Resin, resin precursor composition, coating liquid composition, molded product, and electronic device

Abstract

To provide a resin of at least one of an aromatic polycarbonate and a polyarylate having a new structure, which does not contain a radical initiator, a reaction catalyst or the like causing deterioration of electric characteristics, further can be produced without using UV, an electron beam or the like deteriorating a charge transport material (CTM), and does not substantially contain a polymer of only a single component when there are multiple polymerizable components.SOLUTION: A resin is at least one resin selected from a group consisting of an aromatic polycarbonate and a polyarylate, in which the resin has a bond between polymer chains due to a Diels-Alder reaction.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Polycarbonate resins have been used as 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 utilize their optical properties, etc. As the range of applications expands, the performance requirements for polycarbonate resins have become more diverse, and in addition to the polycarbonate resins that have been used traditionally, polycarbonate resins with various chemical structures have been proposed.

[0003] An example of a functional product is an organic electrophotographic photoreceptor that uses a polycarbonate resin as a binder resin for functional materials such as a charge generating material and a charge transporting material. These organic electrophotographic photoreceptors are required to have the required sensitivity, electrical characteristics, and optical characteristics depending on the electrophotographic process used. The surface of the photosensitive layer of an electrophotographic photoreceptor undergoes repeated operations such as corona charging, toner development, paper transfer, and cleaning, and electrical or mechanical external forces are applied with each of these operations. Therefore, to maintain the image quality of electrophotographs over a long period of time, the photosensitive layer on the surface of the electrophotographic photoreceptor must be durable against these external forces. Furthermore, because organic electrophotographic photoreceptors are typically manufactured by dissolving a binder resin along with functional materials in an organic solvent and casting the resulting film onto a conductive substrate, they must be stable and soluble in organic solvents.

[0004] Conventionally, polycarbonate resins made from raw materials such as 2,2-bis(4-hydroxyphenyl)propane and 1,1-bis(4-hydroxyphenyl)cyclohexane have been used as binder resins for photoreceptors, but they have not been fully satisfactory in terms of durability. One possible way to improve durability is to improve the abrasion resistance of the photosensitive layer. A known effective technique for improving the abrasion resistance of the photosensitive layer is to crosslink polycarbonate.

[0005] Patent Document 1 discloses a technique for crosslinking PC having an allyl group using a radical initiator, resulting in a resin with better mechanical strength (such as tensile strength) than bisphenol A polycarbonate resin.

[0006] Patent Document 2 describes a resin crosslinked by an ionic mechanism, such as an epoxy group, in a polycarbonate copolymer. Furthermore, Patent Document 3 describes a crosslinking technique in which a polycarbonate having a double bond is reacted with a compound having multiple silicon-hydrogen bonds in the presence of a platinum catalyst, and a crosslinking technique in which a polycarbonate having a double bond is reacted with a compound having an alkoxy group and hydrogen on the silicon atom in the presence of a platinum catalyst, followed by hydrolysis and condensation reactions.

[0007] Furthermore, Patent Document 4 discloses a crosslinking technique in which polycarbonate having allyl groups is heated to 120°C to 260°C and then irradiated with an electron beam. Patent Document 5 discloses a method of crosslinking a polycarbonate having an allyl group by heating without a catalyst using a triarylamine of a specific structure and a radical polymerizable compound not having a triarylamine structure.

[0008] Patent Document 6 reports a resin in which the chain length of a resin having an anthracene skeleton at the end of an aliphatic-aromatic polyester is extended with bismaleimide. Furthermore, Patent Document 7 discloses a crosslinked resin obtained by reacting an aliphatic polyester, polyamide, or polyurea having a furan structure with a polyfunctional maleimide. Patent Document 8 discloses a curable composition in which a polymerizable functional group such as an acrylic group is introduced into an anthracene skeleton, and a crosslinking reaction occurs at the functional group. Non-Patent Document 1 discloses a resin in which an anthracenedicarboxylic acid skeleton is introduced into a part of an aliphatic-aromatic polyester, and the resin is crosslinked with a bifunctional maleimide compound. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 10-77338 [Patent Document 2] Japanese Patent Application Publication No. 9-319102 [Patent Document 3] Japanese Patent Application Laid-Open No. 2000-44668 [Patent Document 4] Japanese Patent Application Laid-Open No. 2007-314719 [Patent Document 5] Japanese Patent Application Laid-Open No. 2010-72019 [Patent Document 6] Japanese Patent Application Laid-Open No. 2003-286347 [Patent Document 7] U.S. Patent No. 3,435,003 [Patent Document 8] Japanese Patent Application Laid-Open No. 2012-224569 [Non-patent literature]

[0010] [Non-Patent Document 1] Macromolecules 1999,32,5786~5792 Summary of the Invention [Problem to be solved by the invention]

[0011] However, the polycarbonate described in Patent Document 1 had problems such as the charge transport material (CTM) being altered by the use of a radical initiator, and the added initiator remaining in the photoreceptor, resulting in an increase in residual potential when used as a photoreceptor.

[0012] Furthermore, the polycarbonate described in Patent Document 2 uses a compound having a nucleophilic group such as an amino group or an acidic group such as a carboxylic anhydride group in the initiation reaction, which causes problems such as deterioration of the CTM and an increase in residual potential when used as a photoreceptor because the added compound remains in the photoreceptor. Furthermore, there is no description confirming that the disclosed resin is crosslinked, making it unclear whether the disclosed effect of improving physical properties is due to the crosslinked structure.

[0013] Furthermore, the polycarbonate described in Patent Document 3 uses a platinum catalyst, which causes problems such as deterioration of the CTM and an increase in residual potential when used as a photoreceptor because the added catalyst remains in the photoreceptor. Furthermore, it is difficult to suppress the reaction in the coating liquid, which causes problems such as an increase in viscosity and gelation during storage of the coating liquid.

[0014] Furthermore, the polycarbonate described in Patent Document 4 has a problem in that the CTM changes when irradiated with an electron beam, and the residual potential increases when used as a photoreceptor.

[0015] As seen above, there are examples where cross-linked polycarbonate and cross-linked polyarylate can be obtained without using radical initiators or reaction catalysts that can deteriorate electrical properties, or without using UV or electron beams that can alter CTM. As an example of this, Patent Document 5 reports a technology in which a monomer with high radical polymerization activity undergoes radical polymerization simply by heating without the use of an initiator or UV irradiation is used, and a polycarbonate containing an allyl group is coexisted with the monomer. However, because a monomer that undergoes radical polymerization without the use of an initiator or light irradiation is used, a polymer of the polymerizable monomer alone is primarily produced, and the probability of reaction between the polymerizable monomer and the polycarbonate containing an allyl group, which has relatively low radical polymerization activity, is thought to be low. Therefore, rather than having a dense three-dimensional polymer network structure, the resulting composition is thought to be a composition in which the polycarbonate resin and the crosslinked polymer of the radical polymerization monomer exist separately, with only a portion of them bonded together. Furthermore, the effect of improving physical properties due to the increase in molecular weight of the charge transport material, which is usually present as a low molecular weight, is dominant, and the improvement in physical properties due to the crosslinking of the polycarbonate portion is insufficient. Furthermore, because a highly active compound that undergoes radical polymerization even without an initiator is used, it is difficult to suppress polymerization at the coating liquid composition stage, resulting in problems such as increased viscosity and gelation during storage of the coating liquid.

[0016] As a crosslinking technology that can meet these requirements, Patent Document 6 discloses a linear polymer obtained by the molecular weight elongation reaction of an aliphatic-aromatic polyester via the Diels-Alder reaction, using a resin other than polycarbonate. However, the purpose of the invention described in Patent Document 6 is to utilize the retro-Diels-Alder reaction, in which bonds formed by the Diels-Alder reaction dissociate at high temperatures, thereby improving thermoformability by reducing the melt viscosity at high temperatures, improving mechanical properties by increasing the molecular weight at practical temperatures, and maintaining solubility by maintaining a linear structure. However, this purpose differs from the purpose of the present invention, which aims to improve solvent resistance and mechanical strength by introducing a crosslinked structure. Furthermore, Patent Document 6 does not describe or suggest the application of the technology described in Patent Document 6 to aromatic polycarbonates or wholly aromatic polyesters.

[0017] Furthermore, Patent Document 7 describes an example of crosslinking aliphatic polyesters, polyamides, or polyureas by the Diels-Alder reaction. However, these examples aim to impart solvent resistance by crosslinking soft aliphatic resins and to obtain elastomers suitable for use in diaphragm seals and adhesives. The technical concepts of these examples differ from the concept of the present invention, which aims to further increase the strength of aromatic polycarbonates, which have high mechanical strength, or wholly aromatic polyesters by crosslinking. Furthermore, Patent Document 7 does not describe or suggest the application of the technology described therein to aromatic polycarbonates or wholly aromatic polyesters. Non-Patent Document 1 describes an example in which an anthracene dicarboxylic acid skeleton is introduced into polyethylene terephthalate (PET) and crosslinked with a bifunctional maleimide compound. The purpose of this example is similar to that of the present invention in that mechanical properties are improved by thermal crosslinking, but Non-Patent Document 1 does not describe or suggest examples of application to polycarbonate or polyarylate. Furthermore, considering its use in electrophotographic photoreceptors, PET has low solubility in organic solvents such as THF, which are commonly used as coating solvents, and poor compatibility with charge transport materials such as triarylamine, making it unusable for such applications.

[0018] Patent Document 8 discloses an example in which a polymerizable functional group such as an acrylic group is introduced into an anthracene skeleton and a crosslinking reaction is carried out at the functional group. However, Patent Document 8 does not describe or suggest using the anthracene moiety in a crosslinking reaction. In addition, the invention described in Patent Document 8 aims to retain the functionality of the anthracene skeleton, and the technology of the present invention, which applies a Diels-Alder reaction that eliminates the anthracene skeleton through the reaction, is contrary to this aim.

[0019] The first object of the present invention is to provide a resin of at least one of aromatic polycarbonate and polyarylate having a novel structure that does not contain a radical initiator or a reaction catalyst that would deteriorate electrical properties, can be produced without using UV or electron beams that would alter charge transport materials (CTMs), and is substantially free of polymers of only one component when multiple polymerizable components are present. The second object of the present invention is to provide a resin precursor composition and a coating composition that are characterized by minimal changes in properties due to the fact that reactions are unlikely to occur at the coating composition stage. The third object of the present invention is to provide an electrophotographic photoreceptor that contains the resin, and thereby has excellent solvent resistance and abrasion resistance, is resistant to mechanical degradation, and does not deteriorate residual potential. [Means for solving the problem]

[0020] According to one aspect of the present invention, there is provided at least one resin selected from the group consisting of aromatic polycarbonates and polyarylates, the resin having bonds between polymer chains formed by a Diels-Alder reaction.

[0021] According to one aspect of the present invention, there is provided a resin precursor composition capable of producing the resin according to the above-described aspect of the present invention through a crosslinking reaction.

[0022] According to one aspect of the present invention, there is provided a coating composition comprising the resin precursor composition according to the above-described aspect of the present invention and an organic solvent.

[0023] According to one aspect of the present invention, there is provided an electrophotographic photoreceptor characterized in that the outermost layer contains the resin according to the aspect of the present invention described above.

[0024] According to one aspect of the present invention, there is provided a method for producing an electrophotographic photoreceptor, comprising: a step of applying the coating composition according to the above-described aspect of the present invention to a conductive substrate by a wet molding method; a step of removing an organic solvent from the coating composition by heating; and a step of causing a crosslinking reaction of a resin precursor composition in the coating composition by heating simultaneously with or subsequent to the heating in the step of removing the organic solvent.

[0025] According to one aspect of the present invention, there is provided a molded article comprising the resin according to the above-described aspect of the present invention.

[0026] According to one aspect of the present invention, there is provided an electronic device comprising the resin according to the above-described aspect of the present invention.

[0027] According to one aspect of the present invention, there is provided a resin having a novel structure that is substantially free of homopolymers of polymerizable components, and that is at least one of an aromatic polycarbonate and a polyarylate resin. The resin does not contain a radical initiator or a reaction catalyst that would cause deterioration of electrical properties, and can be produced without using UV or electron beams that would alter the charge transport material (CTM). Another aspect of the present invention provides a resin precursor composition and a coating composition that are characterized by minimal changes in properties due to the fact that reactions are unlikely to occur at the coating composition stage. Another aspect of the present invention provides an electrophotographic photoreceptor that contains the resin, exhibiting excellent solvent resistance, excellent abrasion resistance, resistance to mechanical degradation, and no deterioration in residual potential. [Brief explanation of the drawings]

[0028] [Figure 1] 1 is a graph showing the measurement results of electrophotographic photosensitive member characteristics for samples obtained in Example 2 and Comparative Examples 2 and 101. [Figure 2] 1 is a graph showing the results of measurement of the sample obtained in Example 3 using a differential scanning calorimeter. [Figure 3]10 is a graph showing the results of excitation fluorescence three-dimensional spectrum measurement for the samples obtained in Example 3 and Comparative Example 3-1. DETAILED DESCRIPTION OF THE INVENTION

[0029] [resin] The resin according to this 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 may also be simply referred to as "PCs"). The resin according to this embodiment has bonds between polymer chains formed by the Diels-Alder reaction. The resin having bonds between polymer chains has a structure represented by the following general formula (S1): In the following general formula (S1), * indicates a bonding position. The structure of the portion beyond the wavy line is not particularly limited, but any portion beyond the wavy line has at least one bonding position. The portion beyond the wavy line may form a linked cyclic structure (including an aromatic ring and a heterocyclic ring). The aromatic ring and the heterocyclic ring may be any of a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, and a seven-membered ring. The structure of the crosslinking moiety connecting the polymer chains has a bonding pattern, for example, as shown in the following general formula:

[0030] [ka]

[0031] [ka]

[0032] In the above general formula, *PC represents a polymer chain of PCs. As described above, the crosslinking method according to this embodiment differs from crosslinking by general radical reactions, which results in a linear structure, in that it has a rigid cyclic structure. The cyclic structure results in a stronger structure than linear crosslinking, which is thought to be one of the reasons why the mechanical strength is improved compared to resins with a linear crosslinking method at the same crosslink density. As a result of extensive research aimed at solving the problems of the present invention, the inventors have found that PCs that crosslink via the Diels-Alder reaction have excellent solution stability, crosslink at temperatures currently used in photoreceptor manufacturing processes, and the resulting crosslinked resins have excellent abrasion resistance and do not exhibit deterioration in electrical properties. The present invention was completed based on these findings.

[0033] The resin according to this embodiment can be obtained by crosslinking a polymer having at least one of a Diels-Alder reactive conjugated diene and a dienophile in its structure with a crosslinking agent or polymer having the corresponding group. The bond between polymer chains according to this embodiment can be formed, for example, by the reaction of the following combinations. (i) Reaction of a polymer having two or more conjugated diene structures in the polymer chain with a compound having a dienophile group with two or more functionalities. (ii) Reaction of a polymer having two or more dienophile structures in the polymer chain with a compound having a dienophile group with two or more functionalities. (iii) Reaction of a polymer having two or more conjugated diene structures in the polymer chain with a polymer having two or more dienophile structures in the polymer chain. (iv) Reaction of a polymer having both a conjugated diene structure and a dienophile structure in one polymer chain, in which the average number of the conjugated diene structure and the average number of the dienophile structure per polymer chain are each one or more.

[0034] The bond between polymer chains in the resin according to this embodiment may be, for example, the following reaction (i-1). (i-1) Reaction of a polymer having two or more conjugated diene structures in the main chain of the polymer chain with a compound having two or more functional dienophile groups

[0035] The bond between polymer chains in the resin according to this embodiment may be, for example, at least one of the following reactions (iii-1) to (iii-8).

[0036] (iii-1) A polymer having two dienophile structures, each of which is located at one end of the polymer chain; Reaction with polymers having more than two conjugated diene structures in the polymer chain

[0037] (iii-2) A polymer having two dienophile structures, each of which is located at one end of the polymer chain; A reaction with a polymer having more than two conjugated diene structures in the polymer chain, with one conjugated diene structure at each end of the polymer chain and one or more conjugated diene structures in the main chain.

[0038] (iii-3) A polymer having two dienophile structures, each of which is located at one end of the polymer chain; A reaction with a polymer having more than two conjugated diene structures in the polymer chain, wherein the polymer chain has one of the conjugated diene structures at one end and no conjugated diene structure at the other end, and the polymer has two or more of the conjugated diene structures in the main chain.

[0039] (iii-4) A polymer having two dienophile structures, each of which is located at one end of the polymer chain; Reaction with a polymer that does not have a conjugated diene structure at both ends of the polymer chain and has more than two conjugated diene structures in the main chain

[0040] (iii-5) a polymer having two conjugated diene structures, each of which is located at one end of a polymer chain; Reaction with polymers containing more than two dienophile structures in the polymer chain

[0041] (iii-6) a polymer having two conjugated diene structures, each of which is located at one end of a polymer chain; Reaction with a polymer having more than two dienophile structures in the polymer chain, with one dienophile structure at each end of the polymer chain and one or more dienophile structures in the main chain.

[0042] (iii-7) a polymer having two conjugated diene structures, each of which is located at one end of a polymer chain; A polymer having more than two dienophile structures in the polymer chain, wherein the polymer has one dienophile structure at one end of the polymer chain and no dienophile structure at the other end, and has two or more dienophile structures in the main chain.

[0043] (iii-8) a polymer having two conjugated diene structures, each of which is located at one end of a polymer chain; Reaction with a polymer that does not have a dienophile structure at both ends of the polymer chain and has more than two dienophile structures in the main chain

[0044] It is also preferable that the polymer used for bonding between polymer chains in the resin according to this embodiment does not have two or more conjugated diene structures or dienophile structures at the ends of the polymer chain.

[0045] For example, in the case of the reaction (i) above, in a polymer having two or more conjugated diene structures, at least one of one end and the other end of the polymer chain may not have a conjugated diene structure bonded thereto, and further, the end of the polymer chain may not have a conjugated diene structure bonded thereto.

[0046] For example, in the case of the reaction (ii) above, in a polymer having two or more dienophile structures, at least one of the ends of the polymer chain may not have a dienophile structure bonded thereto, and the end of the polymer chain may not have a dienophile structure bonded thereto.

[0047] For example, in the case of the reaction (iii) above, in a polymer having two or more conjugated diene structures, at least one of the ends of the polymer chain does not have to have a conjugated diene structure bonded thereto, and in a polymer having two or more dienophile structures, at least one of the ends of the polymer chain does not have to have a dienophile structure bonded thereto, and further, at least one of the ends of the polymer chain does not have to have a conjugated diene structure or a dienophile structure bonded thereto.

[0048] The polymer used for bonding between polymer chains in the resin according to this embodiment also preferably has at least one conjugated diene structure and / or dienophile structure in the main chain of the polymer chain.

[0049] For example, in the case of the reaction (i) above, in a polymer having two or more conjugated diene structures, one or more conjugated diene structures may be bonded to the main chain of the polymer chain, or all of the conjugated diene structures may be bonded to the main chain of the polymer chain.

[0050] For example, in the case of the reaction (ii) above, in a polymer having two or more dienophile structures, one or more dienophile structures may be bonded to the main chain of the polymer chain, or all of the dienophile structures may be bonded to the main chain of the polymer chain.

[0051] For example, in the case of the reaction (iii) above, in a polymer having two or more conjugated diene structures, one or more conjugated diene structures may be bonded to the main chain of the polymer chain, and in a polymer having two or more dienophile structures, one or more dienophile structures may be bonded to the main chain of the polymer chain. Furthermore, for example, in the case of the reaction (iii) above, in a polymer having two or more conjugated diene structures, all of the conjugated diene structures may be bonded to the main chain of the polymer chain, and in a polymer having two or more dienophile structures, all of the dienophile structures may be bonded to the main chain of the polymer chain.

[0052] When a conjugated diene structure or a dienophile structure is bonded to the main chain of a polymer chain, the conjugated diene structure or the dienophile structure may be bonded directly to the main chain of the polymer chain, or may be bonded to the main chain of the polymer chain via another group.

[0053] It is also preferable that the polymer used for bonding between polymer chains in the resin according to this embodiment does not have two or more conjugated diene structures or dienophile structures at the ends of the polymer chains.

[0054] For example, in the case of the reaction (iv) above, examples of a polymer having both a conjugated diene structure and a dienophile structure in one polymer chain include polymers of the following embodiments. (iv-1) A polymer in which a conjugated diene structure and a dienophile structure are not bonded to at least one end of the polymer chain. (iv-2) A polymer in which one end of the polymer chain is bonded to either a conjugated diene structure or a dienophile structure, the other end of the polymer chain is not bonded to either a conjugated diene structure or a dienophile structure, and at least one other of the conjugated diene structure and the dienophile structure is bonded to the main chain of the polymer chain. (iv-3) Polymers in which the conjugated diene structure and dienophile structure are not bonded to the ends of the polymer chain

[0055] The polymer used for bonding between polymer chains in the resin according to this embodiment also preferably has at least one conjugated diene structure and / or dienophile structure in the main chain of the polymer chain.

[0056] For example, in the case of the reaction (iv) above, in a polymer having both a conjugated diene structure and a dienophile structure in a single polymer chain, one or more of the conjugated diene structure and the dienophile structure may be bonded to the main chain of the polymer chain, or all of the conjugated diene structure and the dienophile structure may be bonded to the main chain of the polymer chain.

[0057] For example, in the case of the reaction (iv) above, examples of a polymer having both a conjugated diene structure and a dienophile structure in one polymer chain include polymers of the following embodiments. (iv-4) A polymer in which one dienophile structure is bonded to each end of the polymer chain and at least one conjugated diene structure is bonded to the main chain of the polymer chain.

[0058] When a conjugated diene structure or a dienophile structure is bonded to the main chain of a polymer chain, the conjugated diene structure or the dienophile structure may be bonded directly to the main chain of the polymer chain, or may be bonded to the main chain of the polymer chain via another group.

[0059] It is also preferable that the bonds between polymer chains in the resin according to this embodiment are not limited to bonds between the ends of the polymer chains. That is, the bond between polymer chains in the resin according to this embodiment is preferably a bond between one of a conjugated diene structure and a dienophile structure bonded to the end of one polymer and the other of a conjugated diene structure and a dienophile structure bonded to the main chain of the other polymer, or a bond between one of a conjugated diene structure and a dienophile structure bonded to the main chain of one polymer and the other of a conjugated diene structure and a dienophile structure bonded to the main chain of the other polymer.

[0060] By bonding not only the ends of the polymer chains but also three-dimensional crosslinking between the polymer chains occurs, which makes it easier to improve the solvent resistance of the resin. Furthermore, even if the bonding is not between the ends of the polymer chains, but between polymer chains having two reactive groups, three-dimensional crosslinking similarly does not occur, resulting in a linear polymer. Therefore, it is also preferable that the bonding between polymer chains in the resin according to this embodiment is not a bonding due to a reaction only between polymers having two reactive sites (reactive groups) in the polymer chain (for example, polymers having reactive groups at their ends).

[0061] Furthermore, the bond between polymer chains in the resin according to this embodiment may include a bond between the ends of the polymer chains.

[0062] Any conjugated diene structure that undergoes the Diels-Alder reaction can be used, but due to their high reactivity, those with an anthracene skeleton, a furan skeleton, or a styryl skeleton are preferably used. Examples of the conjugated diene structure include groups derived from dihydroxyanthracene, anthracenedicarboxylic acid, 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene, 9-(3-methyl-4-hydroxybenzyl)-10-(3-methyl-4-hydroxyphenyl)anthracene, 9-(4-hydroxyphenyl)anthracene, 9-(3-methyl-4-hydroxyphenyl)anthracene, 9,10-bis(4-hydroxyphenyl)anthracene, 9,10-bis(3-methyl-4-hydroxyphenyl)anthracene, hydroxyanthracene, 1,4-dihydroxyanthracene, anthracenecarboxylic acid, 2-(2-furanylmethyl)hydroquinone, furandicarboxylic acid, and isoeugenol.

[0063] In this embodiment, the conjugated diene structure or conjugated diene group (hereinafter, also simply referred to as "conjugated diene") preferably contains at least one of the structures represented by the following general formula (DE1) and general formula (DE2).

[0064] [ka]

[0065] In the general formula (DE1) and the general formula (DE2), R1 independently represents single bond, Bonding groups to other skeletons, hydrogen atoms, an aliphatic hydrocarbon group having 1 to 12 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, One or two of R1 are a single bond or a linking group to another skeleton, R1 as the linking group contains at least one atom selected from the group consisting of carbon atom, oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, and boron atom, and is a group in which all of the atoms constituting the linking group are bonded together by covalent bonds. In addition, a plurality of R1's may be linked to form a cyclic structure (including an aromatic ring and a heterocyclic ring).

[0066] In the general formulae (DE1) and (DE2), the aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by R1 includes saturated or unsaturated aliphatic hydrocarbon groups (alkyl groups, alkenyl groups, alkynyl groups). Examples of alkyl groups as aliphatic hydrocarbon groups having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, sec-hexyl, tert-hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups. Examples of alkenyl groups as aliphatic hydrocarbon groups having 1 to 12 carbon atoms include vinyl groups, ethenyl groups, 1-propenyl groups, 2-propenyl groups, 2-butenyl groups, 1-butenyl groups, 1-hexenyl groups, octenyl groups, decenyl groups, and dodecenyl groups. Examples of alkynyl groups as aliphatic hydrocarbon groups having 1 to 12 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 3-hexynyl, octynyl, decynyl, and dodecynyl groups.

[0067] In the general formulae (DE1) and (DE2), examples of the aromatic hydrocarbon group having 6 to 12 ring carbon atoms represented by R1 include a phenyl group, a naphthyl group, and a biphenyl group.

[0068] In the general formula (DE1) and the general formula (DE2), the alkoxy group having 1 to 10 carbon atoms represented by R1 is a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an isopentyloxy group, a neopentyloxy group, a tert -pentyloxy group, isohexyloxy group, sec-hexyloxy group, tert-hexyloxy group, isoheptyloxy group, sec-heptyloxy group, tert-heptyloxy group, isooctyloxy group, sec-octyloxy group, tert-octyloxy group, isononyloxy group, sec-nonyloxy group, tert-nonyloxy group, isodecyloxy group, sec-decyloxy group, and tert-decyloxy group.

[0069] In the general formulas (DE1) and (DE2), R1 as a linking group may be a divalent group containing at least one atom selected from the group consisting of carbon, oxygen, nitrogen, sulfur, silicon, phosphorus, and boron. The structure of this divalent group may also contain a divalent aromatic hydrocarbon group. Examples of divalent aromatic hydrocarbon groups include a phenylene group (-Ph-), a naphthylene group, and biphenylene. For example, divalent groups containing a phenylene group include -Ph-O-, -Ph-(C=O)-O-, -Ph-O-(C=O)-O-, -Ph-O-(C=O)-, and -Ph-S-.

[0070] In this embodiment, the conjugated diene more preferably contains at least one of the structures represented by the following general formulae (DE3) to (DE8).

[0071] [ka]

[0072] In the general formulae (DE3) to (DE8), X1 independently represents -O-, -(C=O)-O-, -O-(C=O)-O-, -O-(C=O)-, or -S-, R 11 are each independently hydrogen atoms, an aliphatic hydrocarbon group having 1 to 12 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, Also, multiple R 11 may be linked to form a cyclic structure (including an aromatic ring and a heterocyclic ring). R 12 are each independently hydrogen atoms, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, n represents 0 or a natural number up to which a substitutable number can be assigned. * indicates the bond position.

[0073] In this embodiment, it is particularly preferable that the conjugated diene contains at least one structure represented by the following general formula (DE9) to general formula (DE16).

[0074] [ka]

[0075] In the general formulae (DE9) to (DE16), R 13 are each independently hydrogen atoms, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or It is an aromatic hydrocarbon group having 6 to 12 carbon atoms. In the general formula (DE14), R 13 are each independently an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or An aromatic hydrocarbon group having 6 to 12 carbon atoms is preferred. * indicates the bond position.

[0076] In this embodiment, the conjugated diene preferably contains at least one of the structures represented by the following general formula (DE17) and general formula (DE18).

[0077] [ka]

[0078] In the general formula (DE17) and the general formula (DE18), R 11 are each independently hydrogen atoms, halogen atoms, an aliphatic hydrocarbon group having 1 to 12 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, Also, multiple R 11 may be linked to form a cyclic structure (including an aromatic ring and a heterocyclic ring). In the general formula (DE17), m represents an integer of 0 or more and 8 or less. In the general formula (DE18), n represents an integer of 0 to 4, m represents an integer of 0 or more and 9 or less. * indicates the bond position.

[0079] In this embodiment, the conjugated diene preferably contains at least one of the structures represented by the following general formula (DE19).

[0080] [ka]

[0081] In the general formula (DE19), R 11 are each independently hydrogen atoms, halogen atoms, an aliphatic hydrocarbon group having 1 to 12 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, Also, multiple R 11 may be linked to form a cyclic structure (including an aromatic ring and a heterocyclic ring). n represents an integer of 0 or more and 3 or less. * indicates the bond position.

[0082] Any dienophile structure that undergoes the Diels-Alder reaction can be used, but due to its high reactivity, those with a maleimide skeleton are preferably used. Dienophile structures include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, bisphenol A diphenyl ether bismaleimide, 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'-diphenylsulfone bismaleimide, and 1,3-bis(3-maleimidophenoxy) Examples include bismaleimides such as benzene, 1,3-bis(4-maleimidophenoxy)benzene, diphenylmethane-4,4'-bismaleimide polymer with 4,4'-methylenedianiline, N,N'-(2,2'-diethyl-6,6'-dimethylenediphenylene)bismaleimide, N,N'-(4-methyl-m-phenylene)bismaleimide, N,N'-m-phenylenedimaleimide, N,N'-m-phenylenebismaleimide, polyphenylmethane bismaleimide, monomaleimides such as N-phenylmaleimide, and PCs with a structure in which the molecular terminals are terminated with the following compounds.

[0083] [ka]

[0084] In this embodiment, the dienophile structure or dienophile group (hereinafter, these may also be simply referred to as "dienophile") preferably includes a structure represented by the following general formula (DP1).

[0085] [ka]

[0086] In the general formula (DP1), X2 is a single bond or a linking group to another skeleton, X2 as the linking group contains at least one atom selected from the group consisting of carbon atom, oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, and boron atom, and is a group in which all of the atoms constituting the linking group are bonded together by covalent bonds. * indicates the bond position.

[0087] In this embodiment, the dienophile is more preferably contained in at least one of the structures represented by the following general formula (DP2) and general formula (DP3).

[0088] [ka]

[0089] X2 in the general formula (DP2) and X in the general formula (DP3) 21 and X 22 each independently represents the same as X2 in general formula (DP1), Y2 in the general formula (DP3) is a group containing an aromatic polycarbonate skeleton or a polyarylate skeleton.

[0090] In this embodiment, it is particularly preferable that the dienophile structure or dienophile group contains a structure represented by the following general formula (DP4): In the following general formula (DP4), * indicates the bonding position.

[0091] [ka]

[0092] In this embodiment, the ratio of the conjugated diene to the dienophile can be appropriately set depending on the target physical properties and intended use. The molar ratio of the conjugated diene to the dienophile (conjugated diene / dienophile) is preferably 0.01 or more and 100 or less, more preferably 0.1 or more and 10 or less, and even more preferably 0.2 or more and 5 or less. If the molar ratio of the conjugated diene to the dienophile is less than 0.01 or more than 100, crosslinking may not proceed sufficiently, and improvements in solvent resistance and mechanical properties may be insufficient.

[0093] The resin according to this embodiment preferably contains at least one of the structures represented by the following general formula (UN1) and general formula (UN2).

[0094] [ka]

[0095] In the general formula (UN1) and the general formula (UN2), Ar3, Ar 31 and Ar 32 are each independently a group represented by the following general formula (UN11). * indicates the bond position.

[0096] [ka]

[0097] In the general formula (UN11), m3 is 0, 1 or 2; n3 is 4, The multiple R3s are each independently hydrogen atoms, halogen atoms, Alkyl having 1 to 10 carbon atoms, aryl having 6 to 12 ring carbon atoms, or It is an alkyl fluoride having 1 to 10 carbon atoms, X3 is independently single bond, -C(-R 31 )2-, -O-, -S-, -SO-, -SO2-, -N(-R 32 )-, -P(-R 33 )-, -P=O(-R 34 )-, carbonyl, ester, amides, alkylene having 2 to 20 carbon atoms; alkylidene having 2 to 20 carbon atoms, cycloalkylene having 3 to 20 ring carbon atoms; cycloalkylidene having 3 to 20 ring carbon atoms; arylene having 6 to 20 ring carbon atoms; bicycloalkanediyl having 4 to 20 ring carbon atoms, tricycloalkanediyl having 5 to 20 ring carbon atoms, bicycloalkylidene having 4 to 20 ring carbon atoms, and a group consisting of one or more selected from the group consisting of tricycloalkylidenes having 5 to 20 ring carbon atoms, R 31 From R 34 are each independently hydrogen atoms, halogen atoms, Alkyl having 1 to 10 carbon atoms, aryl having 6 to 12 ring carbon atoms, or It is an alkyl fluoride having 1 to 10 carbon atoms. * indicates the bond position.

[0098] In the general formula (UN11), examples of the halogen atom represented by R3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0099] In general formula (UN11), examples of the alkyl having 1 to 10 carbon atoms represented by R3 include 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.

[0100] In the general formula (UN11), examples of the aryl having 6 to 12 ring carbon atoms represented by R3 include phenyl, naphthyl, and biphenyl groups.

[0101] In the general formula (UN11), examples of the fluorinated alkyl having 1 to 10 carbon atoms represented by R3 include alkyl groups in which at least one hydrogen atom on a carbon atom in the alkyl exemplified as the alkyl having 1 to 10 carbon atoms represented by R3 in the general formula (UN11) above is substituted with a fluorine atom.

[0102] In the general formula (UN11), the alkylene having 2 to 20 carbon atoms represented by X3 includes linear or branched alkylene groups, such as ethylene, propylene, isopropylene, butylene, hexylene, octylene, and decylene. In the general formula (UN11), examples of the alkylidene having 2 to 20 carbon atoms represented by X3 include ethylidene, propylidene, butylidene, hexylidene, octylidene, decylidene, pentadecylidene, and icosylidene groups. In the general formula (UN11), the cycloalkylene having 3 to 20 carbon atoms represented by X3 includes linear or branched alkylene groups, such as cyclopropylene, cyclobutylene, cyclohexylene, cyclooctylene, cyclodecylene, cyclopentadecylene, and cycloicosylene. In the general formula (UN11), cycloalkylidene having 3 to 20 carbon atoms represented by X3 includes groups such as cyclopropylidene, cyclobutylidene, cyclohexylidene, cyclooctylidene, cyclodecylidene, cyclododecylidene, cyclopentadecylidene, and cycloicosylidene. In the general formula (UN11), examples of the arylene having 6 to 20 ring carbon atoms represented by X3 include phenylene, naphthylene, and biphenylene groups.

[0103] In the general formula (UN11), examples of the bicycloalkanediyl having 4 to 20 ring carbon atoms represented by X3 include the above-mentioned bicyclic cycloalkylene rings, and examples of the tricycloalkanediyl having 5 to 20 ring carbon atoms include the above-mentioned tricyclic cycloalkylene rings, such as tricyclodecanediyl and adamantanediyl. In the general formula (UN11), bicycloalkylidene having 4 to 20 ring carbon atoms represented by X3 is exemplified by the bicyclic rings of the above-mentioned cycloalkylidene, and tricycloalkylidene having 5 to 20 ring carbon atoms is exemplified by the tricyclic rings of the above-mentioned cycloalkylidene, for example, adamantylidene and tricyclodecylidene.

[0104] In the general formula (UN11), R of X3 31 From R 34 Examples of the halogen atom, alkyl having 1 to 10 carbon atoms, aryl having 6 to 12 ring carbon atoms, and fluoroalkyl having 1 to 10 carbon atoms represented by the formula (UN11) are the same as the groups represented by R3 in the general formula (UN11) above.

[0105] [Resin precursor composition] The resin precursor composition according to this embodiment can be used to produce the resin according to this embodiment described above through a crosslinking reaction. That is, the resin precursor composition according to this embodiment contains a combination of a polymer having at least one of a conjugated diene and a dienophile with Diels-Alder reactivity in its structure, and a crosslinking agent or polymer having the corresponding group.

[0106] In the resin precursor composition according to this embodiment, the conjugated diene, the dienophile, and the ratio of the conjugated diene to the dienophile are the same as those in the resin according to this embodiment.

[0107] The concentrations of the conjugated diene and dienophile in the resin precursor composition according to this embodiment can be appropriately set depending on the desired physical properties and intended application. When the functional group concentration is calculated based on the total amount of the composition having Diels-Alder reactive groups (at least one of the conjugated diene and the dienophile) and the smaller of the total number of moles of the conjugated diene and the total number of moles of the dienophile groups, this functional group concentration is preferably 0.01 mmol / g or more and 10 mmol / g or less, more preferably 0.03 mmol / g or more and 7 mmol / g or less, even more preferably 0.1 mmol / g or more and 5 mmol / g or less, and particularly preferably 0.3 mmol / g or more and 5 mmol / g or less. If the functional group concentration is less than 0.01 mmol / g, the crosslink density may be low, resulting in insufficient improvement in solvent resistance and mechanical properties. If the functional group concentration exceeds 10 mmol / g, the crosslinking density will be too high, resulting in insufficient toughness of the crosslinked product, and unreacted functional groups will likely remain, and the crosslinking reaction and other side reactions will progress over time, causing changes in the physical properties of the material and making it prone to deterioration, which is undesirable.

[0108] The resin precursor composition according to this embodiment preferably contains, for example, at least one of the following components (b1) to (b4). (b1) A polymer having two or more conjugated diene structures in the polymer chain and a compound having a difunctional or higher dienophile group. (b2) A polymer having two or more dienophile structures in the polymer chain and a compound having a difunctional or higher conjugated diene group. (b3) A polymer having two or more conjugated diene structures in the polymer chain and a polymer having two or more dienophile structures in the polymer chain. (b4) A polymer having both a conjugated diene structure and a dienophile structure in one polymer chain, and the average number of the conjugated diene structure and the dienophile structure per polymer chain is one or more.

[0109] The resin precursor composition according to this embodiment preferably contains, for example, the following component (b1-1).

[0110] (b1-1) A polymer having two or more conjugated diene structures in the main chain of the polymer chain and a compound having two or more functional dienophile groups

[0111] The resin precursor composition according to this embodiment preferably contains, for example, at least one of the following components (b3-1) to (b3-8).

[0112] (b3-1) A polymer having two dienophile structures, each of which is located at one end of the polymer chain; and Polymers with more than two conjugated diene structures in the polymer chain

[0113] (b3-2) A polymer having two dienophile structures, each of which is located at one end of the polymer chain; and A polymer having more than two conjugated diene structures in the polymer chain, with one conjugated diene structure at each end of the polymer chain and one or more conjugated diene structures in the main chain.

[0114] (b3-3) A polymer having two dienophile structures, each of which is located at one end of the polymer chain; and A polymer having more than two conjugated diene structures in the polymer chain, wherein one of the conjugated diene structures is at one end of the polymer chain and the other end does not have the conjugated diene structure, and the polymer has two or more of the conjugated diene structures in the main chain.

[0115] (b3-4) A polymer having two dienophile structures, each of which is located at one end of the polymer chain; and A polymer that does not have a conjugated diene structure at either end of the polymer chain and has more than two conjugated diene structures within the main chain

[0116] (b3-5) A polymer having two conjugated diene structures, each of which is located at one end of a polymer chain; and Polymers with more than two dienophile structures in the polymer chain

[0117] (b3-6) A polymer having two conjugated diene structures, each of which is located at one end of a polymer chain; and A polymer having more than two dienophile structures in the polymer chain, with one dienophile structure at each end of the polymer chain and one or more dienophile structures in the main chain.

[0118] (b3-7) A polymer having two conjugated diene structures, each of which is located at one end of a polymer chain; and A polymer having more than two dienophile structures in the polymer chain, in which one dienophile structure is at one end of the polymer chain and no dienophile structure at the other end, and the polymer has two or more dienophile structures in the main chain.

[0119] (b3-8) A polymer having two conjugated diene structures, each of which is located at one end of a polymer chain; and A polymer that does not have a dienophile structure at either end of the polymer chain and has more than two dienophile structures within the main chain

[0120] It is also preferable that the polymer contained in the resin precursor composition according to this embodiment does not have two or more of at least one of a conjugated diene structure and a dienophile structure at the end of the polymer chain.

[0121] For example, in the case of a composition containing the component (b1), in a polymer having two or more conjugated diene structures, at least one of the ends of the polymer chain may not have a conjugated diene structure bonded thereto, and further, at least one of the ends of the polymer chain may not have a conjugated diene structure bonded thereto.

[0122] For example, in the case of a composition containing the component (b2), in a polymer having two or more dienophile structures, at least one of the ends of the polymer chain may not have a dienophile structure bonded thereto, and the end of the polymer chain may not have a dienophile structure bonded thereto.

[0123] For example, in the case of a composition containing the component (b3), in a polymer having two or more conjugated diene structures, at least one of the ends of the polymer chain does not have to have a conjugated diene structure bonded thereto, and in a polymer having two or more dienophile structures, at least one of the ends of the polymer chain does not have to have a dienophile structure bonded thereto, and further, at least one of the ends of the polymer chain does not have to have a conjugated diene structure or a dienophile structure bonded thereto.

[0124] The polymer contained in the resin precursor composition according to this embodiment preferably has at least one conjugated diene structure and / or dienophile structure in the main chain of the polymer chain.

[0125] For example, in the case of a composition containing the component (b1), in a polymer having two or more conjugated diene structures, one or more of the conjugated diene structures may be bonded to the main chain of the polymer chain, or all of the conjugated diene structures may be bonded to the main chain of the polymer chain.

[0126] For example, in the case of a composition containing the component (b2), in a polymer having two or more dienophile structures, one or more dienophile structures may be bonded to the main chain of the polymer chain, or all of the dienophile structures may be bonded to the main chain of the polymer chain.

[0127] For example, in the case of a composition containing the component (b3), in a polymer having two or more conjugated diene structures, one or more conjugated diene structures may be bonded to the main chain of the polymer chain, and in a polymer having two or more dienophile structures, one or more dienophile structures may be bonded to the main chain of the polymer chain. Furthermore, for example, in the case of a composition containing the component (b3), in a polymer having two or more conjugated diene structures, all of the conjugated diene structures may be bonded to the main chain of the polymer chain, and in a polymer having two or more dienophile structures, all of the dienophile structures may be bonded to the main chain of the polymer chain.

[0128] When a conjugated diene structure or a dienophile structure is bonded to the main chain of a polymer chain, the conjugated diene structure or the dienophile structure may be bonded directly to the main chain of the polymer chain, or may be bonded to the main chain of the polymer chain via another group.

[0129] It is also preferable that the polymer contained in the resin precursor composition according to this embodiment does not have two or more of at least one of a conjugated diene structure and a dienophile structure at the end of the polymer chain.

[0130] For example, in the case of a composition containing the component (b4), examples of a polymer having both a conjugated diene structure and a dienophile structure in one polymer chain include polymers of the following embodiments. (b4-1) A polymer in which a conjugated diene structure and a dienophile structure are not bonded to at least one end of the polymer chain. (b4-2) A polymer in which one end of the polymer chain is bonded to either a conjugated diene structure or a dienophile structure, the other end of the polymer chain is not bonded to either a conjugated diene structure or a dienophile structure, and at least one other of the conjugated diene structure and the dienophile structure is bonded to the main chain of the polymer chain. (b4-3) Polymers in which the conjugated diene structure and dienophile structure are not bonded to the ends of the polymer chain

[0131] The polymer contained in the resin precursor composition according to this embodiment preferably has at least one conjugated diene structure and / or dienophile structure in the main chain of the polymer chain.

[0132] For example, in the case of a composition containing the component (b4), in a polymer having both a conjugated diene structure and a dienophile structure in a single polymer chain, one or more of the conjugated diene structure and the dienophile structure may be bonded to the main chain of the polymer chain, or all of the conjugated diene structure and the dienophile structure may be bonded to the main chain of the polymer chain.

[0133] For example, in the case of a composition containing the component (b4), examples of a polymer having both a conjugated diene structure and a dienophile structure in one polymer chain include polymers of the following embodiments. (b4-4) A polymer in which one dienophile structure is bonded to each end of the polymer chain and at least one conjugated diene structure is bonded to the main chain of the polymer chain.

[0134] When a conjugated diene structure or a dienophile structure is bonded to the main chain of a polymer chain, the conjugated diene structure or the dienophile structure may be bonded directly to the main chain of the polymer chain, or may be bonded to the main chain of the polymer chain via another group.

[0135] It is also preferable that the bonds between polymer chains in the resin formed when the resin precursor composition according to this embodiment is used are not bonds only between the ends of the polymer chains. That is, the bond between polymer chains in the resin formed when the resin precursor composition according to this embodiment is used is preferably a bond between one of the conjugated diene structure and the dienophile structure bonded to the end of one polymer and the other of the conjugated diene structure and the dienophile structure bonded to the main chain of the other polymer, or at least one of a bond between one of the conjugated diene structure and the dienophile structure bonded to the main chain of one polymer and the other of the conjugated diene structure and the dienophile structure bonded to the main chain of the other polymer.

[0136] By bonding not only the ends of the polymer chains but also three-dimensional crosslinking between the polymer chains occurs, which makes it easier to improve the solvent resistance of the resin. Furthermore, even if the bonding is not between the ends of the polymer chains, but between polymer chains having two reactive groups, three-dimensional crosslinking does not occur and a linear polymer is formed. Therefore, it is preferable that the bonding between polymer chains in the resin formed using the resin precursor composition according to this embodiment is not a bonding due to a reaction only between polymers having two reactive sites (reactive groups) in the polymer chain (for example, polymers having reactive groups at their ends).

[0137] Furthermore, the bonds between polymer chains in the resin formed when the resin precursor composition according to this embodiment is used may include bonds between the ends of the polymer chains.

[0138] Of the above components, a polymer (polycarbonate polymer) having two or more conjugated diene structures in the polymer chain will be taken as an example and described in detail.

[0139] A first form of the polycarbonate polymer (hereinafter also referred to as PC polymer) according to this embodiment is a PC polymer having a single repeating unit A represented by the following general formula (1), or a PC polymer having at least a repeating unit selected from the repeating unit A represented by the following general formula (1) and the repeating unit B represented by the following general formula (2), and obtained from at least 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:

[0140] [ka]

[0141] [ka]

[0142] In the general formula (1) and the general formula (1A), Ar 33 is at least one group selected from the group consisting of groups represented by general formula (DE3), general formula (DE5), and general formula (DE8), and n 31 represents the average number of monomers. Also, the average number of monomers, n 31 is greater than or equal to 1.0 and less than or equal to 10. In the general formula (2) and the general formula (2A), Ar 34 is a group represented by the general formula (UN11), and n 32 represents the average number of monomers. Also, the average number of monomers, n 32 is greater than or equal to 1.0 and less than or equal to 10. In the general formula (2C), Ar 33 is at least one group selected from the group consisting of groups represented by general formula (DE3), general formula (DE5), and general formula (DE8), and Ar 34 is a group represented by the general formula (UN11). 33 and n 34and represent the average number of mers, respectively. Also, the average number of mers, n 33 and n 34 The sum of these is greater than or equal to 1.0 and less than or equal to 10. * indicates the bond position. However, Ar 33 and Ar 34 In the general formula (2C), the repeating units do not necessarily have to be consecutive. The average number of monomers can be calculated by the method described in the Examples below.

[0143] Such a PC polymer has a repeating unit A containing a group represented by the general formula (DE3) having a conjugated diene structure, and therefore is a polymer having two or more conjugated diene structures in the polymer chain.

[0144] As the PC polymer having a single repeating unit A represented by the general formula (1) and the PC polymer having a repeating unit A represented by the general formula (1) and a repeating unit B represented by the general formula (2), one represented by the following general formula (100) is preferred.

[0145] [ka]

[0146] In the general formula (100), a represents the molar copolymerization ratio in the repeating unit A, and b represents the molar copolymerization ratio in the repeating unit B. a is [Ar 33 ] / ([Ar 33 ]+[Ar 34 ]), and b is [Ar 34 ] / ([Ar 33 ]+[Ar 34 ]), including the case where b is 0. [Ar 33 ] is the Ar in the PC polymer 33 represents the number of moles of repeating units A containing a group represented by [Ar 34 ] is the Ar in the PC polymer 34represents the number of moles of repeating unit B containing a group represented by the formula:

[0147] In the general formula (100), the repeating units are not necessarily consecutive. The PC polymer represented by the general formula (100) may be any of a block copolymer, an alternating copolymer, a random copolymer, and the like. The second type of PC polymer according to this embodiment has, as a chain end of the PC polymer, any of the structures represented by the general formula (DE4), general formula (DE6), general formula (DE7), general formula (DE9), general formula (DE12), general formula (DE14), general formula (DP1), general formula (DP3) and general formula (DP4). 33 However, in that case, the chain end must contain at least two of the above structures on average per molecule. However, when the polymer chain end does not have two or more conjugated diene structures, the PC polymer (100) does not contain Ar 33 On the other hand, it is preferable that Ar 33 In the case of a skeleton containing Ar per molecule 33 The total number of diene structures contained in the chain terminals and the diene structures contained in the chain terminals may be 2 or more. 33 It is preferable that the number of diene structures contained in the above formula is one or more.

[0148] In addition to the specific terminal groups described above, the chain ends of the PC polymer according to this embodiment are preferably blocked with a monovalent aromatic group or a monovalent fluorine-containing aliphatic group within a range that satisfies the requirements of the present application. The monovalent aromatic group may be a group containing an aliphatic group. The monovalent fluorine-containing aliphatic group may be a group containing an aromatic group. In addition, the monovalent aromatic group and the monovalent fluorine-containing aliphatic group may have at least one substituent selected from the group consisting of an alkyl group, a halogen atom, and an aryl group added thereto. These substituents may further have at least one substituent selected from the group consisting of an alkyl group, a halogen atom, and an aryl group added thereto. In addition, when there are multiple substituents, these substituents may be bonded to each other to form a ring.

[0149] The monovalent aromatic group constituting the chain end preferably contains an aryl group having ring carbon atoms of 6 to 12. Examples of such an aryl group include a phenyl group and a biphenyl group. Examples of the substituent added to the aromatic group and the substituent added to the alkyl group added to the aromatic group include halogen atoms such as fluorine, chlorine, and bromine atoms. Examples of the substituent added to the aromatic group include alkyl groups having 1 to 20 carbon atoms. This alkyl group may be a group having a halogen atom added thereto, as described above, or may be a group having an aryl group added thereto.

[0150] The monovalent fluorine-containing aliphatic group constituting the chain end may be a monovalent group derived from a fluorine-containing alcohol.

[0151] The fluorine-containing alcohol is preferably one in which a plurality of fluoroalkyl chains each having 2 to 6 carbon atoms are linked together via ether bonds and which has a total of 13 to 19 fluorine atoms. 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, a decrease in reactivity during polymerization can be suppressed, and at least one of the mechanical strength, surface hardness, and heat resistance of the obtained PC polymer can be improved. Furthermore, the monovalent fluorine-containing aliphatic group is preferably a monovalent group derived from a fluorine-containing alcohol having two or more ether bonds. The use of such a fluorine-containing alcohol improves the dispersibility of the PC polymer in the coating composition, improves the abrasion resistance of the molded article or electrophotographic photoreceptor, and allows the surface lubricity, water repellency, and oil repellency to be maintained after abrasion.

[0152] Alternatively, the fluorine-containing alcohol may be a fluorine-containing alcohol represented by the following general formula (30) or (31), a fluorine-containing alcohol such as 1,1,1,3,3,3-hexafluoro-2-propanol, or a fluorine-containing alcohol connected via an ether bond represented by the following general formula (32), (33), or (34).

[0153] H(CF2) n1 CH2OH···(30) F(CF2) m1 CH2OH···(31)

[0154] In the general formula (30), n1 is an integer of 1 to 12, and in the general formula (31), m1 is an integer of 1 to 12.

[0155] F-(CF2) n 31 -OCF2CH2-OH···(32) F-(CF2CF2) n 32 -(CF2CF2O) n 33 -CF2CH2OH···(33) CR3-(CF2) n 35 -O-(CF2CF2O) n 34 -CF2CH2OH···(34)

[0156] In the general formula (32), n 31 is an integer from 1 to 10, preferably an integer from 5 to 8. In the general formula (33), n 32is an integer from 0 to 5, preferably an integer from 0 to 3. 33 is an integer from 1 to 5, preferably an integer from 1 to 3. In the general formula (34), n 34 is an integer from 1 to 5, preferably an integer from 1 to 3. 35 is an integer from 0 to 5, preferably an integer from 0 to 3. R is CF3 or F.

[0157] In this embodiment, from the viewpoint of improving electrical properties and abrasion resistance, it is preferable that the chain ends of the PC polymer are blocked with a monovalent group derived from a phenol represented by the following general formula (35) or a monovalent group derived from a fluorine-containing alcohol represented by the following general formula (36).

[0158] [ka]

[0159] In the general formula (35), R 30 represents an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group having 1 to 10 carbon atoms; and p is an integer of 1 to 3. In the general formula (36), R f represents a perfluoroalkyl group having 5 or more carbon atoms and 11 or more fluorine atoms, or a perfluoroalkyloxy group represented by the following general formula (37).

[0160] [ka]

[0161] In the general formula (37), R f2 is a straight-chain or branched perfluoroalkyl group having 1 to 6 carbon atoms; mx is an integer of 1 to 3.

[0162] One aspect of the method for producing a PC polymer according to this embodiment is a production method in which at least one of a bischloroformate oligomer compound represented by the general formula (1A) and a bischloroformate oligomer compound represented by the general formula (2A), an organic solvent, an alkaline aqueous solution, and a monomer such as a bisphenol compound is used, and an organic layer and an aqueous layer are mixed to carry out an interfacial polycondensation reaction.

[0163] In the method for producing a PC polymer according to this embodiment, a monovalent carboxylic acid or a derivative thereof, or a monovalent phenol can be used as an end-capping agent for generating chain ends. For example, p-tert-butyl-phenol, 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-perfluorotridodecyloxy)-1,1,1,3,3,3-hexafluoropropyl]phenol, 3,5-bis(perfluorohexyloxycarbonyl)phenol, perfluorododecyl p-hydroxybenzoate, p-(1H,1H-perfluorooctyloxy)phenol, 2H,2H,9H-perfluorononanoic acid, and the like are preferably used.

[0164] Alternatively, the end-capping agent for generating the chain ends may be a fluorine-containing alcohol represented by the general formula (30) or (31) or a monohydric fluorine-containing alcohol such as 1,1,1,3,3,3-hexafluoro-2-propanol. It is also preferable to use a fluorine-containing alcohol bonded via an ether bond represented by the general formula (32), (33), or (34).

[0165] Among these, it is preferable to use, as the end-capping agent for generating chain ends, a monohydric phenol represented by the general formula (35) or a monohydric fluorine-containing alcohol represented by the general formula (36) in terms of improving electrical properties and abrasion resistance.

[0166] Suitable examples of the monohydric phenol represented by the general formula (35) include p-tert-butylphenol, p-perfluorononylphenol, p-perfluorohexylphenol, p-tert-perfluorobutylphenol, p-perfluorooctylphenol, etc. That is, in this embodiment, the chain ends are preferably blocked with an end-capping agent selected from the group consisting of p-tert-butylphenol, p-perfluorononylphenol, p-perfluorohexylphenol, p-tert-perfluorobutylphenol, and p-perfluorooctylphenol.

[0167] Examples of the fluorine-containing alcohol via an ether bond represented by the general formula (36) include the following compounds: That is, in this embodiment, the chain ends are preferably capped with an end-capping agent selected from any of the following fluorine-containing alcohols.

[0168] [ka]

[0169] The appropriate proportion of end-capping agent varies depending on whether the Diels-Alder reactive functional group (conjugated diene or dienophile) is present at the end or in the main chain or side chain. When a conjugated diene or dienophile is present at the end, the concentration of crosslinkable reactive groups and molecular weight change in conjunction with the fraction of the end. The molar percentage of the copolymer composition of diene or dienophile end groups relative to the total of the main chain and end repeating units is preferably 0.1 mol% to 67 mol%, more preferably 0.5 mol% to 50 mol%. Adding an end-capping agent at a proportion of 67 mol% or less can suppress a decrease in mechanical strength, while adding an end-capping agent at a proportion of 0.1 mol% or more can achieve improved properties through crosslinking. When a conjugated diene or dienophile is not contained, the molar percentage of the copolymer composition of the chain terminal relative to the total of the main chain and terminal repeating units is preferably 0.05 mol% to 40 mol%, more preferably 0.1 mol% to 20 mol%. When the proportion of the end-capping agent added is 40 mol% or less, a decrease in mechanical strength can be suppressed, and when it is 0.05 mol% or more, a decrease in moldability can be suppressed.

[0170] The branching agent that can be used in the method for producing a PC polymer according to this embodiment is not particularly limited. Specific examples of the branching agent include phloroglucin, 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-bis(4-hydroxyphenyl)cyclohexyl]cyclohexane], and the like. [4-hydroxyphenyl]propane, 2,4-bis[2-bis(4-hydroxyphenyl)-2-propyl]phenol, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, tetrakis(4-hydroxyphenyl)methane, tetrakis[4-(4-hydroxyphenylisopropyl)phenoxy]methane, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid, 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole, 3,3-bis(4-hydroxyaryl)oxindole, 5-chloroisatin, 5,7-dichloroisatin, and 5-bromoisatin. The proportion of these branching agents added is preferably 30 mol % or less, more preferably 5 mol % or less, in terms of the molar percentage of the copolymer composition of repeating unit A, repeating unit B, and chain end, or the molar percentage of the copolymer composition of repeating unit A and chain end. When the proportion of branching agent added is 30 mol % or less, deterioration in moldability can be suppressed.

[0171] When performing interfacial polycondensation, examples of the acid binder 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; weak alkali metal acid salts such as sodium carbonate, potassium carbonate, and calcium acetate; weak alkaline earth metal acid salts; and organic bases such as pyridine. Preferred acid binders for performing interfacial polycondensation are alkali metal hydroxides and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide. These acid binders can also be used as mixtures. The proportion of the acid binder used can be appropriately adjusted taking into account the stoichiometric ratio (equivalents) of the reaction. Specifically, 1 equivalent or more of the acid binder can be used per mole of the total hydroxyl groups of the dihydric phenol raw material, and preferably 1 to 10 equivalents of the acid binder can be used.

[0172] The solvent used in the method for producing a PC polymer according to this embodiment is sufficient as long as it exhibits a certain level of solubility for the resulting copolymer. Suitable solvents include, for example, aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as 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, and chlorobenzene; ketones such as cyclohexanone, acetone, and acetophenone; and ethers such as tetrahydrofuran and 1,4-dioxane. These solvents may be used alone or in combination. Furthermore, the interfacial polycondensation reaction may be carried out using two immiscible solvents.

[0173] The organic solvent used in the method for producing a PC polymer according to this embodiment is preferably an organic solvent that is substantially immiscible with water and capable of dissolving 5% by mass or more of the polycarbonate copolymer that is finally obtained.The organic solvent is preferably an organic solvent that is substantially immiscible with water and capable of dissolving 5% by mass or more of the polycarbonate copolymer that is finally obtained. Here, an organic solvent that is "substantially immiscible with water" is an organic solvent that does not give a solution consisting of a uniform layer (a solution in which neither gelled matter nor insoluble matter is observed) when mixed with water in a composition range of 1:9 to 9:1 under normal temperature and pressure conditions. Furthermore, the phrase "the organic solvent is capable of dissolving 5% by mass or more of the finally obtained polycarbonate copolymer" refers to the solubility of the polycarbonate copolymer when measured under conditions of a temperature of 20 to 30°C and normal pressure. The "finally obtained polycarbonate polymer" refers to a polymer obtained through the polymerization step in the method for producing a polycarbonate polymer of the present embodiment, and is a polymer before crosslinking. Examples of such organic solvents include aromatic hydrocarbons such as toluene, ketones such as cyclohexanone, and halogenated hydrocarbons such as methylene chloride, among which methylene chloride is preferred due to its high solubility.

[0174] The catalyst used in the method for producing a PC polymer of this embodiment is not particularly limited, but 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. Furthermore, if necessary, a small amount of an antioxidant such as sodium sulfite or a hydrosulfite salt may be added to the reaction system of the PC polymer of this embodiment.

[0175] [Coating liquid composition] The coating liquid composition according to this embodiment contains the resin precursor composition according to this embodiment and an organic solvent.

[0176] The organic solvent according to this embodiment can be appropriately selected taking into consideration the solubility of materials such as the resin precursor composition, the drying speed after molding, the effect of the solvent remaining on the molded product, and the risk of fire or health hazards. Examples of organic solvents that can be used in this embodiment include cyclic ethers (such as tetrahydrofuran (THF), dioxane, and dioxolane), cyclic ketones (such as cyclohexanone, cyclopentanone, and cycloheptanone), aromatic hydrocarbons (such as toluene, xylene, and chlorobenzene), ketones (such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK)), halogenated hydrocarbons (such as dichloromethane and chloroform), esters (such as ethyl acetate, isopropyl acetate, isobutyl acetate, and butyl acetate), ethers (such as ethylene glycol dimethyl ether and ethylene glycol monoethyl ether), amides (such as dimethylformamide (DMF) and dimethylacetamide (DMAc)), and aprotic polar solvents (such as dimethyl sulfoxide (DMSO)).

[0177] The concentration of the resin precursor composition according to this embodiment in the coating composition according to this embodiment may be a concentration that provides an appropriate viscosity suited to the application of the coating composition, and is preferably 0.1% by mass to 40% by mass, more preferably 1% by mass to 35% by mass, and even more preferably 5% by mass to 30% by mass. A concentration of 40% by mass or less prevents the viscosity from becoming too high, resulting in good coatability. A concentration of 0.1% by mass or more allows for the maintenance of an appropriate viscosity, resulting in the formation of a homogeneous film. This concentration also shortens the drying time after coating and provides an appropriate concentration for easily achieving a target film thickness.

[0178] The coating composition may contain additives in addition to the resin precursor composition according to this embodiment and the organic solvent. Examples of additives include low-molecular-weight compounds, colorants (e.g., dyes and pigments), functional compounds (e.g., charge transport materials, electron transport materials, hole transport materials, and charge generation materials), fillers (e.g., inorganic or organic fillers, fibers, cloths, and fine particles), antioxidants, ultraviolet absorbers, and acid scavengers. The coating composition may also contain resins other than the resin precursor composition according to one embodiment of the present invention. As these additives and other resins, known substances that can be blended with the resin precursor composition can be used.

[0179] Furthermore, when a charge transport substance is contained, from the viewpoint of product performance, the mass ratio of the resin precursor composition to the charge transport substance in the coating liquid composition according to this embodiment is preferably in the range of 20:80 to 80:20, and more preferably in the range of 30:70 to 70:30. In the coating liquid composition according to this embodiment, the resin precursor composition according to this embodiment may be used alone or in combination of two or more kinds.

[0180] The coating composition according to this embodiment is usually suitable for use in forming a photosensitive layer of a multilayer electrophotographic photoreceptor. The photosensitive layer of a multilayer electrophotographic photoreceptor preferably includes at least a charge generation layer and a charge transport layer, and the coating composition according to this embodiment is suitable for use in forming the charge transport layer. Furthermore, by further incorporating the charge generation material into the coating composition according to this embodiment, it is also possible to use the coating composition according to this embodiment in forming a photosensitive layer of a single-layer electrophotographic photoreceptor. It can also be used to form a protective layer for a photoreceptor.

[0181] [Molded product] The molded article according to the present embodiment includes the resin according to the present embodiment. The molded article according to the present embodiment can be used for various purposes in addition to the use of the electrophotographic photoreceptor described below. For example, the molded article can be suitably used for applications such as substrates, insulating layers, protective layers, adhesive layers, conductive layers, and structural materials for electronic devices.

[0182] The molded article according to this embodiment can be produced using the resin precursor composition according to this embodiment. When the resin precursor composition according to this embodiment is used, either a wet molding method or a melt molding method can be used as the molding method.

[0183] When a molded product is obtained by wet molding, (i) a method of molding at a temperature at which the crosslinking reaction proceeds, (ii) a method of obtaining a wet molded product at a temperature at which the crosslinking reaction does not substantially proceed, and then raising the temperature to a temperature at which the crosslinking reaction proceeds during the solvent removal step to simultaneously perform drying and crosslinking, or (iii) a method of obtaining a dry molded product by wet molding at a temperature at which the crosslinking reaction does not substantially proceed and drying, and then raising the temperature to a temperature at which the crosslinking reaction proceeds to crosslink the molded product. Any of these methods may be used. In the wet molding method, the coating liquid composition according to the present embodiment can be used.

[0184] When using melt molding, it is usually performed at a temperature above the temperature at which the Diels-Alder reaction proceeds. Alternatively, a suitable method is to increase the molding temperature until the retro-Diels-Alder reaction occurs, thereby decreasing the melt viscosity and improving flowability. When molding under conditions that cause the retro-Diels-Alder reaction, the progress of the Diels-Alder reaction can be appropriately controlled again by controlling the cooling rate and temperature of the molded product. This allows for the production of molded products made from resins with good molding flowability and improved resin properties due to the presence of a crosslinked structure.

[0185] The crosslinking temperature can be appropriately set depending on the desired properties and intended use. The crosslinking method can be set by adjusting the type of crosslinkable functional group, the ratio of conjugated diene to dienophile, and the functional group concentration in accordance with the crosslinking temperature.

[0186] For example, the crosslinking temperature for electrophotographic photoreceptors is preferably a temperature at which crosslinking is performed in a drying process after obtaining a wet-molded product by normal wet molding, and the temperature must be such that the functional low-molecular-weight compound does not deteriorate. For example, the crosslinking temperature for electrophotographic photoreceptors is preferably 60°C or higher and 170°C or lower, more preferably 80°C or higher and 160°C or lower, and even more preferably 100°C or higher and 150°C or lower. If the crosslinking temperature exceeds 170°C, functional low-molecular-weight compounds such as charge transport materials may deteriorate. If the crosslinking temperature is lower than 60°C, drying may not proceed sufficiently or may take a long time, which is undesirable.

[0187] On the other hand, in applications involving electronic devices, the film properties are adjusted by the drying and curing speed during coating film formation, resulting in high temperatures during the process. Therefore, the crosslinking temperature for electronic devices is preferably 60°C or higher and 250°C or lower, and more preferably 100°C or higher and 200°C or lower. A crosslinking temperature higher than 250°C may result in failure of electronic components or decomposition of other organic materials. A crosslinking temperature lower than 60°C may result in insufficient crosslinking, or materials that crosslink at such low temperatures may undergo partial reaction within the coating composition, resulting in increased viscosity and other problems with the stability of the coating liquid.

[0188] In the present embodiment, crosslinking of the resin precursor composition can be carried out without adding a catalyst, a polymerization initiator, etc. However, as long as the effects of the present embodiment are not impaired, a substance such as a catalyst or a polymerization initiator may be added for the purpose of using it in combination with another crosslinking system.

[0189] [Electrophotographic photoreceptor] The electrophotographic photoreceptor according to this embodiment preferably contains the resin according to this embodiment in the outermost layer. The electrophotographic photoreceptor according to this embodiment has a substrate and a photosensitive layer provided on the substrate, and the photosensitive layer contains the resin according to this embodiment. The electrophotographic photoreceptor of the present embodiment may be any electrophotographic photoreceptor, including various known types of electrophotographic photoreceptors, as long as the resin of the present embodiment is used in the photosensitive layer. However, it is preferred that the photosensitive layer is a multilayer electrophotographic photoreceptor having at least one charge generation layer and at least one charge transport layer, or a single-layer electrophotographic photoreceptor having a charge generation material and a charge transport material in one layer.

[0190] The resin according to this embodiment may be used in any part of the photosensitive layer, but to fully exhibit the effects of this embodiment, it is preferable to use it as a binder resin for a charge transport material in a charge transport layer or as a binder resin for a single photosensitive layer. It is also preferable to use it not only in the photosensitive layer but also in a surface protective layer. In the case of a multilayer electrophotographic photoreceptor having two charge transport layers, it is preferable to use it in one of the charge transport layers. In the electrophotographic photoreceptor of this embodiment, the resin according to this embodiment may be used alone or in combination of two or more. Furthermore, if desired, other binder resin components such as polycarbonates may be contained within a range that does not impair the object of this embodiment. Furthermore, additives such as antioxidants may be contained.

[0191] The electrophotographic photoreceptor of this embodiment has a photosensitive layer on a conductive substrate. When the photosensitive layer has a charge generation layer and a charge transport layer, the charge transport layer may be laminated on the charge generation layer, or conversely, the charge generation layer may be laminated on the charge transport layer. Alternatively, the photosensitive layer may contain both a charge generation material and a charge transport material in one layer. Furthermore, if necessary, a conductive or insulating protective film may be formed on the surface layer. By using the resin according to this embodiment in the outermost layer, an electrophotographic photoreceptor with excellent solvent resistance and abrasion resistance can be obtained. Furthermore, an intermediate layer such as an adhesive layer for improving adhesion between layers or a blocking layer for blocking charges may be formed.

[0192] As the conductive substrate material used in the electrophotographic photoreceptor of this embodiment, various materials such as known materials can be used. Specifically, plates, drums, and sheets made 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: tin-doped indium oxide) or graphite; films, sheets, or seamless belts made of glass, cloth, paper, and plastic that have been treated to be conductive by coating with vapor deposition, sputtering, painting, or the like; and metal drums that have been treated to be metal-oxidized by electrode oxidation or the like can be used.

[0193] The charge generation layer contains at least a charge generation material. This charge generation layer can be obtained by forming a layer of the charge generation material on the underlying substrate by vacuum deposition or sputtering, or by forming a layer of the charge generation material on the underlying substrate by binding it with a binder resin. Various methods, including known methods, can be used to form a charge generation layer using a binder resin. Typically, a suitable method is to apply a coating composition, in which the charge generation material is dispersed or dissolved together with the binder resin in an appropriate solvent, onto a predetermined underlying substrate and then dry the resulting coating composition to obtain a wet-formed product.

[0194] The charge generating material in the charge generating layer can be any of various known materials. Specific examples of the compound include selenium alone (e.g., amorphous selenium and trigonal selenium), selenium alloys (e.g., selenium-tellurium), selenium compounds or selenium-containing compositions (e.g., As2Se3), inorganic materials consisting of elements of Groups 12 and 16 of the periodic table (e.g., zinc oxide and CdS-Se), oxide-based semiconductors (e.g., titanium oxide), silicon-based materials (e.g., amorphous silicon), metal-free phthalocyanine pigments (e.g., τ-type metal-free phthalocyanine pigments), and the like. metal phthalocyanine, and χ-type metal-free phthalocyanine, etc.), metal phthalocyanine pigments (for example, α-type copper phthalocyanine, β-type copper phthalocyanine, γ-type copper phthalocyanine, ε-type copper phthalocyanine, X-type copper phthalocyanine, A-type titanyl phthalocyanine, B-type titanyl phthalocyanine, C-type titanyl phthalocyanine, D-type titanyl phthalocyanine, E-type titanyl phthalocyanine, F-type titanyl phthalocyanine, G-type titanyl phthalocyanine, H-type titanyl phthalocyanine, K-type Titanyl phthalocyanine, L-type titanyl phthalocyanine, M-type titanyl phthalocyanine, N-type titanyl phthalocyanine, Y-type titanyl phthalocyanine, Y-type oxo-titanyl phthalocyanine, α-type oxo-titanyl phthalocyanine, β-type oxo-titanyl phthalocyanine, titanyl phthalocyanine that shows a strong diffraction peak at a Bragg angle 2θ of 27.3±0.2 degrees in the X-ray diffraction diagram, and gallium phthalocyanine, etc.), cyanine dyes, anthracene pigments, bisazo pigments, pyrene Examples of the charge-generating material include pigments, polycyclic quinone pigments, quinacridone pigments, indigo pigments, perylene pigments, pyrylium dyes, squarium pigments, anthanthrone pigments, benzimidazole pigments, azo pigments, thioindigo pigments, quinoline pigments, lake pigments, oxazine pigments, dioxazine pigments, triphenylmethane pigments, azulenium dyes, triarylmethane dyes, xanthine dyes, thiazine dyes, thiapyrylium dyes, polyvinylcarbazole, and bisbenzimidazole pigments. These compounds can be used alone or in combination of two or more compounds as the charge-generating material.Among these charge generating substances, the charge generating substances specifically described in JP-A No. 11-172003 are suitable.

[0195] The charge transport layer can be obtained as a wet molded body by forming a layer of a charge transport material bound with a binder resin on a substrate as a base. The binder resin of the charge generating layer or the charge transport layer is not particularly limited, and various known resins can be used.Specific examples thereof include polystyrene, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl acetal, alkyd resin, acrylic resin, polyacrylonitrile, polycarbonate, polyurethane, epoxy resin, phenol resin, polyamide, polyketone, polyacrylamide, butyral resin, polyester resin, vinylidene chloride-vinyl chloride copolymer, methacrylic resin, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, melamine resin, and polyether resin. , benzoguanamine resin, epoxy acrylate resin, urethane acrylate resin, poly-N-vinylcarbazole, polyvinyl butyral, polyvinyl formal, polysulfone, casein, gelatin, polyvinyl alcohol, ethyl cellulose, nitrocellulose, carboxy-methyl cellulose, vinylidene chloride polymer latex, acrylonitrile-butadiene copolymer, vinyltoluene-styrene copolymer, soybean oil-modified alkyd resin, nitrated polystyrene, polymethylstyrene, polyisoprene, polythiocarbonate, polyarylate, polyhaloarylate, polyallyl ether, polyvinyl acrylate, and polyester acrylate. These may be used alone or in combination of two or more. As the binder resin in the charge generating layer and / or charge transport layer, it is preferable to use the PC polymer of this embodiment described above.

[0196] Although various known methods can be used to form the charge transport layer, a preferred method is to apply a coating composition prepared by dispersing or dissolving a charge transport material together with the PC polymer of this embodiment in an appropriate solvent onto a substrate as a predetermined base and then dry the resulting coating composition to obtain a wet molded body. The blending ratio of the charge transport material to the PC polymer used to form the charge transport layer is preferably in the range of 20:80 to 80:20 by mass, more preferably in the range of 30:70 to 70:30. In this charge transport layer, the PC polymer of this embodiment can be used alone or in combination with two or more other binder resins, provided that the object of the present invention is not impaired.

[0197] The thickness of the charge transport layer thus formed is usually about 5 μm to 100 μm, preferably 10 μm to 50 μm, and more preferably 15 μm to 40 μm. If the thickness is 5 μm or more, the initial potential does not decrease, and if it is 100 μm or less, the electrophotographic properties can be prevented from deteriorating. Various known compounds can be used as charge transport materials together with the PC polymer of this embodiment. Suitable examples of such compounds include carbazole compounds, indole compounds, imidazole compounds, oxazole compounds, pyrazole compounds, oxadiazole compounds, pyrazoline compounds, thiadiazole compounds, aniline compounds, hydrazone compounds, aromatic amine compounds, aliphatic amine compounds, stilbene compounds, fluorenone compounds, butadiene compounds, quinone compounds, quinodimethane compounds, thiazole compounds, triazole compounds, imidazolone compounds, imidazolidine compounds, bisimidazolidine compounds, oxazolone compounds, benzothiazole compounds, benzimidazole compounds, quinazoline compounds, benzofuran compounds, acridine compounds, phenazine compounds, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly-9-vinylphenylanthracene, pyrene-formaldehyde resin, ethylcarbazole resin, and polymers having these structures in the main chain or side chain. These compounds may be used alone or in combination of two or more. Among these charge transport materials, the compounds specifically exemplified in JP-A No. 11-172003 and the charge transport materials represented by the following structures are particularly preferably used.

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[0212] In the electrophotographic photoreceptor according to this embodiment, it is preferable to use the resin precursor composition according to this embodiment as a binder resin in at least one of the charge generation layer, the charge transport layer, and the surface protective layer.

[0213] In the electrophotographic photoreceptor according to this embodiment, a commonly used undercoat layer can be provided between the conductive substrate and the photosensitive layer. This undercoat layer can be made of, for example, fine particles (e.g., titanium oxide, aluminum oxide, zirconia, titanic acid, zirconic acid, lanthanum lead, titanium black, silica, lead titanate, barium titanate, tin oxide, indium oxide, silicon oxide, etc.), polyamide resin, phenolic resin, casein, melamine resin, benzoguanamine resin, polyurethane resin, epoxy resin, cellulose, nitrocellulose, polyvinyl alcohol, or polyvinyl butyral resin. The resin used in this undercoat layer can be the binder resin described above or the resin precursor composition according to this embodiment. These fine particles and resins can be used alone or in various mixtures. When used as a mixture, a combination of inorganic fine particles and resin is preferred because it forms a coating with excellent smoothness.

[0214] The thickness of the undercoat layer is 0.01 μm or more and 10 μm or less, preferably 0.1 μm or more and 7 μm or less. When the thickness is 0.01 μm or more, the undercoat layer can be formed uniformly, and when the thickness is 10 μm or less, deterioration of electrophotographic properties can be suppressed. A commonly used known blocking layer can be provided between the conductive substrate and the photosensitive layer. The same resin as the binder resin can be used for this blocking layer. The resin precursor composition according to this embodiment can also be used. The thickness of this blocking layer is 0.01 μm or more and 20 μm or less, preferably 0.1 μm or more and 10 μm or less. A thickness of 0.01 μm or more allows the blocking layer to be formed uniformly, while a thickness of 20 μm or less can prevent degradation of electrophotographic properties.

[0215] Furthermore, the electrophotographic photoreceptor according to this embodiment may have a protective layer laminated on the photosensitive layer. The same resin as the binder resin described above may be used for this protective layer. It is particularly preferable to use the resin precursor composition according to this embodiment. The thickness of this protective layer is 0.01 μm or more and 20 μm or less, preferably 0.1 μm or more and 10 μm or less. This protective layer may contain the charge generating material, charge transport material, additives, metals and their oxides, nitrides, salts, alloys, carbon black, and conductive materials such as organic conductive compounds.

[0216] Furthermore, to improve the performance of this electrophotographic photoreceptor, binders, plasticizers, curing catalysts, fluidity-imparting agents, pinhole control agents, spectral sensitivity sensitizers (sensitizing dyes), etc. may be added to the charge generation layer and charge transport layer within the range that does not impair the effects of the present invention. Furthermore, for the purpose of preventing an increase in residual potential, a decrease in charging potential, and a decrease in sensitivity due to repeated use, various additives such as chemical substances, antioxidants, surfactants, anti-curl agents, and leveling agents may be added.

[0217] Examples of the binder include 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, phenol resin, phenoxy resin, polyvinyl butyral resin, formal resin, vinyl acetate resin, vinyl acetate / vinyl chloride copolymer resin, and polyester carbonate resin. At least one of thermosetting resin and photocurable resin can also be used. In any case, there are no particular limitations on the resin, as long as it is electrically insulating and can form a film under normal conditions and does not impair the effects of this embodiment.

[0218] Specific examples of the plasticizer include biphenyl, chlorinated biphenyl, o-terphenyl, halogenated paraffin, dimethylnaphthalene, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, diethylene glycol phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methylphthalylethyl glycolate, dimethyl glycol phthalate, methylnaphthalene, benzophenone, polypropylene, polystyrene, and fluorohydrocarbons.

[0219] Specific examples of the curing catalyst include methanesulfonic acid, dodecylbenzenesulfonic acid, and dinonylnaphthalenedisulfonic acid. Examples of the fluidity imparting agent include Modaflow and Acronal 4F. Examples of the pinhole control agent include 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 charge transport material, provided that the effects of the present invention are not lost.

[0220] Furthermore, when a sensitizing dye is used, suitable spectral sensitivity sensitizers include, for example, triphenylmethane dyes (e.g., methyl violet, crystal violet, night blue, and Victoria blue), acridine dyes (e.g., erythrosine, rhodamine B, rhodamine 3R, acridine orange, and flapeocin), thiazine dyes (e.g., methylene blue and methylene green), oxazine dyes (e.g., Capri blue and Meldola blue), cyanine dyes, merocyanine dyes, styryl dyes, pyrylium salt dyes, and thiopyrylium salt dyes.

[0221] An electron-accepting substance can be added to the photosensitive layer to the extent that the effects of the present invention are not lost, for the purposes of improving sensitivity, reducing residual potential, reducing fatigue during repeated use, etc. Specific examples thereof include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, p-nitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, bromanil, benzoquinone, 2,3-dichlorobenzoquinone, dichlorodicyanoparabenzoquinone, naphthoquinone, diphenoquinone, tropoquinone, anthraquinone, 1-chloroanthraquinone, dinitroanthraquinone, 4-nitrobenzophenone, 4,4'-dinitro Compounds with high electron affinity, such as benzophenone, 4-nitrobenzalmalondinitrile, ethyl α-cyano-β-(p-cyanophenyl)acrylate, 9-anthracenylmethylmalondinitrile, 1-cyano-(p-nitrophenyl)-2-(p-chlorophenyl)ethylene, 2,7-dinitrofluorenone, 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, 9-fluorenylidene-(dicyanomethylenemalononitrile), polynitro-9-fluorenylidene-(dicyanomethylenemalonodinitrile), picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, and mellitic acid, are preferred. These compounds may be added to either the charge generation layer or the charge transport layer, and the blending ratio is from 0.01 to 200 parts by weight, preferably from 0.1 to 50 parts by weight, per 100 parts by weight of the charge generation substance or charge transport substance, within a range that does not impair the effects of the present invention.

[0222] To improve surface properties, tetrafluoroethylene resin, trifluorochloroethylene resin, tetrafluoroethylene hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluorodichloroethylene resin, copolymers thereof, and fluorine-based graft polymers may be used within the range that does not impair the effects of the present invention. The blending ratio of these surface modifiers relative to the binder resin is 0.1% by mass to 60% by mass, preferably 5% by mass to 40% by mass, within the range that does not impair the effects of the present invention. If the blending ratio is 0.1% by mass or more, surface modification such as surface durability and surface energy reduction is sufficient, and if it is 60% by mass or less, there is no deterioration in electrophotographic properties.

[0223] Preferred examples of the antioxidant include hindered phenol antioxidants, aromatic amine antioxidants, hindered amine antioxidants, sulfide antioxidants, and organic phosphoric acid antioxidants. The blending ratio of these antioxidants is usually 0.01% by mass to 10% by mass, preferably 0.1% by mass to 2% by mass, based on the charge transport material, within a range that does not impair the effects of the present invention. Specific examples of such antioxidants include compounds represented by general chemical formulas [Chemical Formula 94] to [Chemical Formula 101], which are described in the specification of JP-A-11-172003. These antioxidants may be used alone or in combination of two or more. They may be added to the surface protective layer, undercoat layer, and blocking layer in addition to the photosensitive layer.

[0224] Specific examples of the solvent used in forming at least one of the charge generating 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 and diethylformamide). These solvents may be used alone or in combination of two or more.

[0225] The photosensitive layer of a single-layer electrophotographic photoreceptor can be easily formed by using the charge generating material, charge transport material, and additives described above and applying the resin precursor composition according to this embodiment as a binder resin. It is preferable to add at least one of the hole transport material and the electron transport material described above as the charge transport material. The electron transport material exemplified in JP-A-2005-139339 can be preferably used. The application of each layer can be carried out using various coating devices such as known devices, specifically, for example, an applicator, a spray coater, a bar coater, a tip coater, a roll coater, a dip coater, and a doctor blade.

[0226] The thickness of the photosensitive layer in the electrophotographic photoreceptor is 5 μm to 100 μm, preferably 8 μm to 50 μm. If it is 5 μm or more, a decrease in initial potential can be prevented, and if it is 100 μm or less, a decrease in electrophotographic characteristics can be suppressed. The ratio of the charge generating material to the resin precursor composition used in the production of the electrophotographic photoreceptor is preferably in the range of 20:80 to 80:20 by mass, more preferably in the range of 30:70 to 70:30.

[0227] The electrophotographic photoreceptor thus obtained has a crosslinked resin made of the resin precursor composition according to this embodiment as a binder resin in the photosensitive layer, and therefore has excellent solvent resistance and durability (abrasion resistance), as well as excellent electrical properties (electrophotographic properties), and is a photoreceptor that maintains excellent electrophotographic properties for a long period of time.The electrophotographic photoreceptor is suitable for use in various electrophotographic fields, such as copiers (monochrome, multicolor, full-color, analog, digital), printers (laser, LED, liquid crystal shutter), facsimiles, platemaking machines, and devices having multiple functions thereof.

[0228] [Method of manufacturing an electrophotographic photoreceptor] The method for producing an electrophotographic photoreceptor according to this embodiment includes the steps of applying the coating composition according to this embodiment to a conductive substrate by a wet molding method, removing the organic solvent in the coating composition by heating, and carrying out a crosslinking reaction of the resin precursor composition in the coating composition by heating simultaneously with or subsequent to the heating in the step of removing the organic solvent.

[0229] In the step of applying the coating liquid composition to the conductive substrate, the coating thickness of the coating liquid composition can be appropriately set depending on the thickness of the photosensitive layer of the electrophotographic photoreceptor according to this embodiment. In the step of removing the organic solvent, the amount of the organic solvent can be appropriately set depending on the type of the organic solvent in the coating liquid composition according to this embodiment. In the step of carrying out 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 this exemplary embodiment. [Example]

[0230] Next, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples, and various modifications and applications are possible within the scope of the present invention.

[0231] [Manufacturing Example: Preparation of Oligomers] <Production Example 1: Synthesis of bisphenol Z oligomer (bischloroformate)> 60.0 g (224 mmol) of 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z) was suspended in 1080 mL of methylene chloride, and 66.0 g (667 mmol) of phosgene was added and dissolved. A solution of 44.0 g (435 mmol) of triethylamine in 120 mL of methylene chloride was added dropwise at temperatures between 5 and 15°C. After stirring for 30 minutes, the methylene chloride was distilled off to a predetermined concentration. The remaining liquid was washed with 210 mL of pure water, 1.2 g of concentrated hydrochloric acid, and 450 mg of hydrosulfite. This was followed by five washes with 210 mL of pure water, yielding a methylene chloride solution of bisphenol Z oligomers bearing chloroformate groups at the molecular terminals. The resulting solution had a chloroformate concentration of 1.12 mol / L, a solids concentration of 0.225 kg / L, and an average number of dimers of 1.03. Hereafter, this obtained raw material will be referred to as Z-CF.

[0232] The average number of monomers (n X ) was calculated using the following formula (Equation 1). Average number of molecules (n X )=1+(Mav-M1) / M2...(Number 1) (In the above formula (Math. 1), Mav is (2×1000 / (CF value)), M2 is (M1-98.92), and M1 is n in the following general formula (X1). X= 1, and the CF value (N / kg) is (CF value / concentration), where CF value (N) is the number of chlorine atoms in the bischloroformate compound represented by the following general formula (X1) contained in 1 L of reaction solution, and concentration (kg / L) is the amount of solids obtained by concentrating 1 L of reaction solution. Here, 98.92 is the total atomic weight of two chlorine atoms, one oxygen atom, and one carbon atom that are eliminated by polycondensation of bischloroformate compounds. When calculating the average number of monomers when synthesizing bischloroformate using two or more raw materials, calculate M1 based on the average molecular weight of the raw materials used, calculated by the molar ratio. For example, when synthesis is performed using 366 moles of a monomer with a molecular weight of 268 and 108 moles of a monomer with a molecular weight of 214, M1 can be calculated using the following formula: M1=(268×(366÷(366+108))+214×(108÷(366+108))+124.9 The "124.9" in this formula for M1 is the increase in molecular weight when two hydrogen atoms are lost from the monomer used and two carbon atoms, two oxygen atoms, and two chlorine atoms are added.

[0233] [ka]

[0234] In the general formula (X1), Ar X1 For example, in the case of the bischloroformate compound (bisphenol Z oligomer) according to Production Example 1, the divalent group represented by the following general formula (10) is Ar X1 is equivalent to

[0235] [ka]

[0236] In the case of the bischloroformate oligomer represented by the general formula (1A), Ar 33 But, Ar X1 corresponds to n31 But, n X is equivalent to In the case of the bischloroformate oligomer represented by the general formula (2A), Ar 34 But, Ar X1 corresponds to n 32 But, n X is equivalent to

[0237] <Production Example 2: Synthesis of bisphenol Z·3,3'-dimethyl-4,4'-dihydroxybiphenyl oligomer (bischloroformate)> 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 methylene chloride, and 138 g (1395 mmol) of phosgene was added and dissolved. A solution of 93.8 g (929 mmol) of triethylamine in 256 mL of methylene chloride was added dropwise at a temperature between 16 and 19°C. After stirring for 140 minutes, the methylene chloride was distilled off until the desired concentration was reached. The remaining liquid was washed with 1100 mL of purified water, 2.4 g of concentrated hydrochloric acid, and 450 mg of hydrosulfite. The mixture was then washed five times with 210 mL of pure water to obtain a methylene chloride solution of bisphenol Z oligomer and 3,3'-dimethyl-4,4'-dihydroxybiphenyl oligomer, each with a chloroformate group at the molecular end. The resulting solution had a chloroformate concentration of 0.57 mol / L, a solids concentration of 0.11 kg / L, and an average number of dimers of 1.02. Hereafter, this raw material will be referred to as ZOCBP-CF.

[0238] <Production Example 3: Synthesis of 3,3'-dimethyl-4,4'-dihydroxybiphenyl oligomer (bischloroformate)> 100.4 g (469 mmol) of 3,3'-dimethyl-4,4'-dihydroxybiphenyl was suspended in 2400 mL of methylene chloride, and 138 g (1395 mmol) of phosgene was added and dissolved. A solution of 93.8 g (929 mmol) of triethylamine in 256 mL of methylene chloride was added dropwise at a temperature between 16 and 19°C. After stirring for 140 minutes, the methylene chloride was distilled off to a predetermined concentration. The remaining liquid was washed with 1100 mL of pure water, 2.4 g of concentrated hydrochloric acid, and 450 mg of hydrosulfite. This was followed by five washes with 210 mL of pure water to obtain a methylene chloride solution of bisphenol Z oligomer with chloroformate groups at the molecular terminals and 3,3'-dimethyl-4,4'-dihydroxybiphenyl oligomer. The chloroformate concentration of the obtained solution was 0.52 mol / L, the solid concentration was 0.089 kg / L, and the average number of polymerizations was 1.01. Hereafter, this obtained raw material is referred to as OCBP-CF.

[0239] <Production Example 4: Synthesis of 2,2-bis(4-hydroxyphenyl)butane (BisB)·4,4'-dihydroxydiphenyl ether oligomer (bischloroformate)> 57 g (235 mmol) of 2,2-bis(4-hydroxyphenyl)butane (bisphenol B) and 47 g (233 mmol) of 4,4'-dihydroxydiphenyl ether were suspended in 2400 mL of methylene chloride, and 138 g (1395 mmol) of phosgene was added to dissolve the suspension. 93.8 g (929 mmol) of triethylamine dissolved in 256 mL of methylene chloride was added dropwise at a temperature between 16 and 19 °C. After stirring for 140 minutes, the methylene chloride was distilled off to a predetermined concentration. The remaining liquid was washed with 1100 mL of pure water, 2.4 g of concentrated hydrochloric acid, and 450 mg of hydrosulfite. This was followed by five washes with 210 mL of pure water to obtain a methylene chloride solution of bisphenol B oligomers with terminal chloroformate groups and 4,4'-dihydroxydiphenyl ether oligomers. The chloroformate concentration of the resulting solution was 1.23 mol / L, the solid concentration was 0.233 kg / L, and the average number of polymerizations was 1.05. Hereafter, this resulting raw material will be referred to as BDHDE-CF.

[0240] [Synthesis Example 1] (Production of PC polymer) ZOCBP-CF (368 mL) from Production Example 2 and methylene chloride (82 mL) were poured into a reaction vessel equipped with a mechanical stirrer, a stirring blade, and a baffle plate. To this was added p-tert-butylphenol (hereinafter referred to as PTBP) (0.314 g) as a terminal terminator, and the mixture was stirred to ensure thorough mixing. After cooling the temperature inside the reactor to 10°C, the entire amount of the prepared 3,3'-dimethyl-4,4'-dihydroxybiphenyl and 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene solution (solution preparation method: 120 mL of 2.5 N aqueous potassium hydroxide solution (16.9 g of potassium hydroxide) was prepared, cooled to below room temperature, and then 0.25 g of hydrosulfite as an antioxidant, 9.0 g of 3,3'-dimethyl-4,4'-dihydroxybiphenyl, and 15.8 g of 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene were added and completely dissolved) was added to this solution, and 5.4 mL of an aqueous triethylamine solution (7 vol%) was added with stirring, and stirring was continued for 3 hours. The resulting reaction mixture was diluted with 1 L of methylene chloride and 0.1 L of water and washed. The lower layer was separated and further washed once with 0.25 L of water, once with 0.25 L of 0.03 N hydrochloric acid, and three times with 0.25 L of water, in that order. The resulting methylene chloride solution was added dropwise to methanol with stirring, and the resulting reprecipitate was filtered and dried to obtain a PC polymer (PC-1) with the following structure.

[0241] (Specification of PC polymer) The PC polymer (PC-1) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20 °C was measured and found to be 1.06 dL / g. The structure and composition of the obtained PC-1 were 1 Analysis by 1 H-NMR spectrum confirmed that the polymer was a PC polymer consisting of the following repeating units, number of repeating units and composition: The reduced viscosity was measured using an automatic viscosity measuring device VMR-042 manufactured by Rigo Co., Ltd., with an improved Ubbelohde viscometer for automatic viscosity (RM type). 1 H-NMR spectra were measured using a nuclear magnetic resonance spectrometer JNM-ECZ400S manufactured by JEOL Ltd. 1 The conditions for measuring the H-NMR spectrum are as follows.

[0242] ( 1 H-NMR spectrum measurement conditions) Solvent: CD2Cl2 Measurement concentration (sample volume / solvent volume): 1.5 mg / mL Accumulation count: 64 times (approx. 3 min)

[0243] [ka]

[0244] The composition ratio (mol %) was OCBP:BisZ:BIPANT=3:5:2. The concentration of the conjugated diene group (anthracene skeleton) is 0.71 mmol / g.

[0245] [Synthesis Example 2] (Production of PC polymer) ZOCBP-CF (184 mL) from Preparation Example 2 and methylene chloride (41 mL) were poured into a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles. N-(4-hydroxyphenyl)maleimide (hereinafter referred to as Male 1) (2.968 g) was added as an end-capping agent and stirred thoroughly. After cooling the reactor to 10°C, the entire amount of the 3,3'-dimethyl-4,4'-dihydroxybiphenyl solution (solution preparation method: 60 mL of 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 hydrosulfite and 7.3 g of 3,3'-dimethyl-4,4'-dihydroxybiphenyl were added as antioxidants). 2.7 mL of a 7 vol% aqueous triethylamine solution was added with stirring, and the mixture was continued for 3 hours. The resulting reaction mixture was diluted with 0.5 L of methylene chloride and 0.1 L of water and washed. The lower layer was separated and further washed once with 0.15 L of water, once with 0.15 L of 0.03 N hydrochloric acid, and three times with 0.15 L of water, in that order. The resulting methylene chloride solution was added dropwise to methanol with stirring, and the resulting reprecipitate was filtered and dried to obtain a PC polymer (PC-2) with the following structure.

[0246] (Specification of PC polymer) The PC polymer (PC-2) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20°C was measured and found to be 0.23 dL / g. The structure and composition of the obtained PC-2 were analyzed by 1H-NMR spectroscopy, and it was confirmed that it was a PC polymer consisting of the following repeating units, number of repeating units, and composition:

[0247] [ka]

[0248] The composition ratio (mol %) was OCBP:BisZ:Male1=5:4:1. The dienophile group (maleimide group) concentration is 0.39 mmol / g.

[0249] [Synthesis Example 3] (Production of PC polymer) A PC polymer (PC-3) having the following structure was obtained in the same manner as in Synthesis Example 1, except that the amount of 3,3'-dimethyl-4,4'-dihydroxybiphenyl used was changed to 13.5 g and the amount of 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene used was changed to 7.9 g.

[0250] (Specification of PC polymer) The PC polymer (PC-3) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20 °C was measured and found to be 1.08 dL / g. The structure and composition of the obtained PC-3 were 1 Analysis by 1 H-NMR spectrum confirmed that the polymer was a PC polymer consisting of the following repeating units, number of repeating units and composition:

[0251] [ka]

[0252] The composition ratio (mol %) was OCBP:BisZ:BIPANT=4:5:1. The concentration of the conjugated diene group (anthracene skeleton) is 0.39 mmol / g.

[0253] [Synthesis Example 4] (Production of PC polymer) A PC polymer (PC-4) having the following structure was obtained in the same manner as in Synthesis Example 1, except that in Synthesis Example 1, ZOCBP-CF was changed to OCBP-CF (227 mL) from Production Example 3, the methylene chloride (82 mL) used initially was not used, the amount of PTBP used was changed to 0.53 g, 3,3'-dimethyl-4,4'-dihydroxybiphenyl was not used, the amount of 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene used was changed to 19.6 g, the 2.5 N aqueous potassium hydroxide solution was changed to 75 mL (10.5 g of potassium hydroxide), and the amount of triethylamine used was changed to 2.7 mL.

[0254] (Specification of PC polymer) The PC polymer (PC-4) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20 °C was measured and found to be 0.95 dL / g. The structure and composition of the obtained PC-4 were 1 Analysis by 1 H-NMR spectrum confirmed that the polymer was a PC polymer consisting of the following repeating units, number of repeating units and composition:

[0255] [ka]

[0256] The composition ratio (mol %) was OCBP:BIPANT=55:45. The concentration of the conjugated diene group (anthracene skeleton) is 1.44 mmol / g.

[0257] [Synthesis Example 5] (Production of PC polymer) A PC polymer (PC-5) having the following structure was obtained in the same manner as in Synthesis Example 1, except that in Synthesis Example 1, ZOCBP-CF was replaced with Z-CF (76 mL) from Production Example 1, the amount of methylene chloride initially used was changed to 114 mL, the amount of PTBP used was changed to 0.151 g, 3,3'-dimethyl-4,4'-dihydroxybiphenyl was not used, the amount of 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene used was changed to 16.0 g, the 2.5 N aqueous potassium hydroxide solution was changed to 65 mL of 2.36 N aqueous potassium hydroxide solution (8.6 g of potassium hydroxide), and the amount of triethylamine used was changed to 1.0 mL.

[0258] (Specification of PC polymer) The PC polymer (PC-5) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20 °C was measured and found to be 0.95 dL / g. The structure and composition of the obtained PC-5 were 1 Analysis by 1 H-NMR spectrum confirmed that the polymer was a PC polymer consisting of the following repeating units, number of repeating units and composition:

[0259] [ka]

[0260] The composition ratio (mol %) was BisZ:BIPANT=6:4. The concentration of the conjugated diene group (anthracene skeleton) is 1.44 mmol / g.

[0261] [Synthesis Example 6] (Production of PC polymer) A PC polymer (PC-6) having the following structure was obtained in the same manner as in Synthesis Example 1, except that in Synthesis Example 1, ZOCBP-CF was changed to BHDDE-CF (87 mL) from Production Example 4, the amount of methylene chloride initially used was changed to 138 mL, the amount of PTBP used was changed to 0.142 g, 3,3'-dimethyl-4,4'-dihydroxybiphenyl was changed to 5.3 g of 4,4'-dihydroxydiphenyl ether, the amount of 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene used was changed to 9.8 g, the 2.5 N aqueous potassium hydroxide solution was changed to 75 mL of 2.25 N aqueous potassium hydroxide solution (9.5 g of potassium hydroxide), and the amount of triethylamine used was changed to 1.0 mL.

[0262] (Specification of PC polymer) The PC polymer (PC-6) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20 °C was measured and found to be 1.25 dL / g. The structure and composition of the obtained PC-6 were 1 Analysis by 1 H-NMR spectrum confirmed that the polymer was a PC polymer consisting of the following repeating units, number of repeating units and composition:

[0263] [ka]

[0264] The composition ratio (mol %) was BisB:DHDE:BIPANT=3:5:2. The concentration of the conjugated diene group (anthracene skeleton) is 0.82 mmol / g.

[0265] [Synthesis Example 7] (Production of PC polymer) ZOCBP-CF (184 mL) from Preparation Example 2 and methylene chloride (41 mL) were poured into a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles. N-(4-hydroxyphenyl)maleimide (hereinafter referred to as Male 1) (0.546 g) was added as an end-capping agent and stirred thoroughly. After cooling the reactor to 10°C, 10 mL of a 2.5 mol / L aqueous potassium carbonate solution (3.5 g of potassium carbonate) was added, and 2.7 mL of a 7 vol% aqueous triethylamine solution was added with stirring, followed by stirring for 30 minutes. Next, a solution of 4.5 g of 3,3'-dimethyl-4,4'-dihydroxybiphenyl and 7.9 g of 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene dissolved in 75 mL of 1.7 N aqueous NaOH (5.0 g of NaOH, 100 mg of sodium hydrosulfite added) was added in its entirety and stirred for an additional hour. The resulting reaction mixture was diluted with 0.5 L of methylene chloride and 0.1 L of water and washed. The lower layer was separated and washed once with 0.15 L of water, once with 0.15 L of 0.03 N hydrochloric acid, and three times with 0.15 L of water. The resulting methylene chloride solution was added dropwise to methanol with stirring, and the resulting precipitate was filtered and dried to obtain the PC polymer (PC-7) with the following structure.

[0266] (Specification of PC polymer) The PC polymer (PC-7) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20 °C was measured, which was 0.66 dL / g. The structure and composition of the obtained PC-7 were 1 Analysis by 1 H-NMR spectrum confirmed that the polymer was a PC polymer consisting of the following repeating units, number of repeating units and composition:

[0267] [ka]

[0268] The composition ratio (mol %) was OCBP:BisZ:BIPANT:Male1=22:53:23:2. The concentration of conjugated diene groups (anthracene skeleton) is 0.74 mmol / g. The concentration of the dienophile group (maleimide skeleton) is 0.082 mmol / g.

[0269] [Synthesis Example 8] (Production of PC polymer) A PC polymer (PC-8) having the following structure was obtained in the same manner as in Synthesis Example 1, except that in Synthesis Example 1, ZOCBP-CF was changed to OCBP-CF (112 mL) from Production Example 3, the methylene chloride (82 mL) used initially was not used, the amount of PTBP used was changed to 0.21 g, 3,3'-dimethyl-4,4'-dihydroxybiphenyl was changed to 5.2 g of 4,4'-dihydroxydiphenyl ether (DHDE), the amount of 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene used was changed to 2.4 g, the 2.1 N potassium hydroxide aqueous solution was changed to 50 mL (5.8 g of potassium hydroxide), and the amount of triethylamine used was changed to 1.4 mL.

[0270] (Specification of PC polymer) The PC polymer (PC-8) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20 °C was measured and found to be 1.04 dL / g. The structure and composition of the obtained PC-8 were 1 Analysis by 1 H-NMR spectrum confirmed that the polymer was a PC polymer consisting of the following repeating units, number of repeating units and composition:

[0271] [ka]

[0272] The composition ratio (mol %) was OCBP:DHDE:BIPANT=55:33:12. The concentration of the conjugated diene group (anthracene skeleton) is 0.46 mmol / g.

[0273] [Synthesis Example 9] (Production of PC polymer) A PC polymer (PC-9) having the following structure was obtained in the same manner as in Synthesis Example 1, except that in Synthesis Example 1, ZOCBP-CF was replaced with OCBP-CF (112 mL) from Production Example 3, the methylene chloride (82 mL) initially used was not used, the amount of PTBP used was changed to 0.224 g, 3,3'-dimethyl-4,4'-dihydroxybiphenyl was changed to 6.2 g of 1,1-bis(3-methyl-4-hydroxyphenyl)ethane (hereinafter referred to as BisOCE), the amount of 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene used was changed to 2.4 g, the 2.1 N potassium hydroxide aqueous solution was changed to 50 mL (potassium hydroxide 5.8 g), and the amount of triethylamine used was changed to 1.4 mL.

[0274] (Specification of PC polymer) The PC polymer (PC-9) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20 °C was measured and found to be 1.07 dL / g. The structure and composition of the obtained PC-9 were 1 Analysis by 1 H-NMR spectrum confirmed that the polymer was a PC polymer consisting of the following repeating units, number of repeating units and composition:

[0275] [ka]

[0276] The composition ratio (mol %) was OCBP:BisOCE:BIPANT=56:34:10. The concentration of the conjugated diene group (anthracene skeleton) is 0.39 mmol / g.

[0277] [Synthesis Example 10] (Production of PC polymer) OCBP-CF (57 mL) from Preparation Example 3 was poured into a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles. To this was added 0.107 g of p-tert-butylphenol (PTBP) and 2.48 g of 2-(2-furanylmethyl)hydroquinone (FR) as end terminators. Nitrogen gas was introduced into the gas phase of the reaction vessel at a flow rate of 0.2 L / min while stirring for 20 minutes to ensure thorough mixing. After the oxygen concentration in the gas phase was measured using a dissolved oxygen meter (Model B-506 DO meter, manufactured by Iijima Electronics Co., Ltd.) in the DO mode, the reading fell to 0.5 mg / L or less. The oxygen concentration in the liquid was measured by immersing the measurement probe in the reaction solution, and the reading was confirmed to be 0.5 mg / L or less, similar to the gas phase. After cooling the temperature inside the reactor to 10°C, a 2.3N aqueous potassium carbonate solution (prepared by dissolving 1.26 g of potassium carbonate in 4 mL of ion-exchanged water and adding 50 mg of sodium hydrosulfite) was added, and 0.7 mL of a 7 vol% aqueous triethylamine solution was added with stirring, and stirring was continued for 30 minutes. 20 mL of a 1.9N aqueous sodium hydroxide solution (1.5 g of sodium hydroxide) was prepared and cooled to below room temperature. 50 mg of sodium hydrosulfite was added as an antioxidant and completely dissolved. The entire amount was added, and stirring was continued for another 30 minutes. The resulting reaction mixture was diluted with 200 mL of methylene chloride (oxygen concentration of which had been reduced to 0.1 mg / L or less by nitrogen substitution) and 50 mL of water in a nitrogen atmosphere, and washed. The lower layer was separated and washed once with 100 mL of water, once with 100 mL of 0.03 N hydrochloric acid, and three times with 100 mL of water. The resulting methylene chloride solution was added dropwise to methanol with stirring, and the resulting precipitate was filtered and dried to obtain the PC polymer (PC-10) with the following structure.

[0278] (Specification of PC polymer) The PC polymer (PC-10) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20 °C was measured and found to be 1.56 dL / g. The structure and composition of the obtained PC-10 were 1Analysis by 1 H-NMR spectrum confirmed that the polymer was a PC polymer consisting of the following repeating units, number of repeating units and composition:

[0279] [ka]

[0280] The composition ratio (mol %) was OCBP:FR=57:43. The furan group concentration is 1.89 mmol / g.

[0281] [Synthesis Example 11] (Production of PC polymer) OCBP-CF (56 mL) from Preparation Example 3 was poured into a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles. To this was added 0.077 g of p-tert-butylphenol (PTBP) (hereinafter referred to as PTBP) as an end-capping agent, and 0.68 g of 1,4-dihydroxyanthracene (1,4ANT) (dissolved in 5 mL of acetone). Nitrogen gas was bubbled into the gas phase of the reaction vessel at a flow rate of 0.2 L / min while stirring for 20 minutes to ensure thorough mixing. After the oxygen concentration in the gas phase was measured using a dissolved oxygen meter (Model B-506 DO meter, manufactured by Iijima Electronics Co., Ltd.) in DO mode, the oxygen concentration in the liquid was measured by immersing the measurement probe in the reaction solution. The reading was confirmed to be below 0.5 mg / L, similar to the gas phase. After cooling the reactor to 10°C, a 1.6N potassium carbonate solution (prepared by dissolving 1.07 g of potassium carbonate in 5 mL of ion-exchanged water and adding 50 mg of sodium hydrosulfite) was added, and 0.7 mL of a 7 vol% triethylamine solution was added with stirring. Stirring was continued for 30 minutes. To this solution, the entire amount of the 1,1-bis(3-methyl-4-hydroxyphenyl)ethane (3.1 g) solution (solution preparation method: 16 mL of a 2.4N sodium hydroxide solution (1.5 g of sodium hydroxide) was prepared, cooled to below 10°C, and 50 mg of sodium hydrosulfite was added as an antioxidant and completely dissolved) was added, and stirring was continued for another 2 hours and 30 minutes. The resulting reaction mixture was diluted with 200 mL of methylene chloride (oxygen concentration of which had been reduced to 0.1 mg / L or less by nitrogen substitution) and 50 mL of water in a nitrogen atmosphere, and washed. The lower layer was separated and washed once with 100 mL of water, once with 100 mL of 0.03 N hydrochloric acid, and three times with 100 mL of water. The resulting methylene chloride solution was added dropwise to methanol with stirring, and the resulting precipitate was filtered and dried to obtain the PC polymer (PC-11) with the following structure.

[0282] (Specification of PC polymer) The PC polymer (PC-1) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20 °C was measured and found to be 0.72 dL / g. The structure and composition of the obtained PC-11 were 1 Analysis by 1 H-NMR spectrum confirmed that the polymer was a PC polymer consisting of the following repeating units, number of repeating units and composition:

[0283] [ka]

[0284] The composition ratio (mol %) was BisOCE:OCBP:1,4ANT=28:60:12. The anthracene group concentration is 0.49 mmol / g.

[0285] [Synthesis Example 12] (Production of PC polymer) A PC polymer (PC-12) having the following structure was obtained in the same manner as in Synthesis Example 8, except that in Synthesis Example 8, the amount of OCBP-CF used was changed to 29.2 mL, methylene chloride (16 mL) was added, 0.049 g of 9-(4-hydroxyphenyl)anthracene was used instead of PTBP, the amount of 4,4'-dihydroxydiphenyl ether (DHDE) was changed to 1.23 g, the amount of 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene (hereinafter referred to as ANT1) used was changed to 0.57 g, the 2.1 N potassium hydroxide aqueous solution was changed to 12 mL (potassium hydroxide 1.4 g), and the amount of triethylamine used was changed to 0.3 mL.

[0286] (Specification of PC polymer) The PC polymer (PC-12) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20 °C was measured and found to be 1.37 dL / g. The structure and composition of the obtained PC-12 were 1 Analysis by 1 H-NMR spectrum confirmed that the polymer was a PC polymer consisting of the following repeating units, number of repeating units and composition:

[0287] [ka]

[0288] The composition ratio (mol %) was OCBP:DHDE:BIPANT:ANT1=55:34:10:2. The concentration of the conjugated diene group (anthracene skeleton) is 0.46 mmol / g.

[0289] [Synthesis Example 13] (PAR polymer production) A polyarylate polymer (PAR-1) having the following structure was obtained in the same manner as in Synthesis Example 12, except that in Synthesis Example 12, 2.2 g of 4,4'-biphenyldicarboxylic acid chloride (DPE) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of OCBP-CF, the amount of methylene chloride used was changed to 200 mL, 0.01 g of 2,3,5-trimethylphenol was used instead of PTBP, 0.56 g of 1,1-Bis(3-methyl-4-hydroxyphenyl)ethane was used instead of 4,4'-dihydroxydiphenyl ether (DHDE), 15 mL of 0.15 N potassium hydroxide aqueous solution (1.3 g of potassium hydroxide) was used instead of 2.1 N potassium hydroxide aqueous solution, and the amount of triethylamine used was changed to 0.5 mL.

[0290] (PAR polymer identification) The PC polymer (PAR-1) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20 °C was measured and found to be 0.27 dL / g. The structure and composition of the obtained PAR-1 were 1 Analysis by 1 H-NMR spectrum confirmed that the polymer was a PAR polymer consisting of the following repeating units, number of repeating units, and composition:

[0291] [ka]

[0292] The composition ratio (mol %) was DPE:OCE:BIPANT=52:34:14. The concentration of the conjugated diene group (anthracene skeleton) is 0.52 mmol / g.

[0293] [Example 1] <Preparation of a coating composition comprising a polycarbonate having a conjugated diene group and a polycarbonate having a dienophile group, and preparation of a crosslinked resin film> 1.5 g of PC-1 and 0.3 g of PC-2 were weighed into a screw-capped sample tube and dissolved in 10 mL of tetrahydrofuran to obtain a coating composition. The resulting coating composition was cast onto a 50 μm-thick polyimide film using an applicator with a 200 μm gap. After air-drying for 1 hour, the film was treated in a vacuum dryer at 50°C for 16 hours to remove the solvent, yielding a precursor film. The obtained precursor film was crosslinked by heating it in a vacuum dryer (vacuum degree: 1 to 100 Pa) at a temperature of 200° C. for 3 hours to obtain a resin film.

[0294] [Example 2] <Preparation of a coating composition for a charge transport layer comprising a polycarbonate having a conjugated diene group, a polycarbonate having a dienophile group, and a charge transport material, and preparation of a crosslinked resin film> 1.25 g of PC-1, 0.25 g of PC-2, and 1.0 g of charge transport material (CTM-1) were weighed into a screw-capped sample tube and dissolved in 10 mL of tetrahydrofuran to obtain a coating composition. The resulting coating composition was cast onto a 50 μm-thick polyimide film using an applicator with a 200 μm gap. After air-drying for 1 hour, the film was treated in a vacuum dryer at 50°C for 16 hours to remove the solvent, yielding a precursor film. The obtained precursor film was crosslinked by heating it in a vacuum dryer (vacuum degree: 1 to 100 Pa) at a temperature of 150° C. for 3 hours to obtain a resin film.

[0295] [ka]

[0296] [Comparative Example 1] A resin film (for abrasion test) was obtained in the same manner as in Example 1, except that PC-2 was not used.

[0297] Comparative Example 2 A coating composition and a resin film (for abrasion tests and for evaluating electrical properties) were obtained in the same manner as in Example 2, except that PC-2 was not used and the amount of PC-1 used was changed to 1.5 g.

[0298] [Comparative Example 100] A resin film (for abrasion test) was obtained in the same manner as in Example 1, except that PC-1 and PC-2 were not used and a polycarbonate resin (used amount: 1.5 g) having the following structure was used.

[0299] [ka]

[0300] [Comparative Example 101] A coating composition and a resin film (for abrasion testing and electrical property evaluation) were obtained in the same manner as in Example 2, except that PC-1 and PC-2 were not used in Example 2 and the polycarbonate resin (used amount 1.5 g) used in Comparative Example 100 was used.

[0301] [Evaluation of solvent resistance (methylene chloride solubility)] The resin film after crosslinking treatment was peeled off and placed in methylene chloride to check its appearance. The results are shown in Table 1. The details of the solvent resistance evaluation are as follows. A sample was prepared by cutting a 20-30 μm thick film into a 1 cm x 2 cm rectangle. The sample was placed in an 8 mL sample tube. Next, 8 mL of methylene chloride was added to the sample tube, and the sample was completely immersed in the methylene chloride. The sample tube was shaken at room temperature for 1 hour at a shaking speed of 120 rpm using a shaker, and then the appearance was observed. The evaluation criteria are as follows: D (dissolved): No insoluble matter was observed visually. C (small pieces): There was some small insoluble matter, but most of it was dissolved. B (Swelling): The insoluble matter remains as a lump, but does not maintain its film shape due to solvent swelling. A (insoluble): No swelling or slight swelling, but the film shape is maintained.

[0302] [Wear resistance evaluation] The abrasion resistance of the cast surface of the resin film was evaluated using a Suga Abrasion Tester, Model NUS-ISO-3 (manufactured by Suga Test Instruments Co., Ltd.). The test conditions were as follows: abrasion paper (containing 3 μm alumina particles) was brought into contact with the cast surface (a surface simulating the surface of the photosensitive layer) under a load of 4.9 N, and the abrasion paper was subjected to 2,000 reciprocating motions, and the mass loss (abrasion amount) was measured. The results are shown in Table 1.

[0303] [Table 1]

[0304] [Evaluation of electrophotographic photoreceptor characteristics] An electrophotographic photoreceptor was manufactured using a 100 μm thick aluminum plate as the conductive substrate, with a charge generation layer and a charge transport layer sequentially laminated on its surface to form a laminated photosensitive layer. 0.5 parts by weight of Y-type oxotitanium phthalocyanine was used as the charge generation material, and 0.5 parts by weight of butyral resin was used as the binder resin. These were added to 19 parts by weight of THF solvent and dispersed in a ball mill. The resulting dispersion was applied to the surface of the conductive substrate film using a bar coater and dried at 70°C for 30 minutes to form a charge generation layer approximately 0.5 μm thick. Next, a coating composition for the charge transport layer was prepared in the same manner as in Example 2, except that the amount of CTM-1 used was changed to 0.75 g. The coating composition was applied onto the charge generation layer using an applicator with a gap of 200 μm, and then dried at 50°C for 8 hours and then at 100°C for 8 hours under reduced pressure (vacuum pressure of 1 to 100 Pa) to form a charge transport layer with a thickness of approximately 30 μm. The resulting photoreceptor film was heated at 150°C for 3 hours to obtain a photoreceptor. The obtained electrophotographic photoreceptor film was attached to a φ60 mm aluminum drum, and the electrophotographic characteristics were evaluated for the photo-induced decay characteristics of the surface potential in EV mode using an electrostatic charging tester CYNTHIA54IM (manufactured by Gentec Co., Ltd.). The initial charge amount was set to -750 V. The results obtained are shown in FIG. The coating compositions obtained in Comparative Examples 2 and 101 were also evaluated for their surface potential light attenuation properties in the same manner as above. The results are shown in FIG.

[0305] [Example 3] 1.5 g of PC-5 (a conjugated diene with a composition ratio (mol %) of BisZ:BIPANT = 6:4) and 0.56 g of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane (hereafter referred to as MI-BisA) as a dienophile, represented by the following formula (MI-BisA), were weighed into a screw-capped sample tube and dissolved in 10 mL of tetrahydrofuran to obtain a coating composition. The resulting coating composition was cast onto a 50 μm-thick polyimide film using an applicator with a 200 μm gap. After air-drying for 1 hour, the film was treated in a vacuum dryer at 50°C for 16 hours to remove the solvent, yielding a precursor film. The obtained precursor film was heated in a vacuum dryer (vacuum pressure 1 to 100 Pa) at 200°C for 3 hours for crosslinking treatment to obtain a resin film. The obtained resin film was then evaluated for solvent resistance (methylene chloride solubility) and abrasion resistance using the methods described above. The obtained results are shown in Table 2.

[0306] [ka]

[0307] [Examples 4 to 12] A resin film was obtained in the same manner as in Example 3, except that the conjugated diene, dienophile, and charge transport material were as shown in Table 2 below, and the heating conditions were as shown in Table 2 below. The solvent resistance and abrasion resistance of the obtained resin film were evaluated using the methods described above. The results are shown in Table 2. The charge transport material (CTM-2) is a mixture shown below.

[0308] [ka]

[0309] [Comparative Example 3-1] A resin film was obtained in the same manner as in Example 3, except that MI-BisA was not used and the heating conditions were changed to 100°C for 3 hours. The solvent resistance and abrasion resistance of the obtained resin film were evaluated using the methods described above. The results are shown in Table 2.

[0310] [Comparative Examples 3 to 11] A resin film was obtained in the same manner as in Comparative Example 3-1, except that the conjugated diene, dienophile, and charge transport material were as shown in Table 2 below, and the heating conditions were as shown in Table 2 below.The solvent resistance and abrasion resistance of the obtained resin film were evaluated using the methods described above.The results are shown in Table 2.

[0311] [Table 2]

[0312] [Examples 13 to 17] A resin film was obtained in the same manner as in Example 3, except that the conjugated diene, dienophile, and charge transport material were as shown in Table 3 below, the heating conditions were as shown in Table 3 below, and the number of cycles of the abrasion test was changed to 800. The solvent resistance and abrasion resistance of the obtained resin film were evaluated using the methods described above. The results are shown in Table 3.

[0313] [Comparative Examples 13 to 17] A resin film was obtained in the same manner as in Comparative Example 3-1, except that the conjugated diene, dienophile, and charge transport material were as shown in Table 3 below, the heating conditions were as shown in Table 3 below, and the number of cycles of the abrasion test was changed to 800. The solvent resistance and abrasion resistance of the obtained resin film were evaluated using the methods described above. The results are shown in Table 3.

[0314] [Table 3]

[0315] [Example 18] <Preparation of a coating composition comprising a polyarylate having a conjugated diene group and a polycarbonate having a dienophile group, and preparation of a crosslinked resin film> 1.2 g of PAR-1 and 0.3 g of PC-2 were weighed into a screw-capped sample tube and dissolved in 10 mL of tetrahydrofuran to obtain a coating composition. The resulting coating composition was cast onto a 250 μm-thick PET film using an applicator with a 200 μm gap. After air-drying for 1 hour, the film was treated in a vacuum dryer at 50°C for 16 hours to remove the solvent, yielding a precursor film. The obtained precursor film was crosslinked by heating it in a vacuum dryer (vacuum degree: 1 to 100 Pa) at a temperature of 200° C. for 1 hour to obtain a resin film.

[0316] [Example 19] <Preparation of a coating composition for a charge transport layer comprising a polyarylate having a conjugated diene group, a polycarbonate having a dienophile group, and a charge transport material, and preparation of a crosslinked resin film> 1.25 g of PAR-1, 0.25 g of PC-2, and 1.0 g of charge transport material (CTM-1) were weighed into a screw-capped sample tube and dissolved in 10 mL of tetrahydrofuran to obtain a coating composition. The resulting coating composition was cast onto a 250 μm-thick PET film using an applicator with a 200 μm gap. After air-drying for 1 hour, the film was treated in a vacuum dryer at 50°C for 16 hours to remove the solvent, yielding a precursor film. The obtained precursor film was crosslinked by heating it in a vacuum dryer (vacuum degree: 1 to 100 Pa) at a temperature of 150° C. for 1 hour to obtain a resin film.

[0317] [Comparative Example 18] A resin film was obtained in the same manner as in Example 18, except that PC-2 was not used and the amount of PAR-1 used was changed to 1.5 g.

[0318] [Comparative Example 19] A coating composition and a resin film were obtained in the same manner as in Example 2, except that in Example 19, PC-2 was not used and the amount of PAR-1 used was changed to 1.5 g.

[0319] The solvent resistance of the resin films obtained in Examples 18 and 19 and Comparative Examples 18 and 19 was evaluated by the method described above. The results are shown in Table 4.

[0320] [Table 4]

[0321] [Confirmation of cross-linking reaction] The precursor film obtained in Example 3 was peeled off and subjected to DSC measurement (manufactured by PerkinElmer, "diamond DSC") under the following measurement conditions. The obtained results are shown in FIG.

[0322] (Measurement conditions) Heating rate: 5°C / min. Measurement range: Temperature rise from 50°C to 300°C.

[0323] In FIG. 2, a large exothermic peak was observed in the temperature range around the heat treatment temperature (200° C.) in Example 3, confirming that an exothermic reaction occurred due to heating.

[0324] The film obtained in Example 3 after drying for the purpose of removing the solvent (after drying at 50°C for 16 hours), the film obtained after heat treatment at 200°C for 3 hours, and the film obtained in Comparative Example 3-1 were peeled off and subjected to excitation fluorescence three-dimensional spectrum measurement. The results are shown in Figure 3.

[0325] (Measurement conditions) Equipment used: JASCO "FP-8600" Excitation wavelength: 300-500 nm Fluorescence wavelength: 300-600 nm Data acquisition interval: (Excitation) 5 nm, (Fluorescence) 4 nm Sensitivity: high Fluorescence band: 5.0 nm Excitation bandwidth: 5.0 nm Response: 0.5 sec Scanning speed: 500 nm / min Measurement method: The film was attached to a slide glass and positioned at a 45° angle to the light source and detector for measurement.

[0326] The spectrum shown in FIG. 3 is the result of cutting out the measured three-dimensional fluorescence spectrum at an excitation wavelength of 350 nm and a fluorescence wavelength of 400 to 600 nm. The resin film shown in Comparative Example 3-1 exhibits fluorescence specific to the anthracene skeleton, but in the film mixed with PC having maleimide groups in Example 1, the fluorescence intensity significantly decreased even under drying conditions for solvent removal (50°C, 16 hours). Furthermore, the fluorescence disappeared after heat treatment at 200°C for 3 hours. This confirmed that the anthracene skeleton was converted into a skeleton that did not emit fluorescence through the reaction. The film obtained in Example 3, which had been heat-treated at 200°C for 3 hours, was peeled off, and the carbonate bond was hydrolyzed under alkaline conditions. The fragmented components were analyzed by LC-MS.

[0327] (Conditions for consideration) 0.05 g of sample was dissolved in 15 mL of methylene chloride, and 3 mL of 1N KOH / methanol was added. After stirring the solution for 30 min, nitrogen was blown at 40°C to dry the solvent. The sample was then dissolved in 10 mL of ion-exchanged water and neutralized with 2N HCl. The volume was adjusted to 50 mL with acetonitrile, and solids were removed using a 0.45 μm chromatographic disc. The resulting sample was then subjected to LC-MS analysis under the following conditions. Device: LC section (Waters UPLC Hclass) MS section (Waters XevoG2XS Qtof) Column: BEH C18 (1.7 μm × 2.1 mm × 50 mm) Column temperature: 40 °C Injection volume: 1.0 μL Flow rate: 0.50 mL / min Developing solvent: 0-2 min. Ammonium acetate aqueous solution (0.2 mol / L):acetonitrile = 7:3 2-6 min. Ammonium acetate aqueous solution (0.2 mol / L):acetonitrile = 7:3 6-8 min. Ammonium acetate solution (0.2 mol / L):acetonitrile = 3:7 8–8.5 min. Ammonium acetate aqueous solution (0.2 mol / L):acetonitrile:THF=5:45:50 8.5 minutes to final: Ammonium acetate aqueous solution (0.2 mol / L):acetonitrile = 7:3 MS conditions Ionization method: ESI± Mass range: 50 to 1500

[0328] (Results of the study) A mass peak attributable to a compound with the following assumed structure, having a mass of 1323.48, was detected in the component with an elution time of 7.3 to 7.6.

[0329] [ka]

[0330] This compound is thought to be a component formed by the Diels-Alder reaction of the 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene component in the PC polymer (PC-5) with the 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane used as a crosslinking agent, followed by hydrolysis of the carbonate group with alkali. Based on the above findings and the general reaction pattern of the Diels-Alder reaction, it was confirmed that a resin having the following crosslinked structure was produced when the crosslinked precursor composition was heated.

[0331] [ka]

Claims

1. At least one resin selected from the group consisting of aromatic polycarbonates and polyarylates, The resin has bonds between polymer chains due to a Diels-Alder reaction, a conjugated diene structure or a dienophile structure is bonded to the main chain of the polymer chain of the resin, a conjugated diene structure or a dienophile structure is directly bonded to the main chain of the polymer chain; It contains at least one structure represented by the following general formula (UN1) and general formula (UN2): A resin characterized by: 【Chemistry 1】 (In the general formula (UN1) and the general formula (UN2), Ar ３ , Ar ３１ and Ar ３２ are each independently a group represented by the following general formula (UN11): 【Chemistry 2】 (In the general formula (UN11), m3 is 0, 1 or 2; n3 is 4, Multiple R ３ are each independently hydrogen atoms, halogen atoms, alkyl having 1 to 10 carbon atoms; aryl having 6 to 12 ring carbon atoms, or an alkyl fluoride having 1 to 10 carbon atoms, X ３ are each independently single bond, -C(-R ３１ ) ２ -、 -O-, -S-, -SO-, -SO ２ -、 -N(-R ３２ )-, -P(-R ３３ )-、 -P=O(-R ３４ )-、 carbonyl, ester, amides, alkylene having 2 to 20 carbon atoms; alkylidene having 2 to 20 carbon atoms, cycloalkylene having 3 to 20 ring carbon atoms; cycloalkylidene having 3 to 20 ring carbon atoms, an arylene having 6 to 20 ring carbon atoms; bicycloalkanediyl having 4 to 20 ring carbon atoms, tricycloalkanediyl having 5 to 20 ring carbon atoms, bicycloalkylidene having 4 to 20 ring carbon atoms, and a group consisting of one or more selected from the group consisting of tricycloalkylidenes having 5 to 20 ring carbon atoms, R ３１ From R ３４ are each independently hydrogen atoms, halogen atoms, alkyl having 1 to 10 carbon atoms; aryl having 6 to 12 ring carbon atoms, or It is an alkyl fluoride having 1 to 10 carbon atoms.

2. The resin according to claim 1, The bond between the polymer chains is formed by a reaction between a polymer having two or more conjugated diene structures in the polymer chain and a compound having a difunctional or higher dienophile group. A resin characterized by:

3. The resin according to claim 1, The bond between the polymer chains is formed by a reaction between a polymer having two or more dienophile structures in the polymer chain and a compound having a bifunctional or higher conjugated diene group. A resin characterized by:

4. The resin according to claim 1, The bond between the polymer chains is formed by a reaction between a polymer having two or more conjugated diene structures in the polymer chain and a polymer having two or more dienophile structures in the polymer chain. A resin characterized by:

5. The resin according to any one of claims 2 to 4, The polymer does not have two or more conjugated diene structures or dienophile structures at the ends of the polymer chain. A resin characterized by:

6. The resin according to any one of claims 2 to 5, The polymer has at least one of a conjugated diene structure and a dienophile structure in the main chain of the polymer chain. A resin characterized by:

7. The resin according to claim 1, The bond between the polymer chains is formed by at least one of the following reactions (iii-1) to (iii-8): A resin characterized by: (iii-1) a polymer having two dienophile structures, each of which is at one end of a polymer chain; Reaction with a polymer having more than two conjugated diene structures in the polymer chain (iii-2) a polymer having two dienophile structures, each of which is at one end of a polymer chain; A reaction with a polymer having more than two conjugated diene structures in the polymer chain, the polymer having one conjugated diene structure at each end of the polymer chain and one or more conjugated diene structures in the main chain. (iii-3) a polymer having two dienophile structures, each of which is at one end of a polymer chain; a polymer having more than two conjugated diene structures in the polymer chain, wherein the polymer chain has one of the conjugated diene structures at one end and no conjugated diene structure at the other end, and the polymer has two or more of the conjugated diene structures in the main chain; (iii-4) a polymer having two dienophile structures, each of which is at one end of a polymer chain; Reaction with a polymer that does not have a conjugated diene structure at both ends of the polymer chain and has more than two conjugated diene structures in the main chain. (iii-5) a polymer having two conjugated diene structures, each of which is present at one end of a polymer chain; Reaction with polymers having more than two dienophile structures in the polymer chain (iii-6) a polymer having two conjugated diene structures, each of which is present at one end of a polymer chain; A reaction with a polymer having more than two dienophile structures in the polymer chain, with one dienophile structure at each end of the polymer chain and one or more dienophile structures in the main chain. (iii-7) a polymer having two conjugated diene structures, each of which is present at one end of a polymer chain; A polymer having more than two dienophile structures in the polymer chain, wherein the polymer has one dienophile structure at one end of the polymer chain and no dienophile structure at the other end, and has two or more dienophile structures in the main chain. (iii-8) a polymer having two conjugated diene structures, each of which is present at one end of a polymer chain; Reaction with a polymer that does not have a dienophile structure at both ends of the polymer chain and has more than two dienophile structures in the main chain

8. The resin according to claim 1, The bond between the polymer chains is formed by a reaction of a polymer having both a conjugated diene structure and a dienophile structure in one polymer chain, and the average number of each of the conjugated diene structure and the dienophile structure per polymer chain is one or more. A resin characterized by:

9. The resin according to claim 8, The polymer does not have two or more conjugated diene structures or dienophile structures at the ends of the polymer chain. A resin characterized by:

10. The resin according to claim 8 or claim 9, The polymer has at least one of a conjugated diene structure and a dienophile structure in the main chain of the polymer chain. A resin characterized by:

11. The resin according to any one of claims 2 to 10, The conjugated diene structure or the conjugated diene group includes at least one structure represented by the following general formula (DE1) or general formula (DE2): A resin characterized by: 【Transformation 3】 (In the general formula (DE1) and the general formula (DE2), R １ are each independently single bond, Linking groups to other skeletons, hydrogen atoms, an aliphatic hydrocarbon group having 1 to 12 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, R １ one or two of the groups are single bonds or linking groups to other skeletons, R as the linking group １ is a group containing at least one atom selected from the group consisting of carbon atom, oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom and boron atom, in which all of the atoms constituting the linking group are bonded together by covalent bonds; Multiple R １ may be linked to form a cyclic structure (including an aromatic ring and a heterocyclic ring).

12. The resin according to claim 11, The conjugated diene structure or the conjugated diene group includes at least one structure represented by the following general formula (DE3) to general formula (DE8): A resin characterized by: 【Chemistry 4】 (In the general formulae (DE3) to (DE8), X １ are each independently -O-, -(C=O)-O-, -O-(C=O)-O-, —O—(C═O)—, or -S-, R １１ are each independently hydrogen atoms, an aliphatic hydrocarbon group having 1 to 12 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, Multiple R １１ may form a cyclic structure (including an aromatic ring and a heterocyclic ring) in which R １２ are each independently hydrogen atoms, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, n represents 0 or a natural number up to the number that can be substituted.)

13. The resin according to claim 11, The conjugated diene structure or the conjugated diene group includes at least one structure represented by the following general formula (DE9) to general formula (DE16): A resin characterized by: 【Transformation 5】 (In the general formulae (DE9) to (DE16), R １３ are each independently hydrogen atoms, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or It is an aromatic hydrocarbon group having 6 to 12 carbon atoms.

14. The resin according to claim 11, The conjugated diene structure or the conjugated diene group includes at least one structure represented by the following general formula (DE17) or general formula (DE18): A resin characterized by: 【Transformation 6】 (In the general formula (DE17) and the general formula (DE18), R １１ are each independently an aliphatic hydrocarbon group having 1 to 12 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, Multiple R １１ may form a cyclic structure (including an aromatic ring and a heterocyclic ring) in which In the general formula (DE17), m represents an integer of 0 to 8, In the general formula (DE18), n represents an integer of 0 to 4, m represents an integer of 0 or more and 9 or less.

15. At least one resin selected from the group consisting of aromatic polycarbonates and polyarylates, The resin has bonds between polymer chains due to a Diels-Alder reaction, The bond between the polymer chains is formed by a reaction between a polymer having two or more conjugated diene structures in the polymer chain and a compound having a dienophile group with two or more functionalities, The bond between the polymer chains is formed by a reaction between a polymer having two or more dienophile structures in the polymer chain and a compound having a bifunctional or more conjugated diene group, or The bond between the polymer chains is formed by a reaction between a polymer having two or more conjugated diene structures in the polymer chain and a polymer having two or more dienophile structures in the polymer chain, The conjugated diene structure or the conjugated diene group includes at least one structure represented by the following general formula (DE19): A resin characterized by: 【Transformation 7】 (In the general formula (DE19), R １１ are each independently an aliphatic hydrocarbon group having 1 to 12 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, Multiple R １１ may form a cyclic structure (including an aromatic ring and a heterocyclic ring) in which n is an integer of 0 to 3.

16. The resin according to any one of claims 2 to 15, The dienophile structure or the dienophile group includes a structure represented by the following general formula (DP1): A resin characterized by: 【Transformation 8】 (In the general formula (DP1), X ２ is a single bond or a linking group to another skeleton, X as the linking group ２ contains at least one atom selected from the group consisting of carbon atom, oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom and boron atom, A group in which all of the atoms constituting the linking group are bonded together by covalent bonds.

17. The resin according to any one of claims 2 to 7, The dienophile structure or the dienophile group is contained in at least one structure represented by the following general formula (DP2) or general formula (DP3): A resin characterized by: 【Chemistry 9】 (X in the general formula (DP2) ２ and X in the general formula (DP3) ２１ and X ２２ are each independently a single bond or a linking group to another skeleton, X as the linking group ２ , X ２１ or X ２２ is a group containing at least one atom selected from the group consisting of carbon atom, oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom and boron atom, in which all of the atoms constituting the linking group are bonded together by covalent bonds; Y in the general formula (DP3) ２ is a group containing an aromatic polycarbonate skeleton or a polyarylate skeleton.

18. The resin according to claim 16 or 17, The dienophile structure or the dienophile group includes a structure represented by the following general formula (DP4): A resin characterized by: 【Chemistry 10】

19. By a crosslinking reaction, the resin according to any one of claims 1 to 18 can be produced. A resin precursor composition comprising:

20. A resin precursor composition comprising the resin precursor composition according to claim 19 and an organic solvent. A coating composition characterized by:

21. A resin comprising the resin according to any one of claims 1 to 18. A molded article characterized by the above.

22. A resin comprising the resin according to any one of claims 1 to 18. An electronic device characterized by:

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