WO2014157045A1 - 導電性ロール用架橋性ゴム組成物、導電性ロール用ゴム架橋物、および導電性ロール - Google Patents
導電性ロール用架橋性ゴム組成物、導電性ロール用ゴム架橋物、および導電性ロール Download PDFInfo
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- WO2014157045A1 WO2014157045A1 PCT/JP2014/057997 JP2014057997W WO2014157045A1 WO 2014157045 A1 WO2014157045 A1 WO 2014157045A1 JP 2014057997 W JP2014057997 W JP 2014057997W WO 2014157045 A1 WO2014157045 A1 WO 2014157045A1
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- crosslinkable
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- 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
- C08G65/14—Unsaturated oxiranes
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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'
- C08K5/3725—Sulfides, e.g. R-(S)x-R' containing nitrogen
-
- 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
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
- C08K5/40—Thiurams, i.e. compounds containing groups
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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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
-
- 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
- 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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- 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
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- 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
- F16C2370/00—Apparatus relating to physics, e.g. instruments
- F16C2370/38—Electrographic apparatus
Definitions
- the present invention relates to a crosslinkable rubber composition for a conductive roll, a rubber cross-linked product for a conductive roll, and a conductive roll.
- a conductive mechanism in an image forming apparatus such as a printer, an electrophotographic copying machine, and a facsimile machine includes a charging roll for uniformly charging a photosensitive drum, a toner supply roll for conveying toner, and a toner on a photosensitive member
- Various conductive rolls such as a developing roll for adhering to a toner and a transfer roll for transferring a toner image from a photoreceptor to a sheet are used.
- Such a conductive roll is required to have various performances depending on its application.
- Patent Document 1 a material obtained by kneading carbon black into a rubber component is known.
- Patent Document 1 at least one selected from nitrile rubber, epichlorohydrin rubber, and ethylene oxide-propylene oxide-allyl glycidyl ether terpolymer is used as a rubber component, and carbon black is compounded into these rubbers.
- a rubber composition is disclosed.
- this Patent Document 1 aims to reduce the fluctuation amount of the electric resistance value of the obtained conductive roll, and has low hardness and low electric power required for the performance of the conductive roll, particularly the chargeable roll. It did not satisfy all the requirements of resistance value and compression set resistance. Moreover, in order to reduce hardness, it was necessary to make the rubber layer of a conductive roll into a foam.
- the present invention has been made in view of such a situation, and has a low hardness, a low volume resistivity, and a conductive roll capable of giving a rubber cross-linked product excellent in compression set resistance. It is an object of the present invention to provide a crosslinkable rubber composition.
- the present inventor used three components of a polyether rubber, a solid nitrile rubber, and a liquid nitrile rubber as a rubber component, and a sulfur-containing crosslinking agent, It has been found that the above object can be achieved by a rubber composition obtained by blending a disulfide-based crosslinking accelerator and a predetermined conductive carbon black, and has completed the present invention.
- polyether rubber solid nitrile rubber, liquid nitrile rubber, sulfur-containing crosslinking agent, disulfide-based crosslinking accelerator, and average primary particle diameter of 50 nm or less and BET specific surface area of 600 m 2 /
- a crosslinkable rubber composition for a conductive roll containing a conductive carbon black of g or more is provided.
- the polyether rubber preferably contains a crosslinkable oxirane monomer unit having a vinyl group, an ethylene oxide monomer unit, and an epihalohydrin monomer unit. .
- the content of the polyether rubber in the total rubber component is 19 to 90% by weight
- the content of the solid nitrile rubber is 9 to 80% by weight
- the liquid nitrile rubber is contained.
- the content ratio is preferably 1 to 30% by weight.
- the sulfur-containing crosslinking agent is preferably at least one selected from sulfur and a sulfur-containing compound having a morpholine structure.
- the sulfur-containing compound having a morpholine structure is preferably a compound represented by the following general formula (1).
- Y 1 is a divalent group containing a sulfur atom.
- the disulfide crosslinking accelerator is preferably at least one selected from a thiuram disulfide crosslinking accelerator and a thiazolyl disulfide crosslinking accelerator.
- a rubber cross-linked product for a conductive roll obtained by cross-linking the above-described cross-linkable rubber composition, and a conductive roll having the rubber cross-linked product.
- a crosslinkable rubber composition for a conductive roll that has a low hardness, a low volume specific resistance, and an excellent resistance to compression set, and a crosslinkable rubber composition for this.
- a rubber cross-linked product for conductive rolls and a conductive roll having the rubber cross-linked product there can be provided.
- the crosslinkable rubber composition for conductive rolls of the present invention comprises a polyether rubber, a solid nitrile rubber, a liquid nitrile rubber, a sulfur-containing crosslinking agent, a disulfide crosslinking accelerator, an average primary particle size of 50 nm or less, and a BET It contains conductive carbon black having a specific surface area of 600 m 2 / g or more.
- the polyether rubber used in the present invention is not particularly limited as long as it is a rubber having a main structural unit of an oxyalkylene repeating unit obtained by ring-opening polymerization of an oxirane monomer.
- the polyether rubber used in the present invention is a vinyl based on a crosslinkable oxirane monomer having a vinyl group from the viewpoint of being capable of co-crosslinking with a solid nitrile rubber and a liquid nitrile rubber. Those containing a crosslinkable oxirane monomer unit having a group are preferred.
- crosslinkable oxirane monomer having a vinyl group examples include ethylenically unsaturated glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, o-allylphenyl glycidyl ether; butadiene monoepoxide, etc. Diene monoepoxides; glycidyl esters of ethylenically unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate; and the like.
- glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, o-allylphenyl glycidyl ether; butadiene monoepoxide, etc. Diene monoepoxides; glycidyl
- ethylenically unsaturated glycidyl ethers are preferable, and allyl glycidyl ether is particularly preferable.
- These crosslinkable oxirane monomers having a vinyl group may be used alone or in combination of two or more.
- the content ratio of the crosslinkable oxirane monomer unit having a vinyl group in the polyether rubber used in the present invention is preferably 1 to 15 mol% in the total monomer units of the polyether rubber, and more preferably. It is 2 to 12 mol%, more preferably 3 to 10 mol%. If the content ratio of the crosslinkable oxirane monomer unit having a vinyl group is too small, the compression set rate of the resulting rubber cross-linked product for a conductive roll (hereinafter sometimes referred to as “rubber cross-linked product”) is deteriorated. On the contrary, if the amount is too large, a gelling reaction or the like is liable to occur during the polymerization reaction, and the moldability may be lowered.
- the polyether rubber used in the present invention preferably contains an ethylene oxide monomer unit based on an ethylene oxide monomer in addition to a crosslinkable oxirane monomer unit having a vinyl group.
- the content ratio of the ethylene oxide monomer unit is preferably 40 to 80 mol%, more preferably 45 to 75 mol%, still more preferably 50 to 70 mol% in the total monomer units of the polyether rubber. is there.
- the content ratio of the ethylene oxide monomer unit is too small, the volume specific resistance value of the obtained rubber cross-linked product may be increased.
- the content ratio of the ethylene oxide monomer unit is too large, there is a possibility that the photoreceptor is contaminated when the obtained rubber cross-linked product is used as a conductive roll.
- the polyether rubber used in the present invention contains an epihalohydrin monomer unit based on an epihalohydrin monomer in addition to a crosslinkable oxirane monomer unit having a vinyl group and an ethylene oxide monomer unit. It is preferable.
- epihalohydrin monomer examples include epichlorohydrin, epibromohydrin, epiiodohydrin, epifluorohydrin and the like. Among these, epichlorohydrin is preferable. These epihalohydrin monomers may be used alone or in combination of two or more.
- the content ratio of the epihalohydrin monomer unit in the polyether rubber used in the present invention is preferably 5 to 59 mol%, more preferably 13 to 53 mol%, based on the total monomer units of the polyether rubber. More preferably, it is 20 to 47 mol%.
- the content ratio of the epihalohydrin monomer unit is too small, there is a possibility that the photoreceptor is contaminated when the obtained rubber cross-linked product is used as a conductive roll.
- the content ratio is too large, the volume specific resistance value of the resulting rubber cross-linked product may increase.
- the polyether rubber used in the present invention is a monomer unit copolymerizable with a crosslinkable oxirane monomer unit having a vinyl group, an ethylene oxide monomer unit, and an epihalohydrin monomer unit. May be contained.
- an alkylene oxide monomer other than the ethylene oxide monomer can be used.
- alkylene oxide monomer other than the ethylene oxide monomer examples include propylene oxide, 1,2-epoxybutane, 1,2-epoxy-isobutane, 2,3-epoxybutane, 1,2-epoxyhexane, Linear alkylene oxides such as 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane; 1 Cyclic alkylene oxides such as 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycyclododecane, and the like. These copolymerizable monomers may be used alone or in combination of two or more.
- the content ratio of these copolymerizable monomer units in the polyether rubber used in the present invention is preferably 30 mol% or less, more preferably 20 mol% or less, based on the total monomer units of the polyether rubber. More preferably, it is 10 mol% or less. If the content ratio of these monomer units is too large, the volume specific resistance value of the resulting rubber cross-linked product may be increased.
- the polyether rubber used in the present invention can be obtained, for example, by ring-opening polymerization of the above-described monomers by a solution polymerization method or a solvent slurry polymerization method.
- the polymerization catalyst used for the polymerization is not particularly limited as long as it is a general polyether polymerization catalyst.
- the polymerization catalyst include a catalyst obtained by reacting water and acetylacetone with organoaluminum (Japanese Patent Publication No. 35-15797); a catalyst obtained by reacting phosphoric acid and triethylamine with triisobutylaluminum (Japanese Patent Publication No. 46-27534). Catalyst obtained by reacting triazabutylaluminum with an organic acid salt of diazabicycloundecene and phosphoric acid (Japanese Patent Publication No.
- the polymerization solvent is not particularly limited as long as it is an inert solvent.
- aromatic hydrocarbons such as benzene and toluene
- linear saturated hydrocarbons such as n-pentane and n-hexane
- cyclopentane And cyclic saturated hydrocarbons such as cyclohexane
- aromatic hydrocarbons are preferably used from the viewpoint of solubility of the polyether rubber, and toluene is more preferable.
- the polymerization reaction temperature is preferably 20 to 150 ° C, more preferably 50 to 130 ° C.
- the polymerization mode can be carried out by any method such as batch system, semi-batch system, and continuous system.
- the polyether rubber may be either a block copolymer type or a random copolymer type, but in particular, when ethylene oxide is used as a monomer, the random copolymer has a higher crystallinity of polyethylene oxide. It is preferable because the rubber elasticity is lowered and the rubber elasticity is not easily lost.
- the method for recovering the polyether rubber from the solvent can obtain a solid polyether rubber by appropriately combining solidification, filtration and drying methods according to a conventional method.
- the weight average molecular weight of the polyether rubber used in the present invention is preferably 200,000 to 2,000,000, more preferably 500,000 to 1,500,000 in terms of polystyrene using gel permeation chromatography. If the weight average molecular weight is too high, the Mooney viscosity becomes high and molding may be difficult. On the other hand, if the weight average molecular weight is too low, the compression set of the resulting rubber cross-linked product may be deteriorated.
- the Mooney viscosity (polymer Mooney viscosity ⁇ ML 1 + 4 , 100 ° C.) of the polyether rubber used in the present invention is preferably 20 to 120, and more preferably 30 to 100. If the Mooney viscosity is too high, molding processability is inferior, and molding into a conductive member is difficult. On the other hand, if the Mooney viscosity is too low, the mechanical strength of the resulting rubber cross-linked product may be reduced.
- the content ratio of the polyether rubber in the crosslinkable rubber composition for the conductive roll of the present invention is preferably 19 to 90% by weight, more preferably 29 to 90% by weight, and still more preferably 39% in all rubber components. ⁇ 70% by weight. If the content of the polyether rubber is too small, the hardness and volume resistivity of the resulting rubber cross-linked product may increase. On the other hand, if the content is too high, the compression set resistance of the resulting rubber cross-linked product will decrease. There is a risk of
- the solid nitrile rubber used in the present invention is an ethylenically unsaturated nitrile-conjugated diene copolymer rubber having a solid state at normal temperature (does not flow at normal temperature for a short time).
- the solid nitrile rubber used in the present invention has a polymer Mooney viscosity (ML 1 + 4 , 100 ° C.) measured in accordance with JIS K6300 of usually 15 or more, preferably 15 to 150, more preferably 30 to 100. It is.
- the solid nitrile rubber used in the present invention usually comprises an ethylenically unsaturated nitrile monomer, a conjugated diene monomer, and other monomers that can be copolymerized with these monomers. Obtained by polymerization.
- Examples of the ethylenically unsaturated nitrile monomer include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -methylacrylonitrile, ⁇ -methoxyacrylonitrile, ⁇ -ethoxyacrylonitrile, crotonic nitrile, cinnamic nitrile, itaconic acid Examples include dinitrile, maleic acid dinitrile, and fumaric acid dinitrile. Among these, acrylonitrile is preferable. These ethylenically unsaturated nitrile monomers may be used alone or in combination of two or more.
- the content ratio of the ethylenically unsaturated nitrile monomer unit in the solid nitrile rubber is preferably 10 to 60% by weight, more preferably 15 to 40% by weight, based on all monomer units.
- the content ratio of the ethylenically unsaturated nitrile monomer unit is within this range, the resulting rubber cross-linked product has low hardness.
- conjugated diene monomer examples include 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene, 4,5-diethyl-1,3-octadiene, 3 -Butyl-1,3-octadiene, chloroprene, 2,3-dichlorobutadiene, 1,3-cyclopentadiene and the like. Of these, 1,3-butadiene is preferred.
- These conjugated diene monomers may be used alone or in combination of two or more.
- the content of the conjugated diene monomer unit in the solid nitrile rubber is preferably 40 to 90% by weight, more preferably 50 to 85% by weight, based on the total monomer units.
- ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid
- Ethylenically unsaturated polyvalent carboxylic acids such as citraconic acid and mesaconic acid and their anhydrides
- Monoalkyl esters of ethylenically unsaturated monocarboxylic acids include butyl esters of ethylenically unsaturated monocarboxylic acids; complete alkyl esters of ethylenically unsaturated polyvalent carboxylic acids such as diethyl maleate, dimethyl itaconate, dimethyl maleate; monoethyl maleate, monomethyl itaconate, monomethyl maleate, etc.
- ethylenically unsaturated polycarboxylic acid Alkyl ester; monoamide of ethylenically unsaturated monocarboxylic acid such as acrylamide, methacrylamide, crotonic amide, cinnamic amide; styrene, ⁇ -methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, Fragrances such as pt-butylstyrene, o-methoxystyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 1,1-diphenylethylene, N, N-dimethyl-p-aminostyrene, vinylpyridine, etc.
- monoamide of ethylenically unsaturated monocarboxylic acid such as acrylamide, methacrylamide, crotonic amide, cinn
- Group vinyl monomers vinyl chloride, vinylidene chloride, vinyl acetate, allyl acetate and the like. These other copolymerizable monomers may be used alone or in combination of two or more. The content of other copolymerizable monomer units is preferably 20% by weight or less, more preferably 15% by weight or less.
- acrylonitrile is used as an ethylenically unsaturated nitrile monomer
- 1,3-butadiene is used as a conjugated diene monomer
- Solid acrylonitrile-butadiene rubber obtained by using is preferable.
- the method for producing the solid nitrile rubber is not particularly limited, and can be produced by a known emulsion polymerization method or the like. After polymerization, solid nitrile rubber is obtained through solidification and drying. The obtained solid nitrile rubber may be a hydrogenated nitrile rubber obtained by adding hydrogen to a carbon-carbon unsaturated bond portion in the rubber.
- the content ratio of the solid nitrile rubber in the crosslinkable rubber composition for the conductive roll of the present invention is preferably 9 to 80% by weight, more preferably 9 to 70% by weight, and still more preferably 29% in all rubber components. ⁇ 60% by weight. If the content of the solid nitrile rubber is too small, the hardness of the resulting rubber cross-linked product may be increased. On the other hand, if the content is too high, the volume specific resistance value of the resulting rubber cross-linked product may be increased.
- the liquid nitrile rubber used in the present invention is an ethylenically unsaturated nitrile-conjugated diene copolymer rubber having a liquid state at room temperature (having fluidity at room temperature for a short time), and its weight average molecular weight is gel permeation.
- the polystyrene conversion using chromatography is preferably 1,000 to 50,000, more preferably 3,000 to 30,000, and still more preferably 3,000 to 15,000.
- liquid nitrile rubber used in the present invention has a polymer Mooney viscosity (ML 1 + 4 , 100 ° C.) measured in accordance with JIS K6300, usually 1 or less, or the Mooney viscosity cannot be measured.
- the liquid nitrile rubber used in the present invention usually comprises an ethylenically unsaturated nitrile monomer, a conjugated diene monomer, and other monomers that can be copolymerized with these monomers. Obtained by polymerization.
- ethylenically unsaturated nitrile monomer for example, those similar to the solid nitrile rubber described above can be used, and among them, acrylonitrile is preferable.
- the ethylenically unsaturated nitrile monomer may be used alone or in combination of two or more.
- the content of ethylenically unsaturated nitrile monomer units in the liquid nitrile rubber is preferably 10 to 60% by weight, more preferably 15 to 50% by weight, based on all monomer units.
- conjugated diene monomer for example, those similar to the solid nitrile rubber described above can be used, and among them, 1,3-butadiene is preferable.
- the conjugated diene monomer may be used alone or in combination of two or more.
- the content ratio of the conjugated diene monomer unit in the liquid nitrile rubber is preferably 40 to 90% by weight, more preferably 50 to 85% by weight, based on all monomer units.
- copolymerizable monomers for example, the same monomers as the above-mentioned solid nitrile rubber can be used.
- the other copolymerizable monomers may be used alone or in combination of two or more.
- the content of other copolymerizable monomer units is preferably 20% by weight or less, more preferably 15% by weight or less.
- liquid nitrile rubber used in the present invention acrylonitrile is used as an ethylenically unsaturated nitrile monomer, 1,3-butadiene is used as a conjugated diene monomer, and a monomer copolymerizable with these as required
- a liquid acrylonitrile-butadiene rubber obtained by using is preferable.
- the production method of the liquid nitrile rubber is not particularly limited, and can be produced by a known emulsion polymerization or the like.
- a molecular weight modifier such as a chain transfer agent in order to adjust the molecular weight to a relatively low one.
- the chain transfer agent include t-dodecyl mercaptan.
- hydrogen may be added to the carbon-carbon unsaturated bond portion of the liquid nitrile rubber.
- the content of the liquid nitrile rubber in the crosslinkable rubber composition for the conductive roll of the present invention is preferably 1 to 30% by weight, more preferably 1 to 20% by weight, and still more preferably 1% in all rubber components. ⁇ 10% by weight. If the content of the liquid nitrile rubber is too small, the hardness of the resulting rubber cross-linked product may be increased. On the other hand, if the content is too high, the compression set of the resulting rubber cross-linked product may be reduced. .
- the crosslinkable rubber composition for conductive rolls of the present invention is a rubber component, as long as it does not impair the effects of the present invention, if desired, other than the above-described polyether rubber, solid nitrile rubber, and liquid nitrile rubber.
- the rubber may be contained. Examples of other rubbers include butadiene rubber, styrene-butadiene rubber, isoprene rubber, natural rubber, ethylene-propylene rubber, polyurethane rubber, acrylic rubber, fluorine rubber, and silicone rubber. In the case of containing other rubbers, these rubbers may be used alone or in combination of two or more.
- the sulfur-containing cross-linking agent used in the present invention is not particularly limited as long as it contains a sulfur atom and can cross-link the above-described rubber component.
- polyether rubber, solid nitrile rubber, and liquid nitrile rubber as rubber components From the viewpoint of being capable of co-crosslinking, it is preferably at least one sulfur-containing compound selected from sulfur-containing compounds having a sulfur and morpholine structure.
- Specific examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur.
- Examples of the sulfur-containing compound having a morpholine structure include a compound containing a morpholine ring and a sulfur atom represented by the following general formula (1). These sulfur-containing crosslinking agents may be used alone or in combination of two or more. (In the general formula (1), Y 1 is a divalent group containing a sulfur atom.)
- Y 1 is not particularly limited as long as it contains a sulfur atom and links two morpholine structures, but as a sulfur-containing compound having a morpholine structure, Y 1
- the compound represented by the following general formula (2) or the following general formula (3), wherein 1 is a specific divalent group containing a sulfur atom, is more preferred, and the compound represented by the following general formula (2) Is particularly preferred.
- R 1 and R 2 are each independently a chemical single bond or an alkylene group having 1 to 10 carbon atoms, preferably a chemical single bond or 1 to 3 carbon atoms. More preferably, it is a chemical single bond, and it is particularly preferable that both R 1 and R 2 are chemical single bonds. That is, among the compounds represented by the general formula (2), a compound represented by the following general formula (4) is particularly preferable.
- R 3 and R 4 are each independently a chemical single bond or an alkylene group having 1 to 10 carbon atoms, preferably a chemical single bond or 1 carbon atom. To 3 alkylene groups, more preferably a chemical single bond, and it is particularly preferable that both of R 3 and R 4 are chemical single bonds.
- a compound in which n 4 in the formula (4)), 4-morpholinyl morpholinodithioformate (a compound represented by the above formula (5)), and the like.
- 4,4′-dithiodimorpholine Is particularly preferred.
- the amount of the sulfur-containing crosslinking agent in the crosslinkable rubber composition for the conductive roll of the present invention is preferably 0.1 to 10 parts by weight, preferably 0.2 to 7 parts per 100 parts by weight of the total rubber component. Part by weight is more preferred, and 0.3 to 5 parts by weight is even more preferred. If the blending amount of the crosslinking agent is too small, the crosslinking speed becomes slow, and the productivity of the resulting rubber cross-linked product may decrease, or the abrasiveness may decrease when the rubber cross-linked product is used after being polished. . On the other hand, if the amount is too large, the hardness of the resulting rubber cross-linked product may increase, or the cross-linking agent may bloom.
- the disulfide crosslinking accelerator used in the present invention is not particularly limited as long as it has a disulfide structure (—S—S—) and acts as a crosslinking accelerator in combination with a sulfur-containing crosslinking agent, but thiuram disulfide is not limited. At least one disulfide crosslinking accelerator selected from a system crosslinking accelerator and a thiazolyl disulfide crosslinking accelerator is preferred. By using a thiuram disulfide-based crosslinking accelerator and / or a thiazolyl disulfide-based crosslinking accelerator, the volume specific resistance value of the resulting rubber crosslinked product is appropriately lowered.
- thiuram disulfide crosslinking accelerator examples include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrapentamethylenethiuram disulfide, tetrabenzylthiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide and the like.
- Specific examples of thiazolyl disulfide crosslinking accelerators include dibenzothiazolyl disulfide. These disulfide-based crosslinking accelerators may be used alone or in combination of two or more. Among these, tetraethylthiuram disulfide and dibenzothiazolyl disulfide are preferable.
- a disulfide crosslinking accelerator may be added as a crosslinking accelerator.
- a crosslinking accelerator other than a disulfide crosslinking accelerator that is, a crosslinking accelerator having no disulfide structure is used in combination. Since there is a tendency that the volume specific resistance value of the obtained rubber cross-linked product tends to be high, it is desirable not to use a cross-linking accelerator other than the disulfide-based cross-linking accelerator.
- the blending amount of the disulfide-based crosslinking accelerator in the crosslinkable rubber composition for the conductive roll of the present invention is preferably 0.01 to 15 parts by weight, preferably 0.1 to 0.1 parts by weight with respect to 100 parts by weight of all rubber components. 10 parts by weight is more preferable, and 0.5 to 5 parts by weight is still more preferable. If the amount of the disulfide crosslinking accelerator is too large, the crosslinking rate may become too fast, or the surface of the resulting crosslinked rubber product may bloom. On the other hand, if the amount is too small, the volume specific resistance value of the resulting rubber cross-linked product may be increased.
- the conductive carbon black used in the present invention is a carbon material exhibiting conductivity having an average primary particle diameter of 50 nm or less and a BET specific surface area of 600 m 2 / g or more.
- the conductive carbon black used in the present invention has an average primary particle size of 50 nm or less, preferably 45 nm or less, more preferably 40 nm or less.
- the lower limit of the average primary particle size is not particularly limited, but is usually 10 nm or more.
- the average primary particle diameter is more than 50 nm, the volume specific resistance value of the obtained rubber cross-linked product becomes high, and it becomes unsuitable for conductive roll applications, particularly for charging roll applications.
- the conductive carbon black used in the present invention has an average primary particle diameter in the above range, and a BET specific surface area of 600 m 2 / g or more, preferably 650 m 2 / g or more, more preferably 700 m. 2 / g or more.
- a BET specific surface area 600 m 2 / g or more, preferably 650 m 2 / g or more, more preferably 700 m. 2 / g or more.
- the upper limit of a BET specific surface area is not specifically limited, Usually, it is 1,600 m ⁇ 2 > / g or less.
- the BET specific surface area is less than 600 m 2 / g, the volume specific resistance value of the obtained rubber cross-linked product becomes high, and it becomes unsuitable for conductive roll applications, particularly for charging roll applications.
- the conductive carbon black used in the present invention may be any conductive carbon black having an average primary particle diameter and a BET specific surface area within the above ranges, and is not particularly limited, but the volume resistivity value can be further reduced. From the viewpoint, it is preferable that the primary particles are hollow shell-like particles, the primary particles have a porosity of 50% or more, and such primary particles are secondary aggregated. Specific examples of the conductive carbon black used in the present invention include “Ketjen Black EC”, “Ketjen Black EC300”, “Ketjen Black EC600JD” (manufactured by Lion Corporation), and the like.
- the blending amount of the conductive carbon black in the crosslinkable rubber composition for the conductive roll of the present invention is preferably 3 to 10 parts by weight, more preferably 4 to 9 parts by weight with respect to 100 parts by weight of the total rubber component. Preferably, 5 to 8 parts by weight is more preferable. If the amount of conductive carbon black is too small, the volume specific resistance value of the resulting rubber cross-linked product may be too high. On the other hand, if the amount is too large, the resulting rubber cross-linked product may have a high hardness.
- crosslinking accelerating aid examples include zinc oxide and stearic acid.
- the amount of crosslinking accelerator is preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, and still more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the total rubber component. .
- the crosslinking accelerator proceeds sufficiently and the mechanical properties of the resulting rubber crosslinked product are excellent.
- crosslinkable rubber composition for conductive rolls of the present invention may be blended with other additives usually blended with known rubbers in addition to the components described above.
- additives include, but are not limited to, reinforcing agents; acid acceptors; anti-aging agents; ultraviolet absorbers; light-resistant stabilizers; tackifiers; surfactants; Pigments); flame retardants; antistatic agents; and the like.
- the crosslinkable rubber composition for conductive rolls of the present invention includes the above-described polyether rubber, solid nitrile rubber, liquid nitrile rubber, sulfur-containing crosslinker, disulfide-based crosslink accelerator, conductive carbon black, and Each additive and other rubbers used accordingly can be prepared by blending and kneading by a desired method. For example, it is obtained after mixing polyether rubber, solid nitrile rubber, and liquid nitrile rubber as rubber components, and kneading each component excluding sulfur-containing crosslinking agent and disulfide-based crosslinking accelerator into the obtained rubber mixture.
- the crosslinkable rubber composition for conductive rolls of the present invention can be obtained.
- kneading and molding may be performed using one or a combination of any kneading and molding machines such as a kneader, a banbury, an open roll, a calender roll, and an extruder.
- the kneading temperature of the rubber kneaded product and the additive excluding the sulfur-containing crosslinking agent and disulfide crosslinking accelerator is preferably 20 to 200 ° C., more preferably 20 to 150 ° C., and the kneading time is 30 seconds to 30 minutes.
- the mixing temperature of the obtained kneaded product, the sulfur-containing crosslinking agent and the disulfide-based crosslinking accelerator is preferably 100 ° C. or less, more preferably 0 to 80 ° C., and the kneading time is 30 seconds to 20 Minutes are preferred.
- the polyether rubber dissolved in the solvent and the liquid nitrile rubber are mixed in the solvent. Then, by solidifying by steam stripping or the like, a solid mixture of polyether rubber and liquid nitrile rubber is obtained, and solid nitrile rubber is mixed in a solid state with the obtained solid mixture.
- a kneading method may be adopted. In particular, according to such a method, the contamination of the photoreceptor can be reduced when the obtained rubber cross-linked product is used for a conductive roll used in an image forming apparatus or the like.
- the rubber cross-linked product for a conductive roll of the present invention is obtained by cross-linking the cross-linkable rubber composition for a conductive roll of the present invention described above.
- the method for cross-linking the cross-linkable rubber composition for conductive rolls of the present invention is not particularly limited, but it may be formed and cross-linked simultaneously or after forming.
- the molding temperature is preferably 20 to 200 ° C, more preferably 40 to 180 ° C.
- the heating temperature at the time of crosslinking is preferably from 130 to 200 ° C, more preferably from 140 to 200 ° C. If the temperature at the time of crosslinking is too low, the crosslinking time may be required for a long time, or the crosslinking density of the resulting rubber crosslinked product may be lowered. On the other hand, if the temperature at the time of crosslinking is too high, there is a risk of forming defects.
- the crosslinking time varies depending on the crosslinking method, crosslinking temperature, shape and the like, but a range of 1 minute or more and 5 hours or less is preferable from the viewpoint of crosslinking density and production efficiency.
- a heating method a method such as press heating, oven heating, steam heating, hot air heating, and microwave heating may be appropriately selected.
- secondary cross-linking may be performed by heating.
- the heating temperature in performing the secondary crosslinking is preferably 100 to 220 ° C, more preferably 130 to 210 ° C.
- the heating time is preferably 30 minutes to 5 hours.
- the rubber cross-linked product for conductive rolls of the present invention thus obtained is obtained using the cross-linkable rubber composition for conductive rolls of the present invention described above, and therefore has low hardness and volume resistivity. It has a low value and excellent compression set resistance. Therefore, the rubber cross-linked product for conductive rolls of the present invention takes advantage of such characteristics and is used for conductive rolls used in image forming apparatuses such as printers, electrophotographic copying machines, and facsimile machines, specifically, Can be suitably used as a charging roll, a toner supply roll, a development roll, a transfer roll, and the like.
- the crosslinked rubber of the present invention has a volume resistivity of 23 ° C. and a humidity of 50% in a measurement environment.
- the applied voltage is 10 V, and the value 30 seconds after the start of voltage application is preferably as low as 1 ⁇ 10 6.0 ⁇ ⁇ cm or less.
- Mooney viscosity Mooney viscosity (ML 1 + 4 , 100 ° C.) was measured at 100 ° C. according to JIS K6300.
- the crosslinkable rubber composition is molded and crosslinked by pressing at a temperature of 170 ° C. for 20 minutes, and then secondary crosslinked at a temperature of 150 ° C. for 4 hours to form a cylindrical shape having a diameter of 29 mm and a height of 12.7 mm. A rubber cross-linked product was obtained. And the hardness was measured using the type A durometer according to JISK6253 using the obtained cylindrical rubber cross-linked product.
- a cross-linkable rubber composition is molded and cross-linked by pressing at a temperature of 170 ° C. for 20 minutes, and then subjected to secondary cross-linking at a temperature of 150 ° C. for 4 hours.
- a rubber cross-linked product was obtained.
- voltage application is started under the conditions of a temperature of 23 ° C., a humidity of 50% and an applied voltage of 10 V in accordance with the double ring electrode method of JIS K6271. The value after 30 seconds was measured. The smaller the numerical value of the volume resistivity, the better the conductivity.
- the crosslinkable rubber composition is molded and crosslinked by pressing at a temperature of 170 ° C. for 20 minutes, and then secondary crosslinked at a temperature of 150 ° C. for 4 hours to form a cylindrical shape having a diameter of 29 mm and a height of 12.7 mm.
- a rubber cross-linked product was obtained.
- the obtained cross-linked product was compressed by 25% and placed in an environment at a temperature of 70 ° C. for 22 hours. Then, the compression was released and the compression set was measured.
- the compression set rate is better as the numerical value is smaller and the material is more difficult to deform.
- the obtained polyether rubber had a monomer composition ratio of 56 mol% of ethylene oxide monomer units, 40 mol% of epichlorohydrin monomer units, single units of allyl glycidyl ether. It was confirmed that the polymer contained 4 mol% of the monomer unit.
- Example 1 Into a stirring vessel equipped with stirring blades, 100 parts of the polyether rubber obtained in Production Example 2 and 900 parts of acetone are added, and stirred at 23 ° C. for 12 hours, whereby 10% by weight of the polyether rubber is added. A solution was obtained. In a separate stirring vessel, 900 parts of a 10% by weight acetone solution of the obtained polyether rubber (90 parts in terms of polyether rubber) and liquid nitrile rubber (acrylonitrile-butadiene rubber (acrylonitrile 29.5%) %), Product name “Nipol 1312”, manufactured by Nippon Zeon Co., Ltd.) and stirring at 40 ° C.
- Example 2 The amount of 4,4-dithiodimorpholine as a sulfur-containing crosslinking agent was changed from 2 parts to 1 part, and sulfur (product name "Sulfax PMC", manufactured by Tsurumi Chemical Industry Co., Ltd.) was used as the sulfur-containing crosslinking agent.
- a crosslinkable rubber composition was obtained in the same manner as in Example 1 except that 0.25 part was further added, and each measurement / evaluation was performed in the same manner. The results are shown in Table 1.
- Example 3 A crosslinkable rubber composition was obtained in the same manner as in Example 1 except that tetraethylthiuram disulfide as a disulfide crosslinking accelerator was not blended, and each measurement / evaluation was performed in the same manner. The results are shown in Table 1.
- Example 4 A crosslinkable rubber composition was obtained in the same manner as in Example 1 except that dibenzothiazolyl disulfide as a disulfide crosslinking accelerator was not blended, and each measurement / evaluation was performed in the same manner. The results are shown in Table 1.
- Comparative Example 2 A crosslinkable rubber composition was obtained in the same manner as in Comparative Example 1 except that the amount of carbon black (product name “Asahi # 35”, manufactured by Asahi Carbon Co., Ltd.) was changed from 7 parts to 30 parts. Each measurement / evaluation was performed. The results are shown in Table 1.
- Example 5 The same procedure as in Example 1 was conducted except that 60 parts of the polyether rubber obtained in Production Example 2 was directly added to a Banbury mixer instead of 60 parts of the mixture of polyether rubber and liquid nitrile rubber as a rubber component. Thus, a crosslinkable rubber composition was obtained and each measurement / evaluation was performed in the same manner. That is, in Comparative Example 5, as a rubber component, liquid nitrile rubber was not blended, but only polyether rubber and solid nitrile rubber were blended. The results are shown in Table 1.
- polyether rubber, solid nitrile rubber, liquid nitrile rubber, sulfur-containing crosslinking agent, disulfide-based crosslinking accelerator, and predetermined conductive carbon black (average primary particle diameter is 50 nm or less, and BET A rubber cross-linked product obtained using a cross-linkable rubber composition containing a specific surface area of 600 m 2 / g or more has a low hardness, a low volume resistivity value and a low compression set, and is excellent as a conductive roll application. (Examples 1 to 4).
- the resulting rubber can be obtained regardless of the amount of the compound.
- the cross-linked product resulted in an increase in the volume resistivity, and further, when the blending amount was increased to 30 parts, the hardness increased (Comparative Examples 1 and 2).
- the resulting rubber cross-linked product resulted in increased hardness (Comparative Example 3).
- polyether rubber or liquid nitrile rubber was not blended among the three types of rubber components, the resulting rubber cross-linked product resulted in increased hardness and volume resistivity (Comparative Example 4). , 5).
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Abstract
Description
本発明の架橋性ゴム組成物において、全ゴム成分中における、前記ポリエーテルゴムの含有割合が19~90重量%、前記固形ニトリルゴムの含有割合が9~80重量%、前記液状ニトリルゴムの含有割合の含有割合が1~30重量%であることが好ましい。
本発明の架橋性ゴム組成物において、前記含硫黄架橋剤が、硫黄およびモルホリン構造を有する含硫黄化合物から選ばれる少なくとも1種であることが好ましい。
本発明の架橋性ゴム組成物において、前記モルホリン構造を有する含硫黄化合物が、下記一般式(1)で表される化合物であることが好ましい。
本発明の架橋性ゴム組成物において、前記ジスルフィド系架橋促進剤が、チウラムジスルフィド系架橋促進剤およびチアゾリルジスルフィド系架橋促進剤から選ばれる少なくとも1種であることが好ましい。
本発明で用いるポリエーテルゴムは、オキシラン単量体を開環重合して得られるオキシアルキレン繰り返し単位を主構造単位とするゴムであれば特に限定されない。オキシラン単量体の種類も特に限定されないが、本発明で用いるポリエーテルゴムは、固形ニトリルゴム、および液状ニトリルゴムと共架橋ができる観点より、ビニル基を有する架橋性オキシラン単量体に基づくビニル基を有する架橋性オキシラン単量体単位を含有するものが好ましい。
本発明で用いる固形ニトリルゴムは、常温において固体状態を有する(常温、短時間において流動しない)エチレン性不飽和ニトリル-共役ジエン系共重合ゴムである。本発明で用いる固形ニトリルゴムは、JIS K6300に準拠して測定したポリマームーニー粘度(ML1+4,100℃)が、通常、15以上のものであり、好ましくは15~150、より好ましくは30~100である。
本発明で用いる液状ニトリルゴムは、常温において液体状態を有する(常温、短時間において流動性を有する)エチレン性不飽和ニトリル-共役ジエン系共重合ゴムであり、その重量平均分子量が、ゲルパーミエーションクロマトグラフィを用いたポリスチレン換算として、好ましくは1,000~50,000、より好ましくは3,000~30,000、さらに好ましくは3,000~15,000のものである。また、本発明で用いる液状ニトリルゴムは、JIS K6300に準拠して測定したポリマームーニー粘度(ML1+4,100℃)が、通常、1以下、あるいは、ムーニー粘度測定不可能なものである。
本発明で用いる含硫黄架橋剤としては、硫黄原子を含有し、上述したゴム成分を架橋可能なものであれば特に限定されないが、ゴム成分としてのポリエーテルゴム、固形ニトリルゴム、および液状ニトリルゴムの共架橋ができる観点より、硫黄およびモルホリン構造を有する含硫黄化合物から選ばれる少なくともひとつの含硫黄化合物であることが好ましい。硫黄の具体例としては、粉末硫黄、沈降硫黄、コロイド硫黄、不溶性硫黄、および高分散性硫黄などが挙げられる。モルホリン構造を有する含硫黄化合物としては、たとえば、下記一般式(1)で表される、モルホリン環および硫黄原子を含有する化合物などが挙げられる。これらの含硫黄架橋剤は、1種単独で、または2種以上を組み合わせて用いてもよい。
本発明で用いるジスルフィド系架橋促進剤としては、ジスルフィド構造(-S-S-)を有し、含硫黄架橋剤と組み合わせることで架橋促進剤として作用するものであれば特に限定されないが、チウラムジスルフィド系架橋促進剤およびチアゾリルジスルフィド系架橋促進剤から選ばれる少なくともひとつのジスルフィド系架橋促進剤であることが好ましい。チウラムジスルフィド系架橋促進剤および/またはチアゾリルジスルフィド系架橋促進剤を用いることにより、得られるゴム架橋物の体積固有抵抗値が適切に低くなる。チウラムジスルフィド系架橋促進剤の具体例としては、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、テトラペンタメチレンチウラムジスルフィド、テトラベンジルチウラムジスルフィド、テトラキス(2-エチルヘキシル)チウラムジスルフィドなどが挙げられる。チアゾリルジスルフィド系架橋促進剤の具体例としては、ジベンゾチアゾリルジスルフィドなどが挙げられる。これらのジスルフィド系架橋促進剤は、1種単独で、または2種以上を組み合わせて用いてもよい。これらの中でも、テトラエチルチウラムジスルフィド、およびジベンゾチアゾリルジスルフィドが好ましい。
本発明で用いる導電性カーボンブラックは、平均一次粒子径が50nm以下であり、かつ、BET比表面積が600m2/g以上である導電性を示す炭素材料である。このような導電性カーボンブラックを、上述した各成分と組み合わせて用いることで、得られるゴム架橋物の体積固有抵抗値を適切に低くすることができる。
また、本発明の導電性ロール用架橋性ゴム組成物には、上記した各成分に加えて、架橋促進助剤を配合してもよい。
架橋促進助剤の配合量は、全ゴム成分100重量部に対して、0.01~15重量部が好ましく、0.1~10重量部がより好ましく、0.5~5重量部がさらに好ましい。架橋促進助剤の配合量が上記範囲であると、架橋が十分に進行し、得られるゴム架橋物の機械的特性が優れる。
本発明の導電性ロール用ゴム架橋物は、上述した本発明の導電性ロール用架橋性ゴム組成物を架橋してなるものである。
ムーニー粘度(ML1+4,100℃)は、JIS K6300に従って、100℃で測定した。
架橋性ゴム組成物を温度170℃、20分間のプレスによって成形、架橋し、次いで、温度150℃、4時間の条件にて二次架橋することで、直径29mm、高さ12.7mmの円柱状のゴム架橋物を得た。そして、得られた円柱状のゴム架橋物を用いて、JIS K6253に従い、タイプAデュロメータを使用し、硬度を測定した。
架橋性ゴム組成物を温度170℃、20分間のプレスによって成形、架橋し、次いで、温度150℃、4時間の条件にて二次架橋することで、縦15cm、横15cm、厚さ2mmのシート状のゴム架橋物を得た。そして、得られたシート状のゴム架橋物を用いて、JIS K6271の2重リング電極法に準拠し、温度23℃、湿度50%とし、印加電圧10Vの条件にて、電圧の印加を開始してから30秒後の値を測定した。体積固有抵抗値は、数値が小さいほど、導電性に優れている。
架橋性ゴム組成物を温度170℃、20分間のプレスによって成形、架橋し、次いで、温度150℃、4時間の条件にて二次架橋することで、直径29mm、高さ12.7mmの円柱状のゴム架橋物を得た。そして、JIS K6262に従い、得られた架橋物を25%圧縮させた状態で、温度70℃の環境下に22時間置いた後、圧縮を解放して圧縮永久歪み率を測定した。圧縮永久歪み率は、数値が小さいほど変形しにくい材料となり優れる。
密栓した耐圧ガラスボトルを窒素置換して、トルエン184.8部およびトリイソブチルアルミニウム55.2部を仕込み、ガラスボトルを氷水に浸漬して冷却した後、ジエチルエーテル103.1部をガラスボトルに添加し、攪拌した。次いで、ガラスボトルに、氷水による冷却を継続しながら、リン酸8.18部を添加し、さらに攪拌した。この際、トリイソブチルアルミニウムとリン酸との反応により、ガラスボトルの内圧が上昇するので、適時脱圧を実施した。次いで、ガラスボトルに1,8-ジアザ-ビシクロ(5,4,0)ウンデセン-7のギ酸塩8.27部を添加し、最後に、60℃の温水浴内で1時間熟成反応させることにより、触媒溶液を得た。
オートクレーブに、エピクロロヒドリン212.4部、アリルグリシジルエーテル26.2部、エチレンオキサイド18.4部、およびトルエン2053.8部を入れ、窒素雰囲気下で攪拌しながら内溶液を70℃に昇温し、上記にて調製した触媒溶液を10部添加して、反応を開始した。次いで、反応開始直後から、エチレンオキサイド123.0部をトルエン287.0部に溶解した溶液を、5時間かけて等速度で連続添加した。同時に、上記にて調製した触媒溶液を、30分毎に7部ずつ、5時間にわたり添加した。その後、反応系に水15部を添加し、攪拌することにより反応を終了させ、さらに老化防止剤としての4,4’-チオビス-(6-tert-ブチル-3-メチルフェノール)5重量%トルエン溶液38部を添加し攪拌した。続いて、スチームストリッピングを実施してトルエンを除去し、上澄み水を除去後、60℃で15時間真空乾燥することで、361.0部のポリエーテルゴムを得た。得られたポリエーテルゴムのムーニー粘度は45であった。また、1H-NMR分析の結果、得られたポリエーテルゴムの単量体組成比は、エチレンオキサイド単量体単位56モル%、エピクロロヒドリン単量体単位40モル%、アリルグリシジルエーテル単量体単位4モル%を含有するものであることが確認できた。
攪拌羽を備える撹拌容器に、製造例2にて得られたポリエーテルゴム100部、およびアセトン900部を投入し、23℃にて、12時間撹拌することで、ポリエーテルゴムの10重量%アセトン溶液を得た。そして、上記とは別の撹拌容器に、得られたポリエーテルゴムの10重量%アセトン溶液900部(ポリエーテルゴム換算で90部)と、液状ニトリルゴム(アクリロニトリル-ブタジエンゴム(アクリロニトリル29.5重量%)、製品名「Nipol 1312」、日本ゼオン社製)10部とを投入し、40℃にて、2時間撹拌することで、ポリエーテルゴムおよび液状ニトリルゴムが共に溶解混合されたアセトン溶液であるゴム溶液を得た。次いで、得られたポリエーテルゴムおよび液状ニトリルゴムのアセトン溶液であるゴム溶液について、スチームストリッピングを実施し、その後、スラリーからろ別することにより得られたゴム成分を、60℃で15時間真空乾燥することで、100部の、ポリエーテルゴムと液状ニトリルゴムとの混合物(ポリエーテルゴム:液状ニトリルゴム=90:10(重量比))を得た。
含硫黄架橋剤としての4,4-ジチオジモルホリンの配合量を2部から1部に変更し、かつ、含硫黄架橋剤として、硫黄(製品名「サルファックスPMC」、鶴見化学工業社製)0.25部をさらに配合した以外は、実施例1と同様にして、架橋性ゴム組成物を得て、同様に各測定・評価を行った。結果を表1に示す。
ジスルフィド系架橋促進剤としてのテトラエチルチウラムジスルフィドを配合しなかった以外は、実施例1と同様にして、架橋性ゴム組成物を得て、同様に各測定・評価を行った。結果を表1に示す。
ジスルフィド系架橋促進剤としてのジベンゾチアゾリルジスルフィドを配合しなかった以外は、実施例1と同様にして、架橋性ゴム組成物を得て、同様に各測定・評価を行った。結果を表1に示す。
導電性カーボンブラック(製品名「ケッチェンブラックEC300」、ライオン社製)7部の代わりに、カーボンブラック(製品名「旭#35」、旭カーボン社製、平均一次粒子径:78nm、BET比表面積:24m2/g)7部を使用した以外は、実施例1と同様にして、架橋性ゴム組成物を得て、同様に各測定・評価を行った。結果を表1に示す。
カーボンブラック(製品名「旭#35」、旭カーボン社製)の配合量を7部から30部に変更した以外は、比較例1と同様にして、架橋性ゴム組成物を得て、同様に各測定・評価を行った。結果を表1に示す。
ゴム成分としてのポリエーテルゴムと液状ニトリルゴムとの混合物60部の代わりに、バンバリーミキサーに、製造例2にて得られたポリエーテルゴム95部と液状ニトリルゴム5部とを直接投入し、かつ、ゴム成分としての固形ニトリルゴムを配合しなかった以外は、実施例1と同様にして、架橋性ゴム組成物を得て、同様に各測定・評価を行った。すなわち、比較例3においては、ゴム成分としては、固形ニトリルゴムを配合せず、ポリエーテルゴムおよび液状ニトリルゴムのみを配合した。結果を表1に示す。
ゴム成分としてのポリエーテルゴムと液状ニトリルゴムとの混合物60部の代わりに、バンバリーミキサーに、液状ニトリルゴム5部を直接投入し、かつ、ゴム成分としての固形ニトリルゴムの配合量を40部から95部に変更した以外は、実施例1と同様にして、架橋性ゴム組成物を得て、同様に各測定・評価を行った。すなわち、比較例4においては、ゴム成分としては、ポリエーテルゴムを配合せず、液状ニトリルゴムおよび固形ニトリルゴムのみを配合した。結果を表1に示す。
ゴム成分としてのポリエーテルゴムと液状ニトリルゴムとの混合物60部の代わりに、バンバリーミキサーに、製造例2にて得られたポリエーテルゴム60部を直接投入した以外は、実施例1と同様にして、架橋性ゴム組成物を得て、同様に各測定・評価を行った。すなわち、比較例5においては、ゴム成分としては、液状ニトリルゴムを配合せず、ポリエーテルゴムおよび固形ニトリルゴムのみを配合した。結果を表1に示す。
また、3種のゴム成分のうち、固形ニトリルゴムを配合しなかった場合には、得られるゴム架橋物は、硬度が高くなる結果となった(比較例3)。
さらに、3種のゴム成分のうち、ポリエーテルゴムまたは液状ニトリルゴムを配合しなかった場合には、得られるゴム架橋物は、硬度および体積固有抵抗値が高くなる結果となった(比較例4,5)。
Claims (8)
- ポリエーテルゴム、固形ニトリルゴム、液状ニトリルゴム、含硫黄架橋剤、ジスルフィド系架橋促進剤、および、平均一次粒子径が50nm以下、かつ、BET比表面積が600m2/g以上である導電性カーボンブラックを含有する導電性ロール用架橋性ゴム組成物。
- 前記ポリエーテルゴムが、ビニル基を有する架橋性オキシラン単量体単位、エチレンオキサイド単量体単位、およびエピハロヒドリン単量体単位を含有するものである請求項1に記載の導電性ロール用架橋性ゴム組成物。
- 全ゴム成分中における、前記ポリエーテルゴムの含有割合が19~90重量%、前記固形ニトリルゴムの含有割合が9~80重量%、前記液状ニトリルゴムの含有割合の含有割合が1~30重量%である請求項1または2に記載の導電性ロール用架橋性ゴム組成物。
- 前記含硫黄架橋剤が、硫黄およびモルホリン構造を有する含硫黄化合物から選ばれる少なくとも1種である請求項1~3のいずれかに記載の導電性ロール用架橋性ゴム組成物。
- 前記ジスルフィド系架橋促進剤が、チウラムジスルフィド系架橋促進剤およびチアゾリルジスルフィド系架橋促進剤から選ばれる少なくとも1種である請求項1~5のいずれかに記載の導電性ロール用架橋性ゴム組成物。
- 請求項1~6のいずれかに記載の架橋性ゴム組成物を架橋してなる導電性ロール用ゴム架橋物。
- 請求項7に記載のゴム架橋物を有してなる導電性ロール。
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