WO2022211100A1 - 樹脂、樹脂組成物、塗液組成物、フィルム、コーティング膜、電子写真感光体、絶縁材料、成形物、電子デバイス、および樹脂の製造方法 - Google Patents

樹脂、樹脂組成物、塗液組成物、フィルム、コーティング膜、電子写真感光体、絶縁材料、成形物、電子デバイス、および樹脂の製造方法 Download PDF

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WO2022211100A1
WO2022211100A1 PCT/JP2022/016887 JP2022016887W WO2022211100A1 WO 2022211100 A1 WO2022211100 A1 WO 2022211100A1 JP 2022016887 W JP2022016887 W JP 2022016887W WO 2022211100 A1 WO2022211100 A1 WO 2022211100A1
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Prior art keywords
resin
general formula
group
polymer
carbon atoms
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PCT/JP2022/016887
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English (en)
French (fr)
Japanese (ja)
Inventor
高明 彦坂
浩延 森下
一徳 千葉
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Priority to US18/284,967 priority Critical patent/US20240209144A1/en
Priority to CN202280024538.9A priority patent/CN117083320A/zh
Priority to JP2023511747A priority patent/JP7735388B2/ja
Publication of WO2022211100A1 publication Critical patent/WO2022211100A1/ja
Anticipated expiration legal-status Critical
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0564—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
    • C08G64/12—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/22—General preparatory processes using carbonyl halides
    • C08G64/24—General preparatory processes using carbonyl halides and phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/42—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers

Definitions

  • the present invention relates to a resin, a resin composition, a coating composition, a film, a coating film, an electrophotographic photoreceptor, an insulating material, a molding, an electronic device, and a method for producing a resin.
  • polycarbonate resin Due to its excellent mechanical, thermal, and electrical properties, polycarbonate resin has been used as a material for molded products in various industrial fields. In recent years, polycarbonate resins have also been widely used in the field of functional products that also make use of their optical properties. Along with the expansion of such application fields, the required performance of polycarbonate resins has also diversified, and not only polycarbonate resins that have been used conventionally, but also polycarbonate resins having various chemical structures have been proposed.
  • An example of a functional product is an organic electrophotographic photoreceptor using a polycarbonate resin as a binder resin for functional materials such as a charge generation material and a charge transport material.
  • This organic electrophotographic photoreceptor is required to have predetermined sensitivity, electrical properties, and optical properties according to the electrophotographic process to which it is applied. Since operations such as corona charging, toner development, transfer to paper, and cleaning are repeatedly performed on the surface of the photosensitive layer of the electrophotographic photoreceptor, an external electrical or mechanical force is applied each time these operations are performed. Added. Therefore, in order to maintain electrophotographic image quality for a long period of time, the photosensitive layer provided on the surface of the electrophotographic photoreceptor is required to have durability against these external forces.
  • organic electrophotographic photoreceptors are usually manufactured by dissolving a binder resin together with functional materials in an organic solvent, and casting the film on a conductive substrate or the like. Desired.
  • polycarbonate resins made from 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, etc. have been used as binder resins for photoreceptors. sexually unsatisfactory.
  • One possible way to improve the durability is to improve the abrasion resistance of the photosensitive layer.
  • a technique for improving the abrasion resistance of the photosensitive layer a technique is known in which a reactive functional group is introduced into a polycarbonate to modify it through a polymer reaction.
  • Patent Document 2 describes a polycarbonate copolymer in which a polycarbonate resin having an epoxy group or the like is crosslinked by an ionic mechanism. Furthermore, in Patent Document 3, a polycarbonate having a double bond and a compound having a plurality of silicon-hydrogen bonds are crosslinked by reacting in the presence of a platinum catalyst, and a polycarbonate having a double bond and an alkoxy group on the silicon atom and hydrogen-bearing compounds are reacted in the presence of a platinum catalyst, followed by hydrolysis and condensation reactions.
  • Patent Document 4 discloses a cross-linking technique by irradiating an electron beam while a polycarbonate having an allyl group is heated from 120°C to 260°C.
  • Patent Document 5 discloses a method of cross-linking a polycarbonate having an allyl group by heating without a catalyst using a triarylamine having a specific structure and a radically polymerizable compound having no triarylamine structure.
  • Patent Document 6 reports a resin obtained by chain-extending a resin having an anthracene skeleton at the end of an aliphatic-aromatic polyester with bismaleimide.
  • Patent Document 7 discloses a crosslinked resin obtained by reacting an aliphatic polyester, polyamide, or polyurea having a furan structure with a polyfunctional maleimide.
  • Non-Patent Document 1 discloses a resin obtained by cross-linking a resin obtained by introducing an anthracenedicarboxylic acid skeleton into a part of an aliphatic-aromatic polyester with a bifunctional maleimide compound.
  • Patent Document 5 discloses a monomer that has high radical polymerization activity, does not use an initiator and does not require UV irradiation, and undergoes radical polymerization only by heating, and a polycarbonate having an allyl group is used there. Techniques for coexistence have been reported.
  • the obtained composition does not have a dense three-dimensional network structure of the polymer, but a composition in which the crosslinked polymer of the polycarbonate resin and the radical polymerization monomer exists separately and only a part thereof is bonded.
  • Patent Document 6 discloses, as an example using a resin other than polycarbonate, a linear polymer obtained by a molecular weight elongation reaction of an aliphatic-aromatic polyester by Diels-Alder reaction. ing.
  • the object of the invention described in Patent Document 6 is to utilize the fact that the bond formed by the Diels-Alder reaction causes a retro Diels-Alder reaction that dissociates at high temperature, and the melt viscosity is reduced by lowering the viscosity at high temperature.
  • This technology is characterized by improved thermoformability, improved mechanical properties due to increased molecular weight in the practical temperature range, and retention of solubility due to having a linear structure.
  • Patent Document 6 does not describe or suggest applying the technique described in Patent Document 6 to aromatic polycarbonates or wholly aromatic polyesters.
  • Patent Document 7 describes an example of cross-linking aliphatic polyester, polyamide, or polyurea by Diels-Alder reaction.
  • these examples aim to impart solvent resistance by cross-linking a soft aliphatic resin, and to obtain an elastomer applicable to diaphragm seals and adhesives, which are intended uses.
  • the technical idea of these examples is different from the idea of the present invention, which is to make aromatic polycarbonate or wholly aromatic polyester having high mechanical strength more highly functional by reacting with a modifying component.
  • Patent Document 7 does not describe or suggest applying the technique described in Patent Document 7 to aromatic polycarbonates or wholly aromatic polyesters.
  • Non-Patent Document 1 describes an example in which an anthracenedicarboxylic acid skeleton is introduced into polyethylene terephthalate (PET) and crosslinked with a bifunctional maleimide compound.
  • PET polyethylene terephthalate
  • the purpose of this example is similar to the purpose of the present invention in that the mechanical properties are improved by heat crosslinking, but in Non-Patent Document 1, the technology described in Non-Patent Document 1 is applied to polycarbonate or polyarylate. No examples are given or suggested.
  • PET is used for electrophotographic photoreceptors, PET has low solubility in organic solvents such as THF, which are usually used as coating solvents, and has low compatibility with charge transport substances such as triarylamines. Unfortunately, it cannot be used for this purpose.
  • FR1 general formula
  • the object of the present invention is to provide a resin that is capable of undergoing a polymer reaction and has a furan structure that serves as a reactive group.
  • a resin that has a repeating unit with a specific furan structure.
  • a coating liquid composition containing the aforementioned resin composition according to one aspect of the present invention and an organic solvent.
  • an electrophotographic photoreceptor having a layer containing the resin according to one aspect of the present invention.
  • a molded article containing the resin according to one aspect of the present invention described above there is provided a molded article containing the resin according to one aspect of the present invention described above.
  • a film containing the resin according to one aspect of the present invention described above there is provided a coating film containing the resin according to one aspect of the present invention described above.
  • a insulating material containing the resin according to one aspect of the present invention described above there is provided.
  • an electronic device including the resin according to one aspect of the present invention described above.
  • a method for producing a resin comprising a step of performing a polymer reaction of the resin composition by heating the resin composition according to one aspect of the present invention.
  • a resin that is capable of undergoing a polymer reaction and has a furan structure that serves as a reactive group.
  • 1 is a 1 H-NMR spectrum chart of PC-1, which is a raw material resin obtained in Examples. 1 is a 1 H-NMR spectrum chart of a polymer reactive composition obtained using PC-1, which is a starting resin obtained in Examples. 1 is a 1 H-NMR spectrum chart of PC-2, which is a raw material resin obtained in Examples. 1 is a 1 H-NMR spectrum chart of a polymer reactive composition obtained using PC-2, which is a starting resin obtained in Examples. 4 is a graph showing the relationship between light irradiation energy and surface potential of a multilayer photoreceptor obtained in an example.
  • the resin according to this embodiment has a repeating unit having a structure represented by general formula (FR1) described below.
  • This resin may be referred to as a resin (or polymer) having a specific furan structure in the description of this specification.
  • the resin according to this embodiment is preferably at least one resin selected from the group consisting of aromatic polycarbonates and polyarylates.
  • Specific resins include aromatic polycarbonates, polyarylates, and aromatic polycarbonate-polyarylate copolymers (hereinafter also simply referred to as "PCs").
  • the resin according to this embodiment exhibits the property of causing a polymer reaction through the Diels-Alder reaction.
  • a polymer reaction occurs, the furan structure among the structures represented by general formula (FR1) described later becomes a reactive group.
  • a resin obtained by a polymer reaction of a resin having a repeating unit having a structure represented by general formula (FR1) has a structure represented by general formula (S1) below.
  • S1 represents a bonding position.
  • various structures can be bound to the binding positions represented by *.
  • the resin according to the present embodiment can be used for various purposes (crosslinking, grafting, polymer brushes, supporting functional components, molecular chain elongation, synthesis of block copolymers of different polymers, etc.) by polymer reaction by Diels-Alder reaction. ). Then, the structure of the site obtained by the polymer reaction has, for example, a binding mode as represented by the following general formula (P1).
  • *PC represents a polymer chain of PCs.
  • the elliptical portion represents cross-linking, grafting, resin brushing, carrying of functional ingredients, molecular weight elongation, and the like.
  • the elliptical portion represented by the general formula (P1) may be crosslinked, grafted, resin brushed, supported with a functional component, molecular weight elongation, block copolymer synthesis with a different polymer, etc., and may be appropriately selected depending on the purpose. can.
  • the resin according to this embodiment has a repeating unit having a structure represented by general formula (FR1).
  • the resin according to this embodiment is a polymer having a specific furan structure with Diels-Alder reactivity.
  • R are each independently an aliphatic hydrocarbon group having 1 or more and 6 or less carbon atoms, an aromatic hydrocarbon group having 6 or more ring-forming carbon atoms and 12 or less, an alkoxy group having 1 or more and 10 or less carbon atoms, or is a halogen atom,
  • a cyclic structure (including an aromatic ring and a heterocyclic ring) in which a plurality of R are linked may be formed, Further, when a plurality of R are present, R may be the same or different, n is represents an integer of 0 or more and 3 or less.
  • the aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by R includes a saturated or unsaturated aliphatic hydrocarbon group (alkyl group, alkenyl group, alkynyl group).
  • Alkyl groups as aliphatic hydrocarbon groups having 1 to 6 carbon atoms are, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, isohexyl group, sec-hexyl group, tert-hexyl group and the like.
  • the alkenyl group as an aliphatic hydrocarbon group having 1 or more and 6 or less carbon atoms is, for example, a vinyl group (ethenyl group), 1-propenyl group, 2-propenyl group, 2-butenyl group, 1-butenyl group, 1- A hexenyl group and the like can be mentioned.
  • alkynyl groups as aliphatic hydrocarbon groups having 1 to 6 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl and 3-hexynyl groups.
  • examples of the aromatic hydrocarbon group represented by R and having 6 or more and 12 or less ring-forming carbon atoms include a phenyl group, a naphthyl group, and a biphenyl group.
  • the alkoxy group having 1 to 10 carbon atoms represented by R includes a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, and an n-hexyloxy group.
  • n-heptyloxy group n-octyloxy group, n-nonyloxy group, n-decyloxy group, isopropoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, isopentyloxy group, neopentyloxy group , tert-pentyloxy group, isohexyloxy group, sec-hexyloxy group, tert-hexyloxy group, isoheptyloxy group, sec-heptyloxy group, tert-heptyloxy group, isooctyloxy group, sec-octyloxy group, tert-octyloxy group, isononyloxy group, sec-nonyloxy group, tert-nonyloxy group, isodecyloxy group, sec-decyloxy group, tert-decyloxy group and the like.
  • the halogen atom represented by R includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the molar composition of repeating units having the structure represented by general formula (FR1) in all repeating units is preferably 0.1 mol % or more and 100 mol % or less.
  • the molar composition of the repeating unit having the structure represented by the general formula (FR1) is preferably 0.1 mol% or more from the viewpoint of obtaining the effect of improving properties by introducing the modifying component. It is more preferably mol % or more, and even more preferably 10 mol % or more.
  • the molar composition of the repeating unit having the structure represented by the general formula (FR1) is preferably 100 mol% or less, and 70 mol% or less, from the viewpoint that the introduction of the modified structure can be arbitrarily set. more preferably 50 mol % or less.
  • Any dienophile structure that causes a Diels-Alder reaction can be applied as the dienophile structure that causes a polymer reaction with the resin having the repeating unit of the structure represented by the general formula (FR1). Due to its high reactivity, a substance having a maleimide skeleton is preferably used as a substance having a dienophile structure.
  • the dienophile structure includes 4,4′-diphenylmethanebismaleimide, m-phenylenebismaleimide, bisphenol A diphenyletherbismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 4 -methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3 - bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, diphenylmethane-4,4'-bismaleimide polymer with 4,4'-methylenedianiline, N,N'-( 2,2′-diethyl-6,6′-dimethylenediphenylene)bismaleimide, N,N′-(4-
  • the dienophile structure or dienophile group (hereinafter also simply referred to as "dienophile”) preferably includes a structure represented by the following general formula (DP1).
  • X 2 is a single bond or a linking group with another skeleton
  • X 2 as the linking group contains at least one atom selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom and a boron atom, and atoms constituting the linking group It is a group in which all of the bonding patterns between them are covalent bonds. * indicates the binding position.
  • the dienophile structure or dienophile group particularly preferably includes a structure represented by the following general formula (DP2).
  • DP2 general formula
  • * indicates a binding position.
  • the proportion of furan and dienophile can be appropriately set according to the target physical properties and intended use.
  • the molar ratio of furan to dienophile is preferably 0.01 or more and 100 or less, more preferably 0.1 or more and 10 or less, and 0.2 or more and 5 or less. is more preferable, and 0.5 or more and 1.5 or less is even more preferable. If the molar ratio of furan to the dienophile is less than 0.01 or exceeds 100, the modification effect may not be sufficiently obtained.
  • 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).
  • Ar 3 , Ar 31 and Ar 32 are each independently a group represented by the following general formula (UN11). * indicates the binding position.
  • the halogen atom represented by R3 includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • alkyl having 1 to 10 carbon atoms represented by R 3 is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n -octyl, n-nonyl, n-decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, sec-hexyl, tert-hexyl, isoheptyl, sec-heptyl, tert-heptyl , isooctyl, sec-octyl, tert-octyl, isononyl, sec-nonyl, tert-nonyl, isodecyl, sec-decyl, sec-de
  • the aryl having 6 to 12 ring-forming carbon atoms represented by R 3 includes groups such as phenyl, naphthyl, and biphenyl.
  • the fluorinated alkyl having 1 to 10 carbon atoms represented by R 3 is exemplified by the alkyl having 1 to 10 carbon atoms represented by R 3 in the above general formula (UN11).
  • alkyl groups include alkyl groups in which at least one hydrogen atom of a carbon atom is substituted with a fluorine atom.
  • the alkylene having 2 or more and 20 or less carbon atoms represented by X3 includes linear or branched alkylene groups, such as ethylene, propylene, isopropylene, butylene, hexylene, Groups such as octylene and decylene are included.
  • the alkylidene having 2 to 20 carbon atoms represented by X3 includes groups such as ethylidene, propylidene, butylidene, hexylidene, octylidene, decylidene, pentadecylidene, and icosidene.
  • the cycloalkylene having 3 or more and 20 or less carbon atoms represented by X3 is, for example, cyclopropylene, cyclobutylene, cyclohexylene, cyclooctylene, cyclodecylene, cyclododecylene, cyclopentadecylene, and cyclo Groups such as icosylene may be mentioned.
  • the cycloalkylidene having 3 or more and 20 or less carbon atoms represented by X3 is cyclobutylidene, cyclopentylidene, cyclohexylidene, cyclooctylidene, cyclodecylidene, cyclododecylidene, cyclopentadecylidene. Included are groups such as ridene, and cycloicosidene.
  • the arylene having 6 or more and 20 or less ring-forming carbon atoms represented by X3 includes groups such as phenylene, naphthylene, and biphenylene.
  • the bicycloalkanediyl having 4 or more and 20 or less ring-forming carbon atoms represented by X 3 is exemplified by the above-mentioned cycloalkylene bicyclics, and having 5 or more and 20 or less ring-forming carbon atoms.
  • the tricycloalkanediyl of is exemplified by the above-mentioned cycloalkylene tricyclics. Examples include groups such as adamantanediyl and tricyclodecanediyl.
  • the bicycloalkylidene having 4 or more and 20 or less ring carbon atoms represented by X 3 is exemplified by the bicyclic cycloalkylidene described above, and the tricycloalkylidene having 5 or more and 20 or less ring carbon atoms.
  • the alkylidene is exemplified by the tricyclic cycloalkylidene described above. Examples include groups such as adamantylidene and tricyclodecylidene.
  • halogen atoms represented by R 31 to R 34 of X 3 alkyl having 1 to 10 carbon atoms, aryl having 6 to 12 ring-forming carbon atoms, and 1 to 10 carbon atoms
  • alkyl fluorides are exemplified by the same groups as those represented by R 3 in the general formula (UN11).
  • a method for producing a resin obtained by a polymer reaction has a step of performing a polymer reaction of the resin composition by heating the resin composition according to the present embodiment, which will be described later.
  • Components of the resin composition for polymer reaction include, for example, components exemplified as (i), (ii) and (iii) in the resin composition according to the present embodiment described below.
  • the heating temperature may be determined according to the desired properties, application, and the like.
  • the heating temperature for polymer reaction is, for example, 60° C. or higher and 250° C. or lower.
  • the method for producing a resin obtained by a polymer reaction includes the step of applying a coating composition described below to an object by a wet molding method, and heating to remove the organic solvent in the coating composition. and a step of performing a polymer reaction of the resin composition in the coating liquid composition by heating simultaneously with or subsequently to the heating in the step of removing the organic solvent. .
  • the method for producing a resin obtained by a polymer reaction may be a method in which a resin is previously modified by a polymer reaction and a molded body is obtained using the obtained resin.
  • a polymer (a polycarbonate polymer, specifically an aromatic polycarbonate) having two or more structures represented by the general formula (FR1) in the polymer chain is taken as an example. to explain.
  • a first form of a polycarbonate polymer (hereinafter also referred to as a PC polymer) according to the present embodiment includes a repeating unit A represented by the following general formula (1) and a repeating unit represented by the following general formula (2)
  • Ar 33 is a divalent benzene ring residue in the group represented by the general formula (FR1), and n 31 represents the average number of monomers. . In addition, the average polymer number n31 is 1.0 or more and 10 or less.
  • Ar 34 is a group represented by the general formula (UN11), and n 32 represents the average number of monomers. In addition, the average polymer number n32 is 1.0 or more and 10 or less.
  • Ar 33 is a divalent benzene ring residue in the group represented by the general formula (FR1), and Ar 34 is a group represented by the general formula (UN11). be.
  • n33 and n34 each represent the average number of monomers.
  • the sum of the average polymer numbers n33 and n34 is 1.0 or more and 10 or less.
  • * indicates a bonding position.
  • Ar 33 and Ar 34 are different from each other.
  • each repeating unit does not necessarily have to be continuous. Examples of the method for calculating the average number of monomers include the method described in Examples described later.
  • the divalent benzene ring residue in the group represented by general formula (FR1) is represented by general formula (FR1A) below.
  • R and n of the group represented by (R)n are the same as R and n of the group represented by (R)n of general formula (FR1).
  • Such a PC polymer has a repeating unit A containing a group represented by the general formula (FR1) having a specific furan structure, and thus has a high molecular weight polymer having two or more conjugated diene structures in the polymer chain. become a molecule.
  • FR1 general formula (FR1) having a specific furan structure
  • the PC polymer having units B those represented by the following general formula (100) are preferable. That is, an aromatic polycarbonate having a repeating unit of the repeating unit A alone represented by the general formula (1), a repeating unit A represented by the general formula (1), and a repeating unit A represented by the general formula (2) and a repeating unit B, preferably a polymer represented by the following general formula (100).
  • Ar 33 is a divalent benzene ring residue in the group represented by the general formula (FR1)
  • Ar 34 is the general It is a group represented by the formula (UN11).
  • a represents the molar copolymer weight ratio in the repeating unit A
  • b represents the molar copolymer weight ratio in the repeating unit B.
  • a is [Ar 33 ]/([Ar 33 ]+[Ar 34 ])
  • b is [Ar 34 ]/([Ar 33 ]+[Ar 34 ])
  • b is 0 include.
  • [Ar 33 ] represents the number of moles of the repeating unit A containing the group represented by Ar 33 in the PC polymer
  • [Ar 34 ] represents the repeating unit containing the group represented by Ar 34 in the PC polymer. Represents the number of moles of unit B.
  • each repeating unit is not necessarily continuous.
  • the PC polymer represented by the general formula (100) may be any of block copolymers, alternating copolymers, random copolymers, and the like.
  • the chain end of the PC polymer according to the present embodiment is capped with a monovalent aromatic group or a monovalent fluorine-containing aliphatic group, in addition to the above-mentioned specific terminal groups, within a range that satisfies the requirements of the present application. is preferred.
  • a monovalent aromatic group may be a group containing an aliphatic group.
  • a monovalent fluorine-containing aliphatic group may be a group containing an aromatic group. At least one substituent selected from the group consisting of an alkyl group, a halogen atom, and an aryl group may be added to the monovalent aromatic group and the monovalent fluorine-containing aliphatic group.
  • substituents may further have at least one substituent selected from the group consisting of an alkyl group, a halogen atom and an aryl group. Moreover, 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 6 to 12 ring carbon atoms.
  • aryl groups include phenyl groups and biphenyl groups.
  • substituent added to the aromatic group and the substituent added to the alkyl group attached to the aromatic group include halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom.
  • a C1-C20 alkyl group is mentioned as a substituent added to an aromatic group. This alkyl group may be a group to which a halogen atom is added as described above, or may be a group to which an aryl group is added.
  • the monovalent fluorine-containing aliphatic group constituting the chain end includes a monovalent group derived from a fluorine-containing alcohol.
  • fluorine-containing alcohol those having 13 to 19 total fluorine atoms in which a plurality of fluoroalkyl chains having 2 to 6 carbon atoms are linked via ether bonds are preferred. If the total number of fluorine atoms is 13 or more, sufficient water repellency and oil repellency can be exhibited. On the other hand, if the total number of fluorine atoms is 19 or less, the decrease in reactivity during polymerization can be suppressed, and at least one of the mechanical strength, surface hardness, heat resistance, etc. of the resulting PC polymer can be improved. .
  • the monovalent fluorine-containing aliphatic group a monovalent group derived from a fluorine-containing alcohol having two or more ether bonds is also preferable.
  • a fluorine-containing alcohol By using such a fluorine-containing alcohol, the dispersibility of the PC polymer in the coating liquid composition is improved, the abrasion resistance of the molded article and the electrophotographic photosensitive member is improved, and the surface lubricity and repellency after abrasion are improved. Able to retain water and oil repellency.
  • fluorine-containing alcohols include fluorine-containing alcohols represented by the following general formula (30) or (31), fluorine-containing alcohols such as 1,1,1,3,3,3-hexafluoro-2-propanol, Alternatively, a fluorine-containing alcohol via an ether bond represented by the following general formula (32), (33), or (34) is also preferred.
  • n1 is an integer of 1 to 12
  • m1 is an integer of 1 to 12.
  • n31 is an integer of 1 to 10, preferably an integer of 5 to 8.
  • n32 is an integer of 0 to 5, preferably an integer of 0 to 3.
  • n33 is an integer of 1-5, preferably an integer of 1-3.
  • n34 is an integer of 1 to 5, preferably an integer of 1 to 3.
  • n35 is an integer from 0 to 5, preferably from 0 to 3; R is CF3 or F;
  • the chain end of the PC polymer is a monovalent group derived from phenol represented by the following general formula (35) or ) is preferably capped with a monovalent group derived from a fluorine-containing alcohol represented by
  • R 30 represents an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group having 1 to 10 carbon atoms
  • p is an integer of 1 to 3.
  • R f is 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). show.
  • R f2 is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms.
  • mx is an integer from 1 to 3;
  • the bischloroformate oligomer compound represented by the general formula (1A) and the bischloroformate oligomer represented by the general formula (2A) At least one of the compounds, an organic solvent, an alkaline aqueous solution, and a monomer such as a bisphenol compound are used, and an organic layer and an aqueous layer are mixed to perform an interfacial polycondensation reaction.
  • a monohydric carboxylic acid and its derivatives, a monohydric phenol, and the like can be used as a terminal blocking agent for generating chain ends.
  • a fluorine-containing alcohol represented by the general formula (30) or (31), or 1,1,1,3,3,3-hexafluoro-2-propanol, etc. as a terminal blocking agent that generates a chain terminal.
  • a monovalent fluorine-containing alcohol of is also preferably used. It is also preferable to use a fluorine-containing alcohol via an ether bond represented by the general formula (32), (33), or (34) as a terminal blocking agent that generates a chain terminal.
  • the terminal blocking agent that generates chain ends may be a monohydric phenol represented by the general formula (35) or the general formula (36). It is preferred to use the represented monohydric fluorine-containing alcohols.
  • Examples of the monohydric phenol represented by the general formula (35) include p-tert-butyl-phenol, p-perfluorononylphenol, p-perfluorohexylphenol, p-tert-perfluorobutylphenol, p- Perfluorooctylphenol and the like are preferably used.
  • the chain end is the group consisting of p-tert-butyl-phenol, p-perfluorononylphenol, p-perfluorohexylphenol, p-tert-perfluorobutylphenol, and p-perfluorooctylphenol. It is preferable that it is blocked with a terminal blocking agent selected from.
  • Examples of the fluorine-containing alcohol via an ether bond represented by the general formula (36) include the following compounds. That is, the chain end of the present embodiment is also preferably capped with a terminal capping agent selected from any one of the following fluorine-containing alcohols.
  • the appropriate proportion of the terminal blocker to be added differs depending on whether the Diels-Alder reactive functional group (conjugated diene or dienophile) is at the end or on the main chain or side chain.
  • the concentration of the crosslinkable reactive group and the molecular weight change in conjunction with the fraction of the terminal.
  • the molar percentage of the diene or dienophile terminal group copolymer composition relative to the sum 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 %. It is more than 50 mol% or less.
  • the addition ratio of the end 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 the properties by cross-linking can be obtained.
  • the molar percentage of the copolymer composition of the chain terminal with respect to the total repeating units of the main chain and terminal is preferably 0.05 mol % or more and 40 mol % or less, more preferably is 0.1 mol % or more and 20 mol % or less.
  • the addition ratio of the end blocking agent is 40 mol% or less, the decrease in mechanical strength can be suppressed, and when it is 0.05 mol% or more, the decrease in moldability can be suppressed.
  • the branching agent that can be used in the method for producing a PC polymer according to the present embodiment is not particularly limited, but 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]propane, 2,4-bis[2-bis(4-hydroxyphenyl)- 2-propy
  • the addition ratio of these branching agents is 30 mol % or less in terms of molar percentage of the copolymer composition of the repeating unit A, the repeating unit B and the chain end, or the molar percentage of the copolymer composition of the repeating unit A and the chain end. preferably 5 mol % or less.
  • the addition ratio of the branching agent is 30 mol % or less, deterioration of moldability can be suppressed.
  • examples of acid binders include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, alkaline earth metals such as magnesium hydroxide and calcium hydroxide.
  • Preferred acid binders for interfacial polycondensation are alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, and alkaline earth metal hydroxides. These acid-binding agents can also be used as mixtures.
  • the ratio of the acid binding agent to be used may also be appropriately adjusted in consideration of the stoichiometric ratio (equivalents) of the reaction.
  • the acid binder may be used in an amount of 1 equivalent or more, preferably in an amount of 1 to 10 equivalents, per mol of the total hydroxyl groups of the raw material dihydric phenol. Just do it.
  • solvents include aromatic hydrocarbons such as toluene and xylene, methylene chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1 , 1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, halogenated hydrocarbons such as chlorobenzene, ketones such as cyclohexanone, acetone, acetophenone, tetrahydrofuran, 1,4-dioxane, etc. and the like are suitable examples. These solvents may be used singly or in combination of two or more. Furthermore, the interfacial polycondensation reaction
  • the organic solvent used in the method for producing a PC polymer according to the present embodiment it is preferable to use an organic solvent that is substantially immiscible with water and capable of dissolving 5% by mass or more of the finally obtained polycarbonate copolymer.
  • the organic solvent is preferably an organic solvent that is substantially immiscible with water and capable of dissolving 5 mass % or more of the finally obtained polycarbonate copolymer.
  • the organic solvent "substantially immiscible with water” means that when water and an organic solvent are mixed in a composition range of 1:9 to 9:1 under normal temperature and pressure conditions, a uniform layer to It is an organic solvent that does not give a clear solution (solution in which neither gelled matter nor insoluble matter is observed).
  • the organic solvent "capable of dissolving 5% by mass or more of the finally obtained polycarbonate copolymer” is the solubility of the polycarbonate copolymer when measured under conditions of a temperature of 20°C to 30°C and normal pressure.
  • the “finally obtained polycarbonate polymer” refers to a polymer obtained through the polymerization step in the method for producing a polycarbonate polymer of the present embodiment, and is before cross-linking.
  • organic solvents include aromatic hydrocarbons such as toluene, ketones such as cyclohexanone, and halogenated hydrocarbons such as methylene chloride. Among them, methylene chloride is preferred because of its high solubility.
  • the catalyst used in the method for producing a PC polymer of the present embodiment is not particularly limited, but examples include trimethylamine, triethylamine, tributylamine, N,N-dimethylcyclohexylamine, pyridine, N,N-diethylaniline, N , N-dimethylaniline and other tertiary amines; trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide and other quaternary ammonium salts; Quaternary phosphonium salts such as butylphosphonium chloride and tetrabutylphosphonium bromide are preferred. Furthermore, if necessary, a small amount of an antioxidant such as sodium sulfite or hydrosulfite salt may be added to the reaction
  • the method for producing a resin according to the present embodiment may have, for example, a polymerization step of polymerizing a resin using 2-(2-furanylmethyl)hydroquinone in the presence of an organic solvent and an alkaline aqueous solution.
  • the polymerization step may further use a bischloroformate oligomeric compound and may use a terminal capping agent. It is preferable to reduce the oxygen concentration in the polymerization step.
  • the alkaline aqueous solution in the polymerization step is preferably an alkaline aqueous solution containing a weak base.
  • the polymerization step may include a step of mixing an organic layer containing 2-(2-furanylmethyl)hydroquinone in an organic solvent with an alkaline aqueous solution.
  • the method for producing a resin according to this embodiment may have a washing step. Specifically, the method for producing the PC polymer includes the following methods.
  • the amount of oxygen in the reaction system is reduced during polymerization and, if necessary, washing, since the monomer is easily oxidized to a quinone structure.
  • the oxygen concentration is 1.0 mg/L or less, preferably 0.5 mg/L or less, more preferably 0.2 mg/L or less, and particularly preferably the reading value using the DO meter (dissolved oxygen meter) described in this example. is 0.1 mg/L or less, most preferably 0.05 mg/L or less.
  • the quinone structure is strongly alkaline and is remarkably generated in the presence of oxygen, it is also effective to replace the commonly used strong base such as sodium hydroxide with weak bases such as potassium carbonate and sodium carbonate. is.
  • quinone production can be suppressed by reducing the frequency of contact with alkali during polymerization.
  • the monomer is usually dissolved in an alkaline solution and polymerized.
  • 2-(2-furanylmethyl)hydroquinone comes into contact with the alkali only at the interface and is immediately consumed by the polymer elongation reaction, thereby preventing oxidation to quinone. can be effectively prevented.
  • the resin composition according to this embodiment includes the resin according to this embodiment described above. That is, the resin composition according to this embodiment contains a resin having a specific furan structure. Further, the resin composition according to the present embodiment includes a resin containing at least the structure represented by the general formula (FR1), and a compound containing a dienophile structure or a resin containing a dienophile structure.
  • the resin containing at least the structure represented by the general formula (FR1) is a polymer represented by the general formula (100) described above, and a compound containing a dienophile structure.
  • the resin containing the dienophile structure may contain the structure represented by the above general formula (DP2).
  • the resin composition according to the present embodiment may be one from which the aforementioned resin according to the present embodiment obtained by a polymer reaction can be produced by a polymer reaction. That is, the resin composition according to the present embodiment may contain a combination of a polymer having a specific furan structure with Diels-Alder reactivity and a dienophile group or a reactant having a dienophile structure. Moreover, the resin composition according to the present embodiment may contain a polymer having a specific furan structure and a dienophile structure with Diels-Alder reactivity. When one polymer has a specific furan structure and a dienophile structure, the dienophile structure in the molecule becomes a reactant having a dienophile structure.
  • the resin composition according to the present embodiment may contain a resin after polymer reaction between a polymer having a specific furan structure and a reactant having a dienophile structure.
  • the furan, the dienophile, and the ratio of the furan and the dienophile are the same as those of the resin according to the present embodiment.
  • the concentration of furan and dienophile in the resin composition according to the present embodiment can be appropriately set according to the target physical properties and intended use.
  • the functional group concentration is the number of moles of furan with respect to the total amount of the composition having a Diels-Alder reactive group
  • the functional group concentration is 0.01 mmol/g or more and 10 mmol/g or less. It is preferably 0.03 mmol/g or more and 7 mmol/g or less, more preferably 0.1 mmol/g or more and 5 mmol/g or less, and 0.3 mmol/g or more and 5 mmol/g or less. 0.5 mmol/g or more and 2 mmol/g or less is particularly preferable.
  • the functional group concentration is less than 0.01 mmol/g, the modification effect by polymer reaction may be insufficient. If the functional group concentration exceeds 10 mmol/g, the furan structure density is too high and unreacted functional groups tend to remain, and polymer reactions and other side reactions progress over time, resulting in changes in the physical properties of the material. It is not preferable because it is easy to deteriorate.
  • Examples of the resin composition according to the present embodiment include the following components.
  • the resin composition according to the present embodiment contains any component selected from (i), (ii), and (iii) shown above, the resin composition according to the present embodiment is at room temperature. It has the characteristic of little change in properties because the polymer reaction hardly occurs at a low temperature (for example, 25° C.).
  • a polymer having a structure represented by the general formula (FR1) in the polymer chain and both the structure represented by the general formula (FR1) and the dienophile structure in one polymer chain
  • the polymer having the structure preferably has a structure represented by general formula (FR1) in the main chain of the polymer chain.
  • the number of structures represented by the general formula (FR1) present in the main chain of the polymer and the number of dienophile groups present in the compound having a dienophile structure are both preferably 1 or more.
  • the composition containing the component (ii) in the polymer having one or more structures represented by the general formula (FR1), at least one end and the other end of the polymer chain At least one of one end and the other end of the polymer chain in a polymer having a dienophile structure and having no structure represented by the general formula (FR1) bonded to either end A dienophile structure may not be bonded to the terminal of the polymer chain, and the structure represented by the general formula (FR1) and the dienophile structure may not be bonded to the terminal of the polymer chain.
  • the total number of structures represented by the general formula (FR1) present in the main chain of the polymer, the main chain of the polymer having a dienophile structure, and the number of dienophile groups present at the ends are all It is preferably 1 or more.
  • bonds between polymer chains that can be formed by reacting the composition containing the component (ii) can be formed, for example, by the following combination reactions.
  • (ii-1) a polymer having a dienophile structure, the polymer having at least one dienophile structure at the end of the polymer chain; Reaction with a polymer having one or more structures represented by the general formula (FR1) in the polymer chain.
  • (ii-2) a polymer having a dienophile structure, the polymer having a dienophile structure at the terminal and main chain of the polymer chain; Reaction with a polymer having one or more structures represented by the general formula (FR1) in the polymer chain.
  • the coating liquid composition according to this embodiment contains the resin composition according to this embodiment and an organic solvent. That is, the coating liquid composition according to this embodiment contains the resin according to this embodiment and an organic solvent.
  • the polymer reaction does not easily occur at a low temperature of about room temperature (for example, 25 ° C.), so the characteristics change. It is characterized by less
  • organic solvent considering the solubility of the material such as the resin composition, the drying speed after molding, the influence when it remains on the molded product, and the danger (fire or health hazard), It can be selected as appropriate.
  • organic solvents according to the present embodiment include cyclic ethers (tetrahydrofuran (THF), dioxane, dioxolane, etc.), cyclic ketones (cyclohexanone, cyclopentanone, cycloheptanone, etc.), aromatic hydrocarbons (toluene , xylene, and chlorobenzene), ketones (such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK)), halogenated hydrocarbons (such as dichloromethane and chloroform), esters (ethyl acetate, isopropyl acetate, isobutyl acetate, etc.).
  • THF tetrahydrofuran
  • ethers such as ethylene glycol dimethyl ether and ethylene glycol monoethyl ether
  • amides such as dimethyl fumarate (DMF) and dimethylacetamide (DMAc)
  • aprotic polar solvents such as dimethyl sulfoxide (DMSO), etc.
  • the concentration of the resin composition according to this embodiment in the coating composition according to this embodiment may be a concentration that provides an appropriate viscosity according to the usage of the coating composition, and is 0.1 mass. % or more and 40 mass % or less, more preferably 1 mass % or more and 35 mass % or less, and even more preferably 5 mass % or more and 30 mass % or less. If the content is 40% by mass or less, the viscosity does not become too high and the coatability is improved. If it is 0.1% by mass or more, the viscosity can be maintained at an appropriate level, and a homogeneous film can be obtained. Moreover, if it is 0.1% by mass or more, the concentration is appropriate for shortening the drying time after coating and for easily achieving the target film thickness.
  • the coating liquid composition may contain additives other than the resin composition and the organic solvent according to the present embodiment.
  • Additives include, for example, low-molecular-weight compounds, colorants (e.g., dyes and pigments), functional compounds (e.g., charge-transporting materials, electron-transporting materials, hole-transporting materials, charge-generating materials, etc.), fillers, Materials (eg, inorganic or organic fillers, fibers, cloth, fine particles, etc.), antioxidants, UV absorbers, acid scavengers, and the like.
  • the coating liquid composition may contain other resins 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.
  • the ratio of the resin composition and the charge transport substance in the coating composition according to the present embodiment is in the range of 20:80 to 80:20 in mass ratio from the viewpoint of product performance. and more preferably in the range of 30:70 to 70:30.
  • the resin composition according to this embodiment may be used singly or in combination of two or more.
  • the coating liquid composition according to the present embodiment is usually suitably used for forming a photosensitive layer of a laminated electrophotographic photoreceptor.
  • the photosensitive layer of the laminated electrophotographic photoreceptor preferably includes at least a charge generation layer and a charge transport layer, and the coating composition according to the present embodiment is suitably used for forming the charge transport layer.
  • the coating liquid composition according to the present embodiment can be used for forming a photosensitive layer of a single-layer electrophotographic photoreceptor by further containing the above-mentioned charge-generating substance. It can also be used for forming a protective layer of a photoreceptor.
  • the resin according to the present embodiment is a resin having polymer reactivity, for example, PCs that polymerize by Diels-Alder reaction have excellent solution stability and react at the current photoreceptor manufacturing process temperature, The obtained resin has excellent abrasion resistance and no deterioration in electrical properties is observed.
  • the resin according to the present embodiment does not contain a radical initiator or a reaction catalyst, and can be polymerized without using ultraviolet rays or electron beams, deterioration of electrical properties is suppressed. , the deterioration of the charge transport material (CTM) is suppressed.
  • a molded article according to the present embodiment includes the resin according to the present embodiment.
  • the molded article according to the present embodiment can be used for various applications other than the electrophotographic photoreceptor described below. For example, it can be suitably used for applications such as substrates for electronic devices, insulating layers, protective layers, adhesive layers, conductive layers, and structural materials. 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 the present embodiment.
  • the resin containing at least the structure represented by the general formula (FR1) and the compound containing the dienophile structure or the resin containing the dienophile structure are formed in the same layer. may be included or may be included in different layers.
  • the resin represented by the general formula (FR1) and the compound containing the dienophile structure or the resin containing the dienophile structure are contained in different layers, the resin represented by the general formula (FR1)
  • the resin containing at least the structure and the compound containing the dienophile structure or the resin containing the dienophile structure may be contained in adjacent layers.
  • the film containing the resin according to this embodiment is a resin body formed from the resin according to this embodiment, and refers to a resin body having a thickness smaller than its length and width.
  • the film according to this embodiment is a resin body formed by applying the coating composition according to this embodiment to an object and peeling it off from the object
  • this resin body is a film.
  • a coating film containing a resin according to this embodiment refers to a layer formed by coating an object with the coating composition according to this embodiment. Generally, the coating film remains intact on the object and forms part of the finished product.
  • the molded product according to this embodiment can be produced using the resin composition according to this embodiment.
  • the molding method either a wet molding method or a melt molding method can be applied.
  • a method of molding at a temperature at which the polymer reaction proceeds (i) a method of molding at a temperature at which the polymer reaction proceeds, (ii) after obtaining a wet molded product at a temperature at which the polymer reaction does not substantially proceed, a solvent (iii) wet molding at a temperature at which the polymer reaction does not substantially proceed, and drying to form a dry molded product.
  • a method can be employed in which the temperature of the molded product is raised to a temperature at which the polymer reaction proceeds to carry out the polymer reaction. Any of these methods may be used.
  • the same resin may be used to prepare a coating liquid to obtain a molding.
  • the coating liquid composition according to the present embodiment described above can be used.
  • the temperature of the polymer reaction can be set appropriately according to the target physical properties and intended use.
  • the cross-linking method may be set by adjusting the type of functional groups to be reacted with the polymer, the proportion of furan and dienophile, the concentration of functional groups, etc., according to this reaction temperature.
  • the polymer reaction temperature for an electrophotographic photoreceptor is preferably a temperature at which the polymer reaction is carried out in the drying process after obtaining a wet molded product by wet molding, and the temperature is such that the functional low-molecular-weight compound does not deteriorate. is required to be done in
  • the temperature of the polymer reaction for the electrophotographic photoreceptor is preferably 60° C. or higher and 170° C. or lower, more preferably 80° C. or higher and 160° C. or lower, and 100° C. or higher and 150° C. or lower. More preferred.
  • the polymer reaction temperature for the electrophotographic photoreceptor may be 105° C. or higher and 140° C. or lower, or 110° C.
  • reaction temperature exceeds 170° C., the functional low-molecular-weight compound such as the charge-transporting substance may deteriorate. If the reaction temperature is less than 60°C, the drying may not proceed sufficiently or may require a long time, which is not preferable.
  • the reaction temperature for electronic devices is preferably 60° C. or higher and 250° C. or lower, and more preferably 100° C. or higher and 200° C. or lower. More preferably, the temperature is 110°C or higher and 180°C or lower. Under conditions where the reaction temperature exceeds 250° C., failure of electronic components and decomposition of other organic materials may occur. If the reaction temperature is less than 60°C, the polymer reaction does not proceed sufficiently, and the viscosity of the coating liquid composition increases due to the progress of the reaction in some of the materials that react at such low temperatures. Liquid stability may be a problem.
  • the polymer reaction of the resin composition can be carried out without adding a catalyst, a polymerization initiator, or the like.
  • substances such as catalysts and polymerization initiators may be added for the purpose of combined use with other polymer reaction systems as long as the effects of the present embodiment are not impaired.
  • the electrophotographic photoreceptor according to this embodiment has a layer containing the resin according to this embodiment.
  • the resin according to this exemplary embodiment is preferably included in the outermost layer of the electrophotographic photoreceptor according to this exemplary embodiment.
  • the electrophotographic photoreceptor according to this embodiment has a substrate and a photosensitive layer provided on this substrate, and this photosensitive layer contains the resin according to this embodiment.
  • the electrophotographic photoreceptor of the present embodiment may be any electrophotographic photoreceptor, including various types of known electrophotographic photoreceptors, as long as the resin of the present embodiment is used in the photosensitive layer.
  • the resin according to this embodiment may be used in any part of the photosensitive layer. Alternatively, it is desirable to use it as a binder resin for a single photosensitive layer. Moreover, it is desirable to use it not only as a photosensitive layer but also as a surface protective layer. In the case of a multi-layered electrophotographic photoreceptor having two charge transport layers, it is preferably used in one of the charge transport layers. In the electrophotographic photoreceptor of this embodiment, the resins according to this embodiment may be used singly or in combination of two or more. Further, if desired, other binder resin components such as polycarbonate may be contained within a range not impairing the purpose of the present embodiment. Furthermore, additives such as antioxidants may be included.
  • the electrophotographic photoreceptor of this embodiment has a photosensitive layer on a conductive substrate.
  • 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.
  • It may also be a photosensitive layer containing both a charge-generating substance and a charge-transporting substance in one layer.
  • a conductive or insulating protective film may be formed on the surface layer as required.
  • the conductive substrate material used in the electrophotographic photoreceptor of the present embodiment various materials such as known materials can be used. Specifically, aluminum, nickel, chromium, palladium, titanium, molybdenum, indium , gold, platinum, silver, copper, zinc, brass, stainless steel, lead oxide, tin oxide, indium oxide, ITO (indium tin oxide: tin-doped indium oxide) or graphite, plates, drums and sheets, vapour-deposited, Films, sheets, or seamless belts of glass, cloth, paper, and plastic that are conductively treated by coating by sputtering or coating, and metal drums that are metal-oxidized by electrode oxidation or the like can be used.
  • the charge generation layer has at least a charge generation material.
  • This charge-generating layer is formed by forming a layer of a charge-generating material on the underlying substrate by vacuum deposition, sputtering, or the like, or by binding the charge-generating material onto the underlying substrate using a binder resin. can be obtained by forming different layers.
  • a method for forming the charge generation layer using a binder resin various methods such as known methods can be used. Usually, for example, a method of applying a coating composition in which a charge-generating material is dispersed or dissolved in an appropriate solvent together with a binder resin onto a substrate serving as a predetermined base and drying to obtain a wet molded body is suitable.
  • Various known materials can be used as the charge generation material in the charge generation layer.
  • Specific compounds include simple selenium (eg, amorphous selenium, trigonal selenium, etc.), selenium alloys (eg, selenium-tellurium, etc.), selenium compounds or selenium-containing compositions (eg, As2Se3 , etc.).
  • inorganic materials consisting of elements of groups 12 and 16 of the periodic table (e.g., zinc oxide, CdS—Se, etc.), oxide semiconductors (e.g., titanium oxide, etc.), silicon-based materials (e.g., amorphous silicon etc.), metal-free phthalocyanine pigments (e.g., ⁇ -type metal-free phthalocyanine, ⁇ -type metal-free phthalocyanine, etc.), metal phthalocyanine pigments (e.g., ⁇ -type copper phthalocyanine, ⁇ -type copper phthalocyanine, ⁇ -type copper phthalocyanine, ⁇ -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 phthalo
  • the charge transport layer can be obtained as a wet molded article by forming a layer formed by binding a charge transport material with a binder resin on a substrate serving as a base.
  • the binder resin in at least one of the charge generation layer and the charge transport layer is not particularly limited, and various known resins can be used.
  • the charge transport layer As a method for forming the charge transport layer, various known methods can be used. A preferred method is to coat it on a base substrate and dry it to obtain a wet molded product.
  • the blending ratio of the charge-transporting substance and the PC polymer (charge-transporting substance:PC polymer) used for forming the charge-transporting layer is preferably in the range of 20:80 to 80:20, more preferably 30:20 by weight. It ranges from 70 to 70:30.
  • the PC polymer of this embodiment can be used singly or in combination of two or more.
  • other binder resins can be used in combination with the PC polymer of the present embodiment within a range that does not hinder the object of the present invention.
  • the thickness of the charge transport layer thus formed is usually about 5 ⁇ m to 100 ⁇ m, preferably 10 ⁇ m to 50 ⁇ m, more preferably 15 ⁇ m to 40 ⁇ m. When the thickness is 5 ⁇ m or more, the initial potential does not decrease, and when the thickness is 100 ⁇ m or less, deterioration of electrophotographic properties can be prevented.
  • Various known compounds can be used as the charge transport material that can be used together with the PC polymer of the present embodiment.
  • 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, and aliphatic amine compounds.
  • the resin composition according to the present embodiment as a binder resin for at least one of the charge generation layer, the charge transport layer, and the surface protective layer.
  • a commonly used undercoat layer can be provided between the conductive substrate and the photosensitive layer.
  • the undercoat layer include fine particles (e.g., titanium oxide, aluminum oxide, zirconia, titanate, zirconate, lanthanum lead, titanium black, silica, lead titanate, barium titanate, tin oxide, indium oxide, and silicon oxide, etc.), polyamide resins, phenolic resins, casein, melamine resins, benzoguanamine resins, polyurethane resins, epoxy resins, cellulose, nitrocellulose, polyvinyl alcohol, and polyvinyl butyral resins.
  • fine particles e.g., titanium oxide, aluminum oxide, zirconia, titanate, zirconate, lanthanum lead, titanium black, silica, lead titanate, barium titanate, tin oxide, indium oxide, and silicon oxide, etc.
  • polyamide resins e.g., phenolic resins, casein, melamine resins, benzoguanamine
  • the binder resin may be used, or the resin composition according to the present embodiment may be used.
  • These fine particles and resins can be used alone or in various mixtures. In the case of using a mixture of these, it is preferable to use the inorganic fine particles and the resin in combination, since a film with good smoothness is formed.
  • the thickness of the undercoat layer is 0.01 ⁇ m or more and 10 ⁇ m or less, preferably 0.1 ⁇ m or more and 7 ⁇ m or less.
  • the undercoat layer can be uniformly formed, and when the thickness is 10 ⁇ m or less, deterioration of electrophotographic properties can be suppressed.
  • a conventionally used blocking layer can be provided between the conductive substrate and the photosensitive layer.
  • This blocking layer the same kind of resin as the binder resin can be used.
  • the thickness of this blocking layer is 0.01 ⁇ m or more and 20 ⁇ m or less, preferably 0.1 ⁇ m or more and 10 ⁇ m or less. When the thickness is 0.01 ⁇ m or more, the blocking layer can be uniformly formed, and when the thickness is 20 ⁇ m or less, deterioration of electrophotographic properties can be suppressed.
  • a protective layer may be laminated on the photosensitive layer.
  • the same kind of resin as the binder resin can be used for this protective layer.
  • the thickness of this protective layer is 0.01 ⁇ m or more and 20 ⁇ m or less, preferably 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the protective layer contains conductive materials such as the charge generating substance, charge transporting substance, additives, metals and their oxides, nitrides or salts, alloys, carbon black, and organic conductive compounds. may be
  • the charge generation layer and the charge transport layer may contain a binder, a plasticizer, a curing catalyst, a fluidity imparting agent, and a pinhole, as long as the effects of the present invention are not lost.
  • a control agent, a spectral sensitivity sensitizer (sensitizing dye), and the like may be added.
  • various chemical substances, antioxidants, surfactants, anti-curling agents, leveling agents, etc. are added for the purpose of preventing an increase in residual potential, a decrease in charging potential, and a decrease in sensitivity due to repeated use. agents can be added.
  • binder examples 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, and melamine.
  • resins benzoguanamine resins, polychloroprene resins, polyacrylonitrile resins, ethylcellulose resins, nitrocellulose resins, urea resins, phenolic resins, phenoxy resins, polyvinyl butyral resins, formal resins, vinyl acetate resins, vinyl acetate/vinyl chloride copolymer resins, and Examples include polyester carbonate resins.
  • a thermosetting resin and a photosetting resin can also be used.
  • the resin is electrically insulating and capable of forming a film under normal conditions, and is not particularly limited as long as it does not impair the effects of the present embodiment.
  • plasticizer examples include biphenyl, biphenyl chloride, o-terphenyl, halogenated paraffin, dimethylnaphthalene, dimethylphthalate, dibutylphthalate, dioctylphthalate, diethyleneglycol phthalate, triphenylphosphate, diisobutyladipate, dimethylseba cate, dibutyl sebacate, butyl laurate, methylphthalylethyl glycolate, dimethylglycol phthalate, methylnaphthalene, benzophenone, polypropylene, polystyrene, and fluorohydrocarbons.
  • the curing catalyst include methanesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid, and the like.
  • Fluidity imparting agents include Modaflow and Acronal 4F.
  • Pinhole control agents include, for example, benzoin and dimethylphthalate. These plasticizers, curing catalysts, fluidity imparting agents, and pinhole control agents are preferably used in an amount of 5% by mass or less with respect to the charge transporting substance within a range that does not impair the effects of the present invention.
  • a sensitizing dye when used as a spectral sensitivity sensitizer, examples include 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 frapeocin), thiazine dyes (such as methylene blue and methylene green), oxazine dyes (such as capri blue and meldora blue), cyanine dyes, merocyanine dyes, styryl dyes, Pyrylium salt dyes, as well as thiopyrylium salt dyes and the like are suitable.
  • triphenylmethane dyes e.g., methyl violet, crystal violet, night blue, and Victoria blue
  • acridine dyes e.g., erythrosine , rhodamine B, rh
  • An electron-accepting substance can be added to the photosensitive layer for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use, 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 chlor imido, chloranil, bromanyl, benzoquinone, 2,3-dichlorobenzoquinone, dichlorodicyano-parabenzo
  • tetrafluoroethylene resin In order to improve surface properties, tetrafluoroethylene resin, trifluoroethylene chloride resin, tetrafluoroethylene hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluoride dichloride resin and Copolymers thereof, fluorine-based graft polymers, and the like may be used as long as the effects of the present invention are not lost.
  • the mixing ratio of these surface modifiers to the binder resin is 0.1% by mass or more and 60% by mass or less, preferably 5% by mass or more and 40% by mass or less, as long as the effects of the present invention are not lost. When the blending ratio is 0.1% by mass or more, surface modification such as reduction in surface durability and surface energy is sufficient.
  • 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 generally 0.01% by mass or more and 10% by mass or less, preferably 0.1% by mass or more and 2% by mass, based on the charge transporting substance within a range that does not impair the effects of the present invention. It is below.
  • compounds represented by general chemical formulas [Chemical 94] to [Chemical 101] described in the specification of JP-A-11-172003 are suitable. These antioxidants may be used singly or in combination of two or more. They are added to the surface protective layer, undercoat layer and blocking layer in addition to the photosensitive layer. may
  • 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, chlorobenzene, etc.), ketones (e.g., acetone, methyl ethyl ketone, cyclohexanone, etc.), alcohols (e.g., methanol, ethanol, isopropanol, etc.), esters (e.g., ethyl acetate, ethyl cellosolve, etc.), halogenated hydrocarbons (e.g., carbon tetrachloride, carbon tetrabromide, etc.) , chloroform, dichloromethane, tetrachloroethane, etc.), ethers (e.g., tetrahydrofuran, dioxolane, dioxane, etc.), sulfoxides (e.g., dimethylsulfoxide (
  • the photosensitive layer of the single-layer electrophotographic photoreceptor can be easily formed by using the charge-generating substance, the charge-transporting substance, and the additive, and applying the resin composition according to the present embodiment as a binder resin. can. At least one of the aforementioned hole-transporting substance and electron-transporting substance is preferably added as the charge-transporting substance.
  • As the electron transport material electron transport materials exemplified in JP-A-2005-139339 can be preferably applied.
  • Application of each layer can be performed using various coating devices such as known devices, and specific examples include applicators, spray coaters, bar coaters, chip coaters, roll coaters, dip coaters, and doctor blades. can be done.
  • the thickness of the photosensitive layer in the electrophotographic photoreceptor is 5 ⁇ m or more and 100 ⁇ m or less, preferably 8 ⁇ m or more and 50 ⁇ m or less. It is possible to suppress deterioration of photographic properties.
  • the ratio of the charge-generating substance to the resin composition used in the production of the electrophotographic photoreceptor is preferably in the range of 20:80 to 80:20, more preferably in the range of 30:70 to 70:30. is more preferred.
  • the electrophotographic photoreceptor obtained in this manner has, as a binder resin, a resin modified by a polymer reaction consisting of the resin composition according to the present embodiment in the photosensitive layer, and thus has properties such as durability. It is a photoreceptor that has excellent electrical properties (electrophotographic properties) and maintains excellent electrophotographic properties over a long period of time. Electrophotographic photoreceptors are used in various electronic devices such as copiers (monochrome, multicolor, full color, analog, digital), printers (laser, LED, liquid crystal shutter), facsimiles, plate-making machines, and devices with multiple functions. Suitable for use in the field of photography.
  • the method for producing an electrophotographic photoreceptor according to the present embodiment includes the steps of applying the coating composition according to the present embodiment to a conductive substrate by a wet molding method, and heating the coating composition.
  • a method comprising a step of removing the organic solvent, and a step of performing a polymer reaction of the resin composition in the coating liquid composition by heating simultaneously with or following the heating in the step of removing the organic solvent. is.
  • the coating thickness of the coating composition can be appropriately set according to the thickness of the photosensitive layer of the electrophotographic photoreceptor according to this embodiment.
  • the step of removing the organic solvent it can be appropriately set according to the type of the organic solvent in the coating composition according to the present embodiment.
  • the heating temperature is the same as the reaction temperature for the electrophotographic photoreceptor in the molded article according to the present embodiment.
  • Air calibration was performed using a DO meter MODEL B-506 manufactured by Iijima Denshi Kogyo Co., Ltd. and Wagnit (WA-BRP) as a probe. After that, an aqueous solution prepared by dissolving 25 g of sodium sulfite in 500 mL of ion-exchanged water was performed as zero point calibration, and then the read value in the DO measurement mode was taken as the oxygen concentration. (Oxygen concentrations in the gas phase, methylene chloride layer, and water layer were determined by the above method.)
  • the organic layer was washed once with a 2N—HCl aqueous solution and three times with deionized water, and the organic layer was separated, dried over Na 2 SO 4 , filtered, and concentrated to obtain 280 g of an oily compound. rice field.
  • the average number of monomers (n X ) of the bischloroformate compound represented by the following general formula (X1) was obtained using the following formula (Equation 1).
  • Average number of mers (n X ) 1+(Mav ⁇ M1)/M2 (Equation 1)
  • Mav is (2 ⁇ 1000/(CF value))
  • M2 is (M1 ⁇ 98.92)
  • the CF value (N/kg) is (CF value/concentration)
  • the CF value (N) is contained in 1 L of the reaction solution in the following general formula (X1):
  • the number of chlorine atoms in the represented bischloroformate compound, and the concentration (kg/L) is the amount of solid content obtained by concentrating 1 L of the reaction solution, where 98.92 is bischloroformate.
  • Ar 1 X1 is a divalent group.
  • the divalent group represented by the following general formula (10) corresponds to Ar X1 .
  • a liquid obtained by dissolving 93.8 g (929 mmol) of triethylamine in 256 mL of methylene chloride was added dropwise thereto at a temperature in the range of 16°C to 19°C.
  • methylene chloride was distilled off to a predetermined concentration. 1100 mL of pure water, 2.4 g of concentrated hydrochloric acid, and 450 mg of hydrosulfite were added to the remaining liquid to wash.
  • the resulting reaction mixture was diluted with 200 mL of methylene chloride and 50 mL of water in which the oxygen concentration was reduced to 0.1 mg/L or less by nitrogen replacement separately in a nitrogen atmosphere, and washed.
  • the lower layer was separated and washed once with 100 mL of water, once with 100 mL of 0.03N hydrochloric acid, and three times with 100 mL of water in this order.
  • the resulting methylene chloride solution was added dropwise to methanol with stirring, and the obtained reprecipitate was filtered and dried to obtain a PC polymer (PC-1) having the following structure.
  • PC polymer (PC-1) was dissolved in methylene chloride to prepare a solution having a concentration of 0.5 g/dL.
  • VMR-042 an automatic viscometer
  • RM type automatic viscosity
  • the structure and composition of the obtained PC-1 were analyzed by peak integration values derived from each constituent monomer of the 1 H-NMR spectrum (manufactured by JEOL Ltd., nuclear magnetic resonance apparatus JNM-ECZ400S). It was confirmed to be a PC polymer consisting of units, number of repeating units, and composition.
  • FR1 is a structural unit represented by general formula (FR1).
  • the measurement conditions for the 1 H-NMR spectrum are as follows.
  • the furan group concentration is 0.81 mmol/g.
  • PC-2 PC polymer having the following structure was obtained in the same manner as in Synthesis Example 1 except that
  • PC-2 The PC polymer (PC-2) thus obtained was dissolved in methylene chloride to prepare a solution having a concentration of 0.5 g/dL, and the reduced viscosity [ ⁇ sp/C] at 20°C was measured. It was 1.19 dL/g.
  • the structure and composition of the obtained PC-2 were analyzed by 1 H-NMR spectrum, it was confirmed to be a PC polymer having the following repeating units, number of repeating units, and composition.
  • the measurement conditions for the 1 H-NMR spectrum are as described above.
  • the furan group concentration is 1.63 mmol/g.
  • Example A [Preparation of coating composition and resin film] 2 g of PC-1 was weighed into a sample tube with a screw cap and dissolved in 12 mL of dichloromethane to obtain a coating liquid composition. From this result, it was confirmed that a paint containing PC-1 and an organic solvent can be prepared. The resulting coating composition was cast onto a commercially available polyethylene terephthalate (PET) film having a thickness of 200 ⁇ m using an applicator with a gap of 250 ⁇ m.
  • PET polyethylene terephthalate
  • Example B1 [Preparation of Polymer Reactive Composition Film Consisting of Copolymer and Reactive Substance]
  • PC-1 (2 g: 1.62 mmol) and N-phenylmaleimide (0.28 g: maleimide group 1.62 mmol) were weighed into a sample tube with a screw cap and dissolved in 12 mL of dichloromethane to obtain a coating liquid composition.
  • the resulting coating composition was cast onto a commercially available polyethylene terephthalate (PET) film having a thickness of 200 ⁇ m using an applicator with a gap of 250 ⁇ m. After air-drying for 1 hour, it was treated at 50° C. for 16 hours in a vacuum dryer (degree of pressure reduction: 1 Pa to 100 Pa) to remove the solvent and obtain a resin film having a film thickness of 20 ⁇ m to 30 ⁇ m at the coated portion.
  • PET polyethylene terephthalate
  • FIG. 1 shows the 1 H-NMR spectrum chart of PC-1, which is the starting resin
  • FIG. 2 shows the 1 H-NMR spectrum chart of the polymer reactive composition.
  • the measurement conditions for the 1 H-NMR spectrum are as follows.
  • Example B2 [Preparation of polymer reactive composition film composed of copolymer and reactive substance] A polymer reactive composition film was produced in the same manner as in Example B1 except that PC-1 was changed to PC-2.
  • FIG. 3 shows a 1 H-NMR spectrum chart of PC-2, which is a starting resin
  • FIG. 4 shows a 1 H-NMR spectrum chart of the polymer reactive composition.
  • the measurement conditions for the 1 H-NMR spectrum are as follows.
  • Example C2 [Preparation of Coating Solution for Electrophotographic Photosensitive Layer Containing Copolymer and Reactive Substance, and Production of Laminated Electrophotographic Photoreceptor]
  • An electrophotographic photoreceptor was manufactured by using an aluminum plate having a thickness of 100 ⁇ m as a conductive substrate, and laminating a charge generation layer and a charge transport layer in order on the surface of the plate to form a laminated photosensitive layer.
  • 0.5 parts by mass of Y-type oxotitanium phthalocyanine was used as the charge-generating substance, and 0.5 parts by mass of butyral resin was used as the binder resin.
  • THF tetrahydrofuran
  • PC-2 (1 g: 1.63 mmol of furanyl group), N-phenylmaleimide (0.14 g: 1.62 mmol of maleimide group), and a charge transport substance having the following structure were used as a coating liquid composition for the charge transport layer.
  • CTM-1 (0.67 g)
  • the resulting coating composition was cast into a film on the charge generating layer obtained above using an applicator with a gap of 375 ⁇ m. After air-drying for 1 hour, it was treated in a vacuum dryer (degree of pressure reduction: 1 Pa to 100 Pa) at a temperature of 50°C for 16 hours to remove the solvent and obtain a resin film having a thickness of 30 ⁇ m at the coated portion.
  • PET polyethylene terephthalate
  • the film obtained above was treated in a vacuum dryer at a temperature of 150° C. for 1 hour, and the structural change before and after the treatment was confirmed by 1 H-NMR.
  • the measurement conditions for the 1 H-NMR spectrum are as follows.
  • Example C2-2 A coated film for abrasion test was obtained in the same manner as in Example C2 except that N-phenylmaleimide (0.14 g) was not used in the preparation of the charge transport layer composition coating solution used for the abrasion test.
  • the abrasion resistance of the obtained film and the same film which was further treated in a vacuum dryer at 150° C. for 1 hour was evaluated in the same manner as described above. Table 1 shows the results obtained.
  • Example 1 instead of PC-2 in Example C2, a solution having the following structure and a concentration of 0.5 g / dL was prepared, and a polycarbonate (PCA) having a reduced viscosity [ ⁇ sp / C] at 20 ° C. of 1.19 dL / g was used. A charge transport layer composition film was prepared and evaluated for abrasion resistance in the same manner as above. Table 1 shows the results obtained.
  • PCA polycarbonate
  • Example C2 (after heating at 150° C.), the amount of wear was 7% lower than in Example C2-2 (after heating at 150° C.). Further, in Example C2, the amount of wear was reduced by 25% due to the reaction of the polymer and the low-molecular weight compound by heating at 150° C., and it was confirmed that the wear resistance of the reactive resin is excellent. In addition, since the wear amount of Example C2-2 was 21% smaller than that of Comparative Example 1, it was confirmed that this resin is excellent in wear resistance. Further, structural changes before and after the heat treatment of the charge transport layer film obtained in Example C2 were confirmed by 1 H-NMR.

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JPH09319102A (ja) * 1996-05-28 1997-12-12 Idemitsu Kosan Co Ltd 電子写真感光体
WO2021201228A1 (ja) * 2020-04-01 2021-10-07 出光興産株式会社 樹脂、樹脂前駆体組成物、塗液組成物、電子写真感光体、成形物、電子デバイス、および電子写真感光体の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09319102A (ja) * 1996-05-28 1997-12-12 Idemitsu Kosan Co Ltd 電子写真感光体
WO2021201228A1 (ja) * 2020-04-01 2021-10-07 出光興産株式会社 樹脂、樹脂前駆体組成物、塗液組成物、電子写真感光体、成形物、電子デバイス、および電子写真感光体の製造方法

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