conventional simultaneous exposure method using visible light, so the electrostatic characteristics, especially the dark charge retention characteristics, are limited. , For light sensitivity,
Higher performance is required.

In particular, when a scanning exposure method using a semiconductor laser beam is adopted for an electrophotographic lithographic printing original plate, when the conventional photosensitive member is actually tested, the above electrostatic characteristics are sufficiently satisfactory. It is not satisfactory, especially the difference between E _1/2 and E _1/10 is large, the tone of the copied image is soft, and it is difficult to reduce the residual potential after exposure, and the fog of the copied image is reduced. It becomes noticeable,
Even when printing as an offset master, problems such as sticking marks of a printed original appear on a printed material.

Furthermore, in recent years, it has been desired to realize a technique for faithfully reproducing not only a copied image of an image composed of line drawings and halftone dots but also a high-definition image composed of continuous tones using a liquid developer. The above-mentioned known techniques have not been able to sufficiently satisfy these demands. In the conventionally known technology, the middle to high molecular weight resin used in combination with the low molecular weight resin may lower the electrostatic properties of the low molecular weight resin, which has been improved in performance. An electrophotographic photoreceptor having a photoconductive layer used in combination with a known resin is capable of reproducing a faithful copy image of a high-definition image (particularly a continuous tone image) as described above or a laser beam of low output. For the imaging performance by the scanning exposure method used,
It has been found that problems can arise.

The present invention is to improve the above-mentioned problems of the conventionally known electrophotographic photosensitive member. SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photoreceptor having a stable and good electrostatic property, always having a clear and high-quality image, even when the environment at the time of forming a copy image fluctuates such as low temperature and low humidity or high temperature and high humidity. It is to provide.

Another object of the present invention is to provide a CPC electrophotographic photosensitive member having excellent electrostatic characteristics and low environmental dependency. Another object of the present invention is to provide an electrophotographic photosensitive member effective for a scanning exposure method using a semiconductor laser beam. A further object of the present invention is to provide an electrophotographic planographic printing plate precursor having excellent electrostatic characteristics (particularly dark charge retention and light sensitivity) and an original image (particularly a high-resolution continuous tone image).
And reproduces a faithful copy image, and does not generate not only uniform ground stains on the entire printed matter but also point-like ground stains.
Another object of the present invention is to provide a lithographic printing plate precursor having excellent printing durability.

[0012]

An object of the present invention 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 represented by the following: It has been found that this is achieved by an electrophotographic photoreceptor characterized by comprising at least one kind of resin [A] and at least one kind of resin [B] below. Resin [A] having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , containing at least one kind of a repeating unit represented by the following general formula (I) as a polymer component, and represented by the following B block
And A blocks containing no polymer component containing the specific polar group, -PO ₃ H ₂ group, -SO ₃ H group, -COOH
Group, —P (＝ O) (OH) R ¹ [R ¹ is a hydrocarbon group or —O
And a B block containing at least one polymer component containing at least one polar group selected from R ² (R ² represents a hydrocarbon group) group and a cyclic acid anhydride-containing group. If fewer AB type block polymer chain composed of
Is also a star-type copolymer bonded to three identical organic molecules .

[0013]

Embedded image

[In the formula (I), a ¹ and a ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group.
R ¹¹ represents a hydrocarbon group. Resin [B] A resin having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ and containing at least 30% by weight of a polymer component represented by the following general formula (III).

[0015]

Embedded image

[In the formula (III), X ² is — (CH ₂ ) r COO
_{-, - (CH 2) r} OCO -, - O- or -CO- and expressed (here r is an integer of 0 or 1 to 3).
c ¹ , c ² and R ¹³ are a ¹ , a ² and R ¹¹ in the formula (I)
Represents the same contents. That is, the binder resin of the present invention contains a polymer component represented by the general formula (I) 且
A block containing no specific polar group-containing polymer component and a B block containing the specific polar group-containing polymer component
Same organic matter child AB type block polymer chain of block
A low-molecular-weight star-type copolymer (resin [A]) having at least three bonds to a polymer (resin [B]) containing at least 30% of a polymer component represented by the general formula (III). At least.

As described above, among the acidic group-containing binder resins known to improve the smoothness and electrostatic properties of the photoconductive layer, low-molecular weight polymers are used, and the acidic group-containing polymer component is mainly composed of a polymer. Examples of the resin include a resin randomly present in the chain, a resin in which an acidic group is bonded only to one end of the polymer main chain, and a so-called graft copolymer. On the other hand, the low-molecular-weight binder resin [A] of the present invention is different from known resins in that the binding pattern of the polymerization component is different and the block A containing no polar group is used.
A star-type copolymer having at least three polymer chains composed of AB-type blocks having at least three AB-type blocks having the same polar group-containing block in the same organic molecular chain and having a remarkably specified chemical structure of the polymer molecular chain. is there.

In the resin [A] of the present invention, the polar groups which are unevenly distributed in the polymer chain composed of AB type blocks are sufficiently adsorbed to the stoichiometric defect of the inorganic photoconductor, and It is presumed that the other constituent constituents cover the surface of the inorganic photoconductor slowly and sufficiently. The effect of the sufficient adsorption to the surface of the inorganic photoconductor and the coating of the vicinity of the surface is more effectively performed as compared with the known resin, so that the stoichiometric defect portion of the inorganic photoconductor slightly varies. However, since it has a sufficient adsorption region, it is inferred that the stable interaction between the inorganic photoconductor and the resin [A] is always maintained. In other words, due to the effect of the resin [A] of the present invention, the photoconductor particles are present in a state where they are sufficiently dispersed and not aggregated, and the spectral sensitizing dye is sufficiently adsorbed on the surface of the photoconductor particles. And that the binding resin sufficiently adsorbs excess active sites on the photoconductor surface to compensate for the trap. It is considered to have important effects such as suppressing aggregation due to the extremely short molecular chain and preventing the adsorption and alienation of the spectral sensitizing dye. From such various actions, according to the present invention, the photoconductor trap is sufficiently compensated and the humidity characteristics are improved more excellently than the conventionally known low molecular weight resin containing a polar group, while the photoconductor is improved. Has been found to be sufficiently dispersed to suppress aggregation.

Further, as a result of various studies, it has been found that the low molecular weight polar group-containing resin [A] according to the present invention is a medium to high molecular weight resin containing 30% by weight or more of the polymer component represented by the general formula (III) It has been found that by using in combination with B), the mechanical strength is sufficiently maintained without deteriorating the electrostatic properties of which the high-performance resin has been improved. It is also unexpectedly important that these medium to high molecular weight resins interact more appropriately with the photoconductor, spectral sensitizing dye and low molecular weight resin in the photoconductive layer. It has become clear that this is the cause.

Therefore, the above resin [B] used in combination with the above low molecular weight resin [A] further comprises a —PO ₃ H ₂ group, —SO ₃ H group, —COOH group, −P
(= O) (OH) R ³ (R ³ has the same meaning as R ¹ )
Group and at least one polar group selected from cyclic acid anhydride-containing groups (hereinafter referred to as resin [B
B]).

This is because, due to the further synergistic effect of the binder resins [A] and [B] of the present invention, the photoconductor particles are present in a state where they are sufficiently dispersed and not condensed, and the spectral sensitizing dye is further dispersed. This is presumed to be due to the fact that it is sufficiently adsorbed on the surface of the photoconductor particles and that the binding resin sufficiently adsorbs extra active sites on the surface of the photoconductor to compensate for the trap.

That is, the low molecular weight resin [A] containing a specific polar group is sufficiently adsorbed on the photoconductor particles to uniformly disperse the particles, and the aggregation is suppressed by the short polymer chain. Medium-high-molecular-weight resin [BB] containing a specific polar group at the terminal of the polymer main chain, while having an important effect of not causing adsorption or alienation of the spectral sensitizing dye. Works better, and the mechanical strength of the photoconductive layer is sufficiently maintained. This is because the polar group portion of the high-molecular-weight resin [BB] has a weaker interaction with the photoconductor particles than the resin [A], and between the polymer chains of other portions in the resin [B]. This is probably due to the entanglement effect.

This effect was particularly remarkable with a polymethine dye or a phthalocyanine pigment which is particularly effective as a dye for spectral sensitization of near infrared to infrared light. On the other hand, when the electrophotographic photoreceptor of the present invention using photoconductive zinc oxide as a photoconductor is used as a conventionally known direct printing plate, the electrophotographic photoreceptor exhibits excellent imaging performance and remarkably good water retention.

That is, the photoreceptor of the present invention, on which a copied image is formed through an electrophotographic process, is desensitized by a chemical treatment on a non-image portion using a conventionally known desensitizing solution to form a printing master. Shows excellent performance as a printing original plate when is printed by offset printing. When the photoreceptor of the present invention was desensitized, the non-image area was sufficiently hydrophilized and the water retention was improved, so that the number of printed sheets was dramatically improved. This is because the zinc oxide particles are uniformly dispersed and the presence state of the binder resin present on the surface of the zinc oxide particles is appropriate, and the desensitization reaction with the desensitizing treatment solution is quickly performed without alienation. It is considered that the process proceeds effectively.

Further, in the present invention, the resin [A] has a specific substituent at the 2-position and / or 2- and 6-positions represented by the following general formulas (Ia) and (Ib). Containing a benzene ring or an unsubstituted naphthalene ring,
Resin [A] containing a methacrylate component having a specific substituent and an acidic group component (hereinafter referred to as a resin [A]
A]).

[0026]

Embedded image

[0027]

Embedded image

[In the formulas (Ia) and (Ib), A ¹ and A
² are each independently a hydrogen atom, a carbon number of 1 to 10
Hydrocarbon group, chlorine atom, bromine atom, -COR ¹⁴ or-
COOR ¹⁴ (R ¹⁴ represents a hydrocarbon group having 1 to 10 carbon atoms). Each B ¹ and B ² bind the -COO- and the benzene ring, represents a single bond or a linking atoms 1-4 linking groups. When the above specific resin [AA] is used, the electrophotographic properties (especially V ₁₀ , DRR, E
_1/10 ) improvement can be achieved.

The reason for this is unknown, but one reason is that the photoconductor in the film is formed by the effect of a planar benzene or naphthalene ring having a substituent at the ortho position, which is an ester component of methacrylate. This is probably due to the proper arrangement of these polymer molecular chains at the interface. Hereinafter, the binder resin of the present invention will be described in more detail.

First, the resin [A] of the present invention will be described. The resin [A] includes a block A containing at least a polymer component represented by the general formula (I) and a block B containing at least a polymer component containing at least one kind of polar group selected from specific polar groups. A composed of
A star-type copolymer in which at least three B-type block polymer chains are bonded in the same organic molecule.

Here, the order of the arrangement of the blocks A and B in the polymer chain may be any. That is, the polymer is schematically shown below.

[0032]

Embedded image

[0033]

Embedded image

[Where X represents an organic molecule, (A) represents a block A, (B) represents a block B, and (A)-
(B) represents a polymer chain. ] Further, according AB type block polymer chains, even the upper limit much that bind to organic molecules 15
, Usually about 10. The resin [A] has a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , preferably 3 × 10 ³ to
A 1 × 10 ^4, a glass transition point of the resin (A) is preferably -40 ° C. to 110 ° C., more preferably -20 ° C. to 9
0 ° C.

If the molecular weight of the resin [A] is less than 1 × 10 ³ , the film-forming ability is reduced, and sufficient film strength cannot be maintained.
On the other hand, if the molecular weight is greater than 2 × 10 ^4, the photosensitive member using near infrared to infrared spectral sensitizing dyes, especially, high temperature and high humidity, the electrophotographic characteristics under severe conditions of low temperature and low humidity (especially Variations in the initial potential, dark decay retention, and light sensitivity) are slightly increased, and the effect of the present invention that a stable copied image is obtained is diminished.

The amount of the polar group-containing component contained in the resin [A] of the present invention is 1 to 100 parts by weight in the resin [A].
It is preferably 20 parts by weight, more preferably 3 to
15 parts by weight. When the content of the polar group in the resin [A] is less than 1 part by weight, the initial potential is too low to obtain a sufficient image density. On the other hand, when the polar group content is 20
If the amount is larger than parts by weight, the dispersibility of the low molecular weight compound will be reduced, and the background fouling will increase when used as an offset master.

Star-type copolymer of the present invention (resin [A])
Each block constituting the polymer chain has the following characteristics. General formula (I) in the block A component of the resin [A]
Is preferably 30 to 100% by weight, more preferably 50 to 100% by weight, in the block A component. Block A is characterized in that it does not contain the specific polar group-containing component contained in Block B.

The repeating unit represented by formula (I) will be further described. a ¹ and a ² are each a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.),
A cyano group or a hydrocarbon group (for example, an aliphatic group having 1 to 8 carbon atoms; for example, a group having 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a benzyl group);
To 12 aromatic groups; for example, a phenyl group). a ¹
There represents a hydrogen atom, and a ² are preferably may represent a methyl group.

R ¹¹ 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 ¹¹ preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. As the substituent, any substituent other than the polar group contained in the polymerization component constituting the B block of the AB block copolymer may be used. For example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom) Etc.), —OZ ¹ , —COOZ ¹ , and —OCOZ ¹ (Z ¹ represents an alkyl group having 1 to 22 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, and a decyl group. , A dodecyl group, a hexadecyl group, an octadecyl group, etc.). Preferred hydrocarbon groups include alkyl groups having 1 to 18 carbon atoms which may be substituted (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 and the like, 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.), having 7 to 1 carbon atoms
2 optionally substituted aralkyl groups (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group,
A bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, a cyclohexyl group, A cyclohexylethyl group, a 2-cyclopentylethyl group or the like, or an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, Octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonyl Phenyl group, butoki Carbonyl phenyl, acetamidophenyl group, propionitrile amidophenyl group, dodecane white ylamide phenyl group) and the like.

[0040] In the hydrocarbon group represented by R ^11, R ¹¹ is preferably in the case of an aliphatic group containing more than 60 wt% in component represented a hydrocarbon group having 1 to 5 carbon atoms in formula (I) Is preferred. In such a repeating unit of the general formula (I) is a component having a substituent R ^11, more preferably include polymer component of the repeating unit represented by the general formula (Ia) and / or formula (Ib) is Can be

In the formula (Ia), preferred A ¹ and A
^{As 2} independently independently of each other a hydrogen atom, a chlorine atom and a bromine atom, as a hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group,
Ethyl, propyl, butyl), an aralkyl group (e.g. benzyl group having a carbon number of 7 to 9, phenethyl, 3-phenylpropyl, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloromethyl benzyl groups) and aryl groups (e.g. phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and - CO Z ² and -COOZ
² (preferable Z ² includes those described above as preferred hydrocarbon groups having 1 to 10 carbon atoms).

In the formulas (Ia) and (Ib), B ¹ and B ² each represent a single bond connecting —COO— and a benzene ring or — (CH ₂ ) _a — (a represents an integer of 1 to 3) , -C
_{H 2 OCO -, - CH 2} CH 2 OCO -, - (CH 2 O)
_b - (b represents an integer of 1 or _{2), - CH 2 CH 2} O
And a connecting group having 1 to 4 connecting atoms such as-, more preferably a single bond or a connecting group having 1 to 2 bonding atoms.

The formula (I) used in the resin [A] of the present invention
Specific examples of the repeating unit represented by a) or (Ib) are shown below. However, the scope of the present invention is not limited to this. In addition, the following (a-1) to (a-20)
In, c is an integer of 1 to 4, d is 0 or an integer of 1 to 3, e is an integer of 1-3, R ⁶ are both -CcH2c + 1 or _{- (CH2) d -C 6 H} 5 ( except , C, and d are the same as described above), and D ¹ and D ² may be the same or different and represent any of a hydrogen atom, —Cl, —Br, and —I.

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

The other polymerization components contained in the block A include, for example, components represented by the following general formula (II).

[0050]

Embedded image

[In the formula (II), X ¹ is -COO-, -OC
_{O -, - (CH 2)} p -OCO -, - (CH 2) p -C
OO- (p represents an integer of 1~3), - O -, - SO 2
-, - CO -, - CON (Z 3) -, - SO 2 N (Z 3)
-, -CONHCOO-, -CONHCONH- or-
Represents C ₆ H ₄ — (where Z ³ represents a hydrogen atom or a hydrocarbon group).

R ¹² represents a hydrocarbon group. b ¹ and b
² may be the same or different, and represent the same contents as a ¹ and a ² in the formula (I). Here, in addition to a hydrogen atom, Z ³ is preferably a hydrocarbon group which may be substituted with an alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, Hexyl group, octyl group, decyl group,
Dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), having 4 to 18 carbon atoms Optionally substituted alkenyl group (for example, 2-methyl-
1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group Aralkyl group having 7 to 12 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-
A naphthylethyl group, a chlorobenzyl group, a bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms ( For example, a cyclohexyl group, a 2-cyclohexylethyl group,
2-cyclopentylethyl group or the like and an optionally substituted aromatic group having 6 to 12 carbon atoms (for example, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group,
Butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl Group, ethoxycarboxyphenyl group, butoxycarbonylphenyl group, acetamidophenyl group,
A propioamidophenyl group, a dodecylylamidophenyl group, etc.).

When X ¹ represents —C ₆ H ₄ —, the benzene ring may have a substituent. Examples of the substituent include a halogen atom (eg, a chlorine atom, a bromine atom, etc.), an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group,
Chloromethyl group, methoxymethyl group, etc.) and alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.).

R ¹² represents a hydrocarbon group, and is preferably a hydrocarbon group having 1 to 22 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group). , Hexyl group, octyl group,
Decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-
Methoxycarbonylethyl group, 2-methoxyethyl group,
3-bromopropyl group, etc., an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-−２) An phenyl group, a 1-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 4-methyl-2-hexenyl group and the like, an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group) Group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), carbon number 5 to 8 optionally substituted alicyclic groups (for example, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group and the like) An optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, Ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, A propioamidophenyl group, a dodecylylamidophenyl group, etc.).

More preferably, in the general formula (II):
X ¹ is -COO -, - OCO -, - CH 2 OCO -, -
_{CH 2 COO -, - O -} , - CONH -, - SO 2 NH
- or -C ₆ H ₄ - represents a. Further, as a polymer component which can be contained in the A block together with the polymer component represented by the formula (II), a monomer corresponding to another repeating unit copolymerizable with the polymer component of the formula (II) Such as acrylonitrile, methacrylonitrile, and heterocyclic vinyls (eg, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.). These other monomers are used in an amount not exceeding 20 parts by weight based on 100 parts by weight of the total polymer components of the A block.

Next, the block B constituting the polymer chain of the star-type copolymer will be described in detail. The polar group-containing component constituting the block B will be described. The polar group is -PO
₃ H ₂ group, -SO ₃ H group, -COOH group, -P (= O)
(OH) at least one selected from the group consisting of R ¹ groups and cyclic acid anhydride-containing groups. Here, -P (= O) (OH)
R ¹ represents a group represented by the following formula 17, wherein R ¹ wherein is a hydrocarbon group or -OR ² group (R ² represents a hydrocarbon group), in particular R ¹ is the number of carbon atoms 1-6 optionally substituted hydrocarbon groups (e.g., methyl, ethyl, propyl, butyl, 2-chloroethyl,
-Bromoethyl group, 2-fluoroethyl group, 3-chloropropyl group, 3-methoxypropyl group, 2-methoxybutyl group, benzyl group, phenyl group, propenyl group, methoxymethyl group, ethoxymethyl group, 2-ethoxyethyl group) And R ² represents the same content as R ¹ .

[0057]

Embedded image

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride. Examples of the cyclic acid anhydride include aliphatic dicarboxylic anhydride and aromatic dicarboxylic anhydride. Things. Examples of the aliphatic dicarboxylic anhydride include succinic anhydride, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-
1,2-dicarboxylic anhydride ring, cyclohexane-1,
2-dicarboxylic anhydride ring, cyclohexene-1,2-
Dicarboxylic anhydride ring, 2,3-bicyclo [2.2.
2] octadicarboxylic anhydride rings and the like; these rings include, for example, chlorine atoms, halogen atoms such as bromine atoms,
An alkyl group such as a methyl group, an ethyl group, a butyl group, and a hexyl group may be substituted.

Examples of the aromatic dicarboxylic anhydride include a phthalic anhydride ring, a naphthalene-dicarboxylic anhydride ring, a pyridine-dicarboxylic anhydride ring, and a thiophene-dicarboxylic anhydride ring. These rings are
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,
Hydroxyl group, cyano group, nitro group, alkoxycarbonyl group (for example, methoxy group,
Ethoxy group etc.) may be substituted.

The copolymer component containing a polar group in the resin [A] may be, for example, a compound represented by the general formula (I) [General formulas (Ia), (I)
b) is also included as long as it is a vinyl compound containing the polar group which can be copolymerized with the monomer corresponding to the repeating unit represented by the following formula: Basic Edition] ”, Baifukan (1986) and the like. Specifically, acrylic acid, α
And / or β-substituted acrylic acids (e.g., alpha-acetoxy body, alpha-acetoxymethyl body, alpha-(2-amino) et Chi <br/> Le body, alpha-chloro body, alpha-bromo compound, alpha-off Luo Body,
α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α-chloro-β-methoxy form, α,
β-dichloro compound, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid semiamides, crotonic acid, 2-alkenylcarboxylic acids (for example, 2-pentenoic acid, 2-methyl-2-hexenoic acid, -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 Examples include half-ester derivatives of vinyl or allyl groups of acids and dicarboxylic acids, and ester derivatives of these carboxylic or sulfonic acids, and compounds containing the polar group in the substituents of amide derivatives.

Examples of the copolymer component containing a polar group are described below. Here, d ¹ represents -H or -CH _3, d ² is -H, indicates -CH ₃ or -CH ₂ COOCH _3, R ¹¹ represents an alkyl group having 1 to 4 carbon atoms, R ¹² is Carbon number 1-6
Represents an alkyl group, a benzyl group or a phenyl group, f represents an integer of 1 to 3, g represents an integer of 2 to 11, h represents an integer of 1 to 11, and i represents an integer of 2 to 4. And j represents an integer of 2 to 10.

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

The polymer component containing the specific polar group as described above may be contained in the B block in two or more kinds.
In this case, the two or more polar group-containing components may be contained in the B block in any mode of random copolymerization or block copolymerization. Further, a polymer component other than the polar group-containing polymer component may be contained in the block B, and such a polymer component preferably corresponds to the repeating unit of the general formulas (I) and (II). Polymer component. Further, other monomers other than these may be contained as a copolymer component.

Examples of such other copolymer components include α-olefins, in addition to methacrylates, acrylates, and crotonates having a substituent other than those described in the general formula (I). , Vinyl carboxylate or allyl esters (eg, carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalene carboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic esters (eg, Dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrenes (for example, styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinyl) Naphthalene), vinyl sulfone-containing compounds, vinyl ketones containing compounds, heterocyclic vinyl compounds (e.g., vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline,
Vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.).

On the other hand, the organic molecule according to the present invention comprising at least three polymer chains bonded is not particularly limited as long as the molecular weight of the molecule is 1,000 or less. Examples thereof include trivalent or higher valent hydrocarbon residues such as those shown below.

[0076]

Embedded image

[Here, r ^{1 to} r ⁶ each represent a hydrogen atom or a hydrocarbon group. However, r ¹ and r ² or r ³
At least one of r ⁶ is linked to a polymer chain. These organic residues are composed of a single compound or an arbitrary combination thereof, and in the case of a combination, -O-, -S-, -N
^{(R 7) -, - COO} -, - CON (r 7) -, - SO
_2- , -SO ₂ N (r ⁷ )-{where, r ⁷ represents a hydrogen atom or a hydrocarbon group}, -NHCOO-, -NH
Hetero atoms containing hetero atoms such as CONH-, an oxygen atom, a sulfur atom, and a nitrogen atom (e.g., thiophene ring, pyridine ring, pyran ring, imidazole ring, benzimidazole ring, furan ring, piperidine ring, pyrazine ring, pyrrole ring, piperazine And a combination of bonding units such as rings.

Examples of other organic molecules that bind to the polymer chain include those composed of a combination of the above-mentioned bonding units with the following chemical formulas (1) and (2). However, specific examples of the organic molecule according to the present invention are not limited to these.

[0079]

Embedded image

[0080]

Embedded image

The star copolymer of the present invention can be synthesized by using a conventionally known method for synthesizing a star polymer of a monomer having 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. Morto
n, T. E. FIG. Helminiak et al. Po
lym. Sci. 57, 471 (1962); G
ordonIII, M.C. Blumenthal, J.M.
E. FIG. Loftus, et al, Polym. Bull
l. , 11, 349 (1984); B. Bate
s, W.S. A. Beavers, et al. Org.
Chem. , 44, 3800 (1979).

However, when using this reaction, the "specific polar group" of the present invention is used as a protected functional group, and after polymerization, the protective group is eliminated. The protection of the specific polar group of the present invention by a protective group and the elimination of the protective group (deprotection reaction) can be easily carried out by utilizing conventionally known knowledge. For example, various descriptions are given in the above cited references, and furthermore, Yoshio Iwakura and Keisuke Kurita, "Reactive Polymers", Kodansha Co., Ltd. (1977); W.
Greene, “Protective Groups
in Organic Synthesis ", Jo
hnWiley & Sons (1981);
F. W. McOmie, "Protective Gr
ups in Organic Chemistr
y ", Plenum Press, (1973) and the like.

[0083] Other methods, starting compounds containing a specific reference to monomers which remain protecting the polar group, a compound containing di-thiocarbamate <br/> group and / or a xanthate group of the present invention As an agent, it can also be synthesized by performing a polymerization reaction under light irradiation. For example, Takatsu Otsu, polymer, 3
7 , 248 (1988), Shunichi Himori, 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); Ni
wa, N.M. Higashi, et al. Macro
mol. Sci. Chem. A24 (5), 567 (1
987) and the like.

The adjustment of the weight average molecular weight of the resin [A] of the present invention can be easily carried out by controlling the ratio of the total amount of all monomers used for polymerization to the amount of various polymerization initiators or the polymerization temperature, as is conventionally known in the polymerization reaction. Can be adjusted. Specifically, it can be arbitrarily synthesized depending on the type of the monomer used and the type of the initiator.

Next, the resin [B] will be described below.
The resin [B] of the present invention contains at least one repeating unit represented by the above formula (III) as a polymerization component. In the general formula (III), c ¹ and c ² represent the same contents as a ¹ and a ² in the general formula (I).

X ² is-(CH ₂ ) _r COO-,-(CH ₂ )
_r represents OCO-, -O- or -CO-. Here, r represents 0 or an integer of 1 to 3. X ² is preferably -CO
O -, - OCO -, - O -, - CH 2 COO -, - CH
Represents ₂ OCO- or -O-. R ¹³ has the general formula (I)
The same meaning as R ¹¹ in.

The resin [B] of the present invention comprises -COOH together with a polymerization component comprising a repeating unit represented by the formula (III).
Group, -PO ₃ H ₂ group, -SO ₃ H group, -P (= O) (O
H) A polymerization component containing at least one polar group selected from R ³ (R ³ has the same content as R ¹ ) and a cyclic acid anhydride-containing group can be further contained. Such a polar group-containing copolymer component that can be optionally contained may be any of the polar group-containing monomers that can be polymerized with the monomer corresponding to the formula (III). Compounds similar to the polar group-containing monomer used in the block B of A) are exemplified.

Further, in the resin [BB] in which a polar group is bonded to one terminal of the polymer main chain, preferred polar groups bonded to the polymer main chain terminal are -PO ₃ H ₂ group, -SO ₃ H group,
A —COOH group, a —P (＝ O) (OH) R ³ group, and a cyclic acid anhydride-containing group. These polar groups may be directly bonded to the terminal of the polymer main chain, or may be bonded via a linking group. The linking group may be any of the bonding groups, but specific examples include -C (p ¹ ) (p
² )-｛p ¹ and p ² may be the same or different and each represent a hydrogen atom, a halogen atom (a chlorine atom, a bromine atom, etc.),-
OH group, cyano group, alkyl group (methyl group, ethyl group,
Represents 2-chloroethyl group, 2-hydroxyethyl group, propyl group, butyl group, hexyl group, etc., aralkyl group (benzyl group, phenethyl group, etc.), phenyl group, etc.,
-C (p ¹ ) = C (p ² )-{p ¹ and p ² each represent the same meaning as above}, -C ₆ H _10- , -C ₆ H ₄ -,-
O—, —S—, —N (p ³ ) — [p ³ is a hydrogen atom or a hydrocarbon group ｛specifically a hydrocarbon group having 1 to 12 carbon atoms.
(E.g., methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, 2-methoxyethyl, 2-chloroethyl, 2-cyanoethyl, benzyl, methyl) Benzyl, chlorobenzyl, methoxybenzyl, phenethyl, phenyl, tolyl, chlorophenyl, methoxyphenyl, butylphenyl, etc.).
], -CO-, -COO-, -OCO-, -C
ON (p ³ )-, -SO ₂ N (p ³ )-, -SO _2- , -N
HCONH -, - NHCOO -, - NHSO 2 -, - C
ONHCOO-, -CONHCONH-, heterocyclic ring (a 5- or 6-membered ring containing at least one kind of O, S, N, or the like as a hetero atom or a condensed ring thereof may be used; for example, a thiophene ring, a pyridine ring , A furan ring, an imidazole ring, a piperidine ring, a morpholine ring, etc.) or -Si (p ⁴ ) (p ⁵ )-｛p ⁴ , p ⁵ may be the same or different, and may be a hydrocarbon group or -Op ⁶ (p ⁶
Represents a hydrocarbon group). These hydrocarbon groups, singly or a linking group constituted by a combination of these linking groups, such may be mentioned the same as those mentioned in p ^3}, and the like.

When the resin [BB] also contains a polar group in the copolymer component of the polymer as described above, the resin [BB] binds to the polar group that can be contained in the copolymer component and the terminal of the polymer main chain. The polar group may be the same or different. Specific examples of the polar group that may be contained in these copolymer components or at the terminal of the main chain include the same ones as described for the resin [A].

Further, the resin [B] may contain a copolymer component containing a heat and / or photocurable functional group, and its content is preferably 0.1 to 20% by weight. “Thermal and / or photocurable functional group” refers to a functional group that causes a curing reaction of a resin by at least one of heat and light.
Specific examples of the photocurable functional group include Hideo Inui and Mototaro Nagamatsu, “Photosensitive Polymers” (Kodansha, 1977), Takahiro Kakuta, “New Photosensitive Resins” (publishing department of Printing Society, 1981), E. FIG.
Green and B. P. Strak, J .; Mac
ro. Sci. Reas. Macro. Chem. , C
21 (2), 187-273 (1981-82), C.I.
G. FIG. Rattey, "Photopolymeriza
Tionof Surface Coatings "
(A. Wiley InterScience Pu
b. Functional groups used in conventionally known photosensitive resins and the like are used as the photocurable resin cited in the review article, 1982).

"Thermosetting functional group" in the present invention
Is a functional group other than the specific polar group, for example,
Tsuyoshi Endo, "Refinement of Thermosetting Polymers" (C.M.C.
Ltd., 1986), Yuji Harasaki, "Handbook of the Latest Binder Technologies", Chapter II-I (General Technology Center, 1985), Takayuki Otsu, "Synthesis, design and new application development of acrylic resin" (Chubu Management Development Center Publishing) Department, 1985),
Eizo Omori "Functional acrylic resin" (Techno System,
1985), the functional groups of the references can be used.

For example, an —OH group, a —SH group, a —NH ₂ group,
—NHZ ⁴ group [Z ⁴ represents a hydrocarbon group, for example, an alkyl group having 1 to 10 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group,
Octyl group, decyl group, 2-chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, etc.), having 4 to 8 carbon atoms
An optionally substituted cycloalkyl group (e.g., cycloheptyl group, cyclohexyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group) , A methylbenzyl group, a methoxybenzyl group, etc.), and an optionally substituted aryl group (for example, a phenyl group, a tolyl group, a xylyl group, a chlorophenyl group, a bromophenyl group, a methoxyphenyl group, a naphthyl group, etc.), and the like. A group represented by the following formula: -CONHCH ₂ OZ
⁵ [Z ⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, etc.)], a —N ＝ C ＝ O group and —C (p ⁷ ) = C (p ⁸ ) H group ｛p ⁷ and p ⁸ each represent a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, And the like representing an ethyl group).

[0093]

Embedded image

As the polymerizable double bond group, specifically, CH ₂ ＣＨCH—, CH ₂ ＣＨCHCH ₂ —, CH ₂ ＝
_{CHCOO-, CH 2 = C (CH} 3) COO-, C (CH
_{3) H = CHCOO-, CH 2} = CHCONH-, CH 2
ＣC (CH ₃ ) CONH—, C (CH ₃ ) H ＝ CHCONH
—, CH ₂ ＣＨCHOCO—, CH ₂ （C (CH ₃ ) OCO
_{-, CH 2 = CHCH 2 OCO-} , CH 2 = CHNHC
O—, CH ₂ ＣＨCHCH ₂ NHCO—, CH ₂ ＣＨCHS
O ₂ —, CH ₂ ＣＨCHCO—, CH ₂ ＣＨCHO—, CH
₂ = CHS- and the like.

In the present invention, as a method for causing the resin [B] to contain at least one kind of functional group selected from the group of the curable functional groups, a method of introducing a polymer into a polymer or a method of introducing the functional group One or more monomers containing one or more of the above, a monomer corresponding to the repeating unit of the aforementioned general formula (III), and an optional “polar group-containing copolymer component” By a copolymerization reaction with the monomer to be formed.

For the high-molecular reaction, a conventionally known low-molecular-weight synthesis reaction method can be used as it is. For example, “New Experimental Chemistry Course Vol. 14, edited by The Chemical Society of Japan, Synthesis and Reaction of Organic Compounds [I] to [V]” (Published by Maruzen Co., Ltd.), Yoshio Iwakura, and Keisuke Kurita, "Reactive Polymers", etc., are described in detail in publicly known literature and the like. On the other hand, examples of the monomer containing the “functional group that undergoes a light and / or heat curing reaction” include, for example, the functional group capable of copolymerizing with a monomer corresponding to the repeating unit of the general formula (III). Examples include vinyl compounds containing a group. Specific examples include compounds containing the functional group in the substituents of the same compounds as the “compounds containing a polar group” described above.

Examples of the repeating unit containing a “thermo- and / or photo-curable functional group” will be described. Here, R ³¹ is the aforementioned R ²¹
And e ¹ and e ² are each H or CH
₃ shows a, R ³² is -CH = CH ₂ or -CH ₂ CH = C
Indicates H _2, R ³³ is _{-CH = CH 2, -C (CH} 3) = C
H ₂ or indicates -CH = CHCH _3, R ³⁴ is -CH = C
_{H 2, -CH 2 CH = CH} 2, shows a -C (CH ₃₎ = CH ₂ or _{C 6 H 5 -CH = CH 2} , R 35 is OH or NH
₂ represents, Z represents S or O, s represents an integer of 1 to 4, t represents an integer of 2 to 11, u represents an integer of 1 to 11, v is an integer of 1 to 10 Show.

[0098]

Embedded image

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

Further, the resin [B] of the present invention has the general formula (II)
In addition to the polymer component represented by I) and the polar group-containing polymer component, the polymer component may contain other polymer components polymerizable with these polymer components. Specifically, the same compounds as those exemplified as other polymer components that can be contained in the block B in the resin [A] can be mentioned. However, the proportion of these other polymer components in the resin [B] is 30% by weight or less, preferably 20% by weight or less.

In the resin [BB] used in the present invention,
As a method for bonding the acidic group to one end of the polymer main chain, the above-mentioned polar group or a specific reactive group which can be derived to the polar group during polymerization of each monomer which can be a copolymer component is described in a molecule. It is achieved by using a polymerization initiator or a chain transfer agent in combination, and includes, for example, a method of reacting various reagents with a terminal of a living polymer obtained by conventionally known anionic polymerization or cationic polymerization (method by ionic polymerization method), A method of radical polymerization using a polymerization initiator and / or a chain transfer agent containing a specific polar group in the molecule (a method by a radical polymerization method), or a terminal obtained by the ionic polymerization method or the radical polymerization method as described above. A polymer containing a reactive group (for example, an amino group, a halogen atom, an epoxy group, an acid halide group, etc.) is reacted with a specific polymer of the present invention by a polymer reaction. It can be readily prepared by synthesis methods such as a method of converting the group.

More specifically, P. Dreyfuss, R.A.
P. Quirk, Encycl. Polym. Sci.
Eng. , 7 , 551 (1987), Yoshiki Nakajo, Yuya Yamashita, "Dyes and Chemicals", 30 , 232 (1985), Akira Ueda, Susumu Nagai, "Science and Industry" 60 , 57 (1986), and references cited therein. And the like.

As the chain transfer agent to be used, for example, the polar group or a mercapto compound containing the above-mentioned reactive group (that is, a group derivable to the polar group) (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, -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-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic 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, and the like, or an iodized alkyl compound containing the above polar group or substituent ( For example, iodoacetic acid, iodopropionic acid, 2-
Iodoethanol, 2-iodoethanesulfonic acid, 3-
Iodopropanesulfonic acid). Preferably, a mercapto compound is used.

Specific examples of the polymerization initiator containing the polar group or a specific reactive group include 4,4′-azobis (4-cyanovaleric acid) and 4,4′-azobis (4-cyano Valeric 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].

The amount of the chain transfer agent or polymerization initiator to be used is preferably 0.5 to 15 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of all monomers.
Parts by weight. However, as is conventionally known in the polymerization reaction, the weight average molecular weight of the resin is a predetermined value by appropriately adjusting the type of the polymerization initiator and the chain transfer agent, the amount used, the polymerization temperature, the concentration of the monomer, the polymerization solvent, and the like. Can be set within the range.

In the present invention, when the resin [B] contains a light and / or thermosetting functional group, a crosslinking agent may be used in combination to promote crosslinking in the film. As the crosslinking agent to be used, a compound usually used as a crosslinking agent can be used. Specifically, Shinzo Yamashita and Tosuke Kaneko, “Handbook of Crosslinking Agents”, Taisei Publishing (1981)
Compounds described in “Polymer Data Handbook Basic Edition” edited by the Society of Polymer Science, Baifukan (1986) and the like can be used.

For example, organic silane compounds (for example, vinyltrimethoxysilane, vinylolibutoxysilane,
silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, etc.), polyisocyanate-based compounds (eg, toluylene diisocyanate, o-toluene) Range isocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymer polyisocyanate, etc.), polyol compounds (for example, 1, 4-butanediol, polyoxypropylene glycol, polyoxylene alkylene glycol, 1,1,1-trimethylolpropane, etc.), polyamine compounds (for example, ethylenediamine, γ-hydroxy Propylated ethylenediamine, phenylenediamine hexamethylenediamine, N-
Aminoethylpiperazine, modified aliphatic polyamines, etc., polyepoxy group-containing compounds and epoxy resins (eg, "New Epoxy Resin" edited by Hiroshi Kakiuchi, Shokodo (1985), "Epoxy Resin" edited by Nori Hashimoto, Nikkan Kogyo Shimbun (1
969), melamine resins (for example, compounds described in "Uria Melamine Resin", edited by Ichiro Miwa and Hideo Matsunaga, Nikkan Kogyo Shimbun (1969)), poly (meta) Acrylate-based compounds (for example, compounds described in No. Okawara, Takeo Saegusa, Toshinobu Higashimura, "Oligomer" Kodansha (published in 1976), Eizo Omori, "Functional acrylic resin" Techno System (published in 1985), etc. Specifically, polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol polyacrylate, bisphenol A-diglycidyl ether diacrylate Acrylates and oligoester acrylates: There is Kurirato and the like.

The amount of the crosslinking agent used in the binder resin of the present invention is 0.5 to 30% by weight based on the total amount of the binder resin.
In particular, the content is preferably 1 to 10% by weight. In the present invention, a reaction accelerator may be added to the binder resin, if necessary, in order to promote a crosslinking reaction in the photosensitive layer film. In the case of a reaction mode in which a crosslinking reaction forms a chemical bond between functional groups, for example, an organic acid (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.) and the like can be mentioned.

When the cross-linking reaction is a polymerization reaction mode, a polymerization initiator (peroxide, azobis compound, etc. may be used.
Preferably, an azobis-based polymerization initiator), a polyfunctional polymerizable monomer (for example, vinyl methacrylate, allyl methacrylate, ethylene glycol acrylate,
Polyethylene glycol diacrylate, divinyl succinate, divinyl adipate, diallyl succinate, 2-methylvinyl methacrylate,
Divinylbenzene, etc.).

When the binder resin of the present invention contains a light and / or thermosetting functional group in the resin [B], the resin is crosslinked or thermally cured after applying the photosensitive layer-formed product. In order to carry out crosslinking or thermal curing, for example, the drying conditions are made stricter than the drying conditions at the time of the conventional photoreceptor production. For example, the drying conditions are high temperature and / or long time. Alternatively, it is preferable to further perform a heat treatment after drying the coating solvent. For example, 60
Treat at ~ 120 ° C for 5-120 minutes. When the above-mentioned reaction accelerator is used in combination, the treatment can be performed under milder conditions.

As the binder resin provided for the photoconductive layer of the present invention, the above-mentioned known resin for an inorganic photoconductor can be used in combination in addition to the resin [A] and the resin [B] of the present invention.
However, the usage ratio of these other resins is 10
A range not exceeding 30 parts by weight of 0 parts by weight is preferable. If this ratio is exceeded, the effect of the present invention will be significantly reduced.

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

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

The total amount of the binder resin used in the photoconductive layer of the present invention is 1 to 100 parts by weight of the inorganic photoconductor.
It is preferably from 0 to 100 parts by weight, more preferably from 15 to 50 parts by weight. The use ratio of the resin [A] and the resin [B] of the present invention is 0.05 to 0.8 / 0.95 to 0.2 in a weight ratio of the resin [A] / the resin [B].
0, more preferably 0.10
0.50 / 0.90 to 0.50.

[0117] When the total amount of the binder resin is <br/> Ru less than 10 parts by weight, the film strength of the photoconductive layer can not be maintained. Also 100
When the amount is more than the weight part, the electrostatic characteristics are deteriorated, and the copied image is deteriorated even in the actual imaging performance. Further, when the weight ratio of the resin [A] is less than 0.05 in the usage ratio of the resin [A] and the resin [B] of the present invention, the effect of improving the electrostatic properties is diminished. On the other hand if the film strength of the larger <br/> and the photoconductive layer than 0.8 can not be sufficiently maintained (especially as electrophotographic lithographic printing plate precursor) occurs.

Examples of the inorganic photoconductive material used in the present invention include zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, and lead sulfide. As the spectral sensitizing dye used in the present invention, various dyes are used alone or in combination as needed. For example, Harumi Miyamoto, Hidehiko Takei, Imaging 1973 (No. 8), page 12,
C. J. Young et al., RCA Review 15 ,
469 (1054), Kohei Kiyota, IEICE Transactions
J63- C (No. 2), 97 (1980), Yuji Harasaki et al., Industrial Science Magazines 66 , 78 and 188 (1963),
Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes) described in review articles such as Tadaaki Tani, Journal of the Photographic Society of Japan 35 , 208 (1972). Dyes, rhodacyanine dyes, styryl dyes, etc.) and phthalocyanine dyes (which may contain metals).

More specifically, those using mainly carbonium dyes, triphenylmethane dyes, xanthene dyes and phthalein dyes are described in JP-B-51-45.
No. 2, JP-A-50-90334 and JP-A-50-11422
No. 7, No. 53-39130, No. 53-82353,
U.S. Pat. Nos. 3,052,540 and 4,054,45
0 and JP-A-57-16456.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include those described in F.I. M. H am er "The CyanineD
yes and Related Compound ”
Can be used, more specifically, more specifically,
U.S. Pat. Nos. 3,047,384 and 3,110,59
No. 1, 3,121,008, 3,125,447
Nos. 3,128,179 and 3,132,942
No. 3,622,317, British Patent No. 1,226,
892, 1,309,274, 1,405,8
No. 98, Japanese Patent Publication No. 48-7814, and No. 55-18892
And the like.

Further, as a polymethine dye for spectrally sensitizing the near infrared to infrared light region having a long wavelength of 700 nm or more, Japanese Patent Application Laid-Open No.
No. 7-840, No. 47-44180, Japanese Patent Publication No. 51-4
No. 1061, JP-A-49-5034 and JP-A-49-451
No. 22, No. 57-46245, No. 56-35141
No., 57-157254, 61-26044,
No. 61-27551, U.S. Pat. No. 3,619,154
No. 4,175,956, “Research D
isclosure ", 1982, 216, 117-
And those described on page 118 and the like. The photoreceptor of the present invention is excellent in that even when various sensitizing dyes are used in combination, the performance is hardly changed by the sensitizing dye. Furthermore, various conventionally known additives for an electrophotographic photosensitive layer such as a chemical sensitizer can be used in combination, if necessary. For example,
Review mentioned above: Imaging 1973 (No. 8) No. 1
"Development and commercialization of bacterial photoconductive materials and photoreceptors", such as electron-accepting compounds (eg, halogen, benzoquinone, chloranil, acid anhydride organic carboxylic acid, etc.) and Hiroko Komon, etc. Chapters 4 to 6 include polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, and the like, which are referred to in the review articles of Japan Science Information Co., Ltd., Publishing Division (1986).

The amounts of these various additives are not particularly limited, but are usually 0.04 parts by weight per 100 parts by weight of the photoconductor.
001 to 2.0 parts by weight. The thickness of the photoconductive layer is 1 to 1
00μ, especially 10 to 50μ is preferred. When a photoconductive layer is used as the charge generation layer of the photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is 0.01 to
1μ, particularly 0.05-0.5μ, is preferred.

In some cases, an insulating layer is provided for the main purpose of protecting the photosensitive member, improving the durability, and improving the dark attenuation characteristics.
At this time, the insulating layer is set relatively thin, and the insulating layer provided when the photosensitive member is used in a specific electrophotographic process is set relatively thick. In the latter case, the thickness of the insulating layer is 5
７０70 μm, especially 10-50 μm.

Examples of the charge transporting material for the laminated photoreceptor include polyvinyl carbazole, oxazole dyes, pyrazoline dyes, and triphenylmethane dyes. The thickness of the charge transport layer is preferably 5 to 40 μm, particularly preferably 10 to 30 μm. Typical resins used for forming the insulating layer or the charge transport layer include polystyrene resins, polyester resins, cellulose resins, polyether resins,
Vinyl chloride resins, vinyl acetate resins, vinyl chloride - acetate bi copolymer resins, polyacrylic resins, polyolefin resins, urethane resins, epoxy resins, melamine resins, thermoplastic resins and curable resin silicone resin used as appropriate.

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally, the support of the electrophotographic photosensitive layer is preferably conductive. As the conductive support, a base material such as a metal, paper, or a plastic sheet is impregnated with a low-resistance substance in the same manner as in the related art. those conductive treatment such as by those conductivity is imparted to the back surface of the base body (surface opposite to the surface on which the photosensitive layer), and further coated with at least one or more layers for the purpose of achieving anti-curl,
A substrate provided with a water-resistant adhesive layer on the surface of the support, a substrate provided with at least one or more pre-coat layers on the surface layer of the support as required, a base conductive plastic on which Al or the like is deposited on paper, Can be used.

Specifically, examples of the conductive substrate or the conductive material include Yukio Sakamoto, Electrophotography, 14 (No. 1).
2-11 (1975), Hiroyuki Moriga, "Chemistry of Introductory Special Paper", Polymer Publishing Association (1975); F. Hoove
r, J. et al. Macromol. Sci. Chem. A-4
(6), those described in pages 1327 to 1417 (1970) and the like are used.

The electrophotographic photoreceptor of the present invention can be used in applications utilizing all conventionally known electrophotographic processes. That is, the photoreceptor of the present invention can be used for any of the recording methods of the PPC method and the CPC method.
The developer can be used in any combination of a dry developer and a liquid developer.

In particular, since a high-definition original faithful copy image can be formed, the effect of the present invention is more exerted when used in combination with a liquid developer. In addition, by combining with a color developer, not only black-and-white copy images,
It can also be applied to color copied 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 (1977)
Year) etc.).

Further, the present invention is also effective in a system utilizing another recent electrophotographic process for other uses. For example, the photoreceptor of the present invention using photoconductive zinc oxide as the photoconductor is used as an offset lithographic printing plate precursor, and is also non-polluting and has good whiteness and good photoconductive zinc oxide or photoconductive titanium oxide. The photoreceptor can be used as an underprint material or a color group used in an offset printing process.

[0130]

EXAMPLES Examples of the present invention will be described below, but the content of the present invention is not limited to these examples. [Synthesis of Resin [A]] Synthesis Example 1 of Resin [A]: [A-1] benzyl methacrylate 47.5 g, the following initiator [I-
1] A mixture of 24.8 g and 70 g of tetrahydrofuran was brought to a temperature of 40 ° C. under a nitrogen stream. 400
Photopolymerization was performed by irradiating light from a W high-pressure mercury lamp through a glass filter from a distance of 10 cm for 10 hours.

[0131]

Embedded image

Next, methacrylic acid 2.5 was added to this polymer.
g and a mixed solution of 5 g of tetrahydrofuran were added, and the mixture was further irradiated with light for 1 at a temperature of 40 ° C. in a nitrogen stream.
Performed for 0 hours. The precipitate was reprecipitated in 800 ml of a mixed solution of water / methanol (2/1), and the precipitate was collected and dried. The yield of the obtained polymer was 38 g and Mw was 8.5 × 10 ³ .

[0133]

Embedded image

Synthesis Examples 2 to 10 of Resin [A]: [A-2]
~ [A-10] In Synthesis Example 1 of resin [A], instead of 47.5 g of benzyl methacrylate and 2.5 g of methacrylic acid, each was replaced with a monomer corresponding to the component shown in Table-A below. Otherwise, each polymer was synthesized in the same manner as in Synthesis Example 1 of Resin [A]. Mw of each of the obtained polymers is 7 × 10 ³ to 1
× 10 ⁴ range.

[0135]

[Table 1]

[0136]

[Table 2]

[0137]

[Table 3]

Synthesis Examples 11 to 16 of Resin [A]: [A-1]
1] to [A-16] 40 g of 2-chlorophenyl methacrylate, Table B below
A mixture of 0.02 mol of the initiator and 50 g of tetrahydrofuran was irradiated with light for 8 hours in the same manner as in Synthesis Example 1 of resin [A]. Next, a mixed solution of 7.5 g of benzyl methacrylate, 2.5 g of methacrylic acid and 10 g of tetrahydrofuran was added to the reaction product, and then the above Synthesis Example 1 was added.
The reaction was carried out in the same manner as described above.

The Mw of the obtained polymer is 5 × 10 ^{3 to} 9 ×
It was in the range of 10 ³ .

[0140]

[Table 4]

[0141]

[Table 5]

Synthesis Examples 17 to 25 of Resin [A]: [A-1]
7] to [A-25] A mixed solution of 52.5 g of methyl methacrylate, 17.5 g of methyl acrylate, 44 g of the following initiator [I-8] and 75 g of tetrahydrofuran was added to a resin [A] at a temperature of 50 ° C. under a nitrogen stream. Irradiation was performed for 15 hours under the same conditions as in Synthesis Example 1.

[0143]

Embedded image

To this polymer were added monomers corresponding to the polymerization components in Table C below and 25 g of tetrahydrofuran.
Light irradiation was performed again for 15 hours in the same manner as described above. The Mw of the obtained polymer was in the range of 5 × 10 ³ to 8 × 10 ³ .

[0145]

[Table 6]

[0146]

[Table 7]

[0147]

[Table 8]

Synthesis Examples 26 to 31 of Resin [A]: [A-2]
6] to [A-31] Synthesis of resin [A] except that each monomer corresponding to the polymerization component described in Table D below and 0.03 mol of the following initiator [I-9] were used. By operating in the same manner as in Example 1, each polymer was obtained.
The Mw of the obtained polymer was in the range of 4 × 10 ^{3 to} 9 × 10 ³ .

[0149]

Embedded image

[0150]

[Table 9]

[0151]

[Table 10]

[Synthesis of Resin [B]] Synthesis Example 1 of Resin [B] [B-1] A mixed solution of 100 g of ethyl methacrylate, 150 g of toluene and 50 g of methyl alcohol was heated to a temperature of 75 ° C. under a nitrogen stream. . 0.8 g of 4,4'-azobis (4-cyanovaleric acid) (abbreviated as ACV) was added and reacted for 5 hours. C. V. 0.2 g was added and reacted for 4 hours.
Mw of the obtained polymer was 8 × 10 ⁴ .

[0153]

Embedded image

Synthesis Example 2 of Resin [B]: [B-2] Methyl methacrylate 85 g, methyl acrylate 15
g, 0.8 g of thioglycolic acid and 200 g of toluene were heated to a temperature of 75 ° C. under a nitrogen stream. 0.8 g of 1,1'-azobis (cyclohexane-1-carbonitrile) (abbreviated ABCC) was added thereto, and the mixture was reacted for 5 hours. B. C. C. 0.2 g was added and reacted for 4 hours. Mw of the obtained polymer was 7.5 × 10 ⁴ .

[0155]

Embedded image Synthesis Example 3: Resin [B]: [B-3] Methyl methacrylate 3.5 g, methyl acrylate 1
A mixed solution of 5 g, 10 g of styrene, 1.5 g of acrylic acid and 200 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream. Then, 1.0 g of 2,2'-azobis (isobutyronitrile) (abbreviated as AIBN) was added, and the mixture was reacted for 4 hours. I. B. N. 0.6 g was added and reacted for 4 hours. Mw of the obtained polymer was 5.0 × 10 ⁴ .

[0156]

Embedded image

Synthesis Examples 4 to 28 of Resin [B]: [B-4]
~ [B-28] Resin [B] shown in Table E below was synthesized by the same synthesis method as shown in Synthesis Examples 1 to 3 of resin [B]. The Mw of each of the obtained polymers was in the range of 6 × 10 ^{4 to} 20 × 10 ⁴ .

[0158]

[Table 11]

[0159]

[Table 12]

[0160]

[Table 13]

[0161]

[Table 14]

[0162]

[Table 15]

[0163]

[Table 16]

[0164]

[Table 17]

Example 1 and Comparative Examples 1 and 2 Resin [A-2] 6 g (as solid content), resin [B-2]
4] 34 g (as solid content), photoconductive zinc oxide 20
0 g, a mixture of 0.018 g of the cyanine dye [I] having the following structure, 0.15 g of salicylic acid and 300 g of toluene in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at a rotation speed of 6 × 10
³ r. p. m for 10 minutes and then phthalic anhydride at 0.
20 g and 0.003 g of o-chlorophenol were added, and the number of rotations was 1 × 10 ³ r. p. m for 1 minute. The photosensitive layer formed material prepared in this way is subjected to conductive treatment paper,
It is applied with a wire bar, dried at 110 ° C. for 10 seconds, and further dried at 140 ° C. for 3 seconds so that the dry adhesion amount becomes 22 g / m ^2.
Heated for 0 minutes. Then, the mixture was allowed to stand in a dark place at 20 ° C. and 65% RH for 24 hours to produce an electrophotographic photosensitive material.

[0166]

Embedded image

Comparative Example 1: The resin [A-
2] An electrophotographic photosensitive material was prepared in the same manner as in Example 1, except that 6 g of the resin [R-1] having the following structure was used instead of 6 g.

[0168]

Embedded image

Comparative Example 2: The resin [A-
2] An electrophotographic photosensitive material was prepared in the same manner as in Example 1, except that 6 g of the resin [R-2] having the following structure was used instead of 6 g.

[0170]

Embedded image

With respect to these photosensitive materials, the imaging properties, printability and environmental conditions were set at (20 ° C., 65% RH), (30 ° C.,
(80% RH) and (15 ° C., 30% RH) were examined for imageability and printability. The above results are shown in Table-F.

[0172]

[Table 18]

Embodiments of the evaluation items shown in Table-F are as follows. Note 1) Smoothness of surface layer: The obtained photosensitive material was measured using a Beck smoothness tester (manufactured by Kumagaya Riko Co., Ltd.), and the air capacity was 1c.
Under the condition of c, the smoothness (sec / cc) was measured. Note 2) Image-capturing property: After each photosensitive material was left for one day and night under the following environmental conditions, each photosensitive material was charged at -6 kV, and a 2.8 mW output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm) was used as a light source. ) At a radiation dose of 64 erg / cm ² on the surface of the photosensitive material at a pitch of 25
Developed using ELP-T (manufactured by Fuji Photo Film Co., Ltd.) as a liquid developer after exposure at a speed of 300 μm and a scanning speed of 300 m / sec, and rinsed with isoparaffin isopar G (manufactured by Esso Chemical Co.) solvent Image (fog, image quality) obtained by fixing after washing
Was visually evaluated.

Environmental conditions during imaging are 20 ° C. and 65% RH
(I), 30 ° C, 80% RH (II) and 15 ° C, 30%
Performed at RH (III). Note 3) Raw plate water retention: The degree of hydrophilization due to desensitization treatment when a photosensitive material was used as a printing original plate was examined under the following compulsory conditions.

Each photosensitive material itself (original plate without plate making: abbreviated as raw plate) was etched using an aqueous solution obtained by diluting a desensitizing solution ELP-EX manufactured by Fuji Photo Film Co., Ltd. with distilled water 5 times. I passed the machine once. Next, these plates were transferred to Hamada Star 8005X manufactured by Hamada Star Co., Ltd.
Printing was carried out using a mold, and the presence or absence of background stain on the 50th printed matter from the start of printing was visually evaluated. Note 4) Background smear of printed matter: After making each photosensitive material in the same operation as in the above note 2), after passing through an etching machine once using ELP-EX, the background smear of the printed matter can be visually discriminated. The number of prints up to was examined.

As shown in Table F, the light-sensitive material of the present invention
In the actual copied image, a high-definition image portion such as a fine line, a thin character, or a continuous tone halftone dot portion was obtained without any background fog. And, even when the environmental conditions at the time of imaging are severe conditions such as low temperature / low humidity or high temperature / high humidity,
A stable and clear copy image was obtained. On the other hand, in Comparative Examples 1 and 2, good copy images were obtained under the environmental conditions of normal temperature and normal humidity (I), but when the environmental conditions fluctuated, both of the high-definition image portions (particularly, continuous tone The density unevenness occurred in the intermediate density portion).

Next, the printing plate precursor for offset master was subjected to a desensitization treatment, and the performance as a printing plate precursor was examined. First, each photosensitive material before plate making was subjected to a desensitizing treatment under a forced condition in which the desensitizing power of Note 3) was weakened, actually printed, and the degree of ink adhesion was observed. Was good, and both Comparative Examples 1 and 2 showed occurrence of ink adhesion.

Further, as described in Note 4), the sensitized material actually made was processed under ordinary desensitizing conditions and printed, and the original plate of the present invention was free from background stains and had a faithful image quality. 8,000 prints with reproducibility were obtained. On the other hand, Comparative Example 1 had 4,000 sheets and Comparative Example 2 had 6,000 sheets. Furthermore, the original plate made under severe environmental conditions (II) and (III) had a poor image quality of the printed matter after printing due to poor reproduction of the copied image.

As described above, the resin [A] of the present invention properly interacts with the zinc oxide particles to form a state in which the desensitization reaction by the desensitizing solution easily and sufficiently proceeds. It is considered that this indicates that the film strength has been remarkably improved by the action of the resin [B]. Example 2 Resin [A-15] 6 g (as solid content), Resin [B-
2] 34 g (as solid content), photoconductive zinc oxide 20
0 g, 0.020 g of methine dye [II] having the following structure, N-
0.20 g of hydroxymaleimide and 30 of toluene
By operating 0 g of the mixture in the same manner as in Example 1, an electrophotographic photosensitive material was produced.

[0180]

Embedded image

The film properties (surface smoothness) of this photosensitive material,
The electrostatic characteristics, the imaging properties, and the imaging properties when the environmental conditions were set to 30 ° C. and 80% RH were examined. Further, printability when used as an electrophotographic lithographic printing original plate was examined. The results are shown in Table-G.

[0182]

[Table 19]

Embodiments of the electrostatic characteristics of the evaluation items shown in Table-G are as follows. Note 5) Electrostatic characteristics: in a dark room at a temperature of 20 ° C. and 65% RH.
Using a paper analyzer (Paper Analyzer SP-428 manufactured by Kawaguchi Electric Co., Ltd.) for each photosensitive material, -6
After a corona discharge at kV for 20 seconds, leave for 10 seconds,
The surface potential V ₁₀ at this time was measured. Then measuring the potential V ₁₃₀ after allowed to stand for 120 seconds in as dark, 12
Retention potential after 0 seconds is dark decay, i.e., dark decay retention rate [DRR (%)] [(V ₁₃₀ / V _10] × 100
(%)].

In addition, the surface of the photoconductive layer was reduced by corona discharge.
After being charged to 500 V, it is irradiated with monochromatic light having a wavelength of 780 nm, the time until the surface potential (V ₁₀ ) attenuates to 1/10 is obtained, and the exposure amount E _1/10 (erg / cm ² ) is calculated from this. I do. Furthermore, by corona discharge as in the E _1/10 measurement,
After charging to 500 V, irradiation with monochromatic light having a wavelength of 780 nm was performed, and the time required for the surface potential (V ₁₀ ) to attenuate to 1/100 was determined. From this, the exposure amount E _1/100 (erg / c) was obtained.
m ² ) is calculated. Environmental conditions at the time of imaging are I (20 ° C., 6
5% RH), II (30 ° C., 80% RH) and III (15% RH).
C., 30% RH).

The light-sensitive material of the present invention had good smoothness and was in a sufficiently uniform dispersion state. Further, when the electrostatic characteristics were examined by changing the environmental conditions, the values were stable and good even when the conditions fluctuated. In actual imaging performance, a faithful copy image was reproduced with respect to the original, and no ground fog was recognized. In addition, as a master for offset master, 8,000 sheets of good printed matter were obtained after desensitization treatment and printing. Examples 3 to 22 In Example 2, the resin [A-15] and the resin [B-
Each electrophotographic photoreceptor was produced in the same manner as in Example 1, except that each resin [A] and each resin [B] in Table H below were used instead of [2].

[0186]

[0187]

[Table 20]

Examination of the actual image-capturing properties of these photographic materials revealed that they had clear reproduced images with good reproducibility of fine lines and characters, no generation of halftone unevenness and no background fog. Further, when printing was performed in the same manner as in Example 2 using the offset master master, at least 8,000 or more sheets could be printed. From the above, each photosensitive material of the present invention was excellent in all aspects of the smoothness, electrostatic properties and printability of the photoconductive layer. Examples 23 to 26 Electrophotographic photosensitive materials were prepared under the same conditions as in Example 1 except that the dyes shown in Table I below were used instead of the cyanine dye [I] used in Example 1.

[0189]

[Table 21]

[0190]

[Table 22]

The photosensitive materials of the present invention are all excellent in chargeability, dark charge retention and photosensitivity, and actual copied images can be obtained at high temperature and high humidity (30 ° C., 80% RH) and at low temperature and low humidity (15 ° C.). ,
Even under severe conditions (30% RH), a clear image without fog was obtained. Examples 27 and 28 and Comparative Example 3 6 g of resin [A-26] and 34 g of resin [B-8] (Example 27) or 6 g of resin [A-11] and resin [B-1]
3] 34 g (Example 28), zinc oxide 200 g, uranine 0.02 g, methine dye [VII] 0.0 having the following structure
3 g, methine dye [VIII] having the following structure: 0.03 g, p-
A mixture of 0.18 g of hydroxybenzoic acid and 300 g of toluene was stirred in a homogenizer at a rotation speed of 7 × 10 ³ r. p.
m for 10 minutes to prepare a photosensitive layer-formed product, which was applied to a conductive treated paper with a wire bar so that the dry adhesion amount was 18 g / m ^2, and dried at 110 ° C for 20 seconds.
Next, each electrophotographic photoreceptor was manufactured by being left in a dark place at 20 ° C. and 65% RH for 24 hours.

[0192]

Embedded image

[0193]

Embedded image

Comparative Example 3 A photographic material was prepared in the same manner as in Example 28 except that 6 g of the resin [R-1] was used instead of the resin [A-11]. As in Example 1, each characteristic of each photosensitive material was examined. The results are summarized in Table J below.

[0195]

[Table 23]

In the above measurement, the same operation as in Example 1 was performed, except that the following operations were performed for the electrostatic characteristics and the image pickup properties. Note 6) Method for measuring E _1/10 and E _1/100 of electrostatic characteristics After charging the surface of the photoconductive layer to −400 V by corona discharge, the surface of the photoconductive layer is exposed to visible light having an illuminance of 2.0 lux. The time until the surface potential (V ₁₀ ) attenuates to 1/10 or 1/100 after irradiation is determined, and the exposure amount E _1/10 or E _1/100 (lux seconds) is calculated from this. Note 7) Image-capturing properties After leaving each photosensitive material for one day and night under the following environmental conditions, a fully automatic plate making machine EPL-404V (Fuji Photo Film Co., Ltd.)
Manufactured), and a copy image (fog, image quality) obtained by making a plate using EPL-T as a toner was visually evaluated. Environmental conditions at the time of imaging are 20 ° C., 65% RH (I) 30 ° C.,
Performed at 80% RH (II) and 30% RH (III) at 15 ° C. However, a copy original (that is, a copy original) was prepared by cutting and pasting another original.

In each photosensitive material, the smoothness of the photoconductive layer,
In the electrostatic characteristics, both exhibited good performance. When examining the actual imaging performance, Comparative Example 3 shows that under severe conditions, in addition to the original as a copy image, the frame of the cut and pasted portion (that is, the pasted trace) is used as background stain of the non-image portion or The occurrence of uneven white spots was observed in the solid image portion. However, in each case of the present invention, clear images without background stains were obtained.

Further, when these were subjected to desensitization treatment as an offset printing original plate and then printed, any of the present invention obtained 8,000 or more printed materials of clear image quality without background smear. However, in Comparative Example 3, in the original plate made under severe conditions, the above-mentioned sticking marks were not removed even by the desensitization treatment.
Either it occurred from the printed material or unevenness of the plate image occurred in the printed material.

As described above, only the photosensitive material of the present invention was able to give good characteristics. Example 29 5 g of resin [A-17] and 35 g of resin [B-21], 200 g of zinc oxide, 0.02 g of uranine, 0.04 g of rose bengal, 0.03 g of bromophenol blue, 0.40 g of phthalic anhydride and 300 g of toluene Mixture of
Rotation speed in homogenizer 8 × 10 ³ r. p. m. For 5 minutes, and diacetylacetone zirconium salt was further added.
006 g, and the number of rotations is 1 × 10 ³ r. p. m. For 1 minute. The dispersion was applied to a paper that had been conductively treated with a wire bar, using a wire bar so that the dry adhesion amount was 26 g / m ² , dried at 110 ° C. for 10 seconds, and further dried at 140 ° C.
For 20 minutes. Next, in a dark place, at 20 ° C and 65%
Was left for 24 hours under the above conditions to produce an electrophotographic photosensitive material.

When the photographic material of the present invention was operated in the same manner as in Example 28 to examine its respective performances, all were excellent in chargeability, dark charge holding ratio and photosensitivity. (3
0 ° C, 80% RH) or low temperature / low humidity (15 ° C, 30%)
% RH), a clear image free of background fog and unevenness in the image area was obtained. Furthermore, when this was used as an offset master for printing,
Clear prints were obtained in all places. Examples 30 to 39 In the same manner as in Example 29, except that 5 g of the resin [A] shown in the following Table-K was used instead of 5 g of the resin [A- 17 ], each photosensitive material was produced in the same manner as in Example 29. .

[0201]

[Table 24]

Examination of the actual image-capturing properties of these light-sensitive materials revealed that a clear copy image with good reproducibility of fine lines and characters, no generation of halftone unevenness and no background fog was obtained. Further, when printing was performed in the same manner as in Example 29 using the offset master master, at least 8,000 sheets could be printed. From the above, each photosensitive material of the present invention was excellent in all aspects of the smoothness, electrostatic properties and printability of the photoconductive layer. Examples 40 to 45 In the same manner as in Example 29, except that each compound shown in Table L below was used in place of 35 g of the resin [B- 21 ] and 0.003 g of diacetylacetone zirconium salt, the same operation as in Example 29 was carried out. An electrophotographic photosensitive material was produced.

[0203]

[Table 25]

For these photosensitive materials, the imaging properties, printability and environmental conditions were set at (20 ° C., 65% RH), (30 ° C.,
The imaging performance and printability at (80% RH) and (15 ° C., 30% RH) were examined in the same manner as in Example 28. All of the photosensitive materials of the present invention are excellent in chargeability, dark charge retention, and photosensitivity, and actual copied images can be obtained at high temperature and high humidity (30 ° C., 80%
RH) and low temperature and low humidity (15 ° C., 30% RH) gave a clear image without generation of background fogging, unevenness of the image area, and thin line skipping.

Further, when printing was performed as an offset master, a printed matter of clear image quality free of background stain was obtained even after printing 10,000 sheets.

[0206]

According to the present invention, an electrophotographic photoreceptor having excellent electrostatic characteristics (especially under severe conditions), a clear and high-quality image, and further excellent mechanical strength. Can be obtained. In particular, it is effective for a scanning exposure method using a semiconductor laser beam.

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

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03G 5/05 101

Claims (4)

(57) [Claims] 1. An electrophotographic photosensitive member having a photoconductive layer containing at least an inorganic photoconductive material, a spectral sensitizing dye and a binder resin, wherein the binder resin comprises at least one of the following resins [A] and An electrophotographic photoreceptor comprising at least one resin [B]. Resin [A] having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , containing at least one kind of a repeating unit represented by the following general formula (I) as a polymer component, and represented by the following B block
And A blocks containing no polymer component containing the specific polar group, -PO ₃ H ₂ group, -SO ₃ H group, -COOH
Group, —P (＝ O) (OH) R ¹ [R ¹ is a hydrocarbon group or —O
And a B block containing at least one polymer component containing at least one polar group selected from R ² (R ² represents a hydrocarbon group) group and a cyclic acid anhydride-containing group. If fewer AB type block polymer chain composed of
Is also a star-type copolymer bonded to three identical organic molecules . Embedded image [In the formula (I), a ¹ and a ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ¹¹ represents a hydrocarbon group. Resin [B] A resin having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ and containing at least 30% by weight of a polymer component represented by the following general formula (III). Embedded image [In the formula (III), X ² represents — (CH ₂ ) r COO—, — (CH
₂ ) r represents OCO-, -O- or -CO- (where r represents 0 or an integer of 1 to 3). c ¹ , c ² and R ¹³
Represents the same contents as a ¹ , a ² and R ¹¹ in the formula (I). ] 2. The resin [A] is a copolymer component represented by the general formula (I), which is selected from aryl group-containing methacrylate components represented by the following general formulas (Ia) and (Ib). 2. The electrophotographic photoreceptor according to claim 1, comprising at least one. Embedded image Embedded image [In the formulas (Ia) and (Ib), A ¹ and A ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, —COR ¹⁴ or —COOR ¹⁴ (R ¹⁴ Represents a hydrocarbon group having 1 to 10 carbon atoms), and B ¹ and B ²
Represents a single bond or a linking group having 1 to 4 linking atoms, each linking -COO- and a benzene ring. ] 3. The resin [B] further comprises-
PO ₃ H ₂ group, -SO ₃ H group, -COOH group, -P (= O)
(OH) R ³ (R ³ represents the same content as R ¹⁾ according to claim 1 or 2, characterized in that formed by combining at least one polar group selected from the group and a cyclic acid anhydride-containing group Electrophotographic photoreceptor. 4. The electrophotographic photosensitive member according to claim 1, wherein the resin [B] further contains a heat and / or photocurable functional group.