WO2013076989A1 - ホース用ゴム組成物及びホース - Google Patents
ホース用ゴム組成物及びホース Download PDFInfo
- Publication number
- WO2013076989A1 WO2013076989A1 PCT/JP2012/007512 JP2012007512W WO2013076989A1 WO 2013076989 A1 WO2013076989 A1 WO 2013076989A1 JP 2012007512 W JP2012007512 W JP 2012007512W WO 2013076989 A1 WO2013076989 A1 WO 2013076989A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rubber
- mass
- parts
- hose
- butadiene
- Prior art date
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 140
- 239000005060 rubber Substances 0.000 title claims abstract description 140
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 229920001084 poly(chloroprene) Polymers 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 33
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 33
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- -1 metal hydroxide compound Chemical class 0.000 claims description 14
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 13
- 239000000178 monomer Substances 0.000 description 17
- 230000008034 disappearance Effects 0.000 description 16
- 230000003014 reinforcing effect Effects 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 15
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000013329 compounding Methods 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000004904 shortening Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- 239000004709 Chlorinated polyethylene Substances 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229920006168 hydrated nitrile rubber Polymers 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229960002377 dixanthogen Drugs 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/02—Layered products comprising a layer of natural or synthetic rubber with fibres or particles being present as additives in the layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/12—Layered products comprising a layer of natural or synthetic rubber comprising natural rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
-
- 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
- C08L9/06—Copolymers with styrene
-
- 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
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
- F16L11/081—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more layers of a helically wound cord or wire
- F16L11/083—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more layers of a helically wound cord or wire three or more layers
-
- 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
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L11/12—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting
- F16L11/125—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting non-inflammable or heat-resistant hoses
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/107—Ceramic
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/554—Wear resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2597/00—Tubular articles, e.g. hoses, pipes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
Definitions
- the present invention relates to a rubber composition for a hose and a hose, and in particular, relates to a rubber composition for a hose and a hose that can improve flame retardancy (particularly, shortening of afterglow disappearance time) and wear resistance and ensure workability. .
- chloroprene rubber (CR) as a halogen-based polymer has low storage stability
- the rubber composition using chloroprene rubber (CR) has difficulty in processing when producing a hose using the rubber composition. It has been known.
- the metal hydroxide compound has low reinforcing properties, it is known that the rubber composition using the metal hydroxide compound has a significantly reduced wear resistance and a hose life.
- the hose is inferior in terms of flexibility, weight reduction, and space saving. Therefore, there has been a strong demand for the development of a rubber that exhibits flame resistance (particularly, shortening of the afterglow disappearance time) and is excellent in wear resistance and workability.
- an object of the present invention is to provide a rubber composition for a hose and a hose that can improve flame retardancy (particularly, shortening of afterglow disappearance time) and wear resistance, and can secure processability.
- the rubber composition for a hose of the present invention contains chloroprene rubber, butadiene rubber, and styrene-butadiene rubber as rubber components, and 60 parts by mass to 80 parts by mass of chloroprene rubber in 100 parts by mass of the rubber component, Silica is blended in an amount of 5 to 25 parts by mass with respect to 100 parts by mass of the rubber component.
- the hose of the present invention has a rubber layer made of the rubber composition for a hose of the present invention.
- a rubber composition for a hose and a hose capable of improving flame retardancy (particularly, shortening of afterglow disappearance time) and wear resistance and ensuring workability.
- FIG. 1 is a perspective view showing an example of a laminated structure of a hydraulic hose using the hose rubber composition of the present invention.
- the rubber composition for hose of this invention contains a rubber component and a silica at least, and also contains a metal hydroxide compound and other components as needed.
- the rubber component includes at least chloroprene rubber (CR), butadiene rubber (BR), and styrene-butadiene rubber (SBR), and further includes other polymers as necessary.
- CR chloroprene rubber
- BR butadiene rubber
- SBR styrene-butadiene rubber
- Chloroprene rubber (CR) is a homopolymer of a chloroprene monomer (chloroprene polymer) or a mixture of a chloroprene monomer and one or more other monomers copolymerizable therewith (hereinafter referred to as a chloroprene series).
- a copolymer obtained by polymerizing a monomer hereinafter referred to as a chloroprene polymer).
- the chloroprene rubber is classified into a sulfur-modified type, a mercaptan-modified type, and a xanthogen-modified type according to the type of molecular weight regulator. Any modified type can be used as the chloroprene rubber.
- the sulfur-modified type is inferior in heat resistance of the polymer itself as compared to the mercaptan-modified type and the xanthogen-modified type, so if more heat resistance is required, use the mercaptan-modified or xanthogen-modified type. It is preferable to do.
- the mercaptan-modified type uses alkyl mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan and octyl mercaptan as molecular weight regulators.
- the xanthogen-modified type uses an alkyl xanthogen compound as a molecular weight regulator.
- the alkyl xanthogen compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dimethyl xanthogen disulfide, diethyl xanthogen disulfide, diisopropyl xanthogen disulfide, and diisobutyl xanthogen disulfide.
- the amount of the alkyl xanthogen compound used is not particularly limited as long as the molecular weight (or Mooney viscosity) of the chloroprene rubber is selected appropriately, and depends on the purpose (the structure of the alkyl group and the target molecular weight). However, it is preferably 0.05 parts by weight to 5.0 parts by weight, and 0.3 parts by weight to 1.0 parts by weight with respect to 100 parts by weight of the chloroprene monomer or chloroprene monomer. Part is more preferred.
- the content of the chloroprene rubber (CR) is not particularly limited as long as it is 60 to 80 parts by mass in 100 parts by mass of the rubber component, and can be appropriately selected according to the purpose. -80 parts by mass is preferable, and 65-75 parts by mass is more preferable.
- the content of the chloroprene rubber (CR) is less than 60 parts by mass in 100 parts by mass of the rubber component, the flame retardancy decreases (afterglow disappearance time becomes longer), and 80 parts by mass in 100 parts by mass of the rubber component. When it exceeds the mass part, the workability deteriorates.
- the content of the chloroprene rubber (CR) is within the preferable range, it is advantageous in terms of flame retardancy and processability, and when the content is within the more preferable range, it is further advantageous.
- the butadiene rubber (BR) is a butadiene monomer homopolymer (butadiene polymer), or a mixture of a butadiene monomer and one or more other monomers copolymerizable therewith (hereinafter referred to as a butadiene type). It is a copolymer obtained by polymerizing a monomer (hereinafter referred to as a monomer) (hereinafter referred to as a butadiene polymer).
- BR butadiene rubber
- the amount of cis-1,4 bonds in the butadiene rubber (BR) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 90% or more, more preferably 93% or more, and 95% or more. Is particularly preferred. If the cis-1,4 bond content is less than 90%, the wear resistance may be lowered. On the other hand, when the amount of cis-1,4 bonds is within the preferred range, it is advantageous in terms of wear resistance, and when the amount is within the more preferred range or the particularly preferred range, it is more advantageous. is there.
- the amount of cis-1,4 bond can be measured using 1 H-NMR, 13 C-NMR, FT-IR, or the like.
- BR butadiene rubber
- the content of the butadiene rubber (BR) is not particularly limited and can be appropriately selected depending on the purpose in 100 parts by mass of the rubber component, but is preferably 10 parts by mass to 30 parts by mass, and 15 parts by mass More preferred is 25 parts by mass.
- the content of the butadiene rubber (BR) is less than 10 parts by mass in 100 parts by mass of the rubber component, the wear resistance may be reduced, and when it exceeds 30 parts by mass in 100 parts by mass of the rubber component, As the CR or SBR amount decreases, the workability or flame retardancy may decrease.
- the content of the butadiene rubber (BR) is within the preferable range, it is advantageous in terms of both wear resistance and flame retardancy, and when the content is within the more preferable range, it is further advantageous. .
- the styrene-butadiene rubber is a copolymer of styrene monomer and butadiene monomer (styrene-butadiene copolymer), or copolymerizable with styrene monomer and butadiene monomer.
- a copolymer (hereinafter referred to as a styrene-butadiene copolymer) obtained by polymerizing a mixture with one or more other monomers (hereinafter referred to as a styrene-butadiene monomer).
- the monomer copolymerizable with the styrene monomer and the butadiene monomer is not particularly limited and may be appropriately selected depending on the intended purpose.
- 2-methyl-1,3-butadiene, 2 Conjugated diene monomers having 5 to 8 carbon atoms such as 1,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene; p-methylstyrene, ⁇ -methylstyrene, vinylnaphthalene, etc.
- Aromatic vinyl monomer and the like. These may be used individually by 1 type and may use 2 or more types together.
- SBR styrene-styrene content of butadiene rubber
- SBR styrene-butadiene rubber
- the styrene content of the styrene-butadiene rubber (SBR) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20% by mass to 45% by mass, and more preferably 20% by mass to 35% by mass. More preferred. If the styrene content of the styrene-butadiene rubber (SBR) is less than 20% by mass, the workability may be reduced, and if it exceeds 45% by mass, the wear resistance may be reduced. On the other hand, when the styrene content of the styrene-butadiene rubber (SBR) is within the above preferred range, it is advantageous in terms of workability and wear resistance, and more advantageously within the above preferred range. .
- SBR -Styrene-butadiene rubber
- the content of the styrene-butadiene rubber (SBR) is not particularly limited and can be appropriately selected depending on the purpose in 100 parts by mass of the rubber component, but is preferably 10 to 30 parts by mass. More preferred is from 25 parts by weight.
- SBR styrene-butadiene rubber
- processability may be deteriorated, and when it exceeds 30 parts by mass in 100 parts by mass of the rubber component.
- the wear resistance or flame retardancy may be lowered.
- the content of the styrene-butadiene rubber (SBR) is within the preferred range, it is advantageous in terms of both wear resistance and flame retardancy, and if the content is within the more preferred range, it is more advantageous. It is.
- Mass ratio of butadiene rubber (BR) / styrene-butadiene rubber (SBR) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 30/10 to 10/30, preferably 25/15 to 15/25 is more preferable. When the mass ratio is less than 10/30, the wear resistance may be lowered, and when it is more than 30/10, the workability may be lowered. On the other hand, when the mass ratio is within the preferred range, it is advantageous in terms of both wear resistance and workability, and when the mass ratio is within the more preferred range or within the particularly preferred range, it is further advantageous. is there.
- the rubber component contains 60 to 80 parts by mass of chloroprene rubber, 10 to 30 parts by mass of butadiene rubber, and 10 to 30 parts by mass of styrene-butadiene rubber, flame retardancy (In particular, shortening of afterglow disappearance time) and wear resistance can be improved, and processability can be ensured.
- the other polymer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include natural rubber, chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE), nitrile rubber (NBR), Hydrogenated acrylonitrile butadiene rubber (H-NBR), acrylic rubber (ACM), ethylene propylene rubber (EPDM), epichlorohydrin rubber (CO), hydrin rubber (ECO), silicone rubber (Q), fluorine rubber (FKM), etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, CSM and CPE are preferable in terms of flame retardancy.
- the nitrogen adsorption specific surface area (N 2 SA) of the silica is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 70 m 2 / g to 300 m 2 / g, and preferably 100 m 2 / g to 280 m. 2 / g is more preferable, and 150 m 2 / g to 250 m 2 / g is particularly preferable.
- the nitrogen adsorption specific surface area (N 2 SA) of the silica is less than 70 m 2 / g, flame retardancy and wear resistance may be reduced, and if it exceeds 300 m 2 / g, dispersibility, processing Sexuality may worsen.
- the nitrogen adsorption specific surface area (N 2 SA) of the silica is within the preferred range, it is advantageous in terms of the balance of flame retardancy, wear resistance, and workability, and within the more preferred range, or It is further advantageous if it is within the particularly preferred range.
- the compounding amount of the silica is not particularly limited as long as it is 5 to 25 parts by mass with respect to 100 parts by mass of the rubber component, and can be appropriately selected according to the purpose.
- the amount is preferably 7 parts by mass to 15 parts by mass with respect to parts by mass.
- the blending amount of the silica is less than 5 parts by mass, the flame retardancy decreases (afterglow disappearance time becomes longer), and when it exceeds 25 parts by mass, the wear resistance decreases.
- the blending amount of the silica is within the preferred range, it is advantageous in terms of both flame retardancy and wear resistance.
- Metal hydroxide compound By adding the metal hydroxide compound to the rubber composition for hoses, flame retardancy can be improved, but wear resistance is reduced. Therefore, when more pressure-resistant wear is required, it is preferable not to add (or suppress to a small amount) the metal hydroxide compound to the rubber composition for hoses.
- the metal hydroxide compound There is no restriction
- a compounding quantity of the said metal hydroxide compound there is no restriction
- the other components include fillers other than silica, plasticizers, vulcanizing agents, vulcanization accelerators, anti-aging agents, scorch preventing agents, softening agents, zinc oxide, stearic acid, silane coupling agents, and organic acid cobalt.
- the compounding agents usually used in the rubber industry such as adhesion aids such as resorcin, hexamethylenetetramine, and melamine resin can be appropriately selected and blended within a range that does not impair the object of the present invention. As these compounding agents, commercially available products can be suitably used.
- the said rubber composition can be manufactured by mix
- Carbon black is suitable as the filler other than the silica.
- FEF class iodine adsorption amount 20 g / kg to 50 g / kg, DBP oil supply amount 20 ( ⁇ 10 ⁇ 5 m 3 / kg) to 150 ( ⁇ 10) from the viewpoint of both wear resistance and extrudability. ⁇ 5 m 3 / kg)
- DBP oil supply amount 20 ⁇ 10 ⁇ 5 m 3 / kg
- the hose of the present invention has at least a rubber layer, and further includes a rubber layer other than the rubber layer and other members as necessary.
- the rubber layer is not particularly limited as long as it is composed of the rubber composition for a hose of the present invention, and can be appropriately selected according to the purpose.
- examples thereof include an outer rubber layer.
- the thickness of the outer rubber layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.3 mm to 3.5 mm, more preferably 0.7 mm to 3.2 mm. 0 mm to 3.0 mm is particularly preferable.
- the thickness of the rubber layer is less than 0.3 mm, it may wear out and reach an early life, and if it exceeds 3.5 mm, the flame retardancy decreases due to an increase in the amount of combustion components, or as a hose. May be inferior in terms of flexibility, weight reduction, and space saving.
- the thickness of the rubber layer is within the preferred range, it is advantageous in terms of flame retardancy and wear life, and when the thickness is within the more preferred range or within the particularly preferred range, it is further advantageous. is there.
- the hose includes an inner rubber layer (inner tube rubber) 10, reinforcing layers 12, 14, 16 and 18 having brass plating wires, and intermediate rubber layers (intermediate rubber) 11 and 13. , 15 and 17 and an outer rubber layer (outer rubber) 19.
- the rubber composition for a hose of the present invention is suitable for forming the outer rubber layer (outer rubber) 19.
- the hose has an inner rubber layer (inner tube rubber) 10 from the inside, reinforcing layers 12, 14, 16, 18 and intermediate rubber layers (intermediate rubber) 11, 13, 15, 17 each consisting of four layers. And a plurality of layers in which an outer rubber layer (outer rubber) 19 is arranged, but is not limited to this.
- an inner rubber layer (inner tube rubber), a reinforcing layer, and an outer rubber layer (outer rubber layer) It may be a three-layer structure in which rubber is laminated in sequence, or an inner rubber layer (inner tube rubber), a thread reinforcing layer, an intermediate rubber layer consisting of three layers (intermediate rubber reinforcing layer), and an outer rubber layer ( A six-layer structure in which the outer rubber) is sequentially laminated may be selected as appropriate according to the required characteristics of the hose. Further, it is not necessary for all the reinforcing layers to be formed of a brass plating wire, and a reinforcing layer partially formed of organic fibers can also be used. Further, the present invention can be applied to a hose in which a resin layer such as ultrahigh molecular weight polyethylene is disposed on the outermost layer to improve wear resistance.
- a resin layer such as ultrahigh molecular weight polyethylene
- the hose manufacturing method of the present invention includes, for example, an inner tube extrusion process, a braiding process, an outer casing extrusion process, a resin mold coating process, a vulcanization process, a resin mold peeling process, and a mandrel as follows.
- the inner rubber layer 10 is formed by extruding a rubber composition for the inner rubber layer 10 on the outer side of a core (mandrel) having a diameter approximately equal to the inner diameter of the hose to cover the mandrel (inner tube extrusion) Process).
- a predetermined number of brass plating wires are knitted outside the inner rubber layer 10 formed by the inner tube extrusion step to form a reinforcing layer 12 (knitting step), and the hose of the present invention is formed inside the reinforcing layer 12.
- the intermediate rubber layer 11 is formed by inserting and forming a sheet of the rubber composition. This is repeated a plurality of times to sequentially laminate the reinforcing layers 14, 16, 18 and the intermediate rubber layers 13, 15, 17 to form the outer rubber layer 19 made of the rubber composition for hose of the present invention (outer extrusion process). .
- the outer surface of the outer rubber layer 19 formed in the outer shell extrusion step is appropriately coated with a suitable resin (resin mold coating step), and vulcanized under predetermined conditions (vulcanization step). After vulcanization, the coating resin is peeled off (resin mold peeling step), and the mandrel is removed (mandrel extraction step), whereby intermediate rubber layers 11, 13, 15 are interposed between the inner rubber layer 10 and the outer rubber layer 19. 17 and the reinforcing layer 12, 14, 16, 18 are obtained.
- the rubber compositions of Examples and Comparative Examples include (i) 80 parts by mass of carbon black (# 65, manufactured by Asahi Carbon Co., Ltd.), (ii) aroma oil (Koumolex NH) -60T, manufactured by Nippon Oil Co., Ltd.) 15 parts by mass, (iii) zinc white 5 parts by mass, (iv) magnesium oxide 3 parts by mass, (v) wax (OZOACE0017, Nippon Seiwa Co., Ltd.) 2 parts by mass, vi) Antiaging agent (ANTIGENE6C, manufactured by Sumitomo Chemical Co., Ltd.) 3 parts by mass, (vii) 2 parts by mass of cobalt stearate, (viii) Sulfur 2.5 parts by mass, (ix) Vulcanization accelerator NS 1 part by mass
- the flame retardancy (afterglow disappearance time) was evaluated by the following method based on the flame retardancy (afterglow disappearance time) evaluation of the MSHA standard (mine safety standard).
- MSHA standard mine safety standard
- the thickness of the evaluation sample obtained by press-vulcanizing the rubber sheet with a mold at 150 ° C. for 60 minutes and cutting out to a predetermined size was 3 mm.
- the obtained evaluation results are shown in Tables 1 to 4.
- the evaluation criteria are as follows. ⁇ : 0 second to 90 seconds ⁇ : 90 seconds to 180 seconds or less ⁇ : 180 seconds to 230 seconds or less ⁇ : 230 seconds or more
- the rubber components include chloroprene rubber, butadiene rubber, and styrene-butadiene rubber, and 100 parts by mass of the rubber component includes 60 parts by mass to 80 parts by mass of chloroprene rubber, and 100 parts by mass of the rubber component.
- Examples 1 to 28, in which 5 parts by weight to 25 parts by weight of silica are blended with respect to parts, include chloroprene rubber, butadiene rubber, and styrene-butadiene rubber as rubber components.
- Comparative Examples 1 to 16 which contains 60 parts by weight to 80 parts by weight of chloroprene rubber and 5 parts by weight to 25 parts by weight of silica with respect to 100 parts by weight of the rubber component. It can be seen that the property, wear resistance and workability can be improved.
- the rubber composition for a hose of the present invention can be suitably used for an intermediate rubber layer and / or a jacket rubber layer of a hydraulic hose used for, for example, a construction machine or a roof supporter.
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Abstract
Description
前記油圧ホースは、近年、炭鉱や鉱山での使用が増加しており、作業時の安全性を考慮して、難燃性の向上が要求されている。ここで、油圧ホースに求められる難燃性は、主に、MSHA規格(米国鉱山保安規格)で定められている。
難燃性を発現するために、ホース用ゴム組成物として、燃焼時に不活性ガスを放出するハロゲン系ポリマー(例えば、クロロプレンゴム(CR))を使用しつつ、水酸化金属化合物(例えば、水酸化アルミニウム、水酸化マグネシウム)を多量に添加することが検討されている。
そのため、難燃性(特に、アフターグロー消失時間の短縮)を発現しつつ、耐摩耗性及び加工性に優れるゴムの開発が強く求められていた。
上記構成により、難燃性(特に、アフターグロー消失時間の短縮)及び耐摩耗性を向上させ、かつ加工性を確保できる。
上記構成により、難燃性(特に、アフターグロー消失時間の短縮)及び耐摩耗性を向上させ、かつ加工性を確保できる。
本発明のホース用ゴム組成物は、少なくとも、ゴム成分と、シリカとを含み、さらに必要に応じて、水酸化金属化合物、その他の成分を含む。
前記ゴム成分は、少なくとも、クロロプレンゴム(CR)、ブタジエンゴム(BR)及びスチレン-ブタジエンゴム(SBR)を含み、さらに必要に応じて、その他の重合体を含む。
前記クロロプレンゴム(CR)は、クロロプレン単量体の単独重合体(クロロプレン重合体)、又は、クロロプレン単量体とそれと共重合可能な他の単量体1種以上との混合物(以下、クロロプレン系単量体と称する)を重合させて得られた共重合体(以下、クロロプレン系重合体と称する)である。
前記クロロプレンゴムは、分子量調節剤の種類により、イオウ変性タイプ、メルカプタン変性タイプ、キサントゲン変性タイプに分類される。
前記クロロプレンゴムとしては、いずれの変性タイプも使用可能である。しかしながら、前記イオウ変性タイプは、前記メルカプタン変性タイプ及び前記キサントゲン変性タイプに比較すると、ポリマー自体の耐熱性が劣るため、より耐熱性が要求される場合は、前記メルカプタン変性又は前記キサントゲン変性タイプを使用することが好ましい。
前記イオウ変性タイプは、イオウとクロロプレン単量体又はクロロプレン系単量体を共重合したポリマーをチウラムジスルフィドで可塑化し、所定のムーニー粘度に調整するものである。
前記メルカプタン変性タイプは、n-ドデシルメルカプタン、tert-ドデシルメルカプタン、オクチルメルカプタン等のアルキルメルカプタン類を分子量調節剤に使用するものである。
前記キサントゲン変性タイプは、アルキルキサントゲン化合物を分子量調節剤に使用するものである。前記アルキルキサントゲン化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ジメチルキサントゲンジスルフィド、ジエチルキサントゲンジスルフィド、ジイソプロピルキサントゲンジスルフィド、ジイソブチルキサントゲンジスルフィド、などが挙げられる。
前記アルキルキサントゲン化合物の使用量としては、クロロプレンゴムの分子量(あるいは、ムーニー粘度)が適正となるように選定される限り、特に制限はなく、目的(アルキル基の構造や目標とする分子量)に応じて適宜選択することができるが、クロロプレン単量体又はクロロプレン系単量体100質量部に対して、0.05質量部~5.0質量部が好ましく、0.3質量部~1.0質量部がより好ましい。
前記クロロプレンゴム(CR)の含有量としては、ゴム成分100質量部中において60質量部~80質量部である限り、特に制限はなく、目的に応じて適宜選択することができるが、65質量部~80質量部が好ましく、65質量部~75質量部がより好ましい。
前記クロロプレンゴム(CR)の含有量が、ゴム成分100質量部中において60質量部未満であると、難燃性が低下し(アフターグロー消失時間が長くなり)、ゴム成分100質量部中において80質量部を超えると、加工性が低下する。一方、前記クロロプレンゴム(CR)の含有量が、前記好ましい範囲内であると、難燃性及び加工性の点で有利であり、前記より好ましい範囲内であると、さらに有利である。
前記ブタジエンゴム(BR)は、ブタジエン単量体の単独重合体(ブタジエン重合体)、又は、ブタジエン単量体とそれと共重合可能な他の単量体1種以上との混合物(以下、ブタジエン系単量体と称する)を重合させて得られた共重合体(以下、ブタジエン系重合体と称する)である。
前記ブタジエンゴム(BR)のシス-1,4結合量としては、特に制限はなく、目的に応じて適宜選択することができるが、90%以上が好ましく、93%以上がより好ましく、95%以上が特に好ましい。
前記シス-1,4結合量が、90%未満であると、耐摩耗性が低下することがある。一方、前記シス-1,4結合量が、前記好ましい範囲内であると、耐摩耗性の点で有利であり、前記より好ましい範囲内、又は、前記特に好ましい範囲内であると、さらに有利である。
なお、前記シス-1,4結合量は、1H-NMR、13C-NMR、FT-IR、などを用いて測定することができる。
前記ブタジエンゴム(BR)の含有量としては、ゴム成分100質量部中において、特に制限はなく、目的に応じて適宜選択することができるが、10質量部~30質量部が好ましく、15質量部~25質量部がより好ましい。
前記ブタジエンゴム(BR)の含有量が、ゴム成分100質量部中において10質量部未満であると、耐摩耗性が低下することがあり、ゴム成分100質量部中において30質量部を超えると、CRまたはSBR量が減ることで、加工性または難燃性が低下することがある。一方、前記ブタジエンゴム(BR)の含有量が、前記好ましい範囲内であると、耐摩耗性と難燃性の両立の点で有利であり、前記より好ましい範囲内であると、さらに有利である。
前記スチレン-ブタジエンゴム(SBR)は、スチレン単量体とブタジエン単量体との共重合体(スチレン-ブタジエン共重合体)、又は、スチレン単量体及びブタジエン単量体とそれらと共重合可能な他の単量体1種以上との混合物(以下、スチレン-ブタジエン系単量体と称する)を重合させて得られた共重合体(以下、スチレン-ブタジエン系共重合体と称する)である。
前記スチレン単量体及びブタジエン単量体と共重合可能な単量体としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、2-メチル-1,3-ブタジエン、2,3-ジメチル-1,3-ブタジエン、1,3-ペンタジエン、1,3-ヘキサジエン等の炭素数5~8の共役ジエン単量体;p-メチルスチレン、α-メチルスチレン、ビニルナフタレン等の芳香族ビニル単量体;などが挙げられる。これらは、1種単独で使用してもよいし、2種以上を併用してもよい。
前記スチレン-ブタジエンゴム(SBR)のスチレン含有量としては、特に制限はなく、目的に応じて適宜選択することができるが、20質量%~45質量%が好ましく、20質量%~35質量%がより好ましい。
前記スチレン-ブタジエンゴム(SBR)のスチレン含有量が、20質量%未満であると、加工性が低下することがあり、45質量%超であると、耐摩耗性が低下することがある。一方、前記スチレン-ブタジエンゴム(SBR)のスチレン含有量が、前記好ましい範囲内であると、加工性と耐摩耗性の点で有利であり、前記より好ましい範囲内であると、さらに有利である。
前記スチレン-ブタジエンゴム(SBR)の含有量としては、ゴム成分100質量部中において、特に制限はなく、目的に応じて適宜選択することができるが、10質量部~30質量部が好ましく、10質量部~25質量部がより好ましい。
前記スチレン-ブタジエンゴム(SBR)の含有量が、ゴム成分100質量部中において10質量部未満であると、加工性が低下することがあり、ゴム成分100質量部中において30質量部を超えると、CRまたはBRの含有量が減ることで、耐摩耗性又は難燃性が低下することがある。一方、前記スチレン-ブタジエンゴム(SBR)の含有量が、前記好ましい範囲内であると、耐摩耗性と難燃性の両立の点で有利であり、前記より好ましい範囲内であると、さらに有利である。
ブタジエンゴム(BR)/スチレン-ブタジエンゴム(SBR)の質量比としては、特に制限はなく、目的に応じて適宜選択することができるが、30/10~10/30が好ましく、25/15~15/25がより好ましい。
前記質量比が、10未満/30であると、耐摩耗性が低下することがあり、30超/10であると、加工性が低下することがある。一方、前記質量比が、前記好ましい範囲内であると、耐摩耗性と加工性の両立の点で有利であり、前記より好ましい範囲内、又は、前記特に好ましい範囲内であると、さらに有利である。
前記その他の重合体としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、天然ゴム、クロロスルフォン化ポリエチレン(CSM)、塩素化ポリエチレン(CPE)、ニトリルゴム(NBR)、水素化アクリロニトリル・ブタジエンゴム(H-NBR)、アクリルゴム(ACM)、エチレン・プロピレンゴム(EPDM)、エピクロルヒドリンゴム(CO)、ヒドリンゴム(ECO)、シリコーンゴム(Q)、フッ素ゴム(FKM)、などが挙げられる。これらは、1種単独で使用してもよいし、2種以上を併用してもよい。
これらの中でも、CSM、CPEが、難燃性の点で、好ましい。
前記シリカを前記ホース用ゴム組成物に添加することにより、難燃性を向上させ(特に、アフタグロー消失時間を短くし)、補強性を高くして耐摩耗性を向上させることができる。
前記シリカの窒素吸着比表面積(N2SA)としては、特に制限はなく、目的に応じて適宜選択することができるが、70m2/g~300m2/gが好ましく、100m2/g~280m2/gがより好ましく、150m2/g~250m2/gが特に好ましい。
前記シリカの窒素吸着比表面積(N2SA)が、70m2/g未満であると、難燃性及び耐摩耗性が低下することがあり、300m2/g超であると、分散性、加工性が悪化することがある。一方、前記シリカの窒素吸着比表面積(N2SA)が、前記好ましい範囲内であると、難燃性、耐摩耗性、加工性のバランスの点で有利であり、前記より好ましい範囲内、又は、前記特に好ましい範囲内であると、さらに有利である。
前記シリカの配合量が、5質量部未満であると、難燃性が低下し(アフターグロー消失時間が長くなり)、25質量部超であると、耐摩耗性が低下する。一方、前記シリカの配合量が、前記好ましい範囲内であると、難燃性と耐摩耗性の両立の点で有利である。
前記水酸化金属化合物を前記ホース用ゴム組成物に添加することにより、難燃性を向上させることができるが、耐摩耗性が低下する。よって、より耐圧摩耗性が要求される場合は、前記水酸化金属化合物を前記ホース用ゴム組成物に添加しない(又は、少量に抑える)ことが好ましい。
前記水酸化金属化合物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、水酸化アルミニウム、水酸化マグネシウム、などが挙げられる。
前記水酸化金属化合物の配合量が、前記ゴム成分100質量部に対して10質量部以下であると、耐摩耗性が低下するのを防止することができる。
前記水酸化金属化合物の配合量が、前記ゴム成分100質量部に対して10質量部超であると、耐摩耗性が著しく低下することがある。
前記その他の成分としては、シリカ以外の充填材、可塑剤、加硫剤、加硫促進剤、老化防止剤、スコーチ防止剤、軟化剤、酸化亜鉛、ステアリン酸、シランカップリング剤、有機酸コバルトやレゾルシン、ヘキサメチレンテトラミン、メラミン樹脂などの接着助剤等のゴム業界で通常使用される配合剤を、本発明の目的を害しない範囲内で適宜選択し配合することができる。これら配合剤は、市販品を好適に使用することができる。なお、前記ゴム組成物は、ゴム成分に、必要に応じて適宜選択した各種配合剤を配合して、混練り、熱入れ、押出等することにより製造することができる。
本発明のホースは、少なくとも、ゴム層を有し、さらに必要に応じて、前記ゴム層以外の他ゴム層、その他の部材を有する。
前記ゴム層は、本発明のホース用ゴム組成物からなる限り、特に制限はなく、目的に応じて適宜選択することができ、例えば、外被ゴム層、などが挙げられる。
前記外被ゴム層の形状、構造及び大きさとしては、特に制限はなく、目的に応じて適宜選択することができる。
前記外被ゴム層の厚みとしては、特に制限はなく、目的に応じて適宜選択することができるが、0.3mm~3.5mmが好ましく、0.7mm~3.2mmがより好ましく、1.0mm~3.0mmが特に好ましい。
前記ゴム層の厚みが、0.3mm未満であると、摩耗して早期寿命を迎えることがあり、3.5mm超であると、燃焼成分量増加により難燃性が低下する、またはホースとしての柔軟化、軽量化、省スペース化の面で劣ることがある。一方、前記ゴム層の厚みが、前記好ましい範囲内であると、難燃性と摩耗寿命の点で有利であり、前記より好ましい範囲内、又は、前記特に好ましい範囲内であると、さらに有利である。
本発明のホース用ゴム組成物は、外面ゴム層(外被ゴム)19を形成するのに好適である。
本発明のホースの製造方法は、例えば、以下のように、内管押出工程と、編み上げ工程と、外被押出工程と、樹脂モールド被覆工程と、加硫工程と、樹脂モールド剥離工程と、マンドレル抜出工程とを含み、さらに、必要に応じて適宜選択した、その他の工程を含む。
まず、ホース内径と同程度の直径を有する芯体(マンドレル)の外側に内面ゴム層10用のゴム組成物を押出成形して該マンドレルを被覆し、内面ゴム層10を形成する(内管押出工程)。次いで、該内管押出工程で形成した内面ゴム層10の外側に、所定本数のブラスめっきワイヤーを編み上げて補強層12を形成し(編み上げ工程)、該補強層12の内側に本発明のホース用ゴム組成物のシートを挿入形成して、中間ゴム層11を形成する。これを複数回繰り返して補強層14、16、18及び中間ゴム層13、15、17を順次積層し、本発明のホース用ゴム組成物からなる外面ゴム層19を形成する(外被押出工程)。さらに、外被押出工程で形成した外面ゴム層19の外側を適宜好適な樹脂で被覆し(樹脂モールド被覆工程)、これを所定の条件で加硫する(加硫工程)。加硫後、上記被覆樹脂を剥離し(樹脂モールド剥離工程)、マンドレルを取り除く(マンドレル抜出工程)ことにより、内面ゴム層10と外面ゴム層19との間に中間ゴム層11、13、15、17と補強層12、14、16、18を有するホースが得られる。
(1)難燃性(炎消失時間)
前記難燃性(炎消失時間)は、MSHA規格(米国鉱山保安規格)ASTP5007の難燃性(炎消失時間)評価に基づき、以下の方法により評価した。なお、ゴムシートをモールドで150℃60分プレス加硫し、定められた寸法に切り出すことにより得られた評価サンプルの厚みは、3mm厚にて実施した。
得られた評価結果を表1~4に示す。ここで、炎消失時間は、数値が小さい方が難燃性が良好である。
なお、評価基準は、以下の通りである。
◎:0秒以上10秒以下
○:10秒超30秒以下
△:30秒超60秒以下
×:60秒超
前記難燃性(アフターグロー消失時間)は、MSHA規格(鉱山保安規格)の難燃性(アフターグロー消失時間)評価に基づき、以下の方法により評価した。なお、ゴムシートをモールドで150℃60分プレス加硫し、定められた寸法に切り出すことにより得られた評価サンプルの厚みは、3mm厚にて実施した。
得られた評価結果を表1~4に示す。ここで、アフターグロー消失時間は、数値が小さい方が難燃性が良好である。
なお、評価基準は、以下の通りである。
◎:0秒以上90秒以下
○:90秒超180秒以下
△:180秒超230秒以下
×:230秒超
前記耐摩耗性(DIN摩耗量)は、JIS K 6264に準じて測定した。
得られた評価結果(比較例1を100とした場合の指数)を表1~4に示す。ここで、耐摩耗性(DIN摩耗量)は、数値が(小さい)方が良好である。なお、評価サンプルは、150℃60分加硫したゴムシートから定められた寸法に打ち抜くことにより得られた。
(4)加工性(放置安定性)
前記加工性(放置安定性)は、下記の評価方法に従って評価した。
まず、ゴム練り後、40℃、95%RHの恒温恒湿槽に72時間保管したのち、JIS K 6300に規定されたムーニースコーチ試験を130℃にて実施し、ムーニー粘度とスコーチタイムにて判定した。
得られた評価結果を表1~4に示す。
なお、評価基準は、以下の通りである。
○:ムーニー粘度100未満かつスコーチタイム:10min以上
△:ムーニー粘度が100未満で、スコーチタイム10min未満
×:ムーニー粘度が100以上
*1 クロロプレンゴム(CR):電気化学工業製、電化クロロプレン「M40」
*2 ブタジエンゴム(BR):JSR製、「BR01」(シス-1,4結合量:95%)
*3 スチレン-ブタジエンゴム(SBR):JSR製、「JSR1500」
*4 シリカ:東ソーシリカ製、「Nipsil AQ」
*5 水酸化アルミニウム:昭和電工製、「HIGILITE H-42S」
*6 水酸化マグネシウム:協和化学製、「キスマ5A」
10 内面ゴム層(内管ゴム)
11 中間ゴム層(中間ゴム)
12 補強層
13 中間ゴム層(中間ゴム)
14 補強層
15 中間ゴム層(中間ゴム)
16 補強層
17 中間ゴム層(中間ゴム)
18 補強層
19 外面ゴム層(外被ゴム)
Claims (4)
- ゴム成分として、クロロプレンゴム、ブタジエンゴム、及びスチレン-ブタジエンゴムを含み、
前記ゴム成分100質量部中に、クロロプレンゴムを60質量部~80質量部含み、
前記ゴム成分100質量部に対して、シリカを5質量部~25質量部配合してなることを特徴とするホース用ゴム組成物。 - 前記ゴム成分100質量部中に、クロロプレンゴム60質量部~80質量部と、ブタジエンゴム10質量部~30質量部と、スチレン-ブタジエンゴム10質量部~30質量部とを含むことを特徴とする請求項1に記載のホース用ゴム組成物。
- 前記ゴム成分100質量部に対して、水酸化金属化合物を10質量部以下配合してなることを特徴とする請求項1に記載のホース用ゴム組成物。
- 請求項1に記載のホース用ゴム組成物からなるゴム層を有することを特徴とするホース。
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- 2012-11-21 CN CN201280057311.0A patent/CN103946300B/zh active Active
- 2012-11-21 EP EP12851413.0A patent/EP2784116B1/en active Active
- 2012-11-21 WO PCT/JP2012/007512 patent/WO2013076989A1/ja active Application Filing
- 2012-11-21 US US14/359,766 patent/US20140329035A1/en not_active Abandoned
- 2012-11-21 AU AU2012341843A patent/AU2012341843B2/en not_active Ceased
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104837912A (zh) * | 2013-12-27 | 2015-08-12 | 住友电气工业株式会社 | 耐寒性橡胶组合物 |
US10590253B2 (en) | 2015-07-13 | 2020-03-17 | The Yokohama Rubber Co., Ltd. | Rubber composition for flame-retardant hose, and flame-retardant hose |
WO2023013091A1 (ja) * | 2021-08-04 | 2023-02-09 | 横浜ゴム株式会社 | ホース用ゴム組成物及びホース |
Also Published As
Publication number | Publication date |
---|---|
EP2784116A4 (en) | 2015-07-29 |
AU2012341843A1 (en) | 2014-06-12 |
US20140329035A1 (en) | 2014-11-06 |
AU2012341843B2 (en) | 2015-02-26 |
EP2784116A1 (en) | 2014-10-01 |
CN103946300B (zh) | 2015-09-30 |
EP2784116B1 (en) | 2016-10-12 |
CN103946300A (zh) | 2014-07-23 |
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