WO2011046175A1 - 半導電性ゴム用組成物、ゴム架橋体および半導電性部品 - Google Patents
半導電性ゴム用組成物、ゴム架橋体および半導電性部品 Download PDFInfo
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- WO2011046175A1 WO2011046175A1 PCT/JP2010/068060 JP2010068060W WO2011046175A1 WO 2011046175 A1 WO2011046175 A1 WO 2011046175A1 JP 2010068060 W JP2010068060 W JP 2010068060W WO 2011046175 A1 WO2011046175 A1 WO 2011046175A1
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- epichlorohydrin
- ethylene oxide
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- 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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- 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
-
- 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
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
- C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
-
- 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
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
- C08G65/24—Epihalohydrins
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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
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- 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
- C08L71/03—Polyepihalohydrins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
Definitions
- the present invention relates to a semiconductive composition exhibiting low hardness and low resistance ionic conductivity used for electrophotographic equipment and the like, and a crosslinked rubber product obtained by vulcanizing the composition.
- Epichlorohydrin rubber materials are widely used as components for OA equipment by taking advantage of their unique ionic conductivity. As components of OA equipment, lower resistance and lower hardness have been demanded.
- an electrophotographic apparatus application will be exemplified and described as an example of the semiconductive member, but the present invention is not limited to the electrophotographic apparatus application.
- a direct contact charging method has been adopted as means for charging a surface of a charged body such as a photosensitive member or a dielectric.
- a charging member to which a voltage is applied is brought into direct contact with the surface of the object to be charged to charge the surface of the object to be charged.
- a roller having a semiconductive elastic layer formed on the shaft of a mandrel made of metal or the like is generally used.
- conductive particles such as carbon black are blended in the semiconductive elastic layer, and the semiconductive composition of an electronic conductive system made semiconductive, a method using a rubber cross-linked body, epichlorohydrin rubber and nitrile butadiene rubber A method of using a polar rubber having a semiconducting property is known (see Patent Document 1).
- the present invention is to achieve both a reduction in hardness and a reduction in resistance by blending various additives into an ion conductive polar rubber.
- the present inventors have blended ethylene oxide-modified (meth) acrylate with epichlorohydrin rubber, and are selected from the group consisting of a sulfur crosslinking agent, a quinoxaline crosslinking agent, and a triazine crosslinking agent.
- a sulfur crosslinking agent e.g., a sulfur crosslinking agent, a quinoxaline crosslinking agent, and a triazine crosslinking agent.
- composition of the present invention By crosslinking the composition of the present invention, a uniform low resistance value and low hardness composition was obtained in the epichlorohydrin rubber.
- the semiconductive rubber composition of the present invention refers to a composition before vulcanization, and includes at least (a) epichlorohydrin rubber, (b) ethylene oxide-modified (meth) acrylate, and (c) sulfur. It contains at least one crosslinking agent selected from the group consisting of a crosslinking agent, a quinoxaline crosslinking agent, and a triazine crosslinking agent.
- the (a) epichlorohydrin rubber refers to an epichlorohydrin homopolymer or a copolymer with other epoxides copolymerizable with epichlorohydrin, such as ethylene oxide, propylene oxide, allyl glycidyl ether, and the like. Examples of these are epichlorohydrin homopolymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-propylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, epichlorohydrin-ethylene oxide-propylene oxide-allyl.
- Examples thereof include glycidyl ether quaternary copolymers.
- an epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer that can be crosslinked with the sulfur-based crosslinking agent.
- an epichlorohydrin homopolymer or an epichlorohydrin-ethylene oxide binary copolymer may be blended within a range that does not significantly affect the cross-linking properties.
- the copolymerization ratio of epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer is, for example, epichlorohydrin 4 mol to 94 mol%, preferably 9 mol% to 74 mol%, more preferably 9 to 64 mol%, ethylene oxide 5 mol% to 95 mol%.
- they are 25 mol% to 90 mol%, more preferably 35 mol% to 90 mol%, allyl glycidyl ether 1 mol% to 8 mol%, preferably 1 mol% to 7 mol%, more preferably 1 mol% to 6 mol%.
- the epichlorohydrin rubber is preferably an epichlorohydrin homopolymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl.
- Ether terpolymers are preferred, and epichlorohydrin-ethylene oxide copolymers and epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymers are more preferred. These polymers may be blends.
- the copolymerization ratio thereof is epichlorohydrin 5 mol to 95 mol%, preferably 10 mol% to 75 mol%, more preferably 10 to 65 mol%, ethylene oxide 5 mol% to 95 mol%, preferably 25 mol%. It is ⁇ 90 mol%, more preferably 35 mol% to 90 mol%.
- the copolymerization ratio thereof is, for example, epichlorohydrin 4 mol to 94 mol%, preferably 9 mol% to 74 mol%, more preferably 9 to 64 mol%, ethylene oxide 5 mol%. ⁇ 95 mol%, preferably 25 mol% to 90 mol%, more preferably 35 mol% to 90 mol%, allyl glycidyl ether 1 mol% to 8 mol%, preferably 1 mol% to 7 mol%, more preferably 1 mol% to 6 mol%.
- Ethylene oxide modified (meth) acrylate used in the present invention is represented by the general formula (I).
- n represents an integer of 1 to 30 and R 1 to R 4 may be the same or different and are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a substituted alkyl group having 1 to 5 carbon atoms
- n is preferably 1 to 20, more preferably 6 to 16 in terms of low resistance, environmental dependency, stability of resistance over time, and compatibility with the polymer. Particularly preferred is 7-11.
- R 1 to R 4 are preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group.
- the (b) ethylene oxide-modified (meth) acrylate used in the present invention is preferably methoxypolyethylene glycol methacrylate represented by the general formula (II).
- n represents an integer of 1 to 20.
- n is preferably 6 to 16 and more preferably 7 to 11 in terms of low resistance, environmental dependency, stability of resistance over time, and compatibility with the polymer.
- mPa / S 25 ° C.
- mPa / S 25 ° C.
- the blending ratio of these ethylene oxide-modified (meth) acrylates is 5 to 40 parts by weight, preferably 8 to 35 parts by weight, and more preferably 10 to 30 parts by weight with respect to 100 parts by weight of epichlorohydrin rubber.
- the blending amount is within this range, the cross-linked product can be reduced in hardness and resistance, and the rubber characteristics necessary for the cross-linked product are not impaired.
- Crosslinking agent used in the present invention is selected from the group consisting of (c) a sulfur-based crosslinking agent, a quinoxaline-based crosslinking agent, and a triazine-based crosslinking agent.
- the sulfur-based crosslinking agent is not particularly limited as long as it can crosslink the allyl glycidyl ether group, but sulfur, morpholine polysulfides, thiuram polysulfides and the like are used. Specific examples include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur, non-hazardous sulfur, etc., morpholine polysulfides include morpholine disulfide, and thiuram polysulfides include tetramethyl.
- Examples include thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, dipentamethylene thiuram tetrasulfide, dipentamethylene thiuram hexasulfide and the like.
- quinoxaline crosslinking agents examples include 2,3-dimercaptoquinoxaline, quinoxaline-2,3-dithiocarbonate, 6-methylquinoxaline-2,3-dithiocarbonate, 5,8-dimethylquinoxaline-2,3-dithiocarbonate, etc.
- 6-methylquinoxaline-2,3-dithiocarbonate is used.
- triazine crosslinking agents examples include 2,4,6-trimercapto-1,3,5-triazine, 2-hexylamino-4,6-dimercaptotriazine, 2-diethylamino-4,6-dimercaptotriazine, 2 -Cyclohexylamino-4,6-dimercaptotriazine, 2-dibutylamino-4,6-dimercaptotriazine, 2-anilino-4,6-dimercaptotriazine, 2-phenylamino-4,6-dimercaptotriazine, etc.
- 2,4,6-trimercapto-1,3,5-triazine is used.
- the amount of the crosslinking agent (c) is 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, preferably 0.5 to 1.5 parts by weight based on 100 parts by weight of the epichlorohydrin rubber. More preferred are parts by weight.
- the blending amount is less than 0.1 parts by weight with respect to 100 parts by weight of the terpolymer, crosslinking is insufficient.
- the amount exceeds 10 parts by weight with respect to 100 parts by weight of the terpolymer, crosslinking occurs. The body becomes too rigid and the physical properties normally expected as a rubber cross-linked body cannot be obtained.
- a crosslinking agent may be used individually by 1 type, or may be used in combination of 2 or more type.
- Vulcanization accelerator In the present invention, known vulcanization accelerators that are usually used together with these crosslinking agents can be used.
- any known vulcanization accelerator used with this sulfur-based crosslinking agent can be used without particular limitation, and thiuram polysulfides, mercaptobenzo Examples include thiazoles, morpholine sulfides, and sulfenamides.
- thiuram polysulfides include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide, and dipentamethylenethiuram hexasulfide.
- Mercaptobenzothiazoles include mercaptobenzothiazole, dibenzothiazol.
- Zyl disulfide various metal salts of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 2- (N, N-diethylthio-carbamoylthio) benzothiazole, 2- (4'-monophorino-dithio) benzo
- morpholine sulfides include morpholine disulfide and 2-mercaptobenzothiazole.
- N-cyclohexyl-2-benzothiazyl sulfenamide N, N-dicyclohexyl-2-benzothiazyl sulfenamide, N-oxydiethylene-2-benzothiazyl sulfenamide, N-tert-butyl-2 -Benzothiazyl sulfenamide, N-tert-butyl-di (2-benzothiazole) sulfenimide and the like.
- the blending amount of the vulcanization accelerator used in the present invention is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight based on 100 parts by weight of (a) epichlorohydrin rubber.
- the quinoxaline-based crosslinker and / or triazine-based crosslinker is used as the above-mentioned (c) crosslinker
- known vulcanization accelerators used together with these crosslinkers for example, sulfur, morpholine sulfides, amines, amines Weak acid salts, basic silica, quaternary ammonium salts, quaternary phosphonium salts, alkali metal salts of fatty acids, thiuramsphides, polyfunctional vinyl compounds, mercaptobenzothiazoles, sulfenamides, dimethiocarbamates, etc. be able to.
- DBU 1,8-diazabicyclo (5,4,0) undecene-7
- DBN 1,5-diazabicyclo (4 , 3, 0) Nonene-5
- DBU salt examples include DBU-carbonate, DBU-stearate, DBU-2-ethylhexylate, DBU-benzoate, DBU-salicylate, DBU-3-hydroxy-2-naphthoate, DBU- Examples thereof include phenol resin salts, DBU-2-mercaptobenzothiazole salts, DBU-2-mercaptobenzimidazole salts and the like.
- DBN salt examples include DBN-carbonate, DBN-stearate, DBN-2-ethylhexylate, DBN-benzoate, DBN-salicylate, DBN-3-hydroxy-2-naphthoate, Examples thereof include DBN-phenol resin salt, DBN-2-mercaptobenzothiazole salt, DBN-2-mercaptobenzimidazole salt and the like.
- the blending amount when these DBU salts and / or DBN salts are used as accelerators is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 5 parts by weight per 100 parts by weight of (a) epichlorohydrin rubber. 3 parts by weight.
- Examples of the retarder used in the present invention include N-cyclohexylthiophthalimide, phthalic anhydride, an organic zinc compound, acidic silica and the like.
- the blending amount of the retarder is (a) 100 parts by weight of epichlorohydrin rubber. The amount is preferably 0 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.
- Acid acceptor As the acid acceptor used in the present invention, a known acid acceptor can be used, and a metal compound and / or an inorganic microporous crystal is preferable.
- metal compounds include Group II (Group 2 and Group 12) metal oxides, hydroxides, carbonates, carboxylates, silicates, borates, phosphites, and Group III of the Periodic Table.
- metal oxides Group 3 and Group 13 metal oxides, hydroxides, carboxylates, silicates, sulfates, nitrates, phosphates, Group IV (Groups 4 and 14) metal oxides, Examples thereof include metal compounds such as basic carbonates, basic carboxylates, basic phosphites, basic sulfites, and tribasic sulfates.
- the metal compound include magnesia, magnesium hydroxide, aluminum hydroxide, barium hydroxide, sodium carbonate, magnesium carbonate, barium carbonate, quicklime, slaked lime, calcium carbonate, calcium silicate, calcium stearate, zinc stearate, Calcium phthalate, calcium phosphite, zinc white, tin oxide, lisage, red lead, lead white, dibasic lead phthalate, dibasic lead carbonate, tin stearate, basic lead phosphite, basic phosphorous acid Tin, basic lead sulfite, tribasic lead sulfate and the like can be mentioned, and sodium carbonate, magnesia, magnesium hydroxide, quicklime, slaked lime, calcium silicate, zinc white and the like are preferable.
- the inorganic microporous crystal means a crystalline porous body and can be clearly distinguished from amorphous porous bodies such as silica gel and alumina.
- amorphous porous bodies such as silica gel and alumina.
- examples of such inorganic microporous crystals include zeolites, aluminophosphate type molecular sieves, layered silicates, synthetic hydrotalcites, alkali metal titanates and the like.
- a particularly preferred acid acceptor is synthetic hydrotalcite.
- the zeolites are natural zeolites, A-type, X-type, Y-type synthetic zeolites, sodalites, natural or synthetic mordenites, various zeolites such as ZSM-5, and metal substitutes thereof. It may be used in combination of two or more. Further, the metal of the metal substitution product is often sodium. As the zeolite, those having a large acid-accepting ability are preferable, and A-type zeolite is preferable.
- the synthetic hydrotalcite is represented by the following general formula (3).
- z is a real number from 1 to 5
- w is a real number from 0 to 10, respectively.
- hydrotalcites represented by the general formula (1) examples include Mg 4.5 Al 2 (OH) 13 CO 3 .3.5H 2 O, Mg 4.5 Al 2 (OH) 13 CO 3 , Mg 4 Al 2 (OH) 12 CO 3 .3.5H 2 O, Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O, Mg 5 Al 2 (OH) 14 CO 3 .4H 2 O, Mg 3 Al 2 (OH) 10 CO 3 ⁇ 1.7H 2 O, Mg 3 ZnAl 2 (OH) 12 CO 3 ⁇ 3.5H 2 O, can be cited Mg 3 ZnAl 2 (OH) 12 CO 3 and the like.
- the amount of the acid acceptor is preferably 0.2 to 50 parts by weight, more preferably 0.5 to 50 parts by weight, and particularly 1 to 20 parts by weight with respect to 100 parts by weight of the (a) epichlorohydrin rubber. . If it is in these ranges, it will be fully crosslinked and the crosslinked product will not be too rigid, and the physical properties normally expected as an epichlorohydrin rubber crosslinked product can be obtained.
- the semiconductive rubber composition used in the present invention includes various compounding agents commonly used in the art, such as vulcanization retarders, anti-aging agents, fillers, reinforcing agents, plasticizers, processing aids, A pigment, a flame retardant, etc. can be arbitrarily blended.
- any mixing means conventionally used in the field of polymer processing for example, a mixing roll, a Banbury mixer, various kneaders and the like can be used.
- the semiconductive electronic component of the present invention can be obtained by heating the composition of the present invention to usually 100 to 200 ° C.
- the vulcanization time varies depending on the temperature, but is usually between 0.5 and 300 minutes.
- the vulcanization molding method is not particularly limited, and for example, compression molding using a mold, injection molding, heating using a steam can, an air oven, or the like is preferably used.
- DBU salt-based vulcanization accelerator DBU phenolic resin salt “P-152” manufactured by Daiso Corporation * 15
- Quinoxaline-based cross-linking agent 6-methylquinoxaline-2,3-dithiocarbonate “Daisonette XL-21S” manufactured by Daiso Corporation
- Each material shown in the following Tables 1, 4, and 5 was kneaded with an open roll to prepare an unvulcanized rubber sheet.
- the resulting unvulcanized rubber sheet was press vulcanized at 170 ° C. for 15 minutes.
- the volume resistivity value using a Hiresta made by Mitsubishi Yuka Co., Ltd. using a double ring electrode in accordance with JIS K6271 was measured.
- Each material shown in the following Tables 2, 6, and 7 was kneaded with a kneader mixer and an open roll to prepare an unvulcanized rubber sheet.
- the resulting unvulcanized rubber sheet was press vulcanized at 170 ° C. for 15 minutes.
- a double ring electrode was used in accordance with JIS K6271.
- the volume resistivity value was measured using Hiresta manufactured by Mitsubishi Yuka Co., Ltd., and the environmental dependence of the crosslinked product was evaluated.
- the rubber hardness was measured in accordance with JIS K6253 using an ASKER type A durometer manufactured by Kobunshi Keiki Co., Ltd.
- Examples and Comparative Examples described in Table 1 are cross-linked products obtained by blending only a cross-linking system with epichlorohydrin rubber.
- the crosslinked product blended with the ethylene oxide-modified (meth) acrylate of the example does not blend the ethylene oxide-modified (meth) acrylate of the comparative example or has a low resistance value and low hardness compared to the crosslinked product blended with various acrylic polymers. It was a rubber cross-linked product. Note that Comparative Example 2 could not be evaluated because kneading was impossible.
- Examples and Comparative Examples described in Table 2 are cross-linked products obtained by blending a filler generally used in this application with epichlorohydrin rubber.
- the crosslinked product in which the ethylene oxide-modified (meth) acrylate of the example was blended had a low resistance value and low hardness compared to the crosslinked product in which the ethylene oxide-modified (meth) acrylate of the comparative example was not blended or liquid NBR was blended. It was a rubber cross-linked product.
- Comparative Example 8 in which peroxide crosslinking was performed, the crosslinked product was brittle when taken out from the mold during crosslinking, and thus could not be evaluated.
- Example 5 and Example 6 described in Table 3 evaluate the environmental dependency of the crosslinked product obtained by blending the ethylene oxide-modified (meth) acrylate according to the present invention.
- the number of ethylene oxide units in the ethylene oxide-modified (meth) acrylate is small (for example, the ethylene oxide unit is 6 to 16), the environmental dependency is reduced, which is more preferable.
- Examples and Comparative Examples described in Tables 4 and 5 are cross-linked products obtained by blending only a cross-linking system with epichlorohydrin rubber.
- the crosslinked product in which the ethylene oxide-modified (meth) acrylate of Example was blended was a rubber cross-linked product having a low resistance value and low hardness compared to the crosslinked product in which the ethylene oxide-modified (meth) acrylate of Comparative Example was not blended.
- Examples and Comparative Examples described in Tables 6 and 7 are cross-linked products obtained by blending an epichlorohydrin rubber with a filler generally used in this application.
- the crosslinked product in which the ethylene oxide-modified (meth) acrylate of the example was blended had a low resistance value and low hardness compared to the crosslinked product in which the ethylene oxide-modified (meth) acrylate of the comparative example was not blended or liquid NBR was blended. It was a rubber cross-linked product.
- Comparative Example 15 in which peroxide crosslinking was performed, the crosslinked product was brittle when taken out from the mold during crosslinking, and thus could not be evaluated.
- Examples 15 to 18 described in Tables 8 and 9 were evaluated for the environmental dependency of the cross-linked product obtained by blending the ethylene oxide-modified (meth) acrylate according to the present invention.
- the number of ethylene oxide units in the ethylene oxide-modified (meth) acrylate is small (for example, the ethylene oxide unit is 6 to 16), the environmental dependency is reduced, which is more preferable.
- the rubber cross-linked product of the present invention can be widely applied to fields where usually semiconductive rubber parts are used.
- it is useful for charging rolls, transfer rolls, developing rolls, rubber blades and the like for electrophotographic equipment.
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Abstract
Description
本発明の半導電性ゴム組成物は、加硫前の組成物を指し、少なくとも(a)エピクロルヒドリン系ゴム、(b)エチレンオキサイド変性(メタ)アクリレート、(c)硫黄系架橋剤、キノキサリン系架橋剤、およびトリアジン系架橋剤からなる群より選択される少なくとも1種の架橋剤を含有する。
本発明における(a)エピクロルヒドリン系ゴムとは、エピクロルヒドリン単独重合体またはエピクロルヒドリンと共重合可能な他のエポキシド、例えばエチレンオキサイド、プロピレンオキサイド、アリルグリシジルエーテル等との共重合体をいう。これらを例示すれば、エピクロルヒドリン単独重合体、エピクロルヒドリン-エチレンオキサイド共重合体、エピクロルヒドリン-プロピレンオキサイド共重合体、エピクロルヒドリン-エチレンオキサイド-アリルグリシジルエーテル三元共重合体、エピクロルヒドリン-エチレンオキサイド-プロピレンオキサイド-アリルグリシジルエーテル四元共重合体等を挙げることができる。これら単独重合体または共重合体の分子量は特に制限されないが、通常ムーニー粘度表示でML1+4(100℃)=30~150程度である。
本発明で使用される(b)エチレンオキサイド変性(メタ)アクリレートは一般式(I)で示される。
式中において、低抵抗化、環境依存性、経時変化における抵抗の安定性、ポリマーとの相溶性の点において、nは1~20であることが好ましく、6~16であることがより好ましく、7~11であることが特に好ましい。
R1~R4は、水素原子、または炭素数1~5のアルキル基であることが好ましく、水素原子、メチル基、またはエチル基であることが特に好ましい。
式中において、低抵抗化、環境依存性、経時変化における抵抗の安定性、ポリマーとの相溶性の点において、nは6~16であることが好ましく、7~11であることがより好ましい。
本発明で用いられる架橋剤としては、(c)硫黄系架橋剤、キノキサリン系架橋剤、およびトリアジン系架橋剤からなる群より選択される。
また、本発明においては、通常これらの架橋剤と共に使用される公知の加硫促進剤を用いることができる。
本発明で用いられる受酸剤としては、公知の受酸剤を使用できるが、好ましくは金属化合物および/または無機マイクロポーラス・クリスタルである。金属化合物としては、周期表第II族(2族および12族)金属の酸化物、水酸化物、炭酸塩、カルボン酸塩、ケイ酸塩、ホウ酸塩、亜リン酸塩、周期表III族(3族および13族)金属の酸化物、水酸化物、カルボン酸塩、ケイ酸塩、硫酸塩、硝酸塩、リン酸塩、周期表第IV族(4族および14族)金属の酸化物、塩基性炭酸塩、塩基性カルボン酸塩、塩基性亜リン酸塩、塩基性亜硫酸塩、三塩基性硫酸塩等の金属化合物が挙げられる。
MgXZnYAlZ(OH)(2(X+Y)+3Z-2)CO3・wH2O (3)
[式中、xとyはそれぞれx+y=1~10の関係を有する0~10の実数、zは1~5の実数、wは0~10の実数をそれぞれ示す。]
本発明によるゴム架橋体を製造するには、従来ポリマー加工の分野において用いられている任意の混合手段、例えばミキシングロール、バンバリーミキサー、各種ニーダー類等を用いることができる。本発明の半導電性電子部品は、本発明の組成物を通常100~200℃に加熱することで得られる。加硫時間は温度により異なるが、通常0.5~300分の間である。加硫成型の方法としては特に限定されるものではないが、例えば金型による圧縮成型、射出成型、スチーム缶やエアーオーブン等による加熱の方法などが好適に用いられる。
*1 エピクロルヒドリン系ゴム:エピクロルヒドリン-エチレンオキシド-アリルグリシジルエーテル共重合体 ダイソー社製 「エピオン301」
*2 エチレンオキサイド変性(メタ)アクリレートA:メトキシポリエチレングリコール#400メタクリレート(平均エチレンオキサイドユニット数9(n=9))、
*3 エチレンオキサイド変性(メタ)アクリレートB:メトキシポリエチレングリコール#1000メタクリレート(平均エチレンオキサイドユニット数23(n=23))
*4 OH基含有アクリルポリマーA:東亜合成株式会社製「ARUFON UH-2000」
*5 OH基含有アクリルポリマーB:東亜合成株式会社製「ARUFON UH-2170」
*6 COOH基含有アクリルポリマー:東亜合成株式会社製「ARUFON UC-3000」
*7 チウラム系加硫促進剤:大内新興化学工業社製 「ノクセラーTS」
*8 チアゾール系加硫促進剤:大内新興化学工業社製 「ノクセラーDM」
*9 液状NBR:JSR株式会社製JSR N280
*10 可塑剤:ダイソー社製「DB-02」
*11 チウラム系加硫促進剤:大内新興化学工業社製 「ノクセラーTT」
*12 モルホリンスルフィド系加硫促進剤:大内新興化学工業社製 「バルノックR」
*13 ハイドロタルサイト:合成ハイドロタルサイト 協和化学工業社製 「DHT-4A」
*14 DBU塩系加硫促進剤:DBUのフェノール樹脂塩 ダイソー社製 「P-152」
*15 キノキサリン系架橋剤:6-メチルキノキサリン-2,3-ジチオカーボネート
ダイソー社製 「ダイソネットXL-21S」
下記表2、6、7に示す各材料をニーダーミキサーおよびオープンロールで混練し、未加硫ゴムシートを作製した。得られた未加硫ゴムシートを用い、170℃で15分プレス加硫した。得られた架橋シートを23℃/50%RH環境下にて状態調整を行った後、JIS K6271に準拠し、二重リング電極を用いた三菱油化株式会社製ハイレスタを用いて体積固有抵抗値を測定した。
下記表3、8,9に示す各材料をニーダーミキサーおよびオープンロールで混練し、未加硫ゴムシートを作製した。得られた未加硫ゴムシートを用い、170℃で15分プレス加硫した。得られた架橋シートを10℃/15%RH、23℃/50%RH、35℃/85%RH環境下にて状態調整を行った後、JIS K6271に準拠し、二重リング電極を用いた三菱油化株式会社製ハイレスタを用いて体積固有抵抗値を測定し、架橋物の環境依存性を評価した。
ゴム硬度についてはJIS K6253に準拠し、高分子計器株式会社製ASKER タイプAデュロメーターを用いて測定した。
Claims (7)
- 前記一般式(II)で示されるメトキシポリエチレングリコールメタクリレートが、エチレンオキサイドユニットを6~16個有する(前記一般式(II)のnが6~16である構造を有する)ことを特徴とする請求項2に記載の半導電性加硫ゴム用組成物。
- 前記(a)エピクロルヒドリン系ゴムが、エピクロルヒドリンの単独重合体、エピクロルヒドリン-エチレンオキサイド二元共重合体、エピクロルヒドリン-エチレンオキサイド-アリルグリシジルエーテル三元共重合体から選択される少なくとも一種である請求項1~3いずれかに記載の半導電性加硫ゴム用組成物。
- 前記(a)エピクロルヒドリン系ゴムが、エピクロルヒドリン-エチレンオキサイド-アリルグリシジルエーテルの三元共重合体、あるいはエピクロルヒドリン-エチレンオキサイド-アリルグリシジルエーテルの三元共重合体とエピクロルヒドリン単独重合体とブレンドされた物、エピクロルヒドリン-エチレンオキサイド-アリルグリシジルエーテルの三元共重合体とエピクロルヒドリン-エチレンオキサイド二元共重合体とブレンドされた物であることを特徴とする請求項1~3いずれかに記載の半導電性加硫ゴム用組成物。
- 請求項1~5いずれかに記載の半導電性組成物を架橋して得られるゴム架橋体。
- 請求項6に記載のゴム架橋体を用いた半導電性部品。
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CN201080046717XA CN102597113A (zh) | 2009-10-16 | 2010-10-14 | 半导电性橡胶用组合物、橡胶交联体及半导电性部件 |
US13/501,725 US8735503B2 (en) | 2009-10-16 | 2010-10-14 | Composition for semiconductive rubber, crosslinked rubber product, and semiconductive parts |
JP2011536171A JP5601478B2 (ja) | 2009-10-16 | 2010-10-14 | 半導電性ゴム用組成物、ゴム架橋体および半導電性部品 |
EP10823443.6A EP2489700A4 (en) | 2009-10-16 | 2010-10-14 | COMPOSITION FOR A SEMICONDUCTOR ROLL, NETWORKED RUBBER PRODUCT AND SEMICONDUCTIVE PARTS |
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JP2014234501A (ja) * | 2013-06-05 | 2014-12-15 | 興国インテック株式会社 | イオン導電性ポリマーブレンド及びそれを利用した半導電性部材の製造方法 |
WO2016104269A1 (ja) * | 2014-12-24 | 2016-06-30 | 株式会社大阪ソーダ | 電子写真機器部品用組成物 |
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WO2010021169A1 (ja) * | 2008-08-22 | 2010-02-25 | ダイソー株式会社 | 空気バネ用加硫ゴム組成物及び空気バネ用ゴム成型体 |
KR20150034515A (ko) * | 2013-09-26 | 2015-04-03 | 삼성전자주식회사 | 화상 형성 장치용 반도전성 롤러 |
KR102137558B1 (ko) * | 2013-10-15 | 2020-07-24 | 가부시키가이샤 오사카소다 | 보존 안정성이 우수한 가교용 조성물 |
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KR101755057B1 (ko) | 2017-07-06 |
US20120208966A1 (en) | 2012-08-16 |
JP5601478B2 (ja) | 2014-10-08 |
EP2489700A1 (en) | 2012-08-22 |
JPWO2011046175A1 (ja) | 2013-03-07 |
US8735503B2 (en) | 2014-05-27 |
CN102597113A (zh) | 2012-07-18 |
KR20120085799A (ko) | 2012-08-01 |
EP2489700A4 (en) | 2014-07-02 |
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