Resin, resin precursor composition, coating liquid composition, electrophotographic photoreceptor, method for producing electrophotographic photoreceptor, molded product, and electronic device

Abstract

A resin characterized in that it is at least one resin selected from the group consisting of aromatic polycarbonates and polyarylates, and the resin has a bond between polymer chains formed by a reaction between an allyl group and a maleimide group.

Description

Technical Field

[0001] The present invention relates to a resin, a resin precursor composition, a coating liquid composition, an electrophotographic photoreceptor, a method for producing an electrophotographic photoreceptor, a molded product and an electronic device. Background Art

[0002] Polycarbonate resins have been used as raw materials for molded products in various industrial fields due to their excellent mechanical, thermal and electrical properties. In recent years, polycarbonate resins have also been widely used in the field of functional products that also utilize their optical properties. In addition, as the application fields of polycarbonate resins expand, the performance requirements for polycarbonate resins have also diversified, and polycarbonate resins with various chemical structures have been proposed, not only limited to conventional polycarbonate resins.

[0003] As an example of a functional product, there is an organic electrophotographic photoreceptor using a polycarbonate resin as a binder resin for functional materials such as a charge generating material and a charge transporting material.

[0004] The organic electrophotographic photoreceptor is required to have the specified sensitivity, electrical characteristics and optical characteristics corresponding to the applied electrophotographic process. The electrophotographic photoreceptor repeats the operations such as corona charging, toner development, transfer to paper and cleaning on the surface of its photosensitive layer, so that electrical and mechanical external forces are applied during these operations. Therefore, in order to maintain the image quality of electrophotography for a long time, the photosensitive layer provided on the surface of the electrophotographic photoreceptor is required to be durable against these external forces. In addition, the organic electrophotographic photoreceptor is usually manufactured by dissolving a binder resin together with a functional material in an organic solvent and casting a film on a conductive substrate, etc., so solubility and stability in organic solvents are required.

[0005] In the past, polycarbonate resins made of 2,2-bis(4-hydroxyphenyl)propane or 1,1-bis(4-hydroxyphenyl)cyclohexane have been used as binder resins for photoreceptors, but the durability is not satisfactory. As one of the solutions to improve the durability, it is considered to improve the wear resistance of the photosensitive layer. As an effective technology for improving the wear resistance of the photosensitive layer, a technology for cross-linking polycarbonate is known.

[0006] Patent Document 1 discloses a technique for crosslinking a polycarbonate resin having an allyl group by a crosslinking reaction using a radical initiator. According to Patent Document 1, the crosslinked polycarbonate resin has better mechanical strength (tensile strength, etc.) than bisphenol A polycarbonate resin.

[0007] Patent Document 2 describes a cross-linked polycarbonate resin obtained by cross-linking a polycarbonate resin having an epoxy group or the like by an ionic mechanism.

[0008] Patent Document 3 describes a cross-linking technique based on reacting a polycarbonate having double bonds with a compound having a plurality of silicon-hydrogen bonds in the presence of a platinum catalyst.

[0009] Patent Document 3 describes a crosslinking technique based on reacting a polycarbonate having a double bond with a compound having an alkoxy group and hydrogen on a silicon atom in the presence of a platinum catalyst, followed by hydrolysis and polycondensation.

[0010] Patent Document 4 discloses a cross-linking technique based on irradiating a polycarbonate copolymer having an allyl group with electron beams while being heated to 120° C. or higher and 260° C. or lower.

[0011] Patent Document 5 discloses a method in which a triarylamine having a specific structure and a radical polymerizable compound having no triarylamine structure are used and heated in the absence of a catalyst to crosslink with a polycarbonate having an allyl group.

[0012] Patent Document 6 describes a resin obtained by extending the chain length of a resin having an anthracene skeleton at the terminal of an aliphatic-aromatic polyester using bismaleimide.

[0013] Patent Document 7 discloses a crosslinked resin formed by reacting an aliphatic polyester, polyamide or polyurea having a furan structure with a polyfunctional maleimide.

[0014] Non-Patent Document 1 discloses a resin obtained by cross-linking a resin in which an anthracene dicarboxylic acid skeleton is introduced into a part of an aliphatic-aromatic polyester using a bifunctional maleimide compound.

[0015] Prior art literature

[0016] Patent Literature

[0017] Patent Document 1: Japanese Patent Application Laid-Open No. 10-77338

[0018] Patent Document 2: Japanese Patent Application Laid-Open No. 9-319102

[0019] Patent Document 3: Japanese Patent Application Publication No. 2000-44668

[0020] Patent Document 4: Japanese Patent Application Publication No. 2007-314719

[0021] Patent Document 5: Japanese Patent Application Publication No. 2010-72019

[0022] Patent Document 6: Japanese Patent Application Publication No. 2003-286347

[0023] Patent Document 7: U.S. Patent No. 3435003

[0024] Non-patent literature

[0025] Non-patent document 1: Macromolecules 1999, 32, 5786-5792 Summary of the invention

[0026] Problem that the invention aims to solve

[0027] However, in the polycarbonate resin described in Patent Document 1, there is a concern that the charge transport material (CTM) may be denatured due to the use of a radical initiator, or that the added initiator may remain in the photoreceptor, thereby increasing the residual potential when used as a photoreceptor.

[0028] In the cross-linked polycarbonate resin described in Patent Document 2, a compound having a nucleophilic group such as an amino group or an acidic group such as a carboxylic anhydride group is used to initiate the reaction. Therefore, there is a problem of CTM denaturation or an increase in residual potential when used as a photoreceptor due to the added compound remaining in the photoreceptor. In addition, Patent Document 2 does not confirm that the disclosed resin is cross-linked, and it is unclear whether the disclosed effect of improving physical properties is derived from the cross-linked structure.

[0029] In the polycarbonate described in Patent Document 3, since a platinum catalyst is used, there are problems such as CTM denaturation or increase in residual potential when used as a photoreceptor due to the added catalyst remaining in the photoreceptor. In addition, it is difficult to suppress the reaction in the coating liquid, and there are problems such as increase in viscosity or gelation during storage of the coating liquid.

[0030] The polycarbonate described in Patent Document 4 has a problem that its CTM is denatured when irradiated with electron beams, and the residual potential increases when used as a photoreceptor.

[0031] As is apparent from the above, there are also examples of obtaining crosslinked polycarbonate and crosslinked polyarylate without including a radical initiator or reaction catalyst that causes deterioration of electrical properties and without using UV rays, electron beams, etc. that denature CTM.

[0032] As such an example, a technique is reported in Patent Document 5, which uses monomers with high free radical polymerization activity, which can be free radically polymerized by heating without the use of an initiator or UV irradiation, wherein a polycarbonate having an allyl group coexists. However, it is believed that since a monomer that undergoes free radical polymerization without an initiator or light irradiation is used, a polymer of only the polymerizable monomer is mainly generated, and the probability of the reaction of the polycarbonate having an allyl group with a relatively low free radical polymerization activity with the polymerizable monomer is low. Therefore, it is believed that the resulting composition does not have a dense three-dimensional network structure of the polymer, and the cross-linked polymer of the polycarbonate resin and the free radical polymerization monomer exists separately, becoming a composition in which only a part of them is bonded. In addition, the effect of improving the physical properties obtained by the high molecular weight of the charge transport material that usually exists as a low molecule is decisive, and the physical property improvement obtained by the cross-linking of the polycarbonate part is insufficient. In addition, since a highly active compound that undergoes free radical polymerization without an initiator is used, it is difficult to suppress the progress of polymerization in the stage of the coating liquid composition, and there are problems such as viscosity increase and gelation during the storage of the coating liquid.

[0033] As a cross-linking technology that can meet these requirements, Patent Document 6 discloses a linear polymer obtained by molecular weight elongation reaction of aliphatic-aromatic polyester based on Diels-Alder reaction as an example of using resins other than polycarbonate. However, the purpose of the invention described in Patent Document 6 is a technology having the following characteristics, which utilizes the reverse Diels-Alder reaction in which the bonds formed by the Diels-Alder reaction dissociate at high temperature, and at high temperature, the melt viscosity is reduced due to low viscosity, thereby improving thermoformability, and the molecular weight is increased in the actual temperature range of use, thereby improving mechanical properties, and maintaining solubility due to having a linear structure. Moreover, this purpose is different from the purpose of the present invention, which is intended to improve solvent resistance or mechanical strength by introducing a cross-linking structure. In addition, Patent Document 6 does not record or teach the application of the technology described in Patent Document 6 to aromatic polycarbonate or wholly aromatic polyester.

[0034] In addition, Patent Document 7 records examples of crosslinking aliphatic polyesters, polyamides, or polyureas using the Diels-Alder reaction. However, the purpose of these examples is to impart solvent resistance to soft aliphatic resins by crosslinking, and to obtain an elastomer that can be used as a diaphragm seal or adhesive for the intended use. Moreover, the technical concept of these examples is different from the concept of the present invention of further increasing the strength of aromatic polycarbonates or wholly aromatic polyesters with high mechanical strength by crosslinking. In addition, Patent Document 7 does not record or teach the application of the technology described in Patent Document 7 to aromatic polycarbonates or wholly aromatic polyesters.

[0035] Non-patent document 1 describes an example of introducing an anthracene dicarboxylic acid skeleton into polyethylene terephthalate (PET) and crosslinking using a bifunctional maleimide compound. The purpose of this example is similar to the purpose of the present invention in that the mechanical properties are improved by heating crosslinking, but Non-patent document 1 does not describe or teach an example of applying the technology described in Non-patent document 1 to polycarbonate or polyarylate. In addition, if it is considered to be used for electrophotographic photoreceptor applications, PET generally has low solubility in organic solvents such as THF used as a coating solvent, and has poor compatibility with charge transport materials such as triarylamines, and cannot be used for this purpose.

[0036] The first object of the present invention is to provide at least one of aromatic polycarbonate and polyarylate resins having a novel structure, which substantially does not contain a polymer of only a single component in the presence of a plurality of polymerizable components, and can be manufactured without containing a free radical initiator or reaction catalyst that causes deterioration of electrical properties and without using UV or electron beams that denature charge transport materials (CTM). The second object of the present invention is to provide a resin precursor composition and a coating liquid composition that have the characteristics of less change in properties due to the fact that the reaction is not easy to occur at the stage of the coating liquid composition. In addition, the third object of the present invention is to provide an electrophotographic photoreceptor and a method for manufacturing an electrophotographic photoreceptor that have good solvent resistance, excellent wear resistance, are not prone to mechanical degradation, and do not deteriorate the residual potential by containing the above-mentioned resin.

[0037] Means used to solve problems

[0038] According to one aspect of the present invention, there is provided a resin which is at least one resin selected from the group consisting of aromatic polycarbonates and polyarylates, wherein the resin has a bond between polymer chains formed by a reaction between an allyl group and a maleimide group.

[0039] According to one aspect of the present invention, there is provided a resin precursor composition, which is characterized in that the resin according to one aspect of the present invention can be prepared through a cross-linking reaction.

[0040] According to one aspect of the present invention, there is provided a coating liquid composition comprising the resin precursor composition according to one aspect of the present invention and an organic solvent.

[0041] According to one aspect of the present invention, there is provided an electrophotographic photoreceptor characterized in that the resin according to one aspect of the present invention is contained in an outermost layer.

[0042] According to one embodiment of the present invention, there is provided a method for manufacturing an electronic photographic photosensitive body, characterized in that it comprises: a step of applying the coating liquid composition involved in the above-mentioned one embodiment of the present invention to a conductive substrate by a wet molding method; a step of removing the organic solvent in the above-mentioned coating liquid composition by heating; and a step of causing a resin precursor composition in the above-mentioned coating liquid composition to undergo a cross-linking reaction by continuing to heat simultaneously with or after the heating in the above-mentioned step of removing the organic solvent.

[0043] According to one aspect of the present invention, there is provided a molded product, characterized in that the molded product includes the resin according to one aspect of the present invention described above.

[0044] According to one aspect of the present invention, there is provided an electronic device, characterized in that the electronic device includes the resin according to one aspect of the present invention described above.

[0045] According to one embodiment of the present invention, for at least one of aromatic polycarbonate and polyarylate resins, a resin having a novel structure that can be produced without containing a free radical initiator or reaction catalyst that causes deterioration of electrical properties and without using UV or electron beams that denature charge transport materials (CTM) and that substantially does not contain a homopolymer of a polymerizable component can be provided. In addition, according to one embodiment of the present invention, a resin precursor composition and a coating liquid composition that are not prone to react at the stage of a coating liquid composition and thus have little change in properties can be provided. In addition, according to one embodiment of the present invention, by including the above-mentioned resin, an electrophotographic photoreceptor having excellent wear resistance, being not prone to mechanical degradation, and having no deterioration of residual potential can be provided. DETAILED DESCRIPTION

[0046] The present inventors have conducted intensive studies to solve the above problems and have found that a crosslinking precursor polycarbonate resin, a polyarylate resin and a copolymer thereof having a structure that can be crosslinked by a reaction between an allyl group and a maleimide group have excellent solution stability, and the obtained crosslinked resin has excellent solvent resistance and abrasion resistance, and has good electrical properties when used as an electrophotographic photoreceptor. The present invention has been completed based on such findings.

[0047] [Resin]

[0048] The resin involved in the present embodiment is at least one resin selected from the group consisting of aromatic polycarbonates and polyarylates. Specific examples of the resin include aromatic polycarbonates, polyarylates, and aromatic polycarbonate-polyarylate copolymers (hereinafter, these are also simply referred to as "PCs").

[0049] Hereinafter, PCs according to one embodiment of the present invention, a coating liquid composition using the PCs, an electrophotographic photoreceptor, and an electronic device will be described in detail.

[0050] The resin according to the present embodiment has a bond between polymer chains formed by a reaction between an allyl group and a maleimide group.

[0051] The resin according to the present embodiment can be obtained by combining a polymer having a structure that can be crosslinked by reaction between an allyl group and a maleimide group and having at least one of an allyl group and a maleimide group with a crosslinking agent or a polymer having respective counterpart groups and subjecting them to a crosslinking reaction.

[0052] The bonds between polymer chains in the resin according to the present embodiment can be formed, for example, by the following combined reactions.

[0053] (i) Reaction of a polymer having two or more allyl structures in the polymer chain with a compound having a maleimide group having two or more functional groups

[0054] (ii) Reaction of a polymer having two or more maleimide structures in the polymer chain with a compound having two or more functional groups and an allyl group

[0055] (iii) Reaction of a polymer having two or more allyl structures in the polymer chain with a polymer having two or more maleimide structures in the polymer chain

[0056] (iv) a reaction of a polymer having a structure of both an allyl group and a maleimide group in one polymer chain and wherein the average number of the allyl group and the average number of the maleimide group in each polymer chain is 1 or more

[0057] The bonding between polymer chains in the resin according to the present embodiment may be, for example, the following reaction (i-1).

[0058] (i-1)

[0059] Reaction of a polymer having two or more allyl groups in the main chain of the polymer chain with a compound having a maleimide group having two or more functional groups

[0060] The bonding between polymer chains in the resin according to the present embodiment may be, for example, at least any one of the following reactions (iii-1) to (iii-8).

[0061] (iii-1)

[0062] A polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain, and

[0063] Reaction of polymers with more than two allyl groups in the polymer chain

[0064] (iii-2)

[0065] A polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain, and

[0066] The reaction of a polymer having more than two allyl structures in the polymer chain and one allyl structure at each of the two ends of the polymer chain and one or more allyl structures in the main chain

[0067] (iii-3)

[0068] A polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain, and

[0069] Reaction of a polymer having more than two allyl structures in a polymer chain, having one allyl structure at one end of the polymer chain, having no allyl structure at the other end, and having two or more allyl structures in the main chain

[0070] (iii-4)

[0071] A polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain, and

[0072] Reaction of polymers that do not have an allylic structure at both ends of the polymer chain and have more than two allylic structures in the main chain

[0073] (iii-5)

[0074] A polymer having two allyl structures and one of the allyl structures at each end of the polymer chain, and

[0075] Reaction of polymers having more than two maleimide structures in the polymer chain

[0076] (iii-6)

[0077] A polymer having two allyl structures and one of the allyl structures at each end of the polymer chain, and

[0078] The reaction of a polymer having more than two maleimide structures in the polymer chain and having one maleimide structure at each of the two ends of the polymer chain and having one or more maleimide structures in the main chain

[0079] (iii-7)

[0080] A polymer having two allyl structures and one of the allyl structures at each end of the polymer chain, and

[0081] Reaction of a polymer having more than two maleimide structures in a polymer chain, having one maleimide structure at one end of the polymer chain, having no maleimide structure at the other end, and having two or more maleimide structures in the main chain

[0082] (iii-8)

[0083] A polymer having two allyl structures and one of the allyl structures at each end of the polymer chain, and

[0084] Reaction of polymers that do not have maleimide structures at both ends of the polymer chain and have more than two maleimide structures in the main chain

[0085] The polymer used for bonding between polymer chains in the resin according to the present embodiment also preferably does not have two or more at least one structure selected from the group consisting of allyl structures and maleimide structures at the ends of the polymer chains.

[0086] For example, in the case of the reaction (i) above, in a polymer having two or more allyl structures, an allyl structure may not be bonded to at least one of one end and the other end of the polymer chain, and an allyl structure may not be bonded to the end of the polymer chain.

[0087] For example, in the case of the reaction (ii) above, in a polymer having two or more maleimide structures, the maleimide structure may not be bonded to at least one of one end and the other end of the polymer chain, and the maleimide structure may not be bonded to the end of the polymer chain.

[0088] For example, in the case of the reaction (iii) above, in a polymer having two or more allyl structures, the allyl structure may not be bonded to at least one of one end and the other end of the polymer chain, and in a polymer having two or more maleimide structures, the maleimide structure may not be bonded to at least one of one end and the other end of the polymer chain, and further, the allyl structure and the maleimide structure may not be bonded to the ends of the polymer chain.

[0089] The polymer used for bonding between polymer chains in the resin according to the present embodiment also preferably has one or more structures selected from the group consisting of an allyl structure and a maleimide structure in the main chain of the polymer chain.

[0090] For example, in the case of the reaction (i) above, in a polymer having two or more allyl structures, one or more allyl structures may be bonded to the main chain of the polymer chain, or all the allyl structures may be bonded to the main chain of the polymer chain.

[0091] For example, in the case of the reaction (ii) above, in a polymer having two or more maleimide structures, one or more maleimide structures may be bonded to the main chain of the polymer chain, or all of the maleimide structures may be bonded to the main chain of the polymer chain.

[0092] For example, in the case of the reaction (iii) above, in a polymer having two or more allyl structures, one or more allyl structures may be bonded to the main chain of the polymer chain, and in a polymer having two or more maleimide structures, one or more maleimide structures may be bonded to the main chain of the polymer chain.

[0093] In addition, for example, in the case of the reaction (iii) above, in a polymer having two or more allyl structures, all the allyl structures may be bonded to the main chain of the polymer chain, and in a polymer having two or more maleimide structures, all the maleimide structures may be bonded to the main chain of the polymer chain.

[0094] When the main chain of the polymer chain is bonded to an allyl structure or a maleimide structure, the allyl structure or the maleimide structure may be directly bonded to the main chain of the polymer chain or may be bonded to the main chain of the polymer chain via other groups.

[0095] The polymer used for bonding between polymer chains in the resin according to the present embodiment also preferably does not have two or more at least one group selected from the group consisting of allyl groups and maleimide groups at the ends of the polymer chains.

[0096] For example, in the case of the reaction (iv) above, examples of the polymer having a structure having both an allyl group and a maleimide group in one polymer chain include the following polymers.

[0097] (iv-1) A polymer having no allyl group or maleimide group bonded to at least one of one end and the other end of the polymer chain.

[0098] (iv-2) A polymer having one selected from an allyl group and a maleimide group bonded to one end of the polymer chain, having neither an allyl group nor a maleimide group bonded to the other end of the polymer chain, and having at least one selected from the other selected from the allyl group and the maleimide group bonded to the main chain of the polymer chain.

[0099] (iv-3) A polymer having no allyl group or maleimide group bonded to the end of the polymer chain

[0100] The polymer used for bonding between polymer chains in the resin according to the present embodiment also preferably has one or more at least one group selected from the group consisting of an allyl group and a maleimide group in the main chain of the polymer chain.

[0101] For example, in the case of the reaction (iv) above, in a polymer having a structure in which one polymer chain has both an allyl group and a maleimide group, one or more of the allyl group and the maleimide group may be bonded to the main chain of the polymer chain, and all of the allyl group and the maleimide group may be bonded to the main chain of the polymer chain.

[0102] For example, in the case of the reaction (iv) above, examples of the polymer having a structure having both an allyl group and a maleimide group in one polymer chain include the following polymers.

[0103] (iv-4) A polymer having one maleimide group bonded to each of the two ends of the polymer chain and at least one allyl group bonded to the main chain of the polymer chain.

[0104] When an allyl group or a maleimide group is bonded to the main chain of the polymer chain, the allyl group or the maleimide group may be bonded to the main chain of the polymer chain directly or via other groups.

[0105] It is also preferred that the bonds between polymer chains in the resin according to the present embodiment are not just bonds between the terminals of the polymer chains.

[0106] That is, the bonds between polymer chains in the resin involved in the present embodiment also preferably include at least any one of the bonds selected from the bond between one of the allyl group and the maleimide group bonded to the terminal of one polymer and the other of the allyl group and the maleimide group bonded to the main chain of another polymer, and the bond between one of the allyl group and the maleimide group bonded to the main chain of one polymer and the other of the allyl group and the maleimide group bonded to the main chain of another polymer.

[0107] By causing three-dimensional crosslinking of polymer chains instead of just bonding between the ends of the polymer chains, the solvent resistance of the resin is likely to be improved.

[0108] In addition, even if the ends of the polymer chains are not bonded to each other, three-dimensional crosslinking does not occur in the case of bonding between polymer chains having two reactive groups, and a linear polymer is formed. Therefore, the bonding between polymer chains in the resin involved in the present embodiment is preferably not a bonding formed solely by a reaction between polymers having two reaction points (reactive groups) in the polymer chain (for example, polymers having reactive groups at the ends).

[0109] In addition, the bonding between polymer chains in the resin according to the present embodiment may include bonding between the terminals of the polymer chains.

[0110] In the present embodiment, any allyl group or allyl structure can be used without particular limitation as long as it is a structure that reacts with a maleimide group. Examples of the allyl group or allyl structure include compounds or resins having a diallylbisphenol skeleton, allylphenol, and eugenol due to their high reactivity.

[0111] In the present embodiment, the allyl group or the allyl structure preferably includes at least one of the structures represented by the following formulas (AL1), (AL2), and (AL3). The allyl structure represented by the following formula (AL1) has two allyl groups.

[0112]

Chemical formula 1

[0113]

[0114]

Chemical formula 2

[0115]

[0116] (In the above general formula (AL1),

[0117] X1 is independently selected from

[0118] single bond,

[0119] -C(-R 11 )2-、

[0120] -O-,

[0121] -S-,

[0122] -SO-,

[0123] -SO2-,

[0124] -N(-R 12 )-,

[0125] -P(-R 13 )-、

[0126] -P=O(-R 14 )-、

[0127] Carbonyl,

[0128] Ester group,

[0129] Amide group,

[0130] an alkylene group having 2 to 20 carbon atoms,

[0131] an alkylidene group having 2 to 20 carbon atoms,

[0132] Alkylene arylene alkylidene having 8 to 20 carbon atoms,

[0133] A cycloalkylene group having 3 or more and 20 or less ring carbon atoms,

[0134] A cycloalkylidene group having 3 or more and 20 or less ring carbon atoms,

[0135] an arylene group having 6 or more and 12 or less ring carbon atoms,

[0136] a bicycloalkanediyl group having 4 to 20 ring carbon atoms,

[0137] A tricycloalkanediyl group having 5 to 20 ring carbon atoms,

[0138] A bicycloalkylidene group having 4 to 20 ring carbon atoms,

[0139] a tricycloalkylidene group having 5 to 20 ring carbon atoms, and

[0140] A group consisting of one or more of the group consisting of naphthylene,

[0141] R 11 ~R 14 Each independently

[0142] Hydrogen atoms,

[0143] Halogen atoms,

[0144] an alkyl group having 1 to 10 carbon atoms,

[0145] an aryl group having 6 or more and 12 or less ring carbon atoms, or

[0146] A fluorinated alkyl group having 1 to 10 carbon atoms.

[0147] In the above general formulae (AL1) to (AL3), * represents a bonding position.

[0148] In the present embodiment, the maleimide group or maleimide structure can be applied without particular limitation as long as it is a structure that reacts with an allyl group, and the following groups or structures can be preferably used.

[0149] Examples of the compound or resin having a maleimide group or maleimide structure include: 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide (2,2-bis[4-(4-maleimidephenoxy)phenyl]propane), 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimide)phenyl Bismaleimides such as N,N'-(2,2'-diethyl-6,6'-dimethylenediphenyl)bismaleimide, N,N'-(4-methyl-m-phenylene)bismaleimide, N,N'-m-phenylenebismaleimide, N,N'-m-phenylenebismaleimide, polyphenylmethanebismaleimide, monomaleimides such as N-phenylmaleimide, and PC having a structure in which the molecular ends are capped with the following compound (MA4-1).

[0150]

Chemical formula 3

[0151]

[0152] In the present embodiment, the maleimide group or the maleimide structure preferably includes a structure represented by the following general formula (MA1).

[0153]

Chemical formula 4

[0154]

[0155] (In the above general formula (MA1),

[0156] X2 is a single bond, or a connecting group to other skeletons,

[0157] X2 as the linking group is a group containing at least one atom selected from the group consisting of carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms and boron atoms, and the bonding method between the atoms constituting the linking group is composed of covalent bonds.

[0158] In the above general formula (MA1), * represents a bonding position.

[0159] In the present embodiment, the compound or polymer having a plurality of maleimide groups or maleimide structures also preferably includes a plurality of structures represented by the above general formula (MA1).

[0160] When the compound or polymer contains multiple structures represented by the above-mentioned general formula (MA1), it is preferred that the multiple structures represented by the above-mentioned general formula (MA1) are the same as or different from each other, and the multiple structures represented by the above-mentioned general formula (MA1) are connected to each other by single bonds or via other groups.

[0161] In the present embodiment, it is preferred that the maleimide group or the maleimide structure is included in at least one of the structures represented by the following general formula (MA2) and general formula (MA3).

[0162]

Chemical formula 5

[0163]

[0164]

Chemical formula 6

[0165]

[0166] (X2 in the above general formula (MA2), and X in the above general formula (MA3) 21 and X 22 Each independently has the same meaning as X2 in the above general formula (MA1),

[0167] Y2 in the above general formula (MA3) is a group containing an aromatic polycarbonate skeleton or a polyarylate skeleton.

[0168] In the present embodiment, the maleimide group or the maleimide structure preferably includes a structure represented by the following general formula (MA4): In the following general formula (MA4), * represents a bonding position.

[0169]

Chemical formula 7

[0170]

[0171] In the present embodiment, the ratio of the allyl group or the allyl structure to the maleimide group or the maleimide structure can be appropriately set according to the target physical properties and the target application.

[0172] The molar amount of allyl group M AL Molar amount M relative to maleimide group MA The molar ratio (M AL / M MA ) is preferably 0.01 or more and 100 or less, more preferably 0.1 or more and 10 or less, and still more preferably 0.2 or more and 5 or less. AL / M MA When the ratio is 0.01 to 100, crosslinking proceeds sufficiently, and solvent resistance and mechanical properties are likely to be improved.

[0173] Examples of the bonds between polymer chains formed by the reaction between the allyl group and the maleimide group in the resin according to the present embodiment include bonds having the following structures.

[0174]

Chemical formula 8

[0175]

[0176]

Chemical formula 9

[0177]

[0178] (In the above general formulae (CL-AM11) and (CL-AM12), X1 has the same meaning as X1 in the above general formula (AL1), X2 has the same meaning as X2 in the above general formula (MA1), and * indicates a bonding position.)

[0179] (In the above general formula (CL-AM13), X1 has the same meaning as X1 in the above general formula (AL1), and X 21 and X 22 Each independently has the same meaning as X2 in the above general formula (MA1), Y2 has the same meaning as Y2 in the above general formula (MA3), and * indicates a bonding position.)

[0180]

Chemical formula 10

[0181]

[0182]

Chemical formula 11

[0183]

[0184] (In the above general formulae (CL-AM21), (CL-AM22), (CL-AM31) and (CL-AM32), X2 has the same meaning as X2 in the above general formula (MA1), and * indicates a bonding position.)

[0185] (In the above general formulas (CL-AM23) and (CL-AM33), X 21 and X 22 Each independently has the same meaning as X2 in the above general formula (MA1), Y2 has the same meaning as Y2 in the above general formula (MA3), and * indicates a bonding position.)

[0186]

Chemical formula 12

[0187]

[0188] (In the above general formula (CL-AM14), X1 has the same meaning as X1 in the above general formula (AL1), and in the above general formulas (CL-AM14), (CL-AM24) and (CL-AM34), * represents a bonding position.)

[0189] The bond between polymer chains may be a bond formed by an ene reaction between an allyl group and a maleimide group, or a bond formed by a Diels-Alder reaction that occurs after an ene reaction between an allyl group and a maleimide group. In the resin involved in the present embodiment, as a bond between polymer chains formed by the reaction between an allyl group and a maleimide group, there may be only a bond formed by an ene reaction, or there may be only a bond formed by a Diels-Alder reaction, or there may be both a bond formed by an ene reaction and a bond formed by a Diels-Alder reaction. For example, in the above-mentioned general formula (CL-AM11), for the bond between the two parties formed by the ene reaction, a Diels-Alder reaction may further occur to form a bond shown in the following general formula (CL-AM111). In addition, for example, in the above-mentioned general formula (CL-AM11), one bond formed by the ene reaction may further undergo a Diels-Alder reaction, while the other bond formed by the ene reaction may not undergo a Diels-Alder reaction, thereby forming a bond represented by the following general formula (CL-AM112) or (CL-AM113). Among the bonds represented by the above-mentioned general formulas (CL-AM12), (CL-AM13), (CL-AM14), (CL-AM21), (CL-AM22), (CL-AM23), (CL-AM24), (CL-AM31), (CL-AM32), (CL-AM33) and (CL-AM34), at least any one of the bonds formed by the ene reaction may undergo a Diels-Alder reaction to form a bond.

[0190]

Chemical formula 13

[0191]

[0192]

Chemical formula 14

[0193]

[0194] (In the above general formulae (CL-AM111), (CL-AM112) and (CL-AM113), X1 has the same meaning as X1 in the above general formula (AL1), X2 has the same meaning as X2 in the above general formula (MA1), and * indicates a bonding position.)

[0195] The resin according to the present embodiment preferably includes at least one of the structures represented by the following general formula (UN1) and general formula (UN2).

[0196]

Chemical formula 15

[0197]

[0198] (In the above general formula (UN1) and general formula (UN2), Ar3, Ar 31 and Ar 32 Each is independently a group represented by the following general formula (UN11).

[0199] In the above general formula (UN1) and general formula (UN2), * represents a bonding position.

[0200]

Chemical formula 16

[0201]

[0202] (In the above general formula (UN11),

[0203] m3 is 0, 1, or 2,

[0204] n3 is 4,

[0205] Multiple R3 are independently

[0206] Hydrogen atoms,

[0207] Halogen atoms,

[0208] an alkyl group having 1 to 10 carbon atoms,

[0209] an aryl group having 6 or more and 12 or less ring carbon atoms, or

[0210] a fluorinated alkyl group having 1 to 10 carbon atoms,

[0211] X3 is independently selected

[0212] single bond,

[0213] -C(-R 31 )2-、

[0214] -O-,

[0215] -S-,

[0216] -SO-,

[0217] -SO2-,

[0218] -N(-R 32 )-,

[0219] -P(-R 33)-、

[0220] -P=O(-R 34 )-、

[0221] Carbonyl,

[0222] Ester group,

[0223] Amide group,

[0224] an alkylene group having 2 to 20 carbon atoms,

[0225] an alkylidene group having 2 to 20 carbon atoms,

[0226] A cycloalkylene group having 3 or more and 20 or less ring carbon atoms,

[0227] A cycloalkylidene group having 3 or more and 20 or less ring carbon atoms,

[0228] an arylene group having 6 or more and 20 or less ring carbon atoms,

[0229] a bicycloalkanediyl group having 4 to 20 ring carbon atoms,

[0230] A tricycloalkanediyl group having 5 to 20 ring carbon atoms,

[0231] a bicycloalkylidene group having 4 to 20 ring carbon atoms, and

[0232] a group consisting of one or more of the group consisting of tricycloalkylidene groups having 5 or more and 20 or less ring carbon atoms,

[0233] R 31 ~R 34 Each independently

[0234] Hydrogen atoms,

[0235] Halogen atoms,

[0236] an alkyl group having 1 to 10 carbon atoms,

[0237] an aryl group having 6 or more and 12 or less ring carbon atoms, or

[0238] A fluorinated alkyl group having 1 to 10 carbon atoms.

[0239] In the above general formula (UN11), * represents a bonding position.

[0240] In the above general formula (AL1), R 11 ~R 14 The halogen atom represented by R3 in the general formula (UN11) can be exemplified independently by a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0241] In the above general formula (AL1), R 11 ~R 14 The alkyl group having 1 to 10 carbon atoms represented by R3 in the general formula (UN11) and each independently thereof includes, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, sec-hexyl, tert-hexyl, isoheptyl, sec-heptyl, tert-heptyl, isooctyl, sec-octyl, tert-octyl, isononyl, sec-nonyl, tert-nonyl, isodecyl, sec-decyl and tert-decyl.

[0242] In the above general formula (AL1), R 11 ~R 14 In the general formula (UN11), the aryl group having 6 to 12 ring carbon atoms represented by R3 independently includes, for example, a phenyl group, a naphthyl group, and a biphenyl group.

[0243] In the above general formula (AL1), R 11 ~R 14 And the fluorinated alkyl group having 1 or more and 10 carbon atoms represented by R3 in the above general formula (UN11) can each independently include, for example: an alkyl group in which at least one hydrogen atom on a carbon atom is substituted by a fluorine atom among the alkyl groups exemplified in the alkyl group having 1 or more and 10 carbon atoms represented by R3 in the above general formula (UN11).

[0244] The alkylene groups having a carbon number of 2 or more and 20 or less represented by X1 in the above general formula (AL1) and X3 in the above general formula (UN11) can each independently be straight-chain or branched alkylene groups, for example, ethylene, propylene, isopropylene, butylene, hexylene, octylene and decylene groups.

[0245] The alkylidene groups having a carbon number of 2 or more and 20 or less represented by X1 in the above general formula (AL1) and X3 in the above general formula (UN11) can each independently include groups such as ethylidene, propylidene, butylidene, hexylidene, octylidene, decylidene, pentadecylidene and eicosylidene.

[0246] The cycloalkylene groups having 3 or more and 20 or less carbon atoms represented by X1 in the general formula (AL1) and X3 in the general formula (UN11) can each independently include groups such as cyclopropylene, cyclobutylene, cyclohexylene, cyclooctylene, cyclodecylene, cyclopentadecanylene, and cycloeicosaneylene.

[0247] The cycloalkylidene groups having 3 or more and 20 or less carbon atoms represented by X1 in the above general formula (AL1) and X3 in the above general formula (UN11) can each independently include groups such as cyclopropylidene, cyclobutylidene, cyclohexylidene, cyclooctylidene, cyclodecylidene, cyclopentadecanylidene, cyclododecylidene and cycloeicosylidene.

[0248] The arylene group having 6 to 12 ring carbon atoms represented by X1 in the general formula (AL1) and the arylene group having 6 to 20 ring carbon atoms represented by X3 in the general formula (UN11) can each independently include groups such as phenylene, naphthylene and biphenylene.

[0249] The alkylidene arylene alkylidene group having 8 or more and 20 or less carbon atoms represented by X1 in the general formula (AL1) can be independently a group in which the alkylidene group and the arylene group shown in the above examples are bonded in sequence. As the alkylidene arylene alkylidene group, for example, a group represented by the following formula (L1) or formula (L2) can be mentioned.

[0250]

Chemical formula 17

[0251]

[0252] The bicycloalkanediyl group represented by X1 in the general formula (AL1) and X3 in the general formula (UN11) and having a ring carbon number of 4 or more and 20 or less each independently exemplifies a bicyclic ring of the cycloalkylene group, and the tricycloalkanediyl group represented by X1 in the general formula (AL1) and having a ring carbon number of 5 or more and 20 or less each independently exemplifies a tricyclic ring of the cycloalkylene group. For example, groups such as adamantanediyl and tricyclodecanediyl can be cited.

[0253] The bicycloalkylidene group represented by X1 in the general formula (AL1) and X3 in the general formula (UN11) and having a ring carbon number of 4 or more and 20 or less each independently exemplifies a bicyclic body of the above cycloalkylidene group, and the tricycloalkylidene group represented by X1 in the general formula (AL1) and having a ring carbon number of 5 or more and 20 or less each independently exemplifies a tricyclic body of the above cycloalkylidene group. For example, groups such as adamantylidene, tricyclodecanylidene, and tricyclodecanylidene can be cited.

[0254] In the above general formula (UN11), R of X3 is 31 To R 34 Examples of the halogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 12 ring carbon atoms, and fluoroalkyl group having 1 to 10 carbon atoms are the same as those represented by R3 in the above general formula (UN11).

[0255] [Resin precursor composition]

[0256] The resin precursor composition according to the present embodiment can prepare the resin according to the present embodiment described above through a cross-linking reaction.

[0257] That is, the resin precursor composition according to the present embodiment includes a polymer having a structure that can be crosslinked by reaction between an allyl group and a maleimide group and having at least one of an allyl group and a maleimide group in the structure, and a crosslinking agent or a polymer having respective counterpart groups.

[0258] In addition, as a combination of groups capable of cross-linking reaction, when one is an allyl group, the “counterpart” is a maleimide group, and when the other is a maleimide group, the “counterpart” is an allyl group.

[0259] In the resin precursor composition according to the present embodiment, the compound or polymer having an allyl group or an allyl structure, the compound or polymer having a maleimide group or a maleimide structure, and the ratio of the allyl group to the maleimide group are the same as those of the resin according to the present embodiment.

[0260] The concentrations of the allyl group and the maleimide group in the resin precursor composition can be appropriately set according to the target physical properties and the target application. When the functional group concentration is a value calculated as the smaller molar amount of the total molar amount of the allyl group and the total molar amount of the maleimide group relative to the total amount of the composition having at least one of the allyl group and the maleimide group, the functional group concentration is preferably 0.01 mmol / g to 10 mmol / g, more preferably 0.03 mmol / g to 7 mmol / g, further preferably 0.1 mmol / g to 5 mmol / g, and even more preferably 0.3 mmol / g to 5 mmol / g.

[0261] When the functional group concentration is 0.01 mmol / g or more, a crosslinking density for improving solvent resistance and mechanical properties can be easily obtained.

[0262] If the functional group concentration is 10 mmol / g or less, it is easy to suppress excessive increase in crosslink density. If the crosslink density is too high, the toughness of the crosslinked product may be insufficient, or unreacted functional groups may easily remain, and the crosslinking reaction and other side reactions may advance over time, causing the physical properties of the material to change or deteriorate.

[0263] The resin precursor composition according to the present embodiment preferably contains, for example, at least any one of the following components (b1) to (b4).

[0264] (b1) A polymer having two or more allyl structures in the polymer chain and a compound having maleimide groups having two or more functional groups

[0265] (b2) A polymer having two or more maleimide structures in the polymer chain and a compound having two or more functional groups having allyl groups

[0266] (b3) A polymer having two or more allyl structures in the polymer chain and a polymer having two or more maleimide structures in the polymer chain

[0267] (b4) A polymer having a structure in which one polymer chain has both an allyl group and a maleimide group, and the average number of the allyl group and the average number of the maleimide group per polymer chain is 1 or more.

[0268] The resin precursor composition according to the present embodiment also preferably contains, for example, the following component (b1-1).

[0269] (b1-1)

[0270] A polymer having two or more allyl groups in the main chain of the polymer chain and a compound having two or more functional maleimide groups

[0271] The resin precursor composition according to the present embodiment also preferably contains, for example, at least any one of the following components (b3-1) to (b3-8).

[0272] (b3-1)

[0273] A polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain, and

[0274] Polymers with more than two allyl structures in the polymer chain

[0275] (b3-2)

[0276] A polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain, and

[0277] A polymer having more than two allyl structures in the polymer chain and one allyl structure at each of the two ends of the polymer chain and one or more allyl structures in the main chain

[0278] (b3-3)

[0279] A polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain, and

[0280] A polymer having more than two allyl structures in a polymer chain, having one allyl structure at one end of the polymer chain, having no allyl structure at the other end, and having two or more allyl structures in the main chain

[0281] (b3-4)

[0282] A polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain, and

[0283] A polymer having no allyl structure at both ends of the polymer chain and having more than two allyl structures in the main chain

[0284] (b3-5)

[0285] A polymer having two allyl structures and having one of the allyl structures at each of the two ends of the polymer chain, and

[0286] Polymers having more than two maleimide structures in the polymer chain

[0287] (b3-6)

[0288] A polymer having two allyl structures and having one of the allyl structures at each of the two ends of the polymer chain, and

[0289] A polymer having more than two maleimide structures in a polymer chain and having one maleimide structure at each of the two ends of the polymer chain and having one or more maleimide structures in the main chain

[0290] (b3-7)

[0291] A polymer having two allyl structures and having one of the allyl structures at each of the two ends of the polymer chain, and

[0292] A polymer having more than two maleimide structures in a polymer chain, having one maleimide structure at one end of the polymer chain, having no maleimide structure at the other end, and having two or more maleimide structures in the main chain

[0293] (b3-8)

[0294] A polymer having two allyl structures and having one of the allyl structures at each of the two ends of the polymer chain, and

[0295] A polymer having no maleimide structure at both ends of the polymer chain and having more than two maleimide structures in the main chain

[0296] The polymer contained in the resin precursor composition according to the present embodiment also preferably does not have two or more of at least one structure selected from the group consisting of allyl structures and maleimide structures at the ends of the polymer chains.

[0297] For example, in the case of a composition containing the component (b1) above, in a polymer having two or more allyl structures, the allyl structure may not be bonded to at least one of one end and the other end of the polymer chain, and the allyl structure may not be bonded to the end of the polymer chain.

[0298] For example, in the case of a composition containing the component (b2) above, in a polymer having two or more maleimide structures, the maleimide structure may not be bonded to at least one of one end and the other end of the polymer chain, and the maleimide structure may not be bonded to the end of the polymer chain.

[0299] For example, in the case of a composition containing the above-mentioned component (b3), in a polymer having two or more allyl structures, the allyl structure may not be bonded to at least one of one end and the other end of the polymer chain, and in a polymer having two or more maleimide structures, the maleimide structure may not be bonded to at least one of one end and the other end of the polymer chain, and further, the allyl structure and the maleimide structure may not be bonded to the ends of the polymer chain.

[0300] The polymer contained in the resin precursor composition according to the present embodiment also preferably has one or more structures selected from the group consisting of an allyl structure and a maleimide structure in the main chain of the polymer chain.

[0301] For example, in the case of a composition containing the component (b1) above, in a polymer having two or more allyl structures, one or more allyl structures may be bonded to the main chain of the polymer chain, and all the allyl structures may be bonded to the main chain of the polymer chain.

[0302] For example, in the case of a composition containing the above-mentioned component (b2), in a polymer having two or more maleimide structures, one or more maleimide structures may be bonded to the main chain of the polymer chain, and all the maleimide structures may be bonded to the main chain of the polymer chain.

[0303] For example, in the case of a composition containing the above-mentioned component (b3), in a polymer having two or more allyl structures, one or more allyl structures can be bonded to the main chain of the polymer chain, and in a polymer having two or more maleimide structures, one or more maleimide structures can be bonded to the main chain of the polymer chain.

[0304] In addition, for example, in the case of a composition containing the above-mentioned component (b3), in a polymer having two or more allyl structures, all of the allyl structures may be bonded to the main chain of the polymer chain, and in a polymer having two or more maleimide structures, all of the maleimide structures may be bonded to the main chain of the polymer chain.

[0305] When the main chain of the polymer chain is bonded to an allyl structure or a maleimide structure, the allyl structure or the maleimide structure may be directly bonded to the main chain of the polymer chain or may be bonded to the main chain of the polymer chain via other groups.

[0306] The polymer contained in the resin precursor composition according to the present embodiment also preferably does not have two or more at least one group selected from the group consisting of an allyl group and a maleimide group at the end of the polymer chain.

[0307] For example, in the case of a composition containing the component (b4) above, examples of the polymer having a structure having both an allyl group and a maleimide group in one polymer chain include the following polymers.

[0308] (b4-1) A polymer having no allyl group or maleimide group bonded to at least one of one end and the other end of the polymer chain

[0309] (b4-2) A polymer having one of an allyl group and a maleimide group bonded to one end of the polymer chain, neither an allyl group nor a maleimide group bonded to the other end of the polymer chain, and at least one of the other of the allyl group and the maleimide group bonded to the main chain of the polymer chain

[0310] (b4-3) A polymer having no allyl group or maleimide group bonded to the end of the polymer chain

[0311] The polymer contained in the resin precursor composition according to the present embodiment also preferably has one or more at least one group selected from the group consisting of an allyl group and a maleimide group in the main chain of the polymer chain.

[0312] For example, in the case of a composition containing the above-mentioned component (b4), in a polymer having a structure in which one polymer chain has both an allyl group and a maleimide group, one or more of the allyl group and the maleimide group may be bonded to the main chain of the polymer chain, and all of the allyl group and the maleimide group may be bonded to the main chain of the polymer chain.

[0313] For example, in the case of a composition containing the component (b4) above, examples of the polymer having a structure having both an allyl group and a maleimide group in one polymer chain include the following polymers.

[0314] (b4-4) A polymer having one maleimide group bonded to each of the two ends of the polymer chain and at least one allyl group bonded to the main chain of the polymer chain.

[0315] When an allyl group or a maleimide group is bonded to the main chain of the polymer chain, the allyl group or the maleimide group may be bonded to the main chain of the polymer chain directly or via other groups.

[0316] It is also preferred that the bonds between polymer chains in the resin formed when the resin precursor composition according to the present embodiment is used are not just bonds between the terminals of the polymer chains.

[0317] That is, the bonds between polymer chains in the resin formed when the resin precursor composition involved in this embodiment is used also preferably have at least any one bond selected from the bond between one of the allyl group and the maleimide group bonded to the terminal of one polymer and the other of the allyl group and the maleimide group bonded to the main chain of another polymer and the bond between one of the allyl group and the maleimide group bonded to the main chain of one polymer and the other of the allyl group and the maleimide group bonded to the main chain of another polymer.

[0318] By causing three-dimensional crosslinking of polymer chains instead of just bonding between the ends of the polymer chains, the solvent resistance of the resin is likely to be improved.

[0319] In addition, even if the ends of the polymer chains are not bonded to each other, three-dimensional crosslinking does not occur in the case of bonding between polymer chains having two reactive groups, and a linear polymer is formed. Therefore, the bonding between polymer chains in the resin formed when the resin precursor composition involved in the present embodiment is used is preferably not a bonding formed solely by the reaction between polymers having two reaction points (reactive groups) in the polymer chain (for example, polymers having reactive groups at the ends).

[0320] Furthermore, the bonds between polymer chains in the resin formed when the resin precursor composition according to the present embodiment is used may include bonds between the terminals of the polymer chains.

[0321] Among the above-mentioned components, a polymer (polycarbonate polymer) having two or more allyl structures in the polymer chain will be described in detail as an example.

[0322] The first form of the polycarbonate polymer (hereinafter also referred to as PC polymer) involved in this embodiment is a PC polymer having repeating units consisting only of repeating unit A represented by the following general formula (1), or a PC polymer having repeating unit A represented by the following general formula (1) and repeating unit B represented by the following general formula (2), and is obtained using at least any one of a bischloroformate oligomer represented by the following general formula (1A), a bischloroformate oligomer represented by the following general formula (2A), and a bischloroformate oligomer represented by the following general formula (2C) as a raw material.

[0323]

Chemical formula 18

[0324]

[0325]

Chemical formula 19

[0326]

[0327] In the above general formula (1) and general formula (1A), Ar 33 is a group represented by the following general formula (AL11) in the general formula (AL1), n 31 In addition, the average number of polymerized units n 31 It is 1.0 or more and 10 or less.

[0328]

Chemical formula 20

[0329]

[0330] (In the above general formula (AL11), X1 has the same meaning as X1 in the above general formula (AL1), and * indicates a bonding position.)

[0331] In the above general formula (2) and general formula (2A), Ar 34 is a group represented by the above general formula (UN11), n 32 In addition, the average number of polymerized units n 32 It is 1.0 or more and 10 or less.

[0332] *Indicates keying position.

[0333] In the above general formula (2C), Ar 33 is a group represented by the above general formula (AL11) in the above general formula (AL1), Ar 34 is a group represented by the above general formula (UN11). 33 and n 34 In addition, the average number of polymerized units n 33 and n 34 The total is greater than or equal to 1.0 and less than or equal to 10.

[0334] It should be noted that Ar 33 and Ar 34 In the above general formula (2C), the repeating units do not necessarily have to be continuous.

[0335] The average number of polymerized units can be calculated by the method described in Examples below.

[0336] Such a PC polymer has a repeating unit A including a group represented by the general formula (AL11) in the general formula (AL1) having at least two allyl groups, and thus is a polymer having two or more allyl structures in the polymer chain.

[0337] A PC polymer having repeating units consisting only of the repeating unit A represented by the general formula (1) and a PC polymer having the repeating unit A represented by the general formula (1) and the repeating unit B represented by the general formula (2) are preferably represented by the following general formula (100).

[0338]

Chemical formula 21

[0339]

[0340] In the above general formula (100), a represents the molar copolymerization ratio of the above repeating unit A, and b represents the molar copolymerization ratio of the above repeating unit B.

[0341] a is [Ar 33 ] / ([Ar 33 ]+[Ar 34 ]), b is [Ar 34 ] / ([Ar 33 ]+[Ar 34 ]), including the case where b is 0. 33 ] indicates that the PC polymer contains Ar 33 The molar amount of the repeating unit A of the group shown, [Ar 34 ] indicates that the PC polymer contains Ar 34 The molar amount of repeating unit B of the group shown.

[0342] It should be noted that in the above general formula (100), the repeating units are not necessarily continuous.

[0343] The PC polymer represented by the general formula (100) may be any of a block copolymer, an alternating copolymer and a random copolymer.

[0344] In the second form of the PC polymer involved in this embodiment, as the chain end of the above-mentioned PC polymer, it has any one of the structures represented by the above-mentioned general formula (AL2) and general formula (AL3). In addition, in the PC polymer represented by the above-mentioned general formula (100), Ar 33 , without Ar 33 In the case of a PC polymer having a total of 2 or more structures represented by the general formula (AL2) and the general formula (AL3) per molecule at the chain end, it is necessary to include an average of 2 or more structures represented by the general formula (AL2) and the general formula (AL3) per molecule. It should be noted that when there are no more than 2 allyl groups at the end of the polymer chain, the PC polymer represented by the general formula (100) preferably includes Ar 33 On the other hand, the Ar 33 In the case of a skeleton, as long as the average number of Ar 33 The total number of allyl groups contained in the olefin(e) and the number of allyl groups contained at the chain end may be 2 or more.

[0345] The chain terminal of the PC polymer according to the present embodiment is preferably capped with a monovalent aromatic group or a monovalent fluorinated aliphatic group other than the above-mentioned specific terminal group within the range satisfying the requirements of the present application.

[0346] The monovalent aromatic group may be a group containing an aliphatic group.

[0347] The monovalent fluorinated aliphatic group may be a group containing an aromatic group.

[0348] In addition, at least one substituent selected from the group consisting of alkyl groups, halogen atoms and aryl groups may be added to the monovalent aromatic group and the monovalent fluorinated aliphatic group. At least one substituent selected from the group consisting of alkyl groups, halogen atoms and aryl groups may be further added to these substituents. In addition, when there are multiple substituents, these substituents may be bonded to each other to form a ring.

[0349] The monovalent aromatic group constituting the chain end preferably contains an aryl group having a ring carbon number of 6 to 12. Examples of such an aryl group include a phenyl group and a biphenyl group.

[0350] As a substituent added to an aromatic group and a substituent added to an alkyl group added to an aromatic group, halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms can be mentioned. In addition, as a substituent added to an aromatic group, an alkyl group having 1 to 20 carbon atoms can be mentioned. The alkyl group may be a group to which a halogen atom is added as described above, or a group to which an aryl group is added.

[0351] Examples of the monovalent fluorinated aliphatic group constituting the chain end include monovalent groups derived from fluorinated alcohols.

[0352] As the fluorinated alcohol, a fluorinated alcohol having a plurality of fluoroalkyl chains of 2 to 6 carbon atoms connected to each other via an ether bond and having a total number of fluorine atoms of 13 to 19 is preferred. If the total number of fluorine atoms is 13 or more, sufficient water repellency and oil repellency can be exhibited. On the other hand, if the total number of fluorine atoms is 19 or less, the decrease in reactivity during polymerization is suppressed, and at least any one of the mechanical strength, surface hardness and heat resistance of the obtained PC polymer can be improved.

[0353] In addition, as the monovalent fluorinated aliphatic group, it is also preferred to be a monovalent group derived from a fluorinated alcohol having more than two ether bonds. By using such a fluorinated alcohol, the dispersibility of the PC polymer in the coating liquid composition becomes better, the wear resistance of the molded body and the electrophotographic photoreceptor can be improved, and the surface lubricity, water repellency and oil repellency after wear can be maintained.

[0354] Alternatively, the fluorinated alcohol is preferably a fluorinated alcohol represented by the following general formula (30) or (31), a fluorinated alcohol such as 1,1,1,3,3,3-hexafluoro-2-propanol, or a fluorinated alcohol having an ether bond and represented by the following general formula (32), (33) or (34).

[0355] H(CF2) n1 CH2OH···(30)

[0356] F(CF2) m1 CH2OH···(31)

[0357] In the above general formula (30), n1 is an integer of 1 to 12, and in the above general formula (31), m1 is an integer of 1 to 12.

[0358] F-(CF2) n 31 -OCF2CH2-OH···(32)

[0359] F-(CF2CF2) n 32 -(CF2CF2O) n 33 -CF2CH2OH···(33)

[0360] CR3-(CF2) n 35 -O-(CF2CF2O) n 34 -CF2CH2OH···(34)

[0361] In the above general formula (32), n 31 It is an integer of 1-10, and preferably an integer of 5-8.

[0362] In the above general formula (33), n32 is an integer of 0 to 5, preferably an integer of 0 to 3. 33 It is an integer of 1-5, and preferably an integer of 1-3.

[0363] In the above general formula (34), n 34 is an integer of 1 to 5, preferably an integer of 1 to 3. 35 It is an integer of 0 to 5, preferably an integer of 0 to 3. R is CF3 or F.

[0364] In this embodiment, from the perspective of improving electrical properties and wear resistance, the chain ends of the PC polymer are preferably capped with a monovalent group derived from a phenol represented by the following general formula (35) or a monovalent group derived from a fluorinated alcohol represented by the following general formula (36).

[0365]

Chemical formula 22

[0366]

[0367] In the above general formula (35), R 30 represents an alkyl group having 1 to 10 carbon atoms or a fluorinated alkyl group having 1 to 10 carbon atoms, and p is an integer of 1 to 3.

[0368] In the above general formula (36), R f It represents a perfluoroalkyl group having 5 or more carbon atoms and 11 or more fluorine atoms, or a perfluoroalkoxy group represented by the following general formula (37).

[0369]

Chemical formula 23

[0370]

[0371] In the above general formula (37), R f2 It is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms. mx is an integer of 1 to 3.

[0372] As one of the methods for producing the PC polymer according to the present embodiment, the following production method can be cited: using at least any one of the bischloroformate oligomer represented by the above-mentioned general formula (1A) and the bischloroformate oligomer represented by the above-mentioned general formula (2A), an organic solvent, an alkaline aqueous solution, and monomers such as a bisphenol compound, the organic layer and the aqueous layer are mixed to carry out an interfacial polycondensation reaction.

[0373] In the method for producing a PC polymer according to the present embodiment, a monocarboxylic acid and its derivatives, or a monophenol can be used as a capping agent for forming a chain end.

[0374] For example, p-tert-butylphenol, p-phenylphenol, p-cumylphenol, p-perfluorononylphenol, p-(perfluorononylphenyl)phenol, p-(perfluorohexyl)phenol, p-tert-perfluorobutylphenol, p-perfluorooctylphenol, 1-(p-hydroxybenzyl)perfluorodecane, p-[2-(1H,1H-perfluorotri(dodecyloxy))-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, and the like are preferably used.

[0375] Alternatively, as the end-capping agent for forming the chain end, it is also preferred to use a fluorinated alcohol represented by the general formula (30) or (31) or a monovalent fluorinated alcohol such as 1,1,1,3,3,3-hexafluoro-2-propanol. In addition, as the end-capping agent for forming the chain end, it is also preferred to use a fluorinated alcohol having an ether bond represented by the general formula (32), (33), or (34).

[0376] As the end-capping agent for forming a chain end, it is preferred to use the monohydric phenol represented by the above general formula (35) or the monohydric fluorine-containing alcohol represented by the above general formula (36) from the viewpoint of improving electrical characteristics and wear resistance.

[0377] As the monohydric phenol represented by the general formula (35), for example, p-tert-butylphenol, p-perfluorononylphenol, p-perfluorohexylphenol, p-tert-perfluorobutylphenol, p-perfluorooctylphenol, etc. are preferably used. That is, in the present embodiment, the chain end is preferably capped with a capping agent selected from the group consisting of p-tert-butylphenol, p-perfluorononylphenol, p-perfluorohexylphenol, p-tert-perfluorobutylphenol and p-perfluorooctylphenol.

[0378] Examples of the fluorinated alcohol having an ether bond interposed therebetween represented by the general formula (36) include the following compounds. That is, the chain end of the present embodiment is also preferably capped with a capping agent selected from the following fluorinated alcohols.

[0379]

Chemical formula 24

[0380]

[0381] The appropriate ratio of the end-capping agent to be added is different when the terminal has a cross-linking reactive functional group (allyl group or maleimide group) and when the main chain or side chain has a cross-linking reactive functional group.

[0382] In the case where the terminal contains an allyl group or a maleimide group, the concentration and molecular weight of the crosslinking reactive group change in conjunction with the fraction of the terminal. The molar percentage of the copolymerization composition of the allyl group or the maleimide terminal group relative to the total of the repeating units of the main chain and the terminal is preferably 0.1 mol% or more and 33 mol% or less, and more preferably 0.5 mol% or more and 25 mol% or less. If the addition ratio of the end-capping agent is 33 mol% or less, the decrease in mechanical strength can be suppressed, and if it is 0.1 mol% or more, the effect of improving the characteristics based on crosslinking can be obtained.

[0383] In the case of containing an end other than an allyl group or maleimide, the molar percentage of the copolymer composition of the chain end relative to the sum of the main chain and the terminal repeating units is preferably 0.05 mol% or more and 30 mol% or less, and more preferably 0.1 mol% or more and 10 mol% or less. If the addition ratio of the end-capping agent is 30 mol% or less, the decrease in mechanical strength can be suppressed, and if it is 0.05 mol% or more, the decrease in formability can be suppressed.

[0384] In addition, the branching agent that can be used in the method for producing the PC polymer involved in the present embodiment is not particularly limited. Specific examples of the branching agent include phloroglucinol, 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, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-

[0063] 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)oxidindole, 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like.

[0385] The addition ratio of these branching agents is preferably 30 mol% or less, more preferably 5 mol% or less, based on the mole percentage of the copolymerization composition of the repeating unit A, the repeating unit B and the chain end, or based on the mole percentage of the copolymerization composition of the repeating unit A and the chain end. If the addition ratio of the branching agent is 30 mol% or less, the decrease in moldability can be suppressed.

[0386] In the case of interfacial polycondensation, examples of acid binders include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, alkali metal weak acid salts such as sodium carbonate, potassium carbonate, and calcium acetate, alkaline earth metal weak acid salts, and organic bases such as pyridine. In the case of interfacial polycondensation, preferred acid binders are alkali metal hydroxides and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide. In addition, these acid binders can also be used in the form of a mixture. The proportion of the acid binder used can also be appropriately prepared in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, for every 1 mole of the total hydroxyl group of the dihydric phenol as a raw material, 1 equivalent or more of the acid binder can be used, and preferably 1 to 10 equivalents of the acid binder can be used.

[0387] As the solvent used in the manufacture method of the PC polymer involved in the present embodiment, there is no problem as long as the obtained polymer shows a certain solubility. As the solvent, as a suitable substance, 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, ketones such as cyclohexanone, acetone, acetophenone, tetrahydrofuran, 1,4-dioxane and other ethers can be cited. These solvents can use a single one, and two or more can be used in combination. In addition, two kinds of solvents that are not miscible with each other can be used to carry out interfacial polycondensation reaction.

[0388] As the organic solvent used in the method for producing the PC polymer involved in the present embodiment, it is preferred to use an organic solvent that is substantially immiscible with water and can dissolve 5% by mass or more of the polycarbonate polymer finally obtained. The organic solvent is preferably an organic solvent that is substantially immiscible with water and can dissolve 5% by mass or more of the polycarbonate polymer finally obtained.

[0389] Here, an organic solvent that is "substantially immiscible with water" refers to an organic solvent that does not produce a solution consisting of a uniform layer (a solution in which neither gelled matter nor insoluble matter is observed) when water and the organic solvent are mixed in a composition range of 1:9 to 9:1 under normal temperature and pressure conditions.

[0390] The organic solvent "capable of dissolving 5% by mass or more of the finally obtained polycarbonate polymer" refers to the solubility of the polycarbonate polymer when measured under the conditions of a temperature of 20 to 30°C and normal pressure.

[0391] In addition, the "finally obtained polycarbonate polymer" refers to a polymer obtained through the polymerization step in the method for producing a polycarbonate polymer according to the present embodiment.

[0392] Examples of such an organic solvent include aromatic hydrocarbons such as toluene, ketones such as cyclohexanone, and halogenated hydrocarbons such as dichloromethane. Among them, dichloromethane is preferred because of its high solubility.

[0393] In addition, the catalyst used in the method for producing the PC polymer of the present embodiment is not particularly limited, and suitable examples include tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylcyclohexylamine, pyridine, N,N-diethylaniline, and N,N-dimethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, and tetrabutylammonium bromide; and quaternary phosphonium salts such as tetrabutylphosphonium chloride and tetrabutylphosphonium bromide.

[0394] Furthermore, a small amount of an antioxidant such as sodium sulfite or dithionite may be added to the reaction system of the PC polymer of the present embodiment as needed.

[0395] [Coating liquid composition]

[0396] The coating liquid composition according to the present embodiment contains the resin precursor composition according to the present embodiment and an organic solvent.

[0397] The organic solvent according to the present embodiment can be appropriately selected in consideration of the solubility of materials such as the resin precursor composition, the drying rate after molding, and the influence and danger (fire or health hazard) of the organic solvent remaining in the molded product.

[0398] Examples of the organic solvent involved in this embodiment include cyclic ethers (tetrahydrofuran (THF), dioxane, and dioxolane), cyclic ketones (cyclohexanone, cyclopentanone, and cycloheptanone), aromatic hydrocarbons (toluene, xylene, and chlorobenzene), ketones (methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK), etc.), halogenated hydrocarbons (dichloromethane and chloroform), esters (ethyl acetate, isopropyl acetate, isobutyl acetate, and butyl acetate), ethers (ethylene glycol dimethyl ether and ethylene glycol monoethyl ether), amides (dimethylformamide (DMF) and dimethylacetamide (DMAc)), and aprotic polar solvents (dimethyl sulfoxide (DMSO)).

[0399] In the coating fluid composition that the present embodiment relates to, the concentration of the resin precursor composition that the present embodiment relates to, as long as it is the concentration of the appropriate viscosity corresponding to the method of use of the coating fluid composition, is preferably more than 0.1 mass % and less than 40 mass %, more preferably more than 1 mass % and less than 35 mass %, further preferably more than 5 mass % and less than 30 mass %. If it is less than 40 mass %, then the viscosity will not be excessively increased, and the coating property is good. If it is more than 0.1 mass %, then appropriate viscosity can be maintained, and a homogeneous film can be obtained. In addition, it becomes suitable to shorten the drying time after coating, and easily form the concentration of the film thickness as the target.

[0400] The coating liquid composition may further include additives in addition to the resin precursor composition and the organic solvent involved in the present embodiment. As additives, for example, low molecular weight compounds, colorants (such as dyes and pigments), functional compounds (such as charge transport materials, electron transport materials, hole transport materials, and charge generating materials), filling materials (such as inorganic or organic fillers, fibers, and particles), antioxidants, ultraviolet absorbers, and acid scavengers can be cited. In addition, other resins other than the resin precursor composition involved in one embodiment of the present invention may be included in the coating liquid composition.

[0401] As these additives and other resins, known substances that can be mixed with the resin precursor composition can be used.

[0402] In addition, when a charge transport material is included, from the perspective of product performance, the ratio of the resin precursor composition to the charge transport material in the coating liquid composition involved in this embodiment is preferably in the range of 20:80 to 80:20 in terms of mass ratio, and more preferably in the range of 30:70 to 70:30.

[0403] In the coating liquid composition according to the present embodiment, the resin precursor composition according to the present embodiment may be used alone or in combination of two or more.

[0404] The coating liquid composition involved in this embodiment is usually preferably used to form a photosensitive layer of a laminated electrophotographic photoreceptor. The photosensitive layer of the laminated electrophotographic photoreceptor preferably includes at least a charge generating layer and a charge transport layer, and the coating liquid composition involved in this embodiment is preferably used to form the charge transport layer. In addition, by further containing the above-mentioned charge generating material in the coating liquid composition involved in this embodiment, it can also be used to form a photosensitive layer of a single-layer electrophotographic photoreceptor.

[0405] Furthermore, the coating liquid composition according to the present embodiment can also be used to form a protective layer of a photoreceptor.

[0406] [Molding]

[0407] The molded article of this embodiment includes the resin of this embodiment. The molded article of this embodiment can be used for various purposes other than the use of the electrophotographic photoreceptor described later. For example, it can be suitably used as a substrate, insulating layer, protective layer, adhesive layer, conductive layer and structural material of electronic devices.

[0408] In addition, the molded product according to the present embodiment can be produced using the resin precursor composition according to the present embodiment.

[0409] When the resin precursor composition according to the present embodiment is used, as the molding method thereof, any of a wet molding method and a melt molding method may be applied.

[0410] When a shaped article is obtained by wet forming, the following methods can be used: (i) a method of forming at a temperature at which a crosslinking reaction occurs; (ii) a method of obtaining a wet shaped article at a temperature at which crosslinking does not occur substantially, raising the temperature to a temperature at which a crosslinking reaction occurs in a solvent removal step, and simultaneously performing drying and crosslinking; (iii) a method of wet forming at a temperature at which crosslinking does not occur substantially, drying to obtain a dry shaped article, and then raising the temperature to a temperature at which a crosslinking reaction occurs to crosslink the article. Any of these methods may be used.

[0411] In addition, in a wet forming method, the coating liquid composition according to the present embodiment described above can be used.

[0412] The crosslinking temperature can be appropriately set according to the target physical properties and the target application. The crosslinking method may be set by adjusting the type of crosslinkable functional group, the allyl group / maleimide ratio, and the functional group concentration according to the crosslinking temperature.

[0413] As an example, the crosslinking temperature facing the electrophotographic photoreceptor is usually preferably obtained by wet forming, and then crosslinked in the drying process, and the temperature is required to be carried out at a temperature at which the functional low molecular weight compound does not denature. For example, the crosslinking temperature facing the electrophotographic photoreceptor is preferably above 60°C and below 170°C, more preferably above 80°C and below 160°C, and further preferably above 100°C and below 150°C. If the crosslinking temperature is below 170°C, it is easy to suppress the denaturation of functional low molecular weight compounds such as charge transport materials. If the crosslinking temperature is above 60°C, drying is fully carried out, and it is easy to crosslink even if long-term drying is not performed.

[0414] On the other hand, in the use of electronic devices, in order to dry the coating during film formation and adjust the film properties by the curing speed, there is a case where the process is high temperature. Therefore, the crosslinking temperature for electronic devices is preferably above 60°C and below 250°C, and more preferably above 100°C and below 200°C. If the crosslinking temperature is below 250°C, the failure of electronic components and the decomposition of other organic materials can be prevented. If the crosslinking temperature is above 60°C, the crosslinking is fully carried out. It should be noted that for materials that are crosslinked at a low temperature of less than 60°C, it is possible that a part of the coating liquid composition reacts to increase the viscosity, etc., which may cause problems in the stability of the coating liquid.

[0415] In this embodiment, crosslinking of the resin precursor composition can be performed without adding a catalyst, a polymerization initiator, etc. It should be noted that, unless the effects of this embodiment are impaired, a catalyst, a polymerization initiator, etc. may be added for the purpose of using with other crosslinking systems.

[0416] [Electrophotographic photoreceptor]

[0417] The electrophotographic photoreceptor according to the present embodiment preferably contains the resin according to the present embodiment in the outermost layer.

[0418] The electrophotographic photoreceptor according to the present embodiment includes a substrate and a photosensitive layer provided on the substrate, and the photosensitive layer contains the resin according to the present embodiment.

[0419] For the electronic photographic photoreceptor of this embodiment, as long as the resin involved in this embodiment is used in the photosensitive layer, it can be set not only as various known forms of electronic photographic photoreceptors, but also as any electronic photographic photoreceptor. It is preferably set as a stacked electronic photographic photoreceptor in which the photosensitive layer has at least one charge generating layer and at least one charge transporting layer, or a single-layer electronic photographic photoreceptor having a charge generating material and a charge transporting material in one layer.

[0420] The resin involved in this embodiment can also be used in any part of the photosensitive layer. In order to give full play to the effect of this embodiment, it is expected to be used as a binder resin for charge transfer materials in the charge transport layer, or as a binder resin for a single photosensitive layer. In addition, it is expected to be used not only as a photosensitive layer but also as a surface protective layer. In the case of a multilayer electrophotographic photoreceptor having two charge transport layers, it is preferably used in any of the charge transport layers.

[0421] In the electrophotographic photoreceptor of the present embodiment, the resin involved in the present embodiment can be used alone or in combination of two or more. In addition, other binder resin components such as polycarbonate can be contained as required within the scope that does not damage the purpose of the present embodiment. In addition, additives such as antioxidants can be contained.

[0422] In the electronic photographic photoreceptor of the present embodiment, a photosensitive layer is provided on a conductive substrate. When the photosensitive layer has a charge generating layer and a charge transporting layer, the charge transporting layer may be stacked on the charge generating layer, or vice versa. In addition, the photosensitive layer may contain both a charge generating substance and a charge transporting substance in one layer. Furthermore, a conductive or insulating protective film may be formed on the surface layer as required. By using the resin involved in the present embodiment in the outermost layer, an electronic photographic photoreceptor having excellent solvent resistance and abrasion resistance may be obtained.

[0423] In addition, an intermediate layer such as an adhesive layer for improving the adhesion between the layers or a blocking layer for achieving a function of blocking charges may be formed.

[0424] As the conductive substrate material used in the electronic photographic photoreceptor of this embodiment, various materials such as well-known materials can be used, specifically: plates, drums and sheets formed of aluminum, nickel, chromium, palladium, titanium, molybdenum, indium, gold, platinum, silver, copper, zinc, brass, stainless steel, lead oxide, tin oxide, indium oxide, ITO (indium tin oxide: indium oxide doped with tin) or graphite; films, sheets or seamless belts of glass, cloth, paper and plastic that have been subjected to conductive treatment by coating such as evaporation, sputtering or coating; and metal drums that have been subjected to metal oxidation treatment such as electrode oxidation.

[0425] The charge generating layer at least has a charge generating material. The charge generating layer can be obtained by forming a layer of the charge generating material on a substrate serving as a base thereof by vacuum evaporation or sputtering, or by forming a layer formed by bonding the charge generating material with a binder resin on a substrate serving as a base thereof. As a method for forming a charge generating layer using a binder resin, various methods such as a known method can be used. Generally, for example, the following method is suitable: a coating liquid composition in which a charge generating material and a binder resin are dispersed or dissolved using an appropriate solvent is applied to a predetermined substrate serving as a base, and the coating liquid composition is dried to obtain a charge generating layer as a wet molded body.

[0426] As the charge generating material in the charge generating layer, various known materials can be used. Specific examples of the compounds include: selenium elements (e.g., amorphous selenium and trigonal selenium), selenium alloys (e.g., selenium-tellurium), selenium compounds or selenium-containing compositions (e.g., As2Se3), inorganic materials containing elements of Groups 12 and 16 of the periodic table (e.g., zinc oxide and CdS-Se), oxide semiconductors (e.g., titanium oxide), silicon materials (e.g., amorphous silicon), metal-free phthalocyanine pigments (e.g., τ-type metal-free phthalocyanine and χ-type metal-free phthalocyanine), metal phthalocyanine pigments (e.g., α-type copper phthalocyanine, β-type copper phthalocyanine, γ-type copper phthalocyanine, ε-type copper phthalocyanine, X-type copper phthalocyanine, A-type titanium phthalocyanine, B-type titanium phthalocyanine, C-type titanium phthalocyanine, D-type titanium phthalocyanine, E-type titanium phthalocyanine, F-type titanium phthalocyanine, G-type titanium phthalocyanine, H-type titanium phthalocyanine, K-type titanium phthalocyanine, L-type titanium phthalocyanine, M-type titanium phthalocyanine phthalocyanine, α-oxotitanylphthalocyanine, β-oxotitanylphthalocyanine, phthalocyanine having a strong diffraction peak at a Bragg angle 2θ of 27.3±0.2 degrees in an X-ray diffraction pattern, and gallium phthalocyanine, etc.), cyanine dyes, anthracene pigments, disazo pigments, pyrene pigments, polycyclic quinone pigments, quinacridone pigments, indigo pigments, perylene pigments, pyrylium dyes, squarylium pigments, anthraquinone 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, thiopyranium dyes, polyvinylcarbazole, and bisbenzimidazole pigments, etc. These compounds may be used alone or in combination of two or more compounds to form a charge generating material. Among these charge generating materials, suitable charge generating materials include those specifically described in Japanese Patent Application Laid-Open No. 11-172003.

[0427] The charge transport layer can be obtained as a wet molded body by forming a layer in which a charge transport material is bound with a binder resin on a substrate serving as a base.

[0428] There are no particular restrictions on the binder resins of the charge generation layer and the charge transport layer, and various known resins can be used. Specifically, for example, polystyrene, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl acetal, alkyd resin, acrylic resin, polyacrylonitrile, polycarbonate, polyurethane, epoxy resin, phenolic 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, cyanuric acid Amine resin, polyether resin, benzoguanamine resin, epoxy acrylate resin, urethane acrylate resin, poly-N-vinyl carbazole, polyvinyl butyral, polyvinyl formal, polysulfone, casein, gelatin, polyvinyl alcohol, ethyl cellulose, nitrocellulose, carboxymethyl cellulose, vinyl chloride polymer latex, acrylonitrile-butadiene copolymer, vinyl toluene-styrene copolymer, soybean oil modified alkyd resin, nitrated polystyrene, polymethyl styrene, polyisoprene, polythiocarbonate, polyarylate, polyhalogenated aromatic ester, polyallyl ether, polyvinyl acrylate, and polyester acrylate, etc.

[0429] These may be used alone or in combination of two or more. It is noted that the PC polymer of the present embodiment described above is preferably used as the binder resin in at least one of the charge generating layer and the charge transporting layer.

[0430] As a method for forming a charge transport layer, various known methods can be used, and the following method is suitable: a coating liquid composition obtained by dispersing or dissolving a charge transport material and a PC polymer of the present embodiment in an appropriate solvent is applied to a predetermined substrate as a base, and dried to obtain a charge transport layer as a wet molded body. The proportion of the charge transport material and the PC polymer used to form the charge transport layer is preferably in the range of 20:80 to 80:20 by mass ratio, and more preferably in the range of 30:70 to 70:30.

[0431] In the charge transport layer, the PC polymer of the present embodiment may be used alone or in combination of two or more. In addition, other binder resins may be used in combination with the PC polymer of the present embodiment within the scope of not impairing the purpose of the present embodiment.

[0432] The thickness of the charge transport layer formed in this way is usually 5 μm or more and 100 μm or less, preferably 10 μm or more and 50 μm or less, and more preferably 15 μm or more and 40 μm or less. If the thickness is 5 μm or more, the initial potential will not decrease, and if it is 100 μm or less, the decrease of the electrophotographic characteristics can be prevented.

[0433] As charge transport materials that can be used together with the PC polymer of the present embodiment, various known compounds can be used. As such compounds, for example, 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, stilbene compounds, fluorenone compounds, butadiene compounds, quinone compounds, quinone dimethane compounds, thiazole compounds, triazole compounds, imidazolinone compounds, imidazolidine compounds, bisimidazolidine compounds, oxazole compounds, benzothiazole compounds, benzimidazole compounds, quinazoline compounds, benzofuran compounds, acridine compounds, phenazine compounds, poly-N-vinyl carbazole, polyvinyl pyrene, polyvinyl anthracene, polyvinyl acridine, poly-9-vinyl phenyl anthracene, pyrene formaldehyde resin, ethyl carbazole resin, or polymers having these structures in the main chain or side chain, etc. These compounds can be used alone or in combination of two or more.

[0434] Among these charge transport materials, the compounds specifically exemplified in Japanese Patent Application Laid-Open No. 11-172003 and the charge transport materials represented by the following structures are particularly preferably used.

[0435]

Chemical formula 25

[0436]

[0437]

Chemical formula 26

[0438]

[0439]

Chemical formula 27

[0440]

[0441]

Chemical formula 28

[0442]

[0443]

Chemical formula 29

[0444]

[0445]

Chemical formula 30

[0446]

[0447]

Chemical formula 31

[0448]

[0449]

Chemical formula 32

[0450]

[0451]

Chemical formula 33

[0452]

[0453]

Chemical formula 34

[0454]

[0455]

Chemical formula 35

[0456]

[0457]

Chemical formula 36

[0458]

[0459]

Chemical formula 37

[0460]

[0461]

Chemical formula 38

[0462]

[0463] In the electrophotographic photoreceptor according to the present embodiment, the resin precursor composition according to the present embodiment is preferably used as a binder resin in at least any one of the charge generating layer, the charge transporting layer, and the surface protective layer.

[0464] In the electrophotographic photoreceptor involved in the present embodiment, a commonly used primer layer can be provided between the above-mentioned conductive substrate and the photosensitive layer. As the primer layer, for example, particles (such as titanium oxide, aluminum oxide, zirconium oxide, titanic acid, zirconic acid, lanthanum lead, titanium black, silicon dioxide, lead titanate, barium titanate, tin oxide, indium oxide, and silicon oxide, etc.), polyamide resin, phenolic resin, casein, melamine resin, benzoguanamine resin, polyurethane resin, epoxy resin, cellulose, nitrocellulose, polyvinyl alcohol, and polyvinyl butyral resin and other components can be used. In addition, as the resin for the primer layer, the above-mentioned binder resin can be used, and the resin precursor composition involved in the present embodiment can also be used. These particles and resins can be used alone or in a mixture of multiple. When used in the form of a mixture thereof, if inorganic particles and resins are used together, a film with good smoothness is formed, so it is suitable.

[0465] The thickness of the undercoat layer is 0.01 μm to 10 μm, preferably 0.1 μm to 7 μm. If the thickness is 0.01 μm or more, the undercoat layer can be formed uniformly, and if the thickness is 10 μm or less, the degradation of electrophotographic characteristics can be suppressed.

[0466] In addition, a commonly used known barrier layer may be provided between the conductive substrate and the photosensitive layer. As the barrier layer, a resin of the same type as the binder resin may be used. In addition, the resin precursor composition of the present embodiment may be used. The barrier layer has a thickness of 0.01 μm or more and 20 μm or less, preferably 0.1 μm or more and 10 μm or less. If the thickness is 0.01 μm or more, a uniform barrier layer can be formed, and if it is 20 μm or less, the degradation of the electrophotographic properties can be suppressed.

[0467] In addition, in the electronic photographic photoreceptor involved in this embodiment, a protective layer can be stacked on the photosensitive layer. The protective layer can use the same resin as the above-mentioned binder resin. In addition, it is particularly preferred to use the resin precursor composition involved in this embodiment. The thickness of the protective layer is greater than 0.01 μm and less than 20 μm, preferably greater than 0.1 μm and less than 10 μm. In addition, the protective layer may contain the above-mentioned charge generating material, charge transporting material, additives, metals and their oxides, nitrides, or salts, alloys, carbon black, and conductive materials such as organic conductive compounds.

[0468] In addition, in order to improve the performance of the electrophotographic photoreceptor, a binder, a plasticizer, a curing catalyst, a fluidity imparting agent, a pinhole control agent, and a spectral sensitivity sensitizer (sensitizing dye) etc. may be added to the above-mentioned charge generating layer and charge transporting layer within the range of not losing the effect of the present invention. In addition, various chemical substances, antioxidants, surfactants, anti-warping agents, and additives such as leveling agents are added for the purpose of preventing an increase in residual potential relative to repeated use, a decrease in charging potential, and a decrease in sensitivity.

[0469] As the above-mentioned binder, for example, silicone resin, polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate copolymer, polystyrene resin, polymethacrylate resin, polyacrylamide resin, polybutadiene resin, polyisoprene resin, melamine resin, benzoguanamine resin, polychloroprene resin, polyacrylonitrile resin, ethyl cellulose resin, nitrocellulose resin, urea resin, phenolic resin, phenoxy resin, polyvinyl butyral resin, polyvinyl formal resin, vinyl acetate resin, vinyl acetate / vinyl chloride copolymer resin, and polyester carbonate resin can be cited. In addition, at least one of thermosetting resin and photocurable resin can also be used. In any case, as long as it is electrically insulating, can form a coating under normal conditions and is within the range of not damaging the effect of this embodiment, it is not particularly limited.

[0470] Specific examples of the above-mentioned plasticizers include biphenyl, chlorobiphenyl, o-terphenyl, halogenated alkanes, dimethylnaphthalene, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, diethylene glycol phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methylphthalate ethyl glycolate, di(methylethylene glycol) phthalate, methylnaphthalene, benzophenone, polypropylene, polystyrene, and fluorocarbons.

[0471] Specific examples of the above-mentioned curing catalyst include methanesulfonic acid, dodecylbenzenesulfonic acid, and dinonylnaphthalene disulfonic acid, etc., as the fluidity imparting agent, for example, Modaflow and Acronal 4F, etc., as the pinhole control agent, for example, benzoin and dimethyl phthalate. These plasticizers, curing catalysts, fluidity imparting agents, and pinhole control agents are preferably used in an amount of 5% by mass or less relative to the above-mentioned charge transport material within the range of not losing the effect of the present invention.

[0472] In addition, when a sensitizing dye is used as the spectral sensitivity sensitizer, for example, the following are suitable: triphenylmethane dyes (such as methyl violet, crystal violet, night blue, and victoria blue, etc.), acridine dyes (such as erythrosine, rhodamine B, rhodamine 3R, acridine orange, and flapeosine, etc.), thiazine dyes (such as methylene blue and methylene green, etc.), oxazine dyes (such as Capri Blue and meldola blue, etc.), cyanine dyes, merocyanine dyes, styryl dyes, pyranylium salt dyes, and thiopyrylium salt dyes, etc.

[0473] In the photosensitive layer, for the purposes of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use, an electron-accepting substance can be added within the range that does not impair the effects of the present invention. As specific examples thereof, for example, succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, pyromellitic dianhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, p-nitrobenzonitrile, picryl chloride, quinone chloroimide, chloranil, bromanil, benzoquinone, 2,3-dichlorobenzoquinone, dichlorodicyanoquinone, naphthoquinone, biphenylquinone, tropoquinone, anthraquinone, 1-chloroanthraquinone, dinitroanthraquinone, 4-nitrobenzophenone, 4,4'-dinitrobenzophenone, 4-nitrobenzylidenemalononitrile, ethyl α-cyano-β-(p-cyanophenyl)acrylate, 9-anthrylmethylmalononitrile, 1-cyano-(p-nitrophenyl)-2-(p-chlorophenyl)ethylene, 2,7-dinitrofluorenone, 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, 9-fluorenylidene(dicyanomethylene)malononitrile, poly-nitro-9-fluorenylidene-(dicyanomethylene)malononitrile, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, and mellitic acid, etc., compounds with a large electron affinity. These compounds can be added to either the charge generation layer or the charge transport layer. When the amount of the charge generation substance or the charge transport substance is set to 100 parts by mass, the mixing ratio is 0.01 part by mass or more and 200 parts by mass or less, preferably 0.1 part by mass or more and 50 parts by mass or less, within the range that does not impair the effects of the present invention.

[0474] In addition, in order to improve the surface properties, tetrafluoroethylene resin, trifluorochloroethylene resin, tetrafluoroethylene hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluoroethylene dichloride resin and their copolymers, and fluorine-based graft polymers, etc. can be used within the scope of not losing the effect of the present invention. The mixing ratio of these surface modifiers is 0.1% by mass or more and 60% by mass or less relative to the above-mentioned binder resin within the scope of not losing the effect of the present invention, preferably 5% by mass or more and 40% by mass or less. If the mixing ratio is 0.1% by mass or more, the surface modification such as surface durability and surface energy reduction becomes sufficient, and if it is 60% by mass or less, it will not cause the reduction of electronic photography characteristics.

[0475] As the above-mentioned antioxidant, for example, hindered phenol antioxidants, aromatic amine antioxidants, hindered amine antioxidants, thioether antioxidants, and organic phosphoric acid antioxidants are preferred. The mixing ratio of these antioxidants is usually 0.01 mass % or more and 10 mass % or less, preferably 0.1 mass % or more and 2 mass % or less, within the range that does not lose the effect of the present invention, relative to the above-mentioned charge transport material.

[0476] Specific examples of such antioxidants include compounds of the general chemical formulas [Chemical Formula 94] to [Chemical Formula 101] described in the specification of Japanese Unexamined Patent Publication No. 11-172003.

[0477] These antioxidants may be used alone or in combination of two or more. In addition to being added to the above-mentioned photosensitive layer, they may also be added to the surface protection layer, primer layer or barrier layer.

[0478] Specific examples of the solvent used when forming at least one of the charge generation layer and the charge transport layer include aromatic solvents (e.g., benzene, toluene, xylene, and chlorobenzene), ketones (e.g., acetone, methyl ethyl ketone, and cyclohexanone), alcohols (e.g., methanol, ethanol, and isopropanol), esters (e.g., ethyl acetate, and ethyl cellosolve), halogenated hydrocarbons (e.g., carbon tetrachloride, carbon tetrabromide, chloroform, dichloromethane, and tetrachloroethane), ethers (e.g., tetrahydrofuran, dioxolane, and dioxane), sulfoxides (e.g., dimethyl sulfoxide), and amides (e.g., dimethylformamide, diethylformamide), etc. These solvents may be used alone or in combination of two or more thereof as a mixed solvent.

[0479] The photosensitive layer of the monolayer type electrophotographic photoreceptor can be easily formed by using the above-mentioned charge generating material, charge transporting material, and additives, and using the resin precursor composition involved in this embodiment as a binder resin. In addition, as the charge transporting material, it is preferred to add at least one of the above-mentioned hole transporting material and electron transporting material. As the electron transporting material, the electron transporting material exemplified in Japanese Patent Publication No. 2005-139339 can be preferably applied.

[0480] The coating of each layer can be performed using various coating devices such as a known device, and specifically, for example, an applicator, a spray coater, a bar coater, a chip coater, a roll coater, a dip coater, or a doctor blade can be used.

[0481] The thickness of the photosensitive layer in the electrophotographic photoreceptor is 5 μm or more and 100 μm or less, preferably 8 μm or more and 50 μm or less. If it is 5 μm or more, the initial potential can be prevented from decreasing, and if it is 100 μm or less, the electrophotographic characteristics can be suppressed from decreasing. The ratio of the charge generating material: the binder resin used to manufacture the electrophotographic photoreceptor is in the range of 1:99 to 30:70 by mass ratio, preferably in the range of 3:97 to 15:85. In addition, the ratio of the charge transport material: the binder resin is in the range of 20:80 to 80:20 by mass ratio, preferably in the range of 30:70 to 70:30.

[0482] The electrophotographic photoreceptor thus obtained has a cross-linked resin containing the resin precursor composition according to the present embodiment as a binder resin in the photosensitive layer, and therefore has excellent solvent resistance and durability (wear resistance), and has excellent electrical properties (electrophotographic properties), and is a photoreceptor that maintains excellent electrophotographic properties for a long period of time. In addition, the electrophotographic photoreceptor is preferably used in various electrophotographic fields such as copiers (monochrome, multicolor, full color, analog, digital), printers (laser, LED, liquid crystal shutter), fax machines, platemaking machines, and devices having these multiple functions.

[0483] [Method for producing electrophotographic photoreceptor]

[0484] The method for manufacturing an electronic photographic photosensitive body involved in the present embodiment is a method comprising the following steps: a step of applying the coating liquid composition involved in the present embodiment to a conductive substrate using a wet molding method; a step of removing the organic solvent in the coating liquid composition by heating; and a step of causing a resin precursor composition in the coating liquid composition to undergo a cross-linking reaction by continuing to heat the composition simultaneously with or after the heating in the step of removing the organic solvent.

[0485] In the step of applying the coating on the conductive substrate, the coating thickness of the coating liquid composition can be appropriately set according to the thickness of the photosensitive layer of the electrophotographic photoreceptor according to the present embodiment.

[0486] In the step of removing the organic solvent, the amount of the organic solvent can be appropriately set according to the type of the organic solvent in the coating liquid composition according to the present embodiment.

[0487] In the step of performing the crosslinking reaction of the resin precursor composition, the heating temperature is the same as the crosslinking temperature for the electrophotographic photoreceptor in the molded product according to the present embodiment.

[0488] [Electronic devices]

[0489] The electronic device according to this embodiment preferably includes the resin according to this embodiment.

[0490] In addition, the electronic device according to the present embodiment preferably also includes the molded product according to the present embodiment.

[0491] Example

[0492] Next, the present invention will be described in further detail by way of examples and comparative examples. The present invention is not limited to these examples, and various modifications and applications are possible without departing from the spirit of the present invention.

[0493] [Production Example: Preparation of Oligomer]

[0494] <Production Example 1: Synthesis of Bisphenol Z Oligomer (Bischloroformate)>

[0495] 60.0 g (224 mmol) of 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z) was suspended in 1080 mL of dichloromethane, and 66.0 g (667 mmol) of phosgene was added thereto and dissolved. A solution prepared by dissolving 44.0 g (435 mmol) of triethylamine in 120 mL of dichloromethane was added dropwise thereto at a temperature of 5°C to 15°C. Then, after stirring for 30 minutes, dichloromethane was distilled off to a prescribed concentration. 210 mL of pure water, 1.2 g of concentrated hydrochloric acid, and 450 mg of dithionite were added to the residual liquid for washing. Afterwards, washing was repeated 5 times with 210 mL of pure water to obtain a dichloromethane solution of a bisphenol Z oligomer having a chloroformate group at the end of the molecule. The chloroformate concentration of the obtained solution was 1.12 mol / L, the solid concentration was 0.225 kg / L, and the average number of polymerization units was 1.03. The obtained raw material is hereinafter referred to as Z-CF.

[0496] It should be noted that the average number of polymerization units (n X ) is calculated using the following mathematical formula (Formula 1).

[0497] The average number of polymer units (n X )=1+(Mav-M1) / M2···(Mathematical formula 1)

[0498] (In the above formula (Formula 1), Mav is (2×1000 / (CF value)), M2 is (M1-98.92), and M1 is n in the following general formula (X1) X =1, CF value (N / kg) is (CF value / concentration), CF value (N) is the number of chlorine atoms in the bischloroformate compound represented by the following general formula (X1) contained in 1L of the reaction solution, and concentration (kg / L) is the amount of solid content obtained by concentrating 1L of the reaction solution. Here, 98.92 is the total atomic weight of 2 chlorine atoms, 1 oxygen atom and 1 carbon atom removed in the polycondensation of the bischloroformate compounds.)

[0499] It should be noted that, when obtaining the average number of polymerization units when using more than two kinds of raw material synthetic bischloroformate, the molecular weight of the raw material used is averaged and the molecular weight is calculated M1 and obtained based on the molecular weight calculated M1 of the average molecular weight obtained by molar ratio. As an example, when using 366 moles of monomers with a molecular weight of 268 and 108 moles of monomers with a molecular weight of 214 to synthesize, M1 is calculated by the following calculation formula.

[0500] M1=(268×(366÷(366+108))+214×(108÷(366+108))+124.9

[0501] "124.9" in the calculation formula of M1 is the molecular weight increase when two hydrogen atoms of the monomer used are eliminated and two carbon atoms, two oxygen atoms and two chlorine atoms are added respectively.

[0502]

Chemical formula 39

[0503]

[0504] In the above general formula (X1), Ar X1 For example, in the case of the bischloroformate compound (bisphenol Z oligomer) involved in Production Example 1, the divalent group represented by the following general formula (10) corresponds to Ar X1 .

[0505]

Chemical formula 40

[0506]

[0507] In the case of the bischloroformate oligomer represented by the above general formula (1A), Ar 33 Equivalent to Ar X1 , n31 Equivalent to n X .

[0508] In the case of the bischloroformate oligomer represented by the above general formula (2A), Ar 34 Equivalent to Ar X1 , n 32 Equivalent to n X .

[0509] <Production Example 2: Synthesis of Bisphenol Z·3,3'-dimethyl-4,4'-dihydroxybiphenyl oligomer (bischloroformate)>

[0510] 98 g (366 mmol) of 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z) and 22 g (103 mmol) of 3,3'-dimethyl-4,4'-dihydroxybiphenyl were suspended in 2400 mL of dichloromethane, and 138 g (1395 mmol) of phosgene was added thereto and dissolved. A solution prepared by dissolving 93.8 g (929 mmol) of triethylamine in 256 mL of dichloromethane was added dropwise thereto at a temperature of 16°C to 19°C. Then, after stirring for 140 minutes, dichloromethane was distilled off to a predetermined concentration. 1100 mL of pure water, 2.4 g of concentrated hydrochloric acid, and 450 mg of dithionite were added to the residual liquid for washing. After that, washing was repeated 5 times with 210 mL of pure water to obtain a dichloromethane solution of bisphenol Z oligomer having a chloroformate group at the molecular end and 3,3'-dimethyl-4,4'-dihydroxybiphenyl oligomer. The chloroformate concentration of the obtained solution was 0.57 mol / L, the solid content concentration was 0.11 kg / L, and the average number of polymerization units was 1.02. The obtained raw material is hereinafter referred to as ZOCBP-CF.

[0511] [Synthesis example 1]

[0512] (Manufacturing of PC polymer)

[0513] Into a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, Z-CF (76 mL) and dichloromethane (114 mL) of Preparation Example 1 were injected, and p-tert-butylphenol (hereinafter referred to as PTBP) (0.151 g) as a capping agent was added, and stirred to be thoroughly mixed. After the temperature in the reactor was cooled to 10°C, all the prepared 1,1-bis(4-hydroxyphenyl)cyclohexane and 2,2-bis(3-allyl-4-hydroxyphenyl)propane solutions were added to the solution (solution preparation method: 65 mL of 2.36N potassium hydroxide aqueous solution (8.6 g of potassium hydroxide) was prepared, cooled to below room temperature, and then 0.25 g of dithionite as an antioxidant, 7.9 g of 1,1-bis(4-hydroxyphenyl)cyclohexane and 4.9 g of 2,2-bis(3-allyl-4-hydroxyphenyl)propane were added and completely dissolved), and 1.0 mL of triethylamine aqueous solution (7 vol%) was added while stirring, and stirring was continued for 3 hours.

[0514] The obtained reaction mixture was diluted with 1 L of dichloromethane and 0.1 L of water and washed. The lower layer was separated and washed once with 0.25 L of water, once with 0.03 N hydrochloric acid 0.25 L, and three times with 0.25 L of water. The obtained dichloromethane solution was added dropwise to methanol under stirring, and the obtained reprecipitate was filtered and dried to obtain a PC polymer (PC-1) having the following structure.

[0515] (Identification of PC polymers)

[0516] The PC polymer (PC-1) thus obtained was dissolved in dichloromethane to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20°C was measured to be 1.10 dL / g. 1 As a result of H-NMR spectrum analysis, it was confirmed that the PC polymer consisted of the following repeating units, number of repeating units and composition.

[0517] The reduced viscosity was measured using an automatic viscosity measuring device VMR-042 manufactured by Rikko Co., Ltd. using an automatic viscosity modified Ubbelohde viscometer (RM type). 1 The H-NMR spectrum was measured using a nuclear magnetic resonance apparatus JNM-ECZ400S manufactured by JEOL Ltd.

[0518] 1 The measurement conditions of H-NMR spectrum are as follows.

[0519] ( 1 H-NMR spectrum measurement conditions)

[0520] Solvent: CD2Cl2

[0521] ·Measurement concentration (sample volume / solvent volume): 1.5 mg / mL

[0522] Total times: 64 times (about 3 minutes)

[0523]

Chemical formula 41

[0524]

[0525] The composition ratio (mol%) in the PC polymer (PC-1) is diallylbisA:BisZ=15:85. It should be noted that in this composition ratio, "diallylbisA" is an abbreviation for repeating units derived from 2,2-bis(3-allyl-4-hydroxyphenyl)propane, and "BisZ" is an abbreviation for repeating units derived from bisphenol Z.

[0526] The allyl group concentration in the PC polymer (PC-1) was 1.05 mmol / g.

[0527] [Synthesis example 2]

[0528] (Manufacturing of PC polymer)

[0529] In a reaction vessel equipped with a mechanical stirrer, stirring blades and baffles, ZOCBP-CF (184 mL) and dichloromethane (41 mL) of Preparation Example 2 were injected. N-(4-hydroxyphenyl)maleimide (hereinafter referred to as Male1) (2.968 g) as a capping agent was added thereto, and stirred to be fully mixed. After the temperature in the reactor was cooled to 10°C, the entire amount of the prepared 3,3'-dimethyl-4,4'-dihydroxybiphenyl solution (solution preparation method: 60 mL of a 2.5 mol / L potassium carbonate aqueous solution (20.9 g of potassium carbonate) was prepared, cooled to below room temperature, and then 0.1 g of dithionite and 7.3 g of 3,3'-dimethyl-4,4'-dihydroxybiphenyl were added as antioxidants to prepare the solution), and 2.7 mL of a triethylamine aqueous solution (7 vol%) was added while stirring, and stirring was continued for 3 hours.

[0530] After stirring for 3 hours, the obtained reaction mixture was diluted with 0.5 L of dichloromethane and 0.1 L of water and washed. The washed lower layer was separated, and the upper layer was further washed once with 0.15 L of water, once with 0.03 N hydrochloric acid 0.15 L, and three times with 0.15 L of water. The obtained dichloromethane solution was added dropwise to methanol under stirring, and the obtained reprecipitate was filtered and dried to obtain a PC polymer (PC-2) having the following structure.

[0531] (Identification of PC polymers)

[0532] The PC polymer (PC-2) was dissolved in dichloromethane to prepare a solution with a concentration of 0.5 g / dL. The reduced viscosity [ηsp / C] at 20°C was measured and the result was 0.23 dL / g. The structure and composition of the obtained PC polymer (PC-2) were determined by 1 As a result of H-NMR spectrum analysis, it was confirmed that the PC polymer consisted of the following repeating units, number of repeating units, and composition.

[0533]

Chemical formula 42

[0534]

[0535] The composition ratio (mol%) in the PC polymer (PC-2) is OCBP:BisZ:Male1=50:40:10. It should be noted that in this composition ratio, "OCBP" is the abbreviation of the repeating unit derived from 3,3'-dimethyl-4,4'-dihydroxybiphenyl, "BisZ" is the abbreviation of the repeating unit derived from bisphenol Z, and Male1 is the abbreviation of the unit derived from N-(4-hydroxyphenyl)maleimide.

[0536] The maleimide group concentration in the PC polymer (PC-2) was 0.39 mmol / g.

[0537] (Example 1)

[0538] <Preparation of coating solution containing polycarbonate having allyl group and polycarbonate having maleimide group, and preparation of cross-linked resin film>

[0539] 1.05 g of PC polymer (PC-1) and 0.45 g of 2,2-bis[4-(4-maleimide phenoxy) phenyl] propane represented by the following formula (MA4-2) were weighed into a sample tube with a screw cap, and dissolved in 10 mL of THF to prepare a THF solution. Using an applicator with a gap of 200 μm, a film was cast on a 50 μm thick polyimide film. After the film was cast, it was air-dried for 1 hour, and further heated in a vacuum dryer at 50°C for 16 hours to remove the solvent. The film obtained after the 16-hour heating treatment was cross-linked by heating at 200°C for 3 hours at a reduced pressure of more than 1 Pa and less than 100 Pa using a reduced pressure dryer. 2,2-bis[4-(4-maleimide phenoxy) phenyl] propane is sometimes abbreviated as MI-BisA.

[0540]

Chemical formula 43

[0541]

[0542] (Comparative Example 1)

[0543] An evaluation film according to Comparative Example 1 used in the abrasion test was prepared in the same manner as in Example 1 except that 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane was not used and the amount of PC-1 used was changed to 1.5 g.

[0544] [Performance evaluation]

[0545] (Evaluation of Solvent Resistance (Dichloromethane Solubility))

[0546] The cross-linked film was peeled off from the polyimide film. The peeled cross-linked film was placed in dichloromethane, and the appearance was confirmed and evaluated according to the following evaluation criteria. The obtained results are shown in Table 1.

[0547] The details of the evaluation of solvent resistance are as follows. A film with a thickness of 20 to 30 μm was cut into a rectangle of 1 cm × 2 cm to prepare a sample. The sample was placed in an 8 mL sample tube. Next, 8 mL of dichloromethane was added to the sample tube, and the sample was completely immersed in dichloromethane. Using an oscillator, the sample tube was shaken at room temperature at an oscillation speed of 120 rpm for 1 hour, and the appearance was confirmed. The evaluation criteria are as follows.

[0548] A: Insoluble (no swelling or slight swelling but the film shape is maintained.)

[0549] B: Swelling (Although the insoluble matter is a single mass, the film shape is not maintained due to swelling by the solvent.)

[0550] C: Fragmented (fragmented insoluble matter exists, but most of it is dissolved.)

[0551] D: Dissolved (no insoluble matter was visually confirmed.)

[0552] (Abrasion resistance)

[0553] The wear resistance of the casting surface of the film samples prepared in the above-mentioned embodiments and comparative examples was evaluated using a Suga abrasion tester NUS-ISO-3 (manufactured by Suga Test Instruments). Regarding the test conditions, abrasion paper (containing aluminum oxide particles with a particle size of 3 μm) with a load of 4.9 N was brought into contact with the casting surface (surface simulating the surface of the photosensitive layer) and reciprocated 2000 times to measure the mass reduction (abrasion amount). The obtained results are shown in Table 1.

[0554]

Table 1

[0555]

Claims

1. An aromatic polycarbonate resin, characterized in that The aromatic polycarbonate resin has a bond between polymer chains formed by the reaction of an allyl group and a maleimide group. The bonding between the polymer chains is formed by the reaction of a polymer having two or more allyl structures in the polymer chain and a compound having a maleimide group having two or more functional groups, or by the reaction of a polymer having two or more allyl structures in the polymer chain and a polymer having two or more maleimide structures in the polymer chain. As the bonds between the polymer chains, only bonds formed by ene reaction, only bonds formed by Diels-Alder reaction, or both bonds formed by ene reaction and bonds formed by Diels-Alder reaction are present. The allyl structure includes a structure represented by the following general formula (AL1), The maleimide group or the maleimide structure comprises a structure represented by the following general formula (MA4), In the general formula (AL1), X1 is independently selected from single bond, -C(-R 11 )2-、 -O-、 -S-、 -SO-, -SO2-, -N(-R 12 )-, -P(-R 13 )-、 -P=O(-R 14 )-、 Carbonyl, Ester group, Amide group, an alkylene group having 2 to 20 carbon atoms, an alkylidene group having 2 to 20 carbon atoms, Alkylene arylene alkylidene having 8 to 20 carbon atoms, A cycloalkylene group having 3 or more and 20 or less ring carbon atoms, A cycloalkylidene group having 3 or more and 20 or less ring carbon atoms, an arylene group having 6 or more and 12 or less ring carbon atoms, a bicycloalkanediyl group having 4 to 20 ring carbon atoms, A tricycloalkanediyl group having 5 to 20 ring carbon atoms, a bicycloalkylidene group having 4 to 20 ring carbon atoms, and a group consisting of one or more of the group consisting of tricycloalkylidene groups having 5 or more and 20 or less ring carbon atoms, R 11 ~R 14 Each independently Hydrogen atoms, Halogen atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more and 12 or less ring carbon atoms, or a fluorinated alkyl group having 1 to 10 carbon atoms, In the general formula (AL1), * represents a bonding position, In the general formula (MA4), * represents a bonding position.

2. The aromatic polycarbonate resin according to claim 1, characterized in that The bonds between the polymer chains are formed by the reaction of a polymer having two or more allyl structures in the main chain of the polymer chain and a difunctional or higher-functional compound having a maleimide group.

3. The aromatic polycarbonate resin according to claim 1, characterized in that The arylene group having 6 to 12 ring carbon atoms is a naphthylene group.

4. The aromatic polycarbonate resin according to any one of claims 1 to 3, characterized in that The polymer does not have two or more at least one structure selected from the group consisting of an allyl structure and a maleimide structure at the end of the polymer chain.

5. The aromatic polycarbonate resin according to any one of claims 1 to 3, characterized in that In a polymer having two or more allyl structures in the polymer chain, the allyl structure is not bonded to at least one of one end and the other end of the polymer chain.

6. The aromatic polycarbonate resin according to any one of claims 1 to 3, characterized in that In a polymer having two or more allyl structures in the polymer chain, no allyl structure is bonded to the terminal of the polymer chain.

7. The aromatic polycarbonate resin according to claim 1, characterized in that In a polymer having two or more maleimide structures in a polymer chain, the maleimide structure is not bonded to at least one of one terminal and the other terminal of the polymer chain.

8. The aromatic polycarbonate resin according to claim 1, characterized in that In a polymer having two or more maleimide structures in the polymer chain, no maleimide structure is bonded to the terminal of the polymer chain.

9. The aromatic polycarbonate resin according to claim 1, characterized in that In a polymer having two or more allyl structures in a polymer chain, an allyl structure is not bonded to at least one of one end and the other end of the polymer chain, and In a polymer having two or more maleimide structures in a polymer chain, the maleimide structure is not bonded to at least one of one terminal and the other terminal of the polymer chain.

10. The aromatic polycarbonate resin according to claim 1, characterized in that In a polymer having two or more allyl structures in the polymer chain, no allyl structure is bonded to the end of the polymer chain, and In a polymer having two or more maleimide structures in the polymer chain, no maleimide structure is bonded to the terminal of the polymer chain.

11. The aromatic polycarbonate resin according to any one of claims 1 to 3, characterized in that The polymer has one or more at least one structure selected from an allyl structure and a maleimide structure in the main chain of the polymer chain.

12. The aromatic polycarbonate resin according to any one of claims 1 to 3, characterized in that In a polymer having two or more allyl structures in the polymer chain, one or more allyl structures are bonded to the main chain of the polymer chain.

13. The aromatic polycarbonate resin according to any one of claims 1 to 3, characterized in that In a polymer having two or more allyl structures in the polymer chain, all of the allyl structures are bonded to the main chain of the polymer chain.

14. The aromatic polycarbonate resin according to claim 1, characterized in that In a polymer having two or more maleimide structures in the polymer chain, one or more maleimide structures are bonded to the main chain of the polymer chain.

15. The aromatic polycarbonate resin according to claim 1, characterized in that In a polymer having two or more maleimide structures in the polymer chain, all of the maleimide structures are bonded to the main chain of the polymer chain.

16. The aromatic polycarbonate resin according to claim 1, characterized in that In a polymer having two or more allyl structures in the polymer chain, one or more allyl structures are bonded to the main chain of the polymer chain, and In a polymer having two or more maleimide structures in the polymer chain, one or more maleimide structures are bonded to the main chain of the polymer chain.

17. The aromatic polycarbonate resin according to claim 1, characterized in that In a polymer having two or more allyl structures in the polymer chain, all the allyl structures are bonded to the main chain of the polymer chain, and In a polymer having two or more maleimide structures in the polymer chain, all of the maleimide structures are bonded to the main chain of the polymer chain.

18. The aromatic polycarbonate resin according to claim 11, characterized in that The allyl structure or maleimide structure in the main chain of the polymer chain is directly bonded to the main chain of the polymer chain.

19. The aromatic polycarbonate resin according to claim 11, characterized in that The allyl structure or maleimide structure in the main chain of the polymer chain is bonded to the main chain of the polymer chain via other groups.

20. The aromatic polycarbonate resin according to claim 1, characterized in that The bonds between the polymer chains are formed by at least one of the following reactions (iii-1) to (iii-4), (iii-1) a polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain; and Reaction of polymers having more than 2 allylic structures in the polymer chain; (iii-2) a polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain; and Reaction of a polymer having more than two allyl structures in the polymer chain and one such allyl structure at each of the two ends of the polymer chain and one or more such allyl structures in the main chain; (iii-3) a polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain; and Reaction of a polymer having more than two allyl structures in the polymer chain, having one allyl structure at one end of the polymer chain, having no allyl structure at the other end, and having two or more allyl structures in the main chain; (iii-4) a polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain; and Reaction of a polymer having no allyl structure at both ends of the polymer chain and having more than two allyl structures in the main chain.

21. The aromatic polycarbonate resin according to claim 1, characterized in that The bonding between the polymer chains is not merely bonding between the ends of the polymer chains.

22. The aromatic polycarbonate resin according to claim 1, characterized in that The bonds between the polymer chains include at least one bond selected from a bond between one of an allyl group and a maleimide group bonded to a terminal of one polymer and the other of an allyl group and a maleimide group bonded to a main chain of another polymer, and a bond between one of an allyl group and a maleimide group bonded to a main chain of one polymer and the other of an allyl group and a maleimide group bonded to a main chain of another polymer.

23. The aromatic polycarbonate resin according to claim 1, characterized in that The bonding between the polymer chains includes bonding between the terminals of the polymer chains.

24. The aromatic polycarbonate resin according to claim 1, characterized in that The compound having the maleimide group or the polymer having two or more maleimide structures in the polymer chain is selected from: 2,2-Bis[4-(4-maleimidophenoxy)phenyl]propane, 4,4'-Diphenyl ether bismaleimide, 1,3-Bis(4-maleimidophenoxy)benzene, and PC having a structure in which the molecular ends are capped with the following compound (MA4-1), The PCs are selected from aromatic polycarbonates, polyarylates, and aromatic polycarbonate-polyarylate copolymers.

25. The aromatic polycarbonate resin according to claim 1 or 2, characterized in that The molar amount M of the allyl group or the allyl structure AL Relative to the molar amount M of the maleimide group or the maleimide structure MA The molar ratio M AL / M MA It is 0.01 or more and 100 or less.

26. The aromatic polycarbonate resin according to claim 1 or 2, characterized in that The molar amount M of the allyl group or the allyl structure AL Relative to the molar amount M of the maleimide group or the maleimide structure MA The molar ratio M AL / M MA It is 0.1 or more and 10 or less.

27. The aromatic polycarbonate resin according to claim 1 or 2, characterized in that The molar amount M of the allyl group or the allyl structure AL Relative to the molar amount M of the maleimide group or the maleimide structure MA The molar ratio M AL / M MA It is 0.2 or more and 5 or less.

28. The aromatic polycarbonate resin according to claim 1, characterized in that The bond between polymer chains formed by the reaction between the allyl group and the maleimide group is a bond of a structure represented by the general formula (CL-AM14). In the general formula (CL-AM14), X1 is independently selected from single bond, -C(-R 11 )2-、 -O-、 -S-、 -SO-, -SO2-, -N(-R 12 )-, -P(-R 13 )-、 -P=O(-R 14 )-、 Carbonyl, Ester group, Amide group, an alkylene group having 2 to 20 carbon atoms, an alkylidene group having 2 to 20 carbon atoms, Alkylene arylene alkylidene having 8 to 20 carbon atoms, A cycloalkylene group having 3 or more and 20 or less ring carbon atoms, A cycloalkylidene group having 3 or more and 20 or less ring carbon atoms, an arylene group having 6 or more and 12 or less ring carbon atoms, a bicycloalkanediyl group having 4 to 20 ring carbon atoms, A tricycloalkanediyl group having 5 to 20 ring carbon atoms, a bicycloalkylidene group having 4 to 20 ring carbon atoms, and A tricycloalkylidene group having 5 or more and 20 or less ring carbon atoms A group consisting of one or more of the group consisting of R 11 ~R 14 Each independently Hydrogen atoms, Halogen atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more and 12 or less ring carbon atoms, or a fluorinated alkyl group having 1 to 10 carbon atoms, In the general formula (CL-AM14), * represents a bonding position.

29. The aromatic polycarbonate resin according to claim 28, characterized in that The arylene group having 6 to 12 ring carbon atoms is a naphthylene group.

30. The aromatic polycarbonate resin according to claim 28, characterized in that Among the bonds represented by the general formula (CL-AM14), at least one of the bonds formed by the ene reaction undergoes a Diels-Alder reaction to form a bond.

31. The aromatic polycarbonate resin according to claim 1, characterized in that The aromatic polycarbonate resin includes at least one of the structures represented by the following general formula (UN1) and general formula (UN2), In the general formula (UN1) and the general formula (UN2), Ar3, Ar 31 and Ar 32 Each independently represents a group represented by the following general formula (UN11), wherein in the general formula (UN1) and the general formula (UN2), * represents a bonding position, In the general formula (UN11), m3 is 0, 1, or 2, n3 is 4, Multiple R3 are independently Hydrogen atoms, Halogen atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more and 12 or less ring carbon atoms, or a fluorinated alkyl group having 1 to 10 carbon atoms, X3 is independently selected single bond, -C(-R 31 )2-、 -O-、 -S-、 -SO-, -SO2-, -N(-R 32 )-, -P(-R 33 )-、 -P=O(-R 34 )-、 Carbonyl, Ester group, Amide group, an alkylene group having 2 to 20 carbon atoms, an alkylidene group having 2 to 20 carbon atoms, A cycloalkylene group having 3 or more and 20 or less ring carbon atoms, A cycloalkylidene group having 3 or more and 20 or less ring carbon atoms, an arylene group having 6 or more and 20 or less ring carbon atoms, a bicycloalkanediyl group having 4 to 20 ring carbon atoms, A tricycloalkanediyl group having 5 to 20 ring carbon atoms, a bicycloalkylidene group having 4 to 20 ring carbon atoms, and a group consisting of one or more of the group consisting of tricycloalkylidene groups having 5 or more and 20 or less ring carbon atoms, R 31 ~R 34 Each independently Hydrogen atoms, Halogen atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more and 12 or less ring carbon atoms, or a fluorinated alkyl group having 1 to 10 carbon atoms, In the general formula (UN11), * represents a bonding position.

32. The aromatic polycarbonate resin according to claim 1 or 31, characterized in that In the general formula (AL1), R 11 ~R 14 Alternatively, the halogen atoms represented by R3 in the general formula (UN11) are each independently selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

33. The aromatic polycarbonate resin according to claim 1 or 31, characterized in that In the general formula (AL1), R 11 ~R 14 Or the alkyl group having 1 to 10 carbon atoms represented by R3 in the general formula (UN11) is each independently selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, sec-hexyl, tert-hexyl, isoheptyl, sec-heptyl, tert-heptyl, isooctyl, sec-octyl, tert-octyl, isononyl, sec-nonyl, tert-nonyl, isodecyl, sec-decyl and tert-decyl.

34. The aromatic polycarbonate resin according to claim 1 or 31, characterized in that In the general formula (AL1), R 11 ~R 14 Alternatively, the aryl group having 6 to 12 ring carbon atoms represented by R3 in the general formula (UN11) is independently selected from a phenyl group, a naphthyl group and a biphenyl group.

35. The aromatic polycarbonate resin according to claim 1 or 31, characterized in that In the general formula (AL1), R 11 ~R 14 or the fluoroalkyl group having 1 or more and 10 or less carbon atoms represented by R3 in the general formula (UN11) is independently selected from R 11 ~R 14 Or an alkyl group in which at least one hydrogen atom in a carbon atom of an alkyl group having 1 to 10 carbon atoms represented by R3 of the general formula (UN11) is substituted with a fluorine atom.

36. The aromatic polycarbonate resin according to claim 1 or 31, characterized in that The alkylene group having 2 or more and 20 or less carbon atoms represented by X1 in the general formula (AL1) or X3 in the general formula (UN11) is independently selected from ethylene, propylene, isopropylene, butylene, hexylene, octylene and decylene.

37. The aromatic polycarbonate resin according to claim 1 or 31, characterized in that The alkylidene group having 2 or more and 20 or less carbon atoms represented by X1 in the general formula (AL1) or X3 in the general formula (UN11) is independently selected from ethylidene, propylidene, butylidene, hexylidene, octylidene, decylidene, pentadecylidene and eicosylidene.

38. The aromatic polycarbonate resin according to claim 1 or 31, characterized in that The cycloalkylene group having 3 or more and 20 or less carbon atoms represented by X1 in the general formula (AL1) or X3 in the general formula (UN11) is independently selected from cyclopropylene, cyclobutylene, cyclohexylene, cyclooctylene, cyclodecylene, cyclopentadecanylene, and cycloeicosaneylene.

39. The aromatic polycarbonate resin according to claim 1 or 31, characterized in that The cycloalkylidene group having 3 or more and 20 or less carbon atoms represented by X1 in the general formula (AL1) or X3 in the general formula (UN11) is independently selected from cyclopropylidene, cyclobutylidene, cyclohexylidene, cyclooctylidene, cyclodecylidene, cyclopentadecylidene, cyclododecylidene and cycloeicosylidene.

40. The aromatic polycarbonate resin according to claim 1 or 31, characterized in that The arylene group having 6 to 12 ring carbon atoms represented by X1 in the general formula (AL1) and the arylene group having 6 to 20 ring carbon atoms represented by X3 in the general formula (UN11) are each independently selected from phenylene, naphthylene and biphenylene.

41. The aromatic polycarbonate resin according to claim 1, characterized in that The alkylidene arylene alkylidene groups having 8 or more and 20 or less carbon atoms represented by X1 in the general formula (AL1) are each independently a group in which an alkylidene group and an arylene group are bonded in this order, The alkylidene groups are each independently selected from ethylidene, propylidene, butylidene, hexylidene, octylidene, decylidene, pentadecylidene and eicosylidene, The arylene groups are each independently selected from phenylene, naphthylene and biphenylene.

42. The aromatic polycarbonate resin according to claim 1, characterized in that The alkylidene arylene alkylidene groups having 8 or more and 20 or less carbon atoms represented by X1 in the general formula (AL1) are each independently a group represented by the following formula (L1) or formula (L2), 。 43. The aromatic polycarbonate resin according to claim 1 or 31, characterized in that The bicycloalkanediyl group having 4 or more and 20 or less ring carbon atoms represented by X1 in the general formula (AL1) or X3 in the general formula (UN11) is independently a bicyclic ring of a cycloalkylene group, The cycloalkylene groups are each independently selected from cyclobutylene, cyclohexylene, cyclooctylene, cyclodecylene, cyclopentadecanylene, and cycloeicosylene, The tricycloalkanediyl groups having 5 or more and 20 or less ring carbon atoms are each independently a tricyclic ring of a cycloalkylene group, The cycloalkylene groups are each independently selected from cyclohexylene, cyclooctylene, cyclodecylene, cyclopentadecanylene, and cycloeicosylene.

44. The aromatic polycarbonate resin according to claim 1 or 31, characterized in that The bicycloalkylidene group having 4 or more and 20 or less ring carbon atoms represented by X1 in the general formula (AL1) or X3 in the general formula (UN11) is independently a bicyclic ring of a cycloalkylidene group, The cycloalkylidene group is selected from the group consisting of cyclobutylidene, cyclohexylidene, cyclooctylidene, cyclodecylidene, cyclopentadecylidene, cyclododecylidene and cycloeicosylidene, The tricycloalkylidene groups having 5 or more and 20 or less ring carbon atoms are each independently a tricyclic ring of a cycloalkylidene group, The cycloalkylidene group is selected from the group consisting of cyclohexylidene, cyclooctylidene, cyclodecylidene, cyclopentadecylidene, cyclododecylidene and cycloeicosylidene.

45. The aromatic polycarbonate resin according to claim 1 or 31, characterized in that The tricycloalkanediyl group having 5 to 20 ring carbon atoms represented by X1 in the general formula (AL1) or X3 in the general formula (UN11) is independently selected from adamantanediyl and tricyclodecanediyl, The tricycloalkylidene groups having 5 to 20 ring carbon atoms are each independently selected from adamantylidene groups and tricyclodecanylidene groups.

46. ​​The aromatic polycarbonate resin according to claim 1, characterized in that The bonds between the polymer chains are formed by the reaction of a polycarbonate copolymer represented by the following (PC-1) as a polymer having two or more allyl groups in the main chain of the polymer chain and a compound represented by the following (MA4-2) as a compound having two or more maleimide groups. 。 47. A resin precursor composition, characterized in that The aromatic polycarbonate resin according to any one of claims 1 to 46 can be prepared by a cross-linking reaction.

48. A resin precursor composition, characterized in that The aromatic polycarbonate resin according to any one of claims 1 to 46 can be prepared by a cross-linking reaction. The resin precursor composition contains at least one of the following components (b1) and (b3), (b1) a polymer having two or more allyl structures in the polymer chain and a compound having two or more functional groups and maleimide groups; (b3) a polymer having two or more allyl structures in the polymer chain and a polymer having two or more maleimide structures in the polymer chain, A polymer having two or more allyl structures in the polymer chain is a polycarbonate polymer. The polycarbonate polymer is a PC polymer having repeating units consisting only of a repeating unit A represented by the following general formula (1), or a PC polymer having a repeating unit A represented by the following general formula (1) and a repeating unit B represented by the following general formula (2), and obtained using at least any one of a bischloroformate oligomer represented by the following general formula (1A), a bischloroformate oligomer represented by the following general formula (2A), and a bischloroformate oligomer represented by the following general formula (2C) as a raw material, In the general formula (1) and the general formula (1A), Ar 33 is a group represented by the following general formula (AL11), n 31 represents the average number of aggregation units, the average number of aggregation units n 31 is greater than 1.0 and less than 10, In the general formula (AL11), X1 is independently selected from single bond, -C(-R 11 )2-、 -O-、 -S-、 -SO-, -SO2-, -N(-R 12 )-, -P(-R 13 )-、 -P=O(-R 14 )-、 Carbonyl, Ester group, Amide group, an alkylene group having 2 to 20 carbon atoms, an alkylidene group having 2 to 20 carbon atoms, Alkylene arylene alkylidene having 8 to 20 carbon atoms, A cycloalkylene group having 3 or more and 20 or less ring carbon atoms, A cycloalkylidene group having 3 or more and 20 or less ring carbon atoms, an arylene group having 6 or more and 12 or less ring carbon atoms, a bicycloalkanediyl group having 4 to 20 ring carbon atoms, A tricycloalkanediyl group having 5 to 20 ring carbon atoms, a bicycloalkylidene group having 4 to 20 ring carbon atoms, and A tricycloalkylidene group having 5 or more and 20 or less ring carbon atoms A group consisting of one or more of the group consisting of R 11 ~R 14 Each independently Hydrogen atoms, Halogen atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more and 12 or less ring carbon atoms, or a fluorinated alkyl group having 1 to 10 carbon atoms, *Indicates the key position, In the general formula (2) and the general formula (2A), Ar 34 is a group represented by the following general formula (UN11), n 32 represents the average number of aggregation units, the average number of aggregation units n 32 is 1.0 or more and 10 or less, * indicates the bonding position, In the general formula (2C), Ar 33 is a group represented by the general formula (AL11), Ar 34 is a group represented by the following general formula (UN11), n 33 and n 34 Respectively represent the average number of polymerization units, the average number of polymerization units n 33 and n 34 The total of is greater than 1.0 and less than 10, It should be noted that Ar 33 and Ar 34 Different from each other, in the general formula (2C), each repeating unit is continuous or discontinuous, In the general formula (UN11), m3 is 0, 1, or 2, n3 is 4, Multiple R3 are independently Hydrogen atoms, Halogen atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more and 12 or less ring carbon atoms, or a fluorinated alkyl group having 1 to 10 carbon atoms, X3 is independently selected single bond, -C(-R 31 )2-、 -O-、 -S-、 -SO-, -SO2-, -N(-R 32 )-, -P(-R 33 )-、 -P=O(-R 34 )-、 Carbonyl, Ester group, Amide group, an alkylene group having 2 to 20 carbon atoms, an alkylidene group having 2 to 20 carbon atoms, A cycloalkylene group having 3 or more and 20 or less ring carbon atoms, A cycloalkylidene group having 3 or more and 20 or less ring carbon atoms, an arylene group having 6 or more and 20 or less ring carbon atoms, a bicycloalkanediyl group having 4 to 20 ring carbon atoms, A tricycloalkanediyl group having 5 to 20 ring carbon atoms, a bicycloalkylidene group having 4 to 20 ring carbon atoms, and a group consisting of one or more of the group consisting of tricycloalkylidene groups having 5 or more and 20 or less ring carbon atoms, R 31 ~R 34 Each independently Hydrogen atoms, Halogen atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more and 12 or less ring carbon atoms, or a fluorinated alkyl group having 1 to 10 carbon atoms, In the general formula (UN11), * represents a bonding position, The maleimide group or the maleimide structure comprises a structure represented by the following general formula (MA4), In the general formula (MA4), * represents a bonding position.

49. The resin precursor composition according to claim 48, characterized in that The arylene group having 6 to 12 ring carbon atoms is a naphthylene group.

50. The resin precursor composition according to claim 48, characterized in that The resin precursor composition contains the following component (b1-1), (b1-1) A polymer having two or more allyl groups in the main chain of the polymer chain and a compound having a maleimide group having two or more functional groups.

51. The resin precursor composition according to claim 48, characterized in that The resin precursor composition contains at least any one of the following components (b3-1) to (b3-4), (b3-1) A polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain, and A polymer having more than 2 allyl structures in the polymer chain; (b3-2) A polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain, and A polymer having more than two allyl structures in the polymer chain and one such allyl structure at each of the two ends of the polymer chain and one or more such allyl structures in the main chain; (b3-3) A polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain, and A polymer having more than two allyl structures in the polymer chain, having one such allyl structure at one end of the polymer chain, having no such allyl structure at the other end, and having two or more such allyl structures in the main chain; (b3-4) A polymer having two maleimide structures and one maleimide structure at each of the two ends of the polymer chain, and A polymer that does not have an allyl structure at both ends of the polymer chain and has more than two allyl structures in the main chain.

52. The resin precursor composition according to claim 48, characterized in that The polymer contained in the resin precursor composition does not have two or more at least one structure selected from the group consisting of an allyl structure and a maleimide structure at the end of the polymer chain.

53. The resin precursor composition according to claim 48, characterized in that In a polymer having two or more allyl structures in the polymer chain, the allyl structure is not bonded to at least one of one end and the other end of the polymer chain.

54. The resin precursor composition according to claim 48, characterized in that In a polymer having two or more allyl structures in the polymer chain, no allyl structure is bonded to the terminal of the polymer chain.

55. The resin precursor composition according to claim 48, characterized in that In a polymer having two or more maleimide structures in a polymer chain, the maleimide structure is not bonded to at least one of one terminal and the other terminal of the polymer chain.

56. The resin precursor composition according to claim 48, characterized in that In a polymer having two or more maleimide structures in the polymer chain, no maleimide structure is bonded to the terminal of the polymer chain.

57. The resin precursor composition according to claim 48, characterized in that In a polymer having two or more allyl structures in its polymer chain, the allyl structure is not bonded to at least one of one end and the other end of the polymer chain, and in a polymer having two or more maleimide structures in its polymer chain, the maleimide structure is not bonded to at least one of one end and the other end of the polymer chain.

58. The resin precursor composition according to claim 48, characterized in that In a polymer having two or more allyl structures in the polymer chain, no allyl structure is bonded to the terminal of the polymer chain, and in a polymer having two or more maleimide structures in the polymer chain, no maleimide structure is bonded to the terminal of the polymer chain.

59. The resin precursor composition according to claim 48, characterized in that The polymer contained in the resin precursor composition has one or more at least one structure selected from the group consisting of an allyl structure and a maleimide structure in the main chain of the polymer chain.

60. The resin precursor composition according to claim 48, characterized in that In a polymer having two or more allyl structures in the polymer chain, one or more allyl structures are bonded to the main chain of the polymer chain.

61. The resin precursor composition according to claim 48, characterized in that In a polymer having two or more allyl structures in the polymer chain, all of the allyl structures are bonded to the main chain of the polymer chain.

62. The resin precursor composition according to claim 48, characterized in that In a polymer having two or more maleimide structures in the polymer chain, one or more maleimide structures are bonded to the main chain of the polymer chain.

63. The resin precursor composition according to claim 48, characterized in that In a polymer having two or more maleimide structures in the polymer chain, all of the maleimide structures are bonded to the main chain of the polymer chain.

64. The resin precursor composition according to claim 48, characterized in that In a polymer having two or more allyl structures in the polymer chain, one or more allyl structures are bonded to the main chain of the polymer chain, and in a polymer having two or more maleimide structures in the polymer chain, one or more maleimide structures are bonded to the main chain of the polymer chain.

65. The resin precursor composition according to claim 48, characterized in that In a polymer having two or more allyl structures in the polymer chain, all the allyl structures are bonded to the main chain of the polymer chain, and in a polymer having two or more maleimide structures in the polymer chain, all the maleimide structures are bonded to the main chain of the polymer chain.

66. The resin precursor composition according to any one of claims 59 to 65, characterized in that When the allyl structure or the maleimide structure is bonded to the main chain of the polymer chain, the allyl structure or the maleimide structure is directly bonded to the main chain of the polymer chain.

67. The resin precursor composition according to any one of claims 59 to 65, characterized in that When an allyl structure or a maleimide structure is bonded to the main chain of the polymer chain, the allyl structure or the maleimide structure is bonded to the main chain of the polymer chain via another group.

68. The resin precursor composition according to claim 48, characterized in that The polymer contained in the resin precursor composition does not have two or more at least one group selected from the group consisting of an allyl group and a maleimide group at the end of the polymer chain.

69. The resin precursor composition according to claim 48, characterized in that The polymer contained in the resin precursor composition has one or more at least one group selected from the group consisting of an allyl group and a maleimide group in the main chain of the polymer chain.

70. The resin precursor composition according to claim 48, characterized in that The allyl group or maleimide group is directly bonded to the main chain of the polymer chain.

71. The resin precursor composition according to claim 48, characterized in that The allyl group or maleimide group is bonded to the main chain of the polymer chain via other groups.

72. The resin precursor composition according to claim 48, characterized in that The polycarbonate polymer has any one of the structures represented by the following general formula (AL2) and general formula (AL3) at the chain end, In the general formulae (AL2) to (AL3), * represents a bonding position.

73. The resin precursor composition according to claim 48, characterized in that The polycarbonate polymer has a chain terminal blocked with a monovalent aromatic group or a monovalent fluorinated aliphatic group.

74. The resin precursor composition according to claim 48, characterized in that A polycarbonate copolymer containing the following (PC-1) as a polymer having two or more allyl structures in the polymer chain and the following (MA4-2) as a compound having two or more maleimide groups, The composition ratio of the polycarbonate polymer (PC-1) is 15:85 in terms of mol % for the repeating unit derived from 2,2-bis(3-allyl-4-hydroxyphenyl)propane and the repeating unit derived from bisphenol Z. 。 75. A coating liquid composition, characterized in that The resin precursor composition comprises the resin precursor composition according to any one of claims 47 to 74 and an organic solvent.

76. An electrophotographic photoreceptor, characterized in that The outermost layer contains the aromatic polycarbonate resin according to any one of claims 1 to 46.

77. A method for manufacturing an electrophotographic photoreceptor, characterized in that: It has: A step of applying the coating liquid composition according to claim 75 to a conductive substrate by a wet forming method, a step of removing the organic solvent in the coating liquid composition by heating, and A step of causing the resin precursor composition in the coating liquid composition to undergo a crosslinking reaction by heating simultaneously with or after the heating in the step of removing the organic solvent.

78. A formed article, characterized in that The aromatic polycarbonate resin comprises the aromatic polycarbonate resin according to any one of claims 1 to 46.

79. An electronic device, characterized in that: The aromatic polycarbonate resin comprises the aromatic polycarbonate resin according to any one of claims 1 to 46.

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