CN106795365B - Composition for electrophotographic apparatus member - Google Patents

Composition for electrophotographic apparatus member Download PDF

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Publication number
CN106795365B
CN106795365B CN201580046605.7A CN201580046605A CN106795365B CN 106795365 B CN106795365 B CN 106795365B CN 201580046605 A CN201580046605 A CN 201580046605A CN 106795365 B CN106795365 B CN 106795365B
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crosslinking agent
composition
electrophotographic apparatus
antioxidant
phosphite
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CN106795365A (en
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宇野和树
安田和敬
矢岛尚也
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Osaka Soda Co Ltd
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Osaka Soda Co Ltd
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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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C13/00—Rolls, drums, discs, or the like; Bearings or mountings therefor
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16G—BELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
    • F16G1/00—Driving-belts
    • F16G1/06—Driving-belts made of rubber
    • 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
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G03G15/02—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices
    • G03G15/0208—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices by contact, friction or induction, e.g. liquid charging apparatus
    • G03G15/0216—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices by contact, friction or induction, e.g. liquid charging apparatus by bringing a charging member into contact with the member to be charged, e.g. roller, brush chargers
    • G03G15/0233—Structure, details of the charging member, e.g. chemical composition, surface properties

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Electrostatic Charge, Transfer And Separation In Electrography (AREA)
  • Dry Development In Electrophotography (AREA)
  • Electrophotography Configuration And Component (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

A composition for electrophotographic device members, characterized by comprising (a) a polyether polymer, (b) an antioxidant, and (c) a crosslinking agent, wherein the antioxidant (b) contains at least one selected from the group consisting of a sulfur-based antioxidant and a phosphoric acid-based antioxidant. (b) The age resister is preferably the following age resisters: after the composition comprising (a) a polyether polymer and (b) an antiaging agent is left at 170 ℃ for 2 hours, the Mooney viscosity measured according to JIS K6300-1 is 0 to-33 minutes relative to the Mooney viscosity measured before the leaving.

Description

Composition for electrophotographic apparatus member
Technical Field
The present invention relates to a composition for electrophotographic apparatus members. The electrophotographic apparatus member of the present invention is useful as a semiconductive rubber roller or a rubber belt for charging, developing, transferring, and the like in an electrophotographic process in a copying machine, a printer, and the like.
Background
In recent years, charging rollers, transfer rollers, and developing rollers used in the contact charging system are required to have higher image quality and higher speed.
In general, as the electrical characteristics of the charging roller, the transfer roller, and the developing roller, semiconductivity is required, and since the charging roller, the transfer roller, and the developing roller are in contact with the photoreceptor, the photoreceptor is required to be less likely to be damaged and less staining to the photoreceptor, and members made of a rubber material are frequently used.
In particular, rubber materials for rubber charging rollers, transfer rollers, and the like of electrophotographic copying machines are required to satisfy the following conditions in view of the demand for high image quality and high speed.
(1) The test environment was low temperature and low humidity and high temperature and high humidity, and the test sample had semiconductive characteristics.
(2) It is preferable that the printing characteristics do not change even under low temperature and low humidity conditions or high temperature and high humidity conditions, and therefore the environmental dependence of the volume resistivity is small.
(3) The photoreceptor is less likely to be contaminated with respect to members, charging rollers, transfer rollers, and the like, which are in direct contact with the photoreceptor.
As described above, the above-mentioned photosensitive member has a semiconductive property and a small environmental dependency of volume resistivity in a low-temperature low-humidity environment and a high-temperature high-humidity environment, and studies using a polyether copolymer such as epichlorohydrin polymer have been advanced, but there has been no sufficient study on further reduction of the contamination of the photosensitive member (see patent document 1).
Therefore, further studies have been required for a compounding agent compounded in epichlorohydrin rubber for the purpose of further reducing the staining property of the photoreceptor.
Prior art documents patent documents
Patent document 1 international publication 2011/046175
Disclosure of Invention
Technical problem
The present invention was made in view of the above circumstances, and an object of the present invention is to provide a composition for electrophotographic device members and a crosslinked product thereof, which are used as a raw material for semiconductive rubber rollers and semiconductive belts used in copiers, printers, and the like in electrophotography, and which can further reduce the staining property of photoreceptors when the semiconductive rubber rollers and the semiconductive belts are produced.
Means for solving the problems
The inventor finds that: the present invention has been accomplished by solving the above problems by a composition for electrophotographic device members and a crosslinked product thereof, which comprises (a) a polyether polymer, (b) an antioxidant comprising at least one member selected from the group consisting of a sulfur-based antioxidant and a phosphoric acid-based antioxidant, and (c) a crosslinking agent.
In the composition for electrophotographic apparatus members of the present invention, (b) the age resister is preferably: an anti-aging agent which comprises a composition comprising (a) a polyether polymer and (b) an anti-aging agent and which has a Mooney viscosity measured in accordance with JIS K6300-1 of 0 to-33 minutes after leaving (aging) the composition at 170 ℃ for 2 hours.
In the composition for electrophotographic apparatus members of the present invention, it is preferable that: (a) the polyether polymer contains at least one or more units selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, 2- (methoxyethoxy) ethyl glycidyl ether, allyl glycidyl ether, and glycidyl methacrylate in a structural unit.
Preferably, (b) the age resistor is at least one selected from the group consisting of triphenyl phosphite, tris (nonylphenyl) phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monotridecyl phosphite, dilauryl 3,3 ' -thiodipropionate, distearyl-3, 3 ' -thiodipropionate and dimyristyl-3, 3 ' -thiodipropionate.
The compounding amount of the antioxidant (b) is preferably 3.0 parts by weight or less based on 100 parts by weight of the polyether polymer (a).
In the composition for electrophotographic apparatus members of the present invention, it is preferable that: (c) the crosslinking agent is at least one selected from the group consisting of polyamine-based crosslinking agents, thiourea-based crosslinking agents, thiadiazole-based crosslinking agents, mercaptotriazine-based crosslinking agents, pyrazine-based crosslinking agents, quinoxaline-based crosslinking agents, bisphenol-based crosslinking agents, peroxide-based crosslinking agents and sulfur-based crosslinking agents.
The crosslinked material for electrophotographic apparatus members obtained by crosslinking the composition for electrophotographic apparatus members preferably has a glass transition temperature of from-10 ℃ to-60 ℃ based on JIS K6394.
The crosslinked material for electrophotographic apparatus members obtained by crosslinking the composition for electrophotographic apparatus members of the present invention is a semiconductive rubber roller or a conductive endless rubber belt, and is mainly used as an electrophotographic apparatus member.
The present invention also relates to the use of a composition containing (a) a polyether polymer, (b) an antioxidant selected from at least one of a sulfur-based antioxidant and a phosphoric acid-based antioxidant, and (c) a crosslinking agent, in an electrophotographic device member.
In the composition, (b) the anti-aging agent is preferably: an anti-aging agent which comprises a composition comprising (a) a polyether polymer and (b) an anti-aging agent and which has a Mooney viscosity measured in accordance with JIS K6300-1 of 0 to-33 minutes after leaving (aging) the composition in an environment at 170 ℃ for 2 hours.
Among the compositions, preferred are: (a) the polyether polymer contains at least one or more units selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, 2- (methoxyethoxy) ethyl glycidyl ether, allyl glycidyl ether, and glycidyl methacrylate in a structural unit.
Among the compositions, preferred are: (b) the antiaging agent is at least one selected from the group consisting of triphenyl phosphite, tris (nonylphenyl) phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monotridecyl phosphite, dilauryl 3,3 ' -thiodipropionate, distearyl-3, 3 ' -thiodipropionate and dimyristyl-3, 3 ' -thiodipropionate.
In the composition, the amount of the antioxidant (b) is preferably 3.0 parts by weight or less based on 100 parts by weight of the polyether polymer (a).
In the composition, the crosslinking agent (c) is preferably at least one selected from the group consisting of a polyamine-based crosslinking agent, a thiourea-based crosslinking agent, a thiadiazole crosslinking agent, a mercaptotriazine-based crosslinking agent, a pyrazine-based crosslinking agent, a quinoxaline-based crosslinking agent, a bisphenol-based crosslinking agent, a peroxide-based crosslinking agent and a sulfur-based crosslinking agent.
Effects of the invention
Since a crosslinked material obtained by crosslinking the composition for electrophotographic device members obtained according to the present invention causes less contamination of a photoreceptor than a crosslinked material obtained by crosslinking a polyether polymer used in a conventional charging roller, developing roller, transfer roller, or the like, the crosslinked material is very useful for semiconductive rubber rollers, belts, and the like of copying machines, printers, and the like.
Detailed Description
The present invention will be described in detail below.
The composition for electrophotographic device members is characterized by containing (a) a polyether polymer, (b) an antioxidant containing at least one selected from a sulfur-based antioxidant and a phosphoric acid-based antioxidant, and (c) a crosslinking agent.
The polyether polymer (a) used in the composition for electrophotographic device members of the present invention is a homopolymer or copolymer of a compound selected from the group consisting of glycidyl groups such as ethylene oxide, propylene oxide, butylene oxide, etc., glycidyl groups such as methyl glycidyl ether, ethyl glycidyl ether, 2- (methoxyethoxy) ethyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate, phenyl glycidyl ether, etc., epihalohydrins such as epichlorohydrin and epibromohydrin, and styrene oxide, and one or more of these homopolymers or copolymers may be used or two or more of these may be used in combination.
The polyether polymer (a) preferably contains at least one or more units selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, 2- (methoxyethoxy) ethyl glycidyl ether, allyl glycidyl ether, and glycidyl methacrylate in a constituent unit, more preferably contains two units selected from the group consisting of epichlorohydrin, propylene oxide, ethylene oxide, and allyl glycidyl ether in a constituent unit, further preferably contains units of ethylene oxide and allyl glycidyl ether in a constituent unit, and particularly preferably contains units of epichlorohydrin, ethylene oxide, and allyl glycidyl ether in a constituent unit.
In the case of the epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, the copolymerization ratio thereof is preferably 5 to 95 mol%, more preferably 10 to 75 mol%, and particularly preferably 10 to 65 mol%, based on the structural unit of epichlorohydrin. The structural unit based on ethylene oxide is preferably from 4 to 94 mol%, more preferably from 24 to 89 mol%, particularly preferably from 34 to 89 mol%. The structural unit based on allyl glycidyl ether is preferably 1 to 10 mol%, more preferably 1 to 8 mol%, and particularly preferably 1 to 7 mol%.
The copolymerization composition of the epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer can be determined from the chlorine content and iodine value.
The chlorine content was measured by a potentiometric titration method in accordance with the method described in JIS K7229. From the chlorine content obtained, the molar fraction of structural units based on epichlorohydrin is calculated.
The iodine value was measured by a method in accordance with JIS K6235. From the iodine value obtained, the mole fraction of the structural unit based on allyl glycidyl ether was calculated.
The mole fraction of the structural unit based on ethylene oxide was calculated from the mole fraction of the structural unit based on epichlorohydrin and the mole fraction of the structural unit based on allyl glycidyl ether.
The composition for electrophotographic device members of the present invention may be not only the polyether polymer (a) but also a polymer alloy of the polyether polymer (a) and another rubber, and as the polymer component, it is preferable to use only the polyether polymer (a) or to contain more than 90% by weight of the polyether polymer in the polymer component. The other rubber is preferably a mixture with at least one selected from the group consisting of chloroprene rubber, ethylene-propylene-diene rubber, and acrylonitrile butadiene rubber.
The (b) used in the composition for an electrophotographic device member of the present invention contains at least one kind of antioxidant selected from a sulfur-based antioxidant and a phosphoric acid-based antioxidant, and may contain only one kind of the sulfur-based antioxidant or the phosphoric acid-based antioxidant, or both the sulfur-based antioxidant and the phosphoric acid-based antioxidant.
The sulfur-based antioxidant and the phosphoric acid-based antioxidant used in the composition for electrophotographic device members of the present invention can be used without particular limitation.
Examples of the sulfur-based antioxidant include organic thioacid-based antioxidants, thiourea-based antioxidants, and thioether-based antioxidants.
Examples of the organic thioacid-based antiaging agent include dilauryl 3,3 ' -thiodipropionate, distearyl 3,3 ' -thiodipropionate, dimyristyl 3,3 ' -thiodipropionate, and nickel dibutyldithiocarbamate.
Examples of the thiourea-based antioxidant include 1, 3-bis (dimethylaminopropyl) -2-thiourea and tributylthiourea.
Examples of the thioether-based antioxidant include bis [3- (dodecylthio) propionic acid 2,2 '-bis [ [3- (dodecylthio) -1-oxopropyloxy ] methyl ] -1, 3-propanediyl, 3' -thiodipropionic acid ditridecyl, and bis [ 2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl ] thioether.
Examples of the phosphoric acid-based antioxidant include tris (nonylphenyl) phosphite, triphenyl phosphite, diphenylisodecyl phosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylmonotridecyl phosphite, phenyldiisodecyl phosphite, 4' -butylidene-bis (3-methyl-6-tert-butylphenyl ditridecyl) phosphite, cyclopentylpentaerythritol bis (cyclopentadienetetraylbis), triphosphite, diisodecyl pentaerythritol diphosphite, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3, 5-di-tert-butyl-4-hydroxybenzyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and mixtures thereof, 10-decyloxy-9, 10-dihydro-9-oxa-10-phosphaphenanthrene, tris (2, 4-di-tert-butylphenyl) phosphite, cyclopentylpentaerythritol bis (2, 6-di-tert-butyl-4-methylphenyl) phosphite, 2-methylene-bis (4, 6-di-tert-butylphenyl) octyl phosphite.
The age resister used in the composition for an electrophotographic apparatus member of the present invention is preferably triphenyl phosphite, tris (nonylphenyl) phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monotridecyl phosphite, dilauryl-3, 3 ' -thiodipropionate, distearyl-3, 3 ' -thiodipropionate or dimyristyl-3, 3 ' -thiodipropionate.
The (b) age resisters used in the composition for electrophotographic apparatus members of the present invention are preferably: an anti-aging agent in which the Mooney viscosity measured according to JIS K6300-1 after leaving a composition comprising (a) a polyether polymer and (b) an anti-aging agent at 170 ℃ for 2 hours is 0 to-33 minutes.
The composition for electrophotographic device members of the present invention preferably further contains a phenolic antioxidant as an antioxidant.
Specific examples of the phenol-based antiaging agent include 2, 6-di-t-butyl-4-methylphenol, monophenol, 2 '-methylenebis (4-ethyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), 4 '-butylidenebis (3-methyl-6-t-butylphenol), 4' -thiobis (3-methyl-6-t-butylphenol), butylated reaction product of p-cresol and dicyclopentadiene, 2,5 '-di-t-butylhydroquinone, 2, 5' -di-t-amylhydroquinone, 2, 6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2, 6-di-t-butyl-4-ethylphenol, stearyl- β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) propionate, 1,3, 5-tris (3, 5-t-butyl-4-hydroxybenzyl) propionate, bis (3,5 '-di-t-butylidene) phenol, bis (3, 3' -butylmethyl-4-hydroxy-methylbenzyl) cresol), bis (3,5 '-butylidene) 2, 3' -butylidene) 2, 6-methyl-tert-butyl-4-butylcresol, and bis (3,3 '-butylbis (3, 5' -butylidene) methyl-butyl-methyl-4-tert-butyl-6-tert-butyl-methyl-tert-butyl-methyl-4-tert-butyl-methyl) phenol), and bis (4-butyl-tert-butyl-methyl) cresol.
The amount of at least one antioxidant selected from the sulfur-based antioxidants and the phosphoric acid-based antioxidants used in the composition for electrophotographic apparatus members of the present invention is preferably 3.0 parts by weight or less in the upper limit, more preferably 2.0 parts by weight or less, and particularly preferably 1.0 part by weight or less in the lower limit, and preferably 0.01 part by weight or more, more preferably 0.05 part by weight or more, and particularly preferably 0.1 part by weight or more in the lower limit, based on 100 parts by weight of the polyether polymer (a).
The amount of the phenolic antioxidant used in the composition for electrophotographic device members of the present invention is preferably 3.0 parts by weight or less in the upper limit, more preferably 2.0 parts by weight or less, and particularly preferably 1.0 part by weight or less, and preferably 0.01 parts by weight or more in the lower limit, more preferably 0.05 parts by weight or more, and particularly preferably 0.1 parts by weight or more, based on 100 parts by weight of the polyether polymer (a).
Examples of the crosslinking agent (c) used in the composition for an electrophotographic apparatus member of the present invention include a polyamine-based crosslinking agent, a thiourea-based crosslinking agent, a thiadiazole-based crosslinking agent, a mercaptotriazine-based crosslinking agent, a pyrazine-based crosslinking agent, a quinoxaline-based crosslinking agent, a bisphenol-based crosslinking agent, a peroxide-based crosslinking agent, and a sulfur-based crosslinking agent, and a quinoxaline-based crosslinking agent, a peroxide-based crosslinking agent, and a sulfur-based crosslinking agent are preferable, and a quinoxaline-based crosslinking agent and a sulfur-based crosslinking agent are particularly preferable. The crosslinking agent may be used alone or in combination of 2 or more compounds.
Examples of the polyamine-based crosslinking agent include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, p-phenylenediamine, isopropylphenylenediamine, N' -cinnamylidene-1, 6-hexanediamine, ethylenediamine carbamate, and hexamethylenediamine carbamate.
Examples of the thiourea-based crosslinking agent include ethylenethiourea, 1, 3-diethylthiourea, 1, 3-dibutylthiourea, and trimethylthiourea.
Examples of the thiadiazole-based crosslinking agent include 2, 5-dimercapto-1, 3, 4-thiadiazole, 2-mercapto-1, 3, 4-thiadiazole-5-thiobenzoate, and the like.
Examples of the mercaptotriazine-based crosslinking agent include 2,4, 6-trimercapto-1, 3, 5-triazine, 2-methoxy-4, 6-dimercaptotriazine, 2-hexylamino-4, 6-dimercaptotriazine, 2-diethylamino-4, 6-dimercaptotriazine, 2-cyclohexylamino-4, 6-dimercaptotriazine, 2-dibutylamino-4, 6-dimercaptotriazine, 2-phenylamino-4, 6-dimercaptotriazine, and 2-phenylamino-4, 6-dimercaptotriazine.
Examples of the pyrazine crosslinking agent include 2, 3-dimercaptopyrazine derivatives, and examples of the p-2, 3-dimercaptopyrazine derivatives include pyrazine-2, 3-dithiocarbonate, 5-methyl-2, 3-dimercaptopyrazine, 5-ethylpyrazine-2, 3-dithiocarbonate, 5, 6-dimethyl-2, 3-dimercaptopyrazine, and 5, 6-dimethylpyrazine-2, 3-dithiocarbonate.
Examples of the quinoxaline crosslinking agent include 2, 3-dimercaptoquinoxaline derivatives, and examples of the 2, 3-dimercaptoquinoxaline derivative include quinoxaline-2, 3-dithiocarbonate, 6-methylquinoxaline-2, 3-dithiocarbonate, 6-ethyl-2, 3-dimercaptoquinoxaline, 6-isopropylquinoxaline-2, 3-dithiocarbonate, and 5, 8-dimethylquinoxaline-2, 3-dithiocarbonate.
Examples of the bisphenol-based crosslinking agent include 4,4 '-dihydroxydiphenyl sulfoxide, 4' -dihydroxydiphenyl sulfone (bisphenol S), 1-cyclohexylene-bis (4-hydroxyphenyl), 2-chloro-1, 4-cyclohexylene-bis (4-hydroxyphenyl), 2-isopropylene-bis (4-hydroxyphenyl) (bisphenol a), hexafluoroisopropylene-bis (4-hydroxyphenyl) (bisphenol AF), and 2-fluoro-1, 4-phenylene-bis (4-hydroxyphenyl).
Examples of the peroxide-based crosslinking agent include t-butyl hydroperoxide, p-cumene hydroperoxide, dicumyl peroxide, t-butyl peroxide, 1, 3-bis (t-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, benzoyl peroxide, and t-butyl peroxybenzoate.
Examples of the sulfur-based sulfur crosslinking agent include sulfur, morpholine disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, N '-dimethyl-N, N' -diphenylthiuram disulfide, dipentamethylenethiuram tetrasulfide and dipentamethylenethiuram hexasulfide.
The amount of the crosslinking agent (c) used in the composition for electrophotographic device members of the present invention is 0.1 to 10 parts by weight, preferably 0.5 to 1.5 parts by weight, based on 100 parts by weight of the polyether polymer (a).
In addition, a known accelerator (i.e., a crosslinking accelerator) used together with a crosslinking agent may be directly used for the composition for an electrophotographic apparatus member of the present invention.
Examples of the crosslinking accelerator include thiazole crosslinking accelerators, sulfenamide crosslinking accelerators, and thiuram crosslinking accelerators.
Examples of the thiazole-based crosslinking accelerator include bis-2-benzothiazyl disulfide, 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and zinc salt of 2-mercaptobenzothiazole.
Specific examples of the sulfenamide-based crosslinking accelerator include N-ethyl-2-benzothiazolesulfenamide, N-t-butyl-2-benzothiazolesulfenamide, N-diisopropyl-2-benzothiazolesulfenamide, N-dicyclohexyl-2-benzothiazolesulfenamide, N-oxy-diethylene-2-benzothiazolesulfenamide, and the like.
Specific examples of the thiuram-based crosslinking accelerator include tetramethylthiuram disulfide, tetramethylthiuram monosulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide, and the like.
In the composition for electrophotographic device members of the present invention, the amount of the crosslinking accelerator is 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the polyether polymer (a).
The composition for electrophotographic apparatus members of the present invention may optionally contain compounding agents other than the above, for example, an acid acceptor, a lubricant, an anti-aging agent, a filler, a reinforcing agent, a plasticizer, a processing aid, a flame retardant, a pigment, and the like, as long as the effects of the present invention are not impaired. Further, rubber, resin, and the like, which are generally used in the art, may be mixed within a range in which the characteristics of the present invention are not lost.
As the acid scavenger used in the present invention, a known acid scavenger can be used, and a metal compound and/or an inorganic microporous crystal are preferable. Examples of the metal compound include metal compounds such as oxides, hydroxides, carbonates, carboxylates, silicates, borates, phosphites of group II (group 2 and group 12) metals of the periodic table, oxides, hydroxides, carboxylates, silicates, sulfates, nitrates, phosphates of group III (group 3 and group 13) metals of the periodic table, oxides of group IV (group 4 and group 14) metals of the periodic table, alkali carbonates, alkali carboxylates, alkali phosphites, alkali sulfites, and tribasic sulfates.
Specific examples of the metal compound include magnesium oxide, magnesium hydroxide, aluminum hydroxide, barium hydroxide, sodium carbonate, magnesium carbonate, barium carbonate, quick lime, slaked lime, calcium carbonate, calcium silicate, calcium stearate, zinc stearate, calcium titanate, calcium phosphite, zinc white, tin oxide, lead monoxide, trilead tetroxide, white lead, dibasic lead phthalate, dibasic lead carbonate, tin stearate, basic lead phosphite, basic tin phosphite, basic lead sulfite, tribasic lead sulfate, and the like, and sodium carbonate, magnesium oxide, magnesium hydroxide, quick lime, slaked lime, calcium silicate, zinc white, and the like are preferable.
The term "inorganic microporous crystal" means a crystalline porous body, and is clearly distinguishable from an amorphous porous body, for example, silica gel, alumina, and the like. Examples of such inorganic microporous crystals include zeolites, aluminum phosphate-based molecular sieves, layered silicates, synthetic hydrotalcites, alkali metal titanates, and the like. As a particularly preferred acid acceptor, synthetic hydrotalcite may be mentioned.
The zeolite may be a natural zeolite, a synthetic zeolite of a type, X type or Y type, a sodalite type, a natural or synthetic mordenite, ZSM-5 or other various zeolites, or metal substitutes thereof, and they may be used alone or in combination of 2 or more kinds. In addition, the metal of the metal substitute is usually sodium. As the zeolite, a zeolite having a large acid-absorbing ability is preferable, and a type a zeolite is preferable.
The synthetic hydrotalcite is represented by the following general formula (1).
MgXZnYAlZ(OH)(2(X+Y)+3Z-2)CO3·wH2O(1)
[ wherein x and y each represent a real number of 0 to 10 having a relationship of x + y being 1 to 10, z represents a real number of 1 to 5, and w represents a real number of 0 to 10. ]
Examples of the hydrotalcite compound represented by the general formula (1) include Mg4.5Al2(OH)13CO3·3.5H2O、Mg4.5Al2(OH)13CO3、Mg4Al2(OH)12CO3·3.5H2O、Mg6Al2(OH)16CO3·4H2O、Mg5Al2(OH)14CO3·4H2O、Mg3Al2(OH)10CO3·1.7H2O、Mg3ZnAl2(OH)12CO3·3.5H2O、Mg3ZnAl2(OH)12CO3And the like.
In the composition for electrophotographic device members of the present invention, the amount of the acid acceptor is preferably 0.2 to 50 parts by weight, and particularly preferably 1 to 20 parts by weight, based on 100 parts by weight of the polyether polymer (a).
As a method for compounding the composition for electrophotographic apparatus members of the present invention, any of the apparatuses conventionally used in the field of polymer processing, for example, a mixing roll, a Banbury mixer, various kneading machines, and the like can be used. Examples of the molding method include compression molding, extrusion molding, and injection molding using a mold.
The crosslinked material using the composition for electrophotographic device members of the present invention is obtained by adding (c) a crosslinking agent and heating the mixture to usually 100 to 200 ℃, and the crosslinking time varies depending on the temperature, but usually 0.5 to 300 minutes.
In the composition for electrophotographic apparatus members of the present invention, the glass transition temperature as measured in the dynamic viscoelasticity test is preferably from-10 ℃ to-60 ℃, more preferably from-20 ℃ to-60 ℃, and still more preferably from-40 ℃ to-50 ℃. The glass transition temperature obtained by the dynamic viscoelasticity test can be measured in accordance with JIS K6394.
The electrophotographic apparatus member of the present invention can also be formed by laminating the crosslinked product of the present invention on a substrate. The base material varies depending on the application, and examples thereof include resins and metals such as aluminum and iron. An intermediate layer may be provided between the substrate and the crosslinked material, and a surface layer may be further provided on the crosslinked material. The electrophotographic apparatus member of the present invention can be used as a semiconductive roller, a belt, or the like in electrophotographic apparatuses such as copying machines, printers, and the like.
The following examples and comparative examples specifically illustrate the present invention. It should be noted that the present invention is not limited thereto.
The compounding agents used in examples and comparative examples are shown below.
Separately, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer EPION-301 manufactured by Cao corporation "
The corresponding 2 Sumilizer TPS, a sulfur-series anti-aging agent manufactured by Sumitomo chemical corporation "
Separately, 3 manufactured by ADEKA corporation, phosphoric acid series antiaging agent ADK STAB TPP "
Separately, 4 Antage BHT, a phenol-series anti-aging agent manufactured by Chuanyou chemical company "
Separately, 5 New thiuram series crosslinking accelerator Nocceler TS manufactured by Engineer chemical Co., Ltd "
'Nocceller DM' thiazole cross-linking accelerator manufactured by Hawaii 6 Innov New chemical company "
First, the compounding agents shown in table 1 were kneaded with a 120 ℃ pressure kneader to prepare a kneaded mixture a, and the kneaded mixture a was molded into a sheet using an open roll (open roll) to obtain a kneaded sheet a.
[ TABLE 1 ]
Figure BDA0001234628650000091
Mooney viscosity measurement
The resulting kneaded sheets A of examples 1 to 4 and comparative example 1 were put into a hot air oven set at 170 ℃ and the Mooney viscosity was measured before and after aging (leaving) in an environment of 2 hours (125 ℃ C., using an L-rotor). The results are shown in Table 2. Mooney viscosity was measured according to JIS K6300-1 using a Visometer AM-3 manufactured by Toyo Seiki Seisaku-sho. The Mooney viscosity change (ML viscosity change in Table 2) was calculated from "ML viscosity after aging (ML viscosity after adjustment in Table 2)" and ML viscosity before aging (ML viscosity at the initial stage in Table 2) ".
In the obtained a kneaded sheets of examples 1 to 4 and comparative example 1, 0.5 parts by weight of nocceleler TS, 5 parts by weight of nocceleler DM, 1.0 part by weight of nocceleler DM, and 1.0 part by weight of sulfur were added to 100 parts by weight of the polyether polymer in the a kneaded sheet, and the mixture was sheeted with a mill roll. Thereafter, pressure crosslinking was performed at 170 ℃ for 15 minutes to obtain a crosslinked sheet.
Glass transition temperature
The glass transition temperature was determined by measuring the crosslinked sheet using a dynamic viscoelasticity tester and DMS6100 manufactured by Hitachi high-tech science according to JIS K6394. The results are shown in Table 2.
Polluting property
The crosslinked sheet was cut into 2cm square, and a load of 5g was applied to 1 square centimeter to be pressure-bonded to a photoreceptor, and the sheet was left to stand in an atmosphere of 40 ℃ C.. times.90% RH for 1 week to confirm the deposit on the photoreceptor, and the following evaluation was performed. The results are shown in Table 2.
X: when the photoreceptor after the test was used for printing, a stain trace was printed on the image.
○, almost no stain traces were printed on the image when the image was printed using the photoreceptor after the test (little stain traces were observed).
◎ No traces of contamination were printed on the image when printed using the photoreceptor after the test.
[ TABLE 2 ]
Figure BDA0001234628650000101
The crosslinked sheets of examples 1 and 2 using the sulfur-based antioxidant and the phosphoric acid-based antioxidant as the antioxidants hardly showed any stain on the image when printed on the photoreceptor after the test. The crosslinked sheets of examples 3 and 4 using the sulfur-based antioxidant, the phosphoric acid-based antioxidant, and the phenol-based antioxidant as the antioxidants are particularly preferable because they hardly cause any stain on the image when printed on the photoreceptor after the test.
Industrial applicability of the invention
The electrophotographic device member using the composition for an electrophotographic device member of the present invention is extremely useful for a semiconductive rubber roller, a belt, or the like in an electrophotographic device such as a copying machine or a printer.

Claims (10)

1. A composition for electrophotographic device members, comprising (a) a polyether polymer, (b) an antioxidant, and (c) a crosslinking agent, wherein the antioxidant (b) contains at least one selected from a sulfur-based antioxidant and a phosphoric acid-based antioxidant, and the antioxidant further contains a phenol-based antioxidant.
2. The composition for electrophotographic apparatus member according to claim 1, wherein (b) the age resister is: an anti-aging agent having a Mooney viscosity measured in accordance with JIS K6300-1 of 0 to-33 relative to the Mooney viscosity measured before leaving the composition comprising (a) a polyether polymer and (b) an anti-aging agent after leaving the composition at 170 ℃ for 2 hours.
3. The composition for electrophotographic apparatus members according to claim 1 or 2, wherein the polyether polymer (a) contains at least one or more units selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, 2- (methoxyethoxy) ethyl glycidyl ether, allyl glycidyl ether, and glycidyl methacrylate in a structural unit.
4. The composition for an electrophotographic apparatus member according to claim 1 or 2, characterized in that (b) the age resister is at least one selected from the group consisting of triphenyl phosphite, tris (nonylphenyl) phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monotridecyl phosphite, dilauryl 3,3 ' -thiodipropionate, distearyl-3, 3 ' -thiodipropionate and dimyristyl-3, 3 ' -thiodipropionate.
5. The composition for electrophotographic apparatus member according to claim 1 or 2, wherein the blending amount of the (b) antioxidant is 3.0 parts by weight or less based on 100 parts by weight of the (a) polyether polymer.
6. The composition for electrophotographic apparatus members according to claim 1 or 2, wherein the crosslinking agent (c) is at least one crosslinking agent selected from a polyamine-based crosslinking agent, a pyrazine-based crosslinking agent, a quinoxaline-based crosslinking agent, a bisphenol-based crosslinking agent, a peroxide-based crosslinking agent, and a sulfur-based crosslinking agent.
7. The composition for electrophotographic apparatus member according to claim 1 or 2, wherein the crosslinking agent (c) is at least one crosslinking agent selected from a thiourea crosslinking agent, a thiadiazole crosslinking agent, and a mercaptotriazine crosslinking agent.
8. A crosslinked material for electrophotographic apparatus members, which is obtained by crosslinking the composition for electrophotographic apparatus members according to any one of claims 1 to 7.
9. The crosslinked material for electrophotographic apparatus members according to claim 8, wherein the glass transition temperature is from-10 ℃ to-60 ℃ in accordance with JIS K6394.
10. A semiconductive rubber roller or a semiconductive endless rubber belt, using the crosslinked material for electrophotographic apparatus members as defined in claim 8 or 9.
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