JP5955497B2 - Rubber composition for bonding brass plating wire and hydraulic hose - Google Patents
Rubber composition for bonding brass plating wire and hydraulic hose Download PDFInfo
- Publication number
- JP5955497B2 JP5955497B2 JP2010194022A JP2010194022A JP5955497B2 JP 5955497 B2 JP5955497 B2 JP 5955497B2 JP 2010194022 A JP2010194022 A JP 2010194022A JP 2010194022 A JP2010194022 A JP 2010194022A JP 5955497 B2 JP5955497 B2 JP 5955497B2
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- Prior art keywords
- rubber
- rubber composition
- mass
- organic acid
- acid salt
- Prior art date
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- 229920001971 elastomer Polymers 0.000 title claims description 120
- 239000005060 rubber Substances 0.000 title claims description 120
- 239000000203 mixture Substances 0.000 title claims description 69
- 229910001369 Brass Inorganic materials 0.000 title claims description 24
- 239000010951 brass Substances 0.000 title claims description 24
- 238000007747 plating Methods 0.000 title claims description 15
- 229920000642 polymer Polymers 0.000 claims description 77
- -1 fatty acid salt Chemical class 0.000 claims description 70
- 150000001993 dienes Chemical class 0.000 claims description 64
- 238000004073 vulcanization Methods 0.000 claims description 43
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 34
- 239000000194 fatty acid Substances 0.000 claims description 34
- 229930195729 fatty acid Natural products 0.000 claims description 34
- 150000007524 organic acids Chemical class 0.000 claims description 33
- 230000003014 reinforcing effect Effects 0.000 claims description 22
- 239000000344 soap Substances 0.000 claims description 20
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 19
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 17
- 229960002447 thiram Drugs 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 235000021313 oleic acid Nutrition 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 150000004665 fatty acids Chemical group 0.000 claims description 4
- QHOWYOKUKZPTPL-KVVVOXFISA-N (z)-octadec-9-enoic acid;potassium Chemical compound [K].CCCCCCCC\C=C/CCCCCCCC(O)=O QHOWYOKUKZPTPL-KVVVOXFISA-N 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229940088990 ammonium stearate Drugs 0.000 claims description 3
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical compound [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 229920000459 Nitrile rubber Polymers 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 235000005985 organic acids Nutrition 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 229920003049 isoprene rubber Polymers 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 229910052570 clay Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001084 poly(chloroprene) Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 2
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 229920003054 adipate polyester Polymers 0.000 description 2
- 230000003679 aging effect Effects 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229940096818 dipentamethylenethiuram disulfide Drugs 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 2
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- KNBRWWCHBRQLNY-UHFFFAOYSA-N piperidine-1-carbothioylsulfanyl piperidine-1-carbodithioate Chemical compound C1CCCCN1C(=S)SSC(=S)N1CCCCC1 KNBRWWCHBRQLNY-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 description 1
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- MKZXROSCOHNKDX-UHFFFAOYSA-N 1,4-dinitrosobenzene Chemical compound O=NC1=CC=C(N=O)C=C1 MKZXROSCOHNKDX-UHFFFAOYSA-N 0.000 description 1
- AOGDNNLIBAUIIX-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-1-ylbenzene-1,4-diamine Chemical compound C1=CC=C2C(NC=3C=CC(NC=4C5=CC=CC=C5C=CC=4)=CC=3)=CC=CC2=C1 AOGDNNLIBAUIIX-UHFFFAOYSA-N 0.000 description 1
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
- XRZSSEXEXRGZJQ-UHFFFAOYSA-N 2,2,3-trimethyl-1-nitroso-3,4-dihydroquinoline Chemical compound C1=CC=C2N(N=O)C(C)(C)C(C)CC2=C1 XRZSSEXEXRGZJQ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
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- QJIVRICYWXNTKE-UHFFFAOYSA-N 4-(8-methylnonoxy)-4-oxobutanoic acid Chemical compound CC(C)CCCCCCCOC(=O)CCC(O)=O QJIVRICYWXNTKE-UHFFFAOYSA-N 0.000 description 1
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- XHLHIFBBLKNHQC-UHFFFAOYSA-N 6-(butylamino)-1h-1,3,5-triazine-2,4-dithione Chemical compound CCCCNC1=NC(S)=NC(S)=N1 XHLHIFBBLKNHQC-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
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- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- 239000005909 Kieselgur Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 1
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052794 bromium Inorganic materials 0.000 description 1
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- MEBJLVMIIRFIJS-UHFFFAOYSA-N hexanedioic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)CCCCC(O)=O MEBJLVMIIRFIJS-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- BOIDPNPEIDTKPP-UHFFFAOYSA-N n-naphthalen-2-yl-n-phenylnitrous amide Chemical compound C=1C=C2C=CC=CC2=CC=1N(N=O)C1=CC=CC=C1 BOIDPNPEIDTKPP-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- BPJZKLBPJBMLQG-KWRJMZDGSA-N propanoyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC(=O)CC BPJZKLBPJBMLQG-KWRJMZDGSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
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- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
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- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
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- 238000009864 tensile test Methods 0.000 description 1
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- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011701 zinc Chemical class 0.000 description 1
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Images
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- Rigid Pipes And Flexible Pipes (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ホース用のブラスめっきワイヤ接着用ゴム組成物及び油圧ホースに関する。 The present invention relates to a rubber composition for bonding a brass plating wire for a hose and a hydraulic hose.
近年、建築機械等に用いられる油圧ホース等には、ホースの内管ゴムと外管ゴムとの間に、補強層として、層間ゴム(インシュレーションゴム)とそれを挟んで、補強糸もしくはワイヤを編み上げた編組(ブレード)構造のもの、補強糸もしくはワイヤをスパイラル状に巻き付けたスパイラル構造を有するゴムホース等が用いられている。 In recent years, hydraulic hoses and the like used for construction machinery and the like have a reinforcing yarn or wire sandwiched between an inner rubber and an outer rubber of the hose as a reinforcing layer with an interlayer rubber (insulation rubber) interposed therebetween. A braided (blade) structure, a rubber hose having a spiral structure in which a reinforcing yarn or a wire is wound in a spiral shape, and the like are used.
この油圧ホースは、耐油性等を考慮してクロロプレンゴム(CR)を主成分とする材料が使用されているが、このクロロプレンゴム以外のゴム成分として、溶液重合により調整されるゴム成分に加硫促進剤を添加する油圧ホースが提案されている(例えば、特許文献1及び2参照)。 This hydraulic hose is made of a material mainly composed of chloroprene rubber (CR) in consideration of oil resistance and the like, but as a rubber component other than this chloroprene rubber, vulcanized to a rubber component adjusted by solution polymerization. A hydraulic hose to which an accelerator is added has been proposed (see, for example, Patent Documents 1 and 2).
ところで、ゴム成分に添加する添加剤の添加量は少ない方がゴム特性を発揮する上で好ましいので、特許文献1及び2の更なる改良を図るべく、更に検討した結果、ブラスめっきワイヤとの接着性及び耐熱性が良好なゴム組成物を提案することを見いだした。 By the way, since it is preferable that the amount of additive added to the rubber component is small in order to exhibit rubber characteristics, further studies have been made to further improve Patent Documents 1 and 2, and as a result, adhesion to a brass-plated wire is achieved. It has been found that a rubber composition having good properties and heat resistance is proposed.
本発明は、ブラスめっきワイヤとの接着性及び耐熱性が良好なホース用のブラスめっきワイヤ接着用ゴム組成物及び油圧ホースを提供することを目的とする。 An object of the present invention is to provide a rubber composition for bonding a brass plating wire for a hose and a hydraulic hose that have good adhesion and heat resistance to the brass plating wire.
本発明は、以下の(1)〜(4)を提供する。
(1) ホースのブラスめっきワイヤ補強層を接着するゴム組成物であって、
有機酸、脂肪酸塩及び有機酸塩から選ばれる少なくとも1種の含有量が1.5質量%以下であるジエン系重合体と、チウラム系加硫促進剤とを含み、
前記有機酸がロジン酸、ステアリン酸、パルミチン酸及びオレイン酸の何れか1つ以上であり、前記有機酸塩がロジン酸ナトリウムであり、前記脂肪酸塩が脂肪酸カリ石けん、オレイン酸カリ石けん、ステアリン酸ナトリウム及びステアリン酸アンモニウムの何れか1つ以上であり、前記有機酸と前記脂肪酸塩と前記有機酸塩とを合わせた含有量が、ジエン系重合体100質量部に対して、1.5質量部以下であり、
前記チウラム系加硫促進剤の含有量が、前記ジエン系重合体100質量部に対して、0.1質量部超え0.5質量部未満であることを特徴とするブラスめっきワイヤ接着用ゴム組成物。
(2) 前記ジエン系重合体に含まれる前記有機酸と前記脂肪酸塩と前記有機酸塩とを合わせた含有量が、1.0質量%以下であることを特徴とする上記(1)に記載のブラスめっきワイヤ接着用ゴム組成物。
(3) 前記ジエン系重合体が、溶液重合スチレン−ブタジエンゴム(S−SBR)、溶液重合ブタジエンゴム(S−BR)、イソプレンゴム(IR)、及びエチレン−プロピレン−ジエン共重合ゴム(EPDM)から選ばれる少なくとも1種を主成分とすることを特徴とする上記(1)又は(2)に記載のブラスめっきワイヤ接着用ゴム組成物。
(4) 上記(1)から(3)の何れか一つに記載のブラスめっきワイヤ接着用ゴム組成物を用いて形成されるゴム層と、該ゴム層に隣接するブラスめっきワイヤ補強層とを有することを特徴とする油圧ホース。
The present invention provides the following (1) to ( 4 ).
(1) A rubber composition for bonding a brass plated wire reinforcing layer of a hose,
A diene polymer having a content of at least one selected from an organic acid, a fatty acid salt and an organic acid salt of 1.5% by mass or less, and a thiuram vulcanization accelerator,
The organic acid is one or more of rosin acid, stearic acid, palmitic acid and oleic acid, the organic acid salt is sodium rosinate, and the fatty acid salt is fatty acid potassium soap, oleic acid potassium soap, stearic acid One or more of sodium and ammonium stearate , and the combined content of the organic acid, the fatty acid salt, and the organic acid salt is 1.5 parts by mass with respect to 100 parts by mass of the diene polymer. And
A rubber composition for bonding a brass plating wire, wherein a content of the thiuram vulcanization accelerator is more than 0.1 parts by weight and less than 0.5 parts by weight with respect to 100 parts by weight of the diene polymer. object.
(2) The total content of the organic acid, the fatty acid salt and the organic acid salt contained in the diene polymer is 1.0% by mass or less, as described in (1) above A rubber composition for bonding brass plated wires.
( 3 ) The diene polymer is solution polymerized styrene-butadiene rubber (S-SBR), solution polymerized butadiene rubber (S-BR), isoprene rubber (IR), and ethylene-propylene-diene copolymer rubber (EPDM). The rubber composition for bonding a brass plating wire according to the above (1) or ( 2), wherein at least one selected from the group consisting of:
( 4 ) A rubber layer formed using the rubber composition for bonding a brass plating wire according to any one of (1) to ( 3 ), and a brass plating wire reinforcing layer adjacent to the rubber layer. A hydraulic hose comprising:
本発明によれば、ブラスめっきワイヤとの接着性を良好に維持しつつ、耐熱性が良好なホースを得ることができるゴム組成物及び油圧ホースを提供することができる。従って、本発明のゴム積層体は、自動車用エアコンホース、パワーステアリングホース、建設車両の油圧系等に用いられる油圧ホース等として好適に用いられる。 ADVANTAGE OF THE INVENTION According to this invention, the rubber composition and hydraulic hose which can obtain a hose with favorable heat resistance can be provided, maintaining favorable adhesiveness with a brass plating wire. Therefore, the rubber laminate of the present invention is suitably used as an air conditioner hose for automobiles, a power steering hose, a hydraulic hose used for a hydraulic system of construction vehicles, and the like.
以下、本発明について詳細に説明する。なお、本発明は以下の実施形態及び実施例に記載した内容により限定されるものではない。また、以下に記載した実施形態及び実施例における構成要素には、当業者が容易に想定できるもの、実質的に同一のもの、いわゆる均等の範囲のものが含まれる。さらに、以下に記載した実施形態及び実施例で開示した構成要素は適宜組み合わせても良いし、適宜選択して用いてもよい。 Hereinafter, the present invention will be described in detail. In addition, this invention is not limited by the content described in the following embodiment and an Example. In addition, constituent elements in the embodiments and examples described below include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those in a so-called equivalent range. Furthermore, the constituent elements disclosed in the embodiments and examples described below may be appropriately combined or may be appropriately selected and used.
本発明の実施の形態に係るホース層間ゴム用ゴム組成物(以下、「本発明のゴム組成物」という。)は、ホースのブラスめっきワイヤ補強層を接着するゴム組成物であって、有機酸、脂肪酸塩又は有機酸塩から選ばれる少なくとも1種の含有量が1.5質量%以下であるジエン系重合体と、加硫促進剤と含み、有機酸と脂肪酸塩と有機酸塩とを合わせた含有量が、ジエン系重合体100質量部に対して、1.5質量部以下であり、加硫促進剤の含有量が、ジエン系重合体100質量部に対して、0.1質量部超え1.0質量部以下である。尚、本明細書において、加硫前のゴム組成物は未加硫のゴム組成物といい、加硫後のゴム組成物は加硫したゴム組成物という。 A rubber composition for a hose interlayer rubber according to an embodiment of the present invention (hereinafter referred to as “the rubber composition of the present invention”) is a rubber composition for bonding a brass plated wire reinforcing layer of a hose, and an organic acid A diene polymer having a content of at least one selected from fatty acid salts or organic acid salts of 1.5% by mass or less, a vulcanization accelerator, and a combination of an organic acid, a fatty acid salt, and an organic acid salt The content is 1.5 parts by mass or less with respect to 100 parts by mass of the diene polymer, and the content of the vulcanization accelerator is 0.1 parts by mass with respect to 100 parts by mass of the diene polymer. More than 1.0 parts by mass. In the present specification, the rubber composition before vulcanization is referred to as an unvulcanized rubber composition, and the rubber composition after vulcanization is referred to as a vulcanized rubber composition.
<ジエン系重合体>
本発明のゴム組成物に用いるジエン系重合体は、有機酸、脂肪酸塩、又は有機酸塩から選ばれる少なくとも1種を含む。有機酸には、一般的には脂肪酸が含まれる。有機酸としては、例えば、ロジン酸、ステアリン酸、パルミチン酸又はオレイン酸などを挙げることができる。脂肪酸塩としては、例えば、脂肪酸カリ石けん、オレイン酸カリ石けん、ステアリン酸ナトリウム、ステアリン酸アンモニウム等を挙げることができる。有機酸塩としては、例えば、ロジン酸ナトリウム、ナフテン酸コバルト、ステアリン酸コバルト又はホウ酸三ネオデカン酸コバルトなどを挙げることができる。有機酸、脂肪酸塩、有機酸塩は、各々一種単独で用いてもよいし、二種以上を混合して用いるようにしてもよい。
<Diene polymer>
The diene polymer used in the rubber composition of the present invention contains at least one selected from organic acids, fatty acid salts, or organic acid salts. Organic acids generally include fatty acids. Examples of the organic acid include rosin acid, stearic acid, palmitic acid, and oleic acid. Examples of fatty acid salts include fatty acid potassium soap, oleic acid potassium soap, sodium stearate, ammonium stearate, and the like. Examples of the organic acid salt include sodium rosinate, cobalt naphthenate, cobalt stearate or cobalt trineodecanoate. The organic acid, fatty acid salt, and organic acid salt may be used singly or in combination of two or more.
ジエン系重合体としては、溶液重合のゴムを用いるのが好ましい。ジエン系重合体としては、例えば、溶液重合スチレン−ブタジエンゴム(S−SBR)、溶液重合ブタジエンゴム(S−BR)、イソプレンゴム(IR)、エチレン−プロピレン−ジエン共重合ゴム(EPDM)などのゴム成分が挙げられ、これらを主成分として含む。これらのゴム成分を単独で又は2種類以上混合するようにしてもよい。S−SBRとしては、例えば、旭化成ケミカルズ社製の商品名:タフデン2000Rなどがある。S−BRとしては、例えば、日本ゼオン社製の商品名:ニポールBR1220などがある。イソプレンゴム(IR)としては、日本ゼオン社製の商品名:ニポールIR2200などがある。EPDMとしては、例えば、住友化学社製の商品名:ESPRENE505などがある。 As the diene polymer, it is preferable to use a solution polymerization rubber. Examples of the diene polymer include solution polymerized styrene-butadiene rubber (S-SBR), solution polymerized butadiene rubber (S-BR), isoprene rubber (IR), and ethylene-propylene-diene copolymer rubber (EPDM). A rubber component is mentioned and contains these as a main component. You may make it mix these rubber components individually or in mixture of 2 or more types. S-SBR includes, for example, trade name: Toughden 2000R manufactured by Asahi Kasei Chemicals Corporation. Examples of S-BR include trade name: Nipol BR1220 manufactured by Nippon Zeon. As isoprene rubber (IR), there is trade name: Nipol IR2200 manufactured by Nippon Zeon Co., Ltd. EPDM includes, for example, trade name: ESPRENE 505 manufactured by Sumitomo Chemical Co., Ltd.
ジエン系重合体に含まれる有機酸、脂肪酸塩、又は有機酸塩から選ばれる少なくとも1種の含有量は、1.5質量%以下であり、好ましくは1.0質量%以下である。有機酸、脂肪酸塩、又は有機酸塩とから選ばれる少なくとも1種の含有量を1.5質量%以下とすることで、本発明のゴム組成物に要求されるホース用としての諸物性及び混合加工性・圧延加工性を任意の比率とすることができる。 The content of at least one selected from organic acids, fatty acid salts, or organic acid salts contained in the diene polymer is 1.5% by mass or less, preferably 1.0% by mass or less. Various physical properties and mixing for hoses required for the rubber composition of the present invention by setting the content of at least one selected from an organic acid, a fatty acid salt, or an organic acid salt to 1.5% by mass or less Workability / rolling workability can be set to an arbitrary ratio.
本発明のゴム組成物に含まれる有機酸と脂肪酸塩と有機酸塩は、ジエン系重合体に含まれる有機酸と脂肪酸塩と有機酸塩および別途ゴム組成物に配合する有機酸と脂肪酸塩と有機酸塩とを合わせた含有量であり、ジエン系重合体100質量部に対して、1.5質量部以下である。有機酸と脂肪酸塩と有機酸塩とを合わせた含有量が、ジエン系重合体100質量部に対して1.5質量部を超えると、ジエン系重合体中における有機酸、脂肪酸塩又は有機酸塩の添加量が多いため、接着性が阻害される。このため、ジエン系重合体に含まれる有機酸と脂肪酸塩と有機酸塩とを合わせた含有量を1.5質量部以下とすることで、本発明のゴム組成物は、接着性を発揮することができる。 The organic acid, fatty acid salt and organic acid salt contained in the rubber composition of the present invention are the organic acid, fatty acid salt and organic acid salt contained in the diene polymer, and the organic acid and fatty acid salt separately added to the rubber composition. The total content of the organic acid salt is 1.5 parts by mass or less with respect to 100 parts by mass of the diene polymer. When the total content of the organic acid, fatty acid salt, and organic acid salt exceeds 1.5 parts by mass with respect to 100 parts by mass of the diene polymer, the organic acid, fatty acid salt, or organic acid in the diene polymer Since the amount of salt added is large, adhesion is inhibited. For this reason, the rubber composition of this invention exhibits adhesiveness by making content which combined the organic acid, fatty-acid salt, and organic acid salt which are contained in a diene polymer into 1.5 mass parts or less. be able to.
本発明のゴム組成物は、ジエン系重合体に、本発明の目的を損なわない範囲で、他のジエン系重合体又はジエン系重合体以外の重合体の何れか一方又は両方を加えることができる。追加可能な他のジエン系重合体又はジエン系重合体以外の重合体は、ジエン系重合体と他のジエン系重合体又はジエン系重合体以外の重合体との重合体混合物中、有機酸、脂肪酸塩又は有機酸塩から選ばれる少なくとも1種の含有量が1.5質量%以下、好ましくは1.0質量%以下となる範囲で有機酸、脂肪酸塩又は有機酸塩を任意の量で含有する。有機酸、脂肪酸塩又は有機酸塩から選ばれる少なくとも1種の含有量を、上記範囲内とすることで、上述と同様、本発明のゴム組成物に要求されるホース用としての諸物性及び混合加工性・圧延加工性に応じて任意の比率とすることができる。 In the rubber composition of the present invention, any one or both of another diene polymer and a polymer other than the diene polymer can be added to the diene polymer as long as the object of the present invention is not impaired. . Other diene polymers or polymers other than diene polymers that can be added are polymer solutions of diene polymers and other diene polymers or polymers other than diene polymers, organic acids, Contains at least one organic acid, fatty acid salt or organic acid salt in an amount of at least one selected from fatty acid salt or organic acid salt within a range of 1.5% by mass or less, preferably 1.0% by mass or less To do. By setting the content of at least one selected from an organic acid, a fatty acid salt or an organic acid salt within the above range, various physical properties and mixing for a hose required for the rubber composition of the present invention, as described above. The ratio can be set arbitrarily according to the workability / rolling workability.
他のジエン系重合体、ジエン系重合体以外の重合体としては、例えば、天然ゴム(NR)、乳化重合SBR(E−SBR)、アクリロニトリル−ブタジエンゴム(NBR)、塩素化ポリエチレンゴム(CM)、クロロスルホン化ポリエチレンゴム(CSM)等が挙げられる。好ましくは、ジエン系重合体である天然ゴム(NR)、乳化重合SBR(E−SBR)、アクリロニトリル−ブタジエンゴム(NBR)が本発明のゴム組成物に要求されるホース用としての諸物性を高次元で発揮できるので好ましい。これら他のジエン系重合体又はジエン系重合体以外の重合体を一種または二種以上をジエン系重合体と併用してもよい。 Examples of other diene polymers and polymers other than diene polymers include natural rubber (NR), emulsion polymerization SBR (E-SBR), acrylonitrile-butadiene rubber (NBR), and chlorinated polyethylene rubber (CM). And chlorosulfonated polyethylene rubber (CSM). Preferably, natural rubber (NR) which is a diene polymer, emulsion polymerization SBR (E-SBR), and acrylonitrile-butadiene rubber (NBR) have high properties for hose required for the rubber composition of the present invention. It is preferable because it can be exhibited in a dimension. One or two or more of these other diene polymers or polymers other than the diene polymer may be used in combination with the diene polymer.
このとき、他のジエン系重合体又はジエン系重合体以外の重合体を一種又は二種以上併用する場合でも、他のジエン系重合体又はジエン系重合体以外の重合体に含まれる有機酸、脂肪酸塩、又は有機酸塩から選ばれる少なくとも1種の含有量は、1.5質量%以下であり、好ましくは1.0質量%以下である。他のジエン系重合体又はジエン系重合体以外の重合体に含まれる有機酸、脂肪酸塩又は有機酸塩から選ばれる少なくとも1種の含有量を上記範囲内とすることで、上述と同様、本発明のゴム組成物は接着性を発揮することができる。 At this time, even when using other diene polymers or polymers other than diene polymers alone or in combination of two or more, organic acids contained in other diene polymers or polymers other than diene polymers, The content of at least one selected from fatty acid salts or organic acid salts is 1.5% by mass or less, preferably 1.0% by mass or less. In the same manner as described above, the content of at least one selected from organic acids, fatty acid salts, and organic acid salts contained in other diene polymers or polymers other than diene polymers is within the above range. The rubber composition of the invention can exhibit adhesiveness.
有機酸、脂肪酸塩又は有機酸塩は、予めジエン系重合体に配合されていてもよく、加硫促進剤など他の配合剤と同時に添加するようにしてもよいが、ジエン系重合体に含まれる有機酸と脂肪酸塩と有機酸塩とを合わせた含有量は、ジエン系重合体100質量部に対して1.5質量部以下であり、且つジエン系重合体に含まれる有機酸と脂肪酸塩と有機酸塩と、添加する有機酸と脂肪酸塩と有機酸塩との配合量を合わせた含有量は、ジエン系重合体100質量部に対して、1.5質量部以下とする。 The organic acid, fatty acid salt or organic acid salt may be blended in advance in the diene polymer, and may be added simultaneously with other compounding agents such as a vulcanization accelerator, but is included in the diene polymer. The total content of the organic acid, the fatty acid salt, and the organic acid salt is 1.5 parts by mass or less with respect to 100 parts by mass of the diene polymer, and the organic acid and the fatty acid salt contained in the diene polymer. The combined amount of the organic acid, the fatty acid salt and the organic acid salt to be added is 1.5 parts by mass or less with respect to 100 parts by mass of the diene polymer.
<加硫促進剤>
本発明のゴム組成物においては、本発明のジエン系重合体100質量部に対して、加硫促進剤を0.1質量部超え1.0質量部以下としている。加硫促進剤としては、チウラム系加硫促進剤、スルフェンアミド系加硫促進剤を用いるのが好ましく、チウラム系加硫促進剤を用いるのが特に好ましい。チウラム系加硫促進剤として、具体的には、テトラメチルチウラムモノスルフィド(TS)、テトラメチルチウラムジスルフィド(TT)等を挙げることができる。加硫促進剤としてチウラム系加硫促進剤を用いる場合、チウラム系加硫促進剤の添加量は、ジエン系重合体100質量部に対して、0.1質量部超え0.5質量部未満とするのが好ましく、0.2質量部以上0.4質量部以下とするのがより好ましい。チウラム系加硫促進剤の添加量を0.5質量部未満とするのは、少ない添加量で加硫特性、初期接着性及び耐熱性を全て加味させるためである。
<Vulcanization accelerator>
In the rubber composition of the present invention, the vulcanization accelerator is more than 0.1 parts by mass and 1.0 parts by mass or less with respect to 100 parts by mass of the diene polymer of the present invention. As the vulcanization accelerator, a thiuram vulcanization accelerator or a sulfenamide vulcanization accelerator is preferably used, and a thiuram vulcanization accelerator is particularly preferably used. Specific examples of the thiuram vulcanization accelerator include tetramethylthiuram monosulfide (TS) and tetramethylthiuram disulfide (TT). When a thiuram vulcanization accelerator is used as the vulcanization accelerator, the addition amount of the thiuram vulcanization accelerator is more than 0.1 parts by mass and less than 0.5 parts by mass with respect to 100 parts by mass of the diene polymer. It is preferable to set it to 0.2 parts by mass or more and 0.4 parts by mass or less. The reason why the addition amount of the thiuram vulcanization accelerator is less than 0.5 parts by mass is to add all the vulcanization characteristics, initial adhesiveness and heat resistance with a small addition amount.
また、本発明のゴム組成物は、本発明の目的を損なわない範囲で、必要に応じて、各種の添加剤を含有することができる。添加剤としては、例えば、充填剤、可塑剤、軟化剤、老化防止剤、有機系活性剤、酸化防止剤、帯電防止剤、難燃剤、加硫剤、加橋促進助剤、加硫遅延剤、接着助剤が挙げられる。 Moreover, the rubber composition of this invention can contain various additives as needed in the range which does not impair the objective of this invention. Examples of additives include fillers, plasticizers, softeners, anti-aging agents, organic activators, antioxidants, antistatic agents, flame retardants, vulcanizing agents, vulcanization accelerators, and vulcanization retarders. And an adhesion aid.
充填剤は、例えば、カーボンブラック、シリカ(ホワイトカーボン)、クレー、タルク、酸化鉄、酸化亜鉛(ZnO)、酸化チタン、酸化バリウム、酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、硫酸バリウム、マイカ(雲母)、ケイソウ土などが挙げられる。これらを一種単独で用いても二種以上を併用してもよい。カーボンブラックとしては、得られる本発明のゴム組成物の極薄シート圧延加工性の観点より、FTF級、GPF級、SRF級等の粒径が大きい、いわゆるソフトカーボンが好ましい。シリカは、特に限定されないが、例えば、結晶性シリカ、沈殿シリカ、非晶質シリカ(例えば、高温処理シリカ)、ヒュームドシリカ、焼成シリカ、沈降シリカ、粉砕シリカ、溶融シリカが挙げられる。特に、シリカは、カーボンブラックと同様に、カーボンゲル(バウンドラバー)を生成することが知られており、必要に応じて好適に用いることができる。クレーは、ろう石クレー、カオリンクレー、焼成クレー等が挙げられる。 Examples of the filler include carbon black, silica (white carbon), clay, talc, iron oxide, zinc oxide (ZnO), titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, barium sulfate and mica. (Mica) and diatomaceous earth. These may be used alone or in combination of two or more. As the carbon black, so-called soft carbon having a large particle size such as FTF grade, GPF grade, SRF grade and the like is preferable from the viewpoint of the ultra-thin sheet rolling processability of the rubber composition of the present invention to be obtained. The silica is not particularly limited, and examples thereof include crystalline silica, precipitated silica, amorphous silica (for example, high-temperature treated silica), fumed silica, calcined silica, precipitated silica, pulverized silica, and fused silica. In particular, silica is known to produce carbon gel (bound rubber) like carbon black, and can be suitably used as necessary. Examples of the clay include wax stone clay, kaolin clay, and calcined clay.
可塑剤は、例えば、ジオクチルフタレート(DOP)、ジブチルフタレート(DBP)、アジピン酸ジオクチル(DOA)、コハク酸イソデシル、ジエチレングリコールジベンゾエート、ペンタエリスリトールエステル、オレイン酸ブチル、アセチルリシノール酸メチル、リン酸トリクレジル、リン酸トリオクチル、トリメリット酸エステル、アジピン酸プロピレングリコールポリエステル、アジピン酸ブチレングリコールポリエステル、ナフテンオイルなどが挙げられる。これらを一種単独で用いても二種以上を併用してもよい。 Examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl adipate (DOA), isodecyl succinate, diethylene glycol dibenzoate, pentaerythritol ester, butyl oleate, methyl acetylricinoleate, tricresyl phosphate, Examples include trioctyl phosphate, trimellitic acid ester, propylene glycol adipate polyester, butylene glycol adipate polyester, and naphthene oil. These may be used alone or in combination of two or more.
軟化剤としては、具体的には、例えば、アロマ系オイル、ナフテン系オイル、パラフィン系オイル、石油樹脂、植物油、液状ゴム等が挙げられ、これらを一種単独で用いても二種以上を併用してもよい。 Specific examples of the softener include aroma oils, naphthenic oils, paraffin oils, petroleum resins, vegetable oils, liquid rubbers, etc., and these may be used alone or in combination of two or more. May be.
老化防止剤としては、例えば、N−(1,3−ジメチルブチル)−N′−フェニル−p−フェニレンジアミン(6PPD)、N,N′−ジナフチル−p−フェニレンジアミン(DNPD)、N−イソプロピル−N′−フェニル−p−フェニレンジアミン(IPPD)、スチレン化フェノール(SP)、2,2,4−トリメチル−1,2−ジヒドロキノリン重合物(RD)等が挙げられ、これらを一種単独で用いても二種以上を併用してもよい。 Examples of the antioxidant include N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine (6PPD), N, N′-dinaphthyl-p-phenylenediamine (DNPD), and N-isopropyl. -N'-phenyl-p-phenylenediamine (IPPD), styrenated phenol (SP), 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), etc., and these may be used alone. Two or more types may be used in combination.
有機系活性剤としては、具体的には、例えば、ステアリン酸、オレイン酸、ラウリン酸、ステアリン酸亜鉛等が挙げられ、これらを一種単独で用いても二種以上を併用してもよい。 Specific examples of the organic activator include stearic acid, oleic acid, lauric acid, and zinc stearate. These may be used alone or in combination of two or more.
酸化防止剤としては、例えば、ブチルヒドロキシトルエン(BHT)、ブチルヒドロキシアニソール(BHA)が挙げられる。 Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
帯電防止剤は、例えば、第四級アンモニウム塩;ポリグリコール、エチレンオキサイド誘導体等の親水性化合物が挙げられる。 Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.
難燃剤は、例えば、クロロアルキルホスフェート、ジメチル・メチルホスホネート、臭素・リン化合物、アンモニウムポリホスフェート、ネオペンチルブロマイド−ポリエーテル、臭素化ポリエーテルが挙げられる。また、非ハロゲン系難燃剤として、例えば、水酸化アルミニウム、水酸化マグネシウム、トリクレジル・ホスフェート、ジフェニルクレジル・ホスフェートが挙げられる。 Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether. Examples of non-halogen flame retardants include aluminum hydroxide, magnesium hydroxide, tricresyl phosphate, and diphenyl cresyl phosphate.
加硫剤は、例えば、硫黄系、有機過酸化物系、金属酸化物系、フェノール樹脂、キノンジオキシム等の加硫剤が挙げられる。これらを一種単独で用いても二種以上を併用してもよい。硫黄系の加硫剤としては、例えば、硫黄、テトラメチルチウラムジスルフィド(TMTD)、テトラエチルチウラムジスルフィド(TETD)、ジペンタメチレンチウラムジスルフィド(DPTT)、ジモルフォリンジサルファイド、アルキルフェノールジサルファイドなどの有機含硫黄化合物が挙げられる。硫黄としては、粉末硫黄、沈降性硫黄、高分散性硫黄、表面処理硫黄、不溶性硫黄が挙げられる。有機過酸化物系の加硫剤としては、例えば、ジクミルペルオキシド、ベンゾイルパーオキサイド、t−ブチルヒドロパーオキサイド、2,4−ジクロロベンゾイルパーオキサイド、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキサン、2,5−ジメチルヘキサン−2,5−ジ(パーオキシルベンゾエート)が挙げられる。その他の加硫剤としては、例えば、亜鉛華、酸化マグネシウム、リサージ、フェノール樹脂などの樹脂、p−キノンジオキシム、p−ジベンゾイルキノンジオキシム、ポリ−p−ジニトロソベンゼン、メチレンジアニリンが挙げられる。 Examples of the vulcanizing agent include vulcanizing agents such as sulfur-based, organic peroxide-based, metal oxide-based, phenol resin, and quinone dioxime. These may be used alone or in combination of two or more. Examples of sulfur-based vulcanizing agents include organic sulfur-containing compounds such as sulfur, tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), dipentamethylene thiuram disulfide (DPTT), dimorpholine disulfide, and alkylphenol disulfide. Compounds. Examples of sulfur include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, and insoluble sulfur. Examples of the organic peroxide vulcanizing agent include dicumyl peroxide, benzoyl peroxide, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-di ( t-butylperoxy) hexane, 2,5-dimethylhexane-2,5-di (peroxylbenzoate). Other vulcanizing agents include, for example, resins such as zinc white, magnesium oxide, lisage, phenol resin, p-quinonedioxime, p-dibenzoylquinonedioxime, poly-p-dinitrosobenzene, and methylenedianiline. Can be mentioned.
加橋促進助剤としては、一般的なゴム用助剤を併せて用いることができる。例えば、亜鉛華;ステアリン酸、オレイン酸、これらのZn塩を用いることができる。 As the Kahashi accelerating aid, general rubber auxiliaries can be used together. For example, zinc white; stearic acid, oleic acid, and Zn salts thereof can be used.
加硫遅延剤としては、例えば、無水フタル酸、安息香酸、サリチル酸、アセチルサリチル酸などの有機酸;N−ニトロソージフェニルアミン、N−ニトロソーフェニル−β−ナフチルアミン、N−ニトロソ−トリメチル−ジヒドロキノリンの重合体などのニトロソ化合物;トリクロルメラニンなどのハロゲン化物;2−メルカプトベンツイミダゾール、N−(シクロヘキシルチオ)フタルイミド(PVI)等が挙げられる。これらを一種単独で用いても二種以上を併用してもよい。 Examples of the vulcanization retarder include organic acids such as phthalic anhydride, benzoic acid, salicylic acid, acetylsalicylic acid; N-nitrosodiphenylamine, N-nitrosophenyl-β-naphthylamine, N-nitroso-trimethyl-dihydroquinoline. Nitroso compounds such as polymers; Halides such as trichloromelanin; 2-mercaptobenzimidazole, N- (cyclohexylthio) phthalimide (PVI) and the like. These may be used alone or in combination of two or more.
接着助剤は、トリアジンチオール系化合物(例えば、2,4,6−トリメルカプト−1,3,5−トリアジン、6−ブチルアミノ−2,4−ジメルカプト−1,3,5−トリアジン)、ナフテン酸コバルト、レゾルシン、クレゾール、レゾルシン−ホルマリンラテックス、モノメチロールメラミン、モノメチロール尿素、エチレンマレイミドが挙げられる。 Adhesion aids are triazine thiol compounds (for example, 2,4,6-trimercapto-1,3,5-triazine, 6-butylamino-2,4-dimercapto-1,3,5-triazine), naphthene Examples include cobalt acid, resorcin, cresol, resorcin-formalin latex, monomethylol melamine, monomethylol urea, and ethylene maleimide.
上述した各種添加剤は、それぞれ、単独で用いてもよく、二種以上を併用してもよい。 Each of the various additives described above may be used alone or in combination of two or more.
<ゴム組成物の製造方法>
本発明のゴム組成物の製造方法としては、特に限定されず、従来公知の方法を用いることができ、上記ジエン系重合体と、必要に応じてその他のジエン系重合体又はジエン系重合体以外の重合体と上記各種添加剤等とを配合させることにより製造することができる。例えば、上記ジエン系重合体に、必要に応じてその他のジエン系重合体又はジエン系重合体以外の重合体と上記各種添加剤等とを、バンバリーミキサー、ニーダー等の密閉式混合機、ロールなどの混練ロール機、押出し機、二軸押出機等を用いて混練することによりゴム組成物を製造する方法が挙げられる。
<Method for producing rubber composition>
The method for producing the rubber composition of the present invention is not particularly limited, and a conventionally known method can be used. Other than the above-mentioned diene polymer and other diene polymer or diene polymer as necessary. Can be produced by blending the above polymer with the above-mentioned various additives. For example, the diene polymer, if necessary, other diene polymers or polymers other than diene polymers and the above various additives, closed mixers such as Banbury mixers, kneaders, rolls, etc. And a method of producing a rubber composition by kneading using a kneading roll machine, an extruder, a twin screw extruder or the like.
このように、本発明のゴム組成物は、ブラスめっきワイヤとの接着性を良好に維持しつつ、耐熱性が良好なホースを得ることができるゴム組成物及び油圧ホースを提供することができる。 Thus, the rubber composition of the present invention can provide a rubber composition and a hydraulic hose that can obtain a hose with good heat resistance while maintaining good adhesion to a brass-plated wire.
<ホース>
本発明のホースは、本発明のゴム組成物を用いて形成されるゴム層と、該ゴム層に隣接する補強層とを有するホースである。本発明のホースの好適な実施態様の一例について図1を用いて説明する。図1は、ホースの各層を切り欠いて示す斜視図である。図1に示すように、油圧ホース11は、ゴム内層12を内管として有し、その上層に補強層13およびゴム外層14を外管として有するものである。本発明のホースを構成するゴム層(ゴム内層、ゴム外層)および補強層について詳述する。
<Hose>
The hose of the present invention is a hose having a rubber layer formed using the rubber composition of the present invention and a reinforcing layer adjacent to the rubber layer. An example of a preferred embodiment of the hose of the present invention will be described with reference to FIG. FIG. 1 is a perspective view of each hose layer cut away. As shown in FIG. 1, the
<ゴム層>
上記ゴム層は、補強層13に隣接する層であり、本発明のホースは、ゴム内層12およびゴム外層14を具備するものである。本発明においては、上記ゴム層のうち少なくとも一方の層を本発明のゴム組成物を用いて形成するものであり、ホースの耐候性の観点から、少なくともゴム外層14を本発明のゴム組成物を用いて形成するのが好ましい。このように本発明のゴム組成物を用いてゴム層を形成することにより、補強層として繊維材料を用いた場合であっても、補強層13との接着性を良好に維持しつつ、未加硫時の貯蔵安定性および押出し加工性に優れるホースを得ることができる。
<Rubber layer>
The rubber layer is a layer adjacent to the reinforcing
本発明においては、上記ゴム内層の厚みは、例えば0.2mm以上4.0mm以下であるのが好ましく、0.5mm以上2.0mm以下であるのがより好ましい。同様に、上記ゴム外層の厚みは、例えば0.2mm以上4.0mm以下であるのが好ましく、0.5mm以上2.0mm以下であるのがより好ましい。 In the present invention, the thickness of the rubber inner layer is preferably, for example, from 0.2 mm to 4.0 mm, and more preferably from 0.5 mm to 2.0 mm. Similarly, the thickness of the rubber outer layer is preferably, for example, 0.2 mm or more and 4.0 mm or less, and more preferably 0.5 mm or more and 2.0 mm or less.
<補強層>
補強層13は、ゴム内層12の外側に、強度保持の観点から所望により設けられる層である。本発明においては、補強層13は、補強糸もしくはワイヤ等の補強材を編み上げることにより形成される。補強層13は、その網組の方法を特に限定されず、ブレード状で形成されたものであっても、スパイラル状で形成されたものであってもよく、耐圧力により適宜選択すればよい。また、補強層13は、1層単独で形成されていても複数層で形成されていてもよい。補強糸としては例えば、ポリエステル繊維、ポリアミド繊維、アラミド繊維、ビニロン繊維、レーヨン繊維、PBO(ポリパラフェニレンベンゾビスオキサゾール)繊維、ポリケトン繊維、ポリアリレート繊維等が挙げられる。ワイヤとしては、例えば、通常、ホースに用いられる硬鋼線が挙げられる。具体的には、防錆および接着性付与のために、ブラスめっきワイヤまたは亜鉛めっきワイヤを用いるのが好ましく、ブラスめっきワイヤを用いるのがより好ましい。
<Reinforcing layer>
The reinforcing
上記ゴム層および補強層13を有する本発明のホースの製造方法は特に限定されず、従来公知の方法を用いることができる。具体的には、マンドレル上に、ゴム内層12、補強層13およびゴム外層14をこの順に積層させた後に、それらの層を例えば140℃以上190℃下、30分から180分の条件で、プレス加硫、蒸気加硫、オーブン加硫(熱気加硫)または温水加硫することにより加硫接着させて製造する方法等が好適に例示される。
The manufacturing method of the hose of the present invention having the rubber layer and the reinforcing
従って、本発明の油圧ホースの利用分野は特に限定されるものではなく様々な用途に適用することができるが、例えば、自動車用エアコンホース、パワーステアリングホース、建設車両の油圧系等に用いられる油圧ホース等として好適に用いることができる。 Accordingly, the field of use of the hydraulic hose of the present invention is not particularly limited and can be applied to various uses. For example, the hydraulic pressure hose used in automobiles, power steering hoses, hydraulic systems for construction vehicles, etc. It can be suitably used as a hose or the like.
また、本実施形態においては、ゴム積層体として油圧ホースを用いて説明したが、本発明はこれに限定されるものではなく、例えばコンベヤベルトなど他のゴム積層体においても同様に用いることができる。 In the present embodiment, the hydraulic hose is used as the rubber laminate, but the present invention is not limited to this, and can be used in other rubber laminates such as a conveyor belt. .
以下、本発明を実施例により具体的に説明する。ただし、本発明はこれらに限定されるものではない。
<1.ゴム組成物の調製>
以下に示される原料をそれぞれ表1、2に示される質量比で密閉式混合機に投入し、表1、2に示される各ゴム組成物を得た。実施例1〜11における各成分と、その添加量(質量部)を「表1」に示す。比較例1〜10における各成分と、その添加量(質量部)を「表2」に示す。また、ジエン系重合体中の有機酸塩の量と、ゴム組成物中における有機酸塩の量とを示す。ジエン系重合体中の有機酸塩の配合量は質量%で示し、ゴム組成物中における有機酸塩の配合量は質量部で示す。
Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these.
<1. Preparation of rubber composition>
The raw materials shown below were charged into the closed mixer at the mass ratios shown in Tables 1 and 2, respectively, and the rubber compositions shown in Tables 1 and 2 were obtained. Each component in Examples 1-11 and the addition amount (part by mass) are shown in “Table 1”. Each component in Comparative Examples 1 to 10 and the addition amount (parts by mass) are shown in “Table 2”. Moreover, the amount of organic acid salt in the diene polymer and the amount of organic acid salt in the rubber composition are shown. The compounding amount of the organic acid salt in the diene polymer is shown by mass%, and the compounding amount of the organic acid salt in the rubber composition is shown by parts by mass.
また、実施例5は、予めロジン酸石けん(5.38質量%)を含有したE−SBRを、S−SBRに表1に示す割合で配合して、ジエン系重合体中のロジン酸石けんの含有量を0.8質量%とし、ロジン酸石けんを0.8質量部含むゴム組成物とした。また、実施例6は、予めロジン酸石けん(5.38質量%)を含有したE−SBRを、S−SBRに表1に示す割合で配合して、ジエン系重合体中のロジン酸石けんの含有量を1.0質量%とし、ロジン酸石けんを1.0質量部含むゴム組成物とした。また、実施例7は、予めロジン酸石けん(5.38質量%)を含有したE−SBRを、S−SBRに表1に示す割合で配合して、ジエン系重合体中のロジン酸石けんの含有量を1.5質量%とし、ロジン酸石けんを1.5質量部含むゴム組成物とした。また、実施例10は、予めロジン酸石けん(5.38質量%)を含有したE−SBRを、S−SBRに表1に示す割合で配合して、ジエン系重合体中のロジン酸石けんの含有量を1.0質量%とし、ロジン酸Naを添加して有機酸塩を1.5質量部含むゴム組成物とした。 In Example 5, E-SBR containing rosin acid soap (5.38% by mass) in advance was blended with S-SBR in the ratio shown in Table 1, and the rosin acid soap in the diene polymer was used. A rubber composition containing 0.8% by mass and 0.8 parts by mass of rosin acid soap was obtained. In Example 6, E-SBR containing rosin acid soap (5.38% by mass) in advance was blended with S-SBR in the ratio shown in Table 1, and the rosin acid soap in the diene polymer was used. A rubber composition containing 1.0% by mass and 1.0 part by mass of rosin acid soap was obtained. In Example 7, E-SBR containing rosin acid soap (5.38% by mass) in advance was blended in S-SBR in the ratio shown in Table 1, and the rosin acid soap in the diene polymer was used. The rubber composition contained 1.5% by mass and 1.5 parts by mass of rosin acid soap. In Example 10, E-SBR containing rosin acid soap (5.38% by mass) in advance was blended with S-SBR in the ratio shown in Table 1, and the rosin acid soap in the diene polymer was used. A rubber composition containing 1.5 parts by mass of organic acid salt by adding 1.0 mass% and adding rosin acid Na.
[使用した原料]
・S−SBR:タフデン2000R、旭化成ケミカルズ株式会社製
・溶液重合BR(S−BR):Nipol BR 1220、日本ゼオン株式会社製
・EPDM:ESPRENE 505、住友化学株式会社製
・E−SBR:Nipol 1500、日本ゼオン株式会社製
・ロジン酸ナトリウム(ロジン酸Na):Dresinate、HERCULES社製
・ナフテン酸コバルト(ナフテン酸Co):ナフテン酸コバルト10%、DIC株式会社製
・ステアリン酸コバルト(ステアリン酸Co):ステアリン酸コバルト、DIC株式会社製
・カーボンブラック:HTC#G、新日化カーボン株式会社製
・酸化亜鉛(ZnO):酸化亜鉛三種、正同化学工業株式会社製
・アロマ系オイル:ダイアナ プロセスオイル AH−58、出光興産株式会社製
・硫黄:油処理硫黄、細井化学工業株式会社製
・チウラム系加硫促進剤(TS):サンセラー TS−G、三新化学工業株式会社製
・チウラム系加硫促進剤(TT):サンセラー TT−PO、三新化学工業株式会社製
・加硫遅延剤(PVI):N−シクロヘキシルチオフタルイミド、東レ・ファインケミカル株式会社製
[Raw materials used]
-S-SBR: Toughden 2000R, manufactured by Asahi Kasei Chemicals Corporation-Solution polymerization BR (S-BR): Nipol BR 1220, manufactured by Nippon Zeon Co., Ltd.-EPDM: ESPRENE 505, manufactured by Sumitomo Chemical Co., Ltd.-E-SBR: Nipol 1500 , Nippon Zeon Co., Ltd., sodium rosinate (Na rosinate): Dresinate, HERCULES Co., naphthenic acid cobalt (naphthenic acid Co): 10% cobalt naphthenate, DIC Corporation, cobalt stearate (Co stearate) : Cobalt stearate, manufactured by DIC Corporation ・ Carbon black: HTC # G, manufactured by Nippon Kayaku Carbon Corporation ・ Zinc oxide (ZnO): Three types of zinc oxide, manufactured by Shodo Chemical Co., Ltd. ・ Aroma oil: Diana process oil AH-58, Idemitsu Kosan Co., Ltd.・ Sulfur: Oil-treated sulfur, manufactured by Hosoi Chemical Co., Ltd. ・ Thiuram vulcanization accelerator (TS): Sunseller TS-G, manufactured by Sanshin Chemical Industry Co., Ltd. ・ Thiuram vulcanization accelerator (TT): Sunseller TT- PO, manufactured by Sanshin Chemical Industry Co., Ltd. ・ Vulcanization retarder (PVI): N-cyclohexylthiophthalimide, manufactured by Toray Fine Chemical Co., Ltd.
得られた各ゴム組成物を用いて、ホース状ワイヤ接着試験を行った。加硫条件は148℃で30分行った。 A hose-shaped wire adhesion test was performed using each of the obtained rubber compositions. The vulcanization conditions were 30 minutes at 148 ° C.
<2.ゴム組成物の評価>
上記のようにして得られた各ホース状ワイヤ接着物の未加硫特性、加硫特性、初期接着性及び耐熱性について、各々評価を行った。
<2. Evaluation of rubber composition>
Each hose-like wire adhesive obtained as described above was evaluated for unvulcanized characteristics, vulcanized characteristics, initial adhesiveness, and heat resistance.
[未加硫特性]
得られたゴム組成物について、JIS K6300−2(振動式加硫試験機による加硫特性の求め方)に準拠して、未加硫のゴム組成物の加硫を加硫試験機により148℃で行い、レオメータ曲線から最小トルク(ML)と最大トルク(MH)を検出し、t(95)を求めた。試験結果より求められたt(95)は、以下のように評価した。試験結果を表1、2に示す。
○:t(95)が45分以下のもの
×:t(95)が45分を超えるもの
[Unvulcanized properties]
For the obtained rubber composition, vulcanization of the unvulcanized rubber composition was performed at 148 ° C. using a vulcanization tester in accordance with JIS K6300-2 (How to obtain vulcanization characteristics using a vibration vulcanization tester). The minimum torque (ML) and the maximum torque (MH) were detected from the rheometer curve, and t (95) was obtained. T (95) obtained from the test results was evaluated as follows. The test results are shown in Tables 1 and 2.
○: t (95) is 45 minutes or less x: t (95) is more than 45 minutes
[加硫特性]
得られたゴム組成物を148℃のプレス成型機を用いて、面圧3.0MPaで30分間加硫して、2mm厚の加硫シートを作製した。このシートからJIS3号のダンベル状の試験片を打ち抜き、引っ張り速度500mm/分で引張試験を「JIS K6251−2004」に準じて行い、引張強さ(TB)、切断時伸び(EB)、引張応力100%モジュラス(M100)を求め、加硫特性を評価した。試験結果より求められた加硫特性は、以下のように評価した。試験結果を表1、2に示す。引張強さ(TB)は10MPa以上であれば良好であると判断し、切断時伸び(EB)は、170%以上であれば良好であると判断し、引張応力100%モジュラス(M100)は、7MPa上であれば良好であると判断した。
(引張強さ(TB))
二重丸:15MPa以上のもの
○:10MPa以上15MPa未満のもの
×:10MPa未満のもの
(切断時伸び(EB))
二重丸:200%以上のもの
○:170%以上200%未満のもの
×:170%未満のもの
(引張応力100%モジュラス(M100))
二重丸:10MPa以上のもの
○:7MPa以上10MPa未満のもの
×:7MPa未満のもの
[Vulcanization characteristics]
The obtained rubber composition was vulcanized at a surface pressure of 3.0 MPa for 30 minutes using a press molding machine at 148 ° C. to prepare a vulcanized sheet having a thickness of 2 mm. A JIS3 dumbbell-shaped test piece is punched from this sheet, and a tensile test is conducted according to “JIS K6251-2004” at a pulling speed of 500 mm / min. Tensile strength (TB), elongation at break (EB), tensile stress The 100% modulus (M100) was determined and the vulcanization characteristics were evaluated. The vulcanization characteristics obtained from the test results were evaluated as follows. The test results are shown in Tables 1 and 2. The tensile strength (TB) is judged to be good if it is 10 MPa or more, the elongation at break (EB) is judged to be good if it is 170% or more, and the tensile stress 100% modulus (M100) is It was judged to be good if it was above 7 MPa.
(Tensile strength (TB))
Double circle: 15 MPa or more ○: 10 MPa or more and less than 15 MPa x: Less than 10 MPa (Elongation at cutting (EB))
Double circle: 200% or more ○: 170% or more and less than 200% x: Less than 170% (tensile stress 100% modulus (M100))
Double circle: 10 MPa or more ○: 7 MPa or more and less than 10 MPa x: Less than 7 MPa
[耐熱老化性]
耐熱老化性試験として、老化試験(120℃×72hr)を実施し、老化試験機を用いて加硫ゴムを規定温度で規定時間加熱したのち、ΔTB・ΔEB・ΔM100を測定し、加熱処理前に対する値の変化を求め加硫ゴムの老化性を調べ、耐熱性を評価した。試験結果より求められた耐熱性は、以下のように評価した。試験結果を表1、2に示す。ΔTBは、−40%以上−10%以下、10%以上40%以下であれば良好であると判断し、ΔEBは、−50%以上−30%以下、30%以上50%以下であれば良好であると判断し、ΔM100は、−60%以上−30%以下、30%以上60%以下であれば良好であると判断した。
(ΔTB)
二重丸:±10%以下のもの
○:−40%≦ΔTB<−10%、10%<ΔTB≦40%
×:ΔTB<−40%、40%<ΔTB
(ΔEB)
二重丸:±30%以下のもの
○:−50%≦ΔEB<−30%、30%<ΔEB≦50%
×:ΔEB<−50%、50%<ΔEB
(ΔM100)
二重丸:±30%以下のもの
○:−60%≦ΔM100<−30%、30%<ΔM100≦60%
×:ΔM100<−60%、60%<ΔM100
[Heat aging resistance]
As a heat aging resistance test, an aging test (120 ° C. × 72 hr) was carried out, and after vulcanized rubber was heated at a specified temperature for a specified time using an aging tester, ΔTB · ΔEB · ΔM100 was measured, and before heat treatment The change in value was determined and the aging property of the vulcanized rubber was examined to evaluate the heat resistance. The heat resistance determined from the test results was evaluated as follows. The test results are shown in Tables 1 and 2. ΔTB is judged to be good if it is −40% or more and −10% or less, 10% or more and 40% or less, and ΔEB is good if it is −50% or more and −30% or less, or 30% or more and 50% or less. It was judged that ΔM100 was good when it was −60% to −30% and 30% to 60%.
(ΔTB)
Double circle: ± 10% or less ○: −40% ≦ ΔTB <−10%, 10% <ΔTB ≦ 40%
X: ΔTB <−40%, 40% <ΔTB
(ΔEB)
Double circle: ± 30% or less ○: −50% ≦ ΔEB <−30%, 30% <ΔEB ≦ 50%
X: ΔEB <−50%, 50% <ΔEB
(ΔM100)
Double circle: ± 30% or less ○: −60% ≦ ΔM100 <−30%, 30% <ΔM100 ≦ 60%
X: ΔM100 <−60%, 60% <ΔM100
[接着性]
接着性は、剥離強さ及びゴム付きにより評価した。
(1)剥離強さ
得られた各ゴム組成物をラボ用ロールにより厚み2.5mmのシート状に成形し、真鍮板と組み合わせ、圧着した。ただし、剥離する際にチャックでつかむ部分にはセロハン紙を配し、接着しないようにした。その後、ラボ用プレス成形機を用いて、142℃で95分間、面圧3.0MPaで加圧加硫し、真鍮とゴムの複合体を得た。この複合体を室温で24時間放置した後、25mm幅に切り出して試験片を得た。JIS K6256−1999「金属片と加硫ゴムの90度はく離試験」の規定に準じて、JIS K6256に規定されている引張試験機を用いて、得られた試験片について引張速度50mm/分の条件で、ゴム組成物と真鍮板間の剥離試験を行い、剥離強さを測定した。
(剥離力)
二重丸:100N/25mm以上のもの
○:80N/25mm以上100未満のもの
×:80N/25mm未満のもの
(2)ゴム付き
上記と同様に剥離試験を行い、JIS K6256−1999により、剥離したサンプルの真鍮板上のゴムの被覆%によってゴム付きを測定した。
[Adhesiveness]
Adhesiveness was evaluated by peel strength and rubber attachment.
(1) Peel strength Each rubber composition obtained was formed into a sheet having a thickness of 2.5 mm by a laboratory roll, combined with a brass plate, and pressure-bonded. However, cellophane paper was placed on the part to be gripped by the chuck when peeling, so as not to bond. Then, using a laboratory press molding machine, pressure vulcanization was performed at 142 ° C. for 95 minutes at a surface pressure of 3.0 MPa to obtain a composite of brass and rubber. The composite was allowed to stand at room temperature for 24 hours, and then cut into a width of 25 mm to obtain a test piece. In accordance with JIS K6256-1999 “90 degree peeling test between metal piece and vulcanized rubber”, using a tensile tester specified in JIS K6256, the obtained test piece was subjected to a tensile speed of 50 mm / min. Then, a peel test was performed between the rubber composition and the brass plate, and the peel strength was measured.
(Peeling force)
Double circle: 100 N / 25 mm or more ○: 80 N / 25 mm or more and less than 100 x: 80 N / 25 mm or less (2) With rubber Peel test was performed in the same manner as above, and peeled according to JIS K6256-1999 Rubber coverage was measured by the percentage of rubber coating on the sample brass plate.
剥離強さの値が80N/25mm以上かつゴム付きが75%以上である場合、接着性が良好であると言える。
(ゴム付き)
二重丸:90%以上のもの
○:75%以上90%未満のもの
×:75%未満のもの
When the peel strength value is 80 N / 25 mm or more and the rubber attachment is 75% or more, it can be said that the adhesiveness is good.
(With rubber)
Double circle: 90% or more ○: 75% or more and less than 90% ×: less than 75%
未加硫特性、加硫特性、初期接着性及び耐熱性の結果を総合的に判定して、未加硫特性、加硫特性、初期接着性及び耐熱性の判定を行ない、総合評価をした。 The results of the unvulcanized characteristics, vulcanized characteristics, initial adhesiveness and heat resistance were comprehensively determined, and the unvulcanized characteristics, vulcanized characteristics, initial adhesiveness and heat resistance were determined, and comprehensive evaluation was performed.
表1、2に示すように、比較例1乃至10のゴム組成物は、未加硫物性、加硫物性、初期接着性、耐熱性の少なくとも一つは劣り、特に、比較例7以外のゴム組成物は、初期接着性が劣っていた。これに対し、本発明の実施例1乃至11のゴム組成物は、未加硫物性、加硫物性、初期接着性、耐熱性の全てが良好であった。特に、実施例5のゴム組成物については、上述のように、予めロジン酸石けん(5.38質量%)を含有したE−SBRを、S−SBRに配合して、ジエン系重合体中のロジン酸石けんの含有量を0.8質量%とし、ロジン酸石けんを0.8質量部含むゴム組成物に配合したものであるが、未加硫物性、加硫物性、初期接着性、耐熱性は共に良好であった。また、ロジン酸Naを別途0.5質量部又は1.5質量部添加した実施例8、9においても、未加硫物性、加硫物性、初期接着性、耐熱性は共に良好であった。よって、本発明の実施例1乃至11のゴム組成物によれば、少ない加硫促進剤の添加であっても、熱老化性が改良され、ワイヤ接着性は、良好であることが判明した。 As shown in Tables 1 and 2, the rubber compositions of Comparative Examples 1 to 10 are inferior in at least one of unvulcanized physical properties, vulcanized physical properties, initial adhesive properties, and heat resistance. The composition had poor initial adhesion. On the other hand, the rubber compositions of Examples 1 to 11 of the present invention were all excellent in unvulcanized physical properties, vulcanized physical properties, initial adhesive properties, and heat resistance. In particular, for the rubber composition of Example 5, as described above, E-SBR containing rosin acid soap (5.38% by mass) in advance was blended with S-SBR, and the diene polymer contained in the diene polymer. The rosin acid soap content is 0.8% by mass and is blended in a rubber composition containing 0.8 parts by mass of rosin acid soap, but unvulcanized physical properties, vulcanized physical properties, initial adhesiveness, heat resistance Both were good. Further, in Examples 8 and 9 in which 0.5 parts by mass or 1.5 parts by mass of rosin acid Na was added separately, unvulcanized physical properties, vulcanized physical properties, initial adhesiveness, and heat resistance were all good. Therefore, according to the rubber compositions of Examples 1 to 11 of the present invention, it was found that even with the addition of a small amount of vulcanization accelerator, the heat aging property was improved and the wire adhesion was good.
以上のように、本発明のブラスめっきワイヤ接着用ゴム組成物によれば、熱老化性が改良されたブラスめっきワイヤ接着用ゴム組成物を提供できる。そのため、本発明のブラスめっきワイヤ接着用ゴム組成物は油圧ホース用等に好適に用いることができる。 As described above, according to the rubber composition for bonding a brass plating wire of the present invention, a rubber composition for bonding a brass plating wire with improved heat aging can be provided. Therefore, the rubber composition for bonding a brass plating wire of the present invention can be suitably used for a hydraulic hose or the like.
11 油圧ホース
12 ゴム内層
13 補強層
14 ゴム外層
11
Claims (4)
有機酸、脂肪酸塩及び有機酸塩から選ばれる少なくとも1種の含有量が1.5質量%以下であるジエン系重合体と、チウラム系加硫促進剤とを含み、
前記有機酸がロジン酸、ステアリン酸、パルミチン酸及びオレイン酸の何れか1つ以上であり、前記有機酸塩がロジン酸ナトリウムであり、前記脂肪酸塩が脂肪酸カリ石けん、オレイン酸カリ石けん、ステアリン酸ナトリウム及びステアリン酸アンモニウムの何れか1つ以上であり、
前記有機酸と前記脂肪酸塩と前記有機酸塩とを合わせた含有量が、ジエン系重合体100質量部に対して、1.5質量部以下であり、
前記チウラム系加硫促進剤の含有量が、前記ジエン系重合体100質量部に対して、0.1質量部超え0.5質量部未満であることを特徴とするブラスめっきワイヤ接着用ゴム組成物。 A rubber composition for bonding a brass plated wire reinforcing layer of a hose,
A diene polymer having a content of at least one selected from an organic acid, a fatty acid salt and an organic acid salt of 1.5% by mass or less, and a thiuram vulcanization accelerator,
The organic acid is one or more of rosin acid, stearic acid, palmitic acid and oleic acid, the organic acid salt is sodium rosinate, and the fatty acid salt is fatty acid potassium soap, oleic acid potassium soap, stearic acid One or more of sodium and ammonium stearate,
The total content of the organic acid, the fatty acid salt, and the organic acid salt is 1.5 parts by mass or less with respect to 100 parts by mass of the diene polymer.
A rubber composition for bonding a brass plating wire, wherein a content of the thiuram vulcanization accelerator is more than 0.1 parts by weight and less than 0.5 parts by weight with respect to 100 parts by weight of the diene polymer. object.
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