Resin, resin composition, coating composition, film, coating film, electrophotographic photoreceptor, insulating material, molded product, electronic device, and method for producing resin

Abstract

To provide a resin which is capable of polymer reaction, has an anthracene structure to be a reactive group, is suitably used for wet-molding coating liquid preparation, and has improved characteristics due to end-capping of a polar group such as a hydroxy group present at a resin terminal.SOLUTION: The resin comprises at least one of: a structure represented by an optionally substituted anthracene diol; and a structure represented by the general formula (UN1) and the general formula (UN2) in the figure. In the resin, the molar composition of repeating units of the structure represented by an optionally substituted anthracene diol among all repeating units is from 0.1 mol% to 60 mol% inclusive.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin, a resin composition, a coating composition, a film, a coating film, an electrophotographic photoreceptor, an insulating material, a molded product, an electronic device, and a method for producing a resin. [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 specific 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 soluble in and stable in organic solvents.

[0004] Polycarbonate resins made from raw materials such as 2,2-bis(4-hydroxyphenyl)propane and 1,1-bis(4-hydroxyphenyl)cyclohexane have traditionally been used as binder resins for photoreceptors, but their durability has not been satisfactory. One way to improve durability is to improve the abrasion resistance of the photosensitive layer. One effective technique for improving the abrasion resistance of the photosensitive layer is to introduce reactive functional groups into polycarbonate and modify it through a polymer reaction.

[0005] As an example of a polymer reaction, 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 polycarbonate copolymer in which a polycarbonate resin having an epoxy group or the like is crosslinked by an ionic mechanism. 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. Patent Document 9 discloses a polycarbonate having a 1,4-dihydroxyanthracene skeleton. 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 [Patent Document 9] Japanese Patent Application Publication No. 9-43867 [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 extension 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 reducing the melt viscosity at high temperatures and improving thermoformability, while increasing the molecular weight at practical temperatures and improving mechanical properties, and maintaining solubility through the linear structure. However, this purpose differs from the purpose of the present invention, which aims to impart functionality to a resin by introducing reactive groups and reacting them with components having reactive groups. 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] Patent Document 7 also describes examples of crosslinking aliphatic polyesters, polyamides, or polyureas via 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 enhance the functionality of aromatic polycarbonates, which have high mechanical strength, or wholly aromatic polyesters by reacting them with a modifying component. Furthermore, Patent Document 7 does not describe or suggest the application of the technology described therein to aromatic polycarbonates or wholly aromatic polyesters.

[0018] 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 an example of applying the technology described in Non-Patent Document 1 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 unsuitable for such applications.

[0019] 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. Patent Document 9 discloses a resin containing 75% repeating units identical to the structure represented by general formula (AN1) according to this embodiment, but without end-capping. This structure represented by general formula (AN1) is bonded at the 1,4-position of the anthracene. Due to its high linearity, it has better abrasion resistance than anthracene bonded at other positions. However, due to its high crystallinity, a high content can lead to the formation of components in which multiple anthracene structures are linked, causing the resin to crystallize and become cloudy. Furthermore, unend-capping polycarbonates are thought to have hydroxyl or chloroformate terminal groups, both of which are highly polar and may cause problems such as increased hygroscopicity and a higher-than-design dielectric constant, making them undesirable. Patent Document 9 also mentions the issue of image defects in high-humidity environments, which is thought to be partly due to the presence of OH groups at the polymer terminals. In addition, the invention described in Patent Document 9 is intended to demonstrate the effectiveness of a resin having an aromatic ring or aromatic fused ring of a specific structure including an anthracene skeleton, whereas the present application intends to utilize the anthracene skeleton as a linking part for introducing a functional structure by reaction, and therefore has a different purpose. Furthermore, after the reaction, the anthracene structure is converted into another structure, resulting in a structure different from that of Patent Document 9.

[0020] An object of the present invention is to provide a resin that is capable of polymer reaction, has an anthracene structure that serves as a reactive group, is suitable for use in preparing coating solutions for wet molding, and has improved properties achieved by terminally blocking polar groups such as hydroxyl groups present at the ends of the resin. [Means for solving the problem]

[0021] According to one aspect of the present invention, there is provided a resin having a specific anthracene structure, the resin containing the specific anthracene structure in an amount of 0.1 mol % or more and 60 mol % or less, and having a structure in which molecular terminals are capped with specific groups.

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

[0023] According to one aspect of the present invention, there is provided a coating liquid composition comprising the resin composition according to the above-described aspect of the present invention and an organic solvent.

[0024] According to one aspect of the present invention, there is provided an electrophotographic photoreceptor having a layer containing the resin according to the above-described aspect of the present invention.

[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 a film comprising the resin according to the above-described aspect of the present invention. According to one aspect of the present invention, there is provided a coating film comprising the resin according to the above-described aspect of the present invention. According to one aspect of the present invention, there is provided an insulating material containing the resin according to the above-described aspect of the present invention.

[0027] 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.

[0028] According to one aspect of the present invention, there is provided a method for producing a resin, comprising a step of heating the resin composition according to the above-described aspect of the present invention to cause a polymer reaction of the resin composition. [Effects of the Invention]

[0029] According to one aspect of the present invention, it is possible to provide a resin that is capable of polymer reaction, has an anthracene structure that serves as a reactive group, is suitable for use in preparing a coating liquid for wet molding, and has improved properties by end-capping polar groups, such as hydroxyl groups, present at the ends of the resin. [Brief explanation of the drawings]

[0030] [Figure 1] 1 is a chart of the 1H-NMR spectrum of PC-1, a raw material resin obtained in an example. [Figure 2]1 is a chart of the 1H-NMR spectrum of a polymer reactive composition obtained using PC-1, which is a raw material resin obtained in an example. [Figure 3] 1 is a partially enlarged chart of the 1H-NMR spectrum of a polymer reactive composition obtained using PC-1, which is a raw material resin obtained in an example. DETAILED DESCRIPTION OF THE INVENTION

[0031] [resin] The resin according to this embodiment includes a structure represented by the general formula (AN1) described below and at least one of the structures represented by the general formulas (UN1) and (UN2) described below. Furthermore, in the resin according to this embodiment, the molar composition of repeating units of the structure represented by the general formula (AN1) among all repeating units is 0.1 mol % or more and 60 mol % or less. Furthermore, the resin according to this embodiment has molecular ends capped with a monovalent aromatic group, a monovalent fluorine-containing aliphatic group, a group represented by the following general formula (AN2), or a group represented by the following general formula (DP2). In the description herein, this resin may be referred to as a resin (or polymer) having a specific anthracene structure.

[0032] The resin according to this embodiment is preferably 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").

[0033] The resin according to this embodiment exhibits the property of undergoing a polymer reaction by Diels-Alder reaction. When a polymer reaction occurs, the anthracene structure in the structure represented by general formula (AN1) described below becomes a reactive group. A resin obtained by polymer reaction of a resin having a repeating unit of the structure represented by general formula (AN1) has a structure represented by the following general formula (S1). In the following general formula (S1), * indicates a bonding position.

[0034] [ka]

[0035] The resin according to this embodiment can be used for various purposes (crosslinking, graft polymer synthesis, polymer brushes, functional component loading, molecular chain extension, synthesis of block copolymers with heterogeneous polymers, etc.) through a polymer reaction by the Diels-Alder reaction. The structure of the moiety obtained by the polymer reaction has a bonding pattern such as that shown in the following general formula (P1).

[0036] [ka]

[0037] In the general formula (P1), *PC represents a polymer chain of PC. The oval portion represents crosslinking, grafting, resin brushes, the loading of functional components, molecular weight extension, etc. The oval portion represented by the general formula (P1) may represent any of crosslinking, graft polymer synthesis, resin brushes, the loading of functional components, molecular chain extension, and the synthesis of a block copolymer with a different polymer, and can be appropriately selected depending on the purpose.

[0038] As a result of extensive research into solving the problems of the present invention, the inventors have discovered a novel resin that does not contain a radical initiator or a reaction catalyst, and that undergoes a polymer reaction with a substance having a dienophile structure without using ultraviolet light or an electron beam, is suitable for use in preparing a coating liquid for wet molding, and has improved properties by end-capping polar groups such as hydroxyl groups present at the ends of the resin. The present invention was completed based on this finding.

[0039] The resin according to this embodiment has a repeating unit having a structure represented by general formula (AN1). The resin according to this embodiment is a polymer having a specific anthracene structure that exhibits Diels-Alder reactivity.

[0040] [ka]

[0041] In the general formula (AN1), R is independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms; an alkoxy group having 1 to 10 carbon atoms, or is a halogen atom, In addition, a plurality of R may be linked to form a cyclic structure (including an aromatic ring and a heterocyclic ring), When there are multiple R's, they may be the same or different. n is Represents an integer between 0 and 8.

[0042] In the general formula (AN1), the aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by R includes saturated or unsaturated aliphatic hydrocarbon groups (alkyl groups, alkenyl groups, alkynyl groups). Examples of alkyl groups as aliphatic hydrocarbon groups having 1 to 6 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, and tert-hexyl groups. Examples of alkenyl groups as aliphatic hydrocarbon groups having 1 to 6 carbon atoms include vinyl groups (ethenyl groups), 1-propenyl groups, 2-propenyl groups, 2-butenyl groups, 1-butenyl groups, and 1-hexenyl groups. Examples of the alkynyl group as an aliphatic hydrocarbon group having 1 to 6 carbon atoms include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, and a 3-hexynyl group.

[0043] In the general formula (AN1), examples of the aromatic hydrocarbon group having 6 to 12 ring carbon atoms represented by R include a phenyl group, a naphthyl group, and a biphenyl group.

[0044] In the general formula (AN1), the alkoxy group having 1 to 10 carbon atoms represented by R includes 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, an alkoxy group having 1 to 10 carbon atoms ... Examples thereof include an isohexyloxy group, an isohexyloxy group, a sec-hexyloxy group, a tert-hexyloxy group, an isoheptyloxy group, a sec-heptyloxy group, a tert-heptyloxy group, an isooctyloxy group, a sec-octyloxy group, a tert-octyloxy group, an isononyloxy group, a sec-nonyloxy group, a tert-nonyloxy group, an isodecyloxy group, a sec-decyloxy group, and a tert-decyloxy group.

[0045] In the general formula (AN1), examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0046] In the resin according to this embodiment, the molar composition of repeating units having the structure represented by general formula (AN1) in all repeating units is 0.1 mol % or more and 60 mol % or less. Of all repeating units, the molar composition of repeating units of the structure represented by general formula (AN1) is preferably 1 mol % or more, more preferably 5 mol % or more, and even more preferably 10 mol % or more, from the viewpoint of obtaining the property improvement effect by introducing the modifying component. Resins having a structure represented by general formula (AN1) tend to crystallize easily due to the chain structure of the highly crystalline general formula (AN1). To prevent the resin from becoming cloudy or insoluble due to crystallization, the molar composition of repeating units of the structure represented by general formula (AN1) among all repeating units must be 60% or less. Furthermore, to increase the number of solvents in which the resin can be dissolved and to improve solvent solubility, the molar composition of repeating units of the structure represented by general formula (AN1) among all repeating units is preferably 50 mol% or less, more preferably 40 mol% or less, even more preferably 20 mol% or less, and even more preferably 15 mol% or less.

[0047] Any dienophile structure that undergoes a Diels-Alder reaction can be used as the polymerizable dienophile for this resin, which has a specific anthracene structure. Due to its high reactivity, dienophile compounds with a maleimide skeleton are preferred. Dienophile structures include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, 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'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimide) Examples of suitable bismaleimides include diphenylmethane-4,4'-bismaleimide polymers having N,N'-(2,2'-diethyl-6,6'-dimethylenediphenylene)bismaleimide, N,N'-(4-methyl-m-phenylene)bismaleimide, N,N'-m-phenylenedimaleimide, N,N'-m-phenylene bismaleimide, and polyphenylmethane bismaleimide; monomaleimides such as N-phenylmaleimide; and PCs having a structure in which the molecular ends are capped with the following compounds.

[0048] [ka]

[0049] 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).

[0050] [ka]

[0051] 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.

[0052] In this embodiment, it is particularly preferable that the dienophile structure or dienophile group contains a structure represented by the following general formula (DP2): In the following general formula (DP2), * indicates a bonding position. The molecular terminals of the resin according to this embodiment may be capped with a group represented by the following general formula (DP2):

[0053] [ka]

[0054] In this embodiment, when a function is imparted by a polymer reaction, the ratio of anthracene to dienophile can be appropriately set according to the target physical properties and the intended use. The molar ratio of anthracene to dienophile (anthracene / dienophile) is preferably 0.01 or more and 100 or less, more preferably 0.1 or more and 10 or less, even more preferably 0.2 or more and 5 or less, and even more preferably 0.5 or more and 1.5 or less. If the molar ratio of anthracene to dienophile is less than 0.01 or more than 100, the modification effect may not be sufficient.

[0055] The resin according to this embodiment contains at least one of the structures represented by the following general formula (UN1) and general formula (UN2).

[0056] [ka]

[0057] 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.

[0058] [ka]

[0059] 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, In addition, multiple R3 may be the same or different, 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.

[0060] 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.

[0061] In the 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 groups.

[0062] 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.

[0063] 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.

[0064] 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 groups such as ethylidene, propylidene, butylidene, hexylidene, octylidene, decylidene, pentadecylidene, and icosylidene. In general formula (UN11), examples of cycloalkylene having 3 to 20 carbon atoms represented by X3 include groups such as cyclopropylene, cyclobutylene, cyclohexylene, cyclooctylene, cyclodecylene, cyclododecylene, cyclopentadecylene, and cycloicosylene. In the general formula (UN11), cycloalkylidene having 3 to 20 carbon atoms represented by X3 includes groups such as cyclobutylidene, cyclopentylidene, 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.

[0065] In the general formula (UN11), the bicycloalkanediyl having 4 to 20 ring carbon atoms represented by X3 is exemplified by the above-mentioned bicyclic cycloalkylene, and the tricycloalkanediyl having 5 to 20 ring carbon atoms is exemplified by the above-mentioned tricyclic cycloalkylene. Examples include adamantanediyl and tricyclodecanediyl groups. In the general formula (UN11), bicycloalkylidene having 4 to 20 ring carbon atoms represented by X3 is exemplified by the bicyclic ring of the above-mentioned cycloalkylidene, and tricycloalkylidene having 5 to 20 ring carbon atoms is exemplified by the tricyclic ring of the above-mentioned cycloalkylidene. Examples thereof include groups such as adamantylidene and tricyclodecylidene.

[0066] 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.

[0067] [Method of producing resin obtained by polymer reaction] In the resin of this embodiment, the method for producing a resin obtained by a polymer reaction includes a step of heating the resin composition according to this embodiment described below to cause a polymer reaction of the resin composition. Examples of components of the resin composition for causing the polymer reaction include the components exemplified as (i), (ii), and (iii) in the resin composition according to this embodiment described below. In the step of causing the polymer reaction of the resin composition, the heating temperature may be determined depending on the desired properties, application, etc. The heating temperature for causing the polymer reaction is, for example, 60°C or higher and 250°C or lower. The method for producing a resin obtained by a polymer reaction may include the steps of applying a coating composition (described below) to an object by a wet molding method, removing an organic solvent in the coating composition by heating, and polymerizing the resin composition in the coating composition by heating simultaneously with or subsequent to the heating in the organic solvent removal step. Alternatively, the method may involve modifying a resin by a polymer reaction in advance, and using the resulting resin to obtain a molded product.

[0068] Hereinafter, a detailed description will be given using a polymer (polycarbonate polymer) having a specific anthracene structure in the polymer chain as an example.

[0069] A first form of the polycarbonate polymer according to this embodiment (hereinafter also referred to as PC polymer) has at least a repeating unit selected from a repeating unit A represented by the following general formula (1) and a repeating unit B represented by the following general formula (2), and is 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.

[0070] [ka]

[0071] [ka]

[0072] In the general formula (1) and the general formula (1A), Ar 33 is a divalent anthracene ring residue in the group represented by general formula (AN1), 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 a divalent anthracene ring residue in the group represented by the general formula (AN1), and Ar 34 is a group represented by the general formula (UN11). 33 and n 34 and 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.

[0073] The divalent anthracene ring residue in the group represented by general formula (AN1) is represented by the following general formula (AN1A): In general formula (AN1A), R and n of the group represented by (R)n are the same as R and n of the group represented by (R)n in general formula (AN1).

[0074] [ka]

[0075] Such a PC polymer has a repeating unit A containing a group represented by the general formula (AN1) having a specific anthracene structure, and therefore is a polymer having two or more conjugated diene structures in the polymer chain.

[0076] 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.

[0077] [ka]

[0078] In the general formula (100), a represents the molar copolymer ratio in the repeating unit A, and b represents the molar copolymer 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 34 represents the number of moles of repeating unit B containing a group represented by the formula:

[0079] 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.

[0080] The chain ends of the PC polymer according to this embodiment are blocked with a monovalent aromatic group, a monovalent fluorine-containing aliphatic group, or a group represented by the following general formula (AN2), in addition to the specific terminal groups including the aforementioned general formula (DP2). This reduces the number of polar groups such as hydroxyl groups that are normally present at the ends of a PC polymer, thereby improving properties such as moisture resistance, low dielectric properties, and electrical properties.

[0081] [ka]

[0082] (In general formula (AN2), X1 independently represents -O-, -(C=O)-O-, -O-(C=O)-O-, -O-(C=O)-, or -S-, R 11 are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, 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 an integer between 0 and 4.

[0083] In the general formula (AN2), R 11 and R 12 Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms, the aromatic hydrocarbon group having 6 to 12 ring carbon atoms, and the alkoxy group having 1 to 10 carbon atoms represented by R in general formula (AN1) are the same as the aliphatic hydrocarbon group having 1 to 10 carbon atoms, the aromatic hydrocarbon group having 6 to 12 ring carbon atoms, and the alkoxy group having 1 to 10 carbon atoms represented by R in general formula (AN1).

[0084] In this embodiment, when the chain end of the PC polymer is a group represented by general formula (AN2), the molar percentage of the copolymer composition is preferably 0.1 mol % to 67 mol % and more preferably 0.5 mol % to 50 mol % in terms of improving electrical properties and abrasion resistance. A proportion of the terminal blocking agent added of 67 mol % or less can suppress a decrease in mechanical strength, and a proportion of 0.1 mol % or more is preferred because it can achieve the effect of improving properties by introducing an improved structure. The proportion of the terminal blocking agent added is more preferably 1 mol % or more, and even more preferably 5 mol % or more. It is even more preferred that the proportion of the terminal blocking agent added is 15 mol % or less. Furthermore, when the chain terminal of the PC polymer is a group represented by general formula (DP2), the molar percentage of the copolymer composition is preferably 0.1 mol % to 67 mol % and more preferably 0.5 mol % to 50 mol % in terms of improving electrical properties and abrasion resistance. When the proportion of the end-capping agent is 67 mol % or less, a decrease in mechanical strength can be suppressed, and when it is 0.1 mol % or more, the effect of improving properties can be obtained by introducing an improved structure, which is preferable.

[0085] 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.

[0086] 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.

[0087] The monovalent fluorine-containing aliphatic group constituting the chain end may be a monovalent group derived from a fluorine-containing alcohol.

[0088] 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.

[0089] 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).

[0090] H(CF2) n1 CH2OH···(30) F(CF2) m1 CH2OH···(31)

[0091] 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.

[0092] 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)

[0093] 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 32 is 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.

[0094] In this embodiment, when the chain end of the PC polymer is a monovalent aromatic group or a monovalent fluorine-containing aliphatic group, the chain end of the PC polymer is preferably 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), in order to improve the electrical properties and abrasion resistance.

[0095] [ka]

[0096] 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).

[0097] [ka]

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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).

[0102] 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.

[0103] 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.

[0104] 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.

[0105] [ka]

[0106] 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.

[0107] 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)ethane, 1,3,5-tri ... (4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis[2-bis(4-hydroxyphenyl)-2-propyl]phenol, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, tetrakis(4-hydroxyphenyl)methane, tetrakis[4-(4-hydroxyphenylisopropyl)phenoxy]methane, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid, 3,3-bis(3-methyl-4-hydroxyphenyl) 2-oxo-2,3-dihydroindole, 3,3-bis(4-hydroxyaryl)oxindole, 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin, and the like. The 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.

[0108] 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.

[0109] 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.

[0110] 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 final polycarbonate copolymer" refers to the solubility of the polycarbonate copolymer measured under conditions of a temperature of 20°C to 30°C and atmospheric 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.

[0111] 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.

[0112] The resin production method according to this embodiment may include, for example, a polymerization step of polymerizing a resin using 1,4-dihydroxyanthracene and an end-capping agent in the presence of an organic solvent and an alkaline aqueous solution. A bischloroformate oligomer compound may also be used in the polymerization step. It is preferable to reduce the oxygen concentration in the polymerization step. The alkaline aqueous solution used in the polymerization step is preferably an alkaline aqueous solution containing a weak base. The polymerization step may also include a step of mixing the alkaline aqueous solution with an organic layer containing 1,4-dihydroxyanthracene and an end-capping agent in an organic solvent. The resin production method according to this embodiment may also include a washing step. Specifically, the following methods can be used to produce a PC polymer.

[0113] In the method for producing a PC polymer according to this embodiment, the monomer is easily oxidized to a quinone structure, so oxygen in the reaction system is reduced during polymerization and, if necessary, during washing. The oxygen concentration, as measured using the DO meter (dissolved oxygen meter) described in this example, is 1.0 mg / L or less, preferably 0.5 mg / L or less, more preferably 0.2 mg / L or less, particularly preferably 0.1 mg / L or less, and most preferably 0.05 mg / L or less. If the oxygen concentration exceeds 1.0 mg / L, coloration due to quinone formation may occur, and components altered by oxidation may be introduced as impurities, causing deterioration in the polymerization and washing processes, or may remain in the final polymer and adversely affect its use. The oxygen concentration is preferably reduced in the reaction system, organic solvent, or aqueous solution. For aqueous solutions, the use of oxygen-consuming antioxidants such as sodium sulfite or hydrosulfite salts is also effective as a means of lowering the oxygen concentration reading on the DO meter. Furthermore, since the quinone structure is strongly alkaline and is produced significantly in the presence of oxygen, it is also effective to use a weak base such as a carbonate, e.g., potassium carbonate, sodium carbonate, or calcium carbonate, instead of a strong base such as sodium hydroxide, which is normally used in the polymerization step. Furthermore, quinone generation can be suppressed by reducing the frequency of contact with alkali during polymerization. Specifically, while monomers are usually dissolved in an alkaline solution and polymerized, 1,4-dihydroxyanthracene, the raw material for the polymer of this invention, is dissolved in an organic solvent (dichloromethane, acetone, etc.), added to the organic phase in the polymerization reaction, and then mixed with an alkaline aqueous solution to cause the reaction. 1,4-dihydroxyanthracene comes into contact with alkali only at the interface and is immediately consumed in the polymer elongation reaction, effectively preventing its oxidation to quinone.

[0114] [Resin composition] The resin composition according to this embodiment includes the resin according to this embodiment described above. That is, the resin composition according to this embodiment includes a resin having a specific anthracene structure. The resin composition according to this embodiment also includes a structure represented by the general formula (AN1) and a compound containing a dienophile structure or a resin containing a dienophile structure.

[0115] The resin composition according to the present embodiment may be one that can produce the resin according to the present embodiment described above, which is obtained by a polymer reaction, through a polymer reaction. That is, the resin composition according to this embodiment may contain a combination of a polymer having a specific anthracene structure with Diels-Alder reactivity and a reactant having a dienophile group or a dienophile structure. Furthermore, the resin composition according to this embodiment may contain a polymer having a specific anthracene structure with Diels-Alder reactivity and a dienophile structure before the polymer reaction. When a polymer has a specific anthracene structure and a dienophile structure, the dienophile structure in the molecule becomes a reactant having a dienophile structure.

[0116] The resin composition according to the present embodiment may also contain a resin resulting from a polymer reaction between a polymer having a specific anthracene structure and a reactant having a dienophile structure.

[0117] In the resin composition according to this embodiment, the anthracene, the dienophile, and the ratio of the anthracene to the dienophile are the same as those in the resin according to this embodiment.

[0118] The concentrations of anthracene and dienophile in the resin composition according to this embodiment can be appropriately set depending on the desired physical properties and intended application. When the number of moles of anthracene relative to the total amount of the composition having Diels-Alder reactive groups is taken as the functional group concentration, 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. Furthermore, when the number of moles of anthracene is taken as the functional group concentration, the functional group concentration is even more preferably 0.5 mmol / g or more. When the number of moles of anthracene is taken as the functional group concentration, the functional group concentration is even more preferably 2 mmol / g or less, and even more preferably 1 mmol / g or less. If the functional group concentration is less than 0.01 mmol / g, the modifying effect due to the polymer reaction may be insufficient. If the functional group concentration exceeds 10 mmol / g, the density of the anthracene structure will be too high, leaving unreacted functional groups, which is undesirable because the polymer reaction and other side reactions will progress over time, causing the physical properties of the material to change and deteriorate.Furthermore, if the functional group concentration exceeds 10 mmol / g, the proportion of terminal anthracene structures will be too high, which will result in a decrease in molecular weight and a decrease in mechanical strength, which is also undesirable.

[0119] The resin composition according to this embodiment may include, for example, the following components. (i) A polymer (resin) having a specific anthracene structure in the polymer chain and a compound having a dienophile group. (ii) Polymers (resins) that have specific anthracene structures in the polymer chain and dienophile structures in the polymer chain. (iii) A polymer (resin) having a dienophile structure in a single polymer chain of a resin having a specific anthracene structure. When the resin composition according to the present embodiment contains, for example, any of the components selected from (i), (ii), and (iii) shown above, the resin composition according to the present embodiment is characterized by little change in properties because polymer reactions are unlikely to occur at low temperatures around room temperature (for example, 25°C).

[0120] Of the components exemplified above, the polymer having a structure represented by general formula (AN1) in the polymer chain, and the polymer having both the structure represented by general formula (AN1) and the dienophile structure in one polymer chain, have the structure represented by general formula (AN1) in the main chain of the polymer chain.

[0121] For example, in the case of a composition containing the component (i), in a polymer having one or more structures represented by the general formula (AN1), at least one of the total number of structures represented by the general formula (AN1) present in the main chain of the polymer and the number of dienophile groups present in a compound having a dienophile structure with one or more functionalities may be greater than 1.

[0122] For example, in the case of a composition containing the component (ii), in a polymer having one or more structures represented by the general formula (AN1), at least one end of the polymer chain does not have to be bonded to a structure represented by the general formula (AN1), and in a polymer having two or more dienophile structures, at least one end of the polymer chain does not have to be bonded to a dienophile structure, and the end of the polymer chain does not have to be bonded to a structure represented by the general formula (AN1) or a dienophile structure. Furthermore, at least one of the total number of structures represented by the general formula (AN1) present in the main chain of the polymer, and the total number of dienophile groups present in the main chain and terminals of the polymer having the dienophile structure may be a number greater than 2.

[0123] The bond between polymer chains that can be formed by reacting the composition containing the component (ii) can be formed, for example, by the reaction of the following combinations.

[0124] (ii-1) A polymer having two dienophile structures, each of which is located at one end of the polymer chain; A reaction with a polymer having one or more structures represented by the general formula (AN1) in the polymer chain.

[0125] (ii-2) A polymer having two dienophile structures, wherein the polymer has one dienophile structure at one end of the polymer chain and no dienophile structure at the other end, and has one dienophile structure within the main chain; A reaction with a polymer having one or more structures represented by the general formula (AN1) in the polymer chain.

[0126] (ii-3) a polymer having one or more dienophile structures; A reaction with a polymer having one or more structures represented by the general formula (AN1) in the polymer chain.

[0127] [Coating liquid composition] The coating composition according to the present embodiment includes the resin composition according to the present embodiment and an organic solvent. That is, the coating composition according to the present embodiment includes the resin according to the present embodiment and an organic solvent. The resin according to the present embodiment contained in the coating composition according to the present embodiment is soluble in the organic solvent and is suitable as a coating composition for wet molding. The coating composition according to this embodiment is characterized by little change in properties because polymer reactions are unlikely to occur at low temperatures around room temperature during the coating liquid preparation stage and during storage of the coating composition.

[0128] The organic solvent used in this embodiment can be appropriately selected taking into consideration the solubility of materials such as resin compositions, the drying speed after molding, the effect of the solvent remaining on the molded product, and hazards (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 dimethyl fumarate (DMF) and dimethylacetamide (DMAc)), and aprotic polar solvents (such as dimethyl sulfoxide (DMSO)).

[0129] The concentration of the resin 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. If it is 40% by mass or less, the viscosity will not be too high and the coating properties will be good. If it is 0.1% by mass or more, the viscosity can be maintained at an appropriate level, resulting in a homogeneous film. Furthermore, the concentration is appropriate for shortening the drying time after coating and easily achieving the target film thickness.

[0130] The coating composition may contain additives in addition to the resin composition and organic solvent according to this embodiment. 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 composition according to one embodiment of the present invention. As these additives and other resins, known substances that can be blended with resin compositions can be used.

[0131] Furthermore, when a charge transport substance is contained, from the viewpoint of product performance, the mass ratio of the resin 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 composition according to this embodiment may be used alone or in combination of two or more kinds.

[0132] 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.

[0133] The resin according to this embodiment is a polymer-reactive resin, and therefore, for example, PCs that undergo a Diels-Alder reaction have excellent solution stability and react at temperatures commonly used in photoreceptor manufacturing processes. The resulting resin has excellent abrasion resistance and exhibits no deterioration in electrical properties. Furthermore, the resin according to this embodiment does not contain a radical initiator or reaction catalyst, and can undergo a polymer reaction without the use of ultraviolet light or electron beams, thereby suppressing deterioration in electrical properties and preventing the charge transport material (CTM) from deteriorating.

[0134] [Molded product] The molded article according to this embodiment contains the resin according to this embodiment. The molded article according to this embodiment can be used for various applications in addition to the application of the electrophotographic photoreceptor described below. For example, it can be suitably used for applications such as substrates, insulating layers, protective layers, adhesive layers, conductive layers, and structural materials for electronic devices. Furthermore, the molded article according to this embodiment can also be applied to films, coating films, insulating materials, and the like. The molded article exemplified here may contain at least the resin according to this embodiment. Note that in a molded article containing the resin according to this embodiment, the resin containing at least the structure represented by the general formula (AN1) and the compound containing a dienophile structure or the resin containing a dienophile structure may be contained in the same layer or in different layers. When the resin containing at least the structure represented by the general formula (AN1) and the compound containing a dienophile structure or the resin containing a dienophile structure are contained in different layers, the resin containing at least the structure represented by the general formula (AN1) and the compound containing a dienophile structure or the resin containing a dienophile structure may be contained in adjacent layers.

[0135] Here, in this specification, a film containing the resin according to this embodiment and a coating film containing the resin according to this embodiment are clearly distinguished. The film containing the resin according to the present embodiment is a resin body formed from the resin according to the present embodiment, and refers to a resin body having a thickness smaller than its length and width. For example, when the film according to the present embodiment is a resin body formed by applying the coating composition according to the present embodiment to an object and peeling it off from the object, this resin body is a film. The coating film containing the resin according to the present embodiment refers to a layer formed by coating an object with the paint composition according to the present embodiment. Generally, the coating film remains on the object and constitutes a part of the finished product.

[0136] The molded article according to this embodiment can be produced using the resin composition according to this embodiment. When the resin composition according to this embodiment is used, either a wet molding method or a melt molding method can be used as the molding method.

[0137] When a molded product is obtained by wet molding, (i) a method of molding at a temperature at which the polymer reaction proceeds, (ii) a method of obtaining a wet molded product at a temperature at which the polymer reaction does not substantially proceed, and then raising the temperature to a temperature at which the polymer reaction proceeds during the solvent removal process to simultaneously carry out drying and the polymer reaction, or (iii) a method of obtaining a dry molded product by wet molding and drying at a temperature at which the polymer reaction does not substantially proceed, and then raising the temperature of the molded product to a temperature at which the polymer reaction proceeds to carry out the polymer reaction. Any of these methods may be used. Alternatively, a molded product may be obtained by first obtaining a resin modified by a polymer reaction, and then using this resin to prepare a coating liquid to obtain the molded product. In the wet molding method, the coating liquid composition according to the present embodiment can be used.

[0138] Melt molding is typically performed at temperatures above the temperature at which the Diels-Alder reaction proceeds. Alternatively, increasing the molding temperature until the retro-Diels-Alder reaction occurs can be used to reduce the melt viscosity and improve flowability. When molding under conditions that allow the retro-Diels-Alder reaction to occur, the progress of the Diels-Alder reaction can be appropriately controlled 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 structure obtained through the polymer reaction.

[0139] The temperature of the polymer reaction can be appropriately set depending on the target properties and intended use. The crosslinking method can be set by adjusting the type of functional group to be polymerized, the ratio of anthracene to dienophile, and the functional group concentration, etc., according to the reaction temperature.

[0140] For example, the polymer reaction temperature for electrophotographic photoreceptors is preferably a temperature at which a polymer reaction is carried out 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 polymer reaction 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. The polymer reaction temperature for electrophotographic photoreceptors may be 105°C or higher and 140°C or lower, or 110°C or higher and 130°C or lower. At reaction temperatures above 170°C, functional low-molecular-weight compounds such as charge transport materials may deteriorate. At reaction temperatures below 60°C, drying may not proceed sufficiently or may take a long time, which is undesirable.

[0141] On the other hand, for applications in electronic devices, the film properties are adjusted by the drying and curing speed during coating film formation, which can require high temperatures. Therefore, the reaction temperature for electronic devices is preferably 60°C or higher and 250°C or lower, more preferably 100°C or higher and 200°C or lower. A temperature of 110°C or higher and 180°C or lower is even more preferable. Reaction temperatures above 250°C may result in failure of electronic components or decomposition of other organic materials. Reaction temperatures below 60°C may result in insufficient polymer reaction, or materials that undergo reaction at such low temperatures may undergo partial reaction within the coating liquid composition, resulting in increased viscosity and other problems with the stability of the coating liquid.

[0142] In this embodiment, the polymer reaction of the resin composition can be carried out without adding a catalyst, a polymerization initiator, etc. However, as long as the effects of this embodiment are not impaired, substances such as a catalyst or a polymerization initiator may be added for the purpose of using the resin composition in combination with other polymer reaction systems.

[0143] [Electrophotographic photoreceptor] The electrophotographic photoreceptor according to this embodiment has a layer containing the resin according to this embodiment. The resin according to this embodiment is preferably contained in the outermost layer of the electrophotographic photoreceptor according to this embodiment. 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 this embodiment may be any electrophotographic photoreceptor, including various known types of electrophotographic photoreceptors, as long as the resin of this embodiment is used in the photosensitive layer. However, it is preferred that the photosensitive layer be 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. The electrophotographic photoreceptor of this embodiment has excellent abrasion resistance and no deterioration in residual potential due to the layer containing the resin of this embodiment. Furthermore, the electrophotographic photoreceptor of this embodiment has excellent solvent resistance and is less susceptible to mechanical degradation due to the layer containing the resin of this embodiment.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] 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.

[0149] 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 at least one of the charge generating layer and the charge transport layer, it is preferable to use the PC polymer of this embodiment described above.

[0150] 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.

[0151] 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.

[0152] [ka]

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[0166] In the electrophotographic photoreceptor according to this embodiment, it is preferable to use the resin 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 protection layer.

[0167] 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 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.

[0168] 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 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.

[0169] 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 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.

[0170] 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.

[0171] 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.

[0172] 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.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] 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.

[0179] The photosensitive layer of a single-layer electrophotographic photoreceptor can be easily formed by using the charge generating material, charge transport material, and additives, and applying the resin 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 types of application equipment such as known equipment, specifically, for example, an applicator, a spray coater, a bar coater, a tip coater, a roll coater, a dip coater, a doctor blade, or the like.

[0180] 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 composition used in the production of the electrophotographic photoreceptor is preferably in the range of 20:80 to 80:20, more preferably 30:70 to 70:30, by mass.

[0181] The electrophotographic photoreceptor thus obtained has a resin modified by a polymer reaction of the resin composition according to this embodiment as a binder resin in the photosensitive layer, and therefore has excellent properties such as durability, 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.

[0182] [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 causing a polymer reaction of the resin composition in the coating composition by heating simultaneously with or subsequent to the heating in the step of removing the organic solvent.

[0183] 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 polymer reaction of the resin composition, the heating temperature is the same as the reaction temperature for the electrophotographic photoreceptor in the molded product according to this embodiment. [Example]

[0184] 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.

[0185] (Oxygen concentration measurement) Air calibration was performed using a DO meter MODEL B-506 manufactured by Iijima Electronics Co., Ltd. and a Wagnit (WA-BRP) probe. Then, a solution of 25 g of sodium sulfite dissolved in 500 mL of ion-exchanged water was used for zero-point calibration, and the reading in DO measurement mode was used as the oxygen concentration. (The oxygen concentrations of the gas phase, methylene chloride layer, and water layer were all measured using the same method.)

[0186] [Manufacturing Example: Preparation of Monomer] <Production Example 1: Synthesis of 1,4-dihydroxyanthracene> A reaction vessel equipped with a mechanical stirrer, stirring blades, baffles, and a reflux condenser was purged with Ar, and quinizarin (190 g) and methanol (3.8 L) were added and cooled to below 5°C. Subsequently, NaBH4 (120 g) was added over 5 hours so that the internal temperature was maintained between 0°C and 5°C, and then the mixture was stirred at a temperature below 5°C for 12 hours. Then, 6N hydrochloric acid (2 L) was added dropwise while maintaining the internal temperature at 10°C or less, and the solid matter was filtered and washed with water to obtain a crude product of 1,4-anthraquinone, an intermediate. The crude product was recrystallized from acetone to obtain 114 g of the product. Next, a reaction vessel equipped with a mechanical stirrer, stirring blades, baffles, and a reflux condenser was purged with Ar, and the 1,4-anthraquinone (100 g) obtained above and 1,4-dioxane (2.5 L) were added and cooled to below 15°C while stirring. Next, an aqueous solution of NaSO (334 g) dissolved in ion-exchanged water (2.5 L) was added dropwise over 1 hour, carefully maintaining the internal temperature between 10°C and 20°C. The internal temperature was then raised to 25°C, and the mixture was stirred for 3 hours. The reaction mixture was added to ion-exchanged water (5 L), and a solid was precipitated in an ice bath. The resulting solid was washed with ion-exchanged water to obtain 1,4-dihydroxyanthracene (67 g).

[0187] [Manufacturing Example: Preparation of Oligomers] <Production Example 2: 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.

[0188] Here, 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, M1 is calculated based on the molecular weight averaged by the molar ratio of the molecular weights of the raw materials used. 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 = (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.

[0189] [ka]

[0190] In the general formula (X1), Ar X1 For example, in the case of the bischloroformate compound (bisphenol Z oligomer) according to Production Example 2, the divalent group represented by the following general formula (10) is Ar X1 is equivalent to

[0191] [ka]

[0192] In the case of the bischloroformate oligomer represented by the general formula (1A), Ar 33 But, Ar X1 corresponds to n 31 But, n Xis 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

[0193] <Production Example 3: 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.

[0194] <Production Example 4: 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.

[0195] [Synthesis Example 1] (Production of PC polymer) A reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles was charged with 24 mL of Z-CF (Production Example 2) and 96 mL of methylene chloride. To this was added 0.038 g of p-tert-butylphenol (PTBP) (hereinafter referred to as PTBP) as an end-capping agent, and 0.56 g of 1,4-dihydroxyanthracene (synthesized above) 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 the 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 2.4N aqueous solution of sodium hydroxide (prepared by dissolving 0.39 g of sodium hydroxide in 4 mL of ion-exchanged water and adding 50 mg of sodium hydrosulfite) was added, and 0.6 mL of a 7 vol% aqueous solution of triethylamine 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 (2.6 g) solution (solution preparation method: 16 mL of a 2.4N aqueous solution of sodium hydroxide (1.5 g of sodium hydroxide) was prepared, cooled to below room temperature, and then 50 mg of sodium hydrosulfite was added as an antioxidant and completely dissolved) 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 a PC polymer (PC-1) with the following structure.

[0196] (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. The reduced viscosity [ηsp / C] at 20°C (measured with an automatic viscosity measuring device VMR-042 manufactured by Rigo Co., Ltd., and an improved Ubbelohde viscometer (RM type) for automatic viscosity measurement) was measured to be 1.03 dL / g. The structure and composition of the obtained PC-1 were as follows: 1 Analysis of the peak integrals derived from each constituent monomer in a H-NMR spectrum (JNM-ECZ400S nuclear magnetic resonance spectrometer, manufactured by JEOL Ltd.) confirmed that the polymer was a PC polymer consisting of the following repeating unit, number of repeating units, and molar composition. It was also confirmed that the molecular end of this PC polymer had a structure derived from PTBP, as shown in the following structural formula (ME1). In the following description, "AN1" is the structural unit represented by general formula (AN1). 1 The conditions for measuring the H-NMR spectrum are as follows:

[0197] ( 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)

[0198] [ka]

[0199] [ka]

[0200] The composition ratio (mol %) was BisZ:BisOCE:AN1=61:30:9. The anthracene group concentration is 0.33 mmol / g.

[0201] [Example A] [Preparation of coating composition and resin film] 2 g of PC-1 was weighed into a screw-capped sample tube and dissolved in 12 mL of dichloromethane to obtain a coating composition. These results confirmed that it is possible to prepare a coating material containing PC-1 and an organic solvent. The resulting coating composition was cast onto a commercially available 200 μm-thick polyethylene terephthalate (PET) film using a 250 μm gap applicator. After air-drying for 1 hour, the film was treated in a vacuum dryer (reduced pressure 1 to 100 Pa) at 50°C for 8 hours, and then the solvent was removed at 100°C for 8 hours, yielding a resin film with a coating thickness of 20 to 30 μm. These results confirmed the feasibility of producing PC-1 resin films and coating films.

[0202] [Example B] [Preparation of polymer reactive composition film consisting of copolymer and reactive substance] PC-1 (2 g: 0.65 mmol) and N-phenylmaleimide (0.11 g: 0.65 mmol of maleimide group) were weighed into a sample tube with a screw cap and dissolved in 12 mL of dichloromethane to obtain a coating liquid composition. The resulting coating composition was cast onto a commercially available 200 μm-thick polyethylene terephthalate (PET) film using an applicator with a gap of 250 μm. After air-drying for 1 hour, the film was treated in a vacuum dryer (reduced pressure 1 Pa to 100 Pa) at 50°C for 16 hours to remove the solvent, yielding a resin film with a coating thickness of 20 μm to 30 μm.

[0203] [Confirmation of reactivity of polymer reactive composition] The film obtained above was treated in a vacuum dryer at 200°C for 1 hour to observe the structural changes before and after treatment. 1 This was confirmed by H-NMR. 1 The H-NMR spectrum chart is shown in Figure 2. 1 The H-NMR spectrum chart is shown. 1 The conditions for measuring the H-NMR spectrum are as follows:

[0204] (1 H-NMR spectrum measurement conditions) Solvent: CD2Cl2 Measurement concentration (sample volume / solvent volume): 10mg / mL Number of times accumulated: 16

[0205] A new peak was observed at 3.4-3.5 ppm (representing a proton bonded to the tertiary carbon newly generated by the Diels-Alder reaction) that was not present in the raw resin or N-phenylmaleimide, confirming that this resin can be modified by polymer reactions.

[0206] [Example C1] [Preparation of a coating liquid for coating a photosensitive layer of an electrophotographic photoreceptor containing a copolymer and a reactive substance, and production of a laminated electrophotographic photoreceptor] An electrophotographic photoreceptor was manufactured using a 100 μm-thick aluminum plate as a conductive substrate. A charge generation layer and a charge transport layer were sequentially laminated on the surface of the conductive substrate 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 (tetrahydrofuran) as a solvent and dispersed in a ball mill. The dispersion was applied to the surface of the conductive substrate using a bar coater and dried at 70°C for 30 minutes to form a charge generation layer with a thickness of approximately 0.5 μm.

[0207] Next, to prepare a coating composition for the charge transport layer, PC-1 (1.0 g: 0.33 mmol of anthracene groups), N-phenylmaleimide (0.055 g: 0.32 mmol of maleimide groups), and a charge transport material having the following structure (CTM-1 (0.67 g)) were weighed into a sample tube with a screw cap and dissolved in 10 mL of dichloromethane to obtain a coating composition for the charge transport layer. The coating composition was confirmed to be stable as a coating liquid, with no gelation occurring at room temperature for more than a week.

[0208] [ka]

[0209] The resulting coating composition was cast onto the charge generating layer using an applicator with a gap of 375 μm. After air drying for 1 hour, the coating was treated in a vacuum dryer (reduced pressure 1 Pa to 100 Pa) at 50°C for 16 hours to remove the solvent, yielding a resin film with a coating thickness of 30 μm. The laminated electrophotographic photoreceptor obtained above, and the same electrophotographic photoreceptor further treated in a vacuum dryer at 150°C for 1 hour, were attached to a φ60mm aluminum drum, and the electrophotographic properties were evaluated using a static charge tester CYNTHIA54IM (manufactured by Gentec Co., Ltd.) in EV mode, to evaluate the light decay characteristics of the surface potential. It was confirmed that the surface potential of the obtained photoreceptor decayed depending on the amount of light, decreasing to less than half of the initial charge amount, confirming that the composition containing this resin has charge transport properties and functions as an electrophotographic photoreceptor.

[0210] Next, to confirm the abrasion resistance of the electrophotographic photoreceptor, a coating solution with the same composition as the outermost charge transport layer was prepared and cast onto a commercially available 200 μm thick polyethylene terephthalate (PET) film using an applicator with a gap of 250 μm. After air drying for 1 hour, the coating was treated in a vacuum dryer (reduced pressure 1 Pa to 100 Pa) at 50°C for 16 hours to remove the solvent, yielding a resin film with a coating thickness of 20 μm. The abrasion resistance of the cast surface of the resin film obtained above, and that of the same film further treated in a vacuum dryer at 150°C for 1 hour, were evaluated using a Suga Abrasion Tester NUS-ISO-3 (manufactured by Suga Test Instruments Co., Ltd.). The test conditions were as follows: abrasion paper (containing 3μm alumina particles) was applied with a load of 4.9N and brought into contact with the cast surface (a surface simulating the photosensitive layer surface) and moved back and forth 800 times, and the mass loss (abrasion amount, unit: mg) was measured. The results are shown in Table 1.

[0211] [Example C1-2] A coated film for abrasion testing was obtained in the same manner as in Example C1, except that N-phenylmaleimide (0.022 g) was not used in the preparation of the charge transport layer composition coating liquid used in the abrasion test. The abrasion resistance of the obtained film and the film further treated in a vacuum dryer at 150°C for 1 hour were evaluated in the same manner. The results are shown in Table 1.

[0212] The film obtained in Example C1 was treated in a vacuum dryer at 150°C for 1 hour, and the structural changes before and after treatment were observed. 1 This was confirmed by H-NMR. Figure 3 shows the structure of the polymer reactive composition (after 1 hour of treatment at 150°C). 1 An enlarged view of the H-NMR spectrum chart is shown. 1 The conditions for measuring the H-NMR spectrum are as follows:

[0213] ( 1 H-NMR spectrum measurement conditions) Solvent: CD2Cl2 Measurement concentration (sample volume / solvent volume): 10mg / mL Number of times accumulated: 16

[0214] [Comparative Example] Instead of PC-1 in Example C1, a 0.5 g / dL solution of polycarbonate (PCA) with the following structure and a reduced viscosity [ηsp / C] of 1.19 dL / g at 20°C was prepared, and a charge transport layer composition film was prepared. The abrasion resistance was evaluated in the same manner as above. The results are shown in Table 1.

[0215] [ka]

[0216] [Table 1]

[0217] In Example C1 (after heating at 150°C), the amount of wear was reduced by 5% compared to Example C1-2 (after heating at 150°C). In addition, in Example C1, the amount of wear was reduced by 32% due to the reaction between the polymer and low molecular weight compounds caused by heating at 150°C, confirming that the reactive resin has excellent wear resistance. Furthermore, the amount of wear in Example C1-2 was 40% lower than that in the comparative example, which confirmed that this resin has a skeleton with excellent wear resistance. The structural change of the charge transport layer film obtained in Example C1 before and after the heat treatment was also investigated. 1 When confirmed by H-NMR, similar to the changes in Figures 1 and 2, a new peak at 3.4-3.5 ppm (representing the protons bonded to the tertiary carbon newly generated by the Diels-Alder reaction) was observed, which was not present in the raw resin or N-phenylmaleimide, confirming that this resin can be modified by polymer reactions. The results are shown in Figure 3.

Claims

1. A structure represented by the following general formula (AN1): At least one structure represented by the following general formula (UN1) and the following general formula (UN2), Including, the molar composition of the repeating units having the structure represented by general formula (AN1) in all repeating units is 0.1 mol % or more and 60 mol % or less, the molecular terminals are blocked with a monovalent aromatic group, a monovalent fluorine-containing aliphatic group, a group represented by the following general formula (AN2), or a group represented by the following general formula (DP2), A resin comprising a structure represented by the following general formula (S1): 【Chemical 1】 (In the general formula (AN1), Each R is independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms; an alkoxy group having 1 to 10 carbon atoms, or is a halogen atom, In addition, a plurality of R may be linked to form a cyclic structure (including an aromatic ring and a heterocyclic ring), n is It represents an integer of 0 or more and 8 or less.) 【Chemistry 2】 (In the general formula (UN1) and the general formula (UN2), Ar ３ , Ar ３１ and Ar ３２ are each independently It is a group represented by the following general formula (UN11): 【Chemistry 3】 (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. 【Chemistry 4】 (In the general formula (AN2), X １ are each independently -O-, -(C=O)-O-, -O-(C=O)-O-, —O—(C═O)—, or -S-, R １１ are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, 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 is represents an integer of 0 or more and 4 or less.) 【Chemistry 5】 【Chemistry 6】

2. The resin according to claim 1, The resin is at least one selected from the group consisting of aromatic polycarbonates and polyarylates.

3. The resin according to claim 1 or claim 2 is included. Resin composition.

4. A structure represented by the following general formula (AN1): At least one structure represented by the following general formula (UN1) and the following general formula (UN2), Including, the molar composition of the repeating units having the structure represented by general formula (AN1) in all repeating units is 0.1 mol % or more and 60 mol % or less, a resin whose molecular terminals are blocked with any one of a monovalent aromatic group, a monovalent fluorine-containing aliphatic group, a group represented by the following general formula (AN2), or a group represented by the following general formula (DP2); A compound containing a dienophile structure or a resin containing a dienophile structure, Resin composition. 【Chemical 1】 (In the general formula (AN1), Each R is independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms; an alkoxy group having 1 to 10 carbon atoms, or is a halogen atom, In addition, a plurality of R may be linked to form a cyclic structure (including an aromatic ring and a heterocyclic ring), n is It represents an integer of 0 or more and 8 or less.) 【Chemistry 2】 (In the general formula (UN1) and the general formula (UN2), Ar 3 , Ar 31 and Ar 32 each independently represent: It is a group represented by the following general formula (UN11): 【Chemistry 3】 (In the general formula (UN11), m3 is 0, 1 or 2; n3 is 4, The plurality of R 3 s each independently represent 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, Each X 3 independently represents: 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 to R 34 each independently represent: 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. 【Chemistry 4】 (In the general formula (AN2), Each X 1 independently represents: -O-, -(C=O)-O-, -O-(C=O)-O-, —O—(C═O)—, or -S-, Each R 11 independently represents: an aliphatic hydrocarbon group having 1 to 10 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, Each R 12 independently represents: hydrogen atoms, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, n is represents an integer of 0 or more and 4 or less.) 【Chemistry 5】

5. In the resin composition according to claim 4, A resin composition comprising the structure represented by general formula (AN1) and at least one of the structures represented by general formula (UN1) and general formula (UN2), wherein the molar composition of repeating units of the structure represented by general formula (AN1) in all repeating units is 0.1 mol % or more and 60 mol % or less, and the resin whose molecular terminal is blocked with any of the monovalent aromatic group, the monovalent fluorine-containing aliphatic group, the group represented by general formula (AN2), or the group represented by general formula (DP2) is at least one selected from the group consisting of aromatic polycarbonates and polyarylates.

6. The resin composition according to claim 4 or claim 5, The dienophile structure comprises a structure represented by the following general formula (DP1): 【Chemistry 7】 (In the general formula (DP1), X ２ is a single bond or a linking group to another skeleton, X as the linking group ２ 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, and all of the atoms constituting the linking group are bonded together by covalent bonds.

7. The resin composition according to any one of claims 4 to 6, The resin composition comprises any one component selected from the following component (i), component (ii), and component (iii): (i) a resin comprising the structure represented by the general formula (AN1) and at least one of the structures represented by the general formula (UN1) and the general formula (UN2), wherein the molar composition of the repeating units of the structure represented by the general formula (AN1) in all repeating units is 0.1 mol% or more and 60 mol% or less, and the molecular terminal is blocked with any of the monovalent aromatic group, the monovalent fluorine-containing aliphatic group, the group represented by the general formula (AN2), or the group represented by the general formula (DP2), or the resin is at least one selected from the group consisting of aromatic polycarbonates and polyarylates, and a compound having a dienophile group; (ii) a resin comprising the structure represented by the general formula (AN1) and at least one of the structures represented by the general formula (UN1) and the general formula (UN2), in which the molar composition of the repeating units of the structure represented by the general formula (AN1) in all repeating units is 0.1 mol% or more and 60 mol% or less, and the molecular terminal is blocked with any of the monovalent aromatic group, the monovalent fluorine-containing aliphatic group, the group represented by the general formula (AN2), or the group represented by the general formula (DP2), or the resin is at least one selected from the group consisting of aromatic polycarbonates and polyarylates, and a resin having a dienophile structure in the polymer chain; (iii) A resin comprising a structure represented by the general formula (AN1) and at least one of the structures represented by the general formula (UN1) and the general formula (UN2), in which the molar composition of repeating units of the structure represented by the general formula (AN1) in all repeating units is 0.1 mol% or more and 60 mol% or less, and the molecular terminal is blocked with any of the monovalent aromatic group, the monovalent fluorine-containing aliphatic group, the group represented by the general formula (AN2), or the group represented by the general formula (DP2), or the resin is at least one selected from the group consisting of aromatic polycarbonates and polyarylates, and further has a dienophile structure in one polymer chain.

8. The resin composition according to any one of claims 4 to 7 and an organic solvent is included. Coating liquid composition.

9. The resin according to claim 1 or claim 2, or the resin composition according to any one of claims 4 to 7, film.

10. The resin according to claim 1 or claim 2, or the resin composition according to any one of claims 4 to 7, Coating film.

11. A layer comprising the resin according to claim 1 or claim 2, or the resin composition according to any one of claims 4 to 7, Electrophotographic photoreceptor.

12. A structure represented by the following general formula (AN1): At least one structure represented by the following general formula (UN1) and the following general formula (UN2), Including, the molar composition of the repeating units having the structure represented by general formula (AN1) in all repeating units is 0.1 mol % or more and 60 mol % or less, The polymer contains a resin whose molecular terminals are blocked with any one of a monovalent aromatic group, a monovalent fluorine-containing aliphatic group, a group represented by the following general formula (AN2), or a group represented by the following general formula (DP2): Insulating material. 【Chemical 1】 (In the general formula (AN1), Each R is independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms; an alkoxy group having 1 to 10 carbon atoms, or is a halogen atom, In addition, a plurality of R may be linked to form a cyclic structure (including an aromatic ring and a heterocyclic ring), n is It represents an integer of 0 or more and 8 or less.) 【Chemistry 2】 (In the general formula (UN1) and the general formula (UN2), Ar 3 , Ar 31 and Ar 32 each independently represent: It is a group represented by the following general formula (UN11): 【Chemistry 3】 (In the general formula (UN11), m3 is 0, 1 or 2; n3 is 4, The plurality of R 3 s each independently represent 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, Each X 3 independently represents: 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 to R 34 each independently represent: 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. 【Chemistry 4】 (In the general formula (AN2), Each X 1 independently represents: -O-, -(C=O)-O-, -O-(C=O)-O-, —O—(C═O)—, or -S-, Each R 11 independently represents: an aliphatic hydrocarbon group having 1 to 10 carbon atoms; an aromatic hydrocarbon group having 6 to 12 ring carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, Each R 12 independently represents: hydrogen atoms, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, n is represents an integer of 0 or more and 4 or less.) 【Chemistry 5】

13. The resin according to claim 1 or claim 2, or the resin composition according to any one of claims 4 to 7, Molded object.

14. The resin according to claim 1 or claim 2, or the resin composition according to any one of claims 4 to 7, Electronic devices.

15. A step of heating the resin composition according to claim 7 to cause a polymer reaction of the resin composition, Resin manufacturing method.

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