JP2007314808A - Polycarbonate resin, its producing method, and electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin excellent in optical property and mechanical property, particularly in wear resistance, its producing method, and an electrophotographic photoreceptor excellent in durability using the crosslinked polycarbonate. <P>SOLUTION: The polycarbonate resin comprises a repeating unit having at least a hydrolysable group and a polycarbonate bond. Its producing method is also provided. The crosslinked polycarbonate resin is prepared by crosslinking the polycarbonate resin. The electrophotographic photoreceptor comprises a photosensitive layer containing the crosslinked carbonate resin disposed on a conductive substrate. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a crosslinked polycarbonate resin excellent in mechanical properties, optical properties, and electrophotographic characteristics, a method for producing the same, and an electrophotographic photosensitive material excellent in durability containing the crosslinked polycarbonate resin as a binder resin in a photosensitive layer. It is about the body.

  Polycarbonate resins are excellent in mechanical properties, thermal properties, and electrical properties, and thus have been used as raw materials for molded products in various industrial fields. In recent years, it has been frequently used in the field of functional products that also utilize the optical properties of the polycarbonate resin. With the expansion of such application fields, the required performance for polycarbonate resins has also diversified. In order to meet such demands, only polycarbonate resins made from 2,2-bis (4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) cyclohexane, which have been used in the past, are used. Polycarbonate resins having various chemical structures have been proposed because sufficient measures may not be possible. However, since there are required characteristics peculiar to various applications, there is a demand for the development of a polycarbonate resin having performance that satisfies these requirements.

  As such a functional product, there is an organic electrophotographic photosensitive member in which a photosensitive layer using a polycarbonate resin as a binder resin for an organic charge generating material or a charge transporting material is formed on a conductive substrate. As this electrophotographic photoreceptor, conventionally, those using an inorganic photoconductive material such as selenium and α-silicon were used, but recently, the performance of the organic electrophotographic photoreceptor has been improved. Its usage rate is expanding.

  The organic electrophotographic photosensitive member is required to have predetermined sensitivity, electrical characteristics, and optical characteristics according to the applied electrophotographic process. In this electrophotographic photoreceptor, operations such as corona charging, toner development, transfer to paper, and cleaning treatment are repeatedly performed on the surface of the photosensitive layer. Therefore, an electric and mechanical external force is applied each time these operations are performed. Added. Therefore, in order to maintain the electrophotographic image quality for a long period of time, the photosensitive layer provided on the surface of the electrophotographic photosensitive member is required to have durability against these external forces.

  In order to meet such a demand, a polycarbonate resin having good compatibility with the charge transport material used for the photosensitive layer and good optical characteristics has been used as the binder resin of the organic electrophotographic photoreceptor. However, the durability of the electrophotographic photosensitive member is not obtained using a conventional polycarbonate resin made from 2,2-bis (4-hydroxyphenyl) propane or 2,2-bis (4-hydroxyphenyl) cyclohexane. However, it has not been fully satisfied.

  Therefore, in Patent Document 1, a crosslinkable polycarbonate resin having a carbon-carbon unsaturated bond is used as a binder resin, and after the photosensitive layer containing the resin is applied to a conductive substrate, the crosslinkable polycarbonate resin is crosslinked. An electrophotographic photoreceptor has been proposed. By the way, in this case, since a radical initiator is added to the crosslinkable polycarbonate resin to carry out a crosslinking reaction, the radical generated here causes the molecular chain of the polycarbonate resin to be cut or yellowed due to a chemical change. There is a problem that there is. Another problem is that the charge transport material contained in the binder resin undergoes a chemical change due to the radicals generated here, resulting in a decrease in performance. Accordingly, the electrophotographic photosensitive member is not sufficiently satisfied due to the deterioration of the performance and durability of the electrophotographic photosensitive member accompanying these molecular cutting and chemical change.

JP-A-4-291348

  The present invention has been made based on the above circumstances, and a crosslinked polycarbonate resin capable of obtaining a molded article excellent in optical properties and mechanical properties, in particular, abrasion resistance, a production method thereof, An object of the present invention is to provide an electrophotographic photoreceptor excellent in durability containing a crosslinked polycarbonate resin as a binder resin.

  As a result of intensive studies to solve the above problems, the present inventor has found that a polycarbonate compound having an aliphatic unsaturated hydrocarbon group has a silicon compound having a hydrogen atom bonded to a silicon atom and a hydrolyzable group. By crosslinking a polycarbonate resin composed of specific repeating units obtained by reaction, those having optical properties and mechanical properties, particularly excellent wear resistance, can be obtained, and this can be used as a binder resin. The electrophotographic photoreceptor used was found to be excellent in durability, and the present invention was completed based on these findings.

That is, the gist of the present invention is as follows.
(1) The repeating unit (1) represented by the following general formula [1] and the repeating unit (2) represented by the general formula [2] are added to the total of the repeating unit (1) and the repeating unit (2). A polycarbonate resin having a molar ratio of repeating unit (1) [(1) / ((1) + (2))] of 0.001 to 1.

[In the formula [1], Ar ¹ is represented by the following [1a], [1b] or [1c].

{X ¹ in Formula [1a] is a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —CR ³ R ⁴ — (where R ³ and R ⁴ are Each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a trifluoromethyl group, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms), a substituted or unsubstituted cycloalkylidene having 5 to 12 carbon atoms Group, substituted or unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms, 9,9-fluorenylidene group, 1,8-menthanediyl group, 2,8-menthanediyl group, substituted or unsubstituted pyrazilidene group, carbon A substituted or unsubstituted arylene group of formula 6 to 12, or the following general formula [3],

(In Formula [3], each R ⁵ independently represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a carbon number. 1-12 alkoxy group, a C6-C12 substituted or unsubstituted aryloxy group, t is an integer of 0-6, and g is an integer of 0-200. A in the formulas [1a] to [1c] is — (CH ₂ ) _h —, —O— (CH ₂ ) _h —, —CO— (CH ₂ ) _h —, —COO— (CH ₂ ) _H — (wherein h is an integer of 0-6), FG is —SiR ⁷ _3-m —Z _m (where Z is an alkoxy group having 1 to 6 carbon atoms, aryloxy group having 6 to 12 carbon atoms or a trialkyl siloxy group or a halogen atom, R ⁷ is each independently 1 to carbon atoms Saturated or unsaturated hydrocarbon group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, m is is an integer of 1 to 3), p ^1, p ² is an integer from 0 to 4 ( Wherein p ¹ + p ² is an integer of 1 to 8, q is 1 or 2, s is an integer of 1 to 6, and R ¹ in the formulas [1a] to [1c] is Independently, hydrogen atom, halogen atom, trifluoromethyl group, alkyl group having 1 to 12 carbon atoms, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, 6 to 12 carbon atoms Substituted or unsubstituted aryloxy groups, r is each independently an integer of 0 to 4, and t is each independently an integer of 0 to 6. In general formula [2], Ar ² is represented by the following [2a], [2b], [2c] or [2d].

(X ² , R ⁶ , r, t and g in the formulas [2a] to [2d] have the same meanings as X ¹ , R ¹ , r, t and g, respectively, and k is 0 to 6 ))].

（式（１−１）中、Ａｒ³は、下記一般式[１ｄ]を表す。

式[１ｄ]中のＡは、−（ＣＨ₂）₃−を表わし、ＦＧ及び一般式（２）中のＡｒ²は、上記（１）のＦＧ、Ａｒ²と同じ意味を表わす。）
（３）上記（１）又は（２）に記載のポリカーボネート樹脂を架橋して得られる架橋ポリカーボネート樹脂。
（４）脂肪族不飽和炭化水素基を含有するポリカーボネート樹脂に、珪素原子上に水素原子および加水分解性の基を有する珪素化合物を反応させることを特徴とする上記（１）又は（２）に記載のポリカーボネート樹脂の製造方法。
（５） 前記珪素化合物が珪素原子上に水素原子と加水分解性の基および非加水分解性の基を有する珪素化合物である上記（４）に記載のポリカーボネート樹脂の製造方法。
（６）前記珪素化合物が下記一般式〔４〕で表される珪素化合物である上記（４）又は（５）に記載のポリカーボネート樹脂の製造方法。

〔式〔４〕中のＺ、Ｒ⁷は、前記Ｚ、Ｒ⁷と同じ意味を有し、ｖは１〜３の整数である〕
（７）導電性基体上に少なくとも感光層を有する電子写真感光体において、該感光層に上記（３）記載の架橋ポリカーボネート樹脂を含有していることを特徴とする電子写真感光体。
（８）前記架橋ポリカーボネート樹脂が、請求項５記載の方法で製造したポリカーボネート樹脂を架橋させてなる架橋ポリカーボネート樹脂である上記（７）に記載の電子写真感光体。
（９）前記架橋ポリカーボネート樹脂が、脂肪族不飽和炭化水素基を含有するポリカーボネート樹脂に、トリアルコキシシランを反応させてなるポリカーボネート樹脂の架橋物である上記（７）に記載の電子写真感光体。
（１０）前記架橋ポリカーボネート樹脂が、脂肪族不飽和炭化水素基を含有するポリカーボネート樹脂に、トリストリアルキルシロキシシランを反応させてなるポリカーボネート樹脂の架橋物である上記（８）記載の電子写真感光体。
（１１）前記感光層が、少なくとも電荷発生物質を含有する電荷発生層と、少なくとも電荷輸送物質およびバインダー樹脂を含有する電荷輸送層からなるものである上記（７）〜（１０）のいずれかに記載の電子写真感光体。 (2) The repeating unit (1-1) represented by the following general formula (1-1) and the repeating unit (2) represented by the general formula (2) are substituted with the repeating unit (1-1) and the repeating unit. A polycarbonate resin having a molar ratio [(1-1) / ((1-1) + (2))] of the repeating unit (1) to the sum of (2) in a ratio of 0.001 to 1.

(In the formula (1-1), Ar ³ represents the following general formula [1d].

A in the formula [1d] represents — (CH ₂ ) ₃ —, and FG and Ar ² in the general formula (2) have the same meanings as FG and Ar ^{2 in the} above (1). )
(3) A crosslinked polycarbonate resin obtained by crosslinking the polycarbonate resin according to (1) or (2).
(4) The above (1) or (2), wherein a polycarbonate compound containing an aliphatic unsaturated hydrocarbon group is reacted with a silicon compound having a hydrogen atom and a hydrolyzable group on a silicon atom. The manufacturing method of polycarbonate resin of description.
(5) The method for producing a polycarbonate resin according to (4), wherein the silicon compound is a silicon compound having a hydrogen atom, a hydrolyzable group and a non-hydrolyzable group on a silicon atom.
(6) The method for producing a polycarbonate resin according to the above (4) or (5), wherein the silicon compound is a silicon compound represented by the following general formula [4].

[Z and R ⁷ in formula [4] have the same meaning as Z and R ^7, and v is an integer of 1 to 3]
(7) An electrophotographic photosensitive member having at least a photosensitive layer on a conductive substrate, wherein the photosensitive layer contains the crosslinked polycarbonate resin described in (3) above.
(8) The electrophotographic photosensitive member according to (7), wherein the crosslinked polycarbonate resin is a crosslinked polycarbonate resin obtained by crosslinking the polycarbonate resin produced by the method according to claim 5.
(9) The electrophotographic photosensitive member according to (7), wherein the crosslinked polycarbonate resin is a crosslinked product of a polycarbonate resin obtained by reacting a trialkoxysilane with a polycarbonate resin containing an aliphatic unsaturated hydrocarbon group.
(10) The electrophotographic photosensitive member according to the above (8), wherein the crosslinked polycarbonate resin is a crosslinked product of a polycarbonate resin obtained by reacting a tristrialkylsiloxysilane with a polycarbonate resin containing an aliphatic unsaturated hydrocarbon group. .
(11) Any of the above (7) to (10), wherein the photosensitive layer comprises a charge generation layer containing at least a charge generation material and a charge transport layer containing at least a charge transport material and a binder resin. The electrophotographic photosensitive member described.

  The polycarbonate resin of the present invention has an effect that it is excellent in optical properties, electrical properties, mechanical properties, and particularly wear resistance. In addition, since the electrophotographic photosensitive member of the present invention uses the above-mentioned crosslinked polycarbonate resin as a binder resin for the photosensitive layer, it has excellent durability because the abrasion resistance of the surface of the photosensitive layer is improved as well as electrophotographic characteristics. The effect of being.

  In the polycarbonate resin of the present invention, the repeating unit constituting the polymer is a polymer composed of the repeating unit (1) represented by the general formula [1] or the repeating unit represented by the general formula [1] (1 ) And the repeating unit (2) represented by the general formula [2], and the polymer chain may have any of linear, branched, and cyclic structures. Further, a special terminal structure or a special branched structure may be introduced.

The polycarbonate resin composed of the repeating units represented by the formulas [1] and [2] will be described more specifically. X ¹ represented by the formulas [1a] to [1c] and the formulas [2a] to [2d]. the to X ^2, R ^1, an alkyl group having 1 to 12 carbon atoms R ³ to R ⁶ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, 2-butyl group, t- Examples include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and the aryl group having 6 to 12 carbon atoms includes a phenyl group, a tolyl group, and a styryl group. , Biphenylyl group, naphthyl group and the like. Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, Sobutoxy group, 2-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, etc. Examples of the 6-12 substituted or unsubstituted aryloxy group include a phenoxy group, a tolyloxy group, a styryloxy group, a naphthyloxy group, and a biphenyloxy group.

  When the copolymer is composed of the repeating unit (1) and the repeating unit (2), the molar ratio of the repeating unit (1) [(1) / ((1) + (2))] is Those that are 0.01 or more, preferably those that are in the range of 0.05 to 0.6 are suitably used. When this molar ratio is less than 0.01, the crosslinking density when crosslinked is low, and the effect of improving the mechanical strength may not be sufficiently obtained.

  In addition to the repeating units (1) and (2), the polycarbonate resin has a structural unit other than those defined by the formulas [1] and [2] as long as the object of the present invention is not impaired. It may contain a unit or a unit having a polyester, polyurethane, polyether, or polysiloxane structure.

  The polycarbonate resin preferably has a reduced viscosity [ηsp / c] of 0.01 to 10 deciliter / g measured at a concentration of 0.5 g / deciliter using methylene chloride as a solvent and a temperature of 20 ° C. When the reduced viscosity [ηsp / c] is less than 0.01 deciliter / g, the mechanical strength after crosslinking is insufficient, and when it exceeds 10 deciliter / g, the moldability may be insufficient.

  Next, with respect to a method for producing a polycarbonate resin having such a repeating unit, for example, phosgene or the like is used as a carbonate ester-forming compound, and an aliphatic unsaturated bond is formed in the presence of an appropriate acid binder. A method of reacting a monohydric phenol alone or a dihydric phenol having an aliphatic unsaturated bond with a dihydric phenol having no aliphatic unsaturated bond, or ester using bisaryl carbonate as a carbonate-forming compound A method of manufacturing by an exchange method may be employed. These dihydric phenols having an aliphatic unsaturated bond may be used alone or in combination of two or more, and dihydric phenols having no aliphatic unsaturated bond may be used alone or in combination of two or more. May be. These reactions are performed in the presence of a terminal terminator and / or a branching agent as necessary.

  Examples of the dihydric phenol having an aliphatic unsaturated bond include 4,4′-dihydroxy-3,3′-divinylbiphenyl, 4,4′-dihydroxy-3,3′-diallylbiphenyl, 3,3 ′, 5. , 5′-tetraallyl-4,4′-dihydroxybiphenyl, bis (3-vinyl-4-hydroxyphenyl) methane, bis (3-allyl-4-hydroxyphenyl) methane, bis (3-allyl-4-hydroxyphenyl) ) Diphenylmethane, 1,1-bis (3-vinyl-4-hydroxyphenyl) ethane, 1,1-bis (3-allyl-4-hydroxyphenyl) ethane, 1,1-bis (3-allyl-4-hydroxy) Phenyl) -1-phenylethane, 2,2-bis (3-vinyl-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4-hydroxyphenyl) Enyl) propane, 2,2-bis (3-vinyl-4-hydroxy-5-methylphenyl) propane, 2,2-bis (3-allyl-4-hydroxy-5-methylphenyl) propane, 2,2- Bis (3-allyl-4-hydroxy-5-phenylphenyl) propane, 2,2-bis [3- (3-butenyl) -4-hydroxyphenyl] propane, 2,2-bis [3- (4-pentenyl) ) -4-hydroxyphenyl] propane, 2,2-bis [3- (5-hexenyl) -4-hydroxyphenyl] propane, 2- (4-hydroxyphenyl) -2- (3-allyl-4-hydroxyphenyl) ) Propane, 2,2-bis (3,5-diallyl-4-hydroxyphenyl) propane, 2,2-bis (3-vinyl-4-hydroxyphenyl) butane, 2,2- (3-allyl-4-hydroxyphenyl) butane, 3,3-bis (3-vinyl-4-hydroxyphenyl) pentane, 3,3-bis (3-allyl-4-hydroxyphenyl) pentane, 1,1 -Bis (3-vinyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-allyl-4-hydroxyphenyl) cyclohexane, bis (3-vinyl-4-hydroxyphenyl) ether, bis (3-allyl- 4-hydroxyphenyl) ether, bis (3-vinyl-4-hydroxyphenyl) sulfide, bis (3-allyl-4-hydroxyphenyl) sulfide, bis (3-vinyl-4-hydroxyphenyl) sulfoxide, bis (3- Allyl-4-hydroxyphenyl) sulfoxide, bis (3-vinyl-4-hydroxyphenyl) Sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 3,3′-divinyl-4,4′-dihydroxybenzophenone, 3,3′-diallyl-4,4′-dihydroxybenzophenone, 4,4′- Dihydroxybenzalacetophenone, 9,9-bis (3-vinyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-allyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-allyl-4) -Hydroxy-5-methylphenyl) fluorene, 1,3-bis [2- (3-allyl-4-hydroxyphenyl) propyl] benzene, 1,4-bis [2- (3-allyl-4-hydroxyphenyl) Propyl] benzene, 1,3-dihydroxy-4-allylbenzene, 4,4′-dihydroxy-3-allylbiphenyl, 2,7-dihy Droxy-3,6-diallylnaphthalene, 4,4-bis (4-hydroxyphenyl) -1,6-heptadiene, 1,1-bis (4-hydroxyphenyl) -3-butene, 1,1-bis (4 -Hydroxyphenyl) -2-propene, 1,1-bis (4-hydroxyphenyl) -2-vinylcyclohexane, 1,1-bis (4-hydroxyphenyl) -2-allylcyclohexane, 1,1-bis (4 -Hydroxyphenyl) -2- (1-cyclohexenyl) cyclohexane, and a compound represented by the following formula.

  Among these dihydric phenols, preferred are 3,3′-diallyl-4,4′-dihydroxybiphenyl, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis ( 3-allyl-4-hydroxy-5-methylphenyl) propane, 2,7-dihydroxy-3,6-diallylnaphthalene, 1,1-bis (3-allyl-4-hydroxyphenyl) cyclohexane, 2-allyl-1 , 1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxybenzalacetophenone, and the like.

  Examples of the dihydric phenol having no aliphatic unsaturated bond include 4,4′-dihydroxybiphenyl, 3,3′-difluoro-4,4′-dihydroxybiphenyl, and 4,4′-dihydroxy- 4,4′-dihydroxybiphenyls such as 3,3′-dimethylbiphenyl, 4,4′-dihydroxy-2,2′-dimethylbiphenyl, 4,4′-dihydroxy-3,3′-dicyclohexylbiphenyl; 4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) phenylmethane, bis (3-methyl-4-hydroxyphenyl) methane, bis (3-nonyl-4-hydroxyphenyl) Methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dibromo -4-hydroxyphenyl) methane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3-fluoro-4-hydroxyphenyl) methane, bis (2-tert-butyl-4-hydroxyphenyl) phenylmethane, Bis (2-hydroxyphenyl) methane, 2-hydroxyphenyl-4-hydroxyphenyl) methane, bis (2-hydroxy-4methylphenyl) methane, bis (2-hydroxy-4-methyl-6-tert-butylphenyl) Methane, bis (2-hydroxy-4,6-dimethylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,1-bis (4 -Hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-methyl) Enyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) -1-phenylethane, 2- (4-hydroxy-3-methylphenyl) -2- (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (2-tert-butyl-4-hydroxy-3-methylphenyl) ethane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 1,1-bis (2-hydroxy-4-methylphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (2 -Methyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-) Droxyphenyl) propane, 2,2-bis (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3- Cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3 -Bromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) Propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-diflu) Olophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (3-bromo-4-hydroxy-5-chlorophenyl) propane, 2,2-bis (4 -Hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (2-hydroxy-4-sec-butylphenyl) propane, 2,2-bis (2-hydroxy-) 4,6-dimethylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2- (3-methyl-4-hydroxyphenyl) butane 1,1-bis (4-hydroxyphenyl) -2 -Methylpropane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) -2-methylpropane, 1,1-bis (2-butyl-4-) Droxy-5-methylphenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-methyl-4-hydroxy-5-tert-) Pentylphenyl) butane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) butane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) butane, 2,2-bis (4- Hydroxyphenyl) -3-methylbutane, 1,1-bis (4-hydroxyphenyl) -3-methylbutane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) heptane, 2,2-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) hept 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxyphenyl) nonane, 2,2-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxy) Phenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethyl) Phenyl) cyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl)- 3,3,5-trimethylcyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) -3, Bis (hydroxyphenyl) alkanes such as 3,5-trimethylcyclohexane; Bis (4-hydroxyphenyl) ethers such as bis (4-hydroxyphenyl) ether and bis (3-fluoro-4-hydroxyphenyl) ether; Bis (4-hydroxyphenyl) sulfides such as (4-hydroxyphenyl) sulfide and bis (3-methyl-4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfoxide, bis (3-methyl-4-hydroxy) Bis (4-hydroxyphenyl) sulfoxides such as phenyl) sulfoxide; bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-phenyl-4-hydroxyphenyl) sulfone, etc. Screw ( -Hydroxyphenyl) sulfones; bis (4-hydroxyphenyl) ketones such as 4,4′-dihydroxybenzophenone; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4) -Hydroxyphenyl) fluorene, bis (hydroxyphenyl) fluorenes such as 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene; dihydroxy-p-ter such as 4,4 "-dihydroxy-p-terphenyl Phenyls; dihydroxy-p-quarterphenyls such as 4,4 ′ ″-dihydroxy-p-quaterphenyl; 2,5-bis (4-hydroxyphenyl) pyrazine, 2,5-bis (4-hydroxyphenyl) -3,6-dimethylpyrazine, 2,5-bis (4-hydroxyphenyl) -2,6 Bis (hydroxyphenyl) pyrazines such as diethylpyrazine; 1,8-bis (4-hydroxyphenyl) menthane, 2,8-bis (4-hydroxyphenyl) menthane, 1,8-bis (3-methyl-4) -Hydroxyphenyl) menthane, bis (hydroxyphenyl) menthanes such as 1,8-bis (4-hydroxy-3,5-dimethylphenyl) menthane; 1,4-bis [2- (4-hydroxyphenyl) -2 -Propyl] benzene, bis [2- (4-hydroxyphenyl) -2-propyl] benzenes such as 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene; 1,3-dihydroxy Naphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2, Dihydroxynaphthalenes such as dihydroxynaphthalene; dihydroxybenzenes such as resorcin, hydroquinone and catechol; α, ω-dihydroxypolydimethylsiloxane, α, ω-bis [3- (2-hydroxyphenyl) propyl] polydimethylsiloxane Polysiloxanes; 1,1,8,8-tetrahydro-1,8-dihydroxyperfluorooctane, dihydroperfluoroalkanes such as 1,1,6,6-tetrahydro-1,6-dihydroxyperfluorohexane, etc. Can be mentioned.

  Among these various dihydric phenols, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 4,4 ′ -Dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 3,3-bis (4-hydroxyphenyl) pentane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, bis (4-hydroxyphenyl) ether, 4,4 ′ Dihydroxybenzophenone, 2,2-bis (4-hydroxy-3-methoxyphenyl) 1,1,1,3,3,3-hexafluoropropane, α, ω-bis [3- (2-hydroxyphenyl) propyl] Polydimethylsiloxane, resorcin, 2,7-dihydroxynaphthalene and the like are preferable, and 2,2-bis (4-hydroxyphenyl) propane is particularly preferable.

  As the terminal terminator, monovalent carboxylic acid and derivatives thereof, and monovalent phenol can be used. For example, p-tert-butyl-phenol, p-phenylphenol, p-cumylphenol, p-perfluorononylphenol, p- (perfluorononylphenyl) phenol, p- (perfluoroxylphenyl) phenol, p-tert -Perfluorobutylphenol, 1- (P-hydroxybenzyl) perfluorodecane, p- [2- (1H, 1H-perfluorotridodecyloxy) -1,1,1,3,3,3-hexafluoropropyl] Phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, perfluorododecyl p-hydroxybenzoate, p- (1H, 1H-perfluorooctyloxy) phenol, 2H, 2H, 9H-perfluorononanoic acid, 1,1,1,3,3,3-tetraflo Such as 2-propanol is preferably used. The addition ratio of these end terminators is 1 to 30 mol%, more preferably 1 to 10 mol% as a copolymer composition ratio. If this ratio exceeds 30 mol%, mechanical strength may be lowered. Yes, if it is less than 1 mol%, the moldability may be lowered.

  Specific examples of the branching agent include phloroglysin, pyrogallol, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 2,6-dimethyl-2,4,6. -Tris (4-hydroxyphenyl) -3-heptene, 2,4-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (2-hydroxyphenyl) benzene, , 3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis [2-bis (4-hydroxyphenyl) -2-propyl] phenol, 2,6-bis (2 Hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, tetrakis (4-hydroxyphenyl) methane, tetrakis [4- (4- Hydroxyphenylisopropyl) phenoxy] methane, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid, 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole, 3 , 3-bis (4-hydroxyaryl) oxindole, 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like.

  The addition amount of these branching agents is 30 mol% or less, preferably 5 mol% or less in terms of the copolymer composition ratio, and if this exceeds 30 mol%, moldability may be deteriorated. As the carbonate ester-forming compound, various dihalogenated carbonyls such as phosgene, haloformates such as chloroformate, carbonate ester compounds, etc., and the reaction of performing polycondensation in the presence of an acid binder are usually carried out in a solvent. Do. When a gaseous carbonate-forming compound such as phosgene is used, a method of blowing it into the reaction system can be suitably employed. The proportion of the carbonate ester-forming compound used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction.

  Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, or Mixtures of these can be used. The use ratio of the acid binder may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, 1 equivalent or an excess amount, preferably 1 to 5 equivalents of acid binder may be used per 1 mol of hydroxyl group of the raw material dihydric phenol.

  Solvents used here include aromatic hydrocarbons such as toluene and xylene, methylene chloride, chloroform, 1.1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane. 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, halogenated hydrocarbons such as chlorobenzene, acetophenone, and the like are preferable. These solvents may be used alone or in combination of two or more. Further, the interfacial polycondensation reaction may be performed using two kinds of solvents that are not mixed with each other.

  Examples of the catalyst include trimethylamine, triethylamine, tributylamine, N, N-dimethylcyclohexylamine, tertiary amines such as pyridine and dimethylaniline, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctyl. Quaternary ammonium salts such as methylammonium chloride, tetrabutylammonium chloride and tetrabutylammonium bromide, and quaternary phosphonium salts such as tetrabutylphosphonium chloride and tetrabutylphosphonium bromide are preferred. Furthermore, if desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added to this reaction system.

  Next, as for the reaction conditions for carrying out the polycondensation reaction, the reaction temperature is usually 0 to 150 ° C., preferably 5 to 40 ° C., and the reaction pressure may be any of reduced pressure, normal pressure, and increased pressure. However, it can usually be carried out under normal pressure or a pressure of about the pressure of the reaction system. The reaction time depends on the reaction temperature, but is about 0.5 minutes to 10 hours, preferably about 1 minute to 2 hours.

  The molecular weight of the polycarbonate resin can be adjusted, for example, by selecting the reaction conditions and increasing / decreasing the amount of the terminal terminator or branching agent used. In some cases, the obtained polymer is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, partial decomposition treatment, etc.) to obtain a polymer having a desired molecular weight range. It may be.

  This polycarbonate resin can be produced in various ways, for example, by reacting a dihydric phenol having an aliphatic unsaturated bond and / or a dihydric phenol not having an aliphatic unsaturated bond with phosgene. Then, a polycarbonate oligomer is produced, and then a dihydric phenol having an aliphatic unsaturated bond and / or a dihydric phenol having no aliphatic unsaturated bond is added to the polycarbonate oligomer and an alkali of the solvent and the acid binder. You may employ | adopt the method made to react in presence of the liquid mixture of aqueous solution. Further, a method is adopted in which the dihydric phenol having an aliphatic unsaturated bond and / or the dihydric phenol not having an aliphatic unsaturated bond and phosgene are reacted in a mixed solution of the solvent and an aqueous alkaline solution. May be. Usually, the former method of producing a polycarbonate oligomer in advance is preferable because it is efficient.

  In order to produce a polycarbonate oligomer, first, a dihydric phenol having an aliphatic unsaturated bond and / or a dihydric phenol not having an aliphatic unsaturated bond (including a branching agent if necessary) in an alkaline aqueous solution. Dissolve to prepare an alkaline aqueous solution of dihydric phenol. Next, phosgene is introduced into the mixed solution of the alkaline aqueous solution and an organic solvent such as methylene chloride to cause the reaction, thereby causing dihydric phenol having an aliphatic unsaturated bond and / or divalent phenol having no aliphatic unsaturated bond. Synthesize phenolic polycarbonate oligomers. Next, the reaction solution is separated into an aqueous phase and an organic phase to obtain an organic phase containing a polycarbonate oligomer. At this time, the alkali concentration of the aqueous alkali solution is preferably in the range of 1 to 15% by weight, and the volume ratio of the organic phase to the aqueous phase is 10: 1 to 1:10, preferably 5: 1 to 1: 5. It is a range. The reaction temperature is usually 0 to 70 ° C., preferably 5 to 65 ° C. under cooling, and the reaction time is about 15 minutes to 4 hours, preferably about 30 minutes to 3 hours. The polycarbonate oligomer thus obtained has an average molecular weight of 2000 or less and a polymerization degree of usually 20 or less, preferably 2 to 10-mer.

  The organic phase containing the polycarbonate oligomer thus obtained is reacted by adding the dihydric phenol having an aliphatic unsaturated bond and / or the dihydric phenol not having an aliphatic unsaturated bond. The reaction temperature is usually 10 to 50 ° C., preferably 20 to 40 ° C., and the reaction time is usually about 30 minutes to 2 hours. In this reaction, it is desirable to add a dihydric phenol having an aliphatic unsaturated bond and / or a dihydric phenol not having an aliphatic unsaturated bond as an organic solvent solution and / or an alkaline aqueous solution. There is no restriction | limiting in particular about the addition order. In addition, a catalyst, a terminal terminator, a branching agent, and the like are added and used in the above production method, if necessary, at the time of producing the polycarbonate oligomer, at the time of the subsequent high molecular weight reaction, or both. Can do.

  Next, the thus obtained polycarbonate resin having an aliphatic unsaturated bond is reacted with a silicon compound represented by the following general formula [4]. In the silicon compound of the formula [4], the substituent represented by Z is a hydrolyzable group, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, a trialkylsiloxy group, A triarylsiloxy group and a halogen atom; More specifically, methoxy, ethoxy, proxy, isopropoxy, butoxy, 2-butoxy, isobutoxy, tert-butoxy, phenoxy, naphthoxy, biphenyloxy, trimethylsilyl, triethylsilyl Group, triphenylsilyl group, fluorine, chlorine, bromine and the like. The substituent represented by R7 in the formula is a non-hydrolyzable group, a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. It is a group. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, vinyl group, allyl group, and 3-butenyl. Group, 4-pentenyl group, 5-hexenyl group, isopropenyl group, ethynyl group, propargyl group, phenyl group, naphthyl group, biphenyl group and the like.

[Z and R ⁷ in formula [4] have the same meaning as Z and R ^7, and v is an integer of 1 to 3]

  Specific examples of such silicon compounds include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, methyldiethoxysilane, methyldimethoxysilane, triphenoxysilane, and methyldiphenoxysilane. , Phenyldimethoxysilane, phenyldiethoxysilane, ethyldiethoxysilane, dimethylmethoxysilane, dimethylethoxysilane, dimethylphenoxysilane, diethylmethoxysilane, diethylethoxysilane, diphenylethoxysilane, tris (trimethylsiloxy) silane, tris (triethylsiloxy) ) Silane, methylbis (trimethylsiloxy) silamethylbis (triethylsiloxy) silane, dimethyl (trimethylsiloxy) silane, dimethyl (tri Chirushirokishi) silane and the like.

Regarding the method of introducing these silicon compounds into the polycarbonate resin, the silicon compound may be added and reacted before the synthesis of the polycarbonate resin, or may be introduced by a polymer reaction. A method of reacting this silicon compound with a polycarbonate resin having a group unsaturated bond is preferred. As a method for reacting the aliphatic unsaturated bond with this silicon compound, the reaction is carried out in the presence of one or more substances selected from a transition metal catalyst, a base catalyst and a radical chemical species to hydrosilylate. . Among these, a method using a transition metal catalyst is most preferable from the viewpoint of the reaction yield, the small amount of side reactions, and the small amount of catalyst added. As the transition metal catalyst, a transition metal catalyst of Group VII to Group X in the periodic table is preferable. Specifically, an iron catalyst [Fe (CO) ₅ ], a ruthenium catalyst [RuCl ₃ ], a cobalt catalyst [ Co ₂ (CO) ₈ ], rhodium catalyst [(Ph ₃ P) ₃ RhCl, (Rh (C ₂ H ₄ ) ₂ Cl ₂ ], iridium catalyst [IrCl ₃ ], nickel catalyst [(Ph ₃ P) ₂ Ni, (Ph ₃ P) ₂ NiCl ₂ ], palladium catalyst [(Ph ₃ P) ₄ Pd, (Ph ₃ P) ₂ PdCl ₂ ], platinum catalyst [H ₂ PtCl ₆ · 6H ₂ O, (Ph ₃ P) ₄ Pt , (Pt (C ₂ H ₄ ) Cl ₂ ) ₂ , (Ph ₃ P) ₂ PtCl ₂ , Pt (C ₂ H ₄ ) (Ph ₃ P) Cl ₂ , (PhCN) ₂ PtCl ₂ , K ₂ PtCl ₄ , _{Pt-Al 2 O 3, Pt} -C, platinum-1,1,3,3-tetramethyl-1,3 Divinyl siloxane complex, platinum-carbonyl complex, a platinum -. Etc. cyclovinylmethylsiloxane complex] and the like Among these, Speier catalyst _{(H 2 PtCl 6 · 6H 2} O- isopropanol solution) and platinum -1,1,3, Particularly preferred are 3-tetramethyl-1,3-divinyldisiloxane complex, platinum carbonyl complex, and platinum-cyclovinylmethylsiloxane complex.

  As the base catalyst, for example, various trialkylamines such as trimethylamine and triethylamine can be used. Furthermore, as radical chemical species, for example, peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and azobisisobutyronitrile can be used.

  And the addition amount of these catalysts is suitably selected in consideration of the reactivity in the range of 1 wtPPM-1 wt% with respect to the aliphatic unsaturated bond of the said polycarbonate resin, Preferably it is 100-1000 wtPPM. If the amount of the catalyst added is less than 1 wt PPM, the reaction rate may be slow and the crosslinking reaction may not proceed. Moreover, since there exists a possibility that the product obtained when this exceeds 1 wt% may be contained, it is appropriate to make it into the said range.

  Furthermore, it is suitable that the temperature during this reaction is 20 to 200 ° C, preferably 50 to 150 ° C. If the reaction temperature is lower than 20 ° C., the reaction rate decreases, and even if this is carried out at 200 ° C. or higher, there is no effect corresponding to it, which is uneconomical. The reaction time is 1 second to 24 hours, preferably 1 minute to 12 hours. If the reaction time is less than 1 second, the reaction may not proceed sufficiently, and it is not economical to spend more than 24 hours.

  The polycarbonate resin thus obtained has a structure having a silicon compound residue, as represented by the formulas [1] and [2]. And this polycarbonate resin expresses the outstanding mechanical strength by carrying out a crosslinking process. For this crosslinking treatment, a method of condensing by hydrolysis with moisture in the air and dehydration associated therewith can be suitably employed. In this crosslinking reaction, tin compounds such as tin octylate, dibutyl diacetyloxy tin, tin dibutyl dicytylate, tin dibutyl didodecylate, tetrabutyl titanate, tetrapropyl titanate, dipropoxy bis (ethyl acetoacetate chelate) A catalyst such as a titanium compound such as titanium, a metal fatty acid salt, or a metal alcoholate may be added. The crosslinking treatment conditions vary depending on the chemical structure of the polycarbonate resin and the type of the catalyst, but when the catalyst is used, the concentration is 10 to 50000 wtppm, preferably 100 to 10000 wtppm. The treatment temperature is 0 to 160 ° C., preferably 60 to 140 ° C., and the treatment time is 1 second to 24 hours, preferably 1 minute to 12 hours. The degree of progress of this crosslinking reaction can be quantitatively confirmed from the content ratio of insoluble components with respect to a solvent such as methylene chloride or dimethyl sulfoxide.

  The cross-linked structure of the cross-linked polycarbonate resin of the present invention varies depending on the chemical structure of the polycarbonate resin having a silicon compound residue, particularly the bonding site and number of silicon compound residues to the polycarbonate molecular chain, and the chemical structure of the silicon compound residue. It has become a form. Specific examples of the structure of the crosslinked polycarbonate resin of the present invention include the following.

[In the above formula, Ar ² , X ¹ , R ¹ , p, q, r, s have the same meaning as in the above formulas [1] to [3], and W is

(Wherein, R ^7, t has the same meaning as R ^7, t in Formula (4), u is an integer of 0 to 2) is a group represented by. ]
The cross-linked polycarbonate resin thus obtained maintains high transparency and is suitable for a material that requires a high degree of transparency. In addition, it is excellent in mechanical properties such as heat resistance, impact resistance, wear resistance, and electrical insulation without causing the problem that brittleness decreases even if the crosslink density is increased. Used as a highly useful material in a wide range of industrial fields such as components and parts such as electrical equipment, electronic equipment, and optical equipment, automobile parts, metal or woodwork coating materials, and paints that are required to have properties can do.

  Next, the electrophotographic photosensitive member of the present invention is an electrophotographic photosensitive member in which a photosensitive layer is provided on a conductive substrate, and the photosensitive layer has a surface layer containing the crosslinked polycarbonate resin. The electrophotographic photoreceptor of the present invention is not particularly limited in its structure as long as such a photosensitive layer is formed on a conductive substrate. Various known types such as a single layer type and a multilayer type are available. The electrophotographic photosensitive member may be of any type. In general, a laminated electrophotographic photosensitive member having at least one charge generation layer as a photosensitive layer and at least one charge transport layer forming a surface layer is preferable, and the cross-linking is performed in at least one charge transport layer. A polycarbonate resin is preferably used as a binder resin and / or as the surface protective layer.

  In the electrophotographic photoreceptor of the present invention, when the above-mentioned crosslinked polycarbonate resin is used as a binder resin, the crosslinked polycarbonate resin may be used alone or in combination of two or more thereof. You may use together with resin components, such as another polycarbonate resin, in the range which does not inhibit achievement of the objective. As the conductive substrate used in the electrophotographic photosensitive member of the present invention, various substrates such as known ones can be used. Specifically, aluminum, nickel, chromium, palladium, titanium, molybdenum, indium, gold , Platinum, silver, copper, zinc, brass, stainless steel, lead oxide, tin oxide, indium oxide, ITO or graphite plates, drums, sheets, and glass that has been electrically conductively coated by vapor deposition, sputtering, coating, etc. , Cloth, paper or plastic film, sheet and seamless belt, and plastic film, sheet and seamless belt laminated with metal foil such as aluminum, metal sheet film and seamless belt, and metal oxidation treatment by electrode oxidation, etc. Gold It can be used such as a drum.

  The charge generation layer of the multilayer electrophotographic photosensitive member contains at least a charge generation material, and this charge generation layer is formed on the base substrate by a vacuum evaporation method, a chemical vapor deposition method, or a sputtering method. Or a layer formed by binding a charge generating substance using a binder resin on the underlying layer. Various methods such as a known method can be used as a method for forming a charge generation layer using a binder resin. For example, a coating solution in which a charge generation material is dispersed or dissolved in a suitable solvent together with a binder resin is usually used. Is preferably applied to a layer serving as a predetermined base and dried. The charge generation layer thus obtained has a thickness of 0.01 to 2.0 microns, preferably 0.1 to 0.8 microns. If the thickness of the charge generation layer is less than 0.01 microns, it is difficult to form a uniform thickness, and if it exceeds 2.0 microns, electrophotographic characteristics may be deteriorated. is there.

As the charge generating material used here, for example, various compounds known in JP-A-8-225639 can be used. Specific compounds include selenium such as amorphous selenium and trigonal selenium, tellurium alone, selenium alloys such as selenium-tellurium alloy, selenium-arsenic alloy, selenium compounds such as As ₂ Se ₃ or selenium-containing compositions. , Zinc oxide, cadmium sulfide, antimony sulfide, zinc sulfide, alloys such as CdS-Se, inorganic materials composed of Group 12 and Group 16 elements, oxide-based semiconductors such as titanium oxide, silicon-based materials such as amorphous silicon, Metal-free phthalocyanine pigments such as τ-type metal-free phthalocyanine, χ-type metal-free phthalocyanine, α-type copper phthalocyanine, β-type copper phthalocyanine, γ-type copper phthalocyanine, ε-type copper phthalocyanine, X-type copper phthalocyanine, A-type titanyl phthalocyanine, B-type Titanyl phthalocyanine, C-type titanyl phthalocyanine, D-type titani Phthalocyanine, E-type titanyl phthalocyanine, F-type titanyl phthalocyanine, G-type titanyl phthalocyanine, H-type titanyl phthalocyanine, K-type titanyl phthalocyanine, L-type titanyl phthalocyanine, M-type titanyl phthalocyanine, N-type titanyl phthalocyanine, Y-type titanyl phthalocyanine, oxo titanyl phthalocyanine , Metal phthalocyanine pigments such as titanyl phthalocyanine, cyanine dyes, anthracene pigments, bisazo pigments, pyrene pigments, polycyclic quinone pigments, quinacridones, which show a strong diffraction peak at a black angle 2θ of 27.3 ± 0.2 degrees in the X-ray diffraction pattern Pigments, indigo pigments, perylene pigments, pyrylium dyes, squalium pigments, anthanthrone pigments, benzimidazole pigments, azo pigments, thioindigo pigments, quinoline pigments Lake pigments, oxazine pigments, dioxazine pigments, triphenylmethane pigments, azulenium dyes, triarylmethane dyes, xanthine dyes, thiazine dyes, thiapyrylium dyes, polyvinylcarbazole, and the like bisbenzimidazole pigments.

  Of these compounds, the compounds specifically exemplified in JP-A-8-225639 are preferably used for dyes and pigments. In addition, these compounds can be used as a charge generation material alone or in combination of two or more. Moreover, there is no restriction | limiting in particular as binder resin used for an electric charge generation layer, A well-known various thing can be used. Specifically, polystyrene, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl acetal, alkyd resin, acrylic resin, polyacrylonitrile, polycarbonate, polyurethane, epoxy resin, phenol resin, polyamide, polyketone, Polyacrylamide, butyral resin, polyester resin, vinylidene chloride-vinyl chloride copolymer, methacrylic resin, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone Resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, melamine resin, polyether resin, benzoguanamine resin, epoxy acrylate resin, urea Acrylate resin, poly-N-vinyl carbazole, polyvinyl butyral, polyvinyl formal, polysulfone, casein, gelatin, polyvinyl alcohol, ethyl cellulose, nitrocellulose, carboxy-methyl cellulose, vinylidene chloride polymer latex, acrylonitrile-butadiene copolymer, vinyl toluene- Examples include styrene copolymers, soybean oil-modified alkyd resins, nitrated polystyrene, polymethylstyrene, polyisoprene, polythiocarbonate, polyarylate, polyhaloarylate, polyallyl ether, polyvinyl acrylate, and polyester acrylate. As the binder resin in the charge generation layer, the crosslinked polycarbonate resin of the present invention can also be used.

  Next, the charge transport layer can be obtained by forming a layer formed by binding a charge transport material with a binder resin on a base layer (for example, a charge generation layer). As a method for forming the charge transport layer, various methods such as a known method can be used. Usually, the charge transport material is dispersed or dissolved in a suitable solvent together with the polycarbonate resin before crosslinking in the present invention. A method of applying the coating liquid on a predetermined base layer and drying it is used. The blending ratio of the charge transport material used for forming the charge transport layer and the polycarbonate resin is preferably 20:80 to 80:20, more preferably 30:70 to 70:30, by weight.

  In the charge transport layer, the polycarbonate resin can be used alone or in combination of two or more. In addition, resins such as those mentioned as the binder resin used in the charge generation layer can be used in combination with the polycarbonate resin as long as the object of the present invention is not impaired. The charge transport layer thus formed has a thickness of 5 to 100 microns, preferably 10 to 30 microns. When the thickness is less than 5 microns, the initial potential is lowered, and when it exceeds 100 microns, the electrophotographic characteristics may be deteriorated.

  As the compound that can be used as the charge transport material, various compounds known in JP-A-8-225639 can be used. Such compounds include carbazole compounds, indole compounds, imidazole compounds, oxazole compounds, pyrazole compounds, oxadiazole compounds, pyrazoline compounds, thiadiazole compounds, aniline compounds, hydrazone compounds, aromatic amine compounds, aliphatic amine compounds, stilbenes. Compound, fluorenone compound, quinone compound, quinodimethane compound, thiazole compound, triazole compound, imidazolone compound, imidazolidine compound, bisimidazolidine compound, oxazolone compound, benzothiazole compound, benzimidazole compound, quinazoline compound, benzofuran compound, acridine compound, phenazine Compound, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinyla Lysine, poly-9-vinylphenyl anthracene, pyrene - formaldehyde resin, ethylcarbazole resin, or the like polymers having these structures in the main chain or side chain is preferably used.

  Among these compounds, compounds specifically exemplified in the above-mentioned JP-A-8-225639 are particularly preferably used. These compounds may be used alone or in combination of two or more. In the electrophotographic photosensitive member of the present invention, an undercoat layer that is usually used can be provided between the conductive substrate and the photosensitive layer. As this undercoat layer, fine particles such as titanium oxide, aluminum oxide, zirconia, titanic acid, zirconic acid, lanthanum lead, titanium black, silica, lead titanate, barium titanate, tin oxide, indium oxide, silicon oxide, polyamide Components such as resin, phenol resin, casein, melamine resin, benzoguanamine resin, polyurethane resin, epoxy resin, cellulose, nitrocellulose, polyvinyl alcohol, and polyvinyl butyral resin can be used. Further, as the resin used for the undercoat layer, the binder resin may be used, or the polycarbonate resin of the present invention may be used. These fine particles and resins can be used alone or in various mixtures. In the case of using these as a mixture, it is preferable to use inorganic fine particles and a resin together because a film having good smoothness is formed.

  The thickness of this undercoat layer is 0.01 to 10 microns, preferably 0.01 to 1 microns. If the thickness is less than 0.01 microns, it is difficult to form the undercoat layer uniformly. If the thickness exceeds 10 microns, the electrophotographic characteristics may be deteriorated. Further, a known blocking layer that is usually used can be provided between the conductive substrate and the photosensitive layer. As this blocking layer, the same kind of resin as the binder resin can be used. Moreover, you may use the polycarbonate resin of this invention. The blocking layer has a thickness of 0.01 to 20 microns, preferably 0.1 to 10 microns. If the thickness is less than 0.01 microns, it is difficult to form a blocking layer uniformly. If the thickness exceeds 20 microns, the electrophotographic characteristics may be deteriorated.

  Furthermore, a protective layer may be laminated on the photosensitive layer in the electrophotographic photoreceptor of the present invention. For this protective layer, the same kind of resin as the binder resin can be used. Moreover, it is particularly preferable to use the polycarbonate resin of the present invention. The thickness of this protective layer is 0.01 to 20 microns, preferably 0.1 to 10 microns. The protective layer contains a conductive material such as the charge generating substance, charge transporting substance, additive, metal or oxide thereof, nitride, salt, alloy, carbon black, or organic conductive compound. Also good.

  Further, in order to improve the performance of the electrophotographic photosensitive member, the charge generation layer and the charge transport layer include a binder, a plasticizer, a curing catalyst, a fluidity imparting agent, a pinhole control agent, a spectral sensitivity sensitizer ( Sensitizing dye) may be added. In addition, various chemical substances, antioxidants, surfactants, anti-curling agents, leveling agents, and other additives are added for the purpose of preventing increase in residual potential, decrease in charging potential, and reduction in sensitivity due to repeated use. Can be added.

  Examples of the binder include silicone resin, polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polystyrene resin, polymethacrylate resin, polyacrylamide resin, polybutadiene resin, polyisobrene resin, melamine resin, benzoguanamine resin, Polychloroprene resin, polyacrylonitrile resin, ethyl cellulose resin, nitrocellulose resin, urea resin, phenol resin, phenoxy resin, polyvinyl butyral resin, formal resin, vinyl acetate resin, vinyl acetate / vinyl chloride copolymer resin, polyester carbonate resin, etc. It is done. Also, heat and / or photocurable resins can be used. In any case, any resin that is electrically insulating and can form a film in a normal state is not particularly limited.

  This binder is preferably added in a proportion of 5 to 200% by weight, more preferably 10 to 100% by weight, based on the charge transport material. When the blending ratio of the binder is less than 5% by weight, the coating of the photosensitive layer tends to be non-uniform, and the image quality tends to be inferior. Specific examples of the plasticizer include biphenyl, biphenyl chloride, o-terphenyl, halogenated paraffin, dimethyl naphthalene, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, diethylene glycol phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, Examples include dibutyl sebacate, butyl laurate, methyl phthalyl ethyl glycolate, dimethyl glycol phthalate, methyl naphthalene, benzophenone, polypropylene, polystyrene, and fluorohydrocarbon.

  Specific examples of the curing catalyst include methanesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid, and the like. Examples of the fluidity imparting agent include modaflow, acronal 4F, and the like. , Benzoin, and dimethyl phthalate. These plasticizers, curing catalysts, flow imparting agents, and pinhole control agents are preferably used in an amount of 5% by weight or less based on the charge transport material.

  Further, as a spectral sensitizer, when using a sensitizing dye, for example, triphenylmethane dyes such as methyl violet, crystal violet, knight blue, and victoria blue, erythrosin, rhodamine B, rhodamine 3R, acridine orange, Acridine dyes such as frappeocin, thiazine dyes such as methylene blue and methylene green, oxazine dyes such as capri blue and meldra blue, cyanine dyes, merocyanine dyes, styryl dyes, pyrylium salt dyes and thiopyrylium salt dyes are suitable.

  An electron-accepting substance can be added to the photosensitive layer for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use. Specific examples thereof include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, pyroanhydride Merit acid, merit anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, p-nitrobenzonitrile, picryl chloride, quinone chloride, Chloranil, bromanyl, benzoquinone, 2,3-dichlorobenzoquinone, dichlorodicyanoparabenzoquinone, naphthoquinone, diphenoquinone, tropoquinone, anthraquinone, 1-chloroanthraquinone, dinitroanthraquinone, 4-nitrobenzophenone, 4,4'-dinito Lobenzophenone, 4-nitrobenzalmalondinitrile, ethyl α-cyano-β- (p-cyanophenyl) acrylate, 9-anthracenylmethylmalondinitrile, 1-cyano- (p-nitrophenyl) -2 -(P-chlorophenyl) ethylene, 2,7-dinitrofluorenone, 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, 9-fluorenylidene- (dicyanomethylenemalononitrile), polynitro- 9-fluorenylidene- (dicyanomethylenemalonodinitrile), picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitro Compounds with high electron affinity such as salicylic acid, phthalic acid, and merit acid are preferred. Good. These compounds may be added to either the charge generation layer or the charge transport layer, and the blending ratio is 0.01 to 200% by weight, preferably 0.1 to 50% by weight, based on the charge generation material or charge transport material. It is.

  In order to improve surface properties, tetrafluoroethylene resin, trifluoroethylene chloride resin, tetrafluoroethylene hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluorodiethylene chloride resin and Those copolymers and fluorine-based graft polymers may be used. The blending ratio of these surface modifiers is 0.1 to 60% by weight, preferably 5 to 40% by weight, based on the binder resin. When the blending ratio is less than 0.1% by weight, surface modification such as surface durability and surface energy reduction is not sufficient, and when the blending ratio is more than 60% by weight, electrophotographic characteristics may be deteriorated.

  As the antioxidant, a hindered phenol antioxidant, an aromatic amine antioxidant, a hindered amine antioxidant, a sulfide antioxidant, an organic phosphate antioxidant, and the like are preferable. Among these antioxidants, the compounds specifically exemplified in the above-mentioned JP-A-8-225639 can be used particularly preferably. The mixing ratio of these antioxidants is usually 0.01 to 10% by weight, preferably 0.1 to 2% by weight, based on the charge transport material.

  And these antioxidants may be used individually by 1 type, and 2 or more types may be mixed and used for them. Furthermore, these may be added to the surface protective layer, the undercoat layer, or the blocking layer in addition to the photosensitive layer. Examples of the solvent used for forming the charge generation layer and the charge transport layer include aromatic solvents such as benzene, toluene, xylene, and chlorobenzene, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, methanol, ethanol, and isopropanol. Alcohols such as ethyl acetate, ethyl cellosolve, etc., halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, tetrachloroethane, ethers such as tetrahydrofuran, dioxane, dimethylformamide, dimethylsulfoxide, diethylformamide, etc. Can be mentioned. These solvents may be used alone or in combination of two or more.

  Next, as a method for forming the charge transport layer, a coating liquid prepared by dispersing or dissolving the silyl group-containing polycarbonate resin used for forming the charge transport material, additives, and binder resin in a solvent, This is applied onto, for example, the charge generation layer serving as a predetermined base, and a charge transport layer in a form in which the polycarbonate resin cross-linked with the polycarbonate resin coexists with the charge transport material as a binder resin is formed. Here, the curing catalyst may be not added, or may be added to the coating liquid, or may be added after forming the charge transport layer without being added to the coating liquid.

  As a method for preparing the coating liquid, the blended raw material can be dispersed or dissolved using a ball mill, ultrasonic wave, paint shaker, red devil, sand mill, mixer, attritor or the like. As for the method of applying the coating liquid thus obtained, dip coating method, electrostatic coating method, powder coating method, spray coating method, roll coating method, applicator coating method, spray coater coating method, bar Coater coating method, roll coater coating method, dip coater coating method, doctor blade coating method, wire bar coating method, knife coater coating method, attritor coating method, spinner coating method, bead coating method, blade coating method, curtain coating method, etc. Can be adopted.

  In addition, the photosensitive layer of the single-layer type electrophotographic photosensitive member is prepared by applying a solution obtained by dispersing or dissolving a silyl group-containing polycarbonate resin used in the formation of the charge generation material, charge transport material, additive, and binder resin in a solvent. After the coating on the substrate, the polycarbonate resin is subjected to a crosslinking treatment. In this case, the preparation of the coating liquid, its coating method, additives, and the like are the same as those in the formation of the photosensitive layer of the above-described multilayer electrophotographic photosensitive member. Further, in this single layer type electrophotographic photosensitive member, an undercoat layer, a blocking layer, and a surface protective layer may be provided in the same manner as described above. For the formation of these layers, it is preferable to use the crosslinked polycarbonate resin of the present invention.

  The thickness of the photosensitive layer in the single-layer type electrophotographic photosensitive member is 5 to 100 microns, preferably 8 to 50 microns. If the thickness is less than 5 microns, the initial potential tends to be low. The characteristics may deteriorate. The ratio of charge generating material: binder resin used in the production of this single layer type electrophotographic photosensitive member is 1:99 to 30:70, preferably 3:97 to 15:85 by weight. The ratio of the charge transport material: binder resin is 10:90 to 80:20, preferably 30:70 to 70:30, by weight.

  Next, the silyl group-containing polycarbonate resin in the coating film formed by coating as described above is subjected to crosslinking treatment. In this case, the treatment temperature is 50 to 160 ° C., preferably 60 to 140 ° C. The time is 1 second to 24 hours, preferably 1 minute to 12 hours. The electrophotographic photoreceptor of the present invention thus obtained is a photoreceptor having excellent wear resistance and maintaining excellent printing durability and electrophotographic characteristics over a long period of time. It is suitably used in various electrophotographic fields such as color, full color; analog, digital) printers (lasers, LEDs, liquid crystal shutters), facsimiles, plate-making machines and the like.

  When the electrophotographic photosensitive member of the present invention is used, corona discharge (corotron, scorotron), contact charging (charging roll, charging brush) or the like is used for charging. For the exposure, any of a halogen lamp, a fluorescent lamp, a laser (semiconductor, He—Ne), an LED, and a photoreceptor internal exposure method may be adopted. For the development, dry development methods such as cascade development, two-component magnetic brush development, one-component insulating toner development, and one-component conductive toner development are used. For transfer, electrostatic transfer methods such as corona transfer, roller transfer, and belt transfer, pressure transfer methods, and adhesive transfer methods are used. For fixing, heat roller fixing, radiant flash fixing, open fixing, pressure fixing, or the like is used. Furthermore, brush cleaner, magnetic brush cleaner, electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, etc. are used for cleaning and static elimination.

Hereinafter, the present invention will be described more specifically with reference to examples.
Example 1
(1) Production of polycarbonate resin To a solution of 74 g of 2,2-bis (4-hydroxyphenyl) propane dissolved in 550 ml of a 6 wt% aqueous sodium hydroxide solution, 250 ml of methylene chloride was added and stirred. Under cooling, phosgene gas was blown into the solution at a rate of 950 ml / min for 15 minutes. Then, the reaction solution was allowed to stand to separate the organic layer, and a methylene chloride solution of a polycarbonate oligomer having a polymerization degree of 2 to 4 and a molecular end of a chloroformate group was obtained.

  Methylene chloride was added to 200 ml of this methylene chloride solution of the polycarbonate oligomer to make a total volume of 450 ml, and then 20.6 g of 2,2-bis (3-allyl-4-hydroxyphenyl) bropan was added to 8 wt. The mixture was mixed with 150 ml of an aqueous sodium hydroxide solution having a concentration of 1%, and 2.0 g of p-tert-butylphenol was added as a molecular weight regulator. Next, while vigorously stirring the mixed solution, 2 ml of a 7 wt% aqueous triethylamine solution was added as a catalyst and reacted at 28 ° C. with stirring for 1.5 hours. After completion of the reaction, the reaction product is diluted with 1 liter of methylene chloride, then twice with 1.5 liters of water, once with 1 liter of 0.01N hydrochloric acid, and then twice with 1 liter of water in this order. After washing, the organic layer was poured into methanol, and the precipitated solid was filtered and dried to obtain a polycarbonate resin.

With respect to the polycarbonate resin obtained above, the reduced viscosity [ηsp / c] measured at 20 ° C. in a 0.5 g / deciliter solution containing methylene chloride as a solvent (measured under the same conditions in the following examples) was 0 .89 deciliter / g. The reduced viscosity was measured with an automatic viscosity Ubbelohde improved viscometer (RM type) using an automatic viscosity measuring device VMR-042 manufactured by Rouai Co., Ltd. Further, in the ¹ H-NMR spectrum measured for this polycarbonate resin, absorption peaks based on allyl groups were observed at 3.5 ppm and 5.1 ppm, and absorption peaks based on wholly aromatic were observed at 7-8 ppm, From these intensity ratios, [a] a repeating unit derived from 2,2-bis (4-hydroxyphenyl) propane and [b] derived from 2,2-bis (3-allyl-4-hydroxyphenyl) propane As a result of calculating the copolymer composition with the repeating unit, it was [a]: [b] = 0.85: 0.15.

(2) Production of silyl group-containing polycarbonate resin Next, 0.5 g of the polycarbonate resin obtained here and 0.097 g of methyldiethoxysilane as a silicon compound were dissolved in 20 ml of deuterated chloroform distilled just before use to prepare a catalyst. As a solution, 0.014 g of a platinum-1,3-divinyltetramethyldisiloxane complex in xylene (concentration: 5% by weight) was added and reacted at room temperature with stirring for 1 hour. The polymer obtained here was measured for ¹ H-NMR spectrum, and compared with the measurement results before this reaction, absorption peaks (3.5 ppm and 5.1 ppm) based on the allyl group disappeared. Absorption peaks based on ethoxy groups were observed at 1.2 ppm and 3.7 ppm. Therefore, this polymer was recognized as a silyl group-containing polycarbonate resin having the following chemical structure.

(3) Production of crosslinked polycarbonate resin 0.5 g of the allyl group-containing polycarbonate resin obtained in (1) above and 0.097 g of methyldiethoxysilane as a silicon compound are dissolved in 5 ml of methylene chloride, and platinum-cyclomethyl is used as a catalyst. After adding 0.002 g of a terminal divinylpolydimethylsiloxane solution having a concentration of 5% by weight of a vinylsiloxane complex, this was cast on a polyethylene terephthalate film with an applicator. Next, the cast film was air-dried for 1 hour, reacted at 120 ° C. at normal pressure for 2 hours, and further dried at 120 ° C. and 1 mmHg for 12 hours to perform hydrosilylation and dehydration condensation. A polycarbonate resin film was obtained. This crosslinked polycarbonate resin had the following chemical structure.

(4) Evaluation of cross-linked polycarbonate resin The cross-linked polycarbonate resin film obtained in (3) above was completely insoluble as a result of examining the presence or absence of solubility in methylene chloride at 20 ° C. Next, for this crosslinked polycarbonate resin film, the light transmittance of visible light is measured in order to evaluate its transparency, and the abrasion resistance tester NUS-ISO-3 manufactured by Suga Test Instruments Co., Ltd. is used. A sex evaluation test was conducted. The condition for the abrasion test was as follows: the amount of weight loss of the sample after the sample was reciprocated 2000 times on a worn paper (made by Suga Test Instruments Co., Ltd .; containing alumina particles with a particle size of 3 microns) subjected to a load of 500 g. The method of measuring was adopted. These results are shown in Table 1. In the column of transparency in Table 1, those marked with ◯ indicate that the light transmittance in the entire wavelength range of 350 to 600 nm was 90% or more, and marked with x. Some indicate that there was a wavelength region in which the light transmittance was less than 90% in the wavelength region of 350 to 600 nm.

Example 2
(1) Production of polycarbonate resin Instead of 2,2-bis (3-allyl-4-hydroxyphenyl) propane used in Example 1, 17.8 g of 3,3′-diallyl-4,4′-dihydroxybiphenyl A polycarbonate resin was obtained in the same manner as in Example 1 except that was used. The reduced viscosity [ηsp / c] of the obtained polycarbonate resin was 0.86 deciliter / g. In addition, as a result of measuring ¹ H-NMR spectrum, from the intensity ratio of the absorption peak based on 3.5 ppm and 5.1 ppm allyl group and the absorption peak based on 7-8 ppm total aromatic hydrogen, As a result of calculating the copolymer composition, [a] a repeating unit derived from 2,2-bis (4-hydroxyphenyl) propane and [b] derived from 3,3′-diallyl-4,4′-dihydroxybiphenyl. The repeating unit was [a]: [b] = 0.85: 0.15.

(2) Production of Silyl Group-Containing Polycarbonate Resin Next, a silyl group-containing polycarbonate resin was produced in the same manner as (2) of Example 1 for this polycarbonate resin. This was found to have the following chemical structure.

(3) Production of cross-linked polycarbonate resin The allyl group-containing polycarbonate resin obtained in (1) was treated in the same manner as in (1) of Example 1 to obtain a cross-linked polycarbonate resin. This had the following chemical structure.

(4) Evaluation of crosslinked polycarbonate The crosslinked polycarbonate resin obtained in the above (3) was completely insoluble in methylene chloride at 20 ° C. Further, this resin was also evaluated for transparency and wear resistance in the same manner as in Example 1 (4). The results are shown in Table 1.

Example 3
(1) Production of polycarbonate resin In place of 2,2-bis (4-hydroxyphenyl) propane used in Example 1, 87 g of 1,1-bis (4-hydroxyphenyl) cyclohexane was used and 2,2-bis The same procedure as in Example 1 was conducted except that 30.7 g of 9,9-bis (3-allyl-4-hydroxy-5-methylphenyl) fluorene was used instead of (3-allyl-4-hydroxyphenyl) propane. Thus, a polycarbonate resin was obtained. The polycarbonate resin obtained here had a reduced viscosity [ηsp / c] of 0.85 deciliter / g. Further, as a result of measuring the ¹ H-NMR spectrum, it was found that the polycarbonate resin was found to have a coherence from the intensity ratio of the absorption peak based on 3.5 ppm and 5.1 ppm allyl groups and the absorption peak based on 7-8 ppm total aromatic hydrogen. As a result of calculating the polymerization composition, [a] a repeating unit derived from 1,1-bis (4-hydroxyphenyl) cyclohexane and [b] 9,9-bis (3-allyl-4-hydroxy-5-methylphenyl) ) The repeating unit derived from fluorene was [a]: [b] = 0.80: 0.20.

(2) Production of silyl group-containing polycarbonate resin Next, a silyl group-containing polycarbonate resin was produced in the same manner as (2) of Example 1 for this polycarbonate resin. This was found to have the following chemical structure.

(3) Production of cross-linked polycarbonate resin The allyl group-containing polycarbonate resin obtained in (1) was treated in the same manner as in (1) of Example 1 to obtain a cross-linked polycarbonate resin. This had the following chemical structure.

(4) Evaluation of crosslinked polycarbonate The crosslinked polycarbonate resin obtained in the above (3) was completely insoluble in methylene chloride at 20 ° C. Further, this resin was also evaluated for transparency and wear resistance in the same manner as in Example 1 (4). The results are shown in Table 1.

Example 4
(1) Production of polycarbonate resin In place of 2,2-bis (4-hydroxyphenyl) propane used in Example 1, 83 g of 2,2-bis (3-methyl-4-hydroxyphenyl) propane was used. Instead of 2-bis (3-allyl-4-hydroxyphenyl) propane, 12.8 g of 1,1-bis (4-hydroxyphenyl) -1-phenylethane and 2,7-dihydroxy-3,6-diallylnaphthalene A polycarbonate resin was obtained in the same manner as in Example 1 except that 5.5 g was used. The polycarbonate resin obtained here had a reduced viscosity [ηsp / c] of 0.83 deciliter / g. Moreover, as a result of measuring a ¹ H-NMR spectrum, it was based on absorption peaks based on 3.5 ppm and 5.1 ppm allyl groups and 1.7 ppm 2,2-bis (3-methyl-4-hydroxyphenyl) propane. As a result of calculating the copolymer composition of this polycarbonate resin from the absorption peak and the intensity ratio of the absorption peak based on 7 to 8 ppm of total aromatic hydrogen, [a] 2,2-bis (3-methyl-4-hydroxyphenyl) A repeating unit derived from propane, a repeating unit derived from [b] 1,1-bis (4-hydroxyphenyl) -1-phenylethane, and [c] 2,7-dihydroxy-3,6-diallylnaphthalene. The derived repeating unit was [a]: [b]: [c] = 0.85: 0.10: 0.05.

(2) Production of Silyl Group-Containing Polycarbonate Resin Next, a silyl group-containing polycarbonate resin was produced in the same manner as (2) of Example 1 for this polycarbonate resin. This was found to have the following chemical structure.

(3) Production of cross-linked polycarbonate resin The allyl group-containing polycarbonate resin obtained in (1) was treated in the same manner as in (1) of Example 1 to obtain a cross-linked polycarbonate resin. This had the following chemical structure.

(4) Evaluation of crosslinked polycarbonate The crosslinked polycarbonate resin obtained in the above (3) was completely insoluble in methylene chloride at 20 ° C. Further, this resin was also evaluated for transparency and wear resistance in the same manner as in Example 1 (4). The results are shown in Table 1.

Example 5
(1) Production of polycarbonate resin 1,1,1,3,3,3-hexafluoro-2,2-bis (4 instead of 2,2-bis (4-hydroxyphenyl) propane used in Example 1 -Hydroxyphenyl) propane 109 g, instead of 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenynyl) propane 6.5 g and 1 , 1-bis (3-allyl-4-hydroxyphenyl) cyclohexane 17.4 g was used in the same manner as in Example 1 to obtain a polycarbonate resin. The polycarbonate resin obtained here had a reduced viscosity [ηsp / c] of 0.78 deciliter / g. Moreover, as a result of measuring a ¹ H-NMR spectrum, it was based on absorption peaks based on 3.5 ppm and 5.1 ppm allyl groups, and 6.8 ppm 2,2-bis (3-phenyl-4-hydroxyphenyl) propane. As a result of calculating the copolymer composition of this polycarbonate resin from the absorption peak and the intensity ratio of the absorption peak based on 7 to 8 ppm of total aromatic hydrogen, [a] 1,1,1,3,3,3-hexafluoro was calculated. A repeating unit derived from -2,2-bis (4-hydroxyphenyl) propane, a repeating unit derived from [b] 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, and [c] 1 The repeating unit derived from 1,1-bis (3-allyl-4-hydroxyphenyl) cyclohexane is [a]: [b]: [c] = 0.80: 0.05: It was .15. (2) Production of silyl group-containing polycarbonate resin Next, a silyl group-containing polycarbonate resin was produced in the same manner as (2) of Example 1 for this polycarbonate resin. This was found to have the following chemical structure.

(3) Production of cross-linked polycarbonate resin The allyl group-containing polycarbonate resin obtained in (1) was treated in the same manner as in (1) of Example 1 to obtain a cross-linked polycarbonate resin. This had the following chemical structure.

(4) Evaluation of crosslinked polycarbonate The crosslinked polycarbonate resin obtained in the above (3) was completely insoluble in methylene chloride at 20 ° C. Further, this resin was also evaluated for transparency and wear resistance in the same manner as in Example 1 (4). The results are shown in Table 1.

Example 6
(1) Production of polycarbonate resin In place of 2,2-bis (4-hydroxyphenyl) propane used in Example 1, 73 g of 3,3-bis (4-hydroxyphenyl) -1-propene was used. A polycarbonate resin was prepared in the same manner as in Example 1 except that 23.6 g of bis (4-hydroxyphenyl) diphenylmethane and 1 g of the following silicone-modified bisphenol were used instead of bis (3-allyl-4-hydroxyphenyl) propane. Obtained.

The polycarbonate resin obtained here had a reduced viscosity [ηsp / c] of 0.85 deciliter / g. Moreover, as a result of measuring a ¹ H-NMR spectrum, from an intensity ratio of an absorption peak based on 5 ppm of vinyl group, an absorption peak based on 0 ppm of the above silicone-modified bisphenol, and an absorption peak based on 7 to 8 ppm of total aromatic hydrogen. As a result of calculating the copolymer composition of this polycarbonate resin, [a] a repeating unit derived from 3,3-bis (4-hydroxyphenyl) -1-propene and [b] bis (4-hydroxyphenyl) diphenylmethane The repeating unit derived from [c] and the repeating unit derived from the above silicone-modified bisphenol were [a]: [b]: [c] = 0.85: 0.149: 0.001.
(2) Production of Silyl Group-Containing Polycarbonate Resin Next, a silyl group-containing polycarbonate resin was produced in the same manner as (2) of Example 1 for this polycarbonate resin. This was found to have the following chemical structure.

(3) Production of cross-linked polycarbonate resin The vinyl group-containing polycarbonate resin obtained in (1) above was treated in the same manner as in (1) of Example 1 to obtain a cross-linked polycarbonate resin. This had the following chemical structure.

(4) Evaluation of crosslinked polycarbonate The crosslinked polycarbonate resin obtained in the above (3) was completely insoluble in methylene chloride at 20 ° C. Further, this resin was also evaluated for transparency and wear resistance in the same manner as in Example 1 (4). The results are shown in Table 1.

Example 7
(1) Production of polycarbonate resin In place of 2,2-bis (3-allyl-4-hydroxyphenyl) propane used in Example 1, 5.2 g of 2,2-bis (4-hydroxyphenyl) propane was used, A polycarbonate resin was obtained in the same manner as in Example 1 except that 11.8 g of 2-allylphenol was used instead of p-tert-butylphenol used as the molecular weight regulator.

The polycarbonate resin obtained here had a reduced viscosity [ηsp / c] of 0.18 deciliter / g. Moreover, as a result of measuring a ¹ H-NMR spectrum, the intensity of an absorption peak based on 3.5 ppm and 5.1 ppm allyl groups and an absorption peak based on 1.7 ppm 2,2-bis (4-hydroxyphenyl) propane As a result of calculating the copolymer composition of this polycarbonate resin from the ratio, [a] a repeating unit derived from 2,2-bis (4-hydroxyphenyl) propane, and [b] a repeating unit derived from 2-allylphenol However, it was [a]: [b] = 0.82: 0.18.

(2) Production of silyl group-containing polycarbonate resin Next, a silyl group-containing polycarbonate resin was produced in the same manner as (2) of Example 1 for this polycarbonate resin. This was found to have the following chemical structure.

(3) Production of cross-linked polycarbonate resin The allyl group-containing polycarbonate resin obtained in (1) was treated in the same manner as in (1) of Example 1 to obtain a cross-linked polycarbonate resin. This had the following chemical structure.

(4) Evaluation of crosslinked polycarbonate The crosslinked polycarbonate resin obtained in the above (3) was completely insoluble in methylene chloride at 20 ° C. Further, this resin was also evaluated for transparency and wear resistance in the same manner as in Example 1 (4). The results are shown in Table 1.

Example 8
(1) Production of polycarbonate resin In the same manner as in Example 2, a polycarbonate resin having the same chemical structure as in Example 2 was produced.
(2) Production of silyl group-containing polycarbonate resin In the same manner as (2) of Example 2, except that 0.076 g of dimethylethoxysilane was reacted as a silicon compound with the polycarbonate resin obtained in (1) above. A group-containing polycarbonate resin was obtained. This had the following chemical structure.

(3) Production of crosslinked polycarbonate resin The allyl group-containing polycarbonate resin obtained in (1) above was treated in the same manner as (3) of Example 2 except that 0.076 g of dimethylethoxysilane was used as the silicon compound. Thus, a crosslinked polycarbonate resin was obtained. This had the following chemical structure.

(4) Evaluation of crosslinked polycarbonate The crosslinked polycarbonate resin obtained in the above (3) was completely insoluble in methylene chloride at 20 ° C. Further, this resin was also evaluated for transparency and wear resistance in the same manner as in Example 1 (4). The results are shown in Table 1.

Example 9
(1) Production of polycarbonate resin In the same manner as in Example 2, a polycarbonate resin having the same chemical structure as in Example 2 was produced. (2) Production of Silyl Group-Containing Polycarbonate Resin Similar to (2) of Example 2 except that the polycarbonate resin obtained in (1) above was reacted with 0.215 g of tris (trimethylsiloxy) silane as a silicon compound. Thus, a silyl group-containing polycarbonate resin was obtained. This had the following chemical structure.

(3) Production of crosslinked polycarbonate resin Same as (3) of Example 2 except that the allyl group-containing polycarbonate resin obtained in (1) above was changed to 0.215 g of tris (trimethylsiloxy) silane as a silicon compound. To obtain a crosslinked polycarbonate resin. This had the following chemical structure.

(4) Evaluation of crosslinked polycarbonate The crosslinked polycarbonate resin obtained in the above (3) was completely insoluble in methylene chloride at 20 ° C. Further, this resin was also evaluated for transparency and wear resistance in the same manner as in Example 1 (4). The results are shown in Table 1.

Example 10
(1) Production of polycarbonate resin In the same manner as in Example 2, a polycarbonate resin having the same chemical structure as in Example 2 was produced.
(2) Production of Silyl Group-Containing Polycarbonate Resin In the same manner as (2) of Example 2, except that 0.119 g of triethoxysilane was reacted as a silicon compound with the polycarbonate resin obtained in (1) above. A group-containing polycarbonate resin was obtained. This had the following chemical structure.

(3) Production of cross-linked polycarbonate resin The treatment was performed in the same manner as (3) of Example 2 except that the allyl group-containing polycarbonate resin obtained in (1) above was changed to 0.119 g of triethoxysilane as a silicon compound. Thus, a crosslinked polycarbonate resin was obtained. This had the following chemical structure.

(4) Evaluation of cross-linked polycarbonate The cross-linked polycarbonate resin obtained in the above (3) was completely insoluble in methylene chloride at 20 ° C. Further, this resin was also evaluated for transparency and wear resistance in the same manner as in Example 1 (4). The results are shown in Table 1.

Comparative Example 1
After the polycarbonate resin was produced and crosslinked by the same method as that described in JP-A-4-29314, the obtained crosslinked polycarbonate resin was evaluated for transparency and abrasion resistance. That is, 53.7 parts by weight of an aqueous solution of sodium hydroxide having a concentration of 48.5% by weight and water 230.8 while flowing dry nitrogen gas through a three-necked flask equipped with a stirrer, a thermometer, a gas introduction tube and a reflux condenser. Part by weight, 31.4 parts by weight of 2,2-bis (3-allyl-4-humanoxyphenyl) propane, and 27.3 parts by weight of 1,1-bis (4-hydroxyphenyl) cyclohexane were charged and dissolved. The solution was cooled to 20 ° C., and 26.2 parts by weight of phosgene gas was gradually introduced over 1 hour while stirring. Next, 8.4 parts by weight of a 48.5% by weight sodium hydroxide aqueous solution was added, and 0.61 part by weight of p-tert-butylphenol was added as a reaction stopper, and the polymerization reaction was continued at 30 ° C. for 1 hour. After completion of the reaction, the methylene chloride layer was separated and acidified with hydrochloric acid, and then washed with water to remove dissolved salts. Thereafter, methylene chloride was evaporated to obtain a solid. The reduced viscosity of this polymer was 1.2 deciliter / g.

  Next, 0.5 g of this polycarbonate resin, 0.05 g of pentaerythritol tetrakis (3-mercaptopropionate) and 0.005 g of Irgacure 907 (manufactured by Ciba Geigy) as a crosslinking agent are dissolved in 5 ml of methylene chloride. It was. This solution was cast on a polyethylene terephthalate film having a thickness of 250 microns using an applicator. Furthermore, after air-drying this for 1 hour, it dried at 120 degreeC and 1 mmHg for 12 hours. The obtained sample was irradiated with an 80 w / cm @ 2 high pressure mercury lamp for 5 seconds to obtain a crosslinked polycarbonate resin film. The crosslinked polycarbonate resin thus obtained was evaluated for transparency and abrasion resistance in the same manner as in Example 1 (4). The results are shown in Table 1.

Comparative Example 2
5 ml of methylene chloride was added to and dissolved in 0.5 g of the polycarbonate resin obtained in Comparative Example 1 before the crosslinking treatment and 0.025 g of azobisisobutyronitrile to prepare a coating solution. This coating solution was cast on a polyethylene terephthalate film having a thickness of 250 microns using an applicator. Next, this was heated at 140 ° C. for 1 hour to carry out a crosslinking reaction, and then dried at 120 ° C. and 1 mmHg for 12 hours to obtain a crosslinked polycarbonate resin film.

  The crosslinked polycarbonate resin thus obtained was evaluated for transparency and abrasion resistance in the same manner as in Example 1 (4). The results are shown in Table 1.

Comparative Example 3
After dissolving 0.5 g of a polycarbonate resin having a reduced viscosity of 0.77 deciliter / g produced using 2,2-bis (4-hydroxyphenyl) propane as a raw material dihydric phenol in 5 ml of methylene chloride, polyethylene A cast film was formed on the terephthalate film in the same manner as (3) of Example 1. The crosslinked polycarbonate resin thus obtained was evaluated for transparency and abrasion resistance in the same manner as in Example 1 (4). The results are shown in Table 1.

Example 11
Using a polyethylene terephthalate resin film deposited with aluminum metal as the conductive substrate, a charge generating layer and a charge transport layer were sequentially laminated on the surface to produce an electrophotographic photoreceptor having a laminated photosensitive layer. 0.5 parts by weight of oxotitanium phthalocyanine was used as the charge generating substance, and 0.5 parts by weight of butyral resin was used as the binder resin. These were added to 19 parts by weight of methylene chloride as a solvent, dispersed by a ball mill, and this dispersion was applied to the surface of the conductive substrate film by a bar coater and dried to give a film thickness of about 0.5 microns. A charge generation layer was formed.

  Next, 1 part by weight of 4-dibenzylamino-2-methylbenzaldehyde-1,1-diphenylhydrazone is used as the charge transport material, and the allyl group-containing polycarbonate resin obtained in (1) of Example 1 is used as the binder resin. 1 part by weight, 0.194 part by weight of methyldiethoxysilane and 0.004 part by weight of platinum-cyclomethylvinylsiloxane (concentration 5% by weight) as a catalyst were added to 13 parts by weight of methylene chloride as a solvent. Dissolved to give a coating solution. This coating solution was applied onto the charge generation layer with an applicator and dried. Next, the coating film was subjected to a heat treatment at 120 ° C. and normal pressure for 10 hours to carry out a crosslinking reaction of the silyl group-containing polycarbonate resin in the coating film. In this way, a charge transport layer having a thickness of about 20 microns was formed. In the process of forming this charge transport layer, no decrease in transparency due to crystallization of the polycarbonate resin was observed until the coating liquid was applied, dried and crosslinked.

Subsequently, the electrophotographic characteristics of the electrophotographic photoreceptor thus obtained were evaluated. As the evaluation test apparatus, using an electrostatic charge test apparatus EPA-8100 manufactured by Kawaguchi Electric Manufacturing Co., Ltd., an initial surface potential when performing corona discharge at -6 kv, a residual potential 5 seconds after irradiation of 10 lux light, The half-exposure amount (E _1/2 ) was measured. The measurement results are shown in Table 2.

  Further, in order to evaluate the durability of the electrophotographic photoreceptor, a wear resistance test of the photosensitive layer was performed. As a testing machine, Suga abrasion testing machine NUS-ISO-3 type manufactured by Suga Testing Machine Co., Ltd. was used, and as a condition for the abrasion test, worn paper (containing alumina particles having a particle diameter of 3 μm) loaded with 500 g was used. The amount of weight loss was measured by reciprocating 2000 times in contact with the surface of the photosensitive layer. The results are shown in Table 2.

Examples 12-20
Example 11 is the same as Example 11 except that the allyl group-containing polycarbonate resin described in Examples 2 to 10 was used instead of the allyl group-containing polycarbonate resin described in Example 1 as the binder resin for the charge transport layer. In the same manner as above, an electrophotographic photoreceptor was produced and evaluated. These evaluation results are shown in Table 2.

Comparative Example 4
The same procedure as in Example 11 was used except that a polycarbonate resin (reduced viscosity; 0.77 deciliter / g) made from 2,2-bis (4-hydroxyphenyl) propane was used as the binder resin for the charge transport layer. An electrophotographic photoreceptor was produced and evaluated. The results are shown in Table 2.

Comparative Example 5
As a binder resin for the charge transport layer, 1,1-bis (4-hydroxyphenyl) cyclohexane and 2,2-bis (3--) produced by the same method as in Examples described in JP-A-4-291348. A polycarbonate resin having a molar ratio of repeating units derived from allyl-4-humanoxyphenyl) propane of 1: 1 and a reduced viscosity of 1.2 deciliter / g was used, and pentaerythritol tetrakis ( 3-mercaptopropionate) and a photopolymerization initiator (manufactured by Ciba-Geigy; Irgacure-907) are dissolved in a mixed solvent of monochlorobenzene and dichlorobenzene, and a coating film is formed by an immersion method. did.

  Then, after the coating film was dried, the electrophotographic photosensitive layer was formed in the same manner as in Example 15 except that the charge transport layer was formed by crosslinking the polycarbonate resin in the coating film by light irradiation with a high-pressure mercury lamp. The body was manufactured and evaluated. The results are shown in Table 2.

Claims (11)

The repeating unit (1) represented by the following general formula [1] and the repeating unit (2) represented by the general formula [2] are replaced with the repeating unit (1) and the repeating unit (2) with respect to the total of the repeating unit (2) ( A polycarbonate resin having a molar ratio [(1) / ((1) + (2))] of 1) of 0.001 to 1.

[In the formula [1], Ar ¹ is represented by the following [1a], [1b] or [1c].

{X ¹ in Formula [1a] is a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —CR ³ R ⁴ — (where R ³ and R ⁴ are Each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a trifluoromethyl group, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms), a substituted or unsubstituted cycloalkylidene having 5 to 12 carbon atoms Group, substituted or unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms, 9,9-fluorenylidene group, 1,8-menthanediyl group, 2,8-menthanediyl group, substituted or unsubstituted pyrazilidene group, carbon A substituted or unsubstituted arylene group of formula 6 to 12, or the following general formula [3],

(In Formula [3], each R ⁵ independently represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a carbon number. 1-12 alkoxy group, a C6-C12 substituted or unsubstituted aryloxy group, t is an integer of 0-6, and g is an integer of 0-200. A in the formulas [1a] to [1c] is — (CH ₂ ) _h —, —O— (CH ₂ ) _h —, —CO— (CH ₂ ) _h —, —COO— (CH ₂ ) _H — (wherein h is an integer of 0-6), FG is —SiR ⁷ _3-m —Z _m (where Z is an alkoxy group having 1 to 6 carbon atoms, aryloxy group having 6 to 12 carbon atoms or a trialkyl siloxy group or a halogen atom, R ⁷ is each independently 1 to carbon atoms Saturated or unsaturated hydrocarbon group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, m is is an integer of 1 to 3), p ^1, p ² is an integer from 0 to 4 ( Wherein p ¹ + p ² is an integer of 1 to 8, q is 1 or 2, s is an integer of 1 to 6, and R ¹ in the formulas [1a] to [1c] is Independently, hydrogen atom, halogen atom, trifluoromethyl group, alkyl group having 1 to 12 carbon atoms, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, 6 to 12 carbon atoms Or r is independently an integer of 0 to 4, and t is each independently an integer of 0 to 6. },
Ar ² in the general formula [2] is represented by the following [2a], [2b], [2c] or [2d].

(X ² , R ⁶ , r, t and g in the formulas [2a] to [2d] have the same meanings as X ¹ , R ¹ , r, t and g, respectively, and k is 0 to 6 ))] The repeating unit (1-1) represented by the following general formula (1-1) and the repeating unit (2) represented by the general formula (2) are substituted with the repeating unit (1-1) and the repeating unit (2). Polycarbonate resin having a molar ratio [(1-1) / ((1-1) + (2))] of the repeating unit (1) to the total of 0.001 to 1.

(In the formula (1-1), Ar ³ represents the following general formula [1d].

A in the formula [1d] represents — (CH ₂ ) ₃ —, and FG and Ar ² in the general formula (2) have the same meanings as FG and Ar ^{2 in} claim 1. )   A crosslinked polycarbonate resin obtained by crosslinking the polycarbonate resin according to claim 1.   3. The polycarbonate resin according to claim 1 or 2, wherein a polycarbonate compound containing an aliphatic unsaturated hydrocarbon group is reacted with a silicon compound having a hydrogen atom and a hydrolyzable group on a silicon atom. Method.   The method for producing a polycarbonate resin according to claim 4, wherein the silicon compound is a silicon compound having a hydrogen atom, a hydrolyzable group and a non-hydrolyzable group on the silicon atom. The method for producing a polycarbonate resin according to claim 4 or 5, wherein the silicon compound is a silicon compound represented by the following general formula [4].

[Z and R ⁷ in formula [4] have the same meaning as Z and R ^7, and v is an integer of 1 to 3]   An electrophotographic photosensitive member having at least a photosensitive layer on a conductive substrate, wherein the photosensitive layer contains the crosslinked polycarbonate resin according to claim 3.   The electrophotographic photoreceptor according to claim 7, wherein the crosslinked polycarbonate resin is a crosslinked polycarbonate resin obtained by crosslinking the polycarbonate resin produced by the method according to claim 5.   The electrophotographic photoreceptor according to claim 7, wherein the crosslinked polycarbonate resin is a crosslinked product of a polycarbonate resin obtained by reacting a trialkoxysilane with a polycarbonate resin containing an aliphatic unsaturated hydrocarbon group.   8. The electrophotographic photoreceptor according to claim 7, wherein the crosslinked polycarbonate resin is a crosslinked product of a polycarbonate resin obtained by reacting a tristrialkylsiloxysilane with a polycarbonate resin containing an aliphatic unsaturated hydrocarbon group.   The electrophotographic photoreceptor according to claim 7, wherein the photosensitive layer comprises a charge generation layer containing at least a charge generation material, and a charge transport layer containing at least a charge transport material and a binder resin. .