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WO2018116960A1 - Copolymère de polycarbonate, liquide de revêtement, corps photosensible électrophotographique, appareil électrophotographique, et procédé de production d'un copolymère de polycarbonate - Google Patents

Copolymère de polycarbonate, liquide de revêtement, corps photosensible électrophotographique, appareil électrophotographique, et procédé de production d'un copolymère de polycarbonate Download PDF

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Publication number
WO2018116960A1
WO2018116960A1 PCT/JP2017/044980 JP2017044980W WO2018116960A1 WO 2018116960 A1 WO2018116960 A1 WO 2018116960A1 JP 2017044980 W JP2017044980 W JP 2017044980W WO 2018116960 A1 WO2018116960 A1 WO 2018116960A1
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group
carbon atoms
general formula
substituted
polycarbonate copolymer
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PCT/JP2017/044980
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English (en)
Japanese (ja)
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賢吾 平田
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出光興産株式会社
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Publication of WO2018116960A1 publication Critical patent/WO2018116960A1/fr

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    • 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
    • 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
    • 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
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, 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 polycarbonate copolymer, a coating solution, an electrophotographic photosensitive member, an electrophotographic apparatus, and a method for producing a polycarbonate copolymer.
  • An example of a product utilizing the electrical and optical properties of polycarbonate resin is an electrophotographic photoreceptor using polycarbonate resin as a binder resin for functional materials such as charge generation materials and charge transport materials.
  • the electrophotographic photoreceptor is required to have predetermined sensitivity, electrical characteristics, and optical characteristics according to the electrophotographic process.
  • various operations for example, corona charging, toner development, transfer to paper, cleaning processing, etc.
  • a mechanical external force and / or a mechanical external force are applied. Therefore, in order to maintain the image quality of electrophotography 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.
  • a polycarbonate copolymer is known as an effective technique for improving the mechanical strength of the photosensitive layer.
  • a technique for producing a polycarbonate copolymer by copolymerizing a bisphenol Z skeleton having good solubility with a biphenol having good wear resistance is known.
  • Patent Document 1 discloses a polymer produced from a raw material with a reduced number of oligomers. The polymer of Patent Document 1 has been reported to improve the copolymerization ratio of a skeleton such as biphenol having good wear resistance to 25 to 47 mol%, and to improve the mechanical strength.
  • Resins with higher performance than conventional resins are required to meet these high durability needs. For example, resins that can improve the mechanical strength and electrical strength of electrophotographic photoreceptors are required. .
  • Patent Document 2 discloses a ternary aromatic copolymer polycarbonate containing a urethane group.
  • Urethane resin is originally composed of soft segments and hard segments. Flexibility is achieved by the balance between hard segments that are strongly agglomerated by the strong hydrogen bonds between the urethane groups, which are the bonding units, and flexible soft segments. , Combines toughness and elasticity. By utilizing this property and introducing urethane bonds into the polycarbonate resin, a three-dimensional network structure is formed by hydrogen bonds at the same time as the mechanical strength characteristic of the polycarbonate resin, and a highly hard crosslinked surface with a very high crosslinking density. It was believed that a layer was obtained and high wear resistance was achieved.
  • the urethane copolymer described in Patent Document 2 is extremely excellent in abrasion resistance, but is susceptible to hydrolysis, and a problem of lowering the molecular weight in a highly water-absorbing solvent is a problem, so that it can be applied to functional products. The performance was insufficient.
  • a polycarbonate copolymer having a repeating unit A containing a group represented by the following general formula (1A).
  • Ar 1 and Ar 2 each independently represent a monovalent divalent aromatic group or a monovalent divalent aliphatic group; At least one of Ar 1 and Ar 2 is a monovalent or divalent aromatic group.
  • a coating liquid comprising the polycarbonate copolymer according to the above-described aspect of the present invention and an organic solvent.
  • an electrophotographic photosensitive member comprising the polycarbonate copolymer according to one aspect of the present invention.
  • an electrophotographic apparatus comprising the electrophotographic photosensitive member according to one aspect of the present invention described above.
  • a method for producing a polycarbonate copolymer comprising: At least one of a bischloroformate compound represented by the following general formula (101) and a bischloroformate compound represented by the following general formula (102), an amide bond-containing compound, an organic solvent, and an alkaline aqueous solution , And There is provided a method for producing a polycarbonate copolymer, wherein an organic layer and an aqueous layer are mixed to perform an interfacial polycondensation reaction.
  • Ar 4 is a group represented by the following general formula (7).
  • N 101 in the general formula (101) represents the average number of bischloroformate oligomers.
  • R 8 and R 9 are each independently Hydrogen atom, An alkyl group having 1 to 12 carbon atoms, A perfluoroalkyl group having 1 to 12 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms.
  • X 3 is, -CR 10 R 11 -, A substituted or unsubstituted cycloalkylidene group having 5 to 10 ring carbon atoms or a substituted or unsubstituted arylene group having 6 to 13 ring carbon atoms.
  • R 10 and R 11 are each independently Hydrogen atom, An alkyl group having 1 to 3 carbon atoms, A perfluoroalkyl group having 1 to 3 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms. However, R 10 and R 11 are not both hydrogen atoms.
  • q and r are each independently an integer of 1 to 4, When two or more R 8 are substituted on the aromatic ring (q ⁇ 2), the plurality of R 8 are the same or different from each other, When two or more R 9 are substituted on the aromatic ring (r ⁇ 2), the plurality of R 9 are the same or different from each other. ]]
  • Ar 5 is a group represented by the following general formula (9). However, Ar 4 is a skeleton different from Ar 5 .
  • n 102 represents the average number of bischloroformate oligomers.
  • R 12 and R 13 are each independently Hydrogen atom, An alkyl group having 1 to 12 carbon atoms, A perfluoroalkyl group having 1 to 12 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms,
  • X 4 is, Single bond, -O-, -CO-, -CH 2- , or a substituted or unsubstituted 9,9-fluorenylidene group
  • u and v are each independently an integer of 1 to 4, When two or more R 12 are substituted on the aromatic ring (u ⁇ 2), the plurality of R 12 are the same or different from each other, When two or more R 13 are substituted on the aromatic ring (v ⁇ 2), the plurality of R 13 are the same or different from each other. ]]
  • a polycarbonate copolymer that can improve mechanical strength and hydrolysis resistance while maintaining electrical characteristics can be provided.
  • a method for producing the polycarbonate copolymer can be provided.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the polycarbonate copolymer according to this embodiment has a repeating unit A including a group represented by the following general formula (1A).
  • a polycarbonate copolymer may be abbreviated as a PC copolymer.
  • Ar 1 and Ar 2 each independently represent a monovalent divalent aromatic group or a monovalent divalent aliphatic group; At least one of Ar 1 and Ar 2 is a monovalent or divalent aromatic group.
  • the divalent aliphatic group includes, for example, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted bicycloalkylene group, a substituted or unsubstituted tricycloalkylene group, and perfluoroalkylene. It is preferably any group selected from the group consisting of groups.
  • the divalent aromatic group is preferably, for example, any group selected from the group consisting of a substituted or unsubstituted phenylene group and a substituted or unsubstituted naphthylene group.
  • Monovalent aliphatic groups include, for example, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted bicycloalkyl groups, substituted or unsubstituted tricycloalkyl groups, and perfluoroalkyls. It is preferably any group selected from the group consisting of groups.
  • the monovalent aromatic group is preferably any group selected from the group consisting of, for example, a substituted or unsubstituted phenyl group and a substituted or unsubstituted naphthyl group.
  • Ar 1 and Ar 2 are preferably each independently a divalent aromatic group.
  • one of Ar 1 and Ar 2 may represent a divalent aromatic group or a divalent aliphatic group, and the other may represent a monovalent aromatic group or a monovalent aliphatic group.
  • the general formula (1A) is: It is represented by the following general formula (1A-1).
  • the general formula (1A) Is represented by the following general formula (1A-2).
  • repeating unit A including the group represented by the general formula (1A) is represented by the following general formula (2A).
  • Ar 6 and Ar 7 are each independently a group represented by the following general formula (10) or general formula (11), and Ar 6 and Ar 7 are different skeletons. Or the same skeleton, and n is an integer of 1 to 2.
  • R 16 , R 17 and R 18 are each independently Hydrogen atom, An alkyl group having 1 to 3 carbon atoms, A perfluoroalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, X 5 is, Single bond, -O-, -CO-, —CR 19 R 20 — (wherein R 19 and R 20 each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a trifluoromethyl group, or a substituted or unsubstituted ring forming carbon atom having 6 to 12 carbon atoms) An aryl group of A substituted or unsubstituted cycloalkylidene group having 5 to 10 ring carbon atoms, A substituted or unsubstituted arylene group having 6 to 12 ring carbon atoms, j is an integer of 1 to 4, k is an integer of 1 to 4, m is an
  • repeating unit A including the group represented by the general formula (1A) is represented by the following general formula (3A).
  • R 21 and R 22 are each independently Hydrogen atom, An alkyl group having 1 to 3 carbon atoms, A perfluoroalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, g is an integer of 1 to 4, h is an integer of 1 to 4, When two or more R 21 are substituted on the aromatic ring (g ⁇ 2), the plurality of R 21 are the same or different from each other, When two or more R 22 are substituted on the aromatic ring (h ⁇ 2), the plurality of R 22 are the same or different from each other, n is an integer of 1 to 4, and a plurality of n are the same or different from each other; X 60 is a single bond, —O—, or —CO—. ])
  • repeating unit A including the group represented by the general formula (1A) is represented by the following general formula (4A).
  • X 7 is An alkylene group having 1 to 8 carbon atoms, It is group represented by the following general formula (14a), or group represented by the following general formula (14b).
  • R 23 , R 71 and R 72 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a perfluoroalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms
  • X 70 is a single bond or —O—
  • i, gx, and gy are each independently an integer of 1 to 4, and when two or more R 23 are substituted on the aromatic ring (i ⁇ 2), The plurality of R 23 are the same or different from each other, When two or more R 71 are substituted on the aromatic ring (gx ⁇ 2), the plurality of R 71 are the same or different from each other, When two or more R 72 are substituted on the aromatic ring (gy ⁇ 2), the plurality of R 72 are the same as or different from each other. ]
  • repeating unit A including the group represented by the general formula (1A) is represented by the following general formula (5A).
  • R 24 and R 25 are each independently Hydrogen atom, An alkyl group having 1 to 3 carbon atoms, A perfluoroalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, X 8 represents —CR 26 R 27 —, R 26 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a trifluoromethyl group, and R 27 is represented by the following general formula (15). Or a group represented by the following general formula (16).
  • R 28 and R 29 are each independently An alkyl group having 1 to 3 carbon atoms, A trifluoromethyl group, or a substituted or unsubstituted phenyl group, nx is an integer of 1 to 4. ]
  • the polycarbonate copolymer according to this embodiment preferably has a repeating unit B represented by the following general formula (4).
  • Ar 3 is a group represented by the following general formula (5).
  • R 4 and R 5 are each independently Hydrogen atom, An alkyl group having 1 to 12 carbon atoms, A perfluoroalkyl group having 1 to 12 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms.
  • X 2 is, Single bond, -O-, -CO-, -CR 6 R 7 -, A substituted or unsubstituted cycloalkylidene group having 5 to 10 ring carbon atoms, A substituted or unsubstituted arylene group having 6 to 13 ring carbon atoms, or a substituted or unsubstituted 9,9-fluorenylidene group.
  • R 6 and R 7 are each independently Hydrogen atom, An alkyl group having 1 to 3 carbon atoms, A perfluoroalkyl group having 1 to 3 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms.
  • s and t are each independently an integer of 1 to 4, When two or more R 4 are substituted on the aromatic ring (s ⁇ 2), the plurality of R 4 are the same or different from each other, When two or more R 5 are substituted on the aromatic ring (t ⁇ 2), the plurality of R 5 are the same or different from each other. ]]
  • the polycarbonate copolymer according to this embodiment is also preferably a polycarbonate copolymer having at least the repeating unit A and the repeating unit B.
  • the molar percentage of the repeating unit a: ⁇ M a / (M a + M B) ⁇ ⁇ 100 is at least 3 mol% 30 mol% or less Preferably there is.
  • the polycarbonate copolymer according to this embodiment is also preferably a polycarbonate copolymer containing only the repeating unit A and the repeating unit B as repeating units.
  • the polycarbonate copolymer when one of Ar 1 and Ar 2 is a divalent aromatic group and the other is a divalent aliphatic group, the polycarbonate copolymer is represented by the general formula (4).
  • the repeating unit B is preferably not a skeleton derived from bisphenol A (4,4 ′-(propane-2,2-diyl) diphenol). That is, in the polycarbonate copolymer according to this embodiment, when one of Ar 1 and Ar 2 is a divalent aromatic group and the other is a divalent aliphatic group, the general formula (4) It is preferable that the repeating unit B represented is not a repeating unit represented by the following general formula (4X).
  • the polycarbonate copolymer according to this embodiment preferably has a repeating unit C represented by the following general formula (6) and a repeating unit D represented by the following general formula (8).
  • Ar 4 is a group represented by the following general formula (7).
  • R 8 and R 9 are each independently Hydrogen atom, An alkyl group having 1 to 12 carbon atoms, A perfluoroalkyl group having 1 to 12 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms.
  • X 3 is, -CR 10 R 11 -, A substituted or unsubstituted cycloalkylidene group having 5 to 10 ring carbon atoms or a substituted or unsubstituted arylene group having 6 to 13 ring carbon atoms.
  • R 10 and R 11 are each independently Hydrogen atom, An alkyl group having 1 to 3 carbon atoms, A perfluoroalkyl group having 1 to 3 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms. However, R 10 and R 11 are not both hydrogen atoms.
  • q and r are each independently an integer of 1 to 4, When two or more R 8 are substituted on the aromatic ring (q ⁇ 2), the plurality of R 8 are the same or different from each other, When two or more R 9 are substituted on the aromatic ring (r ⁇ 2), the plurality of R 9 are the same or different from each other. ]]
  • Ar 5 is a group represented by the following general formula (9). However, Ar 4 is a skeleton different from Ar 5 .
  • R 12 and R 13 are each independently Hydrogen atom, An alkyl group having 1 to 12 carbon atoms, A perfluoroalkyl group having 1 to 12 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms,
  • X 4 is, Single bond, -O-, -CO-, -CH 2- , or a substituted or unsubstituted 9,9-fluorenylidene group
  • u and v are each independently an integer of 1 to 4, When two or more R 12 are substituted on the aromatic ring (u ⁇ 2), the plurality of R 12 are the same or different from each other, When two or more R 13 are substituted on the aromatic ring (v ⁇ 2), the plurality of R 13 are the same or different from each other. ]]
  • the polycarbonate copolymer according to this embodiment is also preferably a polycarbonate copolymer having at least the repeating unit A, the repeating unit C, and the repeating unit D.
  • the repeating unit C and the repeating unit D are different from each other.
  • the polycarbonate copolymer according to this embodiment is also preferably a polycarbonate copolymer containing only the repeating unit A, the repeating unit C, and the repeating unit D as repeating units.
  • the number of moles of the repeating unit A M A, wherein the repeating unit C moles of M C of the number of moles of the repeating units D and M D, wherein the repeating units A When the mole percentage of the number of moles (M A + M C + M D ) of the repeating units combined with C and D is 100 mole%, the mole percentage of the repeating unit A: ⁇ M A / (M A + M C + M D ) ⁇ ⁇ 100 is preferably 3 mol% or more and 30 mol% or less. If the molar percentage of the repeating unit A is 3 mol% or more, the effect of interaction between amide groups can be confirmed. When the mole percentage of the repeating unit A is 30 mol% or less, it is possible to suppress the problem that the interaction between amide groups becomes too strong and the resin is hardly dissolved.
  • the molar percentage of the repeating unit C: ⁇ M C / (M A + M C + M D ) ⁇ ⁇ 100 is 15 mol% or more and 87 mol% or less, and the repeating unit D % Of mol: ⁇ M D / (M A + M C + M D ) ⁇ ⁇ 100 is preferably 10 mol% or more and 65 mol% or less.
  • the molar percentage of the repeating unit A: ⁇ M A / (M A + M C + M D) ⁇ ⁇ 100 is 30 mol% or less than 3 mol%
  • the repeating unit C % Of mol: ⁇ M C / (M A + M C + M D ) ⁇ ⁇ 100 is 15 mol% or more and 87 mol% or less
  • the mol percentage of the repeating unit D: ⁇ M D / (M A + M C + M D ) ⁇ ⁇ 100 is more preferably 10 mol% or more and 65 mol% or less.
  • the reduced viscosity [ ⁇ SP / C] of the PC copolymer is a value at 20 ° C. of a methylene chloride solution of the PC copolymer having a concentration of 0.5 g / dL.
  • the reduced viscosity [ ⁇ SP / C] of the PC copolymer of the present embodiment is preferably 0.60 dL / g or more and 4.0 dL / g or less, and 0.80 dL / g or more and 3.0 dL / g or less. More preferably, it is 0.80 dL / g or more and 2.5 dL / g or less.
  • the electrophotographic photosensitive member can obtain sufficient wear resistance.
  • the reduced viscosity [ ⁇ SP / C] is 4.0 dL / g or less, an appropriate coating viscosity can be maintained when a molded body such as an electrophotographic photosensitive member is produced from the coating solution. Productivity of molded bodies such as photographic photoreceptors can be increased.
  • the chain end of the PC copolymer of this embodiment is preferably sealed with a monovalent aromatic group or a monovalent fluorine-containing aliphatic group.
  • the monovalent aromatic group may be a group containing an aromatic group.
  • the monovalent fluorine-containing aliphatic group may be a group containing an aromatic group.
  • 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, an aryl group, and the like. . These substituents may be further added with at least one substituent selected from the group consisting of an alkyl group, a halogen atom, an aryl group and the like. When there are a plurality of substituents, these substituents may be bonded to each other to form a ring.
  • the monovalent aromatic group constituting the chain end preferably includes an aryl group having 6 to 12 ring carbon atoms.
  • 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 a fluorine atom, a chlorine atom, and a bromine atom.
  • examples of the substituent added to the aromatic group include an alkyl group having 1 to 20 carbon atoms.
  • the 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.
  • Examples of the monovalent fluorine-containing aliphatic group constituting the chain end include a monovalent group derived from a fluorine-containing alcohol.
  • those having a total number of fluorine atoms of 13 to 19 are preferably formed by connecting a plurality of fluoroalkyl chains having 2 to 6 carbon atoms via ether bonds. 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 is suppressed, and at least one of mechanical strength, surface hardness, heat resistance, and the like of the obtained PC copolymer is improved. obtain.
  • the monovalent fluorine-containing aliphatic group is preferably a monovalent group derived from a fluorine-containing alcohol having two or more ether bonds.
  • a fluorine-containing alcohol By using such a fluorine-containing alcohol, the dispersibility of the PC copolymer in the coating solution is improved, the wear resistance of the molded product and the electrophotographic photosensitive member is improved, and the surface lubricity and repellency after wear are improved. Water and oil repellency can be maintained.
  • fluorine-containing alcohol 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 the fluorine-containing alcohol through the ether bond represented by the following general formula (32), (33), or (34) is also preferable.
  • n1 is an integer of 1 to 12
  • m1 is an integer of 1 to 12.
  • n 31 is an integer of 1 to 10, and preferably an integer of 5 to 8.
  • n 32 is an integer of 0 to 5, and preferably an integer of 0 to 3.
  • n 33 is an integer of 1 to 5, and preferably an integer of 1 to 3.
  • n 34 is an integer of 1 to 5, preferably an integer of 1 to 3.
  • n 35 is an integer of 0 to 5, and preferably an integer of 0 to 3.
  • R is CF 3 or F.
  • the chain end of the PC copolymer is a monovalent group derived from phenol represented by the following general formula (35) or the following general formula ( It is preferably sealed with a monovalent group derived from a fluorine-containing alcohol represented by 36).
  • 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 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). Show.
  • R f2 is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms.
  • mx is an integer of 1 to 3.
  • the polycarbonate copolymer according to this embodiment can improve mechanical strength and hydrolysis resistance while maintaining electrical characteristics.
  • the polycarbonate copolymer according to the present embodiment has a structure in which an aromatic group is bonded to at least one of a nitrogen atom and a carbon atom of an amide group, and thus an aliphatic group on both the nitrogen atom and the carbon atom of the amide group. It is considered that the mechanical strength is improved as compared with a polycarbonate copolymer having a structure in which groups are bonded.
  • the polycarbonate copolymer according to this embodiment has an amide skeleton, it is considered that the amide skeletons are physically crosslinked (hydrogen bonds).
  • the amide group forms a resonance-stabilized structure, so that the double bond property of —CN—single bond is increased, and attacks of nucleophilic reagents such as alkalis are prevented. As a result, it is considered that the hydrolysis resistance is improved.
  • ⁇ -electron delocalization occurs at —O—C ( ⁇ O) —, and the double bond property of —CN—single bond is weak, and is considered to be susceptible to hydrolysis. .
  • the polycarbonate copolymer according to this embodiment is stable due to resonance stabilization, that is, electrons are widely dispersed, and the degree of polarization is considered to be weak. If a certain part of the polycarbonate copolymer has polarity, the electric characteristics deteriorate, and therefore, it is considered that the polycarbonate copolymer having a repeating unit containing an amide group having a weak polarization can obtain electric characteristics equivalent to those of the conventional one.
  • the adhesiveness is excellent.
  • the said polycarbonate copolymer is excellent in the adhesiveness with respect to a resin base material, and is further excellent in the adhesiveness with respect to a polyimide base material.
  • Ar 4 is a group represented by the general formula (7).
  • N 101 in the general formula (101) represents the average number of bischloroformate oligomers.
  • Ar 5 is a group represented by the general formula (9). However, Ar 4 is a skeleton different from Ar 5 .
  • n 102 represents the average number of bischloroformate oligomers.
  • a dihydric phenolic compound in addition to the bischloroformate compound and the amide bond-containing compound.
  • the dihydric phenolic compound for example, it is preferable to use at least one of the dihydric phenolic compounds represented by the following general formula (103) and the following general formula (104).
  • the PC copolymer of the present embodiment includes, for example, a bischloroformate oligomer represented by the general formula (101), a dihydric phenolic compound represented by the following general formula (104), and the following general formula (105).
  • a carbonic acid ester bond is suitably formed by subjecting at least one amide bond-containing compound selected from the group consisting of the amide bond-containing compounds shown in (108) to interfacial polycondensation in the presence of an acid binder. Is obtained.
  • the PC copolymer of the present embodiment includes, for example, a bischloroformate oligomer represented by the general formula (102), a dihydric phenolic compound represented by the following formula (103), and the following general formula (105) to A carbonate ester bond is suitably formed by subjecting at least one amide bond-containing compound selected from the group consisting of the amide bond-containing compounds shown in (108) to interfacial polycondensation in the presence of an acid binder. ,can get.
  • These synthesis reactions of the PC copolymer are performed, for example, in the presence of an end-capping agent, and a branching agent is also used as necessary.
  • the bischloroformate oligomer represented by the general formula (101) and the general formula (102) is mixed and used, and the dihydric phenolic compound represented by the following general formula (103) or the following general formula (104): At least one of the amide bond-containing compounds represented by the following general formulas (105) to (108) may be subjected to interfacial polycondensation.
  • Ar 4 is a group represented by the general formula (7).
  • Ar 5 is a group represented by the general formula (9).
  • Ar 6, Ar 7 and n are as defined Ar 6, Ar 7 and n in each of the general formula (2A).
  • X 6 has the same meaning as X 6 in the general formula (3A).
  • X 7 has the same meaning as X 7 in the general formula (4A).
  • X 8 has the same meaning as X 8 in the general formula (5A)
  • R 24 and R 25 are the same meanings as R 24 and R 25 in the general formula (5A) .
  • the amide bond-containing compounds represented by the general formulas (105) to (108) can be produced by a known method.
  • 4-hydroxy-N- (4-hydroxyphenyl) benzamide represented by the general formula (105) can be obtained by carrying out a reaction using benzophenone as a starting material as described in US Pat. No. 5,463,091.
  • n 101 in the general formula (101) represents the average number of bischloroformate oligomers.
  • the average monomer number n 101 is preferably in the range of 1.0 to 1.3.
  • n 102 in the general formula (102) also shows the average amount body number of bischloroformate oligomers.
  • the average amount of the number of somatic n 102 is preferably in the range of 1.0 to 1.3.
  • the dihydric phenolic compound represented by the general formula (103) and the general formula (104) Even when the dihydric phenolic compound shown is used in combination, it is possible to suppress the production of a high-mer number block exceeding the number of monomers of the bischloroformate oligomer represented by the general formula (101) or the general formula (102), The production of the PC copolymer is facilitated.
  • a method for calculating the average number of oligomers n 101 and n 102 a method described in Examples described later can be given.
  • Examples of the monomer (divalent phenolic compound) represented by the general formula (103) include bisphenol compounds.
  • Specific examples of the bisphenol compound include 1,1-bis (3-methyl-4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,2-bis (4-hydroxyphenyl).
  • At least one bisphenol compound selected from the group consisting of When this PC copolymer using a bisphenol compound is applied as a PC copolymer for an electrophotographic photoreceptor, a good coating solution can be obtained.
  • examples of the monomer (dihydric phenolic compound) represented by the general formula (104) include a biphenol compound and a bisphenol compound.
  • specific examples of the biphenol compound and the bisphenol compound include 4,4′-biphenol, 2,2′-dimethyl-4,4′-biphenol, 2,2′-diethyl-4,4′-biphenol, 2, 2′-dipropyl-4,4′-biphenol, 2,2′-bis (trifluoromethyl) -4,4′-biphenol, 2,2′-bis (pentafluoroethyl) -4,4′-biphenol, 2,2′-bis (heptafluoropropyl) -4,4′-biphenol, 2,2 ′, 6-trimethyl-4,4′-biphenol, 2,2 ′, 6,6′-tetramethyl-4, 4′-biphenol, 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (3-methyl-4-hydroxyphenyl) methan
  • biphenol compounds and bisphenol compounds 4,4′-biphenol, 2,2′-dimethyl-4,4′-biphenol, 2,2′-diethyl-4,4′-biphenol, 2,2 '-Bis (trifluoromethyl) -4,4'-biphenol, 2,2'-bis (pentafluoroethyl) -4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) methane, 1, 1-bis (3-methyl-4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (3-methyl-4-hydroxyphenyl) ether, 4,4′-dihydroxybenzophenone, and 3,3 ′ -At least one biphenol compound selected from the group consisting of dimethyl-4,4'-dihydroxybenzophenone and bis Phenol compounds are preferred.
  • amide bond-containing compound represented by the general formula (105) for example, compounds represented by the following general formulas (105A), (105B) and (105C) are preferably used.
  • amide bond-containing compound represented by the general formula (106) for example, compounds represented by the following formulas (106A), (106B) and (106C) are preferably used.
  • amide bond-containing compound represented by the general formula (107) for example, compounds represented by the following formulas (107A), (107B) and (107C) are preferably used.
  • amide bond-containing compound represented by the general formula (108) for example, compounds represented by the following formulas (108A), (108B), (108C), (108D) and (108E) are preferably used. .
  • a monovalent carboxylic acid and a derivative thereof, and a monovalent phenol can be used as a terminal blocking agent for generating a chain end.
  • the end capping agent that generates a chain end include 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
  • a fluorine-containing alcohol represented by the general formula (30) or (31), 1,1,1,3,3,3-hexafluoro-2-propanol, or the like Monovalent fluorine-containing alcohol is also preferably used.
  • the fluorine-containing alcohol through the ether bond represented by the said General formula (32), (33), or (34) as an end-capping agent which produces
  • These end capping agents may be used alone or in combination of two or more.
  • the monovalent phenol represented by the general formula (35) or the general formula (36) may be used as an end-capping agent that generates a chain end. It is preferable to use the monovalent fluorine-containing alcohol represented.
  • Examples of the monovalent phenol represented by the general formula (35) include p-tert-butyl-phenol, p-perfluorononylphenol, p-perfluorohexylphenol, p-tert-perfluorobutylphenol, and p.
  • -Perfluorooctylphenol or the like is preferably used. That is, in this embodiment, the chain end is a group consisting of p-tert-butyl-phenol, p-perfluorononylphenol, p-perfluorohexylphenol, p-tert-perfluorobutylphenol, and p-perfluorooctylphenol. It is preferably sealed with an end-capping 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, it is preferable that the chain terminal of this embodiment is sealed using an end-capping agent selected from any of the following fluorine-containing alcohols.
  • the addition ratio of the end-capping agent is the molar percentage of the copolymer composition of the repeating unit A, the repeating unit B, and the chain terminal, or the copolymer composition of the repeating unit A, the repeating unit C, the repeating unit D, and the chain terminal.
  • the mole percentage is preferably 0.05 mol% or more and 30 mol% or less, more preferably 0.1 mol% or more and 10 mol% or less.
  • branching agent that can be used in the method for producing the PC copolymer of the present embodiment is not particularly limited, but specific examples of the branching agent include phloroglucin, pyrogallol, 4,6-dimethyl-2,4,6.
  • branching agents may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the addition ratio of these branching agents is the mole percentage of the copolymer composition of repeating unit A, repeating unit B, and chain end, or the mole of copolymer composition of repeating unit A, repeating unit C, repeating unit D, and chain end.
  • the percentage is preferably 30 mol% or less, and more preferably 5 mol% or less. The fall of a moldability can be suppressed as the addition ratio of a branching agent is 30 mol% or less.
  • examples of the acid binder include alkali metal hydroxides (sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, etc.), alkaline earth metal hydroxides (magnesium hydroxide). , Calcium hydroxide, etc.), alkali metal weak acid salts (sodium carbonate, potassium carbonate, etc.), alkaline earth metal weak acid salts (calcium acetate, etc.), and organic bases such as pyridine.
  • Preferred acid binders for interfacial polycondensation are alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.) and alkaline earth metal hydroxides (calcium hydroxide, etc.).
  • acid binders can also be used as a mixture. What is necessary is just to prepare the usage-amount of an acid binder suitably considering the stoichiometric ratio (equivalent) of reaction. Specifically, one equivalent or an excess amount of the acid binder may be used per 1 mol of the total of hydroxyl groups of the dihydric phenol as the raw material, and preferably 1 to 10 equivalents of the acid binder is used. Good.
  • the solvent used in the method for producing a PC copolymer of the present embodiment, there is no problem as long as it shows a certain solubility or more with respect to the obtained copolymer.
  • the solvent include aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (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, chlorobenzene, etc.), ketones (cyclohexanone, acetone, acetophenone, etc.), and ethers ( Tetrahydrofuran, 1,4-dioxane and the like) are preferable. These solvents may be used alone or in combination of two or more. Further, the interfa
  • the organic solvent used in the method for producing the PC copolymer of the present embodiment it is preferable to use an organic solvent that is substantially immiscible with water and can dissolve 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 can dissolve 5% by mass or more of the finally obtained polycarbonate copolymer.
  • the organic solvent “substantially immiscible with water” is composed of a uniform layer when water and the organic solvent are mixed in a composition range of 1: 9 to 9: 1 under normal temperature and normal pressure conditions. It is an organic solvent from which a solution (a solution in which neither a gelled product nor an insoluble material is found) is obtained.
  • the organic solvent can “dissolve 5% by mass or more of the finally obtained polycarbonate copolymer” means the solubility of the polycarbonate copolymer when measured at a temperature of 20 to 30 ° C. under normal pressure.
  • finally obtained polycarbonate copolymer refers to a copolymer obtained through a polymerization step in the method for producing a polycarbonate copolymer of the present embodiment.
  • organic solvent include aromatic hydrocarbons such as toluene, ketones such as cyclohexanone, and halogenated hydrocarbons such as methylene chloride. Of these, methylene chloride is preferred because of its high solubility.
  • the catalyst used in the method for producing the PC copolymer of the present embodiment is not particularly limited.
  • a tertiary amine trimethylamine, triethylamine, tributylamine, N, N-dimethylcyclohexylamine, pyridine, N, N-diethylaniline, N, N-dimethylaniline, etc.
  • quaternary ammonium salts trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, etc.
  • quaternary phosphonium salts tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, etc.
  • These catalysts may be used individually by 1 type, and may be used in combination of 2 or more type.
  • antioxidants such as sodium sulfite and a hydrosulfite salt, to the reaction system of the PC copolymer of this embodiment as needed.
  • the method for producing the PC copolymer of the present embodiment can be specifically carried out in various modes other than the method for producing the PC copolymer described above.
  • the bisphenol compound of the general formula (103) is reacted with phosgene and the like to produce the bischloroformate oligomer of the general formula (101).
  • an amide bond-containing compound of the general formula (105) and a dihydric phenolic compound of the general formula (104) are used for the bischloroformate oligomer, and an alkaline aqueous solution of the solvent and acid binder is used.
  • a method of reacting in the presence of a mixed solution can be employed.
  • the bischloroformate oligomer is used with the amide bond-containing compound of the general formula (105), the dihydric phenolic compound of the general formula (103) and the general formula (104), and the solvent and the acid.
  • a method of reacting in the presence of a mixed solution of an alkaline aqueous solution of a binder can be employed. These methods are preferable in that the molar percentage of the Ar 4 skeleton unit (repeating unit C represented by the general formula (6)) can be adjusted within a preferable range when the molar percentage of all repeating units is 100 mol%. .
  • n 101 value of the general formula (101) is in the range of 1.0 or more and 1.3 or less.
  • a hydrophobic solvent such as methylene chloride
  • phosgene is further added to form a first solution.
  • a tertiary amine such as triethylamine is dissolved in a hydrophobic solvent such as methylene chloride to form a second solution, and this second solution is dropped into the first solution to be reacted.
  • the dropping temperature and reaction temperature are usually from ⁇ 10 ° C. to 40 ° C., preferably from 0 ° C. to 30 ° C. Both the dropping time and the reaction time are usually from 15 minutes to 4 hours, preferably from 30 minutes to 3 hours.
  • the average number of oligomers (n 101 ) of the polycarbonate oligomer thus obtained is preferably 1.0 or more and 1.3 or less, and more preferably 1.0 or more and 1.2 or less.
  • the use of the polycarbonate oligomer produced by the production method is preferable in that the washing step during the production of the PC copolymer can be simplified.
  • the organic layer containing the low-molecular-weight bischloroformate oligomer thus obtained was added to the aromatic dihydric phenolic compound represented by the general formula (104) and the general formulas (105) to (108).
  • the amide bond-containing compound shown in (2) is added and reacted.
  • the reaction temperature is It is 0 degreeC or more and 150 degrees C or less, Preferably they are 5 degreeC or more and 40 degrees C or less, More preferably, they are 7 degreeC or more and 20 degrees C or less.
  • the reaction pressure may be any of reduced pressure, normal pressure, or increased pressure. Usually, it can be suitably carried out at normal pressure or about the pressure of the reaction system.
  • the reaction time depends on the reaction temperature, but is usually 0.5 minutes to 10 hours, preferably 1 minute to 3 hours.
  • the dihydric phenolic compound represented by the general formula (104) and the amide bond-containing compound represented by the general formulas (105) to (108) are preferably added as an aqueous solution or an organic solvent solution. .
  • a catalyst, a terminal blocking agent, a branching agent, etc. are added in the above production method, if necessary, either during the production of a bischloroformate oligomer, during the subsequent high molecular weight reaction, or both. Can be used.
  • the PC copolymer obtained as described above is represented by the repeating unit A represented by the general formula (2A), the repeating unit C represented by the general formula (6), and the general formula (8). It is a copolymer consisting of the repeating unit D. Further, the PC copolymer is a polycarbonate unit having a structural unit other than the repeating unit A, the repeating unit C and the repeating unit D, a unit having a polyester structure, and a polyether structure, as long as the object of the present invention is not hindered. It may contain a unit having
  • the reduced viscosity [ ⁇ sp / C] of the obtained PC copolymer is adjusted to the above range by various methods such as selection of the reaction conditions and adjustment of the amount of branching agent and terminal blocking agent used. be able to.
  • the obtained PC copolymer is appropriately subjected to at least one of physical treatment (mixing, fractionation, etc.) and chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) It can also be obtained as a PC copolymer having a reduced viscosity [ ⁇ sp / C].
  • the obtained reaction product (crude product) can be recovered as a PC copolymer having a desired purity (purity) by performing various post-treatments such as a known separation and purification method.
  • the coating liquid of this embodiment contains the polycarbonate copolymer which concerns on this embodiment.
  • the coating liquid of this embodiment preferably contains a solvent capable of dissolving or dispersing the polycarbonate copolymer according to this embodiment.
  • the coating liquid of this embodiment preferably contains the polycarbonate copolymer according to this embodiment and an organic solvent.
  • solvent used in this embodiment examples include solubility, dispersibility, viscosity, evaporation rate, chemical stability, and stability against physical changes of the polycarbonate copolymer and other materials according to this embodiment. Can be used alone or in combination with a plurality of solvents.
  • the solvent preferably includes an organic solvent.
  • organic solvent include, for example, aromatic hydrocarbon solvents (for example, benzene, toluene, xylene, and chlorobenzene), ketone solvents (for example, acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, and methyl isobutyl ketone).
  • Etc. ester solvents
  • ester solvents for example, ethyl acetate, ethyl cellosolve, and epsilon caprolactam, etc.
  • halogenated hydrocarbon solvents for example, carbon tetrachloride, carbon tetrabromide, chloroform, dichloromethane, tetrachloroethane, etc.
  • ether System solvents for example, tetrahydrofuran, dioxolane, and dioxane
  • amide solvents for example, dimethylformamide, and diethylformamide
  • sulfoxide solvents for example, dimethylsulfoxide.
  • Door can be.
  • an organic solvent having a boiling point of 160 ° C. or lower is preferable. These solvent may be used individually by 1 type, and may use 2 or more types as a mixed solvent.
  • the organic solvent preferably contains neither an amide-based organic solvent nor a halogen-based organic solvent from the viewpoints of environmental hygiene, evaporation, solubility, handleability, and economy.
  • the organic solvent preferably includes a non-halogen organic solvent.
  • the non-halogen organic solvent include ether solvents (for example, tetrahydrofuran, dioxane, dioxolane, etc.), aromatic hydrocarbon solvents (for example, paraxylene, toluene, etc.), and ketone solvents (for example, methyl ethyl ketone). , Cyclohexanone, cyclopentanone, etc.).
  • an organic solvent containing one or more of tetrahydrofuran, dioxolane, toluene, cyclohexanone, and cyclopentanone is preferable because the polycarbonate copolymer according to the present embodiment has high solubility, and an organic solvent containing tetrahydrofuran is preferable.
  • a solvent is more preferable.
  • the concentration of the polycarbonate copolymer component according to the present embodiment in the coating liquid of the present embodiment may be a concentration that provides an appropriate viscosity according to the usage method of the coating liquid, and is 0.1% by mass. It is preferably 40% by mass or less, more preferably 1% by mass or more and 35% by mass or less, and further preferably 5% by mass or more and 30% by mass or less. If it is 40 mass% or less, a coating property will become favorable, without a viscosity becoming high too much. If it is 0.1 mass% or more, a moderate viscosity can be maintained and a homogeneous film can be obtained. Moreover, if it is 0.1 mass% or more, it will become a moderate density
  • the coating liquid of this embodiment contains the polycarbonate copolymer according to this embodiment, there is little cloudiness and a transparent coating liquid can be obtained.
  • the coating liquid may contain additives in addition to the polycarbonate copolymer and the solvent according to this embodiment.
  • additives include low molecular weight compounds, colorants (for example, dyes and pigments), functional compounds (for example, charge transport materials, electron transport materials, hole transport materials, and charge generation materials), packing Examples thereof include materials (for example, inorganic or organic fillers, fibers, and fine particles), antioxidants, ultraviolet absorbers, and acid scavengers.
  • the coating liquid may contain other resins other than the polycarbonate copolymer according to one embodiment of the present invention. As these additives and other resins, known substances can be used as substances that can be blended with the polycarbonate copolymer.
  • the ratio of the polycarbonate copolymer to the charge transport material in the coating liquid of the present embodiment is 20:80 to 80:20 by mass ratio. Is more preferable, and 30:70 to 70:30 is more preferable.
  • the polycarbonate copolymer of this embodiment may be used individually by 1 type, and may use 2 or more types together.
  • the coating solution of the present embodiment is usually suitably used for forming a photosensitive layer of a multilayer electrophotographic photoreceptor.
  • the photosensitive layer of the multilayer electrophotographic photoreceptor preferably includes at least a charge generation layer and a charge transport layer, and the coating liquid of this embodiment is suitably used for forming the charge transport layer. Further, the coating liquid of the present embodiment can be used for forming a photosensitive layer of a single-layer type electrophotographic photosensitive member by further containing the charge generating substance.
  • the electrophotographic photosensitive member of the present embodiment includes the polycarbonate copolymer according to the present embodiment.
  • the wear resistance of the electrophotographic photoreceptor is improved.
  • the electrophotographic photosensitive member of the present embodiment preferably includes a substrate and a photosensitive layer provided on the substrate, and the photosensitive layer preferably includes the polycarbonate copolymer according to the present embodiment.
  • the photosensitive layer contains the polycarbonate copolymer according to this embodiment, the abrasion resistance of the photosensitive layer is improved.
  • the polycarbonate copolymer according to this embodiment is preferably used as a binder resin for an electrophotographic photoreceptor. It is preferable that the photosensitive layer of the electrophotographic photosensitive member of the present embodiment contains the polycarbonate copolymer according to the present embodiment as a binder resin. By providing such a photosensitive layer, the durability of the electrophotographic photoreceptor is improved.
  • the electrophotographic photosensitive member of this embodiment may have any configuration as well as various known types of electrophotographic photosensitive members.
  • a preferable electrophotographic photosensitive member is a laminated electrophotographic photosensitive member having a photosensitive layer having at least one charge generation layer and at least one charge transport layer, or a charge generation material in one layer.
  • the polycarbonate copolymer according to the present embodiment may be used in any part of the photosensitive layer. However, in order to fully exhibit the effects of the present invention, a binder resin of a charge transfer material in the charge transport layer. Or as a binder resin for a single photosensitive layer.
  • the polycarbonate copolymer according to this embodiment is desirably used not only as a photosensitive layer but also as a surface protective layer. In the case of a multilayer electrophotographic photoreceptor having two charge transport layers, the polycarbonate copolymer according to this embodiment is preferably used for either or both of the charge transport layers.
  • the polycarbonate copolymer according to this embodiment may be used singly or in combination of two or more.
  • binder resin components such as another polycarbonate, in the range which does not inhibit the objective of this invention as desired.
  • the substrate is preferably a conductive substrate.
  • the electrophotographic photosensitive member of the present embodiment is more preferably an aspect including a conductive substrate and a photosensitive layer provided on the conductive substrate.
  • 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 the charge generation layer may be laminated on the charge transport layer.
  • the photosensitive layer may contain 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 necessary.
  • an electrophotographic photoreceptor having no practical problem in sensitivity and electric characteristics in the electrophotographic process can be obtained. Further, an adhesive layer for improving the adhesion between the layers or an intermediate layer such as a blocking layer that serves to block charges may be formed.
  • the conductive substrate material used in the electrophotographic photosensitive member of the present embodiment various materials such as known materials can be used.
  • the conductive substrate material for example, aluminum, nickel, chromium, palladium, titanium, molybdenum, indium, gold, platinum, silver, copper, zinc, brass, stainless steel, lead oxide, tin oxide, Plates, drums, and sheets made of indium oxide, ITO (indium tin oxide: tin-doped indium oxide), graphite, and the like, glass, cloth, paper subjected to conductive treatment (for example, coating by vapor deposition, sputtering, coating, etc.), Plastic films, sheets, seamless belts, and metal drums that have been subjected to metal oxidation treatment by electrode oxidation or the like can be used.
  • the charge generation layer has at least a charge generation material.
  • This charge generation layer is formed by forming a layer of a charge generation material on the underlying conductive substrate by vacuum deposition or sputtering, or binding the charge generation material on the underlying substrate using a binder resin. It can be obtained by forming a layer formed by wearing.
  • a method for forming the charge generation layer using the binder resin various methods such as a known method can be used. Usually, for example, a method in which a coating solution in which a charge generating material is dispersed or dissolved together with a binder resin in a suitable solvent is applied onto a substrate serving as a predetermined base and dried to obtain a wet molded body is a manufacturing cost viewpoint. Therefore, it is preferable.
  • the charge generation material in the charge generation layer various known materials can be used.
  • the compound include selenium alone (for example, amorphous selenium and trigonal selenium), a selenium alloy (for example, selenium-tellurium), a selenium compound or a selenium-containing composition (for example, As 2 Se).
  • metal-free phthalocyanine pigments for example, ⁇ -type metal-free phthalocyanine, ⁇ -type metal-free phthalocyanine, etc.
  • metal phthalocyanine pigments for example, ⁇ -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 Titanyl phthalocyanine, D-type titanyl phthalocyanine, E-type titanyl phthalocyanine, F-type titanyl phthalocyanine, G-type titanyl phthalocyanine, H-
  • the charge transport layer can be obtained as a wet molded body by forming a layer formed by binding a charge transport material with a binder resin on an underlying conductive substrate.
  • the binder resin for the charge generation layer and the charge transport layer is not particularly limited, and various known resins can be used. Specific examples of the binder resin include polystyrene, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl acetal, alkyd resin, acrylic resin, polyacrylonitrile, polycarbonate, polyurethane, and epoxy resin.
  • the charge transport material is dispersed or dissolved in an appropriate solvent together with the polycarbonate copolymer according to the present embodiment.
  • a method in which the coating liquid is applied onto a substrate serving as a predetermined base and dried to obtain a wet molded body is preferable.
  • the blending ratio of the charge transport material used for forming the charge transport layer and the polycarbonate copolymer according to the present embodiment is preferably 20:80 to 80:20, more preferably 30 from the viewpoint of product performance. : 70 to 70:30.
  • the polycarbonate copolymer according to this embodiment may be used alone or in combination of two or more.
  • other binder resins can be used in combination with the polycarbonate copolymer according to this embodiment as long as the object of the present invention is not impaired.
  • the thickness of the charge transport layer thus formed is preferably about 5 ⁇ m to 100 ⁇ m, more preferably 10 ⁇ m to 30 ⁇ m. If this thickness is 5 ⁇ m or more, the initial potential is not lowered, and if it is 100 ⁇ m or less, deterioration of electrophotographic characteristics can be prevented.
  • Various known compounds can be used as the charge transport material that can be used together with the polycarbonate copolymer according to 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.
  • 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 compound, phenazine compound, poly-N-vinylcarbazole, polyvinylpyrene, polyvinyl Anthracene, polyvinyl acridine, poly-9-vinylphenyl anthracene, pyrene - formaldehyde resins, ethylcarbazole resins and polymers such as having these structures in the main chain or side chain is preferably used.
  • These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
  • charge transport materials the compounds specifically exemplified in JP-A-11-172003 and the charge transport materials represented by the following structures are preferably used from the viewpoints of performance and safety.
  • the polycarbonate copolymer according to this embodiment as a binder resin in at least one of the charge generation layer and the charge transport layer.
  • an undercoat layer that is usually used can be provided between the conductive substrate and the photosensitive layer.
  • the undercoat layer include fine particles (for example, titanium oxide, aluminum oxide, zirconia, titanic acid, zirconic acid, lanthanum lead, titanium black, silica, lead titanate, barium titanate, tin oxide, indium oxide, and Components such as silicon oxide, polyamide resin, phenol resin, casein, melamine resin, benzoguanamine resin, polyurethane resin, epoxy resin, cellulose, nitrocellulose, polyvinyl alcohol, and polyvinyl butyral resin can be used.
  • the binder resin may be used, or the polycarbonate copolymer 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 these as a mixture, it is preferable to use inorganic fine particles and a resin together because a film having good smoothness is formed.
  • the thickness of this undercoat layer is preferably 0.01 ⁇ m or more and 10 ⁇ m or less, more preferably 0.1 ⁇ m or more and 7 ⁇ m or less.
  • the undercoat layer can be formed uniformly, and when the thickness is 10 ⁇ m or less, it is possible to suppress deterioration of the electrophotographic characteristics.
  • a known blocking layer that is usually used 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 preferably 0.01 ⁇ m or more and 20 ⁇ m or less, more 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 formed uniformly, and when the thickness is 20 ⁇ m or less, the electrophotographic characteristics can be prevented from being deteriorated.
  • a protective layer may be laminated on the photosensitive layer in the electrophotographic photoreceptor of this embodiment.
  • the same kind of resin as the binder resin can be used.
  • the polycarbonate copolymer which concerns on this embodiment.
  • the thickness of the protective layer is preferably 0.01 ⁇ m or more and 20 ⁇ m or less, more preferably 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the protective layer contains a conductive material such as the charge generation material, charge transport material, additive, metal or oxide thereof, nitride, salt, alloy, carbon black, and organic conductive compound. Also good.
  • the charge generation layer and the charge transport layer include, for example, a binder, a plasticizer, a curing catalyst, a fluidity imparting agent, a pinhole control agent, and a spectral sensitivity increase.
  • a sensitizer (sensitizing dye) or the like may be added.
  • the charge generation layer and the charge transport layer include various chemical substances, antioxidants, and surfactants. Additives such as anti-curl agents and leveling agents can be added.
  • binder examples include silicone resin, polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate copolymer, polystyrene resin, polymethacrylate resin, polyacrylamide resin, polybutadiene resin, polyisoprene resin, melamine.
  • Resin, benzoguanamine resin, polychloroprene resin, polyacrylonitrile resin, ethyl cellulose resin, nitrocellulose resin, urea resin, phenol resin, phenoxy resin, polyvinyl butyral resin, formal resin, vinyl acetate resin, vinyl acetate / vinyl chloride copolymer resin, and Polyester carbonate resin etc. are mentioned.
  • thermosetting resin and a photocurable resin can also be used.
  • the binder is not particularly limited as long as it is an electrically insulating resin that can form a film in a normal state and does not impair the effects of the present invention. From the viewpoint of product performance, the binder is preferably used at 80% by mass or less based on the charge transport material.
  • plasticizer examples include, for example, biphenyl, biphenyl chloride, o-terphenyl, halogenated paraffin, dimethylnaphthalene, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, diethylene glycol phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl seba
  • plasticizer include, for example, biphenyl, biphenyl chloride, o-terphenyl, halogenated paraffin, dimethylnaphthalene, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, diethylene glycol phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl seba
  • Examples thereof include Kate, dibutyl sebacate, butyl laurate, methyl phthalyl ethyl glycolate, dimethyl glycol phthalate, methyl naphthalene, benzo
  • the curing catalyst include, for example, methanesulfonic acid, dodecylbenzenesulfonic acid, and dinonylnaphthalenedisulfonic acid.
  • the fluidity-imparting agent include modaflow, acronal 4F, and the like.
  • the pinhole control agent include benzoin and dimethyl phthalate. From the viewpoint of production cost, these plasticizer, curing catalyst, fluidity imparting agent, and pinhole control agent are preferably used in an amount of 5% by mass or less based on the charge transport material.
  • a sensitizing dye for example, a triphenylmethane dye (for example, methyl violet, crystal violet, knight blue, and Victoria blue)
  • an acridine dye for example, erythrosine
  • 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.
  • Specific examples thereof include, for example, succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, Pyromellitic anhydride, anhydrous meritic acid, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, p-nitrobenzonitrile, picryl chloride, quinone chloride Imido, chloranil, bromanyl, benzoquinone, 2,3-dichlorobenzoquinone, dichlorodicyanoparabenzoquinone, naphthoquinone
  • These compounds may be added to either the charge generation layer or the charge transport layer, and the blending ratio is preferably from the viewpoint of product performance when the amount of the charge generation material or the charge transport material is 100 parts by mass. It is 0.01 mass part or more and 200 mass parts or less, More preferably, it is 0.1 mass part or more and 50 mass parts or less.
  • tetrafluoroethylene resin for example, tetrafluoroethylene resin, trifluoroethylene chloride resin, tetrafluoroethylene hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluoroethylene dichloride Resins and their copolymers, and fluorine-based graft polymers may be used.
  • the blending ratio of these surface modifiers is preferably 0.1% by mass or more and 60% by mass or less, and more preferably 5% by mass or more and 40% by mass or less with respect to the binder resin. If the blending ratio is 0.1% by mass or more, surface modification such as surface durability and surface energy reduction is sufficient, and if it is 60% by mass or less, electrophotographic characteristics are not deteriorated. .
  • antioxidant for example, a hindered phenol antioxidant, an aromatic amine antioxidant, a hindered amine antioxidant, a sulfide antioxidant, and an organic phosphate antioxidant are preferable.
  • the blending ratio of these antioxidants is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 2% by mass or less with respect to the charge transport material from the viewpoint of product performance. is there.
  • the compounds represented by the chemical formulas [Chemical Formula 94] to [Chemical Formula 101] described in the specification of JP-A No. 11-172003 are preferable from the viewpoint of production cost and safety. is there.
  • These antioxidants may be used singly or in combination of two or more, and these are added to the surface protective layer, the undercoat layer and the blocking layer in addition to the photosensitive layer. May be.
  • the solvent used in forming the charge generation layer and the charge transport layer include, for example, aromatic solvents (for example, benzene, toluene, xylene, and chlorobenzene), ketones (for example, acetone, Methyl ethyl ketone, cyclopentanone, and cyclohexanone), alcohols (eg, methanol, ethanol, and isopropanol), esters (eg, ethyl acetate, and ethyl cellosolve), halogenated hydrocarbons (eg, carbon tetrachloride, tetraodor) Carbonated, chloroform, dichloromethane, and tetrachloroethane), ethers (eg, tetrahydrofuran, dioxolane, and dioxane), and amides (eg, dimethylformamide, dimethylsulfoxide, and diethylformamide) ), And the like.
  • the photosensitive layer of the single-layer type electrophotographic photosensitive member can be easily formed by using the above-described charge generating material, charge transporting material, and additive and applying the polycarbonate copolymer according to this embodiment as a binder resin. Can do. From the viewpoint of product performance, it is preferable to add at least one of a hole transport material and an electron transport material as the charge transport material. As the electron transport material, an electron transport material exemplified in JP-A-2005-139339 can be preferably applied from the viewpoint of production cost and safety. Each layer can be applied by using various kinds of application apparatuses such as a known apparatus. Specifically, for example, an applicator, a spray coater, a bar coater, a chip coater, a roll coater, a dip coater, a doctor blade, and the like are used. Can be done.
  • the thickness of the photosensitive layer in the electrophotographic photoreceptor is preferably 5 ⁇ m or more and 100 ⁇ m or less, more preferably 8 ⁇ m or more and 50 ⁇ m or less.
  • the thickness of the photosensitive layer is 5 ⁇ m or more, it is possible to prevent the initial potential from being lowered, and when it is 100 ⁇ m or less, it is possible to suppress deterioration of the electrophotographic characteristics.
  • the ratio of the charge generating material used in the production of the electrophotographic photosensitive member to the binder resin is preferably 1:99 to 30:70 in terms of mass ratio, and 3:97 to 15: More preferably, it is 85.
  • the ratio of the charge transport material: binder resin is preferably 10:90 to 80:20, more preferably 30:70 to 70:30, in terms of mass performance, from the viewpoint of product performance and production cost. .
  • the electrophotographic photosensitive member of this embodiment can be suitably used for an electrophotographic apparatus.
  • charging includes, for example, corona discharge (for example, corotron and scorotron) and contact charging (for example, charging roll and charging brush).
  • the charging roll include a DC charging method and an AC / DC superimposed charging method in which an AC voltage is superimposed.
  • any one of a halogen lamp, a fluorescent lamp, a laser (semiconductor, He—Ne), an LED, and a photoreceptor internal exposure method may be employed.
  • a dry development system for example, cascade development, two-component magnetic brush development, one-component insulating toner development, one-component conductive toner development, etc.
  • a wet development method for example, an electrostatic transfer method (for example, corona transfer, roller transfer, and belt transfer), a pressure transfer method, an adhesive transfer method, or the like is used.
  • fixing for example, heat roller fixing, radiant flash fixing, open fixing, and pressure fixing are used.
  • a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, or the like is used for cleaning / static elimination. A cleaner-less method may be adopted.
  • the toner resin for example, a styrene resin, a styrene-acrylic copolymer resin, a polyester, an epoxy resin, a cyclic hydrocarbon polymer, and the like can be applied.
  • the shape of the toner may be spherical or irregular.
  • a toner controlled to have a certain shape spheroid shape, potato shape, etc.
  • the toner may be any one of a pulverized toner, a suspension polymerization toner, an emulsion polymerization toner, a chemical granulation toner, and an ester extension toner.
  • the polycarbonate copolymer of the above embodiment is not limited to the mode used for the electrophotographic photoreceptor as described above, and can be applied to other uses, for example, an electronic component.
  • CF value (N / kg) is (CF value / solids concentration)
  • the CF value (N) is the number of chloro atoms in the bischloroformate oligomer represented by the general formula (101) or the general formula (102) contained in 1 L of the reaction solution
  • the solid concentration (kg / L) is the amount of solid content obtained by concentrating 1 L of the reaction solution.
  • 98.92 is the total atomic weight of two chlorine atoms, one oxygen atom and one carbon atom that are eliminated by polycondensation between bischloroformate oligomers.
  • OC-BP oligomer (bischloroformate)> 150.0 g (0.701 mol) of 2,2′-dimethyl-4,4′-biphenol (OC-BP) was suspended in 1100 mL of methylene chloride, and 186 g (1.88 mol) of phosgene was added and dissolved therein. It was. A solution prepared by dissolving 199.4 g (1.97 mol) of triethylamine in 460 mL of methylene chloride was added dropwise thereto at 13 ° C. to 16 ° C. over 2 hours and 50 minutes. The reaction mixture was stirred at 14-16 ° C. for 30 minutes.
  • the reaction mixture was washed by adding 5.0 ml of concentrated hydrochloric acid and 200 ml of pure water. Thereafter, washing with water was repeated until the aqueous layer became neutral to obtain a methylene chloride solution of an OC-BP oligomer having a chloroformate group at the molecular end.
  • the resulting solution had a chloroformate concentration of 0.51 mol / L, a solid concentration of 0.09 kg / L, and an average number of monomers of 1.01.
  • the raw material obtained in Production Example 2 is referred to as OCBP-CF.
  • Example 1 Z-CF (191 mL) and methylene chloride (297 mL) of Production Example 1 were injected into a reaction vessel equipped with a mechanical stirrer, a stirring blade, and a baffle plate. To this, p-tert-butylphenol (PTBP) (0.258 g) was added as an end-capping agent, and the mixture was stirred so as to be thoroughly mixed. After cooling to a temperature of 15 ° C. in the reactor, the dihydric phenol solution prepared in this solution (dihydric phenol solution preparation method: 127 N sodium hydroxide aqueous solution 127 mL (sodium hydroxide 11.4 g) was added.
  • PTBP p-tert-butylphenol
  • the reduced viscosity [ ⁇ sp / C] of the PC copolymer (PC-1) was 1.18 dL / g.
  • the structure of the PC copolymer (PC-1) was confirmed to be a PC copolymer comprising the following repeating units and composition from the NMR results.
  • PC-1 The structure of the PC copolymer (PC-1) was confirmed by the following procedure. First, attribution analysis was performed using 1 H-NMR spectrum and 13 C-NMR spectrum, and the molar copolymerization ratio of each skeleton unit, m / (m + n + l), n / (m + n + l), and l / ( m + n + 1) was calculated. The structures of other PC copolymers were confirmed in the same manner.
  • An electrophotographic photoreceptor was produced in which an aluminum foil (film thickness: 50 ⁇ m) was used as the conductive substrate, and a charge generation layer and a charge transport layer were sequentially laminated on the surface to form a laminated photosensitive layer.
  • a charge generation material 0.5 g of oxotitanium phthalocyanine was used, and 0.5 g of butyral resin was used as a binder resin.
  • PC copolymer (2 g) was dissolved in methylene chloride (12 mL) and cast onto a commercially available PET film using an applicator. This film was heated under reduced pressure to remove the solvent, and a film sample having a thickness of about 30 ⁇ m was obtained.
  • Photoreceptor wear resistance evaluation sample preparation PC copolymer (1 g) and the above CTM-1 (1 g) were dissolved in methylene chloride (10 mL) and cast on a commercially available PET film using an applicator. Filmed. This film was heated under reduced pressure to remove the solvent, and a film sample having a thickness of about 30 ⁇ m was obtained.
  • Example 2 Z-CF (191 mL) and methylene chloride (297 mL) of Production Example 1 were injected into a reaction vessel equipped with a mechanical stirrer, a stirring blade, and a baffle plate. To this, p-tert-butylphenol (PTBP) (0.206 g) was added as an end-capping agent, and the mixture was stirred so as to be thoroughly mixed. After cooling to a temperature of 15 ° C. in the reactor, the dihydric phenol solution prepared in this solution (dihydric phenol solution preparation method: 127 N sodium hydroxide aqueous solution 127 mL (sodium hydroxide 11.4 g) was added.
  • PTBP p-tert-butylphenol
  • the reduced viscosity [ ⁇ sp / C] of the PC copolymer (PC-2) was 1.36 dL / g.
  • the structure of the PC copolymer (PC-2) was confirmed to be a PC copolymer comprising the following repeating units and composition from the NMR results.
  • Example 3 Into a reaction vessel equipped with a mechanical stirrer, a stirring blade, and a baffle plate, OCBP-CF (401 mL) of Production Example 2 and methylene chloride (130 mL) were injected. To this was added p-tert-butylphenol (PTBP) (0.174 g) as a terminal blocking agent, Stir to ensure thorough mixing. After the reactor was cooled to 15 ° C., the dihydric phenol solution prepared in this solution (dihydric phenol solution preparation method: 150 mL of 1.45N potassium hydroxide aqueous solution (potassium hydroxide 12.7 g) was added.
  • PTBP p-tert-butylphenol
  • PC-3 PC copolymer
  • the reduced viscosity [ ⁇ sp / C] of the PC copolymer (PC-3) was 1.34 dL / g.
  • the structure of the PC copolymer (PC-3) was confirmed to be a PC copolymer comprising the following repeating units and composition from the NMR results.
  • Example 4 Z-CF (191 mL) and methylene chloride (297 mL) of Production Example 1 were injected into a reaction vessel equipped with a mechanical stirrer, a stirring blade, and a baffle plate. To this, p-tert-butylphenol (PTBP) (0.258 g) was added as an end-capping agent, and the mixture was stirred so as to be thoroughly mixed. After cooling to a temperature of 15 ° C. in the reactor, the dihydric phenol solution prepared in this solution (dihydric phenol solution preparation method: 127 N sodium hydroxide aqueous solution 127 mL (sodium hydroxide 11.4 g) was added.
  • PTBP p-tert-butylphenol
  • the obtained reaction mixture was diluted with 1.0 L of methylene chloride and 0.12 L of water and washed.
  • the lower layer was separated and further washed with 0.20 L of water once, 0.20 L of 0.03N hydrochloric acid once, and 0.20 L of water three times in this order.
  • the obtained methylene chloride solution was dropped into methanol with stirring, and the obtained reprecipitate was filtered and dried to obtain a PC copolymer (PC-7) having the following structure.
  • the reduced viscosity [ ⁇ sp / C] of the PC copolymer (PC-7) was 1.16 dL / g.
  • the structure of the PC copolymer (PC-7) was confirmed to be a PC copolymer comprising the following repeating units and composition from the NMR results.
  • Example 5 Z-CF (191 mL) and methylene chloride (297 mL) of Production Example 1 were injected into a reaction vessel equipped with a mechanical stirrer, a stirring blade, and a baffle plate. To this, p-tert-butylphenol (PTBP) (0.258 g) was added as an end-capping agent, and the mixture was stirred so as to be thoroughly mixed. After cooling to a temperature of 15 ° C. in the reactor, the dihydric phenol solution prepared in this solution (dihydric phenol solution preparation method: 127 N sodium hydroxide aqueous solution 127 mL (sodium hydroxide 11.4 g) was added.
  • PTBP p-tert-butylphenol
  • the obtained reaction mixture was diluted with 1.0 L of methylene chloride and 0.12 L of water and washed. The lower layer was separated and further washed with 0.20 L of water once, 0.20 L of 0.03N hydrochloric acid once, and 0.20 L of water three times in this order.
  • the obtained methylene chloride solution was dropped into methanol with stirring, and the obtained reprecipitate was filtered and dried to obtain a PC copolymer (PC-8) having the following structure.
  • the reduced viscosity [ ⁇ sp / C] of the PC copolymer (PC-8) was 1.17 dL / g.
  • the structure of the PC copolymer (PC-8) was confirmed to be a PC copolymer comprising the following repeating units and composition from the NMR results.
  • Example 6 Z-CF (191 mL) and methylene chloride (297 mL) of Production Example 1 were injected into a reaction vessel equipped with a mechanical stirrer, a stirring blade, and a baffle plate. To this, p-tert-butylphenol (PTBP) (0.258 g) was added as an end-capping agent, and the mixture was stirred so as to be thoroughly mixed. After cooling to a temperature of 15 ° C. in the reactor, the dihydric phenol solution prepared in this solution (dihydric phenol solution preparation method: 127 N sodium hydroxide aqueous solution 127 mL (sodium hydroxide 11.4 g) was added.
  • PTBP p-tert-butylphenol
  • the obtained reaction mixture was diluted with 1.0 L of methylene chloride and 0.12 L of water and washed. The lower layer was separated and further washed with 0.20 L of water once, 0.20 L of 0.03N hydrochloric acid once, and 0.20 L of water three times in this order.
  • the obtained methylene chloride solution was dropped into methanol with stirring, and the obtained reprecipitate was filtered and dried to obtain a PC copolymer (PC-9) having the following structure.
  • the reduced viscosity [ ⁇ sp / C] of the PC copolymer (PC-9) was 1.18 dL / g.
  • the structure of the PC copolymer (PC-9) was confirmed to be a PC copolymer comprising the following repeating units and composition from the NMR results.
  • the reduced viscosity [ ⁇ sp / C] of the PC copolymer (PC-4) was 1.17 dL / g.
  • the structure of the PC copolymer (PC-4) was confirmed to be a PC copolymer having the following repeating units and molar copolymerization ratios from the NMR results.
  • the reduced viscosity [ ⁇ sp / C] of the PC copolymer (PC-5) was 1.36 dL / g.
  • the structure of the PC copolymer (PC-5) was confirmed to be a PC copolymer comprising the following repeating units and molar copolymerization ratios from the NMR results.
  • dihydric phenol solution preparation method 93 mL of 2.3N sodium hydroxide aqueous solution (9.11 g of sodium hydroxide) was prepared in this solution, and after cooling to room temperature or lower, antioxidant was prevented.
  • the reduced viscosity [ ⁇ sp / C] of the PC copolymer (PC-6) was 1.17 dL / g.
  • the structure of the PC copolymer (PC-6) was confirmed to be a PC copolymer comprising the following repeating units and composition from the NMR results.
  • Table 1 shows the evaluation results of Examples 1 to 6 and Comparative Examples 1 to 3.
  • a comparison between Example 1 and Examples 4 to 6 and Comparative Example 1 shows that the PC copolymer of Example 1 containing an amide group-containing skeleton even with a resin containing a BisZ (bisphenol Z) skeleton and a BP (biphenol) skeleton.
  • PC-1 and the PC copolymers (PC-7) to (PC-9) of Examples 4 to 6 improvement in wear resistance was confirmed. Since PC-1 and PC-7 to PC-9 and PC-4 have the same reduced viscosity, it was found that the amide group-containing skeleton contributes to wear resistance.
  • Example 2 and Comparative Example 2 were compared, it was confirmed that the wear resistance of the PC copolymer (PC-2) containing an amide group-containing skeleton was also improved. Since PC-2 and PC-5 have similar reduced viscosities, it was found that the amide group-containing skeleton contributes to wear resistance.
  • the PC copolymer (PC-3) of Example 3 has been confirmed to have sufficiently high wear resistance due to the high content of the OCBP (o-cresol biphenol) skeleton, but it also contains an amide group-containing skeleton. Very good wear resistance was confirmed. It was found that the electrical characteristics of Examples 1 to 6 were maintained equivalent to those of Comparative Examples 1 and 2.
  • Comparative Examples 1 and 2 are sufficient as the characteristics required for the resin used as the electrophotographic photosensitive member, it was found that Examples 1 to 6 also have sufficient electrical characteristics. . Comparing Example 1 and Examples 4 to 6 with Comparative Example 3, both are resins containing a BisZ skeleton and a BP skeleton, but PC copolymers (PC-1) and (PC It was confirmed that -7) to (PC-9) were superior in hydrolysis resistance to the PC copolymer (PC-6) containing a urethane bond.
  • PC copolymer (PC-1) (1 g) or PC copolymer (PC-4) (1 g) and the above CTM-1 (1 g) were dissolved in methylene chloride (10 mL).
  • methylene chloride (10 mL) methylene chloride
  • Table 2 shows the adhesion evaluation results of the PC copolymer (PC-1) of Example 1 and the PC copolymer (PC-4) of Comparative Example 1.
  • PC-1 PC copolymer
  • PC-4 PC copolymer

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Abstract

L'invention concerne un copolymère de polycarbonate, qui est caractérisé en ce qu'il possède un motif répétitif A qui contient un groupe représenté par la formule générale (1A). Dans la formule générale (1A), chacun de Ar1 et Ar2 représente d'une manière indépendante un groupe aromatique monovalent ou divalent ou un groupe aliphatique monovalent ou divalent ; et au moins l'un des fragments Ar1 et Ar2 représente un groupe aromatique monovalent ou divalent.
PCT/JP2017/044980 2016-12-20 2017-12-14 Copolymère de polycarbonate, liquide de revêtement, corps photosensible électrophotographique, appareil électrophotographique, et procédé de production d'un copolymère de polycarbonate WO2018116960A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08248650A (ja) * 1995-03-08 1996-09-27 Idemitsu Kosan Co Ltd 電子写真感光体
JP2009019040A (ja) * 1997-02-18 2009-01-29 Rutgers The State Univ ヒドロキシ酸から誘導されたモノマー及びそれから調製されたポリマー
JP2009517472A (ja) * 2005-11-29 2009-04-30 ゼネラル・エレクトリック・カンパニイ ジヒドロキシ芳香族化合物、調製方法、それにより製造されたポリマー、およびポリマー調製方法
WO2010079698A1 (fr) * 2009-01-08 2010-07-15 出光興産株式会社 Résine de polycarbonate, liquide de revêtement la contenant, et corps photosensible électrophotographique

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11269263B2 (en) * 2015-12-16 2022-03-08 Idemitsu Kosan Co., Ltd. Bischloroformate composition, bischloroformate composition production method, bischloroformate composition-containing solution, polycarbonate resin, polycarbonate resin production method, coating liquid, electrophotographic photoreceptor, and electrophotographic device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08248650A (ja) * 1995-03-08 1996-09-27 Idemitsu Kosan Co Ltd 電子写真感光体
JP2009019040A (ja) * 1997-02-18 2009-01-29 Rutgers The State Univ ヒドロキシ酸から誘導されたモノマー及びそれから調製されたポリマー
JP2009517472A (ja) * 2005-11-29 2009-04-30 ゼネラル・エレクトリック・カンパニイ ジヒドロキシ芳香族化合物、調製方法、それにより製造されたポリマー、およびポリマー調製方法
WO2010079698A1 (fr) * 2009-01-08 2010-07-15 出光興産株式会社 Résine de polycarbonate, liquide de revêtement la contenant, et corps photosensible électrophotographique

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