JP4630243B2 - Polycarbonate-siloxane copolymer resin, process for producing the same, electrophotographic photoreceptor and coating material - Google Patents

Description

  The present invention provides a polycarbonate-siloxane copolymer resin having excellent surface properties, a cross-linked polycarbonate-siloxane copolymer resin having improved mechanical properties such as wear resistance in a well-balanced manner, a method for producing the same, and durability containing the same. The present invention relates to an electrophotographic photosensitive member, a conductive comb roll coating material, a conductive comb roll, a film, and a sheet excellent in the above.

  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.

  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 photosensitive member, operations such as corona charging, toner development, transfer to paper, and cleaning with a blade are repeatedly performed on the surface of the photosensitive layer. External force is applied. 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, foreign substances such as toner and paper dust are not used in the case of using a conventional polycarbonate resin made of 2,2-bis (4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) cyclohexane. So-called filming phenomenon occurs on the photosensitive member, and the electrophotographic photosensitive member has not been sufficiently satisfied in terms of durability.

  Therefore, in order to reduce the surface energy of the polycarbonate resin and improve the stain resistance, polycarbonate resins copolymerized with polydimethylsiloxane have been proposed (JP-A-2-240658 and JP-A-5-188616). Yes. By the way, these polycarbonate copolymer resins are effective in suppressing the above filming phenomenon, but because of their low cohesive energy density, which is an inherent property of polydimethylsiloxane, in terms of mechanical strength, ordinary polycarbonate resins are used. In comparison with the above, there is a problem that the durability is not sufficiently satisfactory due to the significant decrease in the wear resistance, in particular.

  In addition to this electrophotographic photosensitive member, a polycarbonate resin copolymerized with polydimethylsiloxane is used as a surface protective coating material for various conductive rolls (contact charging roll, transfer roll, development roll) used in the electrophotographic process. Has been proposed (Japanese Patent Laid-Open No. 7-230201). However, even in this case, the effect of preventing the adhesion of foreign matters to the surface of the conductive roll coated with the surface protective coating is great. However, since the mechanical strength is insufficient, the wear of the surface protective layer is caused by long-term use. There is a problem in that image deterioration occurs due to damage and scratches.

  The present invention has been made based on the above circumstances, and has excellent contamination resistance and at the same time high wear resistance, and is suitable as a material constituting a member of an electronic device such as an electrophotographic process. The object is to provide a type polycarbonate-siloxane copolymer resin and a method for producing the same, and a durable electrophotographic photosensitive member, a coating material for a conductive roll, a conductive rubber roll, a film, and a sheet using the copolymer resin. To do.

  As a result of intensive studies to solve the above problems, the present inventor has found that a decrease in mechanical strength in a polycarbonate resin copolymerized with a conventionally known polydimethylsiloxane is entangled with a polysiloxane moiety having a low cohesive energy density. Focusing on the fact that it originates from the lowering, the siloxane parts of the polycarbonate-siloxane copolymer resin are fixed by covalent bonds, that is, other polymers through the siloxane part of the polycarbonate-siloxane copolymer chain. By synthesizing a cross-linked polycarbonate-siloxane copolymer resin bonded to the siloxane portion of the chain, while maintaining the properties such as excellent mechanical strength inherent to the polycarbonate resin, We have found that it is possible to impart wear resistance. This has led to the completion of the present invention based on the Luo knowledge.

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 combined with the repeating unit (1) and the repeating unit (2). A polycarbonate-siloxane copolymer resin containing a component having a molar ratio of the repeating unit (1) to ([1] / ((1) + (2))] of 0.0001 to 1.

[R ¹ in Formula [1] is each independently 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. An alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, a is an integer of 1 to 200, b is an integer of 0 to 200, and X ¹ is —O— or The following general formula [3] [4],

(R ¹ in formula [3] has the same meaning as R ¹ , c is an integer from 0 to 6, d is an integer from 0 to 4, and c in formula [4] is c X ² represents —O— or the following general formula [5] [6],

(R ¹ in formula [5] has the same meaning as R ¹ , c is an integer of 0 to 6, d is an integer of 0 to 4, and c in formula [6] is c In the formula [2], Ar represents a phenylene group or the following general formulas [7a] [7b],

(Y in formula [7a] is a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —CR ² R ³ — (wherein R ² and R ³ 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), or a substituted or unsubstituted cycloalkylidene group having 5 to 12 carbon atoms. C2-C12 substituted or unsubstituted α, ω-alkylene group, 9,9-fluorenylidene group, 1,8-menthanediyl group, 2,8-menthanediyl group, substituted or unsubstituted pyrazilidene group, carbon number 6 to 12 substituted or unsubstituted arylene groups, R ¹ in the formulas [7a] and [7b] has the same meaning as R ^1, and e is an integer of 0 to 4 each independently. And f is an integer of 0 to 6). The ]
(2) The repeating unit (3) represented by the following general formula [8] and the repeating unit (2) represented by the above general formula [2] are substituted into the repeating unit (2) and the repeating unit (3). Crosslinked polycarbonate-siloxane copolymer containing a component having a molar ratio of repeating unit (3) to total [(3) / ((2) + (3))] of 0.0001 to 1 resin.

[R ¹ , X ¹ and X ² in the formula [8] have the same meaning as R ¹ , X ¹ and X ^2, and W represents the following general formulas [9a] to [9h],

(R ¹ in the formulas [9a] to [9h] has the same meaning as R ^1, and Z represents an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, and a trialkyl. A siloxy group or a halogen atom, g is an integer of 1 to 6, h is an integer of 0 to 2, i is an integer of 1 to 6, j is an integer of 1 to 100, and k is an integer of 1 to 100) Represents a group represented by ]
(3) A method for producing a crosslinked polycarbonate-siloxane copolymer resin, characterized in that a polycarbonate-siloxane copolymer resin is bonded to another copolymer chain in a repeating unit containing siloxane of the copolymer chain.
(4) In the repeating unit containing the siloxane, a carbon-carbon unsaturated bond, an alkoxysilyl group, a hydrosilyl group, or an aliphatic group in which one or more hydrogen atoms are bonded to a carbon atom adjacent to a silicon atom is selected. The method for producing a crosslinked polycarbonate-siloxane copolymer resin according to the above (3), which has at least one group and forms a bond with another copolymer chain in these groups.
(5) In the repeating unit containing the siloxane, a bond with another copolymer chain is formed by using a polycarbonate-siloxane copolymer having a methyl group and / or a vinyl group directly bonded to a silicon atom. 3) A process for producing a cross-linked polycarbonate-siloxane copolymer resin according to 3).
(6) The process for producing a crosslinked polycarbonate-siloxane copolymer resin according to (3), wherein the repeating unit containing the siloxane is bonded to another copolymer chain using a radical initiator.
(7) The said (4) or (5) description which performs the coupling | bonding with the other copolymer chain in the repeating unit containing the said siloxane using the compound which has two or more silicon-hydrogen bonds in molecular skeleton. A method for producing a cross-linked polycarbonate-siloxane copolymer resin.
(8) The aforementioned siloxane-containing repeating unit is bonded to another copolymer chain using a compound having a silicon-hydrogen bond and a group that generates a silicon-hydroxyl bond by hydrolysis in the molecular skeleton. A process for producing a crosslinked polycarbonate-siloxane copolymer resin according to 4) or (5).
(9) An electrophotographic photoreceptor having at least a photosensitive layer on a conductive substrate, wherein the photosensitive layer contains at least the cross-linked polycarbonate-siloxane copolymer resin described in (2) above. Photoconductor.
(10) The electrophotographic photosensitive member according to (9), 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.
(11) A coating liquid comprising a charge transport material and the polycarbonate-siloxane copolymer described in (1).
(12) A conductive rubber roll coating material comprising the cross-linked polycarbonate-siloxane copolymer resin.
(13) A conductive rubber roll which is coated with the conductive rubber roll coating material according to (12).
(14) The conductive rubber roll according to (13), wherein the conductive rubber roll is a contact charging roll, a transfer roll, or a developing roll.
(15) A film comprising the cross-linked polycarbonate-siloxane copolymer resin.
(16) A sheet comprising the cross-linked polycarbonate-siloxane copolymer resin.

  The cross-linked polycarbonate-siloxane copolymer resin of the present invention has excellent anti-contamination resistance and high wear resistance, and is highly useful as a material constituting an electronic device member such as an electrophotographic process. is there. In addition, since the electrophotographic photosensitive member and the conductive roll coating material, film, and sheet of the present invention all use the above-mentioned crosslinked polycarbonate-siloxane copolymer resin, they are excellent in stain resistance and abrasion resistance. A product with improved durability is obtained.

  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.

More specifically, the polycarbonate resin composed of the repeating units represented by the formulas [1] and [2] will be described in detail. R ^{1 to} R ³ represented by the formulas [1] to [9h] Examples of the 12 alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, 2-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Decyl group, undecyl group, dodecyl group, etc. are mentioned. Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, tolyl group, styryl group, biphenylyl group, naphthyl group, etc., and alkoxy having 1 to 12 carbon atoms. As the group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, 2-butoxy group, t-butoxy group Pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, etc., and substituted or unsubstituted aryloxy groups having 6 to 12 carbon atoms Examples thereof 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 having a value of 0.0001 or more, preferably in the range of 0.001 to 0.6, are preferably used. When the molar ratio is less than 0.0001, the effect of reducing the surface energy of the copolymer due to the introduction of the siloxane unit as the copolymer component is hardly 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 [η _SP / c] measured at a temperature of 20 ° C. of 0.01 to 10 deciliters / g at a concentration of 0.5 g / deciliter using methylene chloride as a solvent. . When the reduced viscosity [η _SP / c] is less than 0.01 deciliter / g, the mechanical strength is not sufficient, and when it exceeds 10 deciliter / g, the moldability may not be sufficient.

  Next, in the crosslinked polycarbonate-siloxane copolymer resin of the present invention, the unit constituting the polymer is a polymer comprising the repeating unit (3) represented by the general formula [8], or the general formula [8]. Is a copolymer composed of the repeating unit (3) represented by the formula (2) and the repeating unit (2) represented by the general formula [2], and the polymer chain has a linear, branched or cyclic structure. In addition, a special terminal structure or a special branched structure may be introduced.

  When the copolymer is composed of the repeating unit (3) and the repeating unit (2), the molar ratio of the repeating unit (3) [(3) / ((3) + (2))] is Those having a value of 0.0001 or more, preferably in the range of 0.001 to 0.6, are preferably used. When the molar ratio is less than 0.0001, the effect of reducing the surface energy of the copolymer due to the introduction of the siloxane unit as the copolymer component is hardly obtained.

  In addition to the repeating units (3) and (2), the cross-linked polycarbonate-siloxane copolymer resin includes those other than those defined by the formulas [8] and [2] as long as the object of the present invention is not impaired. It may contain a polycarbonate unit having the above structural unit or a unit having a polyester, polyurethane, polyether, or polysiloxane structure.

  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-forming compound, and a dihydric phenol and a siloxane structural unit are added in the presence of an appropriate acid binder. What is necessary is just to employ | adopt the method of making it react with the dihydroxy compound which has, or the method of manufacturing by a transesterification method using bisaryl carbonate as a carbonate ester formation compound. The dihydric phenol used here may be used singly or in combination of two or more, and the dihydroxy compound having a siloxane structural unit may be used alone or in combination of two or more. These reactions are performed in the presence of a terminal terminator and / or a branching agent as necessary.

  Examples of the dihydric phenol include 4,4′-dihydroxybiphenyl, 3,3′-difluoro-4,4′-dihydroxybiphenyl, 4,4′-dihydroxy-3,3′-dimethylbiphenyl, and 4,4. 4,4'-dihydroxybiphenyls such as' -dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'-dicyclohexylbiphenyl; bis (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-hydroxyphene) ) 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-methylphenyl) -1-phenyl Luethane, 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-hydroxy) Phenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propyl Lopan, 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-difluorophenyl) propa 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-hydroxy-5-methyl) Phenyl) 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) heptane, 2,2-bis (4 -Hydroxyphenyl) octane, 2,2-bis (4-hydroxyphenyl) nonane, 2,2-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1- Bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) 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) -3,3,5-trimethyl Bis (hydroxyphenyl) alkanes such as rhohexane; bis (4-hydroxyphenyl) ethers such as bis (4-hydroxyphenyl) ether and bis (3-fluoro-4-hydroxyphenyl) ether; bis (4-hydroxyphenyl) ) Sulfides, bis (4-hydroxyphenyl) sulfides such as bis (3-methyl-4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfoxide, bis (3-methyl-4-hydroxyphenyl) sulfoxide, etc. Bis (4-hydroxyphenyl) sulfoxides; bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-phenyl-4-hydroxyphenyl) sulfone, etc. Hydroxypheny ) Sulfones; bis (4-hydroxyphenyl) ketones such as 4,4′-dihydroxybenzophenone; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) ) Bis (hydroxyphenyl) fluorenes such as fluorene, 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene; Dihydroxy-p-terphenyls such as 4,4 "-dihydroxy-p-terphenyl; 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-diethylpyra Bis (hydroxyphenyl) pyrazines such as gin; 1,8-bis (4-hydroxyphenyl) menthane, 2,8-bis (4-hydroxyphenyl) menthane, 1,8-bis (3-methyl-4-hydroxy) Bis (hydroxyphenyl) menthanes such as phenyl) menthane and 1,8-bis (4-hydroxy-3,5-dimethylphenyl) menthane; 1,4-bis [2- (4-hydroxyphenyl) -2-propyl Bis [2- (4-hydroxyphenyl) -2-propyl] benzenes such as benzene and 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene; 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxy Dihydroxynaphthalenes such as naphthalene; dihydroxybenzenes such as resorcin, hydroquinone and catechol; polysiloxanes such as α, ω-dihydroxypolydimethylsiloxane, α, ω-bis [3- (2-hydroxyphenyl) propyl] polydimethylsiloxane And the like; 1,1,8,8-tetrahydro-1,8-dihydroxyperfluorooctane, dihydroperfluoroalkanes such as 1,1,6,6-tetrahydro-1,6-dihydroxyperfluorohexane, etc. .

  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 the 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.

  The method for producing the polycarbonate resin can be carried out in various modes. For example, a polycarbonate oligomer is produced by reacting the dihydroxy compound having the dihydric phenol and / or siloxane structural unit with phosgene, and then producing the polycarbonate oligomer. Alternatively, a method of reacting the dihydroxy compound having the dihydric phenol and / or the siloxane structural unit in the presence of a mixed solution of the solvent and an alkaline aqueous solution of an acid binder may be employed. Moreover, you may employ | adopt the method with which the dihydroxy compound and phosgene which have the said bihydric phenol and / or siloxane structural unit are made to react in the liquid mixture of the said solvent and aqueous alkali solution. 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 dihydroxy compound having a dihydric phenol and / or a siloxane structural unit (including a branching agent if necessary) is dissolved in an alkaline aqueous solution to prepare an alkaline aqueous solution of the dihydric phenol. . Subsequently, phosgene is introduced into the mixed solution of the alkaline aqueous solution and an organic solvent such as methylene chloride and reacted to synthesize a polycarbonate oligomer of a dihydroxy compound having a dihydric phenol and / or a siloxane structural unit. 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 dihydroxy compound having the dihydric phenol and / or the siloxane structural unit is added to the organic phase containing the polycarbonate oligomer thus obtained and reacted. 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, the dihydroxy compound having a dihydric phenol and / or a siloxane structural unit is preferably added 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, a method for producing a crosslinked polycarbonate-siloxane copolymer resin using the polycarbonate-siloxane copolymer resin thus obtained will be described. The raw material polycarbonate-siloxane copolymer resin used in the production of the crosslinked polycarbonate-siloxane copolymer resin has a form in which a chemical bond can be formed between the siloxane structural unit and the siloxane structural unit of another polymer chain. As long as it has a siloxane structural unit, it can be used. However, as a preferred embodiment, the siloxane structural unit has at least one hydrogen atom on a carbon atom adjacent to a vinyl group, an alkoxysilyl group, a hydrosilyl group, or a silicon atom. A polycarbonate-siloxane copolymer resin having a bonded aliphatic group, a methyl group directly bonded to a silicon atom, or a vinyl group is preferably used.

  The crosslinking method of the polycarbonate-siloxane copolymer resin is not particularly limited as long as it is a method in which siloxane structural units of a plurality of polymer chains are bonded to each other. For example, the siloxane structural unit has a vinyl group. , A method of adding a radical initiator, a method of reacting a compound having two or more silicon-hydrogen bonds in one molecule in the presence of a hydrosilylation catalyst, or a silicon atom in the presence of a hydrosilylation catalyst. A method in which a compound having a hydrolyzable group and a hydrogen atom is reacted can be suitably employed.

  In addition, for those having an alkoxysilyl group in the siloxane structural unit, a method by heating, a method by addition of an acid, a method by addition of a base, a tin compound such as dibutyl diacetyloxy tin, tin dibutyl octylate, tin dibutyl dodecylate, etc. A method of adding, a method of adding a titanium compound such as tetrapropoxy titanium or dipropoxy bis (ethyl acetoacetate) titanium, a method of adding a metal fatty acid salt, and a method of adding a metal alcoholate can be suitably employed.

  Further, in the case where the siloxane structural unit has a hydrosilyl group, a method of reacting a polycarbonate-siloxane copolymer resin having a vinyl group in the siloxane structural unit in the presence of a hydrosilylation catalyst, A method of reacting a compound having two or more carbon-carbon unsaturated bonds with can be suitably employed.

  In addition, when the siloxane structural unit has an aliphatic group in which one or more hydrogen atoms are bonded to a carbon atom adjacent to a silicon atom, a method of adding a radical initiator can be suitably employed. As the radical initiator used here, all known thermal initiators and photoinitiators can be used. An organic peroxide is preferably used as the thermal initiator. Specific examples of the compound include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide; acetyl peroxide, propionyl peroxide Oxide, isobutyryl peroxide, octanoyl peroxide, 3,3,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl Diacyl peroxides such as peroxide, acetylcyclohexanesulfonyl peroxide, t-butyl hydroperio Side, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, etc. Hydroperoxides of: di-t-butyl peroxide, t-butyl-α-cumyl peroxide, di-α-cumyl peroxide, 1,4-bis [(t-butyldioxy) isopropyl] benzene, 1,3 -Bis [(t-butyldioxy) isopropyl] benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) Dialkyl peroxides such as -3-hexyne; 1,1-bis (t-butyl -Oxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, peroxyketals such as 2,2-bis (t-butylperoxy) butane; t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyoctoate, t-butylperoxypivalate, t-butylperoxyneodecanoate, t-butylperoxy-3, 5,5-trimethylhexanoate, t-butylperoxybenzoate, di-t-butyldiperoxyphthalate, di-t-butyldiperoxyisophthalate, t-butylperoxylaurate, 2,5-dimethyl Alkyl peresters such as -2,5-bis (benzoylperoxy) hexane; bis (2-ethyl) Hexyl) peroxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, di-n-propylperoxydicarbonate, bis (methoxyisopropyl) peroxydicarbonate, bis (3-methoxybutyl) Peroxycarbonates such as peroxydicarbonate, bis (2-ethoxyethyl) peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, OO-t-butyl-O-isopropyl peroxydicarbonate Succinic acid peroxide; potassium persulfate; ammonium persulfate; potassium peroxodisulfate; ammonium peroxodisulfate; azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobis Azo compounds such as cyclohexanecarbonitrile and azobis-2-amidinopropane hydrochloride; hydrogen peroxide; redox initiator; triethylaluminum; triethylboron; diethylzinc and the like.

Photoinitiators include benzoin, benzoin methyl ether, 4,4′-bis (dimethylamino) benzophenone, 2-chloroanthracene, 2-methylanthraquinone, thioxanthone, diphenyl disulfide, dimethyldithiocarbamate, 2-methyl- 1- [4- (methylthio) phenyl] -2-monforinopropanone and the like can be mentioned. When these photoinitiators are used, the intensity of irradiation with ultraviolet rays or the like is about 1 to 100 mJ / cm ² .

As the hydrosilylation catalyst, a radical catalyst such as benzoyl peroxide or azobisisobutyronitrile, a base catalyst such as trialkylamine, or a group VIII to X transition metal complex catalyst of the periodic table may be used. it can. Among these catalyst systems, the Group VIII to Group X transition metal complex catalysts are preferably used for reasons such as the reaction yield, the small amount of side reactions, and the small amount of catalyst added. Specific examples of the Group VIII to X transition metal complex catalysts include iron catalysts such as Fe (CO) ₅ , ruthenium catalysts such as RuCl ₃ , osmium catalysts, cobalt catalysts such as Co ₂ (CO) ₈ , (Ph ₃ P) ₃ RhCl, rhodium catalyst such as [Rh (C ₂ H ₄ ) ₂ Cl] ₂ , iridium catalyst such as IrCl ₃ , nickel catalyst such as (Ph ₃ P) ₂ Ni, (Ph ₃ P) ₂ NiCl ₂ , Palladium catalysts such as (Ph ₃ P) ₄ Pd, (Ph ₃ P) ₂ PdCl ₂ , 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-divinyldisiloxane Preferred examples include a platinum catalyst such as a complex, a platinum-cyclovinylmethylsiloxane complex, a platinum carbonyl complex, and a Speier catalyst (an isopropanol solution of H ₂ PtCl ₆ .6H ₂ O).

  And the addition amount of these catalysts should just be suitably determined in consideration of the reactivity in the range of 1 wtPPM-1 wt% with respect to a vinyl group, Preferably, it is the range of 100-1000 wtPPM. If the amount of the catalyst added is less than 1 wt PPM, the reaction rate is slow and the crosslinking reaction may not proceed sufficiently. If it exceeds 1 wt%, the resulting product may be colored. Is appropriate.

  Examples of the compound having two or more silicon-hydrogen bonds in the molecule include 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,1,1,3,5,7,7. , 7-octamethyltetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,4-bis (dimethylsilyl) benzene, Preferred examples include 1,1,3,3-tetramethyldisilazane, 1,1,3,3-tetramethyldisiloxane, diphenylsilane and the like.

  Examples of the compound having a hydrolyzable group and a hydrogen atom on the silicon atom include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, tri-t-butoxysilane, methyl Diethoxysilane, dimethylethoxysilane, phenyldiethoxysilane, diphenylethoxysilane, tetrakis (trimethylsiloxy) silane, methylbis (trimethylsiloxy) silane, trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane, diphenylchlorosilane, etc. are suitable It is mentioned as a thing.

  Furthermore, compounds having two or more carbon-carbon unsaturated bonds in the molecule include divinylbenzene, diallyl carbonate, diallyl bisphenols such as diallyl bisphenol A and diallyl biphenol, polycarbonates synthesized from diallyl bisphenols, and diallyl bisphenol. Preferred examples include polyesters synthesized from styrene, polyethers synthesized from diallyl bisphenols, polyepoxides synthesized from diallyl bisphenols, polyformal resins synthesized from diallyl bisphenols, and polyvinylmethylsiloxane.

  As reaction conditions for carrying out the crosslinking reaction of the polycarbonate-siloxane copolymer resin, the reaction temperature 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 crosslinked polycarbonate-siloxane copolymer resin thus obtained is suitable for a material that requires high transparency because it retains high transparency. In addition, it has excellent mechanical properties such as heat resistance, impact resistance, and wear resistance, as well as electrical insulation, so electrical, electronic, and optical devices that are required to have these properties are also required. It can be used as a highly useful material in a wide range of industrial fields such as components and parts such as equipment, automobile parts, coating materials for metal or woodwork products, and paints. 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 cross-linked polycarbonate-siloxane copolymer resin. Is.

  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 type polycarbonate-siloxane copolymer 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 cross-linked polycarbonate-siloxane copolymer resin is used as a binder resin, this cross-linkable polycarbonate-siloxane copolymer resin may be used alone or in combination of two or more. Moreover, it may be used in combination with other resin components such as other polycarbonate resins as long as the object of the present invention is not impaired as desired.

  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 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-siloxane copolymer 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 a polycarbonate-siloxane copolymer resin or a crosslinking catalyst before crosslinking in the present invention, A method of applying a coating solution dispersed or dissolved in a suitable solvent together with a crosslinking compound and the like onto a predetermined base layer and drying the coating solution is used. The blending ratio of the charge transport material used for forming the charge transport layer and the polycarbonate-siloxane copolymer resin is preferably 20:80 to 80:20, more preferably 30:70 to 70:30, by weight.

  In this charge transport layer, the above-mentioned cross-linked polycarbonate-siloxane copolymer resin can be used alone or in combination of two or more. In addition, the resins mentioned as binder resins used for the charge generation layer can be used in combination with the cross-linked polycarbonate-siloxane copolymer 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 cross-linked polycarbonate-siloxane copolymer 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. The cross-linked polycarbonate-siloxane copolymer resin of the present invention may be used. 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 cross-linked polycarbonate-siloxane copolymer 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'-dinini 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, merit acid, etc. Masui. 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, the charge transport material, the additive, the uncrosslinked polycarbonate-siloxane copolymer resin and the crosslinking catalyst used for forming the binder resin are dispersed in a solvent. A form in which a coating solution prepared by dissolution is prepared, and this is coated on, for example, the charge generation layer serving as a predetermined base, and a cross-linked polycarbonate-siloxane copolymer resin coexists with a charge transport material as a binder resin The charge transport layer is formed.

  Here, regarding the crosslinking method using a hydrogen atom on a silicon atom and a compound having a group capable of forming a silicon-hydroxyl bond by hydrolysis, the curing catalyst may be added either in the coating solution or not. You may add this, after forming a charge transport layer, without adding in a 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 includes the charge generation material, the charge transport material, the additive, the uncrosslinked polycarbonate-siloxane copolymer resin used for forming the binder resin, the crosslinking catalyst, and the crosslinking compound. After a solution obtained by dispersing or dissolving in a solvent is applied onto a substrate as a predetermined base, the polycarbonate-siloxane copolymer resin is crosslinked. In this case, the preparation of the coating liquid, the coating method, additives, and the like are the same as those in the formation of the photosensitive layer of the 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-siloxane copolymer 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 crosslinking treatment of the uncrosslinked polycarbonate-siloxane copolymer resin in the coating film thus formed is performed. The treatment conditions in this case depend on the chemical structure of the copolymer and the type of crosslinking catalyst. Thus, the above-mentioned crosslinking treatment conditions may be selected. 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.

  Also, the conductive rubber roll coating material of the present invention is a conductive rubber roll such as a charging roll used for charging the electrophotographic photosensitive member, a transfer roll used in the roller transfer method, and a developing roll used in the developing step. It is a coating material for forming the surface protective layer, and contains the cross-linked polycarbonate-siloxane copolymer resin.

  Since this coating material is required to be composed of a material having excellent contamination resistance and mechanical properties, particularly wear resistance, the cross-linked polycarbonate-siloxane copolymer resin should be used as the base material. Thus, such a request can be met. In the present invention, the composition used for forming the surface protective layer is composed of the cross-linked polycarbonate-siloxane copolymer resin and a conductive substance. The conductive material is used to reduce the electrical resistance of the surface protective layer and prevent dielectric breakdown of the photoreceptor and image defects associated therewith. As the conductive substance, for example, a conductive polymer, conductive inorganic particles, metal powder, and the like are preferably used. Examples of the conductive polymer include polyacetylene, polypyrrole, and polythiophene. Examples of the conductive inorganic particles include particles such as titania, zinc oxide, indium oxide-tin oxide mixture, copper sulfide, carbon black, and graphite. Furthermore, examples of the metal powder include aluminum powder, iron powder, and copper powder.

  Among these conductive materials, carbon black is particularly preferable, and super conductive furnace black, conductive furnace black, extra conductive furnace black, super ablation furnace black, and the like are particularly preferably used. These carbon blacks have an average particle size of 10 to 100 nanometers, preferably 20 to 50 nanometers.

  The blending ratio of both components constituting the coating material is 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, of the conductive material with respect to 100 parts by weight of the cross-linked polycarbonate-siloxane copolymer resin. Part. When the blending ratio of the conductive material is less than 0.1 parts by weight, the electrical resistance value of the surface protective layer may not be sufficiently lowered. When the proportion exceeds 40 parts by weight, the elastic modulus of the surface protective layer is not obtained. Because it becomes too high. Even when the conductive material is within the above range, the conductive material may be contained in a relatively small amount. If the applied voltage during charging is low, the conductivity of the surface protective layer may be low. When the applied voltage is increased, sufficient conductivity can be obtained.

  In the present invention, there is no particular limitation on the method for adjusting the composition comprising the conductive material used for forming the surface protective layer. For example, a method of mixing the non-crosslinked and / or cross-linked polycarbonate-siloxane copolymer resin powder and a conductive material, and mixing and kneading the melt of the non-crosslinked polycarbonate-siloxane copolymer resin and a conductive material. A melt kneading method or a method in which the solvent is appropriately removed after the conductive substance is dispersed in a solution in which the uncrosslinked polycarbonate-siloxane copolymer resin is dissolved in a solvent is preferably used. In particular, in order to uniformly disperse the conductive substance in the composition, a method of dispersing the conductive substance in the above polycarbonate-siloxane copolymer resin solution is preferable. At that time, after mixing the solution of the polycarbonate-siloxane copolymer resin and the conductive material, the conductive material can be more uniformly dispersed by further irradiating with ultrasonic waves.

If desired, additives such as reinforcing materials, fillers, stabilizers, ultraviolet absorbers, antistatic agents, lubricants, mold release agents, dyes, pigments, and flame retardants can be blended with the above composition. The conductive rubber roll that is coated with the coating material of the present invention can be used in various forms. For example, a conductive material is blended on a metal core rod such as stainless steel, copper, or iron. Thus, a conductive elastic layer made of rubber or synthetic resin imparted with conductivity is formed into a roll shape by dip coating or spray coating. As the conductive material used as a constituent component of the conductive elastic layer, a material using a conductive polymer, conductive inorganic particles, metal powder, or the like is preferable. The conductive substance added here is preferably the same substance as the conductive substance added to the coating material. Examples of the conductive polymer include polyacetylene, polypyrrole, and polythiophene, and conductive inorganic substances. As the particles, titania, zinc oxide, indium oxide-tin oxide mixture, copper sulfide, carbon black, graphite and the like are preferable, and as the metal powder, aluminum powder, iron powder, copper powder and the like are preferable. The conductive elastic layer of the conductive rubber roll preferably has a volume resistivity smaller than that of the surface protective layer, and is usually adjusted to 10 ⁵ to 10 ¹⁰ Ω · cm. Preferably used.

  Next, for the method for forming the surface protective layer, the uncrosslinked polycarbonate-siloxane copolymer resin, the crosslinking catalyst and the compound used at the time of crosslinking, and, if necessary, a conductive substance are dissolved in a solvent, In the solution state, a coating film is formed by a method such as a dip method, a cast method, or a spray method, and after removing the solvent and drying, a crosslinking reaction of the polycarbonate-siloxane copolymer resin is performed, or the above composition is formed into a film. Thus, a surface protective layer having conductivity can be obtained by a method such as pasting.

  The surface protective layer thus formed has a suitable thickness range depending on the size and use of the conductive rubber roll, but is usually 6 to 200 μm, preferably 20 to 160 μm. Moreover, you may add the same additive added to the said roll in the range which does not inhibit the effect of this invention to the surface protective layer formed in this invention.

  The coating material for a conductive rubber roller of the present invention can form a surface protective layer in the same manner for the transfer roll and the developing roll used in the electrophotographic process as well as the contact charging roll described above. These rolls can be applied in the same manner regardless of whether the roll is in an active rotation type, a passive rotation type, or used in a stationary state. It is possible to obtain a highly durable conductive rubber roll based on the excellent mechanical strength, particularly wear resistance, of the type polycarbonate-siloxane copolymer resin.

  Furthermore, this cross-linked polycarbonate-siloxane copolymer resin is formed into a film or sheet by a forming method such as general extrusion molding or press molding in addition to forming a coating film by coating in a solution state. It may be used by fusing or adhering to the surface of a member that requires abrasion resistance in various devices such as electrophotographic fields including a conductive rubber roll. In forming these films and sheets, the uncrosslinked polycarbonate-siloxane copolymer resin is molded by adding a crosslinking catalyst, a compound used during crosslinking, additives, and the like, and then molded into a film or sheet. By performing the crosslinking treatment of the resin, it is possible to obtain a film or sheet having appropriate elasticity and excellent wear resistance.

Hereinafter, the present invention will be described more specifically with reference to examples.
[Example 1]
(1) Production of polycarbonate-siloxane copolymer resin To a solution obtained by dissolving 74 g of 2,2-bis (4-hydroxyphenyl) propane in 550 ml of a 6 wt% aqueous sodium hydroxide solution, 250 ml of methylene chloride was added. While stirring, phosgene gas was blown into the solution at a rate of 950 ml / min for 15 minutes while cooling. 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.

  After adding methylene chloride to 200 ml of this methylene chloride solution of polycarbonate oligomer to a total volume of 450 ml, 127 g of a silicone compound represented by the following formula and 2,2-bis (4-hydroxyphenyl) bropan 5.0 g is mixed with 150 ml of an 8 wt% aqueous sodium hydroxide solution, and 2.0 g of p-tert-butylphenol is added as a molecular weight regulator, and the mixture is vigorously stirred and 7 wt% as a catalyst. 2 ml of an aqueous solution of triethylamine was added 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-siloxane copolymer resin.

The reduced viscosity [ηsp / c] of the polycarbonate-siloxane copolymer resin obtained above was measured at 20 ° C. in a 0.5 g / deciliter solution containing methylene chloride as a solvent (the following examples were also measured under the same conditions). ] Was 0.75 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. In the ¹ H-NMR spectrum measured for this polycarbonate-siloxane copolymer resin, an absorption peak based on siloxane was observed at 0 ppm, an absorption peak based on wholly aromatic was observed at 7 to 8 ppm, and 1.7 ppm. Absorption peaks based on isopropylidene groups are observed. From these intensity ratios, [a] a repeating unit derived from 2,2-bis (4-hydroxyphenyl) propane, and [b] derived from the residue of the silicone compound. As a result of calculating the copolymer composition with the repeating unit, it was [a]: [b] = 0.90: 0.10. Therefore, this polymer was recognized as a polycarbonate-siloxane copolymer resin having the following chemical structure.

(2) Production of cross-linked polycarbonate-siloxane copolymer resin Next, 0.5 g of the copolymer resin obtained in (1) and 0.1 g of 1,4-bis (dimethylsilyl) benzene were added to 5 ml of methylene chloride. Dissolve, and add 3 mg of platinum-cyclovinylmethylsiloxane complex (3-3.5 wt% cyclovinylmethylsiloxane solution as platinum atom) as a catalyst to the polyethylene terephthalate film. Used to cast a film. Next, the cast film was air-dried for 1 hour and then reacted at 120 ° C. under normal pressure for 2 hours. Subsequently, the film was dried at 120 ° C. and 1 mmHg for 12 hours to obtain a film of a crosslinked polycarbonate-siloxane copolymer resin crosslinked by hydrosilylation.

  The chemical structure of the cross-linked polycarbonate-siloxane copolymer resin obtained here was measured by infrared absorption spectrum analysis (IR analysis). As a result, the vinyl group-derived absorption peak existing before cross-linking disappeared after cross-linking. Therefore, it was recognized as follows.

(3) Evaluation of cross-linked polycarbonate-siloxane copolymer resin Visible light transmittance was measured for the cross-linked polycarbonate resin film obtained in (2) above in order to evaluate its transparency. In order to evaluate the contamination resistance, the contact angle of water was measured. Furthermore, in order to evaluate the wear resistance, an abrasion resistance evaluation test was performed using a Suga abrasion tester NUS-ISO-3 type manufactured by Suga Test Instruments Co., Ltd. The condition for the abrasion resistance evaluation test was as follows: the weight of the sample after reciprocating the sample 2000 times on a worn paper (made by Suga Test Instruments Co., Ltd .; containing alumina particles having a particle size of 3 microns) subjected to a load of 500 g. A method of measuring the amount of decrease was adopted.

  These results are shown in Table 1. In addition, what is indicated by a circle in the transparency column in Table 1 indicates that the light transmittance in the entire wavelength range of 350 to 600 nm was 90% or more, and an X mark is displayed. It is shown 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-siloxane copolymer resin In the same manner as in Example 1, a polycarbonate oligomer having a chloroformate group at the molecular end was produced, and methylene chloride was added to 200 ml of the methylene chloride solution to obtain 450 ml. did. Thereafter, instead of 127 g of the silicone compound and 5.0 g of 2,2-bis (4-hydroxyphenyl) bropan used in Example 1, 63.0 g of the same silicone compound and 8.4 g of 4,4′-dihydroxybiphenyl were used. A polycarbonate-siloxane copolymer resin was produced in the same manner as in Example 1 except that The reduced viscosity [ηsp / c] of the obtained polycarbonate-siloxane copolymer resin was 0.72 deciliter / g. Moreover, as a result of measuring a ¹ H-NMR spectrum, an intensity ratio of an absorption peak based on 0 ppm of siloxane, an absorption peak based on 7 to 8 ppm of total aromatic hydrogen, and an absorption peak based on 1.7 ppm of isopropylidene group. As a result of calculating the copolymer composition of this product, [a] a repeating unit derived from 2,2-bis (4-hydroxyphenyl) propane, [b] a repeating unit derived from 4,4′-dihydroxybiphenyl, and [C] The repeating unit derived from the residue of the silicone compound was [a]: [b]: [c] = 0.85: 0.10: 0.05. Therefore, this was recognized as having the following chemical structure.

(2) Production of crosslinkable polycarbonate-siloxane copolymer resin The polycarbonate-siloxane copolymer resin obtained in the above (1) was treated in the same manner as in Example 1 (2). Manufactured. The obtained cross-linked polycarbonate-siloxane copolymer resin was confirmed to have the following chemical structure from the results of IR analysis.

(3) Evaluation of crosslinkable polycarbonate-siloxane copolymer resin The crosslinkable polycarbonate-siloxane copolymer resin obtained in (2) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 3
(1) Manufacture of polycarbonate-siloxane copolymer resin Implemented by using 124 g of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane instead of 74 g of 2,2-bis (4-hydroxyphenyl) propane In the same manner as in Example 1, a polycarbonate oligomer having a chloroformate group at the molecular end was produced, and methylene chloride was added to 200 ml of the methylene chloride solution to make 450 ml. Thereafter, 8.4 g of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane was used instead of 5.0 g of 2,2-bis (4-hydroxyphenyl) bropan used in Example 1. Others were carried out similarly to Example 1, and manufactured polycarbonate-siloxane copolymer resin. The reduced viscosity [ηsp / c] of the obtained polycarbonate-siloxane copolymer resin was 0.83 deciliter / g. As a result of measuring the ¹ H-NMR spectrum, the copolymer composition of this was calculated from the intensity ratio of the absorption peak based on 0 ppm of siloxane and the absorption peak based on 7 to 8 ppm of total aromatic hydrogen, a) a repeating unit derived from 2,2-bis (3-phenyl-4-hydroxyphenyl) propane and [b] a repeating unit derived from the residue of the silicone compound [a]: [b] = 0 .90: 0.10 and was found to have the following chemical structure.

(2) Production of crosslinkable polycarbonate-siloxane copolymer resin The polycarbonate-siloxane copolymer resin obtained in the above (1) was treated in the same manner as in Example 1 (2). Manufactured. The obtained cross-linked polycarbonate-siloxane copolymer resin was confirmed to have the following chemical structure from the results of IR analysis.

(3) Evaluation of crosslinkable polycarbonate-siloxane copolymer resin The crosslinkable polycarbonate-siloxane copolymer resin obtained in (2) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 4
(1) Production of Polycarbonate-Siloxane Copolymer Resin In place of 74 g of 2,2-bis (4-hydroxyphenyl) propane, 87.1 g of 1,1-bis (4-hydroxyphenyl) cyclohexane was used. In the same manner as above, a polycarbonate oligomer having a chloroformate group at the molecular end was prepared, and methylene chloride was added to 200 ml of the methylene chloride solution to make 450 ml. Then, instead of 127 g of silicone compound and 5.0 g of 2,2-bis (4-hydroxyphenyl) bropan used in Example 1, the following silicone compound 137 g and 1,1-bis (4-hydroxyphenyl) cyclohexane A polycarbonate-siloxane copolymer resin was produced in the same manner as in Example 1 except that 5.9 g was used.

The reduced viscosity [ηsp / c] of the obtained polycarbonate-siloxane copolymer resin was 0.71 deciliter / g. As a result of measuring the ¹ H-NMR spectrum, the copolymer composition of this was calculated from the intensity ratio of the absorption peak based on 0 ppm of siloxane and the absorption peak based on 7 to 8 ppm of total aromatic hydrogen, a] a repeating unit derived from 1,1-bis (4-hydroxyphenyl) cyclohexane, and [b] a repeating unit derived from the residue of the silicone compound, [a]: [b] = 0.92: 0.08, which was recognized as having the following chemical structure.

(2) Production of crosslinkable polycarbonate-siloxane copolymer resin The polycarbonate-siloxane copolymer resin obtained in the above (1) was treated in the same manner as in Example 1 (2). Manufactured. The obtained cross-linked polycarbonate-siloxane copolymer resin was confirmed to have the following chemical structure from the results of IR analysis.

(3) Evaluation of crosslinkable polycarbonate-siloxane copolymer resin The crosslinkable polycarbonate-siloxane copolymer resin obtained in (2) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 5
(1) Manufacture of polycarbonate-siloxane copolymer resin Implemented using 123 g of 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene instead of 74 g of 2,2-bis (4-hydroxyphenyl) propane In the same manner as in Example 1, a polycarbonate oligomer having a chloroformate group at the molecular end was produced, and methylene chloride was added to 200 ml of the methylene chloride solution to make 450 ml. Thereafter, in place of 127 g of silicone compound and 5.0 g of 2,2-bis (4-hydroxyphenyl) bropan used in Example 1, 40.7 g and 9,9-bis (same silicone compound as in Example 4) were used. A polycarbonate-siloxane copolymer resin was produced in the same manner as in Example 1 except that 20.4 g of 3-methyl-4-hydroxyphenyl) fluorene was used.

The reduced viscosity [ηsp / c] of the obtained polycarbonate-siloxane copolymer resin was 0.73 deciliter / g. As a result of measuring the ¹ H-NMR spectrum, the copolymer composition of this was calculated from the intensity ratio of the absorption peak based on 0 ppm of siloxane and the absorption peak based on 7 to 8 ppm of total aromatic hydrogen, a) a repeating unit derived from 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, and [b] a repeating unit derived from the residue of the silicone compound, [a]: [b] = 0.97: 0.03 and was confirmed to have the following chemical structure.

(2) Production of crosslinkable polycarbonate-siloxane copolymer resin The polycarbonate-siloxane copolymer resin obtained in the above (1) was treated in the same manner as in Example 1 (2). Manufactured. The obtained cross-linked polycarbonate-siloxane copolymer resin was confirmed to have the following chemical structure from the results of IR analysis.

(3) Evaluation of crosslinkable polycarbonate-siloxane copolymer resin The crosslinkable polycarbonate-siloxane copolymer resin obtained in (2) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 6
(1) Production of polycarbonate-siloxane copolymer resin Instead of 74 g of 2,2-bis (4-hydroxyphenyl) propane, 83.2 g of 2,2-bis (3-methyl-4-hydroxyphenyl) propane was used. In the same manner as in Example 1, a polycarbonate oligomer having a chloroformate group at the molecular end was produced, and methylene chloride was added to 200 ml of the methylene chloride solution to make 450 ml. Then, instead of 127 g of silicone compound and 5.0 g of 2,2-bis (4-hydroxyphenyl) bropan used in Example 1, the following silicone compound 54.0 g and 1-phenyl-1,1-bis ( A polycarbonate-siloxane copolymer resin was produced in the same manner as in Example 1 except that 6.4 g of 4-hydroxyphenyl) ethane was used.

The reduced viscosity [ηsp / c] of the obtained polycarbonate-siloxane copolymer resin was 0.74 deciliter / g. Moreover, as a result of measuring a ¹ H-NMR spectrum, an intensity ratio of an absorption peak based on 0 ppm of siloxane, an absorption peak based on 1.7 ppm of isopropylidene group, and an absorption peak based on 7 to 8 ppm of total aromatic hydrogen. As a result of calculating the copolymer composition of this product, [a] a repeating unit derived from 2,2-bis (3-methyl-4-hydroxyphenyl) propane and [b] 1-phenyl-1,1-bis The repeating unit derived from (4-hydroxyphenyl) ethane and [c] the repeating unit derived from the residue of the silicone compound are [a]: [b]: [c] = 0.85: 0.05. : 0.10, and was recognized as having the following chemical structure.

(2) Production of crosslinkable polycarbonate-siloxane copolymer resin The polycarbonate-siloxane copolymer resin obtained in the above (1) was treated in the same manner as in Example 1 (2). Manufactured. The obtained cross-linked polycarbonate-siloxane copolymer resin was confirmed to have the following chemical structure from the results of IR analysis.

(3) Evaluation of crosslinkable polycarbonate-siloxane copolymer resin The crosslinkable polycarbonate-siloxane copolymer resin obtained in (2) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 7
(1) Production of cross-linked polycarbonate-siloxane copolymer resin 1,1,3,3-tetramethyldisiloxane 0 with respect to 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (2) of Example 2 In the same manner as in Example 1 (2), a cross-linked polycarbonate-siloxane copolymer resin was produced using 0.1 g. The obtained cross-linked polycarbonate-siloxane copolymer resin was confirmed to have the following chemical structure from the results of IR analysis.

(2) Evaluation of cross-linked polycarbonate-siloxane copolymer resin The cross-linked polycarbonate-siloxane copolymer resin obtained in (1) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 8
(1) Production of cross-linked polycarbonate-siloxane copolymer resin 0.1 g of diphenylsilane was used for 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 2 ( A crosslinked polycarbonate-siloxane copolymer resin was produced in the same manner as 2). The obtained cross-linked polycarbonate-siloxane copolymer resin was confirmed to have the following chemical structure from the results of IR analysis.

(2) Evaluation of cross-linked polycarbonate-siloxane copolymer resin The cross-linked polycarbonate-siloxane copolymer resin obtained in (1) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 9
(1) Production of cross-linked polycarbonate-siloxane copolymer resin 1,1,3,3-tetramethyldisiloxane 0 with respect to 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (4) of Example 4 In the same manner as in Example 1 (2), a cross-linked polycarbonate-siloxane copolymer resin was produced using 0.1 g. The obtained cross-linked polycarbonate-siloxane copolymer resin was confirmed to have the following chemical structure from the results of IR analysis.

(2) Evaluation of cross-linked polycarbonate-siloxane copolymer resin The cross-linked polycarbonate-siloxane copolymer resin obtained in (1) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 10
(1) Production of cross-linked polycarbonate-siloxane copolymer resin As in Example 1, 0.1 g of diphenylsilane was used for 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 5. By carrying out a crosslinking reaction, a crosslinked polycarbonate-siloxane copolymer resin was obtained. The chemical structure of this cross-linked polycarbonate-siloxane copolymer resin was recognized as shown below.

(2) Evaluation of cross-linked polycarbonate-siloxane copolymer resin The cross-linked polycarbonate-siloxane copolymer resin obtained in (2) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 11
(1) Production of Crosslinked Polycarbonate-Siloxane Copolymer Resin Example 1 Using 0.1 g of methyldiethoxysilane with respect to 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (2) of Example 2 By performing a crosslinking reaction in the same manner as above, a crosslinked polycarbonate-siloxane copolymer resin was obtained. The chemical structure of this cross-linked polycarbonate-siloxane copolymer resin was recognized as shown below.

(2) Evaluation of cross-linked polycarbonate-siloxane copolymer resin The cross-linked polycarbonate-siloxane copolymer resin obtained in (2) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 12
(1) Production of cross-linked polycarbonate-siloxane copolymer resin Using 0.1 g of dimethylethoxysilane with respect to 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 5, By performing a crosslinking reaction in the same manner, a crosslinked polycarbonate-siloxane copolymer resin was obtained. The chemical structure of this cross-linked polycarbonate-siloxane copolymer resin was recognized as shown below.

(2) Evaluation of cross-linked polycarbonate-siloxane copolymer resin The cross-linked polycarbonate-siloxane copolymer resin obtained in (2) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 13
(1) Production of cross-linked polycarbonate-siloxane copolymer resin 0.1 g of tris (trimethylsiloxy) silane was used for 0.5 g of the polycarbonate-siloxane copolymer resin obtained in Example 6 (1). A crosslinking reaction was carried out in the same manner as in Example 1 to obtain a crosslinked polycarbonate-siloxane copolymer resin. The chemical structure of this cross-linked polycarbonate-siloxane copolymer resin was recognized as shown below.

(2) Evaluation of cross-linked polycarbonate-siloxane copolymer resin The cross-linked polycarbonate-siloxane copolymer resin obtained in (2) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 14
(1) Production of cross-linked polycarbonate-siloxane copolymer resin 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 1 and 0.1 g of benzoyl peroxide were dissolved in 5 ml of methylene chloride. This was cast on a polyethylene terephthalate film using an applicator. Subsequently, after air-drying this for 1 hour, it heated up at 120 degreeC and the crosslinking reaction was performed at normal pressure for 8 hours. Subsequently, a film of a polycarbonate-siloxane copolymer resin crosslinked by radicals was obtained by drying for 12 hours under the conditions of 140 ° C. and 1 mmHg. The chemical structure of the crosslinked polycarbonate-siloxane copolymer resin obtained here is as follows because the absorption peak derived from the vinyl group observed before crosslinking disappeared after crosslinking in the results of IR analysis. It was recognized that there was.

(2) Evaluation of cross-linked polycarbonate-siloxane copolymer resin The cross-linked polycarbonate-siloxane copolymer resin obtained in (1) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 15
(1) Production of cross-linked polycarbonate-siloxane copolymer resin The procedure of (14) in Example 14 was repeated except that 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 4 was used. A film of a crosslinked polycarbonate-siloxane copolymer resin was obtained. The chemical structure of the cross-linked polycarbonate-siloxane copolymer resin obtained here was recognized as follows from the results of IR analysis.

(2) Evaluation of cross-linked polycarbonate-siloxane copolymer resin The cross-linked polycarbonate-siloxane copolymer resin obtained in (1) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 16
(1) Production of cross-linked polycarbonate-siloxane copolymer resin The procedure was the same as in Example 14 (1) except that 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 6 was used. A film of a crosslinked polycarbonate-siloxane copolymer resin was obtained. The chemical structure of the cross-linked polycarbonate-siloxane copolymer resin obtained here was recognized as follows from the results of IR analysis.

(2) Evaluation of cross-linked polycarbonate-siloxane copolymer resin The cross-linked polycarbonate-siloxane copolymer resin obtained in (1) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 17
(1) Production of polycarbonate-siloxane copolymer resin In the same manner as in Example 1, except that 74 g of 2,2-bis (4-hydroxyphenyl) propane was used and 114 g of bis (4-hydroxyphenyl) diphenylmethane was used. A polycarbonate oligomer having a chloroformate group at the end was prepared, and methylene chloride was added to 200 ml of the methylene chloride solution to make 450 ml.

Then, instead of 127 g of silicone compound and 5.0 g of 2,2-bis (4-hydroxyphenyl) bropan used in Example 1, the following silicone compound 79.2 g and 2,7-naphthalenediol 7.2 g A polycarbonate-siloxane copolymer resin was produced in the same manner as in Example 1 except that was used. The reduced viscosity [ηsp / c] of the obtained polycarbonate-siloxane copolymer resin was 0.70 deciliter / g. Moreover, as a result of measuring a ¹ H-NMR spectrum, an absorption peak based on 0 ppm of siloxane, an absorption peak based on 7.9 ppm of 2,7-naphthalenediol, and an absorption peak based on 7 to 8 ppm of total aromatic hydrogen were obtained. As a result of calculating the copolymer composition of this product from the intensity ratio, [a] a repeating unit derived from bis (4-hydroxyphenyl) diphenylmethane, [b] a repeating unit derived from 2,7-naphthalenediol, and [c The repeating unit derived from the residue of the silicone compound is [a]: [b]: [c] = 0.85: 0.10: 0.05, which has the following chemical structure: It was accepted.

(2) Manufacture of cross-linked polycarbonate-siloxane copolymer resin Implementation was carried out except that 0.5 g of the polycarbonate-siloxane copolymer resin obtained in the above (1) was used and the amount of benzoyl peroxide used was 0.2 g. In the same manner as in Example 14, (1), a crosslinked polycarbonate-siloxane copolymer resin film was obtained. The chemical structure of the cross-linked polycarbonate-siloxane copolymer resin obtained here was recognized as follows from the results of IR analysis.

(3) Evaluation of crosslinkable polycarbonate-siloxane copolymer resin The crosslinkable polycarbonate-siloxane copolymer resin obtained in (2) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 18
(1) Production of polycarbonate-siloxane copolymer resin Instead of 74 g of 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3 Using 109 g of 3-tetrafluoropropane, a polycarbonate oligomer having a chloroformate group at the molecular end was produced in the same manner as in Example 1, and methylene chloride was added to 200 ml of the methylene chloride solution to make 450 ml. . Then, instead of 127 g of silicone compound and 5.0 g of 2,2-bis (4-hydroxyphenyl) bropan used in Example 1, the following silicone compound 30.0 g and 4,4′-dihydroxybenzophenone 8.6 g A polycarbonate-siloxane copolymer resin was produced in the same manner as in Example 1 except that

The reduced viscosity [ηsp / c] of the obtained polycarbonate-siloxane copolymer resin was 0.77 deciliter / g. Moreover, as a result of measuring the ¹ H-NMR spectrum, the copolymer composition of this product was calculated from the intensity ratio of the absorption peak based on 0 ppm of siloxane and the absorption peak based on 7 to 8 ppm of total aromatic groups and the monomer charge ratio. As a result, [a] a repeating unit derived from 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-tetrafluoropropane and [b] 4,4′-dihydroxybenzophenone And [c] the repeating unit derived from the residue of the silicone compound is [a]: [b]: [c] = 0.80: 0.10: 0.10, This was found to have the following chemical structure.

(2) Manufacture of cross-linked polycarbonate-siloxane copolymer resin Implementation was carried out except that 0.5 g of the polycarbonate-siloxane copolymer resin obtained in the above (1) was used and the amount of benzoyl peroxide used was 0.2 g. In the same manner as in Example 14, (1), a crosslinked polycarbonate-siloxane copolymer resin film was obtained. The chemical structure of the cross-linked polycarbonate-siloxane copolymer resin obtained here was recognized as follows from the results of IR analysis.

(3) Evaluation of crosslinkable polycarbonate-siloxane copolymer resin The crosslinkable polycarbonate-siloxane copolymer resin obtained in (2) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 19
(1) Production of polycarbonate-siloxane copolymer resin Instead of 74 g of 2,2-bis (4-hydroxyphenyl) propane, 65.7 g of 4,4′-dihydroxydiphenyl ether was used in the same manner as in Example 1, A polycarbonate oligomer having a chloroformate group at the molecular end was produced, and methylene chloride was added to 200 ml of the methylene chloride solution to make 450 ml.

  Then, instead of 127 g of silicone compound and 5.0 g of 2,2-bis (4-hydroxyphenyl) bropan used in Example 1, the following silicone compound 60.0 g and 4,4′-dihydroxydiphenylsulfone 11 A polycarbonate-siloxane copolymer resin was produced in the same manner as in Example 1 except that 3 g was used.

The reduced viscosity [ηsp / c] of the obtained polycarbonate-siloxane copolymer resin was 0.68 deciliter / g. Moreover, as a result of measuring the ¹ H-NMR spectrum, the copolymer composition of this product was calculated from the intensity ratio of the absorption peak based on 0 ppm of siloxane and the absorption peak based on 7 to 8 ppm of total aromatic groups and the monomer charge ratio. As a result, [a] a repeating unit derived from 4,4′-dihydroxydiphenyl ether, [b] a repeating unit derived from 4,4′-dihydroxydiphenylsulfone, and [c] derived from a residue of the silicone compound. The repeating unit was [a]: [b]: [c] = 0.85: 0.10: 0.05, and this was recognized as having the following chemical structure.

(2) Production of crosslinked polycarbonate-siloxane copolymer resin Using 0.25 g of the polycarbonate-siloxane copolymer resin obtained in (2) of Example 2, instead of 1,4-bis (dimethylsilyl) benzene, A crosslinked polycarbonate-siloxane copolymer film was obtained in the same manner as in Example 1 except that 0.25 g of the polycarbonate-siloxane copolymer resin obtained in the above (1) was used. From the result of IR analysis, it was recognized that the chemical structure of the obtained cross-linked polycarbonate-siloxane copolymer resin was as follows.

(3) Evaluation of crosslinkable polycarbonate-siloxane copolymer resin The crosslinkable polycarbonate-siloxane copolymer resin obtained in (2) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

Example 20
(1) Production of cross-linked polycarbonate-siloxane copolymer resin Using 0.5 g of the polycarbonate-siloxane copolymer resin obtained in Example 19 (1), instead of 1,4-bis (dimethylsilyl) benzene, A crosslinked polycarbonate-siloxane copolymer resin film was obtained in the same manner as in Example 1 except that 0.1 g of divinylbenzene was used. From the result of IR analysis, it was recognized that the chemical structure of the obtained cross-linked polycarbonate-siloxane copolymer resin was as follows.

(2) Evaluation of cross-linked polycarbonate-siloxane copolymer resin The cross-linked polycarbonate-siloxane copolymer resin obtained in (1) above was evaluated in the same manner as in Example 1 (3). The results are shown in Table 1.

[Comparative Example 1]
Except that 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 17 was dissolved in 5 ml of methylene chloride and cast on a polyethylene terephthalate film using an applicator. A polycarbonate-siloxane copolymer resin film was obtained in the same manner as in Example 1, (2). The crosslinked polycarbonate-siloxane copolymer resin obtained above was evaluated in the same manner as (3) of Example 1. The results are shown in Table 1.

[Comparative Example 2]
The same as the comparative example except that a polycarbonate resin using 2,2-bis (4-hydroxyphenyl) propane as a raw material was used instead of the crosslinked polycarbonate-siloxane copolymer resin used in (1) of Comparative Example 1. A film was obtained. The polycarbonate resin obtained here was evaluated in the same manner as (3) of Example 1. The results are shown in Table 1.

Example 21
Disperse 0.5 part by weight of oxotitanium phthalocyanine as a charge generating substance, 0.5 part by weight of butyral resin as a binder resin and 19 parts by weight of methylene chloride as a solvent using a ball mill. A charge generation layer having a film thickness of about 0.5 μm was formed by coating and drying on a polyethylene terephthalate film on which aluminum used as a substrate was deposited.

  Next, 0.5 g of 4-dibenzylamino-2-methylbenzaldehyde-1,1-diphenylhydrazone as a charge transport material and the polycarbonate-siloxane copolymer resin obtained in (1) of Example 1 as a binder resin are used. After 0.5 g and 0.1 g of 1,4-bis (dimethylsilyl) benzene as a crosslinking compound were dissolved in 5 ml of methylene chloride, a platinum-cyclovinylmethylsiloxane complex (3 to 3.5 as a platinum atom) was used as a catalyst. (3% by weight cyclovinylmethylsiloxane solution) was added to prepare a coating solution. This coating solution was applied onto the charge generation layer with an applicator. Next, a crosslinking reaction is carried out under conditions of 120 ° C. and normal pressure for 4 hours, followed by drying under the conditions of 120 ° C. and 1 mmHg for 12 hours, and a charge of about 20 μm containing a methylene chloride insoluble component (cross-linked product). A transport layer was formed to produce a multilayer electrophotographic photoreceptor. In the process from application to drying, the charge transport layer did not crystallize.

Evaluation of electrical characteristics (electrophotographic characteristics) of the obtained electrophotographic photosensitive member was performed by using an electrostatic charge test apparatus EPA-8100 (manufactured by Kawaguchi Electric Co., Ltd.) and initial surface potential when corona discharge was performed at -6 kv. (V ₀ ), residual potential (V _R ) 5 seconds after light irradiation (10 Lux), and half exposure (E _1/2 ) were measured. Moreover, abrasion resistance was evaluated using Suga abrasion tester NUS-ISO-3 type (made by Suga Test Instruments Co., Ltd.). The test conditions were evaluated by reciprocating the sample 2000 times on a worn paper (Suga Test Instruments Co., Ltd .: Al ₂ O ₃ ; 3 μm) applied with a load of 500 g and measuring the weight loss. Furthermore, the contamination resistance was evaluated by measuring the contact angle with water. These results are shown in Table 2.

[Example 22]
A multilayer electrophotographic photosensitive member was produced in the same manner as in Example 21 except that 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (2) of Example 2 was used as the binder resin for the charge transport layer. . Also in this case, the charge transport layer did not crystallize in the process from coating to drying. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

Example 23
A laminated electrophotographic photosensitive member was produced in the same manner as in Example 21, except that 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 3 was used as the binder resin for the charge transport layer. . In the process from application to drying, the charge transport layer did not crystallize. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

Example 24
A multilayer electrophotographic photosensitive member was produced in the same manner as in Example 21, except that 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 4 was used as the binder resin for the charge transport layer. . In the process from application to drying, the charge transport layer did not crystallize. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

Example 25
A multilayer electrophotographic photosensitive member was produced in the same manner as in Example 21 except that 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 5 was used as the binder resin for the charge transport layer. . In the process from application to drying, the charge transport layer did not crystallize. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

Example 26
A multilayer electrophotographic photosensitive member was produced in the same manner as in Example 21 except that 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 6 was used as the binder resin for the charge transport layer. . In the process from application to drying, the charge transport layer did not crystallize. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

Example 27
As the binder resin for the charge transport layer, 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 2 was used, and 1,1,3 instead of 1,4-bis (dimethylsilyl) benzene. A laminated electrophotographic photosensitive member was prepared in the same manner as in Example 21 except that 0.1 g of 1,3-tetramethyldisiloxane was used. In the process from application to drying, the charge transport layer did not crystallize. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

Example 28
As a binder resin for the charge transport layer, 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 2 was used, and 0.1 g of diphenylsilane was used instead of 1,4-bis (dimethylsilyl) benzene. A laminated electrophotographic photosensitive member was produced in the same manner as in Example 21 except that was used. In the process from application to drying, the charge transport layer did not crystallize. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

Example 29
As a binder resin for the charge transport layer, 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 4 was used, and 1,1,3 instead of 1,4-bis (dimethylsilyl) benzene. A laminated electrophotographic photosensitive member was prepared in the same manner as in Example 21 except that 0.1 g of 1,3-tetramethyldisiloxane was used. In the process from application to drying, the charge transport layer did not crystallize. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

Example 30
As a binder resin for the charge transport layer, 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 5 was used, and 0.1 g of diphenylsilane was used instead of 1,4-bis (dimethylsilyl) benzene. A laminated electrophotographic photosensitive member was produced in the same manner as in Example 21 except that was used. In the process from application to drying, the charge transport layer did not crystallize. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

Example 31
As a binder resin for the charge transport layer, 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 2 was used, and methyldiethoxysilane 0 was used instead of 1,4-bis (dimethylsilyl) benzene. A laminated electrophotographic photosensitive member was produced in the same manner as in Example 21 except that 0.1 g was used. In the process from application to drying, the charge transport layer did not crystallize. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

[Example 32]
As a binder resin for the charge transport layer, 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 5 was used, and dimethylethoxysilane was added in place of 1,4-bis (dimethylsilyl) benzene. A laminated electrophotographic photosensitive member was produced in the same manner as in Example 21 except that 1 g was used. In the process from application to drying, the charge transport layer did not crystallize. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

Example 33
As a binder resin for the charge transport layer, 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 6 was used, and tris (trimethylsiloxy) was used instead of 1,4-bis (dimethylsilyl) benzene. A laminated electrophotographic photosensitive member was produced in the same manner as in Example 21 except that 0.1 g of silane was used. In the process from application to drying, the charge transport layer did not crystallize. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

Example 34
As a binder resin of the charge transport layer, 0.25 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 2 was used, and instead of 1,4-bis (dimethylsilyl) benzene, ( A laminated electrophotographic photosensitive member was produced in the same manner as in Example 21 except that 0.25 g of the polycarbonate-siloxane copolymer resin obtained in 1) was used. In the process from application to drying, the charge transport layer did not crystallize. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

Example 35
As a binder resin for the charge transport layer, 0.5 g of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 19 was used, and 0.1 g of divinylbenzene was used instead of 1,4-bis (dimethylsilyl) benzene. A laminated electrophotographic photosensitive member was produced in the same manner as in Example 21 except that was used. In the process from application to drying, the charge transport layer did not crystallize. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

[Comparative Example 3]
As the binder resin of the charge transport layer, a polycarbonate resin using 1,1-bis (4-hydroxyphenyl) cyclohexane as a raw material was used, and the same procedure as in Example 21 was carried out except that no crosslinking compound and catalyst were used. A laminated electrophotographic photosensitive member was produced. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

[Comparative Example 4]
A laminated electrophotographic photosensitive member was produced in the same manner as in Comparative Example 3 except that the polycarbonate-siloxane copolymer resin obtained in (1) of Example 17 was used as the binder resin for the charge transport layer. The laminated electrophotographic photoreceptor obtained above was evaluated in the same manner as in Example 21 for electrical characteristics (electrophotographic characteristics), abrasion resistance, and contamination resistance. These evaluation results are shown in Table 2.

Example 36
Carbon black (manufactured by Denki Kagaku Co., Ltd .: Denka Black; average particle size of 40 μm, oil absorption of 125 ml / g, surface area of 45 m ² ) was melt-kneaded with 100 parts by weight of chloroprene rubber, and stainless steel with a diameter of 10 mm and a length of 330 mm at the center. A primary charging roll was produced by forming through a shaft so as to have a diameter of 20 mm and a length of 300 mm.

Next, 20 parts by weight of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 1, 2 parts by weight of 1,4-bis (dimethylsilyl) benzene, and carbon black (manufactured by Denki Kagaku Kogyo Co., Ltd .: Denka) Black: 1 part by weight of an average particle diameter of 40 μm, oil absorption of 125 ml / g, surface area of 45 m ² was dissolved in 200 parts by weight of methylene chloride, and then a platinum-cyclovinylmethylsiloxane complex (3-3.5% by weight as platinum atom). Of cyclovinylmethylsiloxane solution) is added to the surface of the primary charging roll and subjected to a crosslinking reaction at 120 ° C. under normal pressure for 4 hours. Drying was performed under conditions of 1 ° C. and 12 mm at 12 ° C. to prepare a charging roll. The thickness of the surface protective layer after drying was 200 μm.

  The uniformity, durability and stain resistance of the surface protective layer of the obtained charging roll were measured by the following methods. Uniformity and durability of charging can be achieved by incorporating the above charging roll into an electrophotographic copying machine and observing image density, image defects, and endurance image defects (streaks due to scratches) for the first 10 copies of the copied image. evaluated. Moreover, the contamination resistance was measured by preparing a surface protective layer having the same composition as described above on an aluminum flat plate and measuring the contact angle of this layer with water. These results are shown in Table 3. The image density can be reproduced to be 1.2 or more when a 1.3 solid document is copied with a Macbeth densitometer, ◯ is 1.1 or more and less than 1.2, and 1.0 or more. In the table, Δ is less than 1.1 and Δ is less than 1.0.

Example 37
In place of the polycarbonate-siloxane copolymer resin used in Example 36, 20 parts by weight of the copolymer resin obtained in (2) of Example 2 was used. Produced. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 38
In place of the polycarbonate-siloxane copolymer resin used in Example 36, 20 parts by weight of the copolymer resin obtained in (1) of Example 3 was used. Produced. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 39
In place of the polycarbonate-siloxane copolymer resin used in Example 36, 20 parts by weight of the copolymer resin obtained in (1) of Example 4 was used. Produced. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 40
In place of the polycarbonate-siloxane copolymer resin used in Example 36, 20 parts by weight of the copolymer resin obtained in (1) of Example 5 was used. Produced. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 41
In place of the polycarbonate-siloxane copolymer resin used in Example 36, 20 parts by weight of the copolymer resin obtained in (1) of Example 6 was used. Produced. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 42
Instead of the polycarbonate-siloxane copolymer resin used in Example 36, 20 parts by weight of the copolymer resin obtained in (1) of Example 2 was used, and instead of 1,4-bis (dimethylsilyl) benzene, A charging roll was produced in the same manner as in Example 36 except that 2 parts by weight of 1,1,3,3-tetramethyldisiloxane was used. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 43
Instead of the polycarbonate-siloxane copolymer resin used in Example 36, 20 parts by weight of the copolymer resin obtained in (1) of Example 2 was used, and instead of 1,4-bis (dimethylsilyl) benzene, A charging roll was produced in the same manner as in Example 36 except that 2 parts by weight of diphenylsilane was used. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 44
Instead of the polycarbonate-siloxane copolymer resin used in Example 36, 20 parts by weight of the copolymer resin obtained in (1) of Example 4 was used, and instead of 1,4-bis (dimethylsilyl) benzene, A charging roll was produced in the same manner as in Example 36 except that 2 parts by weight of 1,1,3,3-tetramethyldisiloxane was used. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 45
Instead of the polycarbonate-siloxane copolymer resin used in Example 36, 20 parts by weight of the copolymer resin obtained in (1) of Example 5 was used, and instead of 1,4-bis (dimethylsilyl) benzene, A charging roll was produced in the same manner as in Example 36 except that 2 parts by weight of diphenylsilane was used. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 46
Instead of the polycarbonate-siloxane copolymer resin used in Example 36, 20 parts by weight of the copolymer resin obtained in (1) of Example 2 was used, and instead of 1,4-bis (dimethylsilyl) benzene, A charging roll was produced in the same manner as in Example 36 except that 2 parts by weight of methyldiethoxysilane was used. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 47
Instead of the polycarbonate-siloxane copolymer resin used in Example 36, 20 parts by weight of the copolymer resin obtained in (1) of Example 5 was used, and instead of 1,4-bis (dimethylsilyl) benzene, A charging roll was produced in the same manner as in Example 36 except that 2 parts by weight of dimethylethoxysilane was used. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 48
Instead of the polycarbonate-siloxane copolymer resin used in Example 36, 20 parts by weight of the copolymer resin obtained in (1) of Example 6 was used, and instead of 1,4-bis (dimethylsilyl) benzene, A charging roll was produced in the same manner as in Example 36 except that 2 parts by weight of tris (trimethylsiloxy) silane was used. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 49
Instead of 1,4-bis (dimethylsilyl) benzene used in Example 36, 4 parts by weight of benzoyl peroxide was used, and a platinum-cyclovinylmethylsiloxane complex (3-3.5% by weight of cyclovinyl as a platinum atom) was used. A charging roll was produced in the same manner as in Example 36 except that the methylsiloxane solution was not added. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 50
In place of the polycarbonate-siloxane copolymer resin used in Example 49, 20 parts by weight of the copolymer resin obtained in (1) of Example 4 was used. Produced. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 51
In place of the polycarbonate-siloxane copolymer resin used in Example 49, 20 parts by weight of the copolymer resin obtained in (1) of Example 6 was used. Produced. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 52
In place of the polycarbonate-siloxane copolymer resin used in Example 49, 20 parts by weight of the copolymer resin obtained in (1) of Example 17 was used. Produced. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 53
In place of the polycarbonate-siloxane copolymer resin used in Example 49, 20 parts by weight of the copolymer resin obtained in (1) of Example 8 was used. Produced. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 54
Instead of the polycarbonate-siloxane copolymer resin used in Example 36, 10 parts by weight of the copolymer resin obtained in (2) of Example 2 was used, and instead of 1,4-bis (dimethylsilyl) benzene, A charging roll was produced in the same manner as in Example 36 except that 10 parts by weight of the polycarbonate-siloxane copolymer resin obtained in (1) of Example 19 was used. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

Example 55
Instead of the polycarbonate-siloxane copolymer resin used in Example 36, 20 parts by weight of the copolymer resin obtained in (1) of Example 19 was used, and instead of 1,4-bis (dimethylsilyl) benzene, A charging roll was produced in the same manner as in Example 36 except that 2 parts by weight of divinylbenzene was used. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

[Comparative Example 5]
A charging roll was manufactured according to the manufacturing method described in Example 1 of JP-A-7-230201. The charging roll obtained above was evaluated in the same manner as in Example 36 for charging uniformity, durability, and contamination resistance. The results are shown in Table 3.

  The cross-linked polycarbonate-siloxane copolymer resin of the present invention has excellent anti-contamination resistance and high wear resistance, and is highly useful as a material constituting an electronic device member such as an electrophotographic process. is there. In addition, since the electrophotographic photosensitive member and the conductive roll coating material, film, and sheet of the present invention all use the above-mentioned crosslinked polycarbonate-siloxane copolymer resin, they are excellent in stain resistance and abrasion resistance. A product with improved durability is obtained.

Claims (5)

A method for producing a crosslinked polycarbonate-siloxane copolymer resin, characterized in that a polycarbonate-siloxane copolymer resin is bonded to another copolymer chain in a repeating unit containing the siloxane of the copolymer chain,
In the repeating unit containing siloxane, at least one selected from a carbon-carbon unsaturated bond, an alkoxysilyl group, a hydrosilyl group, and an aliphatic group in which one or more hydrogen atoms are bonded to a carbon atom adjacent to a silicon atom. It has a group, in these groups, cross-linking type polycarbonate Ru to form bonds with other copolymer chain - preparation of the siloxane copolymer resin. A method for producing a crosslinked polycarbonate-siloxane copolymer resin, characterized in that a polycarbonate-siloxane copolymer resin is bonded to another copolymer chain in a repeating unit containing the siloxane of the copolymer chain,
In the repeating unit containing the siloxane, polycarbonate having a methyl group and / or a vinyl group directly attached to a silicon atom - copolymer with other copolymer cross-linking type polycarbonate Ru to form a bond with the chain -Manufacturing method of siloxane copolymer resin. A method for producing a crosslinked polycarbonate-siloxane copolymer resin, characterized in that a polycarbonate-siloxane copolymer resin is bonded to another copolymer chain in a repeating unit containing the siloxane of the copolymer chain,
Combine, row intends cross-linking type polycarbonate using a radical initiator with other copolymer chain in the repeating unit containing the siloxane - preparation of the siloxane copolymer resin. The crosslinked polycarbonate-siloxane according to claim 1 or 2 , wherein the repeating unit containing siloxane is bonded to another copolymer chain using a compound having two or more silicon-hydrogen bonds in the molecular skeleton. Production method of copolymer resin. Bonds with other copolymer chain in the repeating unit containing the siloxane, in the molecular skeleton, silicon - silicon by hydrogen bonding and hydrolysis - according to claim 1 or 2 carried out using a compound having a group which is generated hydroxyl bond A method for producing a cross-linked polycarbonate-siloxane copolymer resin according to 1.