JP2008163262A - Polycarbonate resin composition and electrophotographic photoreceptor using the same - Google Patents

Abstract

【選択図】なしThe present invention provides a polycarbonate resin composition having excellent metal adhesion, and an electrophotographic photoreceptor having improved adhesion between a photosensitive layer and a metal substrate and wear resistance.
A polycarbonate resin and a polyimide silicone resin represented by the formula (1) are blended to form a polycarbonate resin composition and used as a binder resin for a photosensitive layer.

[Selection figure] None

Description

  The present invention relates to a polycarbonate resin composition containing a polyimide silicone resin and excellent in metal adhesion, and an electrophotographic photoreceptor excellent in wear resistance and durability using the polycarbonate resin composition as a binder resin for a photosensitive layer.

  Polycarbonate resins are used in various fields as engineering plastics having excellent transparency, optical properties, and mechanical strength. As a special specification example, there is an application as a photosensitive layer binder resin of an electrophotographic photosensitive member used in a copying machine, a laser beam printer (hereinafter abbreviated as LBP), a fax machine or the like.

  At present, multilayer electrophotographic photoreceptors in which the photosensitive layer has a charge generation layer and a charge transport layer are the mainstream, and these photosensitive layers are made of metal such as a cylinder made of aluminum or stainless steel or a cylinder or belt made of aluminum-deposited polyester. It is formed by applying a solution in which a polycarbonate resin and a chemical such as a charge generating agent and a charge transporting agent are dissolved on a base material (conductive base material) and performing wet molding.

  The outermost layer of the electrophotographic photosensitive member (the charge transport layer in the case of a laminated electrophotographic photosensitive member) has many opportunities to come into contact with toner, paper, a charging roller, a cleaning blade, etc., and therefore requires particularly wear resistance. Is done. Therefore, conventionally, as a means for improving the wear resistance, a method of adding various silicone-based additives to the photosensitive layer binder resin has been reported (see Patent Documents 1 to 3).

In recent years, recycling of electrophotographic photoreceptors has been actively performed, and a method of removing a charge transport layer on a deteriorated photoreceptor surface and forming a new charge transport layer to obtain a recycled electrophotographic photoreceptor is used. . At this time, since the charge transport layer is formed on the entire surface of the charge generation layer, the part of the charge transport layer that protrudes may directly contact the metal substrate. In that case, the additive tended to reduce the adhesion between the charge transport layer and the metal substrate.
In recent years, in offices and general households, the number of purchasers who replace consumable electrophotographic photoconductors is increasing without relying on specialized contractors for maintenance, and in that case, protection to protect the electrophotographic photoconductor In some cases, the adhesive tape that stops the paper or film is mistakenly attached to the surface of the electrophotographic photosensitive member. In such a case, if the adhesion between the photosensitive layer and the metal substrate is low, there may be a problem that the photosensitive layer is peeled off together with the tape, particularly when the tape adheres to the edge of the photosensitive member. There was room for improvement in adhesion to the substrate.

JP-A-61-219049 JP-A-1-234854 JP-A-5-165244

  The problem to be solved by the present invention is to provide a polycarbonate resin composition having excellent metal adhesion, and to provide an electrophotographic photoreceptor having improved adhesion and abrasion resistance between the photosensitive layer and the metal substrate. .

  As a result of intensive studies to solve the above problems, the inventors of the present invention have a polycarbonate resin composition in which a small amount of a specific polyimide silicone resin that is soluble in a solvent is added to the photosensitive layer, and has excellent metal adhesion, The electrophotographic photoreceptor using this as a binder resin for the photosensitive layer has improved wear resistance and adhesion between the photosensitive layer and the metal substrate, compared to the conventional electrophotographic photoreceptor using the binder resin for the photosensitive layer. The present invention was completed by finding that the property was good and there were few peeling defects.

That is, the present invention relates to the following polycarbonate resin composition and electrophotographic photosensitive member.
(1) A polycarbonate resin composition comprising a polyimide silicone resin having a polycarbonate resin as a main component and having an average molecular weight of 5,000 to 150,000 consisting of repeating units represented by the following general formula (1).

(In the formula, X is a tetravalent organic group, Y is a divalent organic group, Z is a divalent organic group having an organosiloxane structure, and the ratio of p: q is a ratio of 1:99 to 99: 1. .)

(2) The polycarbonate resin composition according to (1), wherein Z in the general formula (1) is a diaminosiloxane residue represented by the following general formula (2).

(Wherein R ₁ to R ₄ are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 8 carbon atoms, which may be the same or different. Q is independently substituted or unsubstituted. A divalent hydrocarbon group having 1 to 8 carbon atoms, a is an integer of 1 to 100.)

(3) The polycarbonate resin composition according to (1) or (2), wherein the polyimide silicone resin is contained in an amount of 0.05 to 5% by weight.
(4) The polycarbonate resin is 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane And a polycarbonate resin composition according to any one of (1) to (3), which is derived from bisphenols selected from the group consisting of 1,1′-biphenyl-4,4′-diol.

(5) The polycarbonate resin composition according to any one of (1) to (4), wherein the intrinsic viscosity of the polycarbonate resin is 0.3 to 2.0 dl / g.
(6) In an electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, the polycarbonate resin composition according to any one of (1) to (5) is used as a binder resin for the photosensitive layer. Electrophotographic photoreceptor.
(7) In the electrophotographic photoreceptor having a photosensitive layer comprising a charge generation layer and a charge transport layer on a conductive substrate, the polycarbonate according to any one of (1) to (5) as a binder resin for the charge transport layer An electrophotographic photosensitive member using a resin composition.

  The polycarbonate resin composition containing the polyimide silicone resin of the present invention is excellent in wear resistance and metal adhesion. Therefore, when used as a binder resin for the photosensitive layer of an electrophotographic photosensitive member, it is possible to greatly prevent the peeling of the photosensitive layer due to adhesion of the tape when replacing the electrophotographic photosensitive member, so the wear resistance and durability are greatly improved. An electrophotographic photosensitive member can be provided.

(1) Polyimide silicone resin The polyimide silicone resin used in the present invention comprises a repeating unit represented by the above general formula (1), and more specifically, a repeating unit represented by the following general formulas (1a) and (1b): A copolymer consisting of

  The repeating units of the general formulas (1a) and (1b) constituting the polyimide silicone resin of the present invention may be bonded in any form of random copolymerization and block copolymerization, but are usually random copolymers. is there.

  Here, in said general formula (1a), X is a tetravalent organic group, Comprising: The tetracarboxylic dianhydride residue which is a raw material of a polyimide silicone resin is represented. Examples of the tetracarboxylic dianhydride residue include an aliphatic tetracarboxylic dianhydride residue, an alicyclic tetracarboxylic dianhydride residue, and an aromatic tetracarboxylic dianhydride residue.

  Examples of the aliphatic tetracarboxylic dianhydride residue include residues such as butane-1,2,3,4-tetracarboxylic dianhydride and pentane-1,2,4,5-tetracarboxylic dianhydride. Groups.

  Examples of the alicyclic tetracarboxylic dianhydride residue include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, and dicyclohexyl-3. , 3 ′, 4,4′-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran Examples include residues such as tetracarboxylic dianhydride.

  As aromatic tetracarboxylic dianhydride residues, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetra Carboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4 '-Benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 4,4'-hexafluoropropylidenebisphthalic dianhydride, 3,3 ', 4 , 4'-diphenylsulfone tetracarboxylic dianhydride and the like.

  1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, Fragrances such as 3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione Mention may also be made of the residues of aliphatic tetracarboxylic dianhydrides having a ring.

  These tetracarboxylic dianhydride residues may be used alone or in combination of two or more. Of these, more preferred are aromatic tetracarboxylic dianhydride residues, and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 4,4′-hexafluoropropylene. Residues of lidenebisphthalic dianhydride and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride are preferred, and residues of 4,4′-hexafluoropropylidenebisphthalic dianhydride Is particularly preferable in terms of compatibility with the resin.

  In the general formula (1a), Y is a divalent organic group and represents a residue of a diamine that is a raw material for the polyimide silicone resin. Examples of the diamine residue include aliphatic diamine, alicyclic diamine, and aromatic diamine residues.

Examples of the aliphatic diamine residue include residues such as trimethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the alicyclic diamine residue include residues such as 1,4-diaminocyclohexane and bis (4-aminocyclohexyl) methane.

  Examples of aromatic diamine residues include 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, Bis {4- (3-aminophenoxy) phenyl} sulfone, bis {4- (4-aminophenoxy) phenyl} sulfone, orthophenylenediamine, metaphenylenediamine, paraphenylenediamine, 4,4′-diaminodiphenyl-2, 2-propane, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis {4- (4-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis (4-aminophenyl) hexa Fluoropropane, 2,2-bis (3-aminophenyl) hexa Fluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4- And residues such as aminophenyl) fluorene.

3,3′-dicarboxy-4,4′-diaminodiphenylmethane, diaminobisphenol A, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 2,2-bis (3-amino-4-hydroxy) Phenyl) hexafluoropropane, 2,2 ′-{2-hydroxy-3- (3,5-methyl-4-amino) -benzyl-5-methyl} -diphenylmethane, and other diamines having functional groups other than amino groups. Residues can also be mentioned.
These diamine residues may be used alone or in combination of two or more. Among these, more preferred are aromatic diamine residues, and bis {4- (4-aminophenoxy) phenyl} sulfone and 1,4-bis (4-aminophenoxy) benzene diamine residues are more preferable. Preferably, the diamine residue of 1,4-bis (4-aminophenoxy) benzene is particularly preferable in terms of compatibility with the resin.

  In the general formula (1b), X is the same as in the general formula (1a). Z is a residue of another diamine (diaminosiloxane) which is a raw material of the polyimide silicone resin, and represents a divalent organic group (diaminosiloxane residue) having an organosiloxane structure. Specifically, a diamine residue represented by the following general formula (2) is preferable.

R < ₁ > -R < ₄ > in the said General formula (2) is C1-C10, Preferably it is a C1-C8 substituted or unsubstituted monovalent hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic ring Either a formula hydrocarbon group or an aromatic hydrocarbon group may be used. These may be the same or different.
Specific examples of R _{1 to} R ₄ include an aliphatic hydrocarbon group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group. Alkyl groups such as groups; alkenyl groups such as vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, isobutenyl groups, hexenyl groups, and the like.
Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclohexyl group and a cyclopentyl group; a cycloalkenyl group such as a cyclohexenyl group, and the like. Aromatic hydrocarbon groups include aryl groups such as phenyl, tolyl and xylyl groups; aralkyl groups such as benzyl, ethylphenyl and propylphenyl groups.
Further, at least one of the hydrogen atoms of these hydrocarbon groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, a cyano group, or the like. Examples of such include chloromethyl group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group, 4-fluorophenyl group, 2-cyanoethyl group and the like.
R _{1 to} R ₄ may be an alkoxy group having 1 to 8 carbon atoms, an alkenoxy group, or a cycloalkyl group. Specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, Examples include isobutoxy group, tert-butoxy group, hexyloxy group, cyclohexyloxy group, octoxy group, vinyloxy group, allyloxy group, propeninoxy group, isopropenoxy group and the like.

Of these, more preferred R _{1 to} R ₄ are a methyl group and a phenyl group.
Further, a combination of a methyl group and a phenyl group is particularly preferable from the viewpoint of compatibility with the polycarbonate resin. When combining a methyl group and a phenyl group, a dimethylsiloxane group represented by — (O—Si (CH ₃ ) ₂ ) — and — (O—Si (Ph)) in the structure represented by the general formula (2). ₂ ) The ratio to the diphenylsiloxane group represented by-("Ph" is a phenyl group) is preferably dimethylsiloxane group: diphenylsiloxane group = 100: 0 to 60:40.

In the general formula (2), Q is independently an unsubstituted or substituted divalent hydrocarbon group having 1 to 8 carbon atoms, and may include an ether bond in the chain. Specific examples of Q include alkylene such as methylene group, ethylene group, propylene group, methylethylene group, tetramethylene group, 2-methylpropylene group, 1-methylpropylene group, ethylethylene group, hexamethylene group and octamethylene group. Groups; arylene groups such as o-, m-, p-phenylene and tolylene groups; ethers such as — (Ph) OCH ₂ —, — (Ph) —CH ₂ — and — (Ph) —CH ₂ CH ₂ — Examples thereof include an alkylene / arylene group which may contain a bond. Of these, a propylene (trimethylene) group is particularly preferred.
In the general formula (2), a is an integer of 1 to 100, preferably 1 to 60. When the value of a is more than this range, the adhesion to the metal substrate may be deteriorated.

  The ratio (p) of the repeating unit represented by the general formula (1a) and the ratio (q) of the repeating unit represented by the general formula (1b) in the polyimide silicone resin are p: q = 1: 99 to 99: 1. Preferably, p: q = 10: 90 to 90:10. If the proportion (p) of the repeating unit represented by the general formula (1a) is too large, the compatibility with the polycarbonate resin may be deteriorated, and the proportion (q) of the repeating unit represented by the general formula (1b) is too large. And wear resistance may deteriorate.

  The average molecular weight of the polyimide silicone resin is 5,000 to 150,000, preferably 20,000 to 150,000. This average molecular weight is a weight average molecular weight (polystyrene conversion) measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. If the average molecular weight is too smaller than the above range, the resin may become brittle, and if it is too large, the compatibility with the polycarbonate resin may deteriorate.

  The manufacturing method of the polyimide silicone resin which consists of a repeating unit represented by the said General formula (1) should just follow a well-known method. First, acid dianhydride, diamine and diaminosiloxane are charged in a solvent and reacted at a low temperature, that is, at about 20 to 50 ° C., to produce a polyamic acid which is a precursor of a polyimide resin. Next, the solution of the obtained polyamic acid is heated to a temperature of preferably 80 to 200 ° C., particularly preferably 140 to 180 ° C. Obtain a solution. Furthermore, this solution is poured into a solvent such as water, methanol, ethanol, acetonitrile or the like to precipitate, and the precipitate is dried, whereby a polyimide silicone resin can be obtained.

  Here, the total ratio of the diamine and the diaminosiloxane to the tetracarboxylic dianhydride is appropriately determined according to the molecular weight of the polyimide silicone resin to be produced, but is preferably a molar ratio ([diamine and diaminosiloxane] / [acid diacid]. Anhydride]) in the range of 0.95 to 1.05, particularly preferably 0.98 to 1.02.

  Moreover, as a solvent used when manufacturing a polyimide silicone resin, N-methyl-2-pyrrolidone, cyclohexanone, (gamma) -butyrolactone, N, N- dimethylacetamide, etc. are mentioned. Moreover, it is also possible to make it easy to remove water generated during imidization by azeotropy by using together aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone or in combination of two or more.

  In addition, in order to adjust the molecular weight of the polyimide silicone resin, it is also possible to add a raw material of a monofunctional group such as phthalic anhydride or aniline. The addition amount in this case is preferably 2 mol% or less with respect to the polyimide silicone resin. Thereby, a polyimide silicone resin having an average molecular weight within a specific range of the present invention can be produced.

  Moreover, you may use the method of imidating by adding a dehydrating agent and an imidation catalyst in an imidation process, and heating to about 50 degreeC as needed. In this method, as the dehydrating agent, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The amount of the dehydrating agent used is preferably 1 to 10 mol per 1 mol of diamine. As the imidization catalyst, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The amount of the imidization catalyst used is preferably 0.5 to 10 mol with respect to 1 mol of the dehydrating agent to be used.

  When using at least one of diamine and tetracarboxylic dianhydride, the reaction method is not particularly limited, for example, a method of co-condensation after mixing all the raw materials in advance, or two or more types used. There is a method of sequentially adding diamine or tetracarboxylic dianhydride while reacting individually.

  The tetracarboxylic dianhydride that is a raw material of the polyimide silicone resin synthesized in the present invention may be any one that induces a tetracarboxylic dianhydride residue represented by X in the general formula (1), Preferably, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride or aromatic tetracarboxylic dianhydride is used.

  Examples of the aliphatic tetracarboxylic dianhydride include butane-1,2,3,4-tetracarboxylic dianhydride and pentane-1,2,4,5-tetracarboxylic dianhydride.

  Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, dicyclohexyl-3,3. ', 4,4'-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic Acid dianhydride or the like is used.

  As aromatic tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′- Benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 4,4′-hexafluoropropylidenebisphthalic dianhydride, 3,3 ′, 4,4 '-Diphenylsulfonetetracarboxylic dianhydride and the like are used.

  1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, Fragrances such as 3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione An aliphatic tetracarboxylic dianhydride having a ring can also be used.

  These tetracarboxylic dianhydrides can be used alone or in combination of two or more. Of these, aromatic tetracarboxylic dianhydrides are more preferred, and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 4,4′-hexafluoropropylidenebis. Phthalic dianhydride and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride are preferred, and 4,4′-hexafluoropropylidenebisphthalic dianhydride is said to be compatible with the resin. Particularly preferred in terms.

  The diamine that is a raw material of the polyimide silicone resin synthesized in the present invention may be any one that induces the diamine residue represented by Y in the general formula (1), and preferably an aliphatic diamine or an alicyclic diamine. Alternatively, an aromatic diamine residue is used.

  As the aliphatic diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine or the like is used. As the alicyclic diamine, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, or the like is used.

  Aromatic diamines include 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, bis { 4- (3-aminophenoxy) phenyl} sulfone, bis {4- (4-aminophenoxy) phenyl} sulfone, orthophenylenediamine, metaphenylenediamine, paraphenylenediamine, 4,4′-diaminodiphenyl-2,2- Propane, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis {4- (4-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane 2,2-bis (3-aminophenyl) hexaful Oropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-amino) Phenyl) fluorene or the like is used.

  3,3′-dicarboxy-4,4′-diaminodiphenylmethane, diaminobisphenol A, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 2,2-bis (3-amino-4-hydroxy) Phenyl) hexafluoropropane, 2,2 ′-{2-hydroxy-3- (3,5-methyl-4-amino) -benzyl-5-methyl} -diphenylmethane and other diamines having functional groups other than amino groups It can also be used.

These diamines may be used alone or in combination of two or more.
Of these, aromatic diamines are more preferable, and bis {4- (4-aminophenoxy) phenyl} sulfone and 1,4-bis (4-aminophenoxy) benzene diamines are preferable. Bis (4-aminophenoxy) benzene diamine is particularly preferred from the standpoint of compatibility with the resin.

  The diaminosiloxane that is another diamine raw material of the polyimide silicone resin synthesized in the present invention may be any one that induces the diaminosiloxane residue represented by Z in the general formula (1), and particularly preferably Diaminosiloxane represented by the general formula (3) is used.

R _{1 to} R ₄ in the general formula (3) are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and are aliphatic hydrocarbon groups and alicyclic rings. Either a formula hydrocarbon group or an aromatic hydrocarbon group may be used. These may be the same or different.
Specific examples of R _{1 to} R ₄ include an aliphatic hydrocarbon group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group. Alkyl groups such as groups; alkenyl groups such as vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, isobutenyl groups, hexenyl groups, and the like.
Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclohexyl group and a cyclopentyl group; a cycloalkenyl group such as a cyclohexenyl group, and the like. Aromatic hydrocarbon groups include aryl groups such as phenyl, tolyl and xylyl groups; aralkyl groups such as benzyl, ethylphenyl and propylphenyl groups.
Further, at least one of the hydrogen atoms of these hydrocarbon groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, a cyano group, or the like. Examples of such include chloromethyl group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group, 4-fluorophenyl group, 2-cyanoethyl group and the like.
R _{1 to} R ₄ may be an alkoxy group having 1 to 8 carbon atoms, an alkenoxy group, or a cycloalkyl group. Specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, Examples include isobutoxy group, tert-butoxy group, hexyloxy group, cyclohexyloxy group, octoxy group, vinyloxy group, allyloxy group, propeninoxy group, isopropenoxy group and the like.

Of these, more preferred R _{1 to} R ₄ are a methyl group and a phenyl group.
Further, a combination of a methyl group and a phenyl group is particularly preferable from the viewpoint of compatibility with the polycarbonate resin. When a methyl group and a phenyl group are combined, a dimethylsiloxane group represented by — (O—Si (CH ₃ ) ₂ ) — and — (O—Si (Ph)) in the structure represented by the general formula (3). ₂ ) The ratio to the diphenylsiloxane group represented by-("Ph" is a phenyl group) is preferably dimethylsiloxane group: diphenylsiloxane group = 100: 0 to 60:40.

In the general formula (3), Q is independently an unsubstituted or substituted divalent hydrocarbon group having 1 to 8 carbon atoms, and may include an ether bond in the chain. Specific examples of Q include alkylene such as methylene group, ethylene group, propylene group, methylethylene group, tetramethylene group, 2-methylpropylene group, 1-methylpropylene group, ethylethylene group, hexamethylene group and octamethylene group. Groups; arylene groups such as o-, m-, p-phenylene and tolylene groups; ethers such as — (Ph) OCH ₂ —, — (Ph) —CH ₂ — and — (Ph) —CH ₂ CH ₂ — Examples thereof include an alkylene / arylene group which may contain a bond. Of these, a propylene (trimethylene) group is particularly preferred.
In the general formula (3), a is an integer of 1 to 100, preferably 1 to 60. When the value of a is more than this range, the adhesion to the metal substrate may be deteriorated.

  What is necessary is just to use what is generally marketed for the said diaminosiloxane, for example, brand name "KF-8010", "X-22-161A", "X-22-9396", "X-22-9409", "X-22-9409S", "X-22-1660B-3" etc. (all are Shin-Etsu Chemical Co., Ltd. product) can be used.

(2) Polycarbonate resin As the polycarbonate resin used in the polycarbonate resin composition of the present invention, known materials conventionally used as a binder resin for a photosensitive layer of an electrophotographic photoreceptor can be used.

  Such a polycarbonate resin is a known method used for producing a polycarbonate from a bisphenol and a carbonate ester-forming compound, for example, a direct reaction between a bisphenol and a phosgene (phosgene method), or a bisphenol and a bisaryl carbonate. It can manufacture by methods, such as transesterification reaction (transesterification method).

  Specific examples of raw material bisphenols used for the production of polycarbonate resin include 1,1′-biphenyl-4,4′-diol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, Bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) ) Propane (bisphenol A; BPA), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 1,1-bis (4 -Hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bi Phenol Z; BPZ), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) cyclodecane, 2,2-bis (4- Hydroxy-3-allylphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisphenol 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 4,4′-butyryl Bis (3-methyl-6-t-butyrylphenol), α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethyldiphenyl random copolymer siloxane, α, ω-bis [3- (o- Hydroxyphenyl) propyl] polydimethylsiloxane and the like.

  Two or more of these may be used in combination. Among these, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1, It is preferably selected from 1′-biphenyl-4,4′-diol, and particularly preferably selected from 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane. .

  On the other hand, examples of the carbonate ester-forming compound include phosgene, triphosgene, and bisallyl carbonate such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. It is done. Two or more of these compounds can be used in combination.

  In the phosgene method, the bisphenols and phosgene are usually reacted in the presence of an acid binder and a solvent. Examples of the acid binder include pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and examples of the solvent include methylene chloride and chloroform. Further, a tertiary amine catalyst such as triethylamine or a quaternary ammonium salt such as benzyltriethylammonium chloride is used to promote the condensation polymerization reaction. Furthermore, monofunctional compounds such as phenol, pt-butylphenol, p-cumylphenol, and long-chain alkyl-substituted phenols are preferably added as molecular weight regulators. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfite, or a branching agent such as phloroglucin, isatin bisphenol, or trisphenol ethane may be added. The reaction is usually in the range of 0 to 150 ° C, preferably 5 to 40 ° C. While the reaction time depends on the reaction temperature, it is generally 0.5 min-10 hr, preferably 1 min-2 hr. Further, during the reaction, it is desirable to maintain the pH of the reaction system at 10 or more.

  On the other hand, in the transesterification method, the bisphenols and bisaryl carbonate are mixed and reacted at a high temperature under reduced pressure. The reaction is usually carried out at a temperature in the range of 150 to 350 ° C., preferably 200 to 300 ° C., and the degree of vacuum is preferably 1 mmHg or less at the end, and phenols derived from the bisaryl carbonate produced by the transesterification reaction Is distilled out of the system. The reaction time depends on the reaction temperature and the degree of reduced pressure, but is usually about 1 to 24 hours. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. Moreover, you may react by adding a molecular weight regulator, antioxidant, and a branching agent as needed.

  When the polycarbonate resin composition of the present invention is used as a molding material, the intrinsic viscosity of the polycarbonate resin as the main component is in the range of 0.3 to 2.0 dl / g because of mechanical strength and ease of molding. preferable. In particular, in order for the photosensitive layer of the electrophotographic photoreceptor formed by wet molding to obtain sufficient film strength, the intrinsic viscosity of the polycarbonate resin is 0.3 to 2.0 dl / g, and further 0.40 to 1. It is preferably 5 dl / g. If the intrinsic viscosity of the polycarbonate resin is too low, the film strength of the photosensitive layer may be insufficient, and if it is too high, film formation may be difficult.

(3) Polycarbonate resin composition The polycarbonate resin composition of this invention has the said polycarbonate resin as a main component, and the said polyimide silicone resin is mix | blended with this. Although the content of the polyimide silicone resin is not particularly limited, 0.05% to 5% by weight of the polyimide silicone resin may be included as a range in which the polycarbonate resin composition of the present invention maintains good metal adhesion and wear resistance. Preferably, it is further preferable to contain 0.1 to 2% by weight.

  In addition, the polycarbonate resin composition of the present invention includes other synthetic resins, for example, vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride, and copolymers, polycarbonates, and polyesters as long as the effect is maintained. Various thermoplastic resins and thermosetting resins such as polysulfone, phenoxy resin, epoxy resin, and silicone resin can be arbitrarily blended. Various ultraviolet absorbers, antioxidants, mold release agents, lubricants, colorants and the like can be added as desired.

  The polycarbonate resin composition of the present invention can be molded by a known molding method, extrusion molding, compression molding, injection molding, blow molding, wet molding or the like.

(4) Electrophotographic Photoreceptor The electrophotographic photoreceptor of the present invention is obtained by providing a photosensitive layer (photoconductive layer) on a conductive substrate (metal substrate). The photosensitive layer is obtained by dispersing in a binder resin a charge generation material that generates charges upon exposure and a charge transport material that transports charges. The structure of the photosensitive layer is not particularly limited, and it may be a single layer type in which both a charge generation material and a charge transport material are dispersed in a binder resin, or a laminated type in which a plurality of functionally separated layers are combined. May be.

  Examples of the laminated type include a layer composed of a charge generation layer mainly composed of a charge generation material and a charge transport layer mainly composed of a charge transport material. In this case, the stacking order of the charge generation layer and the charge transport layer is not particularly limited, and any stacking order of the conductive substrate / charge generation layer / charge transport layer and the conductive substrate / charge transport layer / charge generation layer. But it ’s okay. In general, a charge generation layer is formed on a conductive substrate, and a charge transport layer is provided on the charge generation layer.

  In the present invention, an electrophotographic photosensitive member provided with a laminate type photosensitive layer composed of two layers of a charge generation layer and a charge transport layer is preferred, and the order of lamination is as follows: conductive substrate / charge generation layer / charge transport layer; Preferably it is.

  The conductive substrate used in the electrophotographic photoreceptor of the present invention is provided with a metal material such as aluminum, stainless steel, or nickel, and a conductive layer such as aluminum, palladium, tin oxide, indium oxide, or zinc oxide on the surface. Polyester film, phenol resin, paper, etc. are used. Further, a resin such as polycarbonate, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, or polyimide can be coated and reinforced. Of these, aluminum is particularly preferred. Although the thickness of an electroconductive base material is not specifically limited, It is about 10 micrometers-3 mm.

  In the electrophotographic photosensitive member of the present invention, the photosensitive layer provided on the conductive substrate is formed of a binder resin in which a charge generating material that generates charges upon exposure and a charge transporting material that transports charges are dispersed. .

The polycarbonate resin composition of the present invention can be suitably used as a binder resin for a photosensitive layer of an electrophotographic photoreceptor. When the photosensitive layer is a multilayer type, it may be used as a binder resin for either the charge generation layer or the charge transport layer. However, in the present invention, a multilayer type that sufficiently exhibits the characteristics of the binder resin that holds the charge transport material can be used. It is preferably used for the charge transport layer.

  The charge generation layer of the present invention is formed on a conductive substrate by a known method. As the charge generation material, for example, organic pigments such as azoxybenzene, disazo, trisazo, benzimidazole, polycyclic quinoline, indigoid, quinacridone, phthalocyanine, perylene, and methine can be used. . The charge generation materials may be used alone or in combination of two or more.

  Examples of the charge transport material include polytetracyanoethylene; fluorenone compounds such as 2,4,7-trinitro-9-fluorenone; nitro compounds such as dinitroanthracene; succinic anhydride; maleic anhydride; dibromomaleic anhydride; Triphenylmethane compounds; oxadiazole compounds such as 2,5-di (4-dimethylaminophenyl) -1,3,4-oxadiazole; styryl compounds such as 9- (4-diethylaminostyryl) anthracene Carbazole compounds such as poly-N-vinylcarbazole; pyrazoline compounds such as 1-phenyl-3- (p-dimethylaminophenyl) pyrazoline; 4,4 ′, 4 ″ -tris (N, N-diphenylamino); Triphenylamine, N, N′-bis (3-methylphenyl) -N, N′-bi Amine derivatives such as (phenyl) benzidine; conjugated unsaturated compounds such as 1,1-bis (4-diethylaminophenyl) -4,4-diphenyl-1,3-butadiene; 4- (N, N-diethylamino) benzaldehyde-N Hydrazone compounds such as N-diphenylhydrazone; including indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, pyrazoline compounds, triazole compounds, etc. Examples thereof include nitrogen cyclic compounds, condensed polycyclic compounds, etc. The above charge transport materials may be used alone or in combination.

  When the photosensitive layer of the electrophotographic photosensitive member of the present invention is a single layer type, the polycarbonate resin composition of the present invention is used as the binder resin of the photosensitive layer, and fine particles of the charge generation material and the charge transport material are uniformly dispersed therein. Thus, a photosensitive layer can be formed.

  In the case of the laminated type, it is preferable to use the polycarbonate resin composition of the present invention as a binder resin for at least the charge transport layer, and form a charge transport layer by uniformly dispersing the charge transport material therein. In this case, the binder resin of the charge generation layer is not particularly limited, and the polycarbonate resin composition of the present invention can be used, but is not limited thereto. For example, polyvinyl butyral resin, polyvinyl formal resin, silicone resin, polyamide resin, Other binder resins such as polyester resins, polystyrene resins, other polycarbonate resins, polyvinyl acetate resins, polyurethane resins, phenoxy resins, epoxy resins, and various celluloses can also be used.

  In consideration of the possibility of dissolution of the binder resins in the charge generation layer and the charge transport layer, it is preferable to use a resin other than the binder resin for photosensitive layers of the present invention for the charge generation layer. Particularly preferred binder resin for charge generation layer is polyvinyl butyral resin.

  The photosensitive layer is prepared by dissolving the above charge generating substance and charge transporting substance in a suitable solvent together with the polycarbonate resin composition of the present invention, and dissolving the solution in a solution casting method, a casting method, a spray method, a dip coating method (dip coating). It can be formed by applying onto a conductive substrate using a known wet molding method such as (method) and drying.

Solvents used in the wet molding method include dichloromethane, chloroform, monochlorobenzene, 1,1,1-trichloroethane, monochloroethane, halogenated organic solvents such as carbon tetrachloride, aromatic hydrocarbons such as toluene and xylene, acetone, Ketones such as methyl ethyl ketone, cyclohexanone and isophorone, ethers such as tetrahydrofuran, 1,4-dioxane, ethylene glycol diethyl ether and ethyl cellosolve, esters such as methyl acetate and ethyl acetate, and other dimethylformamide, dimethylsulfoxide, diethylformamide and the like Non-halogen organic solvents can be mentioned. In the present invention, these solvents can be used alone or in combination of two or more. When the charge transport layer is formed by dissolving the polycarbonate resin composition of the present invention in a solvent, it is preferable to prepare and use a resin solution having a concentration range of 1 to 30% by weight.
It is also possible to recycle by dissolving a photosensitive layer of a commercially available electrophotographic photosensitive member with the above-mentioned solvent to form a new photosensitive layer.

  When the photosensitive layer is a single layer type, the thickness of the photosensitive layer is 10 to 40 μm, preferably 20 to 30 μm. Further, the mixing ratio of the charge generating material and charge transporting material to the photosensitive layer binder resin is preferably in the range of 10: 1 to 1:10 by weight.

  When the photosensitive layer is a laminate type, the mixing ratio of the charge generating material and the binder resin is preferably within the range of 10: 1 to 1:20. The charge generation layer has a thickness of 0.01 to 20 μm, preferably 0.1 to 2 μm. The mixing ratio of the charge transport material and the binder resin is preferably in the range of 10: 1 to 1:10. The thickness of the charge transport layer is 2 to 100 μm, preferably 5 to 40 μm.

  Examples of the present invention are shown below together with comparative examples, and the contents of the invention are shown in detail. However, the present invention is not limited to these examples.

<Synthesis Example 1>
(Synthesis of polyimide silicone resin (PI-1))
In a flask equipped with a stirrer, a thermometer and a nitrogen displacement device, 44.4 g (0.1 mol) of 4,4′-hexafluoropropylidenebisphthalic dianhydride and 400 g of n-methyl-2-pyrrolidone. Was charged. Next, 90.9 g (0.075 mol) of diaminosiloxane represented by the following formula (4) (trade name “X-22-9396; manufactured by Shin-Etsu Chemical Co., Ltd.) and 2,2-bis [4- ( While adjusting a solution of 10.3-g (0.025 mol) of 4-aminophenoxy) phenyl] propane in 100 g of n-methyl-2-pyrrolidone so that the temperature of the reaction system does not exceed 50 ° C., the flask After completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours.

  Next, after attaching a reflux condenser with a moisture receiver to the flask, 30 g of xylene was added, the temperature was raised to 150 ° C. and the temperature was maintained for 6 hours, and a yellowish brown solution was obtained. The solution thus obtained was cooled to room temperature (25 ° C.) and then poured into methanol for reprecipitation. The obtained sediment was dried to obtain a polyimide silicone resin having the following formula (5) as a repeating unit.

When the infrared absorption spectrum of the reprecipitated resin was measured, absorption based on unreacted polyamic acid did not appear, and absorption based on imide groups was confirmed at 1780 cm ⁻¹ and 1720 cm ⁻¹ . It was 39,000 when the weight average molecular weight (polystyrene conversion) of this resin was measured by the gel permeation chromatography (GPC) which uses tetrahydrofuran as a solvent. This resin was designated as PI-1.

<Synthesis Example 2>
(Synthesis of polyimide silicone resin (PI-2))
In a flask equipped with a stirrer, a thermometer and a nitrogen displacement device, 44.4 g (0.1 mol) of 4,4′-hexafluoropropylidenebisphthalic dianhydride and 400 g of n-methyl-2-pyrrolidone. Was charged. Next, 63.0 g (0.075 mol) of diaminosiloxane represented by the following formula (6) (trade name “KF-8010”; manufactured by Shin-Etsu Chemical Co., Ltd.) and 2,2-bis [4- (4 -Aminophenoxy) phenyl] propane In a flask, a solution of 10.3 g (0.025 mol) dissolved in 100 g of n-methyl-2-pyrrolidone was adjusted so that the temperature of the reaction system did not exceed 50 ° C. It was dripped in. After completion of dropping, the mixture was further stirred at room temperature for 10 hours.

  Next, after attaching a reflux condenser with a moisture receiver to the flask, 30 g of xylene was added, the temperature was raised to 150 ° C. and the temperature was maintained for 6 hours, and a yellowish brown solution was obtained. The solution thus obtained was cooled to room temperature (25 ° C.) and then poured into methanol for reprecipitation. The obtained sediment was dried to obtain a polyimide silicone resin having the following formula (7) as a repeating unit.

When the infrared absorption spectrum of the reprecipitated resin was measured, absorption based on unreacted polyamic acid did not appear, and absorption based on an imide group was confirmed at 1780 cm ⁻¹ and 1720 cm ⁻¹ . It was 37,000 when the weight average molecular weight (polystyrene conversion) of this resin was measured by the gel permeation chromatography (GPC) which uses tetrahydrofuran as a solvent. This resin was designated as PI-2.

<Synthesis Example 3>
(Synthesis of polyimide silicone resin (PI-3))
In a flask equipped with a stirrer, a thermometer and a nitrogen displacement device, 44.4 g (0.1 mol) of 4,4′-hexafluoropropylidenebisphthalic dianhydride and 400 g of n-methyl-2-pyrrolidone. Was charged. Next, 60.6 g (0.05 mol) of diaminosiloxane represented by the above formula (4) and 20.5 g (0.05 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane were added. A solution dissolved in 100 g of n-methyl-2-pyrrolidone was dropped into the flask while adjusting the temperature of the reaction system so as not to exceed 50 ° C. After completion of dropping, the mixture was further stirred at room temperature for 10 hours.

  Next, after attaching a reflux condenser with a moisture receiver to the flask, 30 g of xylene was added, the temperature was raised to 150 ° C. and the temperature was maintained for 6 hours, and a yellowish brown solution was obtained. The solution thus obtained was cooled to room temperature (25 ° C.) and then poured into methanol for reprecipitation. When the obtained sediment was dried, a polyimide silicone resin having the following formula (8) as a repeating unit was obtained.

When the infrared absorption spectrum of the reprecipitated resin was measured, absorption based on unreacted polyamic acid did not appear, and absorption based on imide groups was confirmed at 1780 cm ⁻¹ and 1720 cm ⁻¹ . It was 36,000 when the weight average molecular weight (polystyrene conversion) of this resin was measured by the gel permeation chromatography (GPC) which uses tetrahydrofuran as a solvent. This resin was designated as PI-3.

<Example 1>
0.1 g of PI-1 was added to 100 g of commercially available bisphenol A type polycarbonate resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name “Iupilon E-2000”, intrinsic viscosity = 0.58 dl / g, hereinafter abbreviated as “PC-1”). 1 g was added and dissolved in 700 g of methylene chloride to obtain a resin solution.
A cast film was prepared with a coater on a stainless steel plate using the obtained resin solution, air-dried and then dried at 120 ° C. for 8 hours to obtain a film having a thickness of about 20 μm. The surface of the obtained film was lightly wiped with methanol, and a 1 mm-interval cross cut test (resin composition peeling test) according to JIS-K5400 was performed to evaluate the adhesion between the stainless steel plate and the film.

Next, 50 g of N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) benzidine (hereinafter abbreviated as “TPD type CT agent”: manufactured by SYNTEC), 50 g of PC-1, PI A coating solution using 0.05 g of -1 and 450 g of methylene chloride was prepared, and the above coating solution was applied to a commercially available LBP photoreceptor (trade name “LPA3ETC4”; manufactured by Seiko Epson Corporation) from which the charge transport layer was previously removed with tetrahydrofuran. The film was applied by an immersion method, air-dried, and then dried at 120 ° C. for 8 hours. A charge transport layer having a thickness of about 20 μm was provided to produce a laminated electrophotographic photosensitive member (hereinafter abbreviated as “OPC”).
After lightly wiping the adhesion part of the created OPC charge transport layer edge (edge part) and the aluminum metal base with methanol, a 1 mm interval cross-cut test according to JIS-K5400 is performed to check the bond interface board The peeling state of the eyes was observed (photosensitive member edge peeling test).

  On the other hand, OPC prepared separately is mounted on a commercially available LBP (trade name “LBP-8400”; manufactured by Seiko Epson Corporation), and recycled paper for OA (trade name “LBP-190R-A4B”; manufactured by 100 million) ) Was used to measure the amount of OPC wear after continuous continuous black printing of 5000 sheets.

<Example 2>
1,1-bis (4-hydroxyphenyl) cyclohexane type polycarbonate resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name “Iupizeta PCZ-500”, intrinsic viscosity = 0.97 dl / g, hereinafter “PC” 2 ”), 1.0 g of PI-2 was used instead of PI-1, and 500 g of toluene was used instead of methylene chloride. The film cross-cut test was conducted.
Further, OPC was used in the same manner as in Example 1 except that PC-2 was used in place of PC-1, 0.5 g of PI-2 was used in place of PI-1, and 300 g of toluene was used in place of methylene chloride. The cross cut test and the OPC wear amount were measured.

<Example 3>
Copolymerization type polycarbonate resin of bisphenol A and 1,1′-biphenyl-4,4′-diol instead of PC-1 (made by Idemitsu Kosan Co., Ltd., trade name “Tufzette B-300”, limiting viscosity = 0. 72 dl / g (hereinafter abbreviated as “PC-3”), 0.5 g of PI-3 was used instead of PI-1, and 500 g of tetrahydrofuran was used instead of methylene chloride. In the same manner, a film grid test on a stainless steel plate was performed.
Further, OPC was prepared in the same manner as in Example 1 except that PC-3 was used instead of PC-1, PI-3 was used instead of PI-1, and 300 g of tetrahydrofuran was used instead of methylene chloride. The cross-cut test and the OPC wear amount were measured.

<Example 4>
Copolymer-type polycarbonate resin of bisphenol A and 2,2-bis (4-hydroxy-3-methylphenyl) propane instead of PC-1 (Mitsubishi Gas Chemical Co., Ltd., trade name “Iupizeta FPC-2136”, limit Viscosity = 0.55 dl / g (hereinafter abbreviated as “PC-4”), 0.5 g of PI-1 was used, and 500 g of tetrahydrofuran was used instead of methylene chloride. A film grid test on a stainless steel plate was performed.
Further, OPC was prepared in the same manner as in Example 1 except that PC-4 was used instead of PC-1, PI-1 was used in an amount of 0.25 g, and methylene chloride was used in an amount of 300 g of tetrahydrofuran. Tests and OPC wear were measured.

<Example 5>
Example 1 except that PC-2 was used instead of PC-1, PI-1 0.5 g was used, and tetrahydrofuran 500 g was used instead of methylene chloride. Tested.
Further, OPC was prepared in the same manner as in Example 1 except that PC-2 was used in place of PC-1, 0.25 g of PI-1 was used, and 300 g of tetrahydrofuran was used in place of methylene chloride. Tests and OPC wear were measured.

<Comparative Example 1>
The same procedure as in Example 1 was carried out except that PI-1 was not used.

<Comparative example 2>
The same procedure as in Example 2 was performed except that PI-2 was not used.

<Comparative Example 3>
It carried out similarly to Example 1 except having used commercially available silicone oil (The Shin-Etsu Chemical Co., Ltd. make, brand name "KF50", abbreviated as "KF50") instead of PI-1.

<Comparative Example 4>
The same procedure as in Example 5 was performed except that a commercially available silicone graft acrylate resin (trade name “Symac US-270”, hereinafter abbreviated as “US-270”) was used instead of PI-1. .

In addition, the description regarding the symbol and measured value in Table 1 is as follows.
(1) Intrinsic viscosity The intrinsic viscosity was measured using an Ubbelohde capillary viscometer at a polycarbonate methylene chloride solution of 20 g, 0.5 g / dl, and a Huggins constant of 0.45.
(2) Addition ratio of additive to the total amount of the polycarbonate resin composition (% by weight)
(3) Peel test A 1 mm-interval cross-cut test according to JIS-K5400 was performed. When the cross-cut peel is 10% or less, the cross mark peel is 10% or less, and the cross-cut peel is over 50%.
(4) Amount of wear The OPC weight after continuous continuous printing of 5,000 sheets was measured, and the decrease from the weight before the test was taken as the amount of wear.

  Since the polycarbonate resin composition of the present invention has high metal adhesion, when used as a binder resin for a photosensitive layer of an electrophotographic photosensitive member, even if the adhesive tape is accidentally attached to the surface of the photosensitive member during replacement or maintenance of the photosensitive member. The occurrence of defects due to peeling of the surface of the photoreceptor (photosensitive layer) is remarkably suppressed. In addition, since it has good wear resistance, it can be applied to an electrophotographic photoreceptor excellent in durability.

Claims (7)

A polycarbonate resin composition comprising a polyimide silicone resin having an average molecular weight of 5,000 to 150,000 comprising a repeating unit represented by the following general formula (1) as a main component.

(In the formula, X is a tetravalent organic group, Y is a divalent organic group, Z is a divalent organic group having an organosiloxane structure, and the ratio of p: q is a ratio of 1:99 to 99: 1. .) 2. The polycarbonate resin composition according to claim 1, wherein Z in the general formula (1) is a diaminosiloxane residue represented by the following general formula (2).

(Wherein R ₁ to R ₄ are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 8 carbon atoms, which may be the same or different. Q is independently substituted or unsubstituted. A divalent hydrocarbon group having 1 to 8 carbon atoms, a is an integer of 1 to 100.)   The polycarbonate resin composition according to claim 1 or 2, wherein the polyimide silicone resin is contained in an amount of 0.05 to 5% by weight.   The polycarbonate resin is 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, and 1 The polycarbonate resin composition according to any one of claims 1 to 3, which is derived from bisphenols selected from the group consisting of 1,1'-biphenyl-4,4'-diol.   The polycarbonate resin composition in any one of Claims 1-4 whose intrinsic viscosity of the said polycarbonate resin is 0.3-2.0 dl / g.   An electrophotographic photosensitive member having a photosensitive layer on a conductive substrate, wherein the polycarbonate resin composition according to any one of claims 1 to 5 is used as a binder resin for the photosensitive layer.   In an electrophotographic photoreceptor having a photosensitive layer comprising a charge generation layer and a charge transport layer on a conductive substrate, the polycarbonate resin composition according to any one of claims 1 to 5 is used as a binder resin for the charge transport layer. An electrophotographic photoreceptor characterized by the above.