KR102625110B1 - Polymer compositions, cross-linked polymers, and tires - Google Patents
Polymer compositions, cross-linked polymers, and tires Download PDFInfo
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- KR102625110B1 KR102625110B1 KR1020217022116A KR20217022116A KR102625110B1 KR 102625110 B1 KR102625110 B1 KR 102625110B1 KR 1020217022116 A KR1020217022116 A KR 1020217022116A KR 20217022116 A KR20217022116 A KR 20217022116A KR 102625110 B1 KR102625110 B1 KR 102625110B1
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- South Korea
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- polymer
- carbon atoms
- thio
- conjugated diene
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- 229920000642 polymer Polymers 0.000 title claims abstract description 174
- 239000000203 mixture Substances 0.000 title claims abstract description 79
- 229920006037 cross link polymer Polymers 0.000 title claims description 32
- -1 diene compound Chemical class 0.000 claims abstract description 100
- 150000001993 dienes Chemical class 0.000 claims abstract description 60
- 239000000835 fiber Substances 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 23
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 83
- 238000006116 polymerization reaction Methods 0.000 claims description 41
- 125000000743 hydrocarbylene group Chemical group 0.000 claims description 27
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- AWIJRPNMLHPLNC-UHFFFAOYSA-N methanethioic s-acid Chemical compound SC=O AWIJRPNMLHPLNC-UHFFFAOYSA-N 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 125000003368 amide group Chemical group 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000005227 gel permeation chromatography Methods 0.000 claims description 9
- NONOKGVFTBWRLD-UHFFFAOYSA-N isocyanatosulfanylimino(oxo)methane Chemical group O=C=NSN=C=O NONOKGVFTBWRLD-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 8
- 125000001302 tertiary amino group Chemical group 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- 239000004760 aramid Substances 0.000 claims description 7
- 229920003235 aromatic polyamide Polymers 0.000 claims description 7
- 125000002883 imidazolyl group Chemical group 0.000 claims description 7
- 125000002560 nitrile group Chemical group 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 239000005077 polysulfide Substances 0.000 claims description 7
- 229920001021 polysulfide Polymers 0.000 claims description 7
- 150000008117 polysulfides Polymers 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 125000004076 pyridyl group Chemical group 0.000 claims description 7
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 7
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 5
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 46
- 238000004898 kneading Methods 0.000 description 36
- 238000000034 method Methods 0.000 description 33
- 239000000377 silicon dioxide Substances 0.000 description 23
- 239000006087 Silane Coupling Agent Substances 0.000 description 20
- 238000004073 vulcanization Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 239000011256 inorganic filler Substances 0.000 description 14
- 229910003475 inorganic filler Inorganic materials 0.000 description 14
- 239000003607 modifier Substances 0.000 description 14
- 239000000178 monomer Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003398 denaturant Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000004606 Fillers/Extenders Substances 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
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- 238000004925 denaturation Methods 0.000 description 6
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001339 alkali metal compounds Chemical class 0.000 description 4
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000006237 Intermediate SAF Substances 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- 125000002993 cycloalkylene group Chemical group 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
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- HFGLXKZGFFRQAR-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-yltetrasulfanyl)propyl-trimethoxysilane Chemical compound C1=CC=C2SC(SSSSCCC[Si](OC)(OC)OC)=NC2=C1 HFGLXKZGFFRQAR-UHFFFAOYSA-N 0.000 description 2
- DIGKGWWSMMWBIZ-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]-n,n-bis(trimethylsilyl)propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN([Si](C)(C)C)[Si](C)(C)C DIGKGWWSMMWBIZ-UHFFFAOYSA-N 0.000 description 2
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- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
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- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- SUQBVXFGGATXQO-UHFFFAOYSA-N tert-butyl-dimethyl-piperazin-1-ylsilane Chemical compound CC(C)(C)[Si](C)(C)N1CCNCC1 SUQBVXFGGATXQO-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 125000005068 thioepoxy group Chemical group S(O*)* 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- XEZVDURJDFGERA-UHFFFAOYSA-N tricosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCC(O)=O XEZVDURJDFGERA-UHFFFAOYSA-N 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- QKJGTZOWMVHEHS-UHFFFAOYSA-N triethoxy-[3-(phenyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSC1=CC=CC=C1 QKJGTZOWMVHEHS-UHFFFAOYSA-N 0.000 description 1
- JSXKIRYGYMKWSK-UHFFFAOYSA-N trimethoxy-[2-(2-trimethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCSSSSCC[Si](OC)(OC)OC JSXKIRYGYMKWSK-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- VTWDHPGFWOGSGR-UHFFFAOYSA-N trimethyl-(1-trimethylsilyl-2,4-dihydro-1,3,5-triazin-3-yl)silane Chemical compound C[Si](N1CN(CN=C1)[Si](C)(C)C)(C)C VTWDHPGFWOGSGR-UHFFFAOYSA-N 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
저(低)로스성 및 웨트 그립성이 우수할 뿐만 아니라, 기계적 강도, 인장 강도 및 조종 안정성에 있어서도 고도로 밸런스가 우수한 타이어의 제조에 적합한 중합체 조성물을 제공한다. 본 발명에 따른 중합체 조성물은, (A) 공액 디엔 화합물의 중합체 또는 공액 디엔 화합물과 방향족 비닐 화합물의 공중합체로서, 활성 중합 말단과 일반식 (1)∼(4)의 어느 것으로 나타나는 화합물과의 반응물인, 공액 디엔계 중합체와, (B) 유기 단섬유를 함유한다.Provided is a polymer composition suitable for the production of tires that not only have excellent low loss properties and wet grip properties, but are also highly balanced in mechanical strength, tensile strength, and steering stability. The polymer composition according to the present invention is (A) a polymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound, which is a reaction product between an active polymerized terminal and a compound represented by any of the general formulas (1) to (4). It contains phosphorus, a conjugated diene polymer, and (B) organic short fibers.
Description
본 발명은, 중합체 조성물, 가교 중합체 및, 당해 가교 중합체를 이용하여 작성된 타이어에 관한 것이다.The present invention relates to a polymer composition, a crosslinked polymer, and a tire produced using the crosslinked polymer.
최근, 환경 문제로의 관심의 높아짐에 수반되는 세계적인 이산화탄소 배출 규제의 움직임에 관련하여, 자동차의 저(低)연비화에 대한 요구가 강해지고 있다. 이러한 요구에 대응하기 위해, 타이어 성능에 대해서도 구름 저항의 저감이 요구되고 있다. 종래, 타이어의 구름 저항을 감소시키는 수법으로서, 타이어 구조를 최적화하는 수법이 검토되어 왔지만, 타이어에 적용되는 중합체 조성물에 대해서, tanδ가 낮고(이하, 「저(低)로스성」이라고도 함), 저발열성이 우수한 것을 이용하는 것도, 현재 일반적인 수법으로서 행해지고 있다.Recently, in connection with the global movement to regulate carbon dioxide emissions accompanied by increased interest in environmental issues, the demand for lower fuel efficiency of automobiles has become stronger. In order to respond to these demands, reduction of rolling resistance is also required for tire performance. Conventionally, as a method of reducing the rolling resistance of a tire, a method of optimizing the tire structure has been examined. However, for the polymer composition applied to the tire, tanδ is low (hereinafter also referred to as "low loss property"). Using materials with excellent low heat generation properties is currently a common method.
이러한 발열성이 낮은 중합체 조성물을 얻는 방법으로서는, 카본 블랙이나 실리카 등의 충전제의 감량, 또는 대(大)입경의 카본 블랙의 사용 등이 고려되지만, 어느 방법에서도, 중합체 조성물의 보강성, 내마모성 및 습윤 노면에서의 그립성(이하, 「웨트 그립성」이라고도 함)의 저하를 피할 수 없다.Methods for obtaining such a polymer composition with low exothermic properties include reducing the amount of filler such as carbon black or silica, or using carbon black with a large particle size. However, in any method, the reinforcement properties, wear resistance, and A decrease in grip properties (hereinafter also referred to as “wet grip properties”) on wet road surfaces cannot be avoided.
그래서, 예를 들면, 금속 말단을 갖는 활성 중합체를 형성하고, 당해 활성 중합체에 특정의 변성제를 도입하여 변성시킨 변성 공액 디엔계 중합체를 타이어의 트레드 재료로서 사용하는 검토가 이루어지고 있다(예를 들면, 특허문헌 1 참조). 특허문헌 1에는, 이 재료를 타이어의 트레드 재료로서 사용하면, 발열성, 내마모성 및, 웨트 그립성이 우수한 것으로 되는 것이 개시되어 있다.Therefore, for example, studies are being made to use a modified conjugated diene polymer as a tire tread material by forming an active polymer having a metal terminal and modifying the active polymer by introducing a specific modifier (e.g. , see Patent Document 1). Patent Document 1 discloses that when this material is used as a tread material for a tire, it has excellent heat generation properties, wear resistance, and wet grip properties.
그러나, 특허문헌 1에 개시된 변성 공액 디엔계 중합체를 타이어의 트레드 재료로서 사용한 경우, 기계적 강도, 인장 강도 및 조종 안정성의 점에서 충분한 성능이 얻어지지 않는다는 과제가 있었다.However, when the modified conjugated diene polymer disclosed in Patent Document 1 was used as a tire tread material, there was a problem that sufficient performance was not obtained in terms of mechanical strength, tensile strength, and steering stability.
그래서, 본 발명에 따른 몇개의 태양은, 저로스성 및 웨트 그립성이 우수할 뿐만 아니라, 기계적 강도, 인장 강도 및 조종 안정성에 있어서도 고도로 밸런스가 우수한 타이어의 제조에 적합한 중합체 조성물을 제공한다. 또한, 본 발명에 따른 몇개의 태양은, 저로스성 및 웨트 그립성이 우수할 뿐만 아니라, 기계적 강도, 인장 강도 및 조종 안정성에 있어서도 고도로 밸런스가 우수한 타이어를 제공한다.Therefore, several aspects of the present invention provide a polymer composition suitable for producing a tire that not only has excellent low-loss properties and wet grip properties, but is also highly balanced in mechanical strength, tensile strength, and steering stability. Additionally, several aspects of the present invention provide tires that not only have excellent low-loss properties and wet grip properties, but are also highly balanced in mechanical strength, tensile strength, and steering stability.
본 발명은 전술의 과제의 적어도 일부를 해결하기 위해 이루어진 것으로, 이하의 태양으로서 실현할 수 있다.The present invention has been made to solve at least part of the above-described problems, and can be realized in the following aspects.
본 발명에 따른 중합체 조성물의 일 태양은, One aspect of the polymer composition according to the present invention is:
(A) 공액 디엔 화합물의 중합체 또는 공액 디엔 화합물과 방향족 비닐 화합물의 공중합체로서, 활성 중합 말단과 하기 일반식 (1)∼(4)의 어느 것으로 나타나는 화합물과의 반응물인, 공액 디엔계 중합체와,(A) a conjugated diene-based polymer, which is a polymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound, which is a reaction product between an active polymerization terminal and a compound represented by any of the following general formulas (1) to (4); ,
(B) 유기 단(短)섬유(organic short fiber)(B) Organic short fibers
를 함유한다.Contains
(식 (1) 중, A1은, 이미노기, 아미드기, (티오)카보닐기, (티오)카보닐옥시기, 술피드 혹은 폴리술피드로 L1과 결합한 1가의 기이거나, 또는, 보호된 1급 아미노기, 보호된 2급 아미노기, 3급 아미노기, 니트릴기, 피리딜기, (티오)에폭시기, (티오)이소시아네이트기, (티오)포르밀기, (티오)카본산 에스테르, (티오)카본산 에스테르의 금속염, 카본산 할로겐 화합물 혹은 이미다졸릴기를 나타내고, L1은 탄소수 1∼20의 하이드로카빌렌기를 나타내고, R1 및 R2는 각각 독립적으로 탄소수 1∼4의 하이드로카빌기를 나타내고, n1은 0 또는 1이다.)(In formula (1), A 1 is a monovalent group bonded to L 1 with an imino group, amide group, (thio)carbonyl group, (thio)carbonyloxy group, sulfide or polysulfide, or a protected Primary amino group, protected secondary amino group, tertiary amino group, nitrile group, pyridyl group, (thio)epoxy group, (thio)isocyanate group, (thio)formyl group, (thio)carboxylic acid ester, (thio)carboxylic acid ester represents a metal salt, a carboxylic acid halogen compound or an imidazolyl group, L 1 represents a hydrocarbylene group with 1 to 20 carbon atoms, R 1 and R 2 each independently represent a hydrocarbyl group with 1 to 4 carbon atoms, and n1 represents a hydrocarbylene group with 1 to 4 carbon atoms. It is 0 or 1.)
(식 (2) 중, A2는, 이미노기, 아미드기, (티오)카보닐기, (티오)카보닐옥시기, 술피드 혹은 폴리술피드로 L2와 결합한 1가의 기이거나, 또는, 보호된 1급 아미노기, 보호된 2급 아미노기, 3급 아미노기, 니트릴기, 피리딜기, (티오)에폭시기, (티오)이소시아네이트기, (티오)포르밀기, (티오)카본산 에스테르, (티오)카본산 에스테르의 금속염, 카본산 할로겐 화합물, 이미다졸릴기 혹은 하기식 (2a)로 나타나는 기를 나타내고, L2 및 L3은 각각 독립적으로 단결합 혹은 탄소수 1∼20의 하이드로카빌렌기를 나타내고, R3 및 R4는 각각 독립적으로 탄소수 1∼4의 하이드로카빌기를 나타내고, n2는 0∼3이고, m1은 0 또는 1이다.)(In formula (2), A 2 is a monovalent group bonded to L 2 with an imino group, amide group, (thio)carbonyl group, (thio)carbonyloxy group, sulfide or polysulfide, or a protected group. Primary amino group, protected secondary amino group, tertiary amino group, nitrile group, pyridyl group, (thio)epoxy group, (thio)isocyanate group, (thio)formyl group, (thio)carboxylic acid ester, (thio)carboxylic acid ester represents a metal salt, a carboxylic acid halogen compound, an imidazolyl group, or a group represented by the formula (2a) below, L 2 and L 3 each independently represent a single bond or a hydrocarbylene group having 1 to 20 carbon atoms, R 3 and R 4 each independently represents a hydrocarbyl group having 1 to 4 carbon atoms, n2 is 0 to 3, and m1 is 0 or 1.)
(식 (2a) 중, L3, R3, R4 및 n2는 식 (2)와 마찬가지이고, *는 L2와 결합하는 부위를 나타낸다.) (In formula (2a), L 3 , R 3 , R 4 and n2 are the same as in formula (2), and * represents the site that binds to L 2. )
(식 (3) 중, A3은 각각 독립적으로, 이미노기, 아미드기, (티오)카보닐기 또는 (티오)카보닐옥시기를 나타내고, Z는 질소 원자를 포함하거나 또는 포함하지 않는 탄소수 1∼20의 t가의 기를 나타내고, L4는 단결합 또는 탄소수 1∼20의 하이드로카빌렌기를 나타내고, L5는 탄소수 1∼20의 하이드로카빌렌기를 나타내고, R5 및 R6은 각각 독립적으로 탄소수 1∼4의 하이드로카빌기를 나타내고, n3은 0 또는 1이고, t는 2 또는 3이다.)(In formula (3), A 3 each independently represents an imino group, an amide group, a (thio) carbonyl group, or a (thio) carbonyloxy group, and Z has 1 to 20 carbon atoms with or without a nitrogen atom. represents a t-valent group, L 4 represents a single bond or a hydrocarbylene group with 1 to 20 carbon atoms, L 5 represents a hydrocarbylene group with 1 to 20 carbon atoms, and R 5 and R 6 each independently represent a hydrocarbylene group with 1 to 4 carbon atoms. represents a hydrocarbyl group, n3 is 0 or 1, and t is 2 or 3.)
(식 (4) 중, R7 및 R8은, 각각 독립적으로 탄소수 1∼20의 하이드로카빌기를 나타내고, R9는, 탄소수 1∼20의 하이드로카빌기, 알킬기가 갖는 수소 원자 및 -CH2-의 적어도 1개가 규소, 질소, 인, 산소 및 황으로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 포함하는 기로 치환된 탄소수 1∼20의 치환 알킬기이거나, 또는 질소, 인, 산소 및 황으로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 포함하는 탄소수 6∼20의 방향족기를 나타내고, R10은, 탄소수 1∼20의 알칸디일기를 나타낸다. n4는 1 또는 2이다.)(In formula (4), R 7 and R 8 each independently represent a hydrocarbyl group having 1 to 20 carbon atoms, and R 9 represents a hydrocarbyl group having 1 to 20 carbon atoms, a hydrogen atom of the alkyl group, and -CH 2 At least one of - is a substituted alkyl group having 1 to 20 carbon atoms substituted with a group containing at least one element selected from the group consisting of silicon, nitrogen, phosphorus, oxygen and sulfur, or consisting of nitrogen, phosphorus, oxygen and sulfur. represents an aromatic group having 6 to 20 carbon atoms containing at least one element selected from the group, and R 10 represents an alkanediyl group having 1 to 20 carbon atoms. n4 is 1 or 2.
상기 중합체 조성물의 일 태양에 있어서,In one aspect of the polymer composition,
상기 (A) 공액 디엔계 중합체 100질량부에 대하여, 상기 (B) 유기 단섬유를 1질량부 이상 20질량부 미만 함유할 수 있다.With respect to 100 parts by mass of the conjugated diene polymer (A), the organic short fibers (B) may be contained in an amount of 1 part by mass or more and less than 20 parts by mass.
상기 중합체 조성물의 어느 것의 태양에 있어서,In any aspect of the above polymer composition,
상기 (A) 공액 디엔계 중합체의, 겔 투과 크로마토그래피로 측정한 폴리스티렌 환산의 중량 평균 분자량이 10,000∼2,000,000일 수 있다.The conjugated diene polymer (A) may have a weight average molecular weight of 10,000 to 2,000,000 in terms of polystyrene, as measured by gel permeation chromatography.
상기 중합체 조성물의 어느 것의 태양에 있어서,In any aspect of the above polymer composition,
상기 (B) 유기 단섬유가, 지방족 폴리아미드, 방향족 폴리아미드 및 셀룰로오스계 폴리머로 이루어지는 군으로부터 선택되는 적어도 1종일 수 있다.The (B) organic short fiber may be at least one selected from the group consisting of aliphatic polyamide, aromatic polyamide, and cellulose polymer.
상기 중합체 조성물의 어느 것의 태양에 있어서,In any aspect of the above polymer composition,
상기 (B) 유기 단섬유는, 평균 길이가 0.01㎜ 이상 20㎜ 이하이고, 또한, 평균 지름이 0.05㎛ 이상 50㎛ 이하일 수 있다.The (B) organic short fibers may have an average length of 0.01 mm to 20 mm and an average diameter of 0.05 μm to 50 μm.
상기 중합체 조성물의 어느 것의 태양에 있어서,In any aspect of the above polymer composition,
추가로, 가교제를 함유할 수 있다.Additionally, it may contain a cross-linking agent.
본 발명에 따른 가교 중합체의 일 태양은,One aspect of the crosslinked polymer according to the present invention is,
상기 태양의 중합체 조성물을 이용하여 제조된 것이다.It is manufactured using the polymer composition of the above aspect.
본 발명에 따른 타이어의 일 태양은, One aspect of the tire according to the present invention is,
상기 태양의 가교 중합체를 사용한 것이다.The crosslinked polymer of the above embodiment was used.
본 발명에 따른 중합체 조성물에 의하면, 저로스성 및 웨트 그립성이 우수할 뿐만 아니라, 기계적 강도, 인장 강도 및 조종 안정성에 있어서도 고도로 밸런스가 우수한 가교 중합체(타이어)를 제조할 수 있다.According to the polymer composition according to the present invention, it is possible to produce a crosslinked polymer (tire) that not only has excellent low loss properties and wet grip properties, but also has a highly excellent balance in mechanical strength, tensile strength, and handling stability.
(발명을 실시하기 위한 형태)(Form for carrying out the invention)
이하, 본 발명에 따른 적합한 실시 형태에 대해서 상세하게 설명한다. 또한, 본 발명은, 이하에 기재된 실시 형태에만 한정되는 것은 아니고, 본 발명의 요지를 변경하지 않는 범위에 있어서 실시되는 각종의 변형예도 포함하는 것으로서 이해되어야 한다.Hereinafter, preferred embodiments according to the present invention will be described in detail. In addition, the present invention is not limited to the embodiments described below, and should be understood as including various modifications implemented without changing the gist of the present invention.
본 명세서에 있어서, 「A∼B」와 같이 기재된 수치 범위는, 수치 A를 하한값으로서 포함하고, 또한, 수치 B를 상한값으로서 포함하는 것으로서 해석된다.In this specification, a numerical range written as “A to B” is interpreted as including the numerical value A as the lower limit and also including the numerical value B as the upper limit.
본 명세서에 있어서, 「(메타)아크릴산∼」이란, 아크릴산∼및 메타크릴산∼의 쌍방을 포함하는 개념이다.In this specification, “(meth)acrylic acid-” is a concept that includes both acrylic acid- and methacrylic acid-.
1. 중합체 조성물1. Polymer composition
본 실시 형태에 따른 중합체 조성물은, (A) 공액 디엔 화합물의 중합체 또는 공액 디엔 화합물과 방향족 비닐 화합물의 공중합체로서, 활성 중합 말단과 하기 일반식 (1)∼(4)의 어느 것으로 나타나는 화합물과의 반응물인, 공액 디엔계 중합체와, (B) 유기 단섬유를 함유한다.The polymer composition according to the present embodiment is (A) a polymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound, comprising an active polymerization terminal and a compound represented by any of the following general formulas (1) to (4) It contains a conjugated diene-based polymer, which is a reaction product of , and (B) organic short fibers.
본 실시 형태에 따른 중합체 조성물은, (A) 공액 디엔계 중합체를 포함하는 중합체 성분과, (B) 유기 단섬유와, 필요에 따라서 다른 첨가제를 혼련함으로써 얻어지는 미(未)가황의 중합체 조성물이다. 본 실시 형태에 따른 중합체 조성물은, 예를 들면 가황 등의 가교 처리를 함으로써, 가교 중합체를 형성하는 것이다.The polymer composition according to the present embodiment is an unvulcanized polymer composition obtained by kneading (A) a polymer component containing a conjugated diene polymer, (B) organic short fibers, and other additives as necessary. The polymer composition according to the present embodiment forms a crosslinked polymer by, for example, subjecting it to crosslinking treatment such as vulcanization.
이하, 본 실시 형태에 따른 중합체 조성물에 포함되는 각 성분에 대해서 설명한다.Hereinafter, each component contained in the polymer composition according to this embodiment will be described.
1.1. (A) 공액 디엔계 중합체1.1. (A) Conjugated diene polymer
본 실시 형태에 따른 중합체 조성물은, (A) 공액 디엔 화합물의 중합체 또는 공액 디엔 화합물과 방향족 비닐 화합물의 공중합체로서, 활성 중합 말단과 하기 일반식 (1)∼(4)의 어느 것으로 나타나는 화합물과의 반응물인, 공액 디엔계 중합체(본 명세서에 있어서, 간단히 「(A) 공액 디엔계 중합체」라고도 함)를 함유한다.The polymer composition according to the present embodiment is (A) a polymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound, comprising an active polymerization terminal and a compound represented by any of the following general formulas (1) to (4) Contains a conjugated diene-based polymer (in this specification, also simply referred to as “(A) conjugated diene-based polymer”), which is a reactant of .
(식 (1) 중, A1은, 이미노기, 아미드기, (티오)카보닐기, (티오)카보닐옥시기, 술피드 혹은 폴리술피드로 L1과 결합한 1가의 기이거나, 또는, 보호된 1급 아미노기, 보호된 2급 아미노기, 3급 아미노기, 니트릴기, 피리딜기, (티오)에폭시기, (티오)이소시아네이트기, (티오)포르밀기, (티오)카본산 에스테르, (티오)카본산 에스테르의 금속염, 카본산 할로겐 화합물 혹은 이미다졸릴기를 나타내고, L1은 탄소수 1∼20의 하이드로카빌렌기를 나타내고, R1 및 R2는 각각 독립적으로 탄소수 1∼4의 하이드로카빌기를 나타내고, n1은 0 또는 1이다.)(In formula (1), A 1 is a monovalent group bonded to L 1 with an imino group, amide group, (thio)carbonyl group, (thio)carbonyloxy group, sulfide or polysulfide, or a protected Primary amino group, protected secondary amino group, tertiary amino group, nitrile group, pyridyl group, (thio)epoxy group, (thio)isocyanate group, (thio)formyl group, (thio)carboxylic acid ester, (thio)carboxylic acid ester represents a metal salt, a carboxylic acid halogen compound or an imidazolyl group, L 1 represents a hydrocarbylene group with 1 to 20 carbon atoms, R 1 and R 2 each independently represent a hydrocarbyl group with 1 to 4 carbon atoms, and n1 represents a hydrocarbylene group with 1 to 4 carbon atoms. It is 0 or 1.)
(식 (2) 중, A2는, 이미노기, 아미드기, (티오)카보닐기, (티오)카보닐옥시기, 술피드 혹은 폴리술피드로 L2와 결합한 1가의 기이거나, 또는, 보호된 1급 아미노기, 보호된 2급 아미노기, 3급 아미노기, 니트릴기, 피리딜기, (티오)에폭시기, (티오)이소시아네이트기, (티오)포르밀기, (티오)카본산 에스테르, (티오)카본산 에스테르의 금속염, 카본산 할로겐 화합물, 이미다졸릴기 혹은 하기식 (2a)로 나타나는 기를 나타내고, L2 및 L3은 각각 독립적으로 단결합 혹은 탄소수 1∼20의 하이드로카빌렌기를 나타내고, R3 및 R4는 각각 독립적으로 탄소수 1∼4의 하이드로카빌기를 나타내고, n2는 0∼3이고, m1은 0 또는 1이다.)(In formula (2), A 2 is a monovalent group bonded to L 2 with an imino group, amide group, (thio)carbonyl group, (thio)carbonyloxy group, sulfide or polysulfide, or a protected group. Primary amino group, protected secondary amino group, tertiary amino group, nitrile group, pyridyl group, (thio)epoxy group, (thio)isocyanate group, (thio)formyl group, (thio)carboxylic acid ester, (thio)carboxylic acid ester represents a metal salt, a carboxylic acid halogen compound, an imidazolyl group, or a group represented by the formula (2a) below, L 2 and L 3 each independently represent a single bond or a hydrocarbylene group having 1 to 20 carbon atoms, R 3 and R 4 each independently represents a hydrocarbyl group having 1 to 4 carbon atoms, n2 is 0 to 3, and m1 is 0 or 1.)
(식 (2a) 중, L3, R3, R4 및 n2는 식 (2)와 마찬가지이고, *는 L2와 결합하는 부위를 나타낸다.)(In formula (2a), L 3 , R 3 , R 4 and n2 are the same as in formula (2), and * represents the site that binds to L 2. )
(식 (3) 중, A3은 각각 독립적으로, 이미노기, 아미드기, (티오)카보닐기 또는 (티오)카보닐옥시기를 나타내고, Z는 질소 원자를 포함하거나 또는 포함하지 않는 탄소수 1∼20의 t가의 기를 나타내고, L4는 단결합 또는 탄소수 1∼20의 하이드로카빌렌기를 나타내고, L5는 탄소수 1∼20의 하이드로카빌렌기를 나타내고, R5 및 R6은 각각 독립적으로 탄소수 1∼4의 하이드로카빌기를 나타내고, n3은 0 또는 1이고, t는 2 또는 3이다.)(In formula (3), A 3 each independently represents an imino group, an amide group, a (thio) carbonyl group, or a (thio) carbonyloxy group, and Z has 1 to 20 carbon atoms with or without a nitrogen atom. represents a t-valent group, L 4 represents a single bond or a hydrocarbylene group with 1 to 20 carbon atoms, L 5 represents a hydrocarbylene group with 1 to 20 carbon atoms, and R 5 and R 6 each independently represent a hydrocarbylene group with 1 to 4 carbon atoms. represents a hydrocarbyl group, n3 is 0 or 1, and t is 2 or 3.)
(식 (4) 중, R7 및 R8은, 각각 독립적으로 탄소수 1∼20의 하이드로카빌기이고, R9는, 탄소수 1∼20의 하이드로카빌기, 알킬기가 갖는 수소 원자 및 -CH2-의 적어도 1개가 규소, 질소, 인, 산소 및 황으로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 포함하는 기로 치환된 탄소수 1∼20의 치환 알킬기이거나, 또는 질소, 인, 산소 및 황으로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 포함하는 탄소수 6∼20의 방향족기를 나타내고, R10은, 탄소수 1∼20의 알칸디일기를 나타낸다. n4는 1 또는 2이다.)(In formula (4), R 7 and R 8 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, and R 9 is a hydrocarbyl group having 1 to 20 carbon atoms, the hydrogen atom of the alkyl group, and -CH 2 - at least one of which is a substituted alkyl group having 1 to 20 carbon atoms substituted with a group containing at least one element selected from the group consisting of silicon, nitrogen, phosphorus, oxygen and sulfur, or a group consisting of nitrogen, phosphorus, oxygen and sulfur represents an aromatic group with 6 to 20 carbon atoms containing at least one element selected from the group, and R 10 represents an alkanediyl group with 1 to 20 carbon atoms. n4 is 1 or 2.
(A) 공액 디엔계 중합체는, 공액 디엔 화합물에 유래하는 구조 단위를 갖고, 또한 활성 중합 말단에, 상기 일반식 (1)∼(4)의 어느 것의 화합물에 유래하는 구조를 갖는다. 이러한 (A) 공액 디엔계 중합체는, 우선, 공액 디엔 화합물을 포함하는 단량체를 중합하여 활성 말단을 갖는 중합체를 얻고(중합 공정), 이어서, 활성 말단을 갖는 중합체와, 상기 일반식 (1)∼(4)의 어느 것의 화합물(이하, 「특정 변성제」라고도 함)을 반응시킴으로써 얻을 수 있다(변성 공정).(A) The conjugated diene polymer has a structural unit derived from a conjugated diene compound and, at the active polymerization terminal, has a structure derived from a compound of any of the above general formulas (1) to (4). This (A) conjugated diene-based polymer first polymerizes a monomer containing a conjugated diene compound to obtain a polymer having an active end (polymerization step), and then a polymer having an active end, and the above general formula (1) - It can be obtained by reacting any of the compounds in (4) (hereinafter also referred to as “specific denaturant”) (denaturation step).
＜중합 공정＞＜Polymerization process＞
중합 시에 있어서 사용할 수 있는 공액 디엔 화합물로서는, 예를 들면, 1,3-부타디엔, 이소프렌, 2,3-디메틸-1,3-부타디엔, 1,3-펜타디엔, 1,3-헥사디엔, 1,3-헵타디엔, 2-페닐-1,3-부타디엔, 3-메틸-1,3-펜타디엔, 2-클로로-1,3-부타디엔 등을 들 수 있다. 이들 중에서도, 1,3-부타디엔, 이소프렌 및 2,3-디메틸-1,3-부타디엔이 바람직하다. 공액 디엔 화합물은, 1종을 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.Conjugated diene compounds that can be used during polymerization include, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chloro-1,3-butadiene, etc. Among these, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene are preferable. Conjugated diene compounds can be used individually or in combination of two or more types.
(A) 공액 디엔계 중합체는, 공액 디엔 화합물의 단독 중합체라도 좋지만, 가교 중합체의 강도를 높이는 관점에서, 공액 디엔 화합물과 방향족 비닐 화합물과의 공중합체인 것이 바람직하다. 그 중에서도, 음이온 중합에 있어서의 리빙성이 높은 점에 있어서, 1,3-부타디엔과 스티렌을 모노머 조성에 포함하는 공중합체인 것이 바람직하다. (A) 공액 디엔계 중합체가 공액 디엔 화합물과 방향족 비닐 화합물과의 공중합체인 경우, (A) 공액 디엔계 중합체는, 전형적으로는, 공액 디엔 화합물과 방향족 비닐 화합물과의 분포가 불규칙한 랜덤 공중합 부분을 갖고, 추가로, 공액 디엔 화합물 또는 방향족 비닐 화합물에 유래하는 구조 단위로 이루어지는 블록 부분을 갖고 있어도 좋다.(A) The conjugated diene-based polymer may be a homopolymer of a conjugated diene compound, but is preferably a copolymer of a conjugated diene compound and an aromatic vinyl compound from the viewpoint of increasing the strength of the crosslinked polymer. Among these, a copolymer containing 1,3-butadiene and styrene in the monomer composition is preferable because of its high living properties in anionic polymerization. (A) When the conjugated diene-based polymer is a copolymer of a conjugated diene compound and an aromatic vinyl compound, (A) the conjugated diene-based polymer typically has a random copolymerization portion in which the distribution of the conjugated diene compound and the aromatic vinyl compound is irregular. It may further have a block portion consisting of a structural unit derived from a conjugated diene compound or an aromatic vinyl compound.
중합 시에 있어서 사용할 수 있는 방향족 비닐 화합물로서는, 예를 들면, 스티렌, 2-메틸스티렌, 3-메틸스티렌, 4-메틸스티렌, α-메틸스티렌, 2,4-디메틸스티렌, 2,4-디이소프로필스티렌, 5-tert-부틸-2-메틸스티렌, 비닐에틸벤젠, 디비닐벤젠, 트리비닐벤젠, 디비닐나프탈렌, tert-부톡시스티렌, 비닐벤질디메틸아민, (4-비닐벤질)디메틸아미노에틸에테르, N,N-디메틸아미노에틸스티렌, N,N-디메틸아미노메틸스티렌, 2-에틸스티렌, 3-에틸스티렌, 4-에틸스티렌, 2-tert-부틸스티렌, 3-tert-부틸스티렌, 4-tert-부틸스티렌, 비닐자일렌, 비닐나프탈렌, 비닐피리딘, 디페닐에틸렌, 3급 아미노기 함유 디페닐에틸렌(예를 들면, 1-(4-N,N-디메틸아미노페닐)-1-페닐에틸렌) 등을 들 수 있다. 이들 중에서도, 스티렌 및 α-메틸스티렌이 바람직하다. 방향족 비닐 화합물은, 1종을 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.Examples of aromatic vinyl compounds that can be used during polymerization include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, and 2,4-dimethylstyrene. Isopropyl styrene, 5-tert-butyl-2-methylstyrene, vinylethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylamino Ethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, vinylxylene, vinylnaphthalene, vinylpyridine, diphenylethylene, diphenylethylene containing a tertiary amino group (e.g., 1-(4-N,N-dimethylaminophenyl)-1-phenyl ethylene), etc. may be mentioned. Among these, styrene and α-methylstyrene are preferable. Aromatic vinyl compounds can be used individually or in combination of two or more types.
(A) 공액 디엔계 중합체가 공액 디엔 화합물과 방향족 비닐 화합물과의 공중합체인 경우, 방향족 비닐 화합물의 함유량(방향족 비닐 함량)은, 얻어지는 가교 중합체의 저로스성과 웨트 그립성과의 밸런스를 양호하게 하는 관점에서, 중합에 사용하는 공액 디엔 화합물 및 방향족 비닐 화합물의 합계 100질량％ 중, 3∼55질량％로 하는 것이 바람직하고, 5∼50질량％로 하는 것이 보다 바람직하다. 또한, (A) 공액 디엔계 중합체의 방향족 비닐 함량은, 1H-NMR에 의해 측정할 수 있다.(A) When the conjugated diene polymer is a copolymer of a conjugated diene compound and an aromatic vinyl compound, the content of the aromatic vinyl compound (aromatic vinyl content) is from the viewpoint of improving the balance between low loss properties and wet grip properties of the resulting crosslinked polymer. It is preferable to set it as 3-55 mass %, and more preferably 5-50 mass % among the total 100 mass % of the conjugated diene compound and aromatic vinyl compound used for polymerization. Additionally, the aromatic vinyl content of the (A) conjugated diene polymer can be measured by 1 H-NMR.
중합 시에 있어서는, 공액 디엔 화합물 및 방향족 비닐 화합물 이외의 다른 모노머를 사용해도 좋다. 다른 모노머로서는, 예를 들면 아크릴로니트릴, (메타)아크릴산메틸, (메타)아크릴산에틸, (메타)아크릴산하이드록시에틸 등을 들 수 있다. 다른 모노머의 사용량은, 중합에 사용하는 모노머의 전체량 100질량％ 중, 25질량％ 이하로 하는 것이 바람직하고, 15질량％ 이하로 하는 것이 보다 바람직하고, 10질량％ 이하로 하는 것이 특히 바람직하다.At the time of polymerization, monomers other than conjugated diene compounds and aromatic vinyl compounds may be used. Examples of other monomers include acrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, and hydroxyethyl (meth)acrylate. The amount of other monomers used is preferably 25% by mass or less, more preferably 15% by mass or less, and especially preferably 10% by mass or less, based on 100% by mass of the total amount of monomers used in polymerization. .
사용하는 중합 방법으로서는, 용액 중합법, 기상 중합법, 벌크 중합법의 어느 것을 이용해도 좋지만, 용액 중합법이 특히 바람직하다. 또한, 중합 형식으로서는, 회분식 및 연속식의 어느 것을 이용해도 좋다. 용액 중합법을 이용하는 경우, 구체적인 중합 방법의 일 예로서는, 유기 용매 중에 있어서, 공액 디엔 화합물을 포함하는 단량체를, 중합 개시제 및 필요에 따라서 이용되는 랜더마이저의 존재하에서 중합하는 방법을 들 수 있다.As the polymerization method to be used, any of the solution polymerization method, gas phase polymerization method, and bulk polymerization method may be used, but the solution polymerization method is particularly preferable. Additionally, as the polymerization method, either batch or continuous methods may be used. When using the solution polymerization method, an example of a specific polymerization method includes a method of polymerizing a monomer containing a conjugated diene compound in an organic solvent in the presence of a polymerization initiator and a randomizer used as necessary.
중합 개시제로서는, 알칼리 금속 화합물 또는 알칼리 토금속 화합물을 이용할 수 있다. 이들의 구체예로서는, 예를 들면 메틸리튬, 에틸리튬, n-프로필리튬, n-부틸리튬, sec-부틸리튬, tert-부틸리튬 등의 알킬리튬, 1,4-디리티오부탄, 페닐리튬, 스틸벤리튬, 나프틸리튬, 1,3-비스(1-리티오-1,3-디메틸펜틸)벤젠, 1,3-페닐렌비스(3-메틸-1-페닐펜틸리덴)디리튬, 3-(디메틸아미노)프로필리튬, 나프틸나트륨, 나프틸칼륨, 디-n-부틸마그네슘, 디-n-헥실마그네슘, 에톡시칼륨, 스테아르산 칼슘 등을 들 수 있다. 이들 중에서도, 리튬 화합물이 바람직하다. 중합 개시제의 합계의 사용량은, 중합에 사용하는 모노머 100g에 대하여, 0.2∼20mmol로 하는 것이 바람직하다. 또한, 중합 개시제는, 1종을 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.As a polymerization initiator, an alkali metal compound or an alkaline earth metal compound can be used. Specific examples thereof include alkyl lithium such as methyl lithium, ethyl lithium, n-propyl lithium, n-butyl lithium, sec-butyl lithium, and tert-butyl lithium, 1,4-dilithiobutane, phenyl lithium, and steel. Benlithium, naphthylithium, 1,3-bis(1-lithio-1,3-dimethylpentyl)benzene, 1,3-phenylenebis(3-methyl-1-phenylpentylidene)dilithium, 3 -(dimethylamino)propyl lithium, naphthyl sodium, naphthyl potassium, di-n-butyl magnesium, di-n-hexyl magnesium, ethoxy potassium, calcium stearate, etc. Among these, lithium compounds are preferable. The total amount of polymerization initiator used is preferably 0.2 to 20 mmol per 100 g of monomer used for polymerization. In addition, the polymerization initiator can be used individually or in combination of two or more types.
또한, 중합 반응은, 알칼리 금속 화합물 또는 알칼리 토금속 화합물과, 실리카와 상호 작용하는 관능기를 갖는 화합물을 혼합하여 얻어지는 화합물(이하, 「변성 개시제」라고도 함)의 존재하에서 행해도 좋다. 변성 개시제의 존재하에서 중합을 행함으로써, (A) 공액 디엔계 중합체의 중합 개시 말단에, 실리카와 상호 작용하는 관능기를 도입할 수 있다. 또한, 본 명세서에 있어서 「상호 작용」이란, 분자 간에서 공유 결합을 형성하거나, 또는 공유 결합보다도 약한 분자간 력(예를 들면, 이온-쌍극자 상호 작용, 쌍극자-쌍극자 상호 작용, 수소 결합, 반데르발스력 등과 같은 분자 간에 작용하는 전자기학적인 힘)을 형성하는 것을 의미한다. 「실리카와 상호 작용하는 관능기」는, 질소 원자, 황 원자, 인 원자 및 산소 원자로 이루어지는 군으로부터 선택되는 적어도 1종을 갖는 것이 바람직하다.Additionally, the polymerization reaction may be performed in the presence of a compound obtained by mixing an alkali metal compound or an alkaline earth metal compound and a compound having a functional group that interacts with silica (hereinafter also referred to as a “modification initiator”). By performing polymerization in the presence of a modification initiator, a functional group that interacts with silica can be introduced into the polymerization start terminal of the (A) conjugated diene polymer. In addition, in this specification, “interaction” means forming a covalent bond between molecules, or an intermolecular force that is weaker than a covalent bond (e.g., ion-dipole interaction, dipole-dipole interaction, hydrogen bond, van der It means forming electromagnetic forces that act between molecules, such as Bals force. The “functional group that interacts with silica” preferably has at least one selected from the group consisting of a nitrogen atom, a sulfur atom, a phosphorus atom, and an oxygen atom.
변성 개시제로서는, 알킬리튬 등의 리튬 화합물과, 제2급 아민 화합물 등의 질소 함유 화합물과의 반응 생성물인 것이 바람직하다. 당해 질소 함유 화합물의 구체예로서는, 예를 들면 디메틸아민, 디에틸아민, 디프로필아민, 디부틸아민, 도데카메틸렌이민, N,N'-디메틸-N'-트리메틸실릴-1,6-디아미노헥산, 피페리딘, 피롤리딘, 헥사메틸렌이민, 헵타메틸렌이민, 디사이클로헥실아민, N-메틸벤질아민, 디-(2-에틸헥실)아민, 디알릴아민, 모르폴린, N-(트리메틸실릴)피페라진, N-(tert-부틸디메틸실릴)피페라진, 1,3-디트리메틸실릴-1,3,5-트리아지난 등을 들 수 있다. 또한, 변성 개시제의 존재하에서 중합을 행하는 경우, 알칼리 금속 화합물 또는 알칼리 토금속 화합물과, 실리카와 상호 작용하는 관능기를 갖는 화합물을 미리 혼합함으로써 변성 개시제를 조제하고, 그 조제한 변성 개시제를 중합계 중에 첨가하여 중합을 행해도 좋다. 혹은, 중합계 중에, 알칼리 금속 화합물 또는 알칼리 토금속 화합물과, 실리카와 상호 작용하는 관능기를 갖는 화합물을 첨가하고, 중합계 중에서 양자를 혼합함으로써 변성 개시제를 조제하여 중합을 행해도 좋다. 또는, 질소 함유의 알킬리튬 화합물을 사용할 수도 있다. 질소 함유의 알킬리튬 화합물의 구체예로서는, 3-디메틸아미노프로필리튬과 이소프렌과의 반응물 등을 사용할 수 있다.The modification initiator is preferably a reaction product between a lithium compound such as alkyl lithium and a nitrogen-containing compound such as a secondary amine compound. Specific examples of the nitrogen-containing compound include dimethylamine, diethylamine, dipropylamine, dibutylamine, dodecamethyleneimine, N,N'-dimethyl-N'-trimethylsilyl-1,6-diamino. Hexane, piperidine, pyrrolidine, hexamethylene imine, heptamethylene imine, dicyclohexylamine, N-methylbenzylamine, di-(2-ethylhexyl)amine, diallylamine, morpholine, N-(trimethyl Silyl)piperazine, N-(tert-butyldimethylsilyl)piperazine, and 1,3-ditrimethylsilyl-1,3,5-triazine. In addition, when polymerization is carried out in the presence of a modification initiator, a modification initiator is prepared by pre-mixing an alkali metal compound or an alkaline earth metal compound and a compound having a functional group that interacts with silica, and the prepared modification initiator is added to the polymerization system. Polymerization may be performed. Alternatively, polymerization may be performed by adding an alkali metal compound or an alkaline earth metal compound and a compound having a functional group that interacts with silica to the polymerization system, and mixing the two in the polymerization system to prepare a modification initiator. Alternatively, a nitrogen-containing alkyl lithium compound may be used. As a specific example of the nitrogen-containing alkyl lithium compound, a reaction product of 3-dimethylaminopropyl lithium and isoprene can be used.
랜더마이저는, 중합체 중에 있어서의 비닐 결합(1,2-결합 및 3,4-결합)의 함유율을 나타내는 비닐 결합 함량의 조정 등을 목적으로 하여 이용할 수 있다. 랜더마이저의 예로서는, 디메톡시벤젠, 테트라하이드로푸란, 디메톡시에탄, 디에틸렌글리콜디부틸에테르, 디에틸렌글리콜디메틸에테르, 2,2-디(테트라하이드로푸릴)프로판, 2-(2-에톡시에톡시)-2-메틸프로판, 트리에틸아민, 피리딘, N-메틸모르폴린, 테트라메틸에틸렌디아민 등을 들 수 있다. 이들은, 1종을 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The randomizer can be used for the purpose of adjusting the vinyl bond content, which represents the content of vinyl bonds (1,2-bond and 3,4-bond) in the polymer. Examples of randomizers include dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-di(tetrahydrofuryl)propane, and 2-(2-ethoxyethyl ether). Toxi)-2-methylpropane, triethylamine, pyridine, N-methylmorpholine, tetramethylethylenediamine, etc. are mentioned. These can be used individually or in combination of two or more types.
중합에 사용하는 유기 용매로서는, 반응에 불활성인 유기 용매이면 좋고, 예를 들면 지방족 탄화수소, 지환식 탄화수소, 방향족 탄화수소 등을 이용할 수 있다. 그 중에서도, 탄소수 3∼8의 탄화수소가 바람직하고, 그의 구체적인 예로서는, 예를 들면 프로판, n-부탄, 이소부탄, n-펜탄, 이소펜탄, n-헥산, 사이클로헥산, 프로펜, 1-부텐, 이소부텐, 트랜스-2-부텐, 시스-2-부텐, 1-펜틴, 2-펜틴, 1-헥센, 2-헥센, 벤젠, 톨루엔, 자일렌, 에틸벤젠, 헵탄, 사이클로펜탄, 메틸사이클로펜탄, 메틸사이클로헥산, 1-펜텐, 2-펜텐, 사이클로헥센 등을 들 수 있다. 또한, 유기 용매는, 1종을 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The organic solvent used for polymerization may be any organic solvent that is inert to the reaction. For example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, etc. can be used. Among them, hydrocarbons having 3 to 8 carbon atoms are preferable, and specific examples thereof include propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, Isobutene, trans-2-butene, cis-2-butene, 1-pentyne, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene, heptane, cyclopentane, methylcyclopentane, Examples include methylcyclohexane, 1-pentene, 2-pentene, and cyclohexene. In addition, organic solvents can be used individually or in combination of two or more types.
용액 중합을 이용하는 경우, 반응 용매 중의 모노머 농도는, 생산성과 중합 컨트롤의 용이성의 밸런스를 유지하는 관점에서, 5∼50질량％인 것이 바람직하고, 10∼30질량％인 것이 보다 바람직하다. 중합 반응의 온도는, -20℃∼150℃인 것이 바람직하고, 0℃∼120℃인 것이 보다 바람직하고, 20℃∼100℃인 것이 특히 바람직하다. 또한, 중합 반응은, 단량체를 실질적으로 액상으로 유지하는데에 충분한 압력의 하에서 행하는 것이 바람직하다. 이러한 압력은, 중합 반응에 대하여 불활성인 가스에 의해, 반응기 내를 가압하는 등의 방법에 의해 얻을 수 있다. 이러한 중합 반응에 의해, 활성 말단을 갖는 공액 디엔계 중합체를 얻을 수 있다.When using solution polymerization, the monomer concentration in the reaction solvent is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass, from the viewpoint of maintaining a balance between productivity and ease of polymerization control. The temperature of the polymerization reaction is preferably -20°C to 150°C, more preferably 0°C to 120°C, and particularly preferably 20°C to 100°C. In addition, the polymerization reaction is preferably performed under sufficient pressure to substantially maintain the monomer in a liquid state. This pressure can be obtained by a method such as pressurizing the inside of the reactor with a gas that is inert to the polymerization reaction. Through this polymerization reaction, a conjugated diene-based polymer having an active end can be obtained.
활성 말단을 갖는 공액 디엔계 중합체에 대해, 공액 디엔 화합물에 유래하는 구조 단위에 있어서의 비닐 결합 함량은, 30∼65몰％인 것이 바람직하고, 33∼62몰％인 것이 보다 바람직하고, 35∼60몰％인 것이 특히 바람직하다. 비닐 결합 함량이 30몰％ 미만이면, 그립 특성이 지나치게 낮아지는 경향이 있고, 65몰％를 초과하면, 얻어지는 가교 중합체의 내마모성이 악화되기 쉬워지는 경향이 있다. 또한, 본 명세서에 있어서 「비닐 결합 함량」은, 공액 디엔계 중합체 중에 있어서, 공액 디엔 화합물에 유래하는 전체 구조 단위에 대한, 비닐 결합을 갖는 구조 단위의 함유 비율을 나타내는 값이고, 1H-NMR에 의해 측정한 값이다.For a conjugated diene polymer having an active terminal, the vinyl bond content in the structural unit derived from the conjugated diene compound is preferably 30 to 65 mol%, more preferably 33 to 62 mol%, and 35 to 65 mol%. It is especially preferable that it is 60 mol%. If the vinyl bond content is less than 30 mol%, the grip properties tend to be excessively low, and if it exceeds 65 mol%, the wear resistance of the resulting crosslinked polymer tends to deteriorate. In addition, in this specification, “vinyl bond content” is a value representing the content ratio of structural units having a vinyl bond with respect to all structural units derived from the conjugated diene compound in the conjugated diene polymer, and 1 H-NMR This is the value measured by .
＜변성 공정＞ ＜denaturation process＞
이어서, 상기 중합 반응에 의해 얻어진 공액 디엔계 중합체에 대해, 당해 중합체의 활성 말단과, 하기 일반식 (1)∼(4)로 나타나는 화합물(특정 변성제)을 반응시킨다. 이러한 공정을 거침으로써, 특정 변성제로 말단 변성된 (A) 공액 디엔계 중합체를 얻을 수 있다. 이러한 특정 변성제로 말단 변성된 (A) 공액 디엔계 중합체는, 말단 변성 부위에 있어서 (B) 유기 단섬유와의 상호 작용이 강해지기 때문에, 기계적 강도 및 인장 강도가 향상되고, 또한 저(低)변형에서의 강성이 높아지기 때문에 조종 안정성도 향상된다.Next, the conjugated diene polymer obtained by the above polymerization reaction is reacted with the active terminal of the polymer and a compound (specific modifier) represented by the following general formulas (1) to (4). By going through this process, it is possible to obtain the (A) conjugated diene-based polymer terminally modified with a specific modifier. The conjugated diene polymer (A), terminally modified with such a specific modifier, has a stronger interaction with the organic short fibers (B) at the terminal modification site, so its mechanical strength and tensile strength are improved, and it also has a low Because the rigidity in deformation increases, steering stability also improves.
(식 (1) 중, A1은, 이미노기, 아미드기, (티오)카보닐기, (티오)카보닐옥시기, 술피드 혹은 폴리술피드로 L1과 결합한 1가의 기이거나, 또는, 보호된 1급 아미노기, 보호된 2급 아미노기, 3급 아미노기, 니트릴기, 피리딜기, (티오)에폭시기, (티오)이소시아네이트기, (티오)포르밀기, (티오)카본산 에스테르, (티오)카본산 에스테르의 금속염, 카본산 할로겐 화합물 혹은 이미다졸릴기를 나타내고, L1은 탄소수 1∼20의 하이드로카빌렌기를 나타내고, R1 및 R2는 각각 독립적으로 탄소수 1∼4의 하이드로카빌기를 나타내고, n1은 0 또는 1이다.)(In formula (1), A 1 is a monovalent group bonded to L 1 with an imino group, amide group, (thio)carbonyl group, (thio)carbonyloxy group, sulfide or polysulfide, or a protected Primary amino group, protected secondary amino group, tertiary amino group, nitrile group, pyridyl group, (thio)epoxy group, (thio)isocyanate group, (thio)formyl group, (thio)carboxylic acid ester, (thio)carboxylic acid ester represents a metal salt, a carboxylic acid halogen compound or an imidazolyl group, L 1 represents a hydrocarbylene group having 1 to 20 carbon atoms, R 1 and R 2 each independently represent a hydrocarbyl group having 1 to 4 carbon atoms, and n1 represents a hydrocarbylene group having 1 to 4 carbon atoms. It is 0 or 1.)
상기식 (1)에 있어서, L1의 탄소수 1∼20의 하이드로카빌렌기로서는, 탄소수 1∼20의 직쇄상 또는 분기상의 알킬렌기, 탄소수 3∼20의 사이클로알킬렌기, 탄소수 6∼20의 아릴렌기 등을 들 수 있다. 상기식 (1)에 있어서, R1 및 R2의 탄소수 1∼4의 하이드로카빌기로서는, 탄소수 1∼4의 직쇄상 또는 분기상의 알킬기, 탄소수 3∼4의 사이클로알킬기를 들 수 있다. 또한, 본 명세서에 있어서, (티오)카보닐기는 카보닐기 및 티오카보닐기를 나타내고, (티오)카보닐옥시기는 카보닐옥시기 및 티오카보닐옥시기를 나타내고, (티오)에폭시기는 에폭시기 및 티오에폭시기를 나타내고, (티오)이소시아네이트기는 이소시아네이트기 및 티오이소시아네이트기를 나타내고, (티오)포르밀기는 포르밀기 및 티오포르밀기를 나타내고, (티오)카본산 에스테르는 카본산 에스테르 및 티오카본산 에스테르를 나타낸다.In the above formula (1), the hydrocarbylene group of 1 to 20 carbon atoms for L 1 is a linear or branched alkylene group of 1 to 20 carbon atoms, a cycloalkylene group of 3 to 20 carbon atoms, and an arylene group of 6 to 20 carbon atoms. etc. can be mentioned. In the above formula (1), examples of the hydrocarbyl group having 1 to 4 carbon atoms for R 1 and R 2 include a linear or branched alkyl group having 1 to 4 carbon atoms, and a cycloalkyl group having 3 to 4 carbon atoms. In addition, in this specification, the (thio)carbonyl group represents a carbonyl group and a thiocarbonyl group, the (thio)carbonyloxy group represents a carbonyloxy group and a thiocarbonyloxy group, and the (thio)epoxy group represents an epoxy group and a thioepoxy group. , (thio)isocyanate group represents isocyanate group and thioisocyanate group, (thio)formyl group represents formyl group and thioformyl group, and (thio)carboxylic acid ester represents carboxylic acid ester and thiocarboxylic acid ester.
상기 일반식 (1)로 나타나는 화합물의 구체예로서는, N,N-디메틸아미노프로필트리에톡시실란, N,N-비스(트리메틸실릴)아미노프로필메틸디에톡시실란 등을 들 수 있다.Specific examples of the compound represented by the general formula (1) include N,N-dimethylaminopropyltriethoxysilane, N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane, and the like.
(식 (2) 중, A2는, 이미노기, 아미드기, (티오)카보닐기, (티오)카보닐옥시기, 술피드 혹은 폴리술피드로 L2와 결합한 1가의 기이거나, 또는, 보호된 1급 아미노기, 보호된 2급 아미노기, 3급 아미노기, 니트릴기, 피리딜기, (티오)에폭시기, (티오)이소시아네이트기, (티오)포르밀기, (티오)카본산 에스테르, (티오)카본산 에스테르의 금속염, 카본산 할로겐 화합물, 이미다졸릴기 혹은 하기식 (2a)로 나타나는 기를 나타내고, L2 및 L3은 각각 독립적으로 단결합 혹은 탄소수 1∼20의 하이드로카빌렌기를 나타내고, R3 및 R4는 각각 독립적으로 탄소수 1∼4의 하이드로카빌기를 나타내고, n2는 0∼3이고, m1은 0 또는 1이다.)(In formula (2), A 2 is a monovalent group bonded to L 2 with an imino group, amide group, (thio)carbonyl group, (thio)carbonyloxy group, sulfide or polysulfide, or a protected group. Primary amino group, protected secondary amino group, tertiary amino group, nitrile group, pyridyl group, (thio)epoxy group, (thio)isocyanate group, (thio)formyl group, (thio)carboxylic acid ester, (thio)carboxylic acid ester represents a metal salt, a carboxylic acid halogen compound, an imidazolyl group, or a group represented by the formula (2a) below, L 2 and L 3 each independently represent a single bond or a hydrocarbylene group having 1 to 20 carbon atoms, R 3 and R 4 each independently represents a hydrocarbyl group having 1 to 4 carbon atoms, n2 is 0 to 3, and m1 is 0 or 1.)
(식 (2a) 중, L3, R3, R4 및 n2는 식 (2)와 마찬가지이고, *는 L2와 결합하는 부위를 나타낸다.)(In formula (2a), L 3 , R 3 , R 4 and n2 are the same as in formula (2), and * represents the site that binds to L 2. )
상기식 (2)에 있어서, L2 및 L3의 탄소수 1∼20의 하이드로카빌렌기로서는, 탄소수 1∼20의 직쇄상 또는 분기상의 알킬렌기, 탄소수 3∼20의 사이클로알킬렌기, 탄소수 6∼20의 아릴렌기 등을 들 수 있다. 상기식 (2)에 있어서, R3 및 R4의 탄소수 1∼4의 하이드로카빌기로서는, 탄소수 1∼4의 직쇄상 또는 분기상의 알킬기, 탄소수 3∼4의 사이클로알킬기를 들 수 있다.In the above formula (2), the hydrocarbylene group having 1 to 20 carbon atoms for L 2 and L 3 is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, and a hydrocarbylene group having 6 to 20 carbon atoms. arylene group, etc. are mentioned. In the above formula (2), examples of the hydrocarbyl group having 1 to 4 carbon atoms for R 3 and R 4 include a linear or branched alkyl group having 1 to 4 carbon atoms, and a cycloalkyl group having 3 to 4 carbon atoms.
상기 일반식 (2)로 나타나는 화합물의 구체예로서는, N,N-비스(트리에톡시실릴프로필)아미노프로필-1-이미다졸, N,N-비스(트리메틸실릴)아미노프로필메틸디에틸실란, N,N,N-트리스(트리에톡시실릴프로필)아민 등을 들 수 있다.Specific examples of the compound represented by the general formula (2) include N,N-bis(triethoxysilylpropyl)aminopropyl-1-imidazole, N,N-bis(trimethylsilyl)aminopropylmethyldiethylsilane, N ,N,N-tris(triethoxysilylpropyl)amine, etc.
(식 (3) 중, A3은 각각 독립적으로, 이미노기, 아미드기, (티오)카보닐기 또는 (티오)카보닐옥시기를 나타내고, Z는 질소 원자를 포함하거나 또는 포함하지 않는 탄소수 1∼20의 t가의 기를 나타내고, L4는 단결합 또는 탄소수 1∼20의 하이드로카빌렌기를 나타내고, L5는 탄소수 1∼20의 하이드로카빌렌기를 나타내고, R5 및 R6은 각각 독립적으로 탄소수 1∼4의 하이드로카빌기를 나타내고, n3은 0 또는 1이고, t는 2 또는 3이다.)(In formula (3), A 3 each independently represents an imino group, an amide group, a (thio) carbonyl group, or a (thio) carbonyloxy group, and Z has 1 to 20 carbon atoms with or without a nitrogen atom. represents a t-valent group, L 4 represents a single bond or a hydrocarbylene group with 1 to 20 carbon atoms, L 5 represents a hydrocarbylene group with 1 to 20 carbon atoms, and R 5 and R 6 each independently represent a hydrocarbylene group with 1 to 4 carbon atoms. represents a hydrocarbyl group, n3 is 0 or 1, and t is 2 or 3.)
상기식 (3)에 있어서, Z는, 질소 원자를 포함해도 좋은 탄소수 1∼20의 2가 혹은 3가의 기이지만, 질소 원자를 포함하고 있는 것이 바람직하다. 상기식 (3)에 있어서, L4의 탄소수 1∼20의 하이드로카빌렌기 및 L5의 탄소수 1∼20의 하이드로카빌렌기로서는, 탄소수 1∼20의 직쇄상 또는 분기상의 알킬렌기, 탄소수 3∼20의 사이클로알킬렌기, 탄소수 6∼20의 아릴렌기 등을 들 수 있다. 상기식 (3)에 있어서, R5 및 R6의 탄소수 1∼4의 하이드로카빌기로서는, 탄소수 1∼4의 직쇄상 또는 분기상의 알킬기, 탄소수 3∼4의 사이클로알킬기를 들 수 있다.In the above formula (3), Z is a divalent or trivalent group of 1 to 20 carbon atoms which may contain a nitrogen atom, but preferably contains a nitrogen atom. In the above formula (3), the hydrocarbylene group with 1 to 20 carbon atoms for L 4 and the hydrocarbylene group with 1 to 20 carbon atoms for L 5 are linear or branched alkylene groups with 1 to 20 carbon atoms, and 3 to 20 carbon atoms. cycloalkylene group, arylene group having 6 to 20 carbon atoms, etc. In the above formula (3), examples of the hydrocarbyl group having 1 to 4 carbon atoms for R 5 and R 6 include a linear or branched alkyl group having 1 to 4 carbon atoms, and a cycloalkyl group having 3 to 4 carbon atoms.
상기 일반식 (3)으로 나타나는 화합물의 구체예로서는, 하기식 (M-1)∼(M-4)로 나타나는 화합물 등을 들 수 있다.Specific examples of the compound represented by the general formula (3) include compounds represented by the following formulas (M-1) to (M-4).
상기식 (M-1) 중, R11은 수소 원자 또는 탄소수 1∼20의 알킬기를 나타내고, n5는 1∼10의 정수를 나타낸다.In the formula (M-1), R 11 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and n5 represents an integer from 1 to 10.
(식 (4) 중, R7 및 R8은, 각각 독립적으로 탄소수 1∼20의 하이드로카빌기이고, R9는, 탄소수 1∼20의 하이드로카빌기, 알킬기가 갖는 수소 원자 및 -CH2-의 적어도 1개가 규소, 질소, 인, 산소 및 황으로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 포함하는 기로 치환된 탄소수 1∼20의 치환 알킬기이거나, 또는 질소, 인, 산소 및 황으로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 포함하는 탄소수 6∼20의 방향족기를 나타내고, R10은, 탄소수 1∼20의 알칸디일기를 나타낸다. n4는 1 또는 2이다.)(In formula (4), R 7 and R 8 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, and R 9 is a hydrocarbyl group having 1 to 20 carbon atoms, the hydrogen atom of the alkyl group, and -CH 2 - at least one of which is a substituted alkyl group having 1 to 20 carbon atoms substituted with a group containing at least one element selected from the group consisting of silicon, nitrogen, phosphorus, oxygen and sulfur, or a group consisting of nitrogen, phosphorus, oxygen and sulfur represents an aromatic group with 6 to 20 carbon atoms containing at least one element selected from the group, and R 10 represents an alkanediyl group with 1 to 20 carbon atoms. n4 is 1 or 2.
상기식 (4)에 있어서, R7 및 R8의 탄소수 1∼20의 하이드로카빌기로서는, 탄소수 1∼20의 직쇄상 또는 분기상의 알킬기, 탄소수 3∼20의 사이클로알킬기, 탄소수 6∼20의 아릴기 등을 들 수 있다.In the above formula (4), the hydrocarbyl group of 1 to 20 carbon atoms for R 7 and R 8 is a linear or branched alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, and aryl group of 6 to 20 carbon atoms. etc. can be mentioned.
상기 일반식 (4)로 나타나는 화합물의 구체예로서는, N-페닐-2,2-디메톡시-1-아자-2-실라사이클로펜탄, N-(3-트리에톡시실릴프로필)-2,2-디메톡시-1-아자-2-실라사이클로펜탄 등을 들 수 있다.Specific examples of the compound represented by the general formula (4) include N-phenyl-2,2-dimethoxy-1-aza-2-silacyclopentane, N-(3-triethoxysilylpropyl)-2,2- Dimethoxy-1-aza-2-silacyclopentane, etc. can be mentioned.
또한, 활성 말단을 갖는 공액 디엔계 중합체의 변성 반응 시에 있어서는, 특정 변성제를 단독으로 사용해도 좋지만, 특정 변성제와 함께 특정 변성제 이외의 변성제(이하, 「그 외의 변성제」라고도 함)를 사용해도 좋다. 그 외의 변성제는, (B) 유기 단섬유나 무기 충전제와 상호 작용하는 관능기를 갖고, 또한 중합체의 활성 말단과 반응할 수 있는 화합물이면 특별히 한정되지 않는다.In addition, in the case of a modification reaction of a conjugated diene polymer having an active terminal, the specific modifier may be used alone, but a modifier other than the specific modifier (hereinafter also referred to as “other modifier”) may be used together with the specific modifier. . The other modifier is not particularly limited as long as it is a compound (B) that has a functional group that interacts with the organic short fibers or inorganic filler and can react with the active terminal of the polymer.
상기의 변성 반응은, 예를 들면 용액 반응으로서 행할 수 있다. 이 용액 반응은, 중합 반응의 종료 후의 미반응 모노머를 포함하는 용액을 이용하여 행해도 좋고, 당해 용액에 포함되는 공액 디엔계 중합체를 단리하여, 사이클로헥산 등의 적당한 용매에 용해한 후에 행해도 좋다. 또한, 변성 반응은, 회분식 및 연속식의 어느 것을 이용하여 행해도 좋다. 이 때, 변성제의 첨가 방법은 특별히 제한되지 않고, 일괄하여 첨가하는 방법, 분할하여 첨가하는 방법, 연속적으로 첨가하는 방법 등을 들 수 있다.The above denaturation reaction can be performed, for example, as a solution reaction. This solution reaction may be performed using a solution containing unreacted monomers after completion of the polymerization reaction, or may be performed after the conjugated diene polymer contained in the solution is isolated and dissolved in a suitable solvent such as cyclohexane. Additionally, the denaturation reaction may be performed using either a batch method or a continuous method. At this time, the method of adding the denaturant is not particularly limited, and includes a method of adding it all at once, a method of adding it in installments, a method of adding it continuously, etc.
특정 변성제의 사용 비율(2종 이상 사용하는 경우에는 그의 합계량)은, 중합 개시제가 갖는 중합 반응에 관여하는 금속 원자 1몰에 대하여, 0.2몰 이상으로 하는 것이 바람직하고, 0.4몰 이상으로 하는 것이 보다 바람직하다. 0.2몰 이상으로 함으로써, 특정 변성제에 의한 중합체 말단의 변성 반응을 충분히 진행시킬 수 있어, 말단 변성 부위에 있어서의 (B) 유기 단섬유와의 상호 작용을 충분히 강하게 할 수 있다. 또한, 변성 반응 후에 있어서의 용액 중의 미반응물을 적게 하는 점에서, 특정 변성제의 사용 비율의 상한값은, 중합 개시제가 갖는 중합 반응에 관여하는 금속 원자 1몰에 대하여, 1.5몰 미만으로 하는 것이 바람직하고, 1.2몰 미만으로 하는 것이 보다 바람직하다.The proportion of specific modifiers used (total amount when two or more types are used) is preferably 0.2 mol or more, and more preferably 0.4 mol or more, per 1 mole of metal atoms involved in the polymerization reaction of the polymerization initiator. desirable. By setting it to 0.2 mol or more, the modification reaction of the polymer terminals by the specific modifier can sufficiently proceed, and the interaction with the (B) organic short fibers at the terminal modification sites can be sufficiently strengthened. In addition, in order to reduce the amount of unreacted substances in the solution after the modification reaction, the upper limit of the usage ratio of the specific modifying agent is preferably less than 1.5 moles per 1 mole of metal atoms involved in the polymerization reaction contained in the polymerization initiator. , it is more preferable to set it to less than 1.2 mol.
또한, 변성 반응 시에 있어서, 특정 변성제와 그 외의 변성제를 병용하는 경우, 그 외의 변성제의 사용 비율은, 공액 디엔계 중합체와 특정 변성제와의 반응을 충분히 진행시키는 관점에서, 특정 변성제와 그 외의 변성제와의 합계의 사용 비율에 대하여, 30몰％ 이하로 하는 것이 바람직하고, 20몰％ 이하로 하는 것이 보다 바람직하고, 10몰％ 이하로 하는 것이 특히 바람직하다.In addition, when using a specific denaturant and another denaturant in combination during the denaturation reaction, the ratio of the other denaturant used is different from the specific denaturant and the other denaturant from the viewpoint of sufficiently advancing the reaction between the conjugated diene polymer and the specific denaturant. With respect to the total usage ratio, it is preferably 30 mol% or less, more preferably 20 mol% or less, and especially preferably 10 mol% or less.
변성 반응의 온도는, 통상, 중합 반응의 온도와 동일하고, －20℃∼150℃로 하는 것이 바람직하고, 0℃∼120℃로 하는 것이 보다 바람직하고, 20℃∼100℃로 하는 것이 특히 바람직하다. 변성 반응의 온도가 낮으면, 변성 후의 공액 디엔계 중합체의 점도가 상승하는 경향이 있다. 한편, 변성 반응의 온도가 높으면, 중합체의 활성 말단이 실활하기 쉬워진다. 변성 반응의 반응 시간은, 바람직하게는 1분∼5시간이고, 보다 바람직하게는 2분∼1시간이다.The temperature of the denaturation reaction is usually the same as the temperature of the polymerization reaction, and is preferably -20°C to 150°C, more preferably 0°C to 120°C, and especially preferably 20°C to 100°C. do. When the temperature of the modification reaction is low, the viscosity of the conjugated diene polymer after modification tends to increase. On the other hand, when the temperature of the modification reaction is high, the active terminals of the polymer become easily deactivated. The reaction time for the modification reaction is preferably 1 minute to 5 hours, and more preferably 2 minutes to 1 hour.
반응 용액에 포함되는 (A) 공액 디엔계 중합체를 단리하기 위해서는, 예를 들면 스팀 스트립핑 등의 공지의 탈용매 방법 및 열처리 등의 건조의 조작에 의해 행할 수 있다. 얻어진 (A) 공액 디엔계 중합체는, 필요에 따라서 신전유 등을 첨가함으로써 무니 점도를 조정해도 좋다. 이 처리에 의해, 가공성을 양호하게 할 수 있다. 신전유로서는, 예를 들면 아로마유, 나프텐유, 파라핀유 등을 들 수 있다. 신전유의 배합량은, 중합에 이용하는 모노머 등에 따라서 적절히 설정하면 좋지만, 예를 들면 공액 디엔계 중합체 100질량부에 대하여, 10∼50질량부이다.In order to isolate the (A) conjugated diene polymer contained in the reaction solution, for example, known solvent removal methods such as steam stripping and drying operations such as heat treatment can be used. The obtained conjugated diene polymer (A) may have its Mooney viscosity adjusted by adding extender oil or the like as needed. This treatment can improve processability. Examples of extender oils include aroma oil, naphthene oil, and paraffin oil. The compounding amount of the extender oil may be set appropriately depending on the monomer used for polymerization, etc., but is, for example, 10 to 50 parts by mass per 100 parts by mass of the conjugated diene polymer.
이와 같이 하여, (A) 공액 디엔계 중합체를 얻을 수 있다. (A) 공액 디엔계 중합체에 의하면, (B) 유기 단섬유나 무기 충전제의 분산성을 향상시킬 수 있다. 이에 따라, 자동차 타이어 등의 용도에 있어서 요구되는 저로스 성능 및 내마모성을 동시에 개선할 수 있는 가교 중합체를 얻을 수 있다. 또한, (A) 공액 디엔계 중합체에 의하면, 가공성이 양호한 중합체 조성물을 얻을 수 있다.In this way, (A) conjugated diene polymer can be obtained. (A) According to the conjugated diene polymer, the dispersibility of (B) organic short fibers and inorganic fillers can be improved. Accordingly, it is possible to obtain a crosslinked polymer that can simultaneously improve low loss performance and wear resistance required for applications such as automobile tires. Moreover, according to (A) conjugated diene polymer, a polymer composition with good processability can be obtained.
(A) 공액 디엔계 중합체는, 당해 중합체의 적어도 편말단에, 상기 일반식 (1)∼(4)의 어느 것의 화합물에 유래하는 구조를 갖는 것이 바람직하다. (A) 공액 디엔계 중합체가 이러한 구조를 가짐으로써, 예를 들면 타이어 용도에 적용한 경우에, 실리카 등의 무기 충전제나 (B) 유기 단섬유의 분산성이 보다 개선되고, 저로스성 및 내마모성에 있어서, 보다 높은 개선 효과를 발휘하는 점에서 바람직하다.(A) The conjugated diene polymer preferably has a structure derived from a compound of any of the above general formulas (1) to (4) at least at one end of the polymer. (A) When the conjugated diene polymer has this structure, for example, when applied to tires, the dispersibility of inorganic fillers such as silica and (B) organic short fibers is further improved, and low loss and wear resistance are achieved. Therefore, it is preferable in that it exhibits a higher improvement effect.
(A) 공액 디엔계 중합체의 겔 투과 크로마토그래피(GPC)로 측정한 폴리스티렌 환산의 중량 평균 분자량(Mw)은, 바람직하게는 10,000∼2,0000,000이다. Mw가 10,000보다도 작으면, 본 실시 형태에 따른 중합체 조성물의 가교 중합체에 있어서, 저로스성 및 내마모성이 저하하기 쉬운 경향이 있고, 2,000,000보다도 크면, 중합체 조성물의 가공성이 저하하기 쉬운 경향이 있다. 얻어지는 (A) 공액 디엔계 중합체의 중량 평균 분자량(Mw)은, 보다 바람직하게는 30,000∼1,500,000이고, 더욱 바람직하게는 50,000∼1,000,000이다.(A) The weight average molecular weight (Mw) of the conjugated diene polymer measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 10,000 to 20,000,000. If Mw is less than 10,000, the low-loss property and wear resistance tend to decrease in the crosslinked polymer of the polymer composition according to the present embodiment, and if it is greater than 2,000,000, the processability of the polymer composition tends to decrease. The weight average molecular weight (Mw) of the obtained conjugated diene polymer (A) is more preferably 30,000 to 1,500,000, and even more preferably 50,000 to 1,000,000.
(A) 공액 디엔계 중합체의 분자량 분포, 즉 중량 평균 분자량(Mw)과 수 평균 분자량(Mn)과의 비(Mw/Mn)는, 바람직하게는 1.5∼3.0이고, 보다 바람직하게는 1.5∼2.5이고, 특히 바람직하게는 1.5∼2.2이다. (A) 공액 디엔계 중합체의 분자량 분포가 상기 범위에 있으면, 보다 우수한 저로스성, 내마모성, 웨트 그립 성능 및 기계적 특성이 얻어지기 쉽다.(A) The molecular weight distribution of the conjugated diene polymer, that is, the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn), is preferably 1.5 to 3.0, more preferably 1.5 to 2.5. and is particularly preferably 1.5 to 2.2. (A) If the molecular weight distribution of the conjugated diene polymer is within the above range, better low loss properties, wear resistance, wet grip performance, and mechanical properties can easily be obtained.
1.2. (B) 유기 단섬유 1.2. (B) Organic short fibers
본 실시 형태에 따른 중합체 조성물은, (B) 유기 단섬유를 함유한다. (B) 유기 단섬유는, 유기 폴리머로 이루어지는 단섬유이다.The polymer composition according to this embodiment contains (B) organic short fibers. (B) Organic short fibers are short fibers made of an organic polymer.
유기 폴리머로서는, 지방족 폴리아미드, 방향족 폴리아미드, 폴리에스테르, 폴리올레핀, 폴리비닐알코올, 셀룰로오스계 폴리머 등을 예시할 수 있다. 이들 유기 폴리머의 구체예로서는, 나일론 6, 나일론 66, 나일론 MXD6 등의 지방족 폴리아미드; 자일릴렌디아민과 아디프산과의 중축합체, 테트라메틸렌디아민과 테레프탈산과의 중축합체, 헥사메틸렌디아민과 테레프탈산과의 중축합체 등의 방향족 폴리아미드; 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트 등의 폴리에스테르; 신디오택틱-1,2-폴리부타디엔, 폴리에틸렌, 폴리프로필렌 등의 폴리올레핀; 비닐론 등의 폴리비닐알코올; 레이온 등의 셀룰로오스계 폴리머를 각각 들 수 있다. 이들 중에서도, 유기 폴리머는, 지방족 폴리아미드, 방향족 폴리아미드 및 셀룰로오스계 폴리머로 이루어지는 군으로부터 선택되는 적어도 1종인 것이 바람직하다.Examples of organic polymers include aliphatic polyamide, aromatic polyamide, polyester, polyolefin, polyvinyl alcohol, and cellulose polymer. Specific examples of these organic polymers include aliphatic polyamides such as nylon 6, nylon 66, and nylon MXD6; aromatic polyamides such as polycondensates of xylylenediamine and adipic acid, polycondensates of tetramethylenediamine and terephthalic acid, and polycondensates of hexamethylenediamine and terephthalic acid; Polyesters such as polyethylene terephthalate and polybutylene terephthalate; Polyolefins such as syndiotactic-1,2-polybutadiene, polyethylene, and polypropylene; polyvinyl alcohol such as vinylon; Cellulose-based polymers such as rayon can be mentioned. Among these, the organic polymer is preferably at least one selected from the group consisting of aliphatic polyamide, aromatic polyamide, and cellulose polymer.
본 실시 형태에 따른 중합체 조성물이 (A) 공액 디엔계 중합체 및 (B) 유기 단섬유를 함유함으로써, 저로스성 및 웨트 그립성이 우수할 뿐만 아니라, 우수한 기계적 강도, 인장 강도 및 조종 안정성을 나타내는 가교 중합체를 얻을 수 있다. 또한, (B) 유기 단섬유는, 이들 중의 1종이 단독으로 사용되어도 좋고, 2종 이상이 조합되어 사용되어도 좋다.Since the polymer composition according to the present embodiment contains (A) a conjugated diene polymer and (B) an organic short fiber, it not only has excellent low loss properties and wet grip properties, but also exhibits excellent mechanical strength, tensile strength, and handling stability. A crosslinked polymer can be obtained. In addition, (B) organic short fibers may be used individually, or two or more types may be used in combination.
(B) 유기 단섬유의 평균 길이는, 가공성에 의해 우수한 중합체 조성물을 얻을 수 있는 점에서, 20㎜ 이하인 것이 바람직하다. (B) 유기 단섬유의 평균 길이는, 보다 바람직하게는 15㎜ 이하, 더욱 바람직하게는 10㎜ 이하, 특히 바람직하게는 5㎜ 이하이다. 또한, (B) 유기 단섬유의 평균 길이는, 보다 고강도인 가교 중합체를 얻을 수 있는 점에서, 바람직하게는 0.01㎜ 이상, 보다 바람직하게는 0.1㎜ 이상, 특히 바람직하게는 0.2㎜ 이상이다.(B) The average length of the organic short fibers is preferably 20 mm or less because a polymer composition excellent in processability can be obtained. (B) The average length of the organic short fibers is more preferably 15 mm or less, further preferably 10 mm or less, and particularly preferably 5 mm or less. In addition, (B) the average length of the organic short fibers is preferably 0.01 mm or more, more preferably 0.1 mm or more, and particularly preferably 0.2 mm or more, since a crosslinked polymer with higher strength can be obtained.
(B) 유기 단섬유의 평균 지름은, 얻어지는 가교 중합체의 강도를 보다 높게 할 수 있는 점에서, 바람직하게는 0.05㎛ 이상, 보다 바람직하게는 0.1㎛ 이상, 더욱 바람직하게는 0.5㎛ 이상, 특히 바람직하게는 1㎛ 이상이다. 또한, (B) 유기 단섬유의 평균 지름은, 바람직하게는 50㎛ 이하, 보다 바람직하게는 30㎛ 이하, 특히 바람직하게는 20㎛ 이하이다.(B) The average diameter of the organic short fibers is preferably 0.05 ㎛ or more, more preferably 0.1 ㎛ or more, further preferably 0.5 ㎛ or more, especially preferably, because the strength of the obtained cross-linked polymer can be higher. Typically, it is 1㎛ or more. Furthermore, the average diameter of (B) the organic short fibers is preferably 50 μm or less, more preferably 30 μm or less, and particularly preferably 20 μm or less.
또한, (B) 유기 단섬유의 평균 길이는, 수 평균 섬유 길이로서 공지의 방법에 의해 측정할 수 있다. (B) 유기 단섬유의 평균 지름은, 수 평균 섬유 지름으로서 공지의 방법에 의해 측정할 수 있다. 예를 들면, 수 평균 섬유 길이 및 수 평균 섬유 지름은, 주사형 원자간력 현미경, 주사형 전자 현미경 또는 투과형 전자 현미경에 의해 촬영한 화상의 해석에 의해 측정할 수 있다.In addition, (B) the average length of the organic short fibers can be measured by a known method as the number average fiber length. (B) The average diameter of organic single fibers can be measured by a known method as the number average fiber diameter. For example, the number average fiber length and number average fiber diameter can be measured by analysis of images taken with a scanning atomic force microscope, scanning electron microscope, or transmission electron microscope.
(B) 유기 단섬유의 함유 비율의 하한은, 중합체 조성물 중에 포함되는 (A) 공액 디엔계 중합체 100질량부에 대하여, 바람직하게는 0.1질량부이고, 보다 바람직하게는 0.5질량부이고, 특히 바람직하게는 1질량부이다. (B) 유기 단섬유의 함유 비율의 하한값이 상기 값이면, 당해 중합체 조성물을 이용하여 얻어지는 가교 중합체에 있어서, (B) 유기 단섬유의 첨가에 의한 강도 및 저변형에서의 강성의 개선 효과를 충분히 높게 할 수 있어 적합하다. 한편, (B) 유기 단섬유의 함유 비율의 상한은, 중합체 조성물 중에 포함되는 (A) 공액 디엔계 중합체 100질량부에 대하여, 바람직하게는 100질량부이고, 보다 바람직하게는 50질량부이고, 보다 더 바람직하게는 20질량부이고, 특히 바람직하게는 20질량부 미만이다. (B) 유기 단섬유의 함유 비율의 상한값이 상기 값이면, 중합체 조성물의 가공성이 보다 양호해진다.(B) The lower limit of the content ratio of organic short fibers is preferably 0.1 part by mass, more preferably 0.5 part by mass, and especially preferred, with respect to 100 parts by mass of the (A) conjugated diene polymer contained in the polymer composition. It is 1 part by mass. (B) If the lower limit of the content ratio of the organic short fibers is the above value, in the crosslinked polymer obtained using the polymer composition, the effect of improving the strength and rigidity at low strain due to the addition of (B) the organic short fibers is sufficiently achieved. It is suitable because it can be set high. On the other hand, the upper limit of the content ratio of (B) organic short fibers is preferably 100 parts by mass, more preferably 50 parts by mass, based on 100 parts by mass of the conjugated diene polymer (A) contained in the polymer composition, More preferably, it is 20 parts by mass, and especially preferably, it is less than 20 parts by mass. (B) If the upper limit of the content ratio of organic short fibers is the above value, the processability of the polymer composition becomes better.
(B) 유기 단섬유를 함유하는 중합체 조성물을 제조할 때, (B) 유기 단섬유를 다른 배합 성분과 함께 배합하여 혼련해도 좋고, 혹은, (B) 유기 단섬유와 소량의 중합체 성분을 미리 혼련하여 중합체 성분과 (B) 유기 단섬유를 포함하는 마스터 배치를 제조하고, 그 제조한 마스터 배치와 다른 배합 성분을 혼련해도 좋다. 후자의 경우, 생산성을 보다 높게 할 수 있어 적합하다.When producing a polymer composition containing (B) organic short fibers, (B) the organic short fibers may be mixed with other mixing components and kneaded, or (B) the organic short fibers and a small amount of the polymer component may be mixed in advance. A masterbatch containing a polymer component and (B) organic short fibers may be produced, and the produced masterbatch may be kneaded with other blending components. The latter case is suitable because it can increase productivity.
1.3. 그 외의 성분1.3. other ingredients
본 실시 형태에 따른 중합체 조성물은, 상기의 성분 외에, 필요에 따라서, (A) 공액 디엔계 중합체 이외의 그 외의 디엔계 중합체, 무기 충전제, 실란 커플링제, 가교제, 산성 화합물, 신전유(프로세스유), 노화 방지제, 가황 촉진제의 외에, 필요에 따라서 가황 조제, 가공 조제, 스코치 방지제 및 산화 아연, 연화제, 착색제, 난연제, 윤활제, 발포제, 가소제, 산화 방지제, 자외선 방지제, 대전 방지제, 착색 방지제 등의 공지의 첨가제를, 중합체 조성물의 사용 목적에 따라서 사용할 수 있다.The polymer composition according to the present embodiment contains, in addition to the above components, as necessary, (A) other diene-based polymers other than the conjugated diene-based polymer, an inorganic filler, a silane coupling agent, a cross-linking agent, an acidic compound, and an extender oil (process oil) ), in addition to anti-aging agents and vulcanization accelerators, vulcanization aids, processing aids, anti-scorch agents, zinc oxide, softeners, colorants, flame retardants, lubricants, foaming agents, plasticizers, antioxidants, ultraviolet ray inhibitors, anti-static agents, anti-coloring agents, etc. as needed. Known additives can be used depending on the intended use of the polymer composition.
＜그 외의 중합체＞ ＜Other polymers＞
본 실시 형태에 따른 중합체 조성물은, (A) 공액 디엔계 중합체 이외의 그 외의 디엔계 중합체를 함유해도 좋다. 이러한 디엔계 중합체로서는, 공액 디엔 화합물에 유래하는 반복 단위를 가지면 특별히 제한되지 않지만, 예를 들면, 천연 고무, 폴리부타디엔, 폴리이소프렌, 에틸렌-프로필렌-디엔 고무, 스티렌-부타디엔 고무, 아크릴로니트릴-부타디엔 고무 등을 들 수 있다.The polymer composition according to this embodiment may contain other diene-based polymers other than the (A) conjugated diene-based polymer. Such diene polymers are not particularly limited as long as they have repeating units derived from conjugated diene compounds, and examples include natural rubber, polybutadiene, polyisoprene, ethylene-propylene-diene rubber, styrene-butadiene rubber, and acrylonitrile-based polymer. Butadiene rubber, etc. can be mentioned.
본 실시 형태에 따른 중합체 조성물이 그 외의 중합체를 함유하는 경우, 그 외의 중합체의 함유 비율은, 중합체 조성물에 함유되는 중합체 성분의 합계량을 100질량부로 했을 때에, 바람직하게는 50질량부 이하이고, 보다 바람직하게는 40질량부 이하이고, 특히 바람직하게는 35질량부 이하이다.When the polymer composition according to the present embodiment contains other polymers, the content ratio of the other polymers is preferably 50 parts by mass or less, when the total amount of polymer components contained in the polymer composition is 100 parts by mass. Preferably it is 40 parts by mass or less, and particularly preferably is 35 parts by mass or less.
＜무기 충전제＞＜Inorganic filler＞
본 실시 형태에 따른 중합체 조성물은, 얻어지는 가교 중합체의 저로스성, 내마모성, 웨트 그립성을 더욱 향상시키기 위해, 무기 충전제를 함유해도 좋다. 무기 충전제로서는, 예를 들면 실리카, 카본 블랙 및, 이들의 혼합물을 들 수 있다.The polymer composition according to the present embodiment may contain an inorganic filler in order to further improve the low loss properties, wear resistance, and wet grip properties of the resulting crosslinked polymer. Examples of inorganic fillers include silica, carbon black, and mixtures thereof.
(실리카)(silica)
실리카로서는, 습식 실리카(함수 규산), 건식 실리카(무수 규산), 규산 칼슘, 규산 알루미늄 등을 들 수 있다. 이들 중에서도, 습식 실리카가 바람직하다. 실리카의 사용 비율은, 중합체 성분 100질량부에 대하여, 바람직하게는 30∼130질량부, 보다 바람직하게는 40∼120질량부, 특히 바람직하게는 50∼110질량부이다. 실리카의 사용 비율이, 상기 하한값 이상이면, 충분한 내마모성, 웨트 그립 성능이 얻어지기 쉽고, 상기 상한값 이하이면, 충분한 저로스성이 얻어지기 쉽다.Examples of silica include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, and aluminum silicate. Among these, wet silica is preferable. The proportion of silica used is preferably 30 to 130 parts by mass, more preferably 40 to 120 parts by mass, and particularly preferably 50 to 110 parts by mass, based on 100 parts by mass of the polymer component. If the silica usage ratio is more than the above lower limit, sufficient wear resistance and wet grip performance can be easily obtained, and if it is less than the above upper limit, sufficient low loss properties can be easily obtained.
또한, 실리카의 사용 비율은, 무기 충전제 성분 100질량％ 중, 바람직하게는 20질량％ 이상, 보다 바람직하게는 50질량％ 이상이다. 이 범위에 있으면, 저로스성, 내마모성, 웨트 그립 성능의 점에서 유리하다.Moreover, the usage ratio of silica is preferably 20% by mass or more, more preferably 50% by mass or more, based on 100% by mass of the inorganic filler component. If it is within this range, it is advantageous in terms of low loss properties, wear resistance, and wet grip performance.
(카본 블랙) (carbon black)
카본 블랙으로서는, 특별히 제한되지 않고, 고무 조성물에 배합되는 일반적인 것을 이용할 수 있고, 구체예로서는, 예를 들면, GPF, FEF, HAF, ISAF, SAF 등을 들 수 있다. 이들 중에서는, ISAF, SAF, HAF가 바람직하고, ISAF가 보다 바람직하다.The carbon black is not particularly limited, and general ones that are blended in rubber compositions can be used. Specific examples include GPF, FEF, HAF, ISAF, and SAF. Among these, ISAF, SAF, and HAF are preferable, and ISAF is more preferable.
카본 블랙의 사용 비율은, 중합체 성분 100질량부에 대하여, 바람직하게는 0∼130질량부이고, 보다 바람직하게는 2∼110질량부이다.The proportion of carbon black used is preferably 0 to 130 parts by mass, more preferably 2 to 110 parts by mass, based on 100 parts by mass of the polymer component.
＜실란 커플링제＞＜Silane coupling agent＞
실란 커플링제로서는, 예를 들면, 비스(3-트리에톡시실릴프로필)테트라술피드, 비스(3-트리에톡시실릴프로필)트리술피드, 비스(3-트리에톡시실릴프로필)디술피드, 비스(2-트리에톡시실릴에틸)테트라술피드, 비스(3-트리메톡시실릴프로필)테트라술피드, 비스(2-트리메톡시실릴에틸)테트라술피드, 3-메르캅토프로필트리메톡시실란, 3-메르캅토프로필트리에톡시실란, 2-메르캅토에틸트리메톡시실란, 2-메르캅토에틸트리에톡시실란; 3-트리메톡시실릴프로필-N,N-디메틸티오카바모일테트라술피드, 3-트리에톡시실릴프로필-N,N-디메틸티오카바모일테트라술피드, 2-트리에톡시실릴에틸-N,N-디메틸티오카바모일테트라술피드, 3-트리메톡시실릴프로필벤조티아졸릴테트라술피드, 3-트리에톡시실릴프로필벤졸릴테트라술피드, 3-트리에톡시실릴프로필메타크릴레이트모노술피드, 3-트리메톡시실릴프로필메타크릴레이트모노술피드, 비스(3-디에톡시메틸실릴프로필)테트라술피드, 3-메르캅토프로필디메톡시메틸실란, 디메톡시메틸실릴프로필-N,N-디메틸티오카바모일테트라술피드, 디메톡시메틸실릴프로필벤조티아졸릴테트라술피드, 3-옥타노일티오-1-프로필트리에톡시실란 등을 들 수 있다. 이들 화합물은, 1종 단독으로 또는 2종 이상 조합하여 이용할 수 있다. 또한, 이들 중에서는, 보강성 개선 효과 등의 관점에서, 비스(3-트리에톡시실릴프로필)트리술피드, 비스(3-트리에톡시실릴프로필)디술피드, 3-트리메톡시실릴프로필벤조티아졸릴테트라술피드가 바람직하다.Silane coupling agents include, for example, bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, Bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxy Silane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane; 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide , 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethyl Thiocarbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, 3-octanoylthio-1-propyltriethoxysilane, etc. are mentioned. These compounds can be used individually or in combination of two or more types. In addition, among these, from the viewpoint of the effect of improving reinforcing properties, etc., bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, and 3-trimethoxysilylpropylbenzo Thiazolyltetrasulfide is preferred.
실란 커플링제의 사용 비율은, 무기 충전제 성분 100질량부에 대하여, 0.5∼20질량부인 것이 바람직하다. 실란 커플링제의 사용 비율이 상기 범위에 있으면, 중합체 조성물로 형성되는 가교 중합체에 충분한 보강성 및 내파괴 특성을 부여할 수 있어, 가교 중합체의 내마모성을 향상할 수 있다.The usage ratio of the silane coupling agent is preferably 0.5 to 20 parts by mass based on 100 parts by mass of the inorganic filler component. If the usage ratio of the silane coupling agent is within the above range, sufficient reinforcing properties and fracture resistance properties can be imparted to the crosslinked polymer formed from the polymer composition, and the wear resistance of the crosslinked polymer can be improved.
＜가교제＞ ＜Cross-linking agent＞
가교제로서는, 황, 할로겐화 황, 유기 과산화물, 퀴논디옥심류, 유기 다가 아민 화합물, 메틸올기를 갖는 알킬페놀 수지 등을 들 수 있다. 이들 중에서는, 통상, 가교제로서 황이 이용된다. 가교제의 사용 비율은, 중합체 성분 100질량부에 대하여, 0.1∼10질량부인 것이 바람직하고, 0.5∼5질량부인 것이 보다 바람직하다.Examples of the crosslinking agent include sulfur, halogenated sulfur, organic peroxides, quinonedioximes, organic polyvalent amine compounds, and alkylphenol resins having a methylol group. Among these, sulfur is usually used as a crosslinking agent. The usage ratio of the crosslinking agent is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the polymer component.
＜산성 화합물＞ ＜Acidic compound＞
산성 화합물로서는, 탄소수 12∼24의 포화 지방산 및 그들의 금속염이 적합하게 이용된다. 산성 화합물의 구체예로서는, 라우르산, 트리데실산, 미리스트산, 펜타데실산, 팔미트산, 마르가르산, 스테아르산, 노나데실산, 아라키드산, 헨에이코실산, 베헨산, 트리코실산, 리그노세르산 및, 이들의 포화 지방산의, 칼슘염, 아연염 등을 들 수 있다. 이들의 산성 화합물은, 1종 단독으로 또는 2종 이상 조합하여 이용할 수 있다. 이들 중에서는, 스테아르산이 바람직하다. 산성 화합물의 사용 비율은, 중합체 성분 100질량부에 대하여, 0.3∼15질량부인 것이 바람직하다.As acidic compounds, saturated fatty acids with 12 to 24 carbon atoms and their metal salts are suitably used. Specific examples of acidic compounds include lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid, and tricosylic acid. , lignoceric acid, and calcium salts and zinc salts of these saturated fatty acids. These acidic compounds can be used individually or in combination of two or more types. Among these, stearic acid is preferable. The usage ratio of the acidic compound is preferably 0.3 to 15 parts by mass based on 100 parts by mass of the polymer component.
＜다른 첨가제＞ ＜Other additives＞
신전유로서는, 예를 들면, 아로마유, 나프텐유, 파라핀유 등을 들 수 있다. 신전유의 사용 비율은, 중합체 성분 100질량부에 대하여, 0∼50질량부이다.Examples of extender oils include aroma oil, naphthene oil, and paraffin oil. The usage ratio of extender oil is 0 to 50 parts by mass per 100 parts by mass of the polymer component.
노화 방지제로서는, 예를 들면, N-(1,3-디메틸부틸)-N'-페닐-p-페닐렌디아민 등을 들 수 있다. 노화 방지제의 사용 비율은, 중합체 성분 100질량부에 대하여, 0.5∼5질량부이다.Examples of anti-aging agents include N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine. The usage ratio of the anti-aging agent is 0.5 to 5 parts by mass based on 100 parts by mass of the polymer component.
가황 조제로서는, 예를 들면, 산화 아연 등을 들 수 있다. 가황 조제의 사용 비율은, 중합체 성분 100질량부에 대하여, 1∼5질량부이다.Examples of vulcanization aids include zinc oxide. The usage ratio of the vulcanization aid is 1 to 5 parts by mass per 100 parts by mass of the polymer component.
가황 촉진제로서는, 구아니딘계, 알데히드-아민계, 알데히드-암모니아계, 티아졸계, 술펜아미드계, 티오우레아계, 티우람계, 디티오카바메이트계, 잔테이트계 등의 화합물을 들 수 있다. 가황 촉진제의 바람직한 구체예로서는, N-사이클로헥실-2-벤조티아질술펜아미드(CBS), N-테트라-부틸-2-벤조티아질술펜아미드(TBBS) 등의 술펜아미드계 가황 촉진제를 들 수 있다. 가황 촉진제의 사용 비율은, 염기성 화합물의 종류 및 사용 비율을 고려하여 적절하게 정해지지만, 중합체 성분 100질량부에 대하여, 0.5∼5질량부인 것이 바람직하다.Examples of the vulcanization accelerator include compounds such as guanidine-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, sulfenamide-based, thiourea-based, thiuram-based, dithiocarbamate-based, and xanthate-based compounds. Preferred specific examples of the vulcanization accelerator include sulfenamide-based vulcanization accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide (CBS) and N-tetra-butyl-2-benzothiazylsulfenamide (TBBS). . The usage ratio of the vulcanization accelerator is appropriately determined in consideration of the type and usage ratio of the basic compound, but is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymer component.
1.4. 중합체 조성물의 제조 방법 1.4. Method for producing polymer compositions
본 실시 형태에 따른 중합체 조성물은, 상기의 각 성분을, 예를 들면 플라스트 밀, 밴버리 믹서, 롤, 인터널 믹서 등의 혼련기를 이용하여 혼련함으로써 조제할 수 있다. 예를 들면, 하기의 방법에 의해 조제하는 것이 바람직하다.The polymer composition according to the present embodiment can be prepared by kneading each of the above components using a kneader such as a plast mill, Banbury mixer, roll, or internal mixer. For example, it is preferable to prepare by the following method.
＜1단째의 혼련＞ ＜1st stage kneading＞
1단째의 혼련에 있어서는, (A) 공액 디엔계 중합체와 함께, (B) 유기 단섬유, 필요에 따라서 무기 충전제 및 실란 커플링제가 혼련되는 것이 바람직하다. 또한, 1단째의 혼련에 있어서는, 필요에 따라서, 그 외의 중합체, 신전유 및 노화 방지제 등도 함께 혼련된다. 또한, 1단째의 혼련에 있어서는, 2단째의 혼련에 있어서 혼련되는 것이 바람직하다고 여겨지는, 산성 화합물이 함께 혼련되어도 좋다.In the first stage of kneading, it is preferable that (A) the conjugated diene polymer, (B) organic short fibers, and, if necessary, an inorganic filler and a silane coupling agent are kneaded. Additionally, in the first stage kneading, other polymers, extender oils, anti-aging agents, etc. are also kneaded as needed. Additionally, in the first stage kneading, acidic compounds that are considered desirable to be kneaded in the second stage kneading may be kneaded together.
(B) 유기 단섬유나 무기 충전제를 1단째의 혼련에 제공함으로써, 이들의 분산성이 양호해지기 쉬워, 얻어지는 중합체 조성물로 형성되는 타이어(가교 중합체)의 저연비 성능이 향상되는 경우가 있다.(B) By providing organic short fibers or inorganic fillers in the first stage of kneading, their dispersibility is likely to improve, and the low fuel efficiency performance of the tire (crosslinked polymer) formed from the resulting polymer composition may be improved.
또한, 1단째의 혼련에 실란 커플링제를 제공하는 경우에는, 우선, (A) 공액 디엔계 중합체, 그 외의 중합체, (B) 유기 단섬유 및, 필요에 따라서 무기 충전제를 혼련하고, 그 후, 실란 커플링제를 첨가(후(後)첨가)하여 추가로 혼련하는 것이 바람직하다.In addition, when providing a silane coupling agent in the first stage kneading, first, (A) the conjugated diene polymer, other polymers, (B) organic short fibers, and, if necessary, an inorganic filler are kneaded, and then, It is preferable to add (post-add) a silane coupling agent and further knead it.
1단째의 혼련에 있어서 실란 커플링제를 후첨가함으로써, 얻어지는 중합체 조성물이 보다 가공성이 우수한 것이 되고, 당해 중합체 조성물로 형성되는 가교 중합체가 보다 우수한 저히스테리시스 특성을 갖는 것이 된다. 또한, 중합체 조성물이 무기 충전제로서 실리카를 함유하는 경우에 있어서는, 실리카의 분산성을 보다 양호한 것으로 할 수 있다.By post-adding a silane coupling agent in the first stage of kneading, the obtained polymer composition has better processability, and the crosslinked polymer formed from the polymer composition has better low hysteresis characteristics. Additionally, when the polymer composition contains silica as an inorganic filler, the dispersibility of silica can be improved.
실란 커플링제를 후첨가하는 경우에 있어서, 실란 커플링제의 첨가 타이밍은, 실리카의 종류, 실리카의 사용 비율 및 혼련 조건 등에 따라, (A) 공액 디엔계 중합체 및 그 외의 중합체의 사용 비율 등을 고려하여 적절히 정해진다.In the case of post-adding the silane coupling agent, the timing of addition of the silane coupling agent depends on the type of silica, the ratio of silica used, kneading conditions, etc., taking into account the ratio of (A) conjugated diene polymer and other polymers used, etc. It is determined appropriately.
또한, 실란 커플링제를 후첨가하는 경우에 있어서는, (A) 공액 디엔계 중합체 및 그 외의 중합체를 배합하여 0.5∼10분간에 걸쳐 혼련한 후, 실란 커플링제를 첨가하여 0.5∼10분간에 걸쳐 혼련하는 것이 바람직하다.In addition, in the case of post-adding a silane coupling agent, (A) the conjugated diene polymer and other polymers are mixed and kneaded for 0.5 to 10 minutes, then the silane coupling agent is added and kneaded for 0.5 to 10 minutes. It is desirable to do so.
1단째의 혼련에 이용되는 혼련기로서는, 플라스트 밀, 밴버리 믹서, 롤, 인터널 믹서 등의 개방식 또는 밀폐식의 혼련기를 들 수 있다. 또한, 1단째의 혼련에 있어서, 혼련 온도는, 30℃∼180℃로 되고, 바람직하게는 50∼160℃이다.Kneaders used for first-stage kneading include open or closed kneaders such as plast mills, Banbury mixers, rolls, and internal mixers. Additionally, in the first stage of kneading, the kneading temperature is 30°C to 180°C, and is preferably 50°C to 160°C.
또한, 1단째의 혼련에 실란 커플링제를 제공하는 경우에 있어서는, 실란 커플링제를 후첨가하여 혼련하는 수법에 한정되지 않고, 실란 커플링제를, 1단째의 혼련에 제공되는 다른 모든 성분과 함께 일제히 혼련하는 수법에 의해, 실란 커플링제를 함유하는 혼련물을 얻어도 좋다. 또한, (A) 공액 디엔계 중합체, (B) 유기 단섬유, 무기 충전제로서의 실리카 및 실란 커플링제가 혼련되는 마스터 배치를 제작한 후에, 그 외의 중합체, 첨가제를 첨가하는 방법이라도 좋다.Additionally, in the case of providing the silane coupling agent in the first stage kneading, the method is not limited to the method of post-adding the silane coupling agent and kneading, and the silane coupling agent is used together with all other components provided in the first stage kneading. A kneaded product containing a silane coupling agent may be obtained by a kneading method. Additionally, after producing a masterbatch in which (A) conjugated diene polymer, (B) organic short fibers, silica as an inorganic filler, and silane coupling agent are mixed, other polymers and additives may be added.
＜2단째의 혼련＞＜2nd stage kneading＞
2단째의 혼련은, 1단째의 혼련에 있어서 얻어진 혼련물에, 적어도 가교제를 첨가하고, 당해 혼련물과 가교제를 혼련하여, 중합체 조성물을 얻는 공정이다. 이 2단째의 혼련에 있어서는, 1단째의 혼련에 있어서 얻어진 혼련물과 가교제와 함께, 산성 화합물이 혼련되는 것이 바람직하다. 또한, 2단째의 혼련에 있어서는, 필요에 따라, 산화 아연 및 가황 촉진제도 함께 혼련된다. 그리고, 2단째의 혼련에 있어서는, 통상, 당해 2단째의 혼련에 제공되는 모든 성분(구체적으로는, 1단째의 혼련에 있어서 얻어진 혼련물, 가교제, 그리고, 필요에 따라서 제공되는, 산성 화합물 및 산화 아연이나 가황 촉진제 등의 그 외의 성분)을 일제히 혼련하는 수법에 의해 중합체 조성물이 얻어진다.The second-stage kneading is a process of adding at least a cross-linking agent to the kneaded product obtained in the first-stage kneading and kneading the kneaded product with the cross-linking agent to obtain a polymer composition. In this second stage kneading, it is preferable that the acidic compound is kneaded together with the crosslinking agent and the kneaded product obtained in the first stage kneading. Additionally, in the second stage of kneading, zinc oxide and a vulcanization accelerator are also kneaded as needed. In the second-stage kneading, all components provided for the second-stage kneading (specifically, the kneaded product obtained in the first-stage kneading, a crosslinking agent, and acidic compounds and oxidizing agents provided as necessary) A polymer composition is obtained by mixing together other components such as zinc and vulcanization accelerators.
2단째의 혼련에 산성 화합물을 제공함으로써, 얻어지는 중합체 조성물이 보다 가공성이 우수한 것이 되고, 또한, 중합체 조성물로 형성되는 가교 중합체가, 보다 우수한 저히스테리시스 특성을 갖는 것이 된다.By providing an acidic compound in the second stage of kneading, the resulting polymer composition has better processability, and the crosslinked polymer formed from the polymer composition has better low hysteresis characteristics.
2단째의 혼련에 있어서는, 1단째의 혼련에 있어서 이용한 혼련기가 이용된다. 또한, 2단째의 혼련에 있어서, 혼련 온도는, 30℃∼130℃로 되고, 바람직하게는 50℃∼110℃이다.In the second stage kneading, the kneader used in the first stage kneading is used. Additionally, in the second stage kneading, the kneading temperature is 30°C to 130°C, and is preferably 50°C to 110°C.
이상과 같은 제조 방법에 의해 얻어지는 중합체 조성물은, 미가황 고무 조성물이고, 예를 들면 가황 등의 가교 처리를 함으로써 가교 중합체가 형성되는 것이다.The polymer composition obtained by the above production method is an unvulcanized rubber composition, and a crosslinked polymer is formed by, for example, crosslinking treatment such as vulcanization.
1.5. 용도 1.5. Usage
본 실시 형태에 따른 중합체 조성물로 형성되는 가교 중합체는, 타이어, 구체적으로는 타이어의 트레드로서 적합하게 이용된다. 본 실시 형태에 따른 중합체 조성물로 형성되는 타이어에는, 트레드에 높은 강도가 얻어지고, 또한 트레드에 소망하는 형상이 얻어지기 때문에, 우수한 성능이 얻어진다. 또한, 본 실시 형태에 따른 중합체 조성물로 형성되는 가교 중합체는, 트레드 이외의 타이어 부재, 방진(防振) 고무, 방현재, 벨트, 호스 및, 그 외의 공업품 등으로서 이용할 수도 있다.The crosslinked polymer formed from the polymer composition according to the present embodiment is suitably used as a tire, specifically, a tire tread. In the tire formed from the polymer composition according to the present embodiment, excellent performance is obtained because the tread has high strength and a desired shape is obtained for the tread. Additionally, the crosslinked polymer formed from the polymer composition according to the present embodiment can also be used as tire members other than treads, anti-vibration rubber, fenders, belts, hoses, and other industrial products.
2. 실시예 2. Example
이하, 본 발명의 구체적인 실시예에 대해서 설명하지만, 본 발명은 이들 실시예에 한정되는 것은 아니다. 또한, 하기 제조예, 실시예 및 비교예 중의 「％」는, 특별히 언급이 없는 한 질량 기준이다.Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to these examples. In addition, “%” in the following production examples, examples, and comparative examples is based on mass unless otherwise specified.
2.1. (A) 공액 디엔계 중합체의 제조예 2.1. (A) Production example of conjugated diene polymer
＜제조예 1＞＜Manufacturing Example 1＞
질소 치환된 내용적 5리터의 오토 클레이브 반응기에, 사이클로헥산 2500g, 비닐기 함량 조정제(랜더마이저)로서 테트라하이드로푸란 50g, 그리고, 모노머로서 스티렌 125g 및 1,3-부타디엔 365g을 넣었다. 반응기의 내용물의 온도를 10℃로 조정한 후, 중합 개시제로서 3-(디메틸아미노)프로필리튬과 이소프렌을 반응시킨 혼합물[반응 비율: 이소프렌/3-(디메틸아미노)프로필리튬＝2/1(몰비), FMC사 제조, 상품명: AI-200CE2(사이클로헥산 용액)] 5.20mmol을 첨가하여 중합을 개시했다. 중합은 단열 조건으로 실시하고, 최고 온도는 85℃에 도달했다.In an autoclave reactor with an internal volume of 5 liters purged with nitrogen, 2500 g of cyclohexane, 50 g of tetrahydrofuran as a vinyl group content adjuster (randomizer), and 125 g of styrene and 365 g of 1,3-butadiene as monomers were added. After adjusting the temperature of the contents of the reactor to 10°C, a mixture of 3-(dimethylamino)propyllithium and isoprene as a polymerization initiator was reacted [reaction ratio: isoprene/3-(dimethylamino)propyllithium=2/1 (molar ratio) ), manufactured by FMC, brand name: AI-200CE2 (cyclohexane solution)] was added to initiate polymerization. Polymerization was carried out under adiabatic conditions, and the maximum temperature reached 85°C.
중합 전화율이 99％에 도달한 시점(중합 개시로부터 25분 경과 후)에서, 1,3-부타디엔 10g을 1분간 걸쳐 추가하고, 그 후, 변성제로서 N,N-비스(트리에톡시실릴프로필)아미노프로필-1-이미다졸 1.15mmol을 더하여 15분간 반응을 행했다. 여기에, 변성제를 더하기 직전에 있어서, 변성 전의 중합체의 중량 평균 분자량을 측정하기 위한 샘플링을 행했다.When the polymerization conversion rate reached 99% (25 minutes after the start of polymerization), 10 g of 1,3-butadiene was added over 1 minute, and then N,N-bis(triethoxysilylpropyl) was added as a modifier. 1.15 mmol of aminopropyl-1-imidazole was added and reaction was performed for 15 minutes. Here, immediately before adding the modifier, sampling was performed to measure the weight average molecular weight of the polymer before modification.
얻어진 변성 공액 디엔계 공중합체를 포함하는 중합체 용액에, 2,6-디-tert-부틸-p-크레졸을 4.40g 첨가했다. 이어서, 스팀 스트립핑에 의해 탈용매를 행하여, 110℃로 온도 조절된 열 롤에 의해 건조를 행함으로써 변성 공액 디엔계 공중합체(이하, 「SBR-1」이라고도 함)를 얻었다.4.40 g of 2,6-di-tert-butyl-p-cresol was added to the polymer solution containing the obtained modified conjugated diene copolymer. Next, solvent removal was performed by steam stripping, and drying was performed using a heat roll temperature-controlled at 110°C to obtain a modified conjugated diene-based copolymer (hereinafter also referred to as “SBR-1”).
＜제조예 2＞＜Manufacture Example 2＞
제조예 1에 있어서, 3-(디메틸아미노)프로필리튬과 이소프렌을 반응시킨 화합물에 대신하여, 3-(디메틸아미노)프로필리튬과 이소프렌을 반응시킨 화합물 2.60mmol과 n-부틸리튬 2.60mmol을 사용하고, N,N-비스(트리에톡시실릴프로필)아미노프로필-1-이미다졸 1.15mmol에 대신하여 N,N-비스(트리메틸실릴)아미노프로필메틸디에톡시실란 2.30mmol을 사용한 이외는 제조예 1과 마찬가지의 조작을 행하여, 변성 공액 디엔계 공중합체(이하, 「SBR-2」라고도 함)를 얻었다.In Preparation Example 1, instead of the compound obtained by reacting 3-(dimethylamino)propyllithium and isoprene, 2.60 mmol of the compound obtained by reacting 3-(dimethylamino)propyllithium and isoprene and 2.60 mmol of n-butyllithium were used. , Preparation Example 1 except that 2.30 mmol of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane was used instead of 1.15 mmol of N, N-bis (triethoxysilylpropyl) aminopropyl-1-imidazole. A similar operation was performed to obtain a modified conjugated diene-based copolymer (hereinafter also referred to as “SBR-2”).
＜제조예 3＞＜Manufacture Example 3＞
제조예 1에 있어서, N,N-비스(트리에톡시실릴프로필)아미노프로필-1-이미다졸 1.15mmol에 대신하여, N-페닐-2,2-디메톡시-1-아자-2-실라사이클로펜탄 2.30mmol을 사용한 이외는 제조예 1과 마찬가지의 조작을 행하여, 변성 공액 디엔계 공중합체(이하, 「SBR-3」이라고도 함)를 얻었다.In Preparation Example 1, instead of 1.15 mmol of N,N-bis(triethoxysilylpropyl)aminopropyl-1-imidazole, N-phenyl-2,2-dimethoxy-1-aza-2-silacyclo The same operation as in Production Example 1 was performed except that 2.30 mmol of pentane was used, and a modified conjugated diene copolymer (hereinafter also referred to as “SBR-3”) was obtained.
＜제조예 4＞＜Manufacture Example 4＞
제조예 1에 있어서, N,N-비스(트리에톡시실릴프로필)아미노프로필-1-이미다졸 1.15mmol에 대신하여, 1,13-비스(트리에톡시실릴)-4,10-디아자-4,9-데카디엔 0.82mmol을 사용한 이외는 제조예 1과 마찬가지의 조작을 행하여, 변성 공액 디엔계 공중합체(이하, 「SBR-4」라고도 함)를 얻었다.In Preparation Example 1, instead of 1.15 mmol of N,N-bis(triethoxysilylpropyl)aminopropyl-1-imidazole, 1,13-bis(triethoxysilyl)-4,10-diaza- The same procedure as in Production Example 1 was performed except that 0.82 mmol of 4,9-decadiene was used to obtain a modified conjugated diene copolymer (hereinafter also referred to as “SBR-4”).
2.2. 물성의 측정 방법2.2. How to measure physical properties
＜수 평균 분자량(Mn) 및 중량 평균 분자량(Mw)의 측정＞ <Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw)>
상기에서 제조된 각 중합체에 대해서, 겔 투과 크로마토그래피(GPC)(토소사 제조의 「HLC-8120」)를 이용하여, 하기의 GPC 조건으로 얻어진 GPC 곡선의 최대 피크의 정점에 상당하는 보존유지 시간으로부터, 폴리스티렌 환산의 수 평균 분자량(Mn) 및 중량 평균 분자량(Mw)을 산출했다.For each polymer produced above, retention time corresponding to the peak of the maximum peak of the GPC curve obtained under the following GPC conditions using gel permeation chromatography (GPC) (“HLC-8120” manufactured by Tosoh Corporation) From this, the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene were calculated.
(GPC 조건) (GPC conditions)
칼럼: 상품명 「GMHXL」(토소사 제조) 2개Column: Product name “GMHXL” (manufactured by Tosoh Corporation) 2 units
칼럼 온도: 40℃ Column temperature: 40℃
이동상: 테트라하이드로푸란Mobile phase: tetrahydrofuran
유속: 1.0ml/분Flow rate: 1.0ml/min
샘플 농도: 10㎎/20mlSample concentration: 10mg/20ml
＜비닐 함량, 결합 스티렌 함량의 측정＞＜Measurement of vinyl content and combined styrene content＞
·비닐 함량(％): 400㎒의 1H-NMR 측정에 의해 측정했다.- Vinyl content (%): Measured by 1 H-NMR measurement at 400 MHz.
·결합 스티렌 함량(％): 400㎒의 1H-NMR 측정에 의해 측정했다. 결합 스티렌 함량은, 방향족 비닐 함량에 상당하는 파라미터이다.· Bound styrene content (%): Measured by 1 H-NMR measurement at 400 MHz. The bound styrene content is a parameter corresponding to the aromatic vinyl content.
2.3. 실시예 1∼6 및 비교예 12.3. Examples 1 to 6 and Comparative Example 1
2.3.1. 중합체 조성물 및 가교 중합체의 제조2.3.1. Preparation of polymer compositions and crosslinked polymers
하기표 2에 나타내는 배합 처방에 의해 각 성분을 배합하고, 그들을 혼련함으로써 중합체 조성물을 제조했다. 혼련은 이하의 방법으로 행했다.A polymer composition was prepared by mixing each component according to the formulation shown in Table 2 below and kneading them. Kneading was performed by the following method.
온도 제어 장치를 부속한 플라스트 밀(내용량: 250ml)을 사용하여, 1단째의 혼련으로서 충전율 72％, 회전수 60rpm의 조건으로, 하기표 2에 나타내는 중합체 성분, 유기 단섬유, 실리카, 카본 블랙, 실란 커플링제, 스테아르산, 노화 방지제, 산화 아연, TDAE 오일을 혼련했다. 이어서, 2단째의 혼련으로서, 상기에서 얻어진 혼련물을 실온까지 냉각 후, 가황 촉진제, 황을 혼련함으로써, 실시예 1∼6 및 비교예 1의 각 중합체 조성물을 얻었다.Using a plast mill (capacity: 250 ml) equipped with a temperature control device, the polymer components, organic short fibers, silica, and carbon black shown in Table 2 below were kneaded in the first stage under the conditions of a filling rate of 72% and a rotation speed of 60 rpm. , silane coupling agent, stearic acid, anti-aging agent, zinc oxide, and TDAE oil were mixed. Next, in the second stage of kneading, the kneaded product obtained above was cooled to room temperature, and then the vulcanization accelerator and sulfur were kneaded to obtain the respective polymer compositions of Examples 1 to 6 and Comparative Example 1.
다음으로, 얻어진 각 중합체 조성물을 성형하여, 160℃에서 소정 시간, 가황 프레스로 가황하여, 하기의 평가 시험에 제공하는 소정의 형상을 갖는 각 가교 중합체를 얻었다.Next, each obtained polymer composition was molded and vulcanized with a vulcanizing press at 160°C for a predetermined time to obtain each crosslinked polymer having a predetermined shape to be subjected to the following evaluation test.
2.3.2. 중합체 조성물 및 가교 중합체의 평가2.3.2. Evaluation of polymer compositions and cross-linked polymers
얻어진 각 중합체 조성물 및 각 가교 중합체에 대해서, 이하의 평가 시험을 행했다. 결과를 하기표 2에 나타낸다.The following evaluation tests were performed on each obtained polymer composition and each crosslinked polymer. The results are shown in Table 2 below.
＜강도＞ ＜Strength＞
인장 시험: JIS K6251: 2010에 준거하여, 시험용 가황 고무 시트로 이루어지는 3호 덤벨형 시험편을 제작하여, 100％ 신장 모듈러스(M100)를 측정했다. 하기표 2에 있어서는, 비교예 1의 측정값을 기준으로서 100으로 한 경우의 지수에 의해 나타내고 있고, 수치가 클수록 고강도이다.Tensile test: In accordance with JIS K6251: 2010, a No. 3 dumbbell-shaped test piece made of a vulcanized rubber sheet for testing was produced, and the 100% elongation modulus (M100) was measured. In Table 2 below, it is expressed by an index based on the measured value of Comparative Example 1 as 100, and the larger the value, the higher the strength.
＜내신장 피로성＞ ＜Height fatigue resistance＞
얻어진 중합체 조성물을 캘린더 가공에 의해 시트 형상으로 성형한 후, 가황 프레스기를 이용하여 160℃에서 소정 시간 가황 처리함으로써, 두께가 2㎜의 가황 고무로 이루어지는 시트를 제작했다. 얻어진 시트에 대하여 펀칭 가공을 실시함으로써, ASTM D638에 기재된 IV형 덤벨로 이루어지는 시험편을 제작했다. 이 때, 덤벨의 길이 방향이 시트의 열리(列理) 방향이 되도록, 시트에 대하여 펀칭 가공을 실시함과 함께, 덤벨에 있어서의 길이 방향의 중앙 위치에 반(反)열리 방향으로 신장하는 균열을 형성했다.The obtained polymer composition was molded into a sheet shape by calendering and then vulcanized at 160°C for a predetermined period of time using a vulcanization press to produce a sheet of vulcanized rubber with a thickness of 2 mm. By performing punching processing on the obtained sheet, a test piece consisting of a type IV dumbbell described in ASTM D638 was produced. At this time, punching processing is performed on the sheet so that the longitudinal direction of the dumbbell is in the sheet opening direction, and a crack extending in the anti-opening direction is formed at the central position in the longitudinal direction of the dumbbell. formed.
얻어진 시험편에 대해서, 신장률이 100％, 측정 온도가 23℃, 회전수가 300cpm의 조건으로 정(定)신장 피로 시험을 행하여, 시험편이 파단할 때까지의 사이클 수를 측정했다. 하기표 2에 있어서는, 비교예 1의 측정값을 기준으로서 100으로 한 경우의 지수에 의해 나타내고 있고, 수치가 클수록 신장 피로성이 양호한 것을 나타낸다.For the obtained test piece, a constant elongation fatigue test was performed under the conditions of an elongation of 100%, a measurement temperature of 23°C, and a rotation speed of 300 cpm, and the number of cycles until the test piece fractured was measured. In Table 2 below, the index is set to 100 based on the measured value of Comparative Example 1, and the larger the value, the better the renal fatigue resistance.
＜웨트 그립성(0℃tanδ)＞ ＜Wet grip properties (0℃tanδ)＞
가황 고무를 측정용 시료로 하여, ARES-RDA(TA Instruments사 제조)를 사용하여, 전단 변형 0.14％, 각속도 100라디안 매초, 0℃의 조건으로, 손실 계수(tanδ(0℃))를 측정했다. 비교예 1의 측정값을 기준으로서 100으로 한 지수로 나타내고, 수치가 클수록 웨트 그립이 양호한 것을 나타낸다.Using vulcanized rubber as a sample for measurement, the loss coefficient (tanδ (0°C)) was measured using ARES-RDA (manufactured by TA Instruments) under the conditions of 0.14% shear strain, angular velocity of 100 radians per second, and 0°C. . It is expressed as an index of 100 based on the measured value of Comparative Example 1, and the larger the number, the better the wet grip.
＜저로스성(50℃tanδ) 및 조종 안정성(50℃ G')＜Low loss resistance (50°C tanδ) and steering stability (50°C G’)
가황 고무를 측정용 시료로 하여, ARES-RDA(TA Instruments사 제조)를 사용하여, 전단 변형 0.7％, 각속도 100라디안 매초, 50℃의 조건으로, 손실 계수(tanδ(50℃)) 및 저장 탄성률(50℃ G')을 측정했다. 비교예 1의 측정값을 기준으로서 100으로 한 지수로 나타내고, 50℃tanδ는 수치가 클수록 에너지 로스가 작고, 저히스테리시스 로스 특성이 양호한 것을 나타내고, 50℃ G'는 수치가 클수록 저변형에서의 강성이 높아, 조종 안정성이 양호한 것을 나타낸다.Using vulcanized rubber as a sample for measurement, using ARES-RDA (manufactured by TA Instruments), loss coefficient (tanδ (50°C)) and storage modulus were measured under the conditions of 0.7% shear strain, angular velocity of 100 radians per second, and 50°C. (50°C G') was measured. It is expressed as an index set to 100 based on the measured value of Comparative Example 1. The larger the value of 50°C tanδ, the smaller the energy loss and the better the low hysteresis loss characteristics, and the larger the value of 50°C G', the stiffness at low deformation. This is high, indicating good steering stability.
2.4. 평가 결과2.4. Evaluation results
하기표 1에, 상기에서 합성한 각 중합체의 물성값을 나타낸다. 하기표 2에, 각 중합체 조성물의 조성 및 평가 결과를 나타낸다.Table 1 below shows the physical properties of each polymer synthesized above. Table 2 below shows the composition and evaluation results of each polymer composition.
상기표 2 중, 중합체 조성물의 조성 중의 각 성분의 수치는 질량부를 나타낸다. 또한, 상기표 2에 나타내는 각 재료는, 각각 이하의 상품을 이용했다.In Table 2 above, the numerical value of each component in the composition of the polymer composition represents parts by mass. In addition, the following products were used for each material shown in Table 2 above.
·BR: 천연 고무, RSS＃3・BR: Natural rubber, RSS #3
·실리카: 로디아사 제조, 상품명 「ZEOSIL 1165MP」・Silica: manufactured by Rhodia, product name “ZEOSIL 1165MP”
·실란 커플링제: 에보닉사 제조, 상품명 「Si75」・Silane coupling agent: manufactured by Evonik, product name “Si75”
·카본 블랙: 토카이 카본사 제조, 상품명 「시스토 KH」・Carbon black: Manufactured by Tokai Carbon Co., Ltd., product name “Sisto KH”
·유기 단섬유 1: 히가시레듀폰사 제조, 상품명 「Kevlar(등록 상표) 컷 파이버」, 방향족 폴리아미드계 섬유, 평균 길이 3㎜・Organic short fiber 1: manufactured by Higashi ReduPont, brand name “Kevlar (registered trademark) cut fiber”, aromatic polyamide-based fiber, average length 3 mm
·유기 단섬유 2: 테이진테크노프로덕츠사 제조, 상품명 「코넥스(등록 상표)」, 방향족 폴리아미드계 섬유, 평균 길이 2㎜· Organic short fiber 2: manufactured by Teijin Techno Products, brand name “Conex (registered trademark)”, aromatic polyamide-based fiber, average length 2 mm
·유기 단섬유 3: 토레이사 제조, 상품명 「토레카(등록 상표) 컷 파이버」, 탄소 섬유, 평균 길이 3㎜・Organic short fiber 3: Toray Co., Ltd., product name “Toreca (registered trademark) cut fiber”, carbon fiber, average length 3 mm
·노화 방지제: 세이코카가쿠사 제조, 상품명 「오조논 6C」, N-(1,3-디메틸부틸)-N'-페닐-p-페닐렌디아민Anti-aging agent: Seiko Chemical Co., Ltd., product name “Ozonon 6C”, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine
·가황 촉진제 D: 오우치신코카가쿠고교사 제조, 상품명 「녹셀러 D」, 1,3-디페닐구아니딘・Vulcanization accelerator D: Manufactured by Ouchi Shinko Chemical Industries, Ltd., brand name “Noxeller D”, 1,3-diphenylguanidine
·가황 촉진제 CZ: 오우치신코카가쿠고교사 제조, 상품명 「녹셀러 CZ」, N-사이클로헥실-2-벤조티아졸릴술펜아미드・Vulcanization accelerator CZ: Manufactured by Ouchi Shinko Chemical Co., Ltd., brand name “Noxeller CZ”, N-cyclohexyl-2-benzothiazolylsulfenamide
상기표 2의 결과로부터, 실시예 1∼6에 따른 중합체 조성물은, 비교예 1에 따른 중합체 조성물에 비하여, 저로스성 및 웨트 그립성이 우수할 뿐만 아니라, 기계적 특성, 인장 강도 및 조종 안정성을 고도로 양립할 수 있는 가교 중합체가 얻어지는 것을 확인할 수 있었다.From the results in Table 2 above, the polymer compositions according to Examples 1 to 6 not only have excellent low loss properties and wet grip properties compared to the polymer compositions according to Comparative Example 1, but also have mechanical properties, tensile strength, and handling stability. It was confirmed that a highly compatible crosslinked polymer was obtained.
본 발명은 상기 실시예에 한정되는 것은 아니고, 여러 가지의 변형이 가능하다. 본 발명은, 실시 형태에서 설명한 구성과 실질적으로 동일한 구성(예를 들면, 기능, 방법 및 결과가 동일한 구성, 또는 목적 및 효과가 동일한 구성)을 포함한다. 또한 본 발명은, 상기의 실시 형태에서 설명한 구성의 본질적이지 않은 부분을 다른 구성으로 치환한 구성을 포함한다. 또한 본 발명은, 상기의 실시 형태에서 설명한 구성과 동일한 작용 효과를 발휘하는 구성 또는 동일한 목적을 달성할 수 있는 구성도 포함한다. 또한 본 발명은, 상기의 실시 형태에서 설명한 구성에 공지 기술을 부가한 구성도 포함한다.The present invention is not limited to the above embodiment, and various modifications are possible. The present invention includes substantially the same configuration (for example, configuration with the same function, method, and result, or configuration with the same purpose and effect) as the configuration described in the embodiments. Additionally, the present invention includes a configuration in which non-essential parts of the configuration described in the above embodiments are replaced with other configurations. Additionally, the present invention also includes a configuration that exhibits the same effects as the configuration described in the above embodiments or a configuration that can achieve the same purpose. Additionally, the present invention also includes a configuration in which known techniques are added to the configuration described in the above embodiment.
Claims (8)
(B) 유기 단(短)섬유
를 함유하는, 중합체 조성물.
(식 (2) 중, A2는, 이미노기, 아미드기, (티오)카보닐기, (티오)카보닐옥시기, 술피드 혹은 폴리술피드로 L2와 결합한 1가의 기이거나, 또는, 보호된 1급 아미노기, 보호된 2급 아미노기, 3급 아미노기, 니트릴기, 피리딜기, (티오)에폭시기, (티오)이소시아네이트기, (티오)포르밀기, (티오)카본산 에스테르, (티오)카본산 에스테르의 금속염, 카본산 할로겐 화합물, 이미다졸릴기 혹은 하기식 (2a)로 나타나는 기를 나타내고, L2 및 L3은 각각 독립적으로 단결합 혹은 탄소수 1∼20의 하이드로카빌렌기를 나타내고, R3 및 R4는 각각 독립적으로 탄소수 1∼4의 하이드로카빌기를 나타내고, n2는 0∼3이고, m1은 0 또는 1임)
(식 (2a) 중, L3, R3, R4 및 n2는 식 (2)와 마찬가지이고, *는 L2와 결합하는 부위를 나타냄)
(식 (3) 중, A3은 각각 독립적으로, 이미노기, 아미드기, (티오)카보닐기 또는 (티오)카보닐옥시기를 나타내고, Z는 질소 원자를 포함하거나 또는 포함하지 않는 탄소수 1∼20의 t가의 기를 나타내고, L4는 단결합 또는 탄소수 1∼20의 하이드로카빌렌기를 나타내고, L5는 탄소수 1∼20의 하이드로카빌렌기를 나타내고, R5 및 R6은 각각 독립적으로 탄소수 1∼4의 하이드로카빌기를 나타내고, n3은 0 또는 1이고, t는 2 또는 3임)
(식 (4) 중, R7 및 R8은, 각각 독립적으로 탄소수 1∼20의 하이드로카빌기를 나타내고, R9는, 탄소수 1∼20의 하이드로카빌기, 알킬기가 갖는 수소 원자 및 -CH2-의 적어도 1개가 규소, 질소, 인, 산소 및 황으로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 포함하는 기로 치환된 탄소수 1∼20의 치환 알킬기이거나, 또는 질소, 인, 산소 및 황으로 이루어지는 군으로부터 선택되는 적어도 1종의 원소를 포함하는 탄소수 6∼20의 방향족기를 나타내고, R10은, 탄소수 1∼20의 알칸디일기를 나타내고; n4는 1 또는 2임)(A) a conjugated diene-based polymer, which is a polymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound, which is a reaction product between an active polymerization terminal and a compound represented by any of the following general formulas (2) to (4); ,
(B) Organic short fibers
A polymer composition containing.
(In formula (2), A 2 is a monovalent group bonded to L 2 with an imino group, amide group, (thio)carbonyl group, (thio)carbonyloxy group, sulfide or polysulfide, or a protected group. Primary amino group, protected secondary amino group, tertiary amino group, nitrile group, pyridyl group, (thio)epoxy group, (thio)isocyanate group, (thio)formyl group, (thio)carboxylic acid ester, (thio)carboxylic acid ester represents a metal salt, a carboxylic acid halogen compound, an imidazolyl group, or a group represented by the formula (2a) below, L 2 and L 3 each independently represent a single bond or a hydrocarbylene group having 1 to 20 carbon atoms, R 3 and R 4 each independently represents a hydrocarbyl group having 1 to 4 carbon atoms, n2 is 0 to 3, and m1 is 0 or 1)
(In formula (2a), L 3 , R 3 , R 4 and n2 are the same as in formula (2), and * indicates the site that binds to L 2 )
(In formula (3), A 3 each independently represents an imino group, an amide group, a (thio) carbonyl group, or a (thio) carbonyloxy group, and Z has 1 to 20 carbon atoms with or without a nitrogen atom. represents a t-valent group, L 4 represents a single bond or a hydrocarbylene group with 1 to 20 carbon atoms, L 5 represents a hydrocarbylene group with 1 to 20 carbon atoms, and R 5 and R 6 each independently represent a hydrocarbylene group with 1 to 4 carbon atoms. represents a hydrocarbyl group, n3 is 0 or 1, and t is 2 or 3)
(In formula (4), R 7 and R 8 each independently represent a hydrocarbyl group having 1 to 20 carbon atoms, and R 9 represents a hydrocarbyl group having 1 to 20 carbon atoms, a hydrogen atom of the alkyl group, and -CH 2 At least one of - is a substituted alkyl group having 1 to 20 carbon atoms substituted with a group containing at least one element selected from the group consisting of silicon, nitrogen, phosphorus, oxygen and sulfur, or consisting of nitrogen, phosphorus, oxygen and sulfur. represents an aromatic group having 6 to 20 carbon atoms containing at least one element selected from the group; R 10 represents an alkanediyl group having 1 to 20 carbon atoms; n4 is 1 or 2)
상기 (A) 공액 디엔계 중합체 100질량부에 대하여, 상기 (B) 유기 단섬유를 1질량부 이상 20질량부 미만 함유하는, 중합체 조성물.According to paragraph 1,
A polymer composition containing 1 part by mass or more and less than 20 parts by mass of the organic short fibers (B) relative to 100 parts by mass of the conjugated diene polymer (A).
상기 (A) 공액 디엔계 중합체의, 겔 투과 크로마토그래피로 측정한 폴리스티렌 환산의 중량 평균 분자량이 10,000∼2,000,000인, 중합체 조성물.According to paragraph 1,
A polymer composition wherein the conjugated diene polymer (A) has a weight average molecular weight of 10,000 to 2,000,000 in terms of polystyrene, as measured by gel permeation chromatography.
상기 (B) 유기 단섬유가, 지방족 폴리아미드, 방향족 폴리아미드 및 셀룰로오스계 폴리머로 이루어지는 군으로부터 선택되는 적어도 1종인, 중합체 조성물.According to paragraph 1,
A polymer composition wherein the (B) organic short fibers are at least one selected from the group consisting of aliphatic polyamide, aromatic polyamide, and cellulose polymer.
상기 (B) 유기 단섬유는, 평균 길이가 0.01㎜ 이상 20㎜ 이하이고, 또한, 평균 지름이 0.05㎛ 이상 50㎛ 이하인, 중합체 조성물.According to paragraph 1,
The (B) organic short fibers have an average length of 0.01 mm to 20 mm and an average diameter of 0.05 μm to 50 μm.
추가로, 가교제를 함유하는, 중합체 조성물.According to any one of claims 1 to 5,
A polymer composition further comprising a crosslinking agent.
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| JP6516462B2 (en) | 2013-12-13 | 2019-05-22 | 旭化成株式会社 | Method for producing modified conjugated diene polymer, modified conjugated diene polymer, and modified conjugated diene polymer composition |
| JP6487220B2 (en) * | 2015-01-22 | 2019-03-20 | 旭化成株式会社 | Modified conjugated diene polymer, method for producing modified conjugated diene polymer, and composition thereof |
| WO2017126629A1 (en) | 2016-01-19 | 2017-07-27 | 株式会社ブリヂストン | Rubber composition and tire |
| TWI636997B (en) * | 2016-06-24 | 2018-10-01 | 日商Ｊｓｒ股份有限公司 | Method for producing modified conjugated diene polymer, modified conjugated diene polymer, polymer composition, crosslinked body, tire and compound |
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2020
- 2020-03-19 JP JP2021509289A patent/JP7458373B2/en active Active
- 2020-03-19 CN CN202080012707.8A patent/CN113396070A/en active Pending
- 2020-03-19 KR KR1020217022116A patent/KR102625110B1/en active IP Right Grant
- 2020-03-19 WO PCT/JP2020/012194 patent/WO2020196220A1/en active Application Filing
- 2020-03-25 TW TW109109879A patent/TW202102586A/en unknown
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| WO2003087171A1 (en) | 2002-04-12 | 2003-10-23 | Bridgestone Corporation | Process for producing modified polymer, modified polymer obtained by the process, and rubber composition |
| JP2006290986A (en) | 2005-04-08 | 2006-10-26 | Bridgestone Corp | Rubber composition and tire using same |
| JP2010254858A (en) * | 2009-04-27 | 2010-11-11 | Bridgestone Corp | Rubber composition and tire for winter using the same |
| JP2011088988A (en) | 2009-10-21 | 2011-05-06 | Bridgestone Corp | Tire |
| JP2017508841A (en) | 2014-11-26 | 2017-03-30 | エルジー・ケム・リミテッド | Conjugated diene polymer rubber composition containing dispersant |
Also Published As
| Publication number | Publication date |
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| KR20210102405A (en) | 2021-08-19 |
| JP7458373B2 (en) | 2024-03-29 |
| WO2020196220A1 (en) | 2020-10-01 |
| CN113396070A (en) | 2021-09-14 |
| TW202102586A (en) | 2021-01-16 |
| JPWO2020196220A1 (en) | 2020-10-01 |
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