JP7717658B2 - Resin, resin composition, coating composition, film, coating film, electrophotographic photoreceptor, insulating material, molded product, electronic device, and method for producing resin - Google Patents

Description

The present invention relates to resins, resin compositions, coating compositions, films, coating films, electrophotographic photoreceptors, insulating materials, molded articles, electronic devices, and methods for producing resins.

Due to its excellent mechanical, thermal, and electrical properties, polycarbonate resin has been used as a material for molded products in a variety of industrial fields. In recent years, polycarbonate resin has also come to be widely used in functional products that take advantage of its optical properties. As the range of applications expands, the performance requirements for polycarbonate resin have become more diverse, and in addition to the polycarbonate resins that have been used traditionally, polycarbonate resins with a variety of chemical structures have been proposed.

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.
This organic electrophotographic photoreceptor is required to have predetermined sensitivity, electrical characteristics, and optical characteristics depending on the electrophotographic process to be applied. Since the surface of the photosensitive layer of an electrophotographic photoreceptor is repeatedly subjected to operations such as corona charging, toner development, transfer to paper, and cleaning, electrical or mechanical external forces are applied each time these operations are performed. Therefore, in order to maintain the image quality of electrophotography over a long period of time, the photosensitive layer provided on the surface of the electrophotographic photoreceptor must be durable against these external forces. Furthermore, since organic electrophotographic photoreceptors are typically manufactured by dissolving a binder resin together with functional materials in an organic solvent and casting the resulting solution onto a conductive substrate or the like, they are required to be soluble in and stable with the organic solvent.

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

As an example of a polymer reaction, Patent Document 1 discloses a technique for crosslinking PC containing allyl groups using a radical initiator, resulting in resins with better mechanical strength (such as tensile strength) than bisphenol A polycarbonate resin.

Patent Document 2 also describes a resin in a polycarbonate copolymer that is crosslinked by an ionic mechanism, such as an epoxy group. 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.

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.

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 resin obtained by bonding a composition containing a resin such as polyarylethersulfone (PAES) containing an anthracene structure and a resin such as PAES having a maleimide structure through a Diels-Alder reaction.
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.

Japanese Patent Application Publication No. 10-77338 Japanese Patent Application Publication No. 9-319102 Japanese Patent Application Laid-Open No. 2000-44668 Japanese Patent Application Laid-Open No. 2007-314719 JP 2010-72019 A Japanese Patent Application Laid-Open No. 2003-286347 U.S. Pat. No. 3,435,003 JP 2012-224569 A Special Publication No. 2020-509140

Macromolecules 1999, 32, 5786-5792

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.

Furthermore, the polycarbonate described in Patent Document 2 uses a compound with 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 alteration 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 statement confirming that the disclosed resin is crosslinked, making it unclear whether the disclosed effect of improving physical properties is due to the crosslinked structure.

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

Furthermore, the polycarbonate described in Patent Document 4 has the problem that the CTM changes when irradiated with an electron beam, resulting in an increase in residual potential when used as a photoreceptor.

As seen above, there are also examples where crosslinked polycarbonates and crosslinked polyarylates can be obtained without using radical initiators or reaction catalysts that cause deterioration of electrical properties, and without using UV or electron beams that alter CTM.
As an example of such a technique, 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 having 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 mainly produced, and the probability of reaction between the polymerizable monomer and the polycarbonate having an allyl group, which has relatively low radical polymerization activity, is thought to be low. Therefore, the resulting composition does not have a dense three-dimensional polymer network structure, but rather 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 the progression of polymerization at the coating liquid composition stage, resulting in problems such as increased viscosity and gelation during storage of the coating liquid.

As an example of a crosslinking technology that can meet these requirements, Patent Document 6 discloses a linear polymer obtained by a molecular weight extension reaction of an aliphatic-aromatic polyester via a Diels-Alder reaction, using a resin other than polycarbonate. However, Patent Document 6 does not state or suggest that the technology described therein can be applied to aromatic polycarbonates or wholly aromatic polyesters.

Furthermore, Patent Document 7 describes an example of crosslinking aliphatic polyesters, polyamides, or polyureas by the Diels-Alder reaction. However, these examples aim to impart solvent resistance by crosslinking soft aliphatic resins and to obtain elastomers applicable to diaphragm seals and adhesives, which are intended uses. 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.
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 application to polycarbonate or polyarylate. Furthermore, considering its use in electrophotographic photoreceptors, PET has low solubility in organic solvents such as THF, which are commonly used as coating solvents, and poor compatibility with charge transport materials such as triarylamines, making it unusable for such applications.

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 an example in which PAES having an anthracene skeleton reacts with PAES having maleimide terminals to produce a high molecular weight. The claims also disclose that the method is applicable to polycarbonates. However, the specific structure of the polycarbonate is not disclosed, and application of the exemplified method requires a polycarbonate having amino groups. However, synthesis of polycarbonates having amino groups involves the following problems: (i) the amino groups act as trifunctional reactive groups, generating a multi-branched structure during the polymerization process, resulting in a gel. (ii) The hydrophilic amino terminals act similarly to surfactants during the polymerization process, significantly impairing separation of the organic and aqueous layers during the washing process during production. For these reasons, it is considered difficult, and the disclosure of Patent Document 9 does not necessarily mean that the method can be adequately implemented with polycarbonates, and the invention is not adequately disclosed.

The first object of the present invention is to provide a resin capable of undergoing a polymer reaction and having an anthracene structure as a reactive group. The second object of the present invention is to provide at least one of aromatic polycarbonate and polyarylate resins having an anthracene structure as a reactive group, which can be used for various purposes such as crosslinking, polymer elongation, grafting, functional component loading, synthesis of block copolymers of heterogeneous polymers, or polymer brushes through a polymer reaction, without containing radical initiators or reaction catalysts that can deteriorate electrical properties, and without using UV or electron beams that alter charge transport materials (CTMs). The third object of the present invention is to provide a resin composition and a coating composition characterized by minimal changes in properties due to the fact that reactions are unlikely to occur at the coating composition stage. The fourth object of the present invention is to provide an electrophotographic photoreceptor containing the above resin, which has excellent solvent resistance and abrasion resistance, is resistant to mechanical degradation, and does not deteriorate residual potential.

According to one aspect of the present invention, there is provided at least one resin selected from the group consisting of aromatic polycarbonates and polyarylates, the resin having a component with a specific anthracene structure.

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

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.

According to one aspect of the present invention, a molded article is provided that includes the resin according to the above-described aspect of the present invention.

According to one aspect of the present invention, a film is provided that includes 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 containing the resin according to the above-mentioned 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-mentioned aspect of the present invention.

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.

According to one aspect of the present invention, there is provided a method for producing a resin, comprising the step of heating the resin composition according to the aforementioned aspect of the present invention to cause a polymer reaction of the resin composition.

According to one aspect of the present invention, a resin capable of polymerizing and having an anthracene structure as a reactive group can be provided. According to another aspect of the present invention, a resin having a novel structure, substantially free of homopolymers of polymerizable components, can be produced without using UV or electron beams that alter the charge transport material (CTM) and is at least one of aromatic polycarbonate and polyarylate resins. This resin does not contain a radical initiator or reaction catalyst that can deteriorate electrical properties, and the resin can be produced without using UV or electron beams that alter the charge transport material (CTM). Furthermore, according to another aspect of the present invention, a resin composition and a coating composition can be provided that are characterized by minimal changes in properties due to the fact that reactions are unlikely to occur at the coating composition stage. Furthermore, according to another aspect of the present invention, an electrophotographic photoreceptor containing the resin can be provided that has excellent solvent resistance, excellent abrasion resistance, is resistant to mechanical degradation, and does not deteriorate residual potential.

1 is a graph showing the results of gel permeation chromatography measurement of the sample obtained in Example 1 when heat treatment was performed. 1 is a graph showing the relationship between molecular weight and heating temperature and heating time when the sample obtained in Example 1 was subjected to heat treatment. 10 is a graph showing the relationship between light irradiation energy and surface potential of the laminated electrophotographic photosensitive member obtained in Example 2.

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

The resin according to this embodiment exhibits the property of undergoing a polymer reaction via a Diels-Alder reaction. When a polymer reaction occurs, the anthracene structure in the structure represented by general formula (DE1) described below becomes the reactive group. A resin obtained by polymerizing a resin having a structure represented by general formula (DE1) has a structure represented by general formula (S1) below. In general formula (S1) below, * represents a bond position.

The resin according to this embodiment can be used for a variety of purposes (crosslinking, grafting, polymer brushes, functional component loading, block copolymerization of different polymers, molecular chain extension, etc.) through a polymer reaction via the Diels-Alder reaction. The structure of the crosslinking moiety that connects the polymer chains has a bonding pattern such as that shown in the following general formula (P1).

In the general formula (P1), *PC represents a polymer chain of PCs. The oval portion represents crosslinking, grafting, resin brushes, the support of a functional component, molecular weight extension, etc. The oval portion represented by the general formula (P1) may represent any of crosslinking, graft polymer synthesis, resin brushes, the support of a functional component, molecular chain extension, synthesis of a block copolymer with a different polymer, etc., and can be appropriately selected depending on the purpose.
Furthermore, in Patent Document 9, the reactive group anthracene is introduced by a polymerizing reaction, but the reaction yield is low at around 22%, resulting in a structure that is difficult to "polymerize by reaction." The reason for this is that "both ends must react" to increase the molecular weight. Even if the anthracene end reacts, the end on the opposite side of the molecule is likely to be an end other than anthracene, which is present in 78% of cases. It is thought that in most cases, one molecule terminates simply by bonding to a maleimide group. Therefore, a method for efficiently introducing an anthracene structure close to 100% is required. In contrast, the resin according to this embodiment can improve the reaction yield by having a specific anthracene structure.
As a result of extensive research into solving the problems of the present invention, the inventors have found that PCs that undergo a polymer reaction via the Diels-Alder reaction have excellent solution stability, react at temperatures currently used in photoreceptor manufacturing processes, and do not exhibit deterioration in the electrical properties of the resulting resin. The present invention was completed based on this finding.

The resin according to this embodiment is a polymer having a specific anthracene structure with Diels-Alder reactivity, i.e., a structure represented by the following general formula (DE1):

In the general formula (DE1),
Each R is independently
an aliphatic hydrocarbon group having 1 to 12 carbon atoms;
an aromatic hydrocarbon group having 6 to 12 ring carbon atoms;
It is an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.
Furthermore, a plurality of Rs may be linked to form a cyclic structure (including an aromatic ring and a heterocyclic ring).
When a plurality of R's are present, they may be the same or different.
n represents an integer of 0 to 4,
m represents an integer of 0 or more and 9 or less.

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

In the general formula (DE1), examples of aromatic hydrocarbon groups represented by R and having 6 to 12 ring carbon atoms include phenyl, naphthyl, and biphenyl groups.

In the general formula (DE1), the alkoxy group having 1 to 10 carbon atoms represented by R is a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an isopentyloxy group, a neopentyloxy group, or a tert-pentyloxy group. Examples of such groups include oxy, isohexyloxy, sec-hexyloxy, tert-hexyloxy, isoheptyloxy, sec-heptyloxy, tert-heptyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, isononyloxy, sec-nonyloxy, tert-nonyloxy, isodecyloxy, sec-decyloxy, and tert-decyloxy groups.

In the general formula (DE1), examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Any dienophile structure that undergoes a Diels-Alder reaction can be used as the dienophile structure that undergoes a polymer reaction with the resin of this embodiment, but due to its high reactivity, one having a maleimide skeleton is preferably used.
Dienophile structures include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, and 1,3-bis(3-maleimidophenoxy) Examples include bismaleimides such as benzene, 1,3-bis(4-maleimidophenoxy)benzene, diphenylmethane-4,4'-bismaleimide polymer having 4,4'-methylenedianiline, N,N'-(2,2'-diethyl-6,6'-dimethylenediphenylene)bismaleimide, N,N'-(4-methyl-m-phenylene)bismaleimide, N,N'-m-phenylenedimaleimide, N,N'-m-phenylenebismaleimide, polyphenylmethane bismaleimide, monomaleimides such as N-phenylmaleimide, and PCs having a structure in which the molecular terminals are terminated with the following compounds:

In this embodiment, the dienophile structure or dienophile group (hereinafter also simply referred to as "dienophile") preferably includes a structure represented by the following general formula (DP1):

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.

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 the bonding position.

In this embodiment, when functionality is imparted by a polymer reaction, the ratio of anthracene to dienophile can be set appropriately depending on the target physical properties and 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 particularly 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, there is a risk that the modification effect will be insufficient due to the small amount of structure introduced by the polymer reaction.

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

In the general formulae (UN1) and (UN2), Ar ₃ , Ar ₃₁ and Ar ₃₂ are each independently a group represented by the following general formula (UN11).
* indicates the bond position.

In the general formula (UN11),
m3 is 0, 1 or 2;
n3 is 4,
A plurality of _R3 's each independently represent a hydrogen atom,
halogen atoms,
alkyl having 1 to 10 carbon atoms;
an aryl having 6 to 12 ring carbon atoms, or a fluoroalkyl having 1 to 10 carbon atoms;
When a plurality of _R3 's are present, _they may be the same or different.
Each _X3 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,
a group consisting of one or more selected from the group consisting of bicycloalkylidene having 4 to 20 ring carbon atoms, and tricycloalkylidene 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;
It is an aryl having 6 to 12 ring carbon atoms, or a fluoroalkyl having 1 to 10 carbon atoms.
* indicates the bond position.

In the general formula (UN11), examples of the halogen atom represented by R ₃ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In general formula (UN11), examples of the alkyl having 1 to 10 carbon atoms represented by R ₃ 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.

In the general formula (UN11), the aryl having 6 to 12 ring carbon atoms represented by R ₃ is
Examples include groups such as phenyl, naphthyl, and biphenyl.

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) is substituted with a fluorine atom.

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 X ₃ include ethylidene, propylidene, butylidene, hexylidene, octylidene, decylidene, pentadecylidene, and icosylidene groups.
In the general formula (UN11), the cycloalkylene having 3 to 20 carbon atoms represented by _X3 includes a linear or branched alkylene group, 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 X ₃ includes groups such as cyclopropylidene, cyclobutylidene, cyclohexylidene, cyclooctylidene, cyclodecylidene, cyclododecylidene, cyclopentadecylidene, and cycloicosylidene.
In the general formula (UN11), examples of the arylene having 6 to 20 ring carbon atoms represented by X ₃ include phenylene, naphthylene, and biphenylene groups.

In the general formula (UN11), examples of the bicycloalkanediyl having 4 to 20 ring carbon atoms represented by _X3 include the above-mentioned bicyclic cycloalkylene rings, and examples of the tricycloalkanediyl having 5 to 20 ring carbon atoms include the above-mentioned tricyclic cycloalkylene rings, such as adamantanediyl and tricyclodecanediyl.
In the general formula (UN11), examples of bicycloalkylidene having 4 to 20 ring carbon atoms represented by _X3 include the above-mentioned bicyclic cycloalkylidene, and examples of tricycloalkylidene having 5 to 20 ring carbon atoms include the above-mentioned tricyclic cycloalkylidene, for example, adamantylidene and tricyclodecylidene.

In general formula (UN11), examples of the halogen atom, alkyl having 1 to 10 carbon atoms, aryl having 6 to 12 ring carbon atoms, and fluorinated alkyl having 1 to 10 carbon atoms represented by R ₃₁ to R ₃₄ of X ₃ include the same groups as the group represented by R ₃ in general formula (UN11).

[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. In the step of causing a 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 may be, for example, 60°C or higher and 250°C or lower. The method for producing a resin obtained by a polymer reaction may include a step of applying the coating composition described below to an object using a wet molding method, a step of removing the organic solvent in the coating composition by heating, and a step of 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. Alternatively, a method may be used in which a resin is modified in advance by a polymer reaction and then a molded product is obtained using the resulting resin.

[Resin composition]
The resin composition according to the present embodiment includes the resin according to the present embodiment described above. That is, the resin composition according to the present embodiment includes a resin having a specific anthracene structure and a compound or resin having a dienophile structure.
The resin composition according to this embodiment may be one that can produce the resin according to this embodiment described above, which is obtained by a polymer reaction.
That is, the resin composition according to this embodiment may contain a polymer having a specific anthracene structure with Diels-Alder reactivity in its structure, and a reactant or polymer having a dienophile group or dienophile structure in combination. Also, 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 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.

The resin composition according to this 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.

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

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 functional group concentration is the number of moles of anthracene relative to the total amount of the composition having Diels-Alder reactive groups, this functional group concentration is preferably 0.01 mmol/g or more and 10 mmol/g or less, more preferably 0.03 mmol/g or more and 7 mmol/g or less, even more preferably 0.1 mmol/g or more and 5 mmol/g or less, even more preferably 0.3 mmol/g or more and 5 mmol/g or less, and particularly preferably 0.5 mmol/g or more and 2 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 proportion of terminal anthracene structures is too high, resulting in a lower molecular weight and a decrease in mechanical strength, which is undesirable.

The resin composition according to this embodiment may include, for example, the following components (i) to (iii).
(i) A polymer having a structure represented by the general formula (DE1) in the polymer chain and a compound having a dienophile group. (ii) A polymer having a structure represented by the general formula (DE1) in the polymer chain and a polymer having a dienophile structure in the polymer chain. (iii) A polymer having both the structure represented by the general formula (DE1) and a dienophile structure in a single polymer chain.

In the case of a composition containing component (i), at least one of the total number of structures represented by general formula (DE1) present at the polymer terminals and the number of dienophile groups present in the compound having a difunctional or higher dienophile structure may be greater than 2. In this case, the polymer chain may have one structure represented by general formula (DE1) at each end.

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 (DE1), a structure represented by the general formula (DE1) may be bonded to at least one of the ends of the polymer chain, and in a polymer having two or more dienophile structures, a dienophile structure may be bonded to at least one of the ends of the polymer chain, and
In addition, at least one of the total number of structures represented by the general formula (DE1) present in the main chain and terminals of the polymer, and the total number of dienophile groups present in the main chain and terminals of the polymer having a dienophile structure may be a number greater than 2.

The bonds between polymer chains that can be formed by reacting a composition containing component (ii) can be formed, for example, by the reaction of the following combinations:

(ii-1)
A polymer having two dienophile structures, each of which is located at one end of a polymer chain;
a reaction with a polymer having one or more structures represented by the general formula (DE1) in the polymer chain (in this case, the polymer chain may have one structure represented by the general formula (DE1) at each end).

(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 (DE1) in the polymer chain (in this case, the polymer chain may have one structure represented by the general formula (DE1) at each end).

(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 (DE1) in the polymer chain (in this case, the polymer chain may have one structure represented by the general formula (DE1) at each end).

Next, the polycarbonate polymer according to this embodiment will be described.
A first form of the polycarbonate polymer (hereinafter also referred to as PC polymer) according to this embodiment has at least a repeating unit selected from the group consisting of 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). The raw materials used in this embodiment are not limited to the raw materials used in this first form. For example, a bischloroformate oligomer represented by the following general formula (2A) having a repeating unit selected from the group consisting of a repeating unit B represented by the following general formula (2) may be used as the raw material.

In the general formula (1) and the general formula (1A), _Ar33 is a group represented by the general formula (UN11), and _n31 represents the average number of monomers. The average number of monomers, _n31 , is 1.0 or more and 10 or less.
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. The average number of monomers, n ₃₂ , is 1.0 or more and 10 or less.
In the general formula (2C), _Ar33 is a group represented by the general formula (UN11), and _Ar34 is a group represented by the general formula (UN11). Furthermore, _n33 and _n34 each represent an average number of monomers. Furthermore, the sum of the average numbers of monomers _{, n33} and _n34 , is 1.0 or more and 10 or less.
* indicates the bond position.
However, Ar ₃₃ and Ar ₃₄ are different from each other. 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.

As a PC polymer having a single repeating unit A represented by the general formula (1), and a 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.

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 ] represents the number of moles of repeating units A containing a group represented by Ar ₃₃ in the PC polymer, and [Ar ₃₄ ] represents the number of moles of repeating units B containing a group represented by Ar ₃₄ in the PC polymer.

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.
In a first embodiment of the PC polymer according to this embodiment, the chain terminal of the PC polymer has the structure represented by the general formula (DE1), and therefore the polymer has a conjugated diene structure in the polymer chain.

The chain ends of the PC polymer according to this embodiment may be blocked with a monovalent aromatic group or a monovalent fluorine-containing aliphatic group in addition to the specific terminal groups described above, as long as the requirements of the present application are met.
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.

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 atoms, chlorine atoms, 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 to which a halogen atom has been added as described above, or may be a group to which an aryl group has been added.

Examples of the monovalent fluorine-containing aliphatic group constituting the chain end include monovalent groups derived from fluorine-containing alcohols.

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 the total number of fluorine atoms is 13 to 19. 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.

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 via an ether bond represented by the following general formula (32), (33), or (34).

H(CF ₂ ) _n1 CH ₂ OH...(30)
F( _CF2 ) _{m1 CH2OH} ...(31)

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

F-(CF ₂ ) _n ³¹ -OCF ₂ CH ₂ -OH...(32)
F-(CF ₂ CF ₂ ) _n ³² -(CF ₂ CF ₂ O) _n ³³ -CF ₂ CH ₂ OH...(33)
CR ₃ -(CF ₂ ) _n ³⁵ -O-(CF ₂ CF ₂ O) _n ³⁴ -CF ₂ CH ₂ OH...(34)

In the general formula (32), n ³¹ is an integer of 1 to 10, and preferably an integer of 5 to 8.
In the general formula (33), ⁿ³² is an integer of 0 to 5, preferably an integer of 0 to 3. ⁿ³³ is an integer of 1 to 5, preferably an integer of 1 to 3.
In the general formula (34), ⁿ³⁴ is an integer of 1 to 5, preferably an integer of 1 to 3. ⁿ³⁵ is an integer of 0 to 5, preferably an integer of 0 to 3. R is _CF3 or F.

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

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 represents an integer of 1 to 3.
In the general formula (36), _Rf 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).

In the general formula (37), _Rf2 is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms. mx is an integer of 1 to 3.

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

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.

Alternatively, as an end-capping agent for generating chain ends, fluorine-containing alcohols represented by the above general formula (30) or (31), or monohydric fluorine-containing alcohols such as 1,1,1,3,3,3-hexafluoro-2-propanol, are also preferably used. It is also preferable to use fluorine-containing alcohols via an ether bond represented by the above general formula (32), (33), or (34) as an end-capping agent for generating chain ends.

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

Suitable examples of the monohydric phenol represented by general formula (35) include p-tert-butylphenol, p-perfluorononylphenol, p-perfluorohexylphenol, p-tert-perfluorobutylphenol, and p-perfluorooctylphenol. In other words, in this embodiment, the chain ends are preferably capped with an end-capping agent selected from the group consisting of p-tert-butylphenol, p-perfluorononylphenol, p-perfluorohexylphenol, p-tert-perfluorobutylphenol, and p-perfluorooctylphenol.

Examples of the fluorine-containing alcohol via an ether bond represented by 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 fluorine-containing alcohols listed below.

The addition ratio of the terminal blocking agent changes depending on the fraction of the terminal, and the concentration of crosslinkable reactive groups and molecular weight change in conjunction with each other.The molar percentage of the copolymer composition of the structure represented by the general formula (DE1) relative to the total of the main chain and terminal repeating units is preferably 0.1 mol% or more and 67 mol% or less, more preferably 0.5 mol% or more and 50 mol% or less.When the addition ratio of the terminal blocking agent is 67 mol% or less, the decrease in mechanical strength can be suppressed, and when it is 0.1 mol% or more, the effect of improving properties by crosslinking can be obtained.
The proportion of the structure represented by general formula (DE1) in all terminals of the resin according to this embodiment is 50% or more, preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, and particularly preferably 95% or more, by molar ratio. When this proportion is 50% or more, the modifying effect due to the polymer reaction can be efficiently exerted.

The branching agent that can be used in the method for producing a PC polymer according to this embodiment is not particularly limited. Specific examples of the branching agent include phloroglucin, pyrogallol, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-2-heptene, 2,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-3-heptene, 2,4-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(2-hydroxyphenyl)benzene, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]cyclohexane], and the like. [4-hydroxyphenyl]propane, 2,4-bis[2-bis(4-hydroxyphenyl)-2-propyl]phenol, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, tetrakis(4-hydroxyphenyl)methane, tetrakis[4-(4-hydroxyphenylisopropyl)phenoxy]methane, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid, 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole, 3,3-bis(4-hydroxyaryl)oxindole, 5-chloroisatin, 5,7-dichloroisatin, and 5-bromoisatin.
The proportion of these branching agents added is preferably 30 mol % or less, more preferably 5 mol % or less, in terms of the molar percentage of the copolymer composition of repeating unit A, repeating unit B, and chain terminals, or the molar percentage of the copolymer composition of repeating unit A and chain terminals. When the proportion of branching agent added is 30 mol % or less, deterioration in moldability can be suppressed.

When performing interfacial polycondensation, examples of acid binders include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; 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 acid binder used can be adjusted appropriately, taking into account the stoichiometric ratio (equivalents) of the reaction. Specifically, 1 equivalent or more of 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 acid binder can be used.

The solvent used in the PC polymer production method 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 of two or more. Furthermore, the interfacial polycondensation reaction may be carried out using two immiscible solvents.

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" refers to an organic solvent that does not give a solution consisting of a uniform layer (a solution in which neither a gelled substance nor an insoluble substance is observed) when mixed with water in a composition range of 1:9 to 9:1 under normal temperature and pressure conditions.
Furthermore, the phrase "the organic solvent is capable of dissolving 5% by mass or more of the finally obtained polycarbonate copolymer" refers to the solubility of the polycarbonate copolymer when measured under conditions of a temperature of 20 to 30° C. and 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.

The catalyst used in the method for producing a PC polymer of the present 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.

[Coating liquid composition]
The coating composition according to this embodiment includes the resin composition according to this embodiment and an organic solvent. That is, the coating composition according to this embodiment includes the resin according to this embodiment and an organic solvent.

The organic solvent according to the present embodiment can be appropriately selected taking into consideration the solubility of materials such as the resin composition, the drying speed after molding, the effect of the solvent remaining on the molded product, and the risk of fire or health hazards.
Examples of organic solvents according to the present 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)).

The concentration of the resin composition according to this embodiment in the coating composition according to this embodiment may be any concentration that provides an appropriate viscosity for the intended use of the coating composition, and is preferably 0.1% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 35% by mass or less, and even more preferably 5% by mass or more and 30% by mass or less. If it is 40% by mass or less, the viscosity will not become too high and coatability will be good. If it is 0.1% by mass or more, it will be possible to maintain an appropriate viscosity and obtain a homogeneous film. In addition, it will be an appropriate concentration that shortens the drying time after coating and easily achieves the target film thickness.

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.

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.

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.

[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 purposes 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 (DE1) 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 (DE1) 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 (DE1) and the compound containing a dienophile structure or the resin containing a dienophile structure may be contained in adjacent layers.

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.

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.

When a molded product is obtained by a wet molding method, (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 perform 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 perform 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 the 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.

When melt molding is performed, it is usually carried out at a temperature above the temperature at which the Diels-Alder reaction proceeds. However, a suitable method is to increase the molding temperature until the retro Diels-Alder reaction occurs, thereby reducing the melt viscosity and improving fluidity. When molding is performed under conditions that cause the retro Diels-Alder reaction, the progress of the Diels-Alder reaction can be appropriately controlled again by controlling the cooling rate and temperature of the molded product. This allows for the production of molded products made from resins with good molding fluidity and improved resin properties due to the structure obtained through the polymer reaction.

The temperature of the polymer reaction can be set appropriately depending on the target physical properties and intended application. 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., in accordance with this reaction temperature.

As an example, the polymer reaction temperature for electrophotographic photoreceptors is preferably set in the 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. It may also be 110°C or higher and 140°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.

On the other hand, for applications in electronic devices, the process can be very high, as the film properties are adjusted by the drying and curing speed during coating film formation. Therefore, the reaction temperature for electronic devices is preferably between 60°C and 250°C, more preferably between 100°C and 200°C, and even more preferably between 110°C and 180°C. 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 composition, increasing viscosity and posing problems with the stability of the coating liquid.

In this embodiment, the polymer reaction of the resin composition can be carried out without adding a catalyst, polymerization initiator, or the like. However, as long as the effects of this embodiment are not impaired, substances such as catalysts and polymerization initiators may be added for purposes such as combined use with other polymer reaction systems.

[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 the present embodiment may be any electrophotographic photoreceptor, including various known types of electrophotographic photoreceptors, as long as the resin of the present embodiment is used in the photosensitive layer. However, it is preferred that the photosensitive layer is a multilayer electrophotographic photoreceptor having at least one charge generation layer and at least one charge transport layer, or a single-layer electrophotographic photoreceptor having a charge generation material and a charge transport material in one layer.

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.

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.

Conductive substrate materials used in the electrophotographic photoreceptor of this embodiment can be various materials, including well-known materials. 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 can be used; glass, cloth, paper, and plastic films, sheets, or seamless belts that have been treated to be conductive by coating using vapor deposition, sputtering, or painting; and metal drums that have been treated to be metal-oxidized by electrochemical oxidation or the like can be used.

The charge generation layer contains at least a charge generation material. This charge generation layer can be obtained by forming a layer of charge generation material on the underlying substrate by vacuum deposition or sputtering, or by forming a layer of charge generation material bound to the underlying substrate using a binder resin. Various methods, including well-known methods, can be used to form a charge generation layer using a binder resin. A commonly used 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, to the underlying substrate, and then dry it to obtain a wet-formed body.

As the charge generating material in the charge generating layer, various known materials can be used. Specific compounds include selenium alone (e.g., amorphous selenium and trigonal selenium), selenium alloys (e.g., selenium-tellurium), selenium compounds or selenium-containing compositions (e.g., As ₂ Se ₃ , etc.), inorganic materials consisting of elements of Groups 12 and 16 of the periodic table (for example, zinc oxide and CdS—Se, etc.), oxide-based semiconductors (for example, titanium oxide, etc.), silicon-based materials (for example, amorphous silicon, etc.), metal-free phthalocyanine pigments (for example, τ-type metal-free 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, [0033] Examples of suitable pigments include phthalocyanines, Y-type titanyl phthalocyanines, Y-type oxo-titanyl phthalocyanines, α-type oxo-titanyl phthalocyanines, β-type oxo-titanyl phthalocyanines, titanyl phthalocyanines that exhibit a strong diffraction peak at a Bragg angle 2θ of 27.3±0.2 degrees in an X-ray diffraction diagram, and gallium phthalocyanines), cyanine dyes, anthracene pigments, bisazo pigments, pyrene pigments, polycyclic quinone pigments, quinacridone pigments, indigo pigments, perylene pigments, pyrylium dyes, squalium pigments, anthanthrone pigments, benzimidazole pigments, azo pigments, thioindigo pigments, quinoline pigments, lake pigments, oxazine pigments, dioxazine pigments, triphenylmethane pigments, azulenium dyes, triarylmethane dyes, xanthine dyes, thiazine dyes, thiapyrylium dyes, polyvinylcarbazole, and bisbenzimidazole pigments. These compounds can be used alone or in combination as a charge generating material. Among these charge generating materials, the charge generating materials specifically described in JP-A-11-172003 are preferred.

The charge transport layer can be obtained as a wet molded body by forming a layer on a substrate, which serves as a base, in which a charge transport material is bound with a binder resin.
The binder resin for the charge generating layer and charge transport layer is not particularly limited, and various known resins can be used. Specific examples 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-vinyl carbazole, polyvinyl butyral, polyvinyl formal, polysulfone, casein, gelatin, polyvinyl alcohol, ethyl cellulose, nitrocellulose, carboxy-methyl cellulose, vinylidene chloride polymer latex, acrylonitrile-butadiene copolymer, vinyltoluene-styrene copolymer, soybean oil-modified alkyd resin, nitrated polystyrene, polymethylstyrene, polyisoprene, polythiocarbonate, polyarylate, polyhaloarylate, polyallyl ether, polyvinyl acrylate, and polyester acrylate.
These may be used alone or in combination of two or more. As the binder resin in the charge generating layer and/or charge transport layer, it is preferable to use the PC polymer of this embodiment described above.

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 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 the 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.

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.
The charge transport material that can be used with the PC polymer of this embodiment may be any of various known compounds. 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 suitable.

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, charge transport layer, and surface protection layer.

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 components such as 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, and silicon oxide), polyamide resin, phenolic resin, casein, melamine resin, benzoguanamine resin, polyurethane resin, epoxy resin, cellulose, nitrocellulose, polyvinyl alcohol, and 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, combining inorganic fine particles with a resin is preferable because it forms a coating with excellent smoothness.

The thickness of the undercoat layer is from 0.01 μm to 10 μm, preferably from 0.1 μm to 7 μm. 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 as the blocking layer. The resin composition according to this embodiment can also be used. The thickness of the 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, and a thickness of 20 μm or less can prevent deterioration of electrophotographic properties.

Furthermore, the electrophotographic photoreceptor according to this embodiment may have a protective layer laminated on the photosensitive layer. This protective layer may be made of the same resin as the binder resin described above. 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, and preferably 0.1 μm or more and 10 μm or less. This protective layer may contain the charge generation material, charge transport material, additives, metals and their oxides, nitrides, salts, alloys, carbon black, and conductive materials such as organic conductive compounds.

Furthermore, to improve the performance of this electrophotographic photoreceptor, binders, plasticizers, curing catalysts, fluidity-imparting agents, pinhole control agents, and spectral sensitivity enhancers (sensitizing dyes) may be added to the charge generation layer and charge transport layer, as long as the effects of the present invention are not lost. Furthermore, various additives such as chemicals, antioxidants, surfactants, anti-curl agents, and leveling agents can be added to prevent an increase in residual potential, a decrease in charging potential, and a decrease in sensitivity due to repeated use.

Examples of binders include silicone resins, polyamide resins, polyurethane resins, polyester resins, epoxy resins, polyketone resins, polycarbonate copolymers, polystyrene resins, polymethacrylate resins, polyacrylamide resins, polybutadiene resins, polyisoprene resins, melamine resins, benzoguanamine resins, polychloroprene resins, polyacrylonitrile resins, ethyl cellulose resins, nitrocellulose resins, urea resins, phenolic resins, phenoxy resins, polyvinyl butyral resins, formal resins, vinyl acetate resins, vinyl acetate/vinyl chloride copolymer resins, and polyester carbonate resins. Thermosetting resins and/or photocurable resins can also be used. In any case, there are no particular limitations on the resin, as long as it is electrically insulating and capable of forming a film under normal conditions and does not impair the effects of this embodiment.

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.

Specific examples of the curing catalyst include methanesulfonic acid, dodecylbenzenesulfonic acid, and dinonylnaphthalenedisulfonic acid. Examples of fluidity imparting agents include Modaflow and Acronal 4F. Examples of pinhole control agents include benzoin and dimethyl phthalate. These plasticizers, curing catalysts, fluidity imparting agents, and pinhole control agents are preferably used in amounts of 5% by mass or less relative to the charge transport material, as long as the effects of the present invention are not lost.

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.

Electron-accepting substances can be added to the photosensitive layer to improve sensitivity, reduce residual potential, and reduce fatigue during repeated use, as long as the effects of the present invention are not lost. Specific examples 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 having a large electron affinity, such as benzophenone, 4-nitrobenzalmalondinitrile, α-cyano-β-(p-cyanophenyl)ethyl 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.

In addition, 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 as long as the effects of the present invention are not lost. 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, as long as the effects of the present invention are not lost. A blending ratio of 0.1% by mass or more ensures sufficient surface modification, such as improved surface durability and reduced surface energy, while a blending ratio of 60% by mass or less does not result in a deterioration in electrophotographic properties.

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] 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.

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

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

The thickness of the photosensitive layer in the electrophotographic photoreceptor is 5 μm or more and 100 μm or less, preferably 8 μm or more and 50 μm or less. A thickness of 5 μm or more can prevent a decrease in initial potential, while a thickness of 100 μm or less can suppress a decrease in electrophotographic characteristics. The ratio of charge-generating material to resin composition used in the manufacture of the electrophotographic photoreceptor is preferably in the range of 20:80 to 80:20 by mass, and more preferably in the range of 30:70 to 70:30.

The electrophotographic photoreceptor obtained in this manner has a resin modified by a polymer reaction from the resin composition according to this embodiment as a binder resin in the photosensitive layer. Therefore, it has excellent properties such as durability, as well as excellent electrical properties (electrophotographic properties), and is a photoreceptor that maintains excellent electrophotographic properties over an extended period of time. The electrophotographic photoreceptor is suitable for use in a variety of electrophotographic applications, including copiers (monochrome, multicolor, full-color, analog, digital), printers (laser, LED, liquid crystal shutter), facsimiles, platemaking machines, and devices with multiple functions.

[Method of Manufacturing 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.

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.

Next, the present invention will be explained in more detail using examples and comparative examples, but the present invention is not limited to these examples, and various modifications and applications are possible within the scope of the concept of the present invention.

[Production Example: Preparation of Monomer]
<Production Example 1: Synthesis of 9-(4-hydroxyphenyl)anthracene>
A reaction vessel equipped with a mechanical stirrer, a stirring blade, a baffle, and a reflux condenser was purged with Ar, and 9-bromoanthracene (117 g), 4-methoxyphenylboronic acid (117 g), and a toluene/ethanol mixed solvent (3.0 L) were charged and stirred at room temperature for 10 minutes.
Subsequently, 2N aqueous _K2CO3 solution (875 _mL ) was added, and argon was bubbled into the reaction solution for 30 minutes. After degassing, tetrakistriphenylphosphine palladium (32.4 g) was added, and the mixture was stirred under heating and reflux for 18 hours.
Ethyl acetate was added to the reaction mixture for extraction, and the organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated to obtain a crude product (360 g).
Subsequently, impurities were removed by column chromatography using toluene as a developing solvent, and the residue was recrystallized from a toluene/hexane mixed solvent to obtain 9-(4-methoxyphenyl)anthracene (145 g).
A reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles was purged with Ar, and the 9-(4-methoxyphenyl)anthracene (97 g) obtained above and dichloromethane (1.2 L) were charged and cooled to -75°C. A dichloromethane solution (0.5 L) of boron tribromide (98 g) was added dropwise to the vessel over 3 hours. After the dropwise addition was completed, the temperature was gradually raised to room temperature, and stirring was continued for 24 hours.
The reaction mixture was then poured into ice water and extracted three times with ethyl acetate. Ion-exchanged water (1 L) was added, and the mixture was extracted twice with ethyl acetate (1 L). The organic layer was washed with saturated brine, dehydrated over sodium sulfate, and concentrated to obtain a crude product (120 g).
Subsequently, impurities were removed by column chromatography using ethyl acetate/hexane as a developing solvent, and the residue was recrystallized from an ethyl acetate/hexane mixed solvent, followed by reprecipitation from chloroform/hexane to obtain 9-(4-hydroxyphenyl)anthracene (66 g).

[Production Example: Preparation of Oligomer]
<Production Example 2: Synthesis of bisphenol CZ oligomer (bischloroformate)>
66.3 g (224 mmol) of 1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane (bisphenol Z) was suspended in 1,080 mL of methylene chloride, and 66.0 g (667 mmol) of phosgene was added and dissolved therein. A solution of 44.0 g (435 mmol) of triethylamine dissolved in 120 mL of methylene chloride was added dropwise to the suspension at a temperature between 5°C and 15°C. After stirring for 30 minutes, the methylene chloride was distilled off until the desired concentration was reached. 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 CZ oligomer having chloroformate groups at the molecular terminals. The resulting solution had a chloroformate concentration of 1.13 mol/L, a solids concentration of 0.247 kg/L, and an average number of monomers of 1.05. Hereinafter, this obtained raw material will be referred to as CZ-CF.

The average number of monomers (n _x ) of the bischloroformate compound represented by the following general formula (X1) was calculated using the following formula (Equation 1).
Average number of molecules ( _n
(In the above formula (Mathematical Formula 1), Mav is (2×1000/(CF value)), M2 is (M1−98.92), M1 is the molecular weight of the bischloroformate compound when _nX = 1 in the following general formula (X1), the CF value (N/kg) is (CF value/concentration), the 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 the concentration (kg/L) is the amount of solids obtained by concentrating 1 L of the reaction solution. Here, 98.92 is the total atomic weight of the two chlorine atoms, one oxygen atom, and one carbon atom that are eliminated by polycondensation of the bischloroformate compounds themselves.)
When synthesizing bischloroformate using two or more raw materials, the average number of monomers is calculated by averaging the molecular weights of the raw materials used in the synthesis using a molar ratio to calculate M1. 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 is calculated using the following formula:
M1=(268×(366÷(366+108)))+214×(108÷(366+108))+124.9
The "124.9" in the formula for M1 is the molecular weight increase when two hydrogen atoms are lost from the monomer used and two carbon atoms, two oxygen atoms, and two chlorine atoms are added.

In the general formula (X1), Ar _X1 is a divalent group. For example, in the case of the bischloroformate compound (bisphenol CZ oligomer) according to Production Example 2, a divalent group represented by the following general formula (10) corresponds to Ar _X1 :

In the case of the bischloroformate oligomer represented by the general formula (1A), Ar ₃₃ corresponds to Ar _X1 , and n ₃₁ corresponds to _nX .
In the case of the bischloroformate oligomer represented by the general formula (2A), Ar ₃₄ corresponds to Ar _X1 , and n ₃₂ corresponds to _nX .

<Production Example 3: Synthesis of bisphenol C oligomer (bischloroformate)>
57.3 g (224 mmol) of 2,2-bis(3-methyl-4-hydroxyphenyl)propane (bisphenol C) was suspended in 1,080 mL of methylene chloride, and 66.0 g (667 mmol) of phosgene was added and dissolved therein. A solution of 44.0 g (435 mmol) of triethylamine dissolved in 120 mL of methylene chloride was added dropwise to the suspension at a temperature between 5 and 15°C. After stirring for 30 minutes, the methylene chloride was distilled off until the desired concentration was reached. 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 CZ oligomer having chloroformate groups at the molecular terminals. The resulting solution had a chloroformate concentration of 1.13 mol/L, a solids concentration of 0.215 kg/L, and an average number of monomers of 1.00. Hereinafter, this obtained raw material will be referred to as C-CF.

[Synthesis Example 1]
(Production of PC polymer)
CZ-CF (69 mL) from Production Example 2 and methylene chloride (121 mL) were poured into a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles. 9-(4-hydroxyphenyl)anthracene (0.637 g) from Production Example 1 was added as an end-capping agent, and the mixture was stirred to ensure thorough mixing. After cooling the temperature inside the reactor to 10°C, the entire amount of the 1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane potassium hydroxide solution (solution preparation method: 63 mL of 1.8 N aqueous potassium hydroxide solution (7.3 g of potassium hydroxide) was prepared, cooled to below room temperature, and then 100 mg of hydrosulfite was added as an antioxidant and completely dissolved) was added to the solution. While stirring, 1.0 mL of an aqueous triethylamine solution (7 vol%) was added, and stirring was continued for 1 hour.
The resulting reaction mixture was diluted with 300 mL of methylene chloride and 50 mL of water and washed. The lower layer was separated and further 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, in that order. The resulting methylene chloride solution was added dropwise to methanol with stirring, and the resulting reprecipitate was filtered and dried to obtain a PC polymer (PC-1) having the following structure.

(Identification of PC polymer)
The PC polymer (PC-1) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g/dL, and the reduced viscosity [ηsp/C] at 20°C was measured and found to be 1.06 dL/g. Analysis of the structure and composition of the obtained PC-1 by ^1H -NMR spectroscopy confirmed that it was a PC polymer consisting of the following repeating unit, number of repeating units, composition, and terminal composition. In the following description, "DE1" refers to the structure represented by general formula (DE1).
The reduced viscosity was measured with an improved Ubbelohde viscometer for automatic viscosity (RM type) using an automatic viscosity measuring device VMR-042 manufactured by Rigo Co., Ltd. The ¹ H-NMR spectrum was measured with a nuclear magnetic resonance spectrometer JNM-ECZ400S manufactured by JEOL Ltd. The measurement conditions for the ¹ H-NMR spectrum were as follows:

( ^1H -NMR spectrum measurement conditions)
_Solvent : _CD2Cl2
Measurement concentration (sample amount/solvent amount): 10 mg/mL
・Number of times accumulated: 16 times

The composition ratio (mol %) of BisCZ:DE1 was 97:3.
The molar composition of the DE1 component relative to all terminals was 98.7%, with the remaining 1.3% being unreacted OH groups remaining in 1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane.
The anthracene concentration is 0.09 mmol/g.

[Synthesis Example 2]
(Production of PC polymer)
C-CF (109 mL) from Production Example 3 and methylene chloride (91 mL) were poured into a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles. To this was added 2.87 g of N-(4-hydroxyphenyl)maleimide (hereinafter referred to as Male 1) dissolved in 40 mL of acetone as a terminal terminator, followed by stirring to ensure thorough mixing. After cooling the reactor to a temperature of 10°C, 10 mL of a 2.4 mol/L aqueous potassium carbonate solution (3.3 g of potassium carbonate and 0.1 g of hydrosulfite as an antioxidant) was added, followed by stirring for 30 minutes. To this solution, the entire amount of the prepared 2,2-bis(3-methyl-4-hydroxyphenyl)propane (BisC) solution (solution preparation method: 57 mL of a 2.0 mol/L aqueous potassium hydroxide solution (6.3 g of potassium hydroxide was prepared, cooled to room temperature or below, and then 8.1 g of BisC was added) was added, and stirring was continued for another 30 minutes.
The resulting reaction mixture was diluted with 0.5 L of methylene chloride and 0.1 L of water and washed. The lower layer was separated and further washed once with 0.15 L of water, once with 0.15 L of 0.03 N hydrochloric acid, and three times with 0.15 L of water, in that order. The resulting methylene chloride solution was added dropwise to methanol with stirring, and the resulting reprecipitate was filtered and dried to obtain a PC polymer (PC-2) having the following structure.

(Identification of PC polymer)
The PC polymer (PC-2) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g/dL, and the reduced viscosity [ηsp/C] at 20°C was measured and found to be 0.19 dL/g. The structure and composition of the obtained PC-2 were analyzed by ¹ H-NMR spectroscopy, and it was confirmed that the PC-2 was a PC polymer consisting of the following repeating units, number of repeating units, and composition:

The composition ratio (mol %) of BisC:Male1 was 86:14.
The dienophile group (maleimide group) concentration is 0.50 mmol/g.

[Example 1]
[Preparation 1] Confirmation of Polymer Reaction 2.97 g of PC-1 and 0.53 g of PC-2 were weighed out into a sample tube with a screw cap and dissolved in 15 mL of dichloromethane to obtain a coating liquid composition.
The resulting coating composition was cast onto a smooth glass plate using an applicator with a gap of 500 μm to form a film. After air-drying for 1 hour, the film was peeled off from the glass plate and treated in a vacuum dryer (reduced pressure: 1 to 100 Pa) at a temperature of 50°C for 16 hours to remove the solvent, yielding a resin film with a coating thickness of 70 μm.
The obtained resin film was used as a sample and was heat-treated in a vacuum dryer under the following heat treatment conditions, and the change in molecular weight distribution was confirmed by gel permeation chromatography (GPC) under the following conditions.
The sample was prepared by weighing 10 mg of sample into a 20 mL sample bottle using a precision balance, dissolving it in 10 mL of THF, and passing it through a 0.45 μm cartridge filter into a vial.
(GPC conditions)
SEC device: Tosoh Corporation HLC-8420 GPC column: Tosoh Corporation TSKguard column HXL-H 1 tube + TSKgel GMH-XL 2 tubes + G2000H-XL 1 tube
Main solvent: THF (special grade without stabilizers manufactured by Wako Pure Chemical Industries)
Detector: Refractive index (RI) detector Concentration: 0.1 w/v%
Injection volume: 100μL
Flow rate: 1.0mL/min
Column temperature: 40°C
Standard sample for calibration curve: TSK standard polystyrene manufactured by Tosoh Corporation The molecular weight distribution obtained is shown in Figure 1. Figure 2 is a graph showing the relationship between molecular weight, heating temperature, and heating time for each heat treatment condition.
(Heat treatment conditions)
(i) Temperature 150℃, 1 hour (ii) Temperature 150℃, 2 hours (iii) Temperature 150℃, 3 hours (iv) Temperature 200℃, 1 hour

[Example 2]
(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, with a charge generation layer and a charge transport layer sequentially laminated on its surface to form a laminated photosensitive layer. 0.5 parts by weight of Y-type oxotitanium phthalocyanine was used as the charge generation material, and 0.5 parts by weight of butyral resin was used as the binder resin. These were added to 19 parts by weight of THF solvent and dispersed in a ball mill. The dispersion was applied to the surface of the conductive substrate film using a bar coater and dried at 70° C. for 30 minutes to form a charge generation layer with a thickness of approximately 0.5 μm.
Next, PC-1 (2.97 g: 0.27 mmol of anthracene groups), PC-2 (0.53 g: 0.27 mmol of maleimide groups), and a charge transport material having the following structure (CTM-1 (2.34 g)) were weighed into a screw-capped sample tube and dissolved in 30 mL of dichloromethane to obtain a coating composition for the charge transport layer. The resin coating liquid was confirmed to be stable as a coating liquid, remaining at room temperature for more than one week without gelling.

The resulting coating composition was cast onto the charge generating layer using an applicator with a gap of 375 μm to form a film. 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 30 μm.
The laminated electrophotographic photoreceptor obtained above, and the electrophotographic photoreceptor further treated in a vacuum dryer at 150°C for 1 hour, were attached to a φ60mm aluminum drum, and the electrophotographic characteristics were evaluated using a CYNTHIA54IM electrostatic charge tester (manufactured by Gentec Co., Ltd.) in EV mode to evaluate the photoelectric 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 functions as an electrophotographic photoreceptor. The results are shown in Figure 3.
Next, to check the abrasion resistance of the electrophotographic photoreceptor, a coating liquid having the same composition as the outermost charge transport layer was prepared, and cast onto a commercially available polyethylene terephthalate (PET) film having a thickness of 200 μm 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 a temperature of 50° C. for 16 hours to remove the solvent, yielding a resin film having a thickness of 20 μm in the coated area.
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 model (manufactured by Suga Test Instruments Co., Ltd.). The test conditions were as follows: abrasion paper (containing 3 μm alumina particles) was applied with a load of 4.9 N 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.

[Comparative Example 1]
Instead of PC-1 and PC-2 in Example 2, a 0.5 g/dL solution of polycarbonate (PCA) having the following structure and a reduced viscosity [ηsp/C] at 20°C of 1.19 dL/g 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.

From the results shown in Table 1, it was confirmed that in Example 2, heating at 150°C caused the polymerization reaction between PC-1 and PC-2 to proceed, resulting in a high molecular weight, which reduced the amount of wear by 47%, demonstrating the excellent wear resistance of the reactive resin.
Furthermore, the amount of wear in Example 2 was 9% smaller than that in Comparative Example 1, confirming that the resin of the present invention has excellent wear resistance.

Claims (13)

At least one resin selected from the group consisting of aromatic polycarbonates and polyarylates, which has a structure represented by the following general formula (DE1):
resin.
(In the general formula (DE1),
Each R is independently
an aliphatic hydrocarbon group having 1 to 12 carbon atoms;
an aromatic hydrocarbon group having 6 to 12 ring carbon atoms;
an alkoxy group having 1 to 10 carbon atoms, or 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 represents an integer of 0 to 4,
m represents an integer of 0 or more and 9 or less. The resin according to claim 1,
Including a structure represented by the following general formula (S1):
resin.
The resin according to claim 1 and a compound or resin containing a dienophile structure.
Resin composition. The resin composition according to claim 3,
The dienophile structure includes a structure represented by the following general formula (DP1):
Resin composition.
(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. The resin composition according to claim 3 or claim 4,
The resin composition comprises any one component selected from the following component (i), component (ii), and component (iii):
(i) A polymer having a structure represented by the general formula (DE1) in the polymer chain and a compound having a dienophile group. (ii) A polymer having a structure represented by the general formula (DE1) in the polymer chain and a polymer having a dienophile structure in the polymer chain. (iii) A polymer having both the structure represented by the general formula (DE1) and a dienophile structure in a single polymer chain. The resin composition according to any one of claims 3 to 5 and an organic solvent,
Coating liquid composition. The resin according to claim 1 or claim 2 is included.
film. The resin according to claim 1 or claim 2 is included.
Coating film. A layer containing the resin according to claim 1 or 2.
Electrophotographic photoreceptor. The resin according to claim 1 or claim 2 is included.
Insulating material. The resin according to claim 1 or claim 2 is included.
Molded object. The resin according to claim 1 or claim 2 is included.
Electronic devices. A step of heating the resin composition according to any one of claims 3 to 5 to perform a polymer reaction of the resin composition,
Resin manufacturing method.