CN104159753B - Tire - Google Patents
Tire Download PDFInfo
- Publication number
- CN104159753B CN104159753B CN201380011721.6A CN201380011721A CN104159753B CN 104159753 B CN104159753 B CN 104159753B CN 201380011721 A CN201380011721 A CN 201380011721A CN 104159753 B CN104159753 B CN 104159753B
- Authority
- CN
- China
- Prior art keywords
- thermoplastic
- elastomer
- tire
- tyre framework
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001971 elastomer Polymers 0.000 claims abstract description 335
- 239000000806 elastomer Substances 0.000 claims abstract description 297
- 230000002787 reinforcement Effects 0.000 claims abstract description 206
- 239000000203 mixture Substances 0.000 claims abstract description 203
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 151
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 151
- 239000002253 acid Substances 0.000 claims abstract description 147
- 239000000463 material Substances 0.000 claims abstract description 136
- 229920005989 resin Polymers 0.000 claims abstract description 124
- 239000011347 resin Substances 0.000 claims abstract description 124
- 239000002184 metal Substances 0.000 claims abstract description 117
- 229910052751 metal Inorganic materials 0.000 claims abstract description 117
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 103
- 239000004793 Polystyrene Substances 0.000 claims abstract description 79
- 229920002397 Thermoplastic olefin Polymers 0.000 claims abstract description 79
- 229920002223 polystyrene Polymers 0.000 claims abstract description 79
- 229920002803 Thermoplastic polyurethane Polymers 0.000 claims abstract description 34
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 31
- 239000004952 Polyamide Substances 0.000 claims description 61
- 229920002647 polyamide Polymers 0.000 claims description 61
- 239000011528 polyamide (building material) Substances 0.000 claims description 61
- 150000001875 compounds Chemical class 0.000 claims description 31
- 150000001336 alkenes Chemical class 0.000 claims description 24
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 abstract description 19
- 238000006011 modification reaction Methods 0.000 abstract description 19
- 229920001577 copolymer Polymers 0.000 description 114
- 229920000642 polymer Polymers 0.000 description 54
- 229910000831 Steel Inorganic materials 0.000 description 50
- 239000010959 steel Substances 0.000 description 50
- -1 diol compound Chemical class 0.000 description 45
- 239000005060 rubber Substances 0.000 description 38
- 238000004519 manufacturing process Methods 0.000 description 37
- 229920002725 Thermoplastic elastomer Polymers 0.000 description 35
- 239000004215 Carbon black (E152) Substances 0.000 description 23
- 239000011324 bead Substances 0.000 description 22
- 150000002430 hydrocarbons Chemical class 0.000 description 22
- 150000001408 amides Chemical class 0.000 description 21
- 229910052799 carbon Inorganic materials 0.000 description 21
- 125000004432 carbon atoms Chemical group C* 0.000 description 20
- 229920000570 polyether Polymers 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 19
- 229920000728 polyester Polymers 0.000 description 19
- 230000002093 peripheral Effects 0.000 description 18
- 239000000126 substance Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000007334 copolymerization reaction Methods 0.000 description 14
- 238000005755 formation reaction Methods 0.000 description 14
- 150000003951 lactams Chemical class 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 12
- 239000004721 Polyphenylene oxide Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 230000001629 suppression Effects 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 10
- 238000009833 condensation Methods 0.000 description 10
- 230000005494 condensation Effects 0.000 description 10
- 238000010276 construction Methods 0.000 description 9
- 229920000098 polyolefin Polymers 0.000 description 9
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 9
- 125000001118 alkylidene group Chemical group 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N benzohydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 238000011068 load Methods 0.000 description 8
- 229920001195 polyisoprene Polymers 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 239000004677 Nylon Substances 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 6
- 239000004698 Polyethylene (PE) Substances 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 150000001261 hydroxy acids Chemical group 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001897 terpolymer Polymers 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 5
- 238000009434 installation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 230000003252 repetitive Effects 0.000 description 5
- 238000005987 sulfurization reaction Methods 0.000 description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- 210000002356 Skeleton Anatomy 0.000 description 4
- 229920003750 UBESTA® 3024 U Polymers 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive Effects 0.000 description 4
- 229920003232 aliphatic polyester Polymers 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- XVBLEUZLLURXTF-UHFFFAOYSA-N 2,4-dimethylbenzene-1,3-diamine Chemical compound CC1=CC=C(N)C(C)=C1N XVBLEUZLLURXTF-UHFFFAOYSA-N 0.000 description 3
- LDHQCZJRKDOVOX-IHWYPQMZSA-N Isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N Itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 229920002521 Macromolecule Polymers 0.000 description 3
- 229920001225 Polyester resin Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229920001451 Polypropylene glycol Polymers 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000002788 crimping Methods 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 3
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000088 plastic resin Substances 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-Butanediol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N Diphenylmethane p,p'-diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 229940117927 Ethylene Oxide Drugs 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N Isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 2
- 229920001748 Polybutylene Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N Suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229920003736 UBESTA® 3014 U Polymers 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N carbodiimide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000001413 cellular Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 2
- 230000004059 degradation Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N fumaric acid Chemical compound OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920000406 phosphotungstic acid polymer Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920002745 polystyrene-block- poly(ethylene /butylene) Polymers 0.000 description 2
- 229920001098 polystyrene-block-poly(ethylene/propylene) Polymers 0.000 description 2
- 229920002743 polystyrene-poly(ethylene-ethylene/propylene) block-polystyrene Polymers 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 230000002040 relaxant effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- UDGHHRGDHFMRBM-UHFFFAOYSA-N 1,2-diisocyanoethane Chemical compound [C-]#[N+]CC[N+]#[C-] UDGHHRGDHFMRBM-UHFFFAOYSA-N 0.000 description 1
- XFNJVJPLKCPIBV-UHFFFAOYSA-N 1,3-Diaminopropane Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-Propanediol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N 1,6-Hexanediol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- XAUQWYHSQICPAZ-UHFFFAOYSA-N 10-aminodecanoic acid Chemical compound NCCCCCCCCCC(O)=O XAUQWYHSQICPAZ-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 1
- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N 2,6-Naphthalenedicarboxylic acid Chemical class C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N 2-Pyrrolidone Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- REFDOIWRJDGBHY-UHFFFAOYSA-N 2-bromobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(Br)=C1 REFDOIWRJDGBHY-UHFFFAOYSA-N 0.000 description 1
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxybenzene-1,4-diol Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 1
- XCZKKZXWDBOGPA-UHFFFAOYSA-N 2-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1 XCZKKZXWDBOGPA-UHFFFAOYSA-N 0.000 description 1
- PUCZDHXCCADDII-UHFFFAOYSA-N 3-methylpentane-1,1-diamine Chemical compound CCC(C)CC(N)N PUCZDHXCCADDII-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N 4,4'-Biphenol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical class C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-Ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- UQXNEWQGGVUVQA-UHFFFAOYSA-N 8-aminooctanoic acid Chemical compound NCCCCCCCC(O)=O UQXNEWQGGVUVQA-UHFFFAOYSA-N 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N Azelaic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 210000000988 Bone and Bones Anatomy 0.000 description 1
- 229960003563 Calcium Carbonate Drugs 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- TVIDDXQYHWJXFK-UHFFFAOYSA-N Dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 1
- 240000008528 Hevea brasiliensis Species 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N Hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N Hexamethylenediamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- ZJTLZYDQJHKRMQ-UHFFFAOYSA-N Menadiol Chemical compound C1=CC=CC2=C(O)C(C)=CC(O)=C21 ZJTLZYDQJHKRMQ-UHFFFAOYSA-N 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- 229940117969 NEOPENTYL GLYCOL Drugs 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- YMVIYCFGOTYKGI-UHFFFAOYSA-N OC.OC.C1CCCCCCCCC1 Chemical compound OC.OC.C1CCCCCCCCC1 YMVIYCFGOTYKGI-UHFFFAOYSA-N 0.000 description 1
- 241000218970 Pepper golden mosaic virus - [Mexico] Species 0.000 description 1
- 240000005158 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N Phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- WLJVNTCWHIRURA-UHFFFAOYSA-N Pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 1
- 229920001083 Polybutene Polymers 0.000 description 1
- 229920000451 Polycaprolactone-block-polytetrahydrofuran-block-polycaprolactone Polymers 0.000 description 1
- 239000004146 Propane-1,2-diol Substances 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N Sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 210000003491 Skin Anatomy 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920003734 UBESTA® Polymers 0.000 description 1
- 229920003741 UBESTA® 3020 U Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229940106691 bisphenol A Drugs 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N butylene glycol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 102220350010 c.119C>A Human genes 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000039 congener Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009114 investigational therapy Methods 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical class C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N nonane-1,9-diol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- CFVVSQSFKWLGAX-UHFFFAOYSA-N phenol;propane Chemical compound CCC.OC1=CC=CC=C1 CFVVSQSFKWLGAX-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 150000004291 polyenes Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000035935 pregnancy Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QVKOLZOAOSNSHQ-UHFFFAOYSA-N prop-1-ene;prop-2-enoic acid Chemical compound CC=C.OC(=O)C=C QVKOLZOAOSNSHQ-UHFFFAOYSA-N 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 239000004589 rubber sealant Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N γ-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
Abstract
Epicycle mold has: formed by resin material and for ring-type tyre framework body；With the metal reinforcement cord component being wound to tyre framework outer circumferential portion.At least some of capped of this metal reinforcement cord component covers with mixture, and this covering mixture includes the specific elastomer of at least group that thermoplastic resin and choosing following (1) form to (3): (1) thermoplastic polyurethanes elastomer；(2) thermoplastic polystyrene class elastomer；(3) at least one of the group of thermoplastic olefin class elastomer, its thermoplastic olefin class elastomer comprising the acid modification selecting free elastic modelling quantity less than 140MPa and the elastic modelling quantity thermoplastic olefin class elastomer composition that acid is not modified less than 140MPa.
Description
Technical field
The present invention relates to for installing to the tire of wheel rim, and at least some of by setting particularly to wherein tire casing
The tire that fat material is formed.
Background technology
The pneumatic tire becoming known for the vehicles such as car is made up of rubber, organic fibrous material and steel beam column etc..
In recent years, from lightweight, easily shaping, the angle easily reclaimed, use resin material, particularly thermoplasticity are being studied
Plastics and thermoplastic elastomer (TPE) etc., as tire material.
Such as, patent documentation 1 (Japanese Patent Application Laid-Open (JP-A) 2003-104008 publication) and patent documentation 2
(JP-A H03-143701 publication) describes a kind of pneumatic tire, and this pneumatic tire is by thermoplastic macromolecule material, especially
It is that thermoplastic poly esters elastomer is formed.
Compared with traditional rubber ratch tire, use the tire of the macromolecular material (resin material) with thermoplastic characteristics more
Easily manufacture, and cost is lower.
In the case of using thermoplastic macromolecule material to manufacture tire, realization is needed to have compared with traditional rubber ratch tire
The performance (requirements of tire characteristics) of profit, the most also realizing manufacturing efficiency at low cost increases.
But, when tire is only formed by the uniform thermoplastic resin not comprising reinforcement members such as casingply, root
According to JP-A 2003-104008 publication, compare with traditional rubber ratch tire, it is difficult to realize equal compression resistance, internal pressure resistance
And rigidity.But, according to JP-A H03-143701 publication, it is wound with benefit with continuous helical shape along tire circumferential direction
The strengthening course of strong cord, is arranged at the outer surface radially of the tire bottom the tyre surface of tire body (tyre framework body), and tire
Cutting resistance and the puncture resistance of skeleton body are improved.
Propose about all-steel cord (steel wire) technology as strengthening course (belt), including can be used for radial
Body piles, tyre ring reinforcement layer, and the tire of belt all-steel cord (with reference to No. 4423772 publications of Japanese Patent No.), with
And the steel wire that covered by composition for thermoplastic elastomer of all-steel cord thereon is formed and is used as belt (belt portion) or carcass portion
The pneumatic tire (with reference to No. 4465916 publications of Japanese Patent No.) of the supporting material divided.
Summary of the invention
The problem that invention is to be solved
Generally, when using reinforcement cord, at the aspect of performance of tire, reinforcement cord is needed to be adequately secured to tire bone
On support body.But, when hardware such as all-steel cord is used as reinforcement cord, under common condition of molding, it is difficult to mended
Strong cohesiveness good between cord and tyre framework body.
After investigation, the inventors have discovered that the durability of tire self can be by improving tyre framework body and reinforcement structure
Adhesion durability between part such as all-steel cord and be improved, in order in run duration opposing vibration etc..
No. 4423772 publications of Japanese Patent No. describe a kind of tire all-steel cord, and it has thermoplastic elastomer (TPE) group
Compound, loads to the steel construction that torsion (twisted) structure of core and the sheath (sheath) being formed of a wire is formed.But, when
When this technology is for installing to rubber system radial tire, it is not involved with between tire and the reinforcement members of use resin material
Relation.And, No. 4465916 publications of Japanese Patent No. describe a kind of tire, are tyre framework about using resin material
The tire of body is also not involved with improving the adhesion durability between reinforcement members and tyre framework body.
The present invention provides a kind of tire, and it is formed by resin material, and has excellent between reinforcement cord and tyre framework body
Different adhesion durability.
For solving the scheme of problem
As the first embodiment, the present invention provides a kind of tire, comprising:
The ring-type tyre framework body formed by resin material；With
The metal reinforcement cord component being wound on tyre framework external week, at least of this metal reinforcement cord component
The covering mixture being included thermoplastic resin and thermoplastic polyurethanes elastomer is divided to cover.
As the second embodiment, the present invention provides a kind of tire, comprising:
The ring-type tyre framework body formed by resin material；With
The metal reinforcement cord component being wound on tyre framework external week, at least of this metal reinforcement cord component
The covering mixture being included thermoplastic resin and thermoplastic polystyrene class elastomer is divided to cover.
As the 3rd embodiment, the present invention further provides a kind of tire, comprising:
The ring-type tyre framework body formed by resin material；With
The metal reinforcement cord component being wound on tyre framework external week, wherein,
This metal reinforcement cord component be included thermoplastic resin and thermoplastic olefin class elastomer at least partially
Covering mixture covers, and this thermoplastic olefin class elastomer selects the thermoplasticity that free elastic modelling quantity is modified less than the acid of 140MPa
The group of olefin type elastomer and the elastic modelling quantity thermoplastic olefin class elastomer composition that acid is not modified less than 140MPa is at least
A kind of.
Accompanying drawing explanation
Figure 1A is the perspective cross-sectional view that a part for tire according to embodiments of the present invention is described.
Figure 1B is the cross section in the tire bead portion according to embodiment of the present invention, and bead part has been installed to wheel rim.
Fig. 2 be along the first embodiment tire tire rotary shaft intercept and illustrate that wherein reinforcement cord is embedded in tire
The cross section of the state of the bizet of casing.
Fig. 3 is saying of the operation of the bizet explaining that reinforcement cord is embedded in tire casing by use cord heater and roller
Bright figure.
Fig. 4 is to intercept along the tire rotary shaft of the second embodiment tire and illustrate and comprise reinforcement cord cover layer state
Cross section, on this reinforcement cord cover layer, metal reinforcement cord component has been embedded in the bizet of the tire casing of tire.
Detailed description of the invention
The tire of the present invention includes the ring-type tyre framework body formed by resin material, and is wound on tyre framework external week
On metal reinforcement cord component, wherein at least some of capped mixture of this metal reinforcement cord component is (referred to hereinafter as
For " specific covering mixture ") cover, this covering mixture includes that at least thermoplastic resin and choosing following (1) are extremely
(3) elastomer (hereinafter referred to as " specific elastomer ") of the group formed:
(1) thermoplastic polyurethanes elastomer；
(2) thermoplastic polystyrene class elastomer；With
(3) thermoplastic olefin class elastomer, it comprises the thermoplasticity selecting free elastic modelling quantity modified less than the acid of 140MPa
The group of olefin type elastomer and the elastic modelling quantity thermoplastic olefin class elastomer composition that acid is not modified less than 140MPa is at least
A kind of.
When forming the tire using metal reinforcement cord component, from the angle of tyre last, need metal reinforcement curtain
Line components is adequately secured to tyre framework body.From the angle of tyre last, when forming tire, air is preferably avoided to remain
(bubble) occurs in around cord, and it is the reason that metal reinforcement cord component moves.And, from riding quality in automobile etc.
Angle, the material on the tyre framework body of resin tire is preferably soft.But, when rigid member such as all-steel cord is used
When making metal reinforcement cord component, the difference existed between the elastic modelling quantity of flexible resin material and metal reinforcement cord component
(poor rigidity) is big so that hardly result in, between tyre framework body and metal reinforcement cord component, durability of sufficiently adhering.
If the thermoplastic resin contacting metal surface of molten condition, and allow hardening in this condition, can realize gold
The firm adhesion of metal surface, thus increase the covering mixture resistance to pull out (pull-out to metal reinforcement cord component
resistance).And, comprise the covering mixture of at least thermoplastic resin and specific elastomer, be present in metal reinforcement
Interface between cord component and the resin material forming tyre framework body, it is possible to make metal reinforcement cord component and tyre framework
Poor rigidity between body relaxes.Especially, the characteristic of specific covering mixture, such as flexible (tensile modulus of elasticity), hot strength
And elongation at break, and can only use thermoplasticity by adjusting the content of thermoplastic resin and specific elastomer than easily adjusting
Resin-phase ratio, makes flexible being easier to improve.And, specific covering mixture has thermoplastic resin and specific elastomer conduct
Key component is therefore the most excellent to the cohesiveness of the tyre framework body using resin material.Therefore, metal reinforcement cord structure
Part is coated with specific covering mixture, can efficiently improve the resistance to pull out of metal reinforcement cord component, and to tyre framework body
Cohesiveness, the most effectively relaxes the poor rigidity between the resin material and the metal reinforcement cord component that form tire, by increasing capacitance it is possible to increase
Adhesion durability between metal reinforcement cord component and tyre framework body.
" at least some of of metal reinforcement cord component is used by the covering comprising at least thermoplastic resin and specific elastomer
Mixture covers " refer to, part or all of metal reinforcement cord component surface is covered by specific covering mixture
State.Such as, specific covering mixture covers the some or all of shape of the metal reinforcement cord component periphery as core
State；Or when reinforcement cord cover layer is constituted by comprising specific covering mixture, and when being arranged at the periphery of tyre framework body, gold
Part or all belonging to reinforcement cord component is embedded in the state of reinforcement cord cover layer.
Such structure, at least some of of metal reinforcement cord component can be used to be buried to underground tyre framework body.Such as,
When specific covering mixture covers part or all of the metal reinforcement cord component periphery as core, if metal is mended
Strong cord component is embedded in tyre framework body, can increase tyre framework body and cover the covering mixing of metal reinforcement cord component
Contact surface area between thing.Therefore the adhesion durability of metal reinforcement cord component can further improve.Specific by comprising
In the case of the reinforcement cord cover layer that covering mixture is formed is arranged at the periphery of tyre framework body, metal reinforcement cord structure
The adhesion durability of part is available to be increased further because metal reinforcement cord component can be tightly fixed on tyre framework body and
It is in close contact, and as between specific covering mixture and the tyre framework body of reinforcement cord cover layer, by by metal
Reinforcement cord component is embedded in tyre framework surface, can form broad surface area and be in close contact and adhesion.
Will be described below the metal reinforcement cord component of the present invention；With cover metal reinforcement cord component and comprise the hottest
The covering mixture of plastic resin and specific elastomer；With form the resin material of tyre framework body, next to that referring to the drawings
Explanation to the specific embodiments of tire of the present invention.
In this specification, " resin " comprises thermoplastic resin and thermosetting resin, but does not include natural rubber." thermoplasticity
Elastomer " refer to the thermoplastic resin material that formed by copolymer, this copolymer include by crystallinity and have dystectic firmly
Segment, or the polymer that the hard segment with high cohesion is formed, and amorphism and there is the soft chain of lower glass transition temperatures
The polymer that section is formed.In the following description of resin, " identical type " represents that both are esters, or both are phenylethylene etc..
<metal reinforcement cord component>
Cord is as prepared by metal and for the cord of traditional rubber ratch tire, can be used as metal reinforcement if appropriate
Cord component.The example that can be used as metal reinforcement cord component includes monofilament (sub-thread) metallic fiber, or multifilament (twists with the fingers stock
(twisted strands)) torsioned fibres, as reversed the all-steel cord of steel fibre.Not special provision metal reinforcement cord component
Shape of cross section or size (diameter) etc., and these suitably can select according to desired tire.
Sub-thread or the multiple stock of metal reinforcement cord component can along the circumferential direction be wound on tyre framework body, and can be continuous
Helical form winds continuously in the circumferential direction.Metal reinforcement cord component can wind along the circumferencial direction of tyre framework body, in order to can
Along tyre framework body width uniform intervals, or can crossover winding.
And, in order to improve cohesiveness, metal reinforcement cord component can bear surface and process, and can be activated, can be coated with viscous
Mixture.
(in following this specification, " elastic modelling quantity " refers to draw the tensile modulus of elasticity of metal reinforcement cord component self
Stretching elastic modelling quantity, unless stated otherwise), ordinarily be about 100000MPa to 300000MPa, preferably 120000MPa is extremely
270000MPa, more preferably 150000MPa to 250000MPa.It should be noted that the stretching bullet of metal reinforcement cord component
The gradient calculation of the property modulus load-deformation curve by drawing with ZWICK type chuck (chuck) in cupping machine obtains
's.
The elongation at break (Tensile elongation at break) of metal reinforcement cord component self ordinarily be about 0.1% to 15%,
It is preferably 1% to 15%, more preferably 1% to 10%.The Tensile elongation at break of metal reinforcement cord component is selected from stretching
The strain of the load-deformation curve that ZWICK type chuck is drawn in testing machine.
<covering mixture>
The covering mixture covering metal reinforcement cord component comprises at least thermoplastic resin and specific elastomer.Specific
The characteristic of covering mixture, such as flexibility (elastic modelling quantity), hot strength and the elongation at break of covering mixture, can pass through
The content adjusting thermoplastic resin and specific elastomer adjusts than easily, particularly compared with only using thermoplastic resin, it is possible to
Flexible being easier to is made to improve.
At least some of metal reinforcement cord component is covered by specific covering mixture and is sufficient to, and as it has been described above,
Specific covering mixture cover as core metal reinforcement cord component periphery some or all of in the case of, and
Formed by comprising specific covering mixture at reinforcement cord cover layer, and in the case of being arranged at the periphery of tyre framework body,
Part or all of metal reinforcement cord component is buried reinforcement cord cover layer underground and is sufficient to.Preferably metal reinforcement cord component
And all positions by the interface between the tyre framework body of specific covering mixture covering, more preferably covered with mixed by specific
The whole surface of the metal reinforcement cord component that compound covers.
Without particular limitation of the method covering metal reinforcement cord component with specific covering mixture, and can use as one sees fit
Know cord covering method etc..Such as, one of the metal reinforcement cord component periphery as core is covered at specific covering mixture
In the case of Bu Fenhuoquanbu, available known cross-head extruder is covered all-steel cord by the thermoplastic resin of molten condition
Method.And, when forming reinforcement cord cover layer, all-steel cord can be embedded in the reinforcement cord cover layer of molten condition, or
Reinforcement curtain face cover layer can be formed after being wound up into by all-steel cord on tyre framework body.And, can use wherein that all-steel cord has been
After being embedded in the reinforcement cord cover layer of molten condition, the covering mixture of molten condition is by further lamination, by steel wire
Cord is embedded in the method etc. of reinforcement cord cover layer completely.
From the effectively angle of poor rigidity, specific covering mixture between suppression tyre framework body and metal reinforcement cord component
The tensile modulus of elasticity of self is preferably 50MPa to 2000MPa, more preferably 50MPa extremely according to JIS K7113:1995 definition
1700MPa, and particularly preferably 50MPa to 1600MPa.
From the angle of the poor rigidity effectively relaxed between metal reinforcement cord component and tyre framework body, specific covering is with mixed
The elastic modelling quantity of compound self is preferably set to 0.1 times to 20 times of the elastic modelling quantity of the resin material of formation tyre framework body
In the range of, more preferably it is set as, in the range of 0.2 times to 10 times, being particularly preferably set as in the range of 0.5 times to 5 times.Work as spy
Determine the elastic modelling quantity that the elastic modelling quantity of covering mixture is the thermoplastic resin material forming tyre framework body less than 20 times
Time, poor rigidity is relaxed, it addition, crown part will not become too hard and easily realize to the installation (fittability) of wheel rim.
When the elastic modelling quantity that the elastic modelling quantity of specific covering mixture is the thermoplastic resin material forming tyre framework body 0.1 times
Time above, covering mixture is not too soft, and has belt inplane shear rigidity and the lateral deviation power of raising of excellence
The tire of (cornering force) is attainable.
From the angle of the poor rigidity effectively relaxed between tyre framework body and metal reinforcement cord component, specific covering is with mixed
The elastic modelling quantity of compound self is preferably arranged to the elastic modelling quantity higher than tyre framework body, and less than metal reinforcement cord component
Elastic modelling quantity.
The tensile modulus of elasticity of specific covering mixture self ordinarily be about according to JIS K7113 (1995) definition
50MPa to 2000MPa, preferably 50MPa to 1700MPa, more preferably 50MPa to 1600MPa.
About the tensile modulus of elasticity of specific covering mixture self, from effectively relaxing the resin forming tyre framework body
The poor rigidity of material and metal reinforcement cord component and improve the angle of durability of adhering, the tensile modulus of elasticity of tyre framework body
(x1), the tensile modulus of elasticity (x2) of covering mixture, and the tensile modulus of elasticity (x3) of metal reinforcement cord component is preferred
Meet relation x1 < x2 < x3.
The Tensile elongation at break of specific covering mixture self is according to JIS K7113 (1995) definition the most about
10% to 600%, preferably 10% to 500%, more preferably 10% to 300%.
For the elongation at break of specific covering mixture self, from effectively relaxing the resinous wood forming tyre framework body
Poor rigidity between material and metal reinforcement cord component and the angle of raising adhesion durability, the elongation at break of tyre framework body
(y1), the elongation at break (y2) of covering mixture, and the elongation at break (y3) of metal reinforcement cord component is the most satisfied
Relation y1 > y2 > y3.
(thermoplastic resin)
It is comprised in and specific covering mixture can be used as the suitable example of thermoplastic resin includes following for taking turns
The polymer forming thermoplastic resin hard segment of tire skeleton body.The example of this thermoplastic resin includes thermal plastic urethane class tree
Fat, thermoplastic olefin resinoid, thermoplasticity vinyl chloride resin, polyamide thermoplastic resinoid, thermoplastic polyester resin and
Thermoplastic polystyrene resinoid, wherein particularly preferred polyamide thermoplastic resinoid.Plasticity polyamide-based resin is used to make
Thermoplastic resin for specific covering mixture can make to improve the resistance to pull out of metal reinforcement cord component further.
The thermoplastic resin material being contained in covering mixture preferably considers the resin material for tyre framework body
Cohesiveness.Especially, use the resin material resin material forming tyre framework body of identical type, and be contained in covering
The cohesiveness between tyre framework body and covering mixture can be made to improve further with the thermoplastic resin of mixture.Use phase
Congener resin refers to, such as, is used as to be contained in the thermoplastic resin of covering mixture at polyamide thermoplastic resinoid
In the case of, using polyamide thermoplastic class elastomer is the resin material forming tyre framework body.
The tensile modulus of elasticity of the thermoplastic resin self being contained in covering mixture defines according to JISK7113:1995
Preferably from 50MPa to 2000MPa, more preferably 50MPa to 1700MPa, and particularly preferably 50MPa to 1600MPa.
The following is the polyamide thermoplastic resinoid thermoplastic resin as the covering mixture that is contained in the present invention
The explanation of related example, but the present invention is not limited to this.
-polyamide thermoplastic resinoid-
The resinoid example of polyamide thermoplastic includes the polyamide forming following polyamide thermoplastic resinoid hard segment.
The resinoid example of polyamide thermoplastic includes the polyamide (amide 6) of the open loop condensation polymer of epsilon-caprolactams, 11 lactams
The polyamide (amide 11) of open loop condensation polymer, the polyamide (amide 12) of the open loop condensation polymer of dodecanoic lactam, diamidogen and
The polyamide (amide 66) of the condensation polymer of diacid, and there is the polyamide (amide MX) that m-xylene diamine is construction unit.
Amide 6 can be by such as, { CO-(CH2)5-NH}nRepresent (wherein n represents the number of repetitive).Amide 11 can be by
Such as, { CO-(CH2)10-NH}nRepresent (wherein n represents the number of repetitive).Amide 12 can be by such as, { CO-(CH2)11-
NH}nRepresent (wherein n represents the number of repetitive).Amide 66 can be by such as, { CO (CH2)4CONH(CH2)6NH}nRepresent (its
Middle n represents the number of repetitive).And, having amide MX that m-xylene diamine is construction unit can be by such as, following knot
Structure unit (A-1) represents (wherein the n in (A-1) represents the number of repetitive).Such as, commercially available prod can be used as by Ube
" UBE NYLON " 1022B or 1011FB that Industries, Ltd. manufacture is as amide 6.Can use and to be manufactured by ArkemaAs amide 11." UBESTA 3024U " can be used, " UBESTA 3020U ", " UBESTA 3014U " (business
The name of an article, by Ube Industries, Ltd. manufacture) etc. as amide 12." UBE NYLON 2020B " or " UBE can be used
NYLON 2015B " (trade name) etc. as amide 66.And, commercially available prod such as can be used as by Mitsubishi Gas
MX NYLON S6001, the MX NYLON S6021 of Chemical Company, Inc. manufacture or MX NYLON S6011 etc. make
For amide MX.
Polyamide thermoplastic resinoid can be the homopolymer being only made up of construction unit (A-1), can be maybe construction unit (A-
1) and the copolymer of other monomer.In the case of the copolymer, construction unit (A-1) is in each polyamide thermoplastic resinoid
Content than preferably 40 mass % more than, more than more preferably 60 mass %.
From the angle of the elastic modelling quantity etc. improving covering mixture, the resinoid number-average molecular weight of polyamide thermoplastic is excellent
Elect 300 to 30000 as.And, from toughness and the angle of low temperature flexibility, the number-average molecular weight of the polymer forming soft chain segment is preferred
Be 200 to 20000.
(specific elastomer)
The group that the specific elastomer choosing following (1) being contained in specific covering mixture forms to (3).
(1) thermoplastic polyurethanes elastomer
(2) thermoplastic polystyrene class elastomer
(3) thermoplastic olefin class elastomer, it comprises the thermoplasticity selecting free elastic modelling quantity modified less than the acid of 140MPa
Olefin type elastomer, and the group of the thermoplastic olefin class elastomer composition that acid is not modified that elastic modelling quantity is less than 140MPa is at least
A kind of.
" thermoplastic elastomer (TPE) " refers to the thermoplastic resin material formed by copolymer, and this copolymer includes: form crystallization
Property and there is dystectic hard segment or there is the polymer of hard segment of high cohesion, and form amorphism and there is low glass
Change the polymer of the soft chain segment of transition temperature.
(thermoplastic polyurethanes elastomer)
Owing to fusing point (softening point) can be set near 85 DEG C to 220 DEG C, comprise as specific so easily using
The thermoplastic resin material of the thermoplastic polyurethanes elastomer of elastomer (1).Especially, thermoplastic polyurethanes elastomer pair
Metal reinforcement cord component has high adhesion, and when metal reinforcement cord component is made up of torsioned fibres, not only at metal
Between the fiber of reinforcement cord component self, and it is easy to be impregnated with between cord reversing.Thermoplastic polyurethanes elastomer
Elongation characteristics excellent, and fracture excellent in te pins of durability.And, thermoplastic polyurethanes elastomer often has excellence to other resin
Cohesiveness.Therefore, the adhesive angle between tyre framework body and specific covering mixture, select resin material to use
Tend to higher in the degree of freedom forming tyre framework body.
The example of thermoplastic polyurethanes elastomer includes having assembles (physical at least through physics
Aggregation) form vacation crosslinking (pseudo-crosslinks) and form the polyurethane of hard segment and form amorphism and tool
There is the material of other polymer of the soft chain segment of lower glass transition temperatures, such as according to the thermoplastic of JISK6418:2007 definition
Property polyurethane elastomer (TPU).Thermoplastic polyurethanes elastomer can be by comprising containing the cellular construction represented by following formula A
Soft chain segment and copolymer containing the hard segment of cellular construction represented by following formula B represent.
Formula A
Formula B
In formula, P represents long-chain fat adoption ether, or long-chain fat adoption ester.R represents aliphatic hydrocarbon, clicyclic hydrocarbon or virtue
Fragrant race hydrocarbon.P' represents short-chain aliphatic hydrocarbon, clicyclic hydrocarbon or aromatic hydrocarbon.
In formula A, such as molecular weight be 500 to 5000 material can be used as the long-chain fat adoption ether or the long-chain that are represented by P
Aliphatic polyester.P is selected from and comprises the long-chain fat adoption ether or the diol compound of long-chain fat adoption ester represented by P, this type of
The example of diol compound includes having the Polyethylene Glycol of molecular weight within the above range, polypropylene glycol, polytetramethylene ether
Glycol, poly-(tetramethylene adipate) glycol, poly-6-caprolactone glycol, poly-(carbonic acid pregnancy ester) glycol and ABA type three block are poly-
Ether (polyethers is represented by above formula (3)).
These compounds can individually or use with its two or more combination.
In formula A and B, R is selected from the two isocyanide acids comprising the aliphatic hydrocarbon, clicyclic hydrocarbon or the aromatic hydrocarbon that are represented by R
Compound.The example of the aliphatic two Carbimide. compounds comprising the aliphatic hydrocarbon represented by R includes 1,2-ethylene isocyanide
Acid esters, 1,3-trimethylene diisocyanate, 1,4-butane diisocyanate and 1,6-hexamethylene diisocyanate.
And, the example of the two Carbimide. compounds comprising the clicyclic hydrocarbon represented by R includes that Isosorbide-5-Nitrae-hexamethylene two is different
Cyanate or 4,4-cyclohexane diisocyanate.And the aromatic diisocyanates class chemical combination containing the aromatic hydrocarbon represented by R
The example of thing includes 4,4' diphenylmethane diisocyanate or toluene di-isocyanate(TDI).
These compounds can individually or use with its two or more combination.
In formula B, short-chain aliphatic hydrocarbon that the such as molecular weight material less than 500 can be used as being represented by P', clicyclic hydrocarbon or
Aromatic hydrocarbon.And, P' is selected from the glycol chemical combination comprising the short-chain aliphatic hydrocarbon, clicyclic hydrocarbon or the aromatic hydrocarbon that are represented by P'
Thing.The example of the aliphatic diol compound containing the short-chain aliphatic hydrocarbon represented by P' includes glycols and poly alkylene glycol
Class, it may for example comprise ethylene glycol, propylene glycol, trimethylene glycol, BDO, 1,3 butylene glycol, 1,5-PD, 1,6-oneself
Glycol, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol and decamethylene-glycol.
And, the example of the alicyclic diol compound containing the clicyclic hydrocarbon represented by P' includes Pentamethylene .-1,2-bis-
Alcohol, hexamethylene-1,2-glycol, hexamethylene-1,3-glycol, hexamethylene-1,4-glycol and hexamethylene-1,4-dimethanol.
Additionally, the example containing the aromatic diol compound of aromatic hydrocarbon represented by P' include hydroquinone, resorcinol,
Chlorohydroquinone, bromo hydroquinone, methylnaphthohydroquinone, pheny lhydro quinone, methoxyhydroquinon, phenoxy group hydroquinone, 4,4' dihydroxy diphenyl, 4,
4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl thioether, 4,4'-dihydroxydiphenylsulisomer, 4,4'-dihydroxy hexichol first
Double (4-hydroxy phenyl) ethane of ketone, 4,4'-dioxydiphenyl methane, bisphenol-A, 1,1-bis-(4-hydroxy phenyl) hexamethylene, 1,2-,
1,4-dihydroxy naphthlene and 2,6-dihydroxy naphthlene.
These compounds can individually or use with its two or more combination.
From the angle of melt-shaping character, the number-average molecular weight of the polymer (polyurethane) forming hard segment is preferably 300
To 1500.And, from flexibility and the angle of heat stability of thermoplastic polyurethanes elastomer, form the polymer of soft chain segment
Number-average molecular weight is preferably 500 to 20000, and more preferably 500 to 5000, and particularly preferably 500 to 3000.And, from one-tenth
The viewpoint of shape, hard segment (x) is preferably 15:85 to 90:10, more preferably 30:70 with the mass ratio (x:y) of soft chain segment (y)
To 90:10.
Thermoplastic polyurethanes elastomer can use known method by the polymer of above-mentioned formation hard segment and to be formed soft
The polymer copolymerization of segment synthesizes.Such as, the thermoplastic polyurethane recorded according to JP-A H05-331256 can be used as thermoplasticity
Polyurethane elastomer.
Specifically, what thermoplastic polyurethanes elastomer was preferably made up of aromatic diol and aromatic diisocyanate is hard
Segment, and the combination of the soft chain segment being made up of Merlon, preferably toluene di-isocyanate(TDI) (TDI)/polyester polyol copolymerization
Thing, TDI/ polyethers class polyols Polyol copolymer, TDI/ caprolactone class polyol copolymer, TDI/ are polycarbonate-based polynary
Alcohol copolymer, 4,4' diphenylmethane diisocyanate (MDI)/polyester polyol copolymer, MDI/ polyether alcohol copolymerization
Thing, MDI/ caprolactone class polyol copolymer, the polycarbonate-based polyol copolymer of MDI/ or MDI+ hydroquinone/polyhexamethylene
Carbonate copolymer, more preferably TDI/ polyester polyol copolymer, TDI/ polyether alcohol copolymer, MDI/ polyesters are many
Unit's alcohol copolymer, MDI/ polyether alcohol copolymer or MDI+ hydroquinone/polyhexamethylene carbonate copolymer.
And, the example of the commercially available prod that can be used as thermoplastic polyurethanes elastomer includes being manufactured by BASF SE(example includes seriesET680, ET880, ET690 and ET890), by
Kuraray Co., Ltd. manufactureSeries (such as, 2000 series, 3000 series, 8000 be
Row and 9000 series), and manufactured by Nippon Miractran Co., Ltd.Series is (such as,XN-2001, XN-2004, P390RSUP, P480RSUI, P26MRNAT, E490, E590 and P890).
(thermoplastic polystyrene class elastomer)
Thermoplastic polystyrene class elastomer as specific elastomer (2) often has good adhesion to other resin
Property.Therefore, the adhesive angle between tyre framework body and specific covering mixture material, it is used for forming tyre framework
The selection degree of freedom of the resin material of body tends to higher.The thermoplastic polystyrene class modified by the acid that acidic-group is modified is elastic
Body, or unmodified thermoplastic polystyrene class elastomer, can be used as thermoplastic styrene class elastomer.Unmodified thermoplasticity
Polystyrene type elastomer also can be used in conjunction with by the thermoplastic polystyrene class elastomer modified with acid.Unmodified thermoplastic poly
Styrenic elastomer be have especially excellence to metal reinforcement cord component resistance to pull out, material flowability (operating characteristic) and
Material adhesive to tyre framework body.The thermoplastic polystyrene class elastomer of acid modification is that the fracture especially with excellence is stretched
The material of long rate.And, it is used in conjunction with the modified thermoplastic polystyrene class elastomer of acid and unmodified thermoplasticity polyphenyl second
During alkenes elastomer, it is possible to realize the cohesiveness to tyre framework body and metal is increased the resistance to pull out of cord component, the most real
Existing excellent elongation at break characteristic.
The example of thermoplastic polystyrene class elastomer includes having the polystyrene at least forming hard segment, and forms tool
Have the soft chain segment of lower glass transition temperatures other polymer (such as polybutadiene, polyisoprene, polyethylene, hydrogenation gather
Butadiene or hydrogenated polyisoprene etc.) material.Synthetic rubber, such as sulfuration SBR resin etc., can be used as thermoplasticity polyphenyl second
Alkenes elastomer.
The example that can be suitable as being formed the polystyrene of hard segment includes using known free radical polymerisation process to obtain
Those, or use those that known ion polymerization obtains, such as, there is the polyphenyl of living anion polymerization thing form
Ethylene.Form the example of polymer of soft chain segment and include polybutadiene, polyisoprene and poly-(2,3-dimethyl-butadiene)
Deng.The thermoplastic polystyrene class elastomer of acid modification can be as described by elastic to unmodified thermoplastic polystyrene class
Body carries out acid modification and obtains.
Above-mentioned hard segment and the respective example being combined as hard segment and soft chain segment combinations thereof of soft chain segment.The most preferred
The combination of polystyrene/polybutadiene, or the combination of polystyrene/polyisoprene.And, in order to suppress thermoplastic elastomer (TPE)
Involuntary cross-linking reaction, soft chain segment be preferably hydrogenation.
Form the number-average molecular weight of polymer (polystyrene) of hard segment and be preferably 5000 to 500000, and preferably
10000 to 200000.
And, the number-average molecular weight of the polymer forming soft chain segment is preferably 5000 to 1000000, and more preferably 10000
To 800000, and particularly preferably 30000 to 500000.And, from formability angle, the hard segment (x) body to soft chain segment (y)
Long-pending than (x:y) preferably 5:95 to 80:20, be still more preferably from 10:90 to 70:30.
Thermoplastic polystyrene class elastomer can use the known method polymer by above-mentioned formation hard segment and formation
The polymer copolymerization of soft chain segment synthesizes.
The example of thermoplastic polystyrene class elastomer includes styrene-butadiene analog copolymer [SBS (polystyrene-poly
(butylene) block-polystyrene) and SEBS (polystyrene-poly (ethylene/butylene) block-polystyrene)], styrene-isoamyl
Type copolymers [polystyrene-polyisoprene block-polystyrene], styrene-propene analog copolymer [SEP (polyphenyl second
Alkene-(ethylene/propene) block), SEPS (polystyrene-poly (ethylene/propene) block-polystyrene), SEEPS (polystyrene-
Poly-(ethylene-vinyl/propylene) block-polystyrene)], and SEB (polystyrene (ethylene/butylene) block), and particularly preferably
SEBS。
The example of the commercially available prod that can be used as unmodified thermoplastic polystyrene class elastomer includes that those select free Asahi
Kasei Corporation manufacturesSeries (such as, H1031, H1041, H1043, H1051, H1052,
H1053, H1062, H1082, H1141, H1221 or H1272), and the SEBS manufactured by Kuraray Co., Ltd. is (such as5127 or 5125), SEPS is (such as2002,2063, S2004 or S2006).
" acid modified thermoplastic polystyrene class elastomer " refers to have acidic-group such as hydroxy-acid group, sulfur by making
The unsaturated compound of acid groups or phosphate group is bonded with unmodified thermoplastic polystyrene class elastomer and acid is modified
Thermoplastic polystyrene class elastomer.The thermoplastic polystyrene class elastomer of acid modification can make unsaturated carboxylic acid by such as
Or the unsaturated binding site of unsaturated carboxylic acid anhydrides is bonded (such as, passing through glycerol polymerization) with thermoplastic polystyrene class elastomer
And obtain.
From the angle of suppression thermoplastic polystyrene class elastomer degradation, (unsaturated) compound with acidic-group is excellent
Electing the compound with the hydroxy-acid group as faintly acid group as, the most spendable example includes acrylic acid, metering system
Acid, itaconic acid .beta.-methylacrylic acid, iso-crotonic acid and maleic acid.
The example of the thermoplastic polystyrene class elastomer that acid is modified includes being manufactured by Asahi Kasei Corporation
'sSuch asM1943, M1911 or M1913, and the FG19181G (business manufactured by Kraton Inc.
The name of an article).
The acid number of the thermoplastic polystyrene class elastomer that acid is modified is preferably greater than 0mg (CH3ONa)/g and 20mg
(CH3ONa)/below g, more preferably higher than 0mg (CH3ONa)/g and 17mg (CH3ONa)/below g, and particularly preferably greater than
0mg(CH3ONa)/g and 15mg (CH3ONa)/below g.
(the thermoplastic olefin class elastomer of acid modification and the thermoplastic olefin class elastomer of acid modification)
Thermoplastic olefin class elastomer is to have resilient macromolecular compound, and is to comprise formation crystallinity and have height
The polymer of the hard segment of fusing point, and comprise and form amorphism and there is the polymer of soft chain segment of lower glass transition temperatures
The thermoplastic resin material of copolymer, wherein, the polymer forming hard segment is polyolefin such as polypropylene or polyethylene.
Thermoplastic olefin class elastomer as specific elastomer (3) comprises the acid selecting free elastic modelling quantity less than 140MPa
Modified thermoplastic olefin class elastomer (the thermoplastic olefin class elastomer that specific acid is modified) and elastic modelling quantity are less than 140MPa
The group that constitutes of the thermoplastic olefin class elastomer that acid is modified (the specific thermoplastic olefin class elastomer that acid is modified) extremely
Few one.
As it has been described above, the thermoplastic olefin class elastomer that acid is not modified that elastic modelling quantity is less than 140MPa (is referred to hereinafter as sometimes
For " the specific thermoplastic olefin class elastomer that acid is modified ") there is the flexibility of abundance, and good the hottest to other resin
The cohesiveness of plastic resin.The flexibility of specific covering mixture is prone to by by the specific thermoplastic olefin class bullet that acid is not modified
Gonosome is included in specific covering mixture and adjusts.The thermoplastic olefin class bullet that elastic modelling quantity is modified less than the acid of 140MPa
Gonosome (the most hereinafter referred to as " the thermoplastic polyolefin-like elastomer that specific acid is modified "), except the specific thermoplasticity that acid is not modified
Outside the character of olefin type elastomer, it is also equipped with the affinity to thermoplastic resin excellent especially, and suppresses specific covering with mixed
Being separated of compound, it is possible to make the durability of specific covering mixture be improved.Especially, when the specific heat that acid is not modified
When plasticity ethylene octane copolymer is used as specific elastomer, because the existence of the modified body (acid-modified bodies) of acid makes
Form the affinity between thermoplastic resin and the thermoplastic elastomer (TPE) of specific covering mixture with excellence so that be separated
It is less likely to occur.
The elastic modelling quantity of elastomer (3) refers to defining according to JISK7113:1995 of specific elastomer (3) less than 140MPa
Specific tensile modulus of elasticity is less than 140MPa.
From the angle of elastic modelling quantity, " 140MPa " is the elastic modelling quantity of thermoplastic olefin class elastomer, is as distinguishing bag
The thermoplastic resin in specific covering mixture containing specific elastomer (3) and the numerical value of the boundary line of specific elastomer (3).
I.e. in the macromolecular compound formed by covering mixture thermoplastic resin and specific elastomer (3), there is 140MPa
The macromolecular compound of above elastic modelling quantity is thermoplastic resin, has the macromolecule chemical combination of the elastic modelling quantity less than 140MPa
Thing is specific elastomer (3).
From gluing between the intensity and specific covering mixture and metal reinforcement cord component of specific covering mixture
The angle of the property, the elastic modelling quantity of specific elastomer (3) is preferably more than 0.1MPa, but less than 140MPa, more preferably 1MPa
To 120MPa, and particularly preferably 1MPa to 100MPa.
" acid is not modified " in the thermoplastic olefin class elastomer that acid is not modified refers to that thermoplastic olefin class elastomer does not has
Modified by acid.
The specific not thermoplastic olefin class elastomer that acid is modified and the thermoplasticity alkene of specific acid modification will be described separately below
Hydrocarbon elastomer.
(elastic modelling quantity thermoplastic olefin class elastomer that acid is not modified less than 140MPa)
The specific not thermoplastic olefin class elastomer that acid is modified is the thermoplastic olefin class elastomer also not having acid modified.
The example of thermoplastic polyolefin-like elastomer includes having and at least forms crystallinity and have dystectic hard segment
Polyolefin, and form amorphism and there is the polyolefin of soft chain segment of lower glass transition temperatures and to be different from this polyolefinic
The material of alkene.The polyolefinic example forming hard segment includes polyethylene, polypropylene, isotactic polypropylene and poly-fourth
Alkene.
The polyolefinic example forming hard segment includes polypropylene, isotactic polypropylene, polyethylene and 1-butylene.
The example of thermoplastic polyolefin-like elastomer include ethylene-propylene copolymer, propylene-1-hexene copolymer, propylene-
4-methyl isophthalic acid pentene copolymer, propene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl pentene copolymerization
Thing, ethylene-butene-1 copolymer, 1-butylene-1-hexene copolymer, 1-butylene-4-methyl pentene copolymer, ethylene-methyl-prop
Olefin(e) acid copolymer, ethylene methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-metering system
Butyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, Ethylene-butyl acrylate copolymerization
Thing, propylene-methacrylic acid copolymer, propylene-methylmethacrylate copolymer, propylene-ethyl methacrylate copolymers,
Propylene-butyl methacrylate copolymer, propylene acrylic acid methyl terpolymer, propylene acrylic acid methacrylate copolymers, propylene-the third
Olefin(e) acid acrylate copolymer, vinyl-vinyl acetate copolymer and propylene-vinyl acetate copolymer.
The preferred embodiment of thermoplastic polyolefin-like elastomer include ethylene-propylene copolymer, propylene-1-hexene copolymer,
Propylene-4-methyl isophthalic acid pentene copolymer, propene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl pentene
Copolymer, ethylene-butene-1 copolymer, ethylene-methacrylic acid copolymer, ethylene methyl methacrylate copolymer, second
Alkene-ethyl methacrylate copolymers, ethylene-methyl methacrylate acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-
Ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, propylene-methacrylic acid copolymer, propylene-methacrylic acid
Methyl terpolymer, propylene-ethyl methacrylate copolymers, propylene-butyl methacrylate copolymer, propylene acrylic acid first
Ester copolymer, propylene acrylic acid methacrylate copolymers, propylene acrylic acid acrylate copolymer, vinyl-vinyl acetate copolymer, and
Propylene-vinyl acetate copolymer, example the most still more preferably includes ethylene-propylene copolymer, propylene-1-butylene copolymerization
Thing, ethylene-butene-1 copolymer, ethylene-1-hexene copolymer and propylene-1-hexene copolymer.
The number-average molecular weight of thermoplastic olefin class elastomer is preferably 5,000 to 10,000,000.If thermoplastic polyolefin
The number-average molecular weight of hydrocarbon elastomer is 5, more than 000, and the deterioration of the mechanical-physical character of resin complexes will be suppressed.As
Really 10, less than 000,000, resin complexes is prone to processing.From similar angle, the equal molecule of number of thermoplastic olefin class elastomer
Amount more preferably 7,000 to 1,000,000.The number-average molecular weight of thermoplastic olefin class elastomer is particularly preferably 10,000 to 1,
000,000.Therefore this mechanical-physical character that can improve resin composite materials further and processability.
Thermoplastic olefin class elastomer can use known method pass through the above-mentioned polymer forming hard segment and formed soft
The polymer copolymerization of segment synthesizes.
Commercially available prod, the PRIME TPO (registered trade mark) such as manufactured by Prime Co., Ltd., or by Mitsui
The TAFMER (registered trade mark) that Chemicals Inc. manufactures, can be used as above-mentioned thermoplastic polyolefin-like elastomer.
(thermoplastic olefin class elastomer [the thermoplasticity alkene that specific acid is modified that elastic modelling quantity is modified less than the acid of 140MPa
Hydrocarbon elastomer])
The thermoplastic olefin class elastomer (the thermoplastic olefin class elastomer that specific acid is modified) of acid modification refers to acidifying
Product, by thermoplastic olefin class elastomer acidic-group such as hydroxy-acid group, sulfate group or the phosphoric acid modified from not acid
Group is acidified.The example that the acid of thermoplastic olefin class elastomer is modified is the compound general by use with acidic-group
Acidic-group introduces thermoplastic olefin class elastomer.From the angle of suppression thermoplastic olefin class elastomer degradation, modified for acid
The compound with acidic-group of thermoplastic olefin class elastomer preferably has the insatiable hunger of the hydroxy-acid group for faintly acid group
And compound, the most spendable example includes acrylic acid, methacrylic acid, itaconic acid .beta.-methylacrylic acid, iso-crotonic acid and Malaysia
Acid.
As the thermoplastic olefin class elastomer modified by acid, example includes the above-mentioned specific thermoplasticity alkene that acid is not modified
Hydrocarbon elastomer, and those of the most specific and preferred embodiment and the specific thermoplastic olefin class elastomer that acid is modified
Equally.
As the acid number of the thermoplastic olefin class elastomer of specific acid modification, any more than 0mg (CH3The value of ONa)/g is
Enough.
" acid number of the thermoplastic olefin class elastomer that specific acid is modified " refers to the thermoplasticity modified relative to specific acid
The gross mass of olefin type elastomer, the first of the acidified portion of the thermoplastic olefin class elastomer that required neutralization specific acid is modified
Sodium alkoxide CH3The gross mass of ONa.The thermoplastic olefin class elastomer modified in the acid being contained in specific covering mixture is single
In the case of kind, acid number is calculated by following calculating formula (1), in the heat that the acid being contained in specific covering mixture is modified
In the case of plastomeric olefin class elastomer is two kinds and above kind, acid number is calculated by following calculating formula (2).Should be noted that
, this acid number can be similar to the acid number of the modified thermoplastic polystyrene class elastomer of acid and calculates.
Calculating formula (1)
[(acid number of the thermoplastic olefin class elastomer A that specific acid is modified) × (thermoplastic olefin class bullet that specific acid is modified
The gross mass of gonosome A)]/(gross mass of the thermoplastic olefin class elastomer A that specific acid is modified)
Calculating formula (2)
[(acid number of the thermoplastic olefin class elastomer A that specific acid is modified) × (thermoplastic olefin class bullet that specific acid is modified
The gross mass of gonosome A)+(acid number of the thermoplastic olefin class elastomer B that specific acid is modified) × (thermoplasticity alkene that specific acid is modified
The gross mass of hydrocarbon elastomer B)+...]/(the thermoplastic olefin class bullet that in specific covering mixture, all specific acid are modified
The quality of gonosome)
It should be noted that the acid number of the modified thermoplastic olefin class elastomer A of specific acid in calculating formula (1), and meter
The acid number of thermoplastic olefin class elastomer A, B etc. that the specific acid in formula (2) is modified, according to using Feldalat NM (CH3ONa) in
Feldalat NM (the CH of the thermoplastic olefin class elastomer modified with the titration each specific acid of 1g3ONa) quality (mg) is measured.
Hereinafter, the unit of the acid number of the thermoplastic polyolefin-like elastomer that each specific acid is modified is mg (CH3ONa)/g。
From the angle of the injection moulding character of specific covering mixture, the thermoplastic olefin class elastomer that specific acid is modified
Acid number be preferably 0.1mg (CH3ONa)/more than g, but less than 20mg (CH3ONa)/g, more preferably 0.1mg (CH3ONa)/g is extremely
17.0mg(CH3ONa)/g, and particularly preferably 0.1mg (CH3ONa)/g to 15.0mg (CH3ONa)/g。
The number-average molecular weight of the thermoplastic polyolefin-like elastomer that specific acid is modified is preferably 5,000 to 10,000,000.
If the number-average molecular weight of the thermoplastic polyolefin-like elastomer that specific acid is modified is 5,000 to 10,000,000, specific acid changes
Property the elastic modelling quantity of thermoplastic polyolefin-like elastomer easily realize more than 140MPa, the thermoplastic polyolefin-like that specific acid is modified
Elastomer has sufficient mechanical-physical character and excellent processability.From similar angle, number-average molecular weight is more preferably 7,
000 to 1,000,000, and particularly preferably 10,000 to 1,000,000.
-content in covering mixture of thermoplastic resin and thermoplastic elastomer (TPE)-
From characteristic such as tensile yield strength and elongation at break and improve metal reinforcement cord component relative to specific
The angle of the resistance to pull out of covering mixture, specific covering mixture preferably has island structure, including containing thermoplastic resin
The marine facies (sea phase) of the substrate phase of fat, and the island phase for dispersion phase (island phase) containing specific elastomer.Compose
Give specific covering mixture to be dispersed in the substrate of thermoplastic resin with island structure, the most specific elastomer, it is possible to make spy
Determine the tensile modulus of elasticity of covering mixture, character such as hot strength and elongation at break, and metal reinforcement cord component
It is improved relative to the resistance to pull out of specific covering mixture.
Without particular limitation of thermoplastic resin content in specific covering mixture.Such as, have containing heat when formation
The marine facies of plastic resin and during containing the island structure of the island phase of specific elastomer, relative to always containing of specific covering mixture
Amount, the content of thermoplastic resin is preferably 51 volume % to 95 volume %, more preferably 60 volume % to 90 bodies by volume
Long-pending %, and more preferably 60 volume % to 85 volume %.Similarly, although depend on the specific heavy of selected thermoplastic resin
Amount, relative to the total content of specific covering mixture, the content of thermoplastic resin is preferably 55 mass % in mass to 95
Quality %, more preferably 60 mass % are to 90 mass %, and particularly preferably 60 mass % are to 85 mass %.
Similarly, without particular limitation of specific elastomer content in specific covering mixture.Such as, have when formation
Marine facies containing thermoplastic resin and during containing the island structure of the island phase of specific elastomer, relative to specific covering mixture
Total content, the content of specific elastomer by volume be preferably 5 volume % to 49 volume %, more preferably 10 volume % to 40
Volume %, and more preferably 15 volume % to 40 volume %.Similarly, although depend on the specific of selected thermoplastic resin
Weight, relative to the total content of specific covering mixture, the content of thermoplastic resin is preferably 5 mass % in mass to 45
Quality %, more preferably 10 mass % are to 40 mass %, and particularly preferably 15 mass % are to 40 mass %.
It is easily formed calmly and is formed island structure by the marine facies comprising thermoplastic resin mutually with the island comprising specific elastomer
Angle, thermoplastic resin (p) and thermoplastic styrene class elastomer (e) mass ratio (p/e) in specific covering mixture
It is preferably 95/5 to 55/45, more preferably 90/10 to 60/40, and particularly preferably 85/15 to 70/30.
In island structure, in thermoplastic resin, impact resistance character is improved on fine dispersion island the most especially.
When the thermoplastic polystyrene class elastomer that acid is modified is used as specific elastomer (2), and when the heat of specific acid modification
During specific elastomer (3) that plasticity cluster elastomer is used as in island structure, the acid number of the specific elastomer that acid is modified is the highest, island
Xiang Yue little；Acid number is the lowest, and island is the biggest.The acid number of the specific elastomer that acid is modified is the highest, resinoid with polyamide thermoplastic
Interact the biggest, and the melt viscosity of resin material increases.By using the elastomer of acid modification and unmodified elastomer
Combination (that is, in the case of using specific elastomer (2), use the modified thermoplastic polystyrene class elastomer of acid and not
The combination of modified thermoplastic polystyrene class elastomer, and in the case of using specific elastomer (3), use specific acid to change
Property thermoplastic polyolefin-like elastomer and the combination of the specific thermoplastic olefin class elastomer that acid is modified) adjust acid number,
The melt viscosity that can suppress specific covering mixture becomes the highest.
And, using unmodified thermoplastic polystyrene class elastomer (w) and the thermoplastic polystyrene of acid modification
In the case of the combination of class elastomer (z) is as thermoplastic polystyrene class elastomer, or using the specific heat that acid is not modified
The combination of thermoplastic olefin class elastomer (z) of plastomeric olefin class elastomer (w) and specific acid modification is as thermoplastic olefin class
In the case of elastomer, from easily operation angularly, mass ratio (w/z) range preferably from 10/90 to 90/10, more preferably
15/85 to 85/15, and particularly preferably 20/80 to 80/20.
Typically when using modified elastomer such as acid modified elastomer, show mixing (knead-mixing) (dispersion)
Time need a small amount of than energy (specific energy) and need not the effect that high-tech is mixing.But, when compounding amount therein is got over
Greatly, the gelation of resin the most easily occurs, and extrusion time flaw outward appearance (flake) such as rough surface it some times happens that.From these
Angle, when using the specific elastomer of acid modification, the specific elastomer of acid modification content in specific covering mixture
It is preferably less than 20 mass %, such as, from 5 mass % to 20 mass %.
Comprise the island of the specific elastomer fine dispersion in the marine facies comprising thermoplastic resin, can be used by inspection
The image viewing that scanning electron microscope (SEM) obtains.
Comprise the island phase of specific elastomer size (major axis of island phase) be preferably about 0.4 μm to 10.0 μm, more preferably from about
Be 0.5 μm to 7 μm, and particularly preferred 0.5 μm is to 5 μm.The big I of each phase is by checking that the image using SEM to obtain is surveyed
Amount.
[resin material]
The following is the explanation to the resin material forming tyre framework body." resin material " refers to thermoplastic resin (bag herein
Include thermoplastic elastomer (TPE)) and thermosetting resin, and do not comprise vulcanite.
In the tire of the present invention, tyre framework body is formed by resin material.Therefore, there is no need in traditional rubber ratch tire
Necessary operation sulfuration processing, such as, tyre framework body can be formed by injection moulding etc..Therefore manufacturing process it is achieved simple
Changing, it is possible to make productivity ratio improve, the time that such as reduces reduces cost.Additionally, when resin material is used as tyre framework body, tire
Structure can simplify compared to traditional rubber ratch tire, and result tire weight to alleviate be possible.Therefore this can make tire resistance to
Mill property and durability increase are achieved.
The example of thermosetting resin includes phenolic resin, urea resin, melmac, epoxy resin and polyamide resin
Fat etc..The example of thermoplastic resin includes polyurethane resin, olefin resin, vinyl chloride resin and polyamide.
Thermoplastic elastomer (TPE) generally refers to by including being formed the polymer of hard segment and including being formed the polymer of soft chain segment
Copolymer formed thermoplastic resin material.The example of thermoplastic elastomer (TPE) includes the thermoplastic poly according to JISK6418 definition
Amide-type elastomer (TPA), thermoplastic poly esters elastomer (TPC), thermoplastic polyolefin-like elastomer (TPO), thermoplastic poly
Styrenic elastomer (TPS), thermoplastic polyurethanes elastomer (TPU) and the rubber (TPV) of thermoplasticity crosslinking, and other
Thermoplastic elastomer (TPE) (TPZ).Formability etc., wheel during elasticity needed for it should be noted that in view of run duration and manufacture
It is resin material that tire skeleton body is preferably used thermoplastic resin, more preferably uses thermoplastic elastomer (TPE).
When polyamide thermoplastic resinoid is used as the thermoplastic resin covering metal reinforcement cord component, particularly preferably make
With polyamide thermoplastic class elastomer.
-polyamide thermoplastic class elastomer-
" polyamide thermoplastic class elastomer " refers to form crystallinity and have the polymerization of dystectic hard segment by having
Thing and formed amorphism and have lower glass transition temperatures soft chain segment polymer copolymer formed thermoplastic resin
Material, the polymer wherein forming hard segment has amido link (-CONH-) on its main chain.Polyamide thermoplastic class elastomer
Example include thermoplasticity amide-type elastomer (TPA) according to JIS K6418:2007 definition, and JP-A2004-346273
Polyamide-based elastomer described in number.
The example of polyamide thermoplastic class elastomer includes having and at least forms crystallinity and have dystectic hard segment
Polyamide and have formed amorphism and have lower glass transition temperatures soft chain segment other polymer (such as polyester or
Polyethers etc.) material.Polyamide thermoplastic class elastomer is used as cahin extension agent such as dicarboxylic acids, and hard segment and soft chain segment.
The polyamide that the monomer represented by following formula (1) or formula (2) for being formed the example of the polyamide of hard segment to include produces.
Formula (1): H2N-R1-COOH
In formula (1), R1Represent the hydrocarbon molecule chain with 2-20 carbon atom, or there is the alkylidene of 2-20 carbon atom.
Formula (2)
In formula (2), R2Represent the hydrocarbon molecule chain with 3-20 carbon atom, or there is the alkylidene of 3-20 carbon atom.
In formula (1), R1Preferably there is the hydrocarbon molecule chain of 3-18 carbon atom or there is the alkylidene of 3-18 carbon atom,
Be still more preferably from there is the hydrocarbon molecule chain of 4-15 carbon atom or there is the alkylidene of 4-15 carbon atom, and particularly preferably tool
There is the hydrocarbon molecule chain of 10-15 carbon atom or there is the alkylidene of 10-15 carbon atom.And, in formula (2), R2It is preferably tool
There is the hydrocarbon molecule chain of 3-18 carbon atom or there is the alkylidene of 3-18 carbon atom, be still more preferably from there is 4-15 carbon atom
Hydrocarbon molecule chain or there is the alkylidene of 4-15 carbon atom, and particularly preferably there is the hydrocarbon molecule chain of 10-15 carbon atom
Or there is the alkylidene of 10-15 carbon atom.
The example of the monomer represented by above formula (1) or formula (2) includes omega-amino carboxylic acid and lactams.And, form hard chain
The example of the polyamide of section includes these omega-amino carboxylic acids and the condensation polymer of lactams and diamidogen and the copolycondensation of dicarboxylic acids
Thing etc..
The example that can be used as omega-amino carboxylic acid includes having the aliphatic omega-amino carboxylic acid of 5-20 carbon atom, such as
6-aminocaprolc acid, 7-aminoheptylic acid, 8-aminocaprylic acid, 10-aminocapric acid, 11-amino undecanoic acid or 12 amino dodecanoic acid
Deng.The example that can be used as lactams includes having the aliphatic lactams of 5-20 carbon atom, such as lauric lactam, ε-oneself in
Amide, 11 lactams, ω-oenantholcatam or 2-Pyrrolidone.
The example that can be used as diamidogen includes diamine compound, such as, have the aliphatic diamine such as sub-second of 2-20 carbon atom
Base diamidogen, trimethylene diamine, tetra-methylenedimine, hexamethylene diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, 11
Support diamidogen, dodecamethylene diamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 3-methyl
Pentanediamine or m-xylene diamine.And, HOOC-(R3) m-COOH (wherein R3For having the hydrocarbon molecule chain of 3-20 carbon atom,
And m is 0 or 1) can represent dicarboxylic acids, such as, have the aliphatic dicarboxylic acid such as oxalic acid, succinic acid of 2-20 carbon atom, penta
Diacid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid, decanedioic acid or dodecanedioic acid.
As the polyamide of formation hard segment, preferably use by acyl in lauric lactam, epsilon-caprolactams or 11
The polyamide that the open loop polycondensation of amine is formed.
The example of the polymer forming soft chain segment includes polyester, polyethers, and the example includes Polyethylene Glycol, polypropylene glycol, gathers
Tetramethylene ether glycol and ABA type triblock polyether.These can individually or use with its two or more combination.And, can
To use the polyether diamine etc. reacted and obtain by the terminal units (terminal unit) of ammonia etc. with polyethers.
Wherein, " ABA type triblock polyether " refers to the polyethers represented by following formula (3).
Formula (3)
In formula (3), x and z represents the integer of 1-20, and y represents the integer of 4-50.
As the value of x and z in formula (3), it is respectively preferably the integer of the integer of 1-18, more preferably 1-16, and most preferably
Integer for 1-12.And, as the value of y in formula (3), it is respectively preferably the integer of the integer of 5-45, more preferably 6-40, special
Not You Xuanwei the integer of 7-35, and the integer of most preferably 8-30.
Above-mentioned hard segment and soft chain segment be respectively combined as hard segment and the example of soft chain segment combination.From these preferably
It is combined as the open loop condensation polymer of the combination of open loop condensation polymer, lauric lactam and the polypropylene glycol of lauric lactam and Polyethylene Glycol
Combination, the combination of open loop condensation polymer of lauric lactam and polytetramethylene ether diol, lauric lactam and ABA type three block
The combination of the open loop condensation polymer of polyethers.The particularly preferably combination of the open loop condensation polymer of lauric lactam and ABA type triblock polyether.
From the angle of melt molding character, the number-average molecular weight of the polymer (polyamide) forming hard segment is preferably 300
To 15000.From toughness and the angle of low temperature flexibility, the number-average molecular weight of the polymer forming soft chain segment is preferably 200 to 6000.
From the angle of formability, hard segment (x) is preferably 50:50 to 90:10 with the mass ratio (x:y) of soft chain segment (y), more preferably
50:50 to 80:20.
Polyamide thermoplastic class elastomer can make polymer and the formation of above-mentioned formation hard segment by using known method
The polymer copolymerization of soft chain segment synthesizes.
The example of the commercially available prod that can be used as polyamide thermoplastic class elastomer includes coming free Ube Industries,
Ltd. manufactureXPA " (example includes series of productsXPA9063X1、XPA9055X1、
XPA9048X2, XPA9048X1, XPA9040X1 and XPA9040X2XPA9044), and manufactured by Daicel-Evonik Ltd.
'sSeries of products are (such asE40-S3、E47-S1、E47-S3、E55-S1、E55-
S3, EX9200 and E50-R2).
From such as elastic modelling quantity (flexible) and the angle of intensity, polyamide thermoplastic class elastomer meets tyre framework body
Performance requirement, is suitable resin material, and often has the cohesiveness of excellence to thermoplastic resin.Therefore, from tyre framework body
And the adhesive angle between specific covering mixture, use polyamide thermoplastic class elastomer to be formed as resin material
Tyre framework body tends to improving the degree of freedom of the material selecting specific covering mixture.
-thermoplastic polystyrene class elastomer-
The example of thermoplastic polystyrene class elastomer includes having the polystyrene at least forming hard segment, and has shape
Other polymer becoming amorphism and the soft chain segment with lower glass transition temperatures is (such as polybutadiene, polyisoprene, poly-
Ethylene, hydrogenated butadiene polymer or hydrogenated polyisoprene etc.) material.Can be suitable for being formed the reality of the polystyrene of hard segment
Example includes using those that known free radical polymerisation process obtains, or uses known ion polymerization obtains those,
Such as there is the polystyrene of living anion polymerization thing form.
Polybutadiene, polyisoprene and poly-(2,3-dimethyl-fourth is included for forming the example of the polymer of soft chain segment
Diene) etc..
The example of the combinations thereof being respectively combined as hard segment and soft chain segment of above-mentioned hard segment and soft chain segment.The most poly-
The combination of styrene/polybutadiene, or the combination of polystyrene/polyisoprene.And, for suppressing the non-of thermoplastic elastomer (TPE)
Deliberately cross-linking reaction, soft chain segment is preferably hydrogenation.
The number-average molecular weight of the polymer (polystyrene) forming hard segment is preferably 5000 to 500000, and is preferably
10000 to 200000.
And, the number-average molecular weight of the polymer forming soft chain segment is preferably 5000 to 1000000, and more preferably 10000
To 800000, and particularly preferably 30000 to 500000.And, from the angle of formability, hard segment (x) and soft chain segment (y)
Volume ratio (x:y) is preferably 5:95 to 80:20, and more preferably 10:90 to 70:30.
Thermoplastic polystyrene class elastomer can use known method make the polymer of above-mentioned formation hard segment and formed soft
The polymer copolymerization of segment synthesizes.
The example of thermoplastic polystyrene class elastomer includes styrene-butadiene analog copolymer [SBS (polystyrene-poly
(butylene) block-polystyrene), and SEBS (polystyrene-poly (ethylene/butylene) block-polystyrene)], styrene-isoamyl
Type copolymers [polystyrene-polyisoprene block-polystyrene], styrene-propene analog copolymer [SEP (polyphenyl second
Alkene-(ethylene/propene) block), SEPS (polystyrene-poly (ethylene/propene) block-polystyrene), SEEPS (polystyrene-
Poly-(ethylene-vinyl/propylene) block-polystyrene)], and SEB (polystyrene (ethylene/butylene) block), and particularly preferably
SEBS。
The example of the commercially available prod that can be used as unmodified thermoplastic polystyrene class elastomer includes those choosings freely
Asahi Kasei Corporation manufacturesSeries (such as, H1031, H1041, H1043, H1051,
H1052, H1053, H1062, H1082, H1141, H1221 or H1272), Kuraray CO., Ltd the SEBS manufactured is (such as8007 or 8076) and SEPS (such as2002 or 2063).
-thermoplastic polyurethanes elastomer-
Being similar to can be used on those of specific covering mixture, thermoplastic polyurethanes elastomer can be used as thermoplasticity
Polyurethane elastomer.
-thermoplastic polyolefin-like elastomer-
The example of thermoplastic polyolefin-like elastomer include having at least formed crystallinity and have dystectic firmly
The polyolefin of segment, and form amorphism and there is the polyolefin of soft chain segment of lower glass transition temperatures and be different from this polyene
The material of the alkene (such as said polyolefins, other polyolefin, or polyvinyl compound) of hydrocarbon.Form the polyolefin of hard segment
Example include polyethylene, polypropylene, isotactic polypropylene and polybutene.
The example of thermoplastic polyolefin-like elastomer includes alkene-alpha-olefin random copolymer and olefin block copolymers,
Wherein example includes propylene-based block copolymer, ethylene-propylene copolymer, propylene-1-hexene copolymer, propylene-4-methyl isophthalic acid penta
Alkene copolymer, propene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl pentene copolymer, ethylene-1-fourth
Alkene copolymer, 1-butylene-1-hexene copolymer, 1-butylene-4-methyl pentene, ethylene-methacrylic acid copolymer, ethylene-first
Base methyl acrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-methyl methacrylate acrylate copolymer, ethylene-
Methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, propylene-methacrylic acid
Copolymer, propylene-methylmethacrylate copolymer, propylene-ethyl methacrylate copolymers, propylene-methacrylic acid fourth
Ester copolymer, propylene acrylic acid methyl terpolymer, propylene acrylic acid methacrylate copolymers, propylene acrylic acid acrylate copolymer, second
Alkene-vinyl acetate copolymer and propylene-vinyl acetate copolymer.
The preferred embodiment of thermoplastic polyolefin-like elastomer include propylene-based block copolymer, ethylene-propylene copolymer, third
Alkene-1-hexene copolymer, propylene-4-methyl isophthalic acid pentene copolymer, propene-1-butene copolymer, ethylene-1-hexene copolymer,
Ethylene-4-methyl pentene copolymer, ethylene-butene-1 copolymer, ethylene-methacrylic acid copolymer, ethylene-metering system
Acid methyl terpolymer, ethylene-ethyl methacrylate copolymer, ethylene-methyl methacrylate acrylate copolymer, ethylene-acrylic acid
Methyl terpolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, propylene-methacrylic acid copolymer,
Propylene-methylmethacrylate copolymer, propylene-ethyl methacrylate copolymers, propylene-butyl methacrylate copolymerization
Thing, propylene acrylic acid methyl terpolymer, propylene acrylic acid methacrylate copolymers, propylene acrylic acid acrylate copolymer, ethylene-second
Vinyl acetate copolymer and propylene-vinyl acetate copolymer, the most more preferably example include ethylene-propylene copolymer, third
Alkene-butene-1 copolymer, ethylene-butene-1 copolymer, ethylene methyl methacrylate copolymer, ethylene-methyl acrylate are common
Polymers, ethylene-ethyl acrylate copolymer and ethylene-butyl acrylate copolymer.
And, two or more vistanexes, such as ethylene and propylene, can be combined and use.And, thermoplastic polyolefin-like
In elastomer polyolefinic content than preferably 50 mass % to 100 mass %.
The number-average molecular weight of thermoplastic polyolefin-like elastomer is preferably 5,000 to 10,000,000.If thermoplastic poly
The number-average molecular weight of olefin type elastomer is 5,000 to 10,000,000, and thermoplastic resin material has sufficient mechanical-physical
Character and excellent processability.From similar angle, number-average molecular weight is more preferably 7,000 to 1,000,000, and particularly preferably
Be 10,000 to 1,000,000.Therefore this mechanical-physical character that can improve thermoplastic resin material further and processability.
From toughness and the angle of low temperature flexibility, the number-average molecular weight of the polymer forming soft chain segment is preferably 200 to 6000.From formability
Angle, the mass ratio (x:y) of hard segment (x) and soft chain segment (y) is preferably 50:50 to 95:5, and be still more preferably from 50:50 is extremely
90:10。
Thermoplastic polyolefin-like elastomer can synthesize by using conventional method copolymerization.
The thermoplastic elastomer (TPE) of acid modification can be used as thermoplastic polyolefin-like elastomer.
" acid modified thermoplastic polyolefin-like elastomer " refers to have acidic-group such as hydroxy-acid group, sulphuric acid by making
The unsaturated compound of group or phosphate group is bonded with unmodified thermoplastic polyolefin-like elastomer and the thermoplastic of acid modification
Property ethylene octane copolymer.Such as, it is used as the unsaturation with acidic-group when unsaturated carboxylic acid (general, maleic anhydride)
During compound, the unsaturated bond site of unsaturated carboxylic acid is made to be bonded with thermoplastic polyolefin-like elastomer (such as, poly-by grafting
Close).
From the angle of degraded of suppression thermoplastic polyolefin-like elastomer, have the compound of acidic-group preferably have for
The compound of the hydroxy-acid group of faintly acid group, the most spendable example includes acrylic acid, methacrylic acid, itaconic acid, bar
Bean acid, iso-crotonic acid and maleic acid.
The example of thermoplastic polyolefin-like elastomer include by Mitsui Chemicals, Inc. manufacture fromThe commercially available prod of series is (such as,A0550S、A1050S、A4050S、A1070S、A4070S、
A35070S、A1085S、A4085S、A7090、A70090、MH7007、MH7010、XM-7070、XM-7080、BL4000、
BL2481, BL3110, BL3450, P-0275, P-0375, P-0775, P-0180, P-0280, P-0480 and P-0680), and by
Du Pont-Mitsui Polychemicals Co., Ltd. manufacture fromThe product of series is (such asAN4214C、AN4225C、AN42115C、N0903HC、N0908C、AN42012C、N410、N1050H、
N1108C, N1110H, N1207C, N1214, AN4221C, N1525, N1560, N0200H, AN4228C, AN4213C and N035C)
With fromThe product of AC series is (such as1125AC、1209AC、1218AC、1609AC、
1820AC, 1913AC, 2112AC, 2116AC, 2615AC, 2715AC, 3117AC, 3427AC and 3717AC), and by Sumitomo
Chemical Co., Ltd. manufacture fromSeries product and fromThe product of series
Product, and by Tosoh Corporation manufacture fromThe product of series.
And, the commercially available prod that can be used as thermoplastic polyolefin-like elastomer also includes, such as by Prime Polymer
Co., Ltd. manufacture from PRIME(example includes PRIME to the product of seriesE-2900H、F-3900H、
E-2900、F-3900、J-5900、E-2910、F-3910、J-5910、E-2710、F-3710、J-5910、E-2740、F-3740、
R110MP, R110E, T310E and M142E).
-thermoplastic poly esters elastomer-
The example of thermoplastic poly esters elastomer is to include at least forming crystallinity and having the poly-of dystectic hard segment
Ester, and form amorphism and there is the material of other polymer (such as polyester or polyethers) of soft chain segment of lower glass transition temperatures
Material.
Aromatic polyester can be used as being formed the polyester of hard segment.Aromatic polyester can by such as, aromatic dicarboxylic acid or
Its ester forms derivant and aliphatic diol is formed.Aromatic polyester preferably comes from p-phthalic acid and/or p-phthalic acid
Dimethyl ester and the polybutylene terephthalate (PBT) of 1,4-butanediol.And, aromatic polyester can be to come from dicarboxylic acid component's example
Such as M-phthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acids, naphthalene-2,7-dicarboxylic acids, biphenyl-4,4'-dicarboxylic acids, two phenoxy groups
Ethane dicarboxylic acids, or 5-sulfonic group M-phthalic acid, or its ester formation derivant, and there is the glycol of the molecular weight of less than 300
Polyester, described in have less than 300 molecular weight glycol such as, aliphatic diol such as ethylene glycol, trimethylene, five sub-
Methyl glycol, hexamethylene glycol, neopentyl glycol or decamethylene glycol；Alicyclic diol such as 1,4 cyclohexane dimethanol or three
Cyclodecane dimethanol；Double with aromatic diol such as benzene dimethanol, double (to hydroxyl) biphenyl, double (p-hydroxybenzene) propane, 2,2-
[4-(2-hydroxyl-oxethyl) phenyl] propane, double [4-(2-hydroxyl) phenyl] sulfone, 1,1-are double [4-(2-hydroxyl-oxethyl) phenyl]
Hexamethylene, 4,4'-dihydroxy-para-terpheny or 4,4'-dihydroxy are to quaterphenyl.And, aromatic polyester can be, uses two kinds
Above above-mentioned dicarboxylic acid component and the copolyester of diol component combination.There is the polyfunctional carboxylic acids of the functional group of more than 3
Component, multifunctional oxyacid component or multifunctional hydroxy component etc. can also copolymerization in the scope of 5 moles of below %.
Formed the example of polyester of hard segment include polyethylene terephthalate, polybutylene terephthalate (PBT),
Polymethylene terephthalate, PEN and PBN, preferably poly terephthalic acid
Butanediol ester.
Aliphatic polyester and aliphatic polyether are the examples of the polymer forming soft chain segment.
The example of aliphatic polyether includes poly-(oxirane) glycol, poly-(expoxy propane) glycol, poly-(oxolane) two
Alcohol, poly-(oxepane) glycol, oxirane and the copolymer of expoxy propane, the ethyleneoxide addition of poly-(expoxy propane) glycol
Thing, and oxirane and the copolymer of oxolane.
The example of aliphatic polyester includes poly-(6-caprolactone), poly-enanthol lactone (polyenantholactone), poly-pungent
Lactone (polycaprylolactone), poly adipate succinic acid ester and 10PE27 etc..
In these aliphatic polyethers and aliphatic polyester, from the angle of the elastic characteristic of gained polyester block copolymer, excellent
Select poly-(oxolane) glycol, for poly-(expoxy propane) glycol of ethylene oxide adduct, poly-(6-caprolactone), polyadipate fourth
Diol ester and 10PE27 etc..
And, from the angle that toughness and low temperature are flexible, the number-average molecular weight of the polymer forming soft chain segment is preferably 300
To 6000.And, from the mass ratio (x:y) of the angle of formability, hard segment (x) and soft chain segment (y) preferably 99:1 to 20:
80, be still more preferably from 98:2 to 30:70.
The example of the combinations thereof of hard segment and soft chain segment can include each combination of above-mentioned hard segment and soft chain segment.Its
In, polybutylene terephthalate (PBT) is hard segment and aliphatic polyether is the combination of soft chain segment preferably wherein, wherein
Polybutylene terephthalate (PBT) is hard segment and poly-(oxirane) glycol is the combination of soft chain segment.
Can use such as thermoplastic poly esters elastomer, come what free Du Pont-Toray Co., Ltd. manufacturedSeries is (such as3046,5557,6347,4047,4767 and 7247) and come free Toyobo
Co., Ltd. manufacturesSeries is (such asP30B、 P40B、P40H、P55B、P70B、
P150B, P280B, P450B, P150M, S1001, S2001, S5001, S6001 and S9001) commercially available prod.
Above-mentioned thermoplastic elastomer (TPE) can use known method will to form the polymer of hard segment and form the polymerization of soft chain segment
Thing copolymerization synthesizes.
The fusing point of resin material ordinarily be about 100 DEG C to 350 DEG C.And from the angle of tire manufacturability, preferably about 100
DEG C to 250 DEG C, more preferably 100 DEG C to 200 DEG C.
And, the durability of tire and productivity ratio can be enhanced.Various additives, such as rubber, elastomer, thermoplastic resin
Fat, various filler (such as silicon dioxide, calcium carbonate or clay), age resistor, oil, plasticizer, coloring agent or weather resisting agent, can be on-demand
It is included in (be blended into) resin material.
The tensile modulus of elasticity according to JIS K7113:1995 definition of resin material (tyre framework body) self is preferably
50MPa to 1000MPa, more preferably 50MPa to 800MPa, and particularly preferably 50MPa to 700MPa.100MPa is extremely
Tyre framework height can be imitated while keeping tyre framework shape by the tensile modulus of elasticity of the resin material of 1000MPa
Install to wheel rim.
The hot strength defined according to JIS K7113 (1995) of resin material (tyre framework body) self ordinarily be about
15MPa to 70MPa, preferably 17MPa to 60MPa, more preferably 20MPa to 55MPa.
The tensile yield strength according to JIS K7113:1995 definition of resin material (tyre framework body) self is preferably
More than 5MPa, preferably 5MPa to 20MPa, more preferably 5MPa to 17MPa.The tensile yield of the resin material of more than 5MPa is strong
Degree can make tire in the case of load and stand deformation during travelling.
The tensile yield percentage elongation according to JIS K7113:1995 definition of resin material (tyre framework body) self is preferred
It is more than 10%, preferably 10% to 70%, more preferably 15% to 60%.The tensile yield of the resin material of more than 10% is stretched
Long rate can make elastic interval big and to wheel rim installation good.
The Tensile elongation at break according to JIS K7113:1995 definition of resin material (tyre framework body) self is preferred
It is more than 50%, preferably more than 100%, more preferably more than 150%, and particularly preferably more than 200%.More than 50%
The Tensile elongation at break of resin material, it is possible to make well and to lower the sensitivity that impact injures to the installation of wheel rim.
The temperature of deflection under load according to ISO75-2 or ASTM D648 definition of resin material (tyre framework body) self
(under the load of 0.45MPa) is preferably more than 50 DEG C, preferably 50 DEG C to 150 DEG C, more preferably 50 DEG C to 130 DEG C.50℃
Even if the temperature of deflection under load of above resin material can make tyre framework in the case of vulcanizing during Tire production
Body deformability is suppressed.
[the first embodiment]
The following is referring to the drawings explanation according to the first embodiment of the invention.
The following is the explanation of the tire 10 to the present embodiment.Figure 1A is that tire according to embodiments of the present invention is described
A part of perspective cross-sectional view.Figure 1B is the cross section installing the bead part to wheel rim.According to Fig. 1, embodiment party of the present invention
The tire 10 of case shows the shape of cross section substantially the same with normal conventional rubber pneumatic tire.In the present embodiment,
Reinforcement cord 26 use have torsion structure all-steel cord be used as metal reinforcement cord component (tensile modulus of elasticity:
210000MPa, elongation at break: 8%), and it serves as core, core be covered over comprising at least thermoplastic resin and specific
The covering mixture of elastomer.In the present embodiment, the following is using as the resinoid amide of polyamide thermoplastic 12
Explanation with the particular instance of the mixture of specific elastomer.As the UBESTA3024U of 80 mass %, (trade name, by Ube
Industries, Ltd. manufacture) it is used as amide 12, and the ET680 of 20 mass %, thermoplastic polyurethanes elastomer, by BASF
When manufacturing (trade name, softening point: 107 DEG C) as specific elastomer, the covering mixture tensile modulus of elasticity of gained is
1088MPa, elongation at break is 335%, and hot strength is 47MPa.When 70 mass % UBESTA3024U (trade name, by
Ube Industries, Ltd. manufacture) it is used as amide 12, and TUFTEC (registered trade mark) H1052 of 30 mass % is (by Asahi
Kasei Chemicals Corporation manufactures, unmodified SEBS), thermoplastic polystyrene class elastomer, as specific
During elastomer, the covering mixture tensile modulus of elasticity of gained is 740MPa, and elongation at break is 35%, and hot strength is
22MPa.UBESTA3014U (trade name is manufactured by Ube Industries, Ltd.) and UBESTA3024U when 60 mass %
1:1 (mass ratio) mixture of (trade name, by Ube Industries, Ltd. manufacture) is used as amide 12, and 40 mass %
The mixture of TAFMER (registered trade mark) MH7010 (being manufactured by Mitsui Chemicals, Inc.), thermoplastic olefin class is elastic
When body is used as specific elastomer, the covering mixture tensile modulus of elasticity of gained is 600MPa, and elongation at break is 290%,
Hot strength is 24MPa.
Along the cross-sectional view axially intercepted of the ring-type tyre framework body (tire casing 17) of the present embodiment, cover
The reinforcement of weld cord component (that is, reinforcement cord 26) having thermoplastic resin is embedded in tyre framework body with at least a portion
The state of periphery spirally wind.
According to Figure 1A, tire 10 equipped with tire casing 17, tire casing 17 be equipped with comprise respectively with Figure 1B institute
The pair of bead portion 12 that the bcad seats 21 of the wheel rim 20 shown contacts with rim flange 22, respectively from bead part 12 along tire radially to
The sidewall 14 that outside extends, and the tire radial outside end by the tire radial outside end of sidewall 14 Yu another sidewall 14
The bizet 16 (periphery) being connected.
Tire casing 17 configuration of the present embodiment uses polyamide thermoplastic class elastomer (such as
XPA9055X1, is manufactured by Ube Industries Ltd., tensile modulus of elasticity: 303MPa, elongation at break: 350%, stretching
Intensity: 41MPa).
The tire casing 17 of the present embodiment is formed by single resin material (thermoplastic polyester resin), but the present invention
Structure be not limited thereto, and be similar to normal conventional rubber pneumatic tire, thermoplastic resin material of different nature can
Each several part (such as sidewall 14, bizet 16 and bead part 12) as tire casing 17.Casing 17 can be by burying supporting material underground
(such as fiber, cord, non-woven fabrics or macromolecular material or hardware cloth) at tire casing 17 (such as in bead part 12, sidewall 14
With bizet 16 etc.) in carry out reinforcement by supporting material.
In the tire casing 17 of the present embodiment, formed by the resin material comprising polyamide thermoplastic class elastomer for a pair
Tire casing halfbody (half parts) (tyre framework body sheet) 17A be bonded together.Tire casing halfbody 17A is by injection
Molding etc. are respectively formed single carcass (single by the bizet 16 of 12, sidewall 14 of a bead part and a half width
Body), to provide the tire casing halfbody 17A with identical tubular shape, then they are alignd face-to-face and at wheel abnormal red skin of infant
Road face (equatorial plane portions) is bonded together.It should be noted that tire casing 17 is not limited to
Formed by engaging two components, and can be formed by engaging the component of more than three.
The tire casing halfbody 17A formed by resin material vacuum forming, press molding, can be injected into by such as
Type or founding etc. carry out molding.Therefore, compared with the casing formed by rubber in normal conditions, it is not necessary to vulcanize, energy
Gou Shi manufacturing process significantly simplifies and can reduce molding time.
In the present embodiment, tire casing halfbody 17A is formed with symmetrical shape, i.e. a tire casing halfbody
17A forms the shape identical with another tire casing halfbody 17A, has a kind of mould and just meets forming tire casing halfbody
The advantage of the needs of 17A.
In the present embodiment, according to Figure 1B, all-steel cord the ring-type bead core 18 formed is embedded in bead part 12
In, it is similar in normal conventional pneumatic tire.But, the invention is not limited in that this constructs, as long as and guaranteeing bead part 12
Rigidity and installation are no problem to wheel rim 20, can omit bead core 18.In addition to all-steel cord, bead core 18 can also be by example
Formed such as organic fiber cord, the organic fiber cord of resin coating or hard resin etc..
In the present embodiment, there is the material such as rubber of the sealing property more excellent than the resin material constituting tire casing 17
The annular seal layer 24 that glue is formed is formed in the part of contact bead part 12 of wheel rim 20, and at least at the wheel rim with wheel rim 20
In the part of flange 22 contact.Sealant 24 also may be formed at what tire casing 17 (bead part 12) and bcad seats 21 contacted with each other
Part.The material more soft than the resin material forming tire casing 17 can be used as having the resinous wood than forming tire casing 17
Expect the material of more excellent sealing property.As can be used as the rubber of sealant 24, be preferably used with in normal conventional rubber system
The rubber of the rubber identical type used in the outer surface of airtyred bead part.As long as the sealing property of wheel rim 20 can only by
The resin material forming tire casing 17 guarantees, it is possible to omits rubber sealant 24, or is used as having than resin material more
Other thermoplastic resin (thermoplastic elastomer (TPE)) of excellent sealing property.The example of this type of other thermoplastic resin includes as poly-
The resins such as urethane resinoid, polyolefin resin, thermoplastic polystyrene resinoid and polyester resin, or these resins and rubber
Or the blend etc. of elastomer.It is used as thermoplastic elastomer (TPE), and the example includes thermoplastic poly esters elastomer, thermoplasticity
Group between polyurethane elastomer, thermoplastic polystyrene class elastomer, thermoplastic polyolefin-like elastomer, these elastomers
Close, and the blend of these elastomers and rubber.
According to Figure 1A, reinforcement cord 26, be configured with formed the all-steel cord and being coated with of tire casing 17 comprise to
Few thermoplastic resin and the covering mixture of specific elastomer, the circumferencial direction along tire casing 17 is wound on bizet 16.
Reinforcement cord 26 spirally winds, so that it is at least partially at bizet in the cross section axially intercepted of tire casing 17
For burying state underground in 16.By the material such as rubber shape with the wearability more excellent than the resin material forming tire casing 17
The tyre surface 30 become, is arranged on the tire outer radial periphery side of reinforcement cord 26.
The following is with reference to the Fig. 2 explanation to reinforcement cord 26.Fig. 2 is to intercept along tire rotary shaft and illustrate wherein to mend
The cross section of the state in the bizet of the casing that strong cord is embedded in the tire of the first embodiment.According to Fig. 2, reinforcement curtain
Line 26 spirally winds so that in the cross section that tire casing 17 axially intercepts its at least partially in bizet 16 for burying
If state.The part of the reinforcement cord 26 being embedded in bizet 16 is and resin material (the tire casing 17) place forming bizet 26
In the state being in close contact.
According to Fig. 2, reinforcement cord 26 has the specific covering comprising at least thermoplastic resin and specific elastomer and uses
Mixture 28 covers the structure of the all-steel cord 27 reversing steel wire fibre as core.Without particular limitation of covering all-steel cord 27
The thickness of specific covering mixture 28, and average thickness is preferably 0.2mm to 4.0mm, more preferably 0.5mm to 3.0mm, and
Particularly preferably 0.5mm to 2.0mm.As it has been described above, the elastic modelling quantity of specific covering mixture 28 is preferably arranged to form wheel
0.1 times of the elastic modelling quantity of the resin material of tire casing 17 is to 20 times.
Depth of burying L in fig. 2 represents relative to reinforcement cord 26 in tire casing 17 (bizet 16) along tire rotation
The axial depth of burying.Reinforcement cord 26 is preferably the 1/ of the diameter D of reinforcement cord 26 relative to depth of burying L of bizet 16
More than 5, more preferably more than its 1/2.Most preferably reinforcement cord 26 entirety is embedded in bizet 16.From the size angle of reinforcement cord
Degree, if the depth of burying of reinforcement cord 26 exceedes the 1/2 of reinforcement cord 26 diameter D, reinforcement cord 26 is difficult to from burying part underground
Peel off.Reinforcement cord 26 entirety is embedded in bizet 16, it is provided that plane (outer peripheral face), and can suppress at reinforcement curtain circumferential section
Introduce air, even if be placed in the bizet 16 being embedded with reinforcement cord 26 at component in the case of.
As it has been described above, tyre surface 30 is arranged on the tire outer radial periphery side of reinforcement cord 26.Preferred for the rubber of tyre surface 30
With the rubber for traditional rubber system airtyred rubber identical type.It should be noted that replacement tyre surface 30, can use by
The thermoplastic resin material of other kind with the wearability more excellent than the resin material forming tire casing 17 is formed
Tyre surface.Being similar to traditional rubber pneumatic tire, the tread pattern of multiple groove (plural grooves) is formed at the road of tyre surface 30
Face contact surface.
The following is the explanation of manufacture method to the tire according to the present embodiment.
(tire casing molding procedure)
First, faced each other alignment by the tire casing halfbody of thin metal support ring support.Configuration is the most not
The jointing die that illustrates is so that the outer peripheral face of abutting part (abutting protions) of tire casing halfbody contacts.Structure
Jointing die is with the junction surface (bonding section) (abutting part) of specified pressure crimping tire casing halfbody 17A outward
Week.Subsequently, the periphery at the junction surface of tire casing halfbody formed tire casing resin material fusing point (or softening point) with
Crimp at a temperature of on.The junction surface of tire casing halfbody is by jointing die heating pressurization, and melted junction surface, by tire casing half
Body welding (welding) together, and by single carcass that these component formings are tire casing 17.It should be noted that to the greatest extent
In pipe the present embodiment, the junction surface of tire casing halfbody uses jointing die heating, but the invention is not limited in this, such as
Junction surface can be heated by the heating generator etc. being separately provided, maybe can be by using hot blast or infra-red radiation irradiation etc. the softest
Change or melted, be engaged mould crimping the most again.Therefore tire casing halfbody can be joined together.
(reinforcement cord component rolling step)
The following is with reference to the Fig. 3 explanation to reinforcement cord rolling step.Fig. 3 is for for explaining by using cord to add hot charging
Put the explanatory diagram of the operation being embedded in the bizet of tire casing by reinforcement cord with roller.In Fig. 3, cord feed apparatus 56 is equipped
Have: be wound with the spool 58 of reinforcement cord 26；At the cord heater that the downstream of the cord conveying direction of spool 58 configures
59；At the first roller 60 that the downstream of the conveying direction of reinforcement cord 26 configures；Along towards or away from the outer peripheral face direction of tire
First cylinder device 62 of mobile first roller 60；Second configured in the downstream of reinforcement cord 26 conveying direction of the first roller 60
Roller 64；With along towards or move the second cartridge apparatus 66 of the second roller 64 away from the outer surface direction of tire.Second roller 64 can
It is used as the chill roll being made of metal.In the present embodiment, the surface-coated of the first roller 60 or the second roller 64 has fluororesin (this reality
Execute in scheme, TEFLON (registered trade mark)) to suppress the adhesion of resin material that is melted or that soften.It should be noted that this reality
Executing in scheme, structure cord feed apparatus 56 is to have the first roller 60 or two rollers of the second roller 64, but the present invention does not limit to
Construct in this, and cord can be constructed only to have one of two rollers (that is, single roller).The cord component being wound in around spool 58
26 is the cord component 26 of the specific covering mixture 28 being configured with all-steel cord 27 with being covered in all-steel cord 27.
Cord heater 59 is equipped with the heater 70 for producing hot blast and fan 72.Cord heater 59 also fills
Have that inside is fed with that hot blast and reinforcement cord 26 pass from its inner space adds hot tank 74；Heat with discharging (dispense)
The outlet 76 of reinforcement cord 26.
In this operation, in cord heater 59, raise the temperature of heater 70, and heated around by heater 70
Air forms air-flow by the rotation of fan 72 and is transported to add hot tank 74.The reinforcement cord 26 not being wound on spool 58 enters
It is given to inner space and is added in hot tank 74 by what thermal current heated and heat.The reinforcement cord 26 of heating through outlet 76, and
On the outer peripheral face of the bizet 16 spirally winding the tire casing 17 rotated along arrow R direction in figure 3 under some tension.When
When the reinforcement cord 26 of heating contacts the outer surface of bizet 16, the resin material of contact site is melted or softens, and at least one
The reinforcement cord 26 dividing heating is embedded in the outer peripheral face of bizet 16.Now it is embedded in melted or soft due to the reinforcement cord 26 of heating
In the resin material changed, it is achieved there is not the state in gap, i.e. close contact state between resin material and reinforcement cord 26.
Therefore suppression air introduces the part burying reinforcement cord 26 underground.Therefore this can make reinforcement cord 26 be prone to be embedded in bizet 16
In outer peripheral face, and can effectively suppress the introducing of air.It should be noted that specific elastomer glues covering curtain component 26B
The property (stationarity (bondability)) is the highest.
Depth of burying L of reinforcement cord 26 can use the heating-up temperature of reinforcement cord 26, apply opening to reinforcement cord 26
The pressure etc. of power and the first roller 60 regulates.In the present embodiment, depth of burying L of reinforcement cord 26 is set to reinforcement cord 26
More than the 1/5 of diameter D.The 1/2 of the diameter D of depth of burying L of reinforcement cord 26 more preferably more than reinforcement cord 26, and optimum
Elect reinforcement cord 26 entirety as to be buried underground.
Then the belt-tread 30 of sulfuration is wound a circle (single turn), and tire along the outer peripheral face of tire casing 17
Face 30 uses binding agent etc. to be bonded to the outer peripheral face of tire casing 17.It should be noted that tyre surface 30 can such as use for often
The precured tread of the known retreads of rule.This operation is similar to be bonded to outside the carcass of retreads precured tread
The operation of side face.
Then, the sealant 24 formed uses binding agent etc. to be bound to the bead part 12 of tire casing 17 to vulcanite,
Thus obtain tire 10.
(acting on)
In the tire 10 of the present embodiment, reinforcement cord 26, there is all-steel cord 27 and as core and be coated with specific covering
With mixture 28, it is wound on the outer peripheral face of the tire casing 17 formed by polyamide thermoplastic class elastomer.Comprise specific bullet
The specific covering mixture 28 of gonosome has high adhesion to the polyamide thermoplastic class elastomer forming tire casing 17, and
Polyamide thermoplastic class elastomer had the poor rigidity lower than all-steel cord.Owing to reinforcement cord 26 is coated with bag in like fashion
Covering mixture containing polyamide thermoplastic resinoid and specific elastomer, is only fixed by yielding rubber with at all-steel cord 27
In the case of compare, difference of hardness less between tire casing 17 and reinforcement cord 16 can be realized.Therefore can realize that there is steel wire
Cord 27 is as reinforcement cord 26 adhesion strength sufficient to tire casing 17 of core and fixing.And, specific covering mixture
28 have the resistance to pull out to all-steel cord 27 excellence and the cohesiveness good to tire casing 17.Therefore due to can be in tire system
It is effectively prevented the residual of bubble during making, can effectively prevent the motion of metal reinforcement cord component during travelling.And, bag
Covering mixture containing polyamide thermoplastic resinoid and specific elastomer, and only uses single polyamide thermoplastic resinoid
Situation compare, it is easier to give with flexibility.Therefore, compared with when only using single polyamide thermoplastic resinoid, use less
Overlay capacity can be achieved with required flexibility.
In the tire 10 of the present embodiment, owing to winding has the reinforcement cord 26 of rigidity higher than resin material to by setting
On the outer peripheral face of the bizet 16 of the tire casing 17 that fat material is formed, the puncture resistance of tire 10, cutting resistance and circumferencial direction
Rigidity is improved, so that being circumferentially formed thereon helical form.The circumferencial direction rigidity improving tire 10 can prevent by resinous wood
The creep (creep) of the tire casing 17 that material is formed.
In the cross section (cross section is as shown in Figure 1) that tire casing 17 axially intercepts, due at least some of reinforcement curtain
The outer peripheral face of the bizet 16 of the tire casing 17 that line 26 is formed at resin material buried underground and is in close contact with resin material, manufacturing
Period air introduces and is suppressed, and suppression travel during apply the mobile etc. of the reinforcement cord 26 that causes of power.Therefore suppress to mend
The generation of the separation etc. of strong cord 26, tire casing 17 and tyre surface 30, and improve the durability of tire 10.
According to Fig. 2, depth of burying L of reinforcement cord 26 is more than the 1/5 of diameter D, therefore can effectively suppress system
Making the air of period to introduce, suppression applies the movement of the reinforcement cord 26 that power causes in periods such as travelings further.
And, metal material the ring-type bead core 18 formed is embedded in bead part 12, is therefore similar to traditional rubber
Pneumatic tire processed, tire casing 17, i.e. tire 10, it is securely maintained on wheel rim 20.
The embodiment above of tire is constructed by heating reinforcement cord 26, and wherein the reinforcement cord 26 in heating contacts
The melt surface of the tire casing 17 of part or softening；But, the invention is not limited in that this constructs, and reinforcement cord 26 can be
By use thermal current generator heating bizet 16 will bury the outer peripheral face at reinforcement cord 26 underground after be embedded in bizet 16,
And be not added with vulcanizing strong cord 26.
In first embodiment of tire, the thermal source of cord heater 59 is heater and fan；But, the present invention
It is not limited thereto structure, and wherein reinforcement cord 26 can be used direct-fired by radiant heat (such as, infra-red radiation)
Structure.
First embodiment is constructed so as to so that the melted or softening part of the resin material being embedded with reinforcement cord 26 makes
Cooling is forced with metal the second roller 64；But, the present invention is not limited to this structure, and wherein cold airflow can also be used directly to blow
To the melted of resin material or softening part, so that the melted or softening part of resin material forces to cool down and the structure of solidification
Make.
It is helically wrapped reinforcement cord 26 to promote to manufacture；However, it is also contemplated that other method, such as reinforcement curtain on width
The discontinuous method of line 26.
In the tire 10 of the first implementation, bead part 12 is installed to wheel rim 20 to be formed between tire 10 and wheel rim 20
Air chamber, it is referred to as tubeless tyre (tubeless tire).But the present invention is not limited to this structure, and can be formed
Whole inner tube of a tyre shape.
[the second embodiment]
It it is hereinafter the explanation of referring to the drawings the second embodiment of tire to the present invention.Fig. 4 is the second embodiment
Wheel tyre bead tire rotary shaft intercept and illustrate that comprising wherein metal reinforcement cord component has been embedded in the tire casing of tire
The cross section of the embodiment of the reinforcement cord cover layer on bizet.According to Fig. 4, the tire of the present embodiment has reinforcement
Cord cover layer 29, wherein all-steel cord 27 (metal reinforcement cord component) is embedded in the surface of the bizet 16 of tire casing, and
Tyre surface 30 is placed on increase cord cover layer 29.Tire according to the second embodiment has and is similar to the first embodiment
Structure, in addition to above-mentioned point, same reference numbers is additional to the structure being similar to the first embodiment.
The tire of the second embodiment has tire casing 17 and all-steel cord 27, and is similar to the first embodiment, makes
Use thermoplastic polyurethanes elastomeric construction.
The tire of the present embodiment, according to Fig. 4, is provided with reinforcement cord cover layer 29, makes to bury all-steel cord 27 underground
Circumferencial direction along tire casing 17 is wound to bizet 16.The part of all-steel cord 27 is embedded in the bizet 16 of tire casing 17
Surface.Reinforcement cord cover layer 29 is configured with and includes that at least thermoplastic resin is (similar with the covering mixture of specific elastomer
Covering mixture in the first embodiment).Without particular limitation of the thickness of reinforcement cord cover layer 29, and in view of tire
Body 17 and the durability of tyre surface 30 and cohesiveness, average thickness is preferably 0.2mm to 4.0mm, more preferably 0.5mm to 3.0mm,
And particularly preferably 0.5mm to 2.0mm.
The elastic modelling quantity of reinforcement cord cover layer 29 is preferably set at the bullet higher than the resin material forming tire casing 17
Property modulus, and less than all-steel cord 27 elastic modelling quantity in the range of.Elastic modelling quantity at reinforcement cord cover layer 29 is formation
In the case of less than 20 times of the elastic modelling quantity of the thermoplastic resin material of tire casing 17, bizet will not be too hard, and makes tire
Easy to the installation of wheel rim.
The following is the explanation of the manufacture method of the tire to the present embodiment.
(skeleton formation process)
First, it is similar to the tire of the first embodiment, forms tire casing halfbody 17A, and pass through in jointing die
Heating and crimping tire casing halfbody 17A form tire casing 17.
(metal reinforcement cord component rolling step)
The manufacture equipment of the tire of the present embodiment, is similar to the first embodiment, with reference to shown in the first embodiment Fig. 3
Cord feed apparatus 56 preparation be wound to the all-steel cord 27 of spool 58.Subsequently all-steel cord 27 is wound on spool 58,
Being similar to the first embodiment, the outer peripheral face along tire casing 17 winds, and buries one part underground on outer peripheral face simultaneously.This enforcement
Scheme, by burying all-steel cord 27 underground in the layer formed by reinforcement cord cover layer 29, the surface of all-steel cord 27 is coated with
At least include the covering mixture of thermoplastic resin and specific elastomer.Diameter D relative to all-steel cord 272Tire casing
Depth of burying L in 17 is preferably set to the diameter D of all-steel cord 271Less than 1/5.
(stacking operation (layering process))
It follows that specific covering mixture is applied to the outer surface of tire casing 17, wherein it is embedded with all-steel cord
27, in use accompanying drawing, unaccounted melt extruder etc. form reinforcement cord cover layer 29.
Then the yielding rubber 29 of one week unvulcanised state is wound to reinforcement cord cover layer 29, then by binding agent such as
Rubber slurry compositions is applied to yielding rubber 29, and by wound on it with sulfuration or semi-cure state for one week tread-rubber 30A
To provide the state of crude tyre casing (raw tire case).
Then the belt-tread 30 of sulfuration is enclosed along the outer peripheral face winding one of tire casing 17, and tyre surface 30 uses binding agent
Etc. the outer peripheral face being bound to tire casing 17.It should be noted that tyre surface 30 can such as use for conventionally known renovation wheel
The precured tread of tire.This operation is similar to be bound to precured tread the operation of the outer peripheral face of the carcass of retreads.
The sealant 24 formed by vulcanite uses binding agent etc. to be bound to the bead part 12 of tire casing 17, thus obtains
To tire 10.
(acting on)
According to the present embodiment, remove the effect of the first embodiment, reinforcement cord cover layer 29 is arranged at tire
The outer peripheral face of body 17 can make all-steel cord 27 more be fixedly secured on tire casing 17.
Second embodiment is configured with the all-steel cord 27 being spirally wound to bizet 16；But, the present invention not office
It is limited to this, and all-steel cord 27 can wind the most discontinuously.
Although embodiment illustrates according to above embodiment of the present invention, but these embodiments are only
It is example, and various amendment can be realized in the scope without departing from spirit of the present invention.Obviously the present invention interest field not
It is confined to these embodiments.
Embodiment
Hereafter will further illustrate the present invention based on embodiment.
<evaluation of elongation at break, tensile modulus of elasticity and hot strength>
The component of the resin (including covering mixture) listed by table 1 mixes (quality criteria) and uses by Toyo
Biaxial extruder LABO PLASTOMILL50MR (trade name) that Seiki Seisaku-sho, Ltd. manufacture is mixing, obtains
Grain.
The granule obtained hot pressing at 200 DEG C is pressurizeed, and gains deburring (trimming) is had greatly to manufacture
Little is the sample of 2.0mm for 120mm × 120mm thickness.
According to JIS K6251:1993 definition by each sample cross cutting (die-cutting) to prepare the test sample of dumb-bell shape
Product (No. 5 test specimens).
Then the accurate universal testing machine SHIMADZU AUTOGRAPH manufactured by Shimadzu Corporation is used
AGS-J (trade name, load 5KN), in the tensile elasticity that elongation speed is the test specimen measuring each dumb-bell shape under 200mm/min
Modulus, elongation at break and elongation intensity.Result is as shown in following table.
<heat melts peeling strength>
The resin (covering mixture) that Tables 1 and 2 is listed uses hot pressing to pressurize at 200 DEG C, and deburring is to manufacture thickness
Sheet A for 2.5mm.By by obtained sheet A be used for the thermoplastic polyurethanes elastomer of tyre framework body (by Ube
Industries Ltd. manufactures) (UBESTA (registered trade mark) XPA9055X1, (tensile modulus of elasticity 303MPa, elongation at break
350%, hot strength 41MPa) melt to produce the thickness sheet as 4.5mm by heat.It is that 25mm is to produce chi that sheet is switched to width
Very little is the sample strip of 130 mm × 25mm × 4mm.The heat of the sample strip produced is melted peeling strength and is separated by T-shaped (180 DEG C)
Tension test uses SHIMADZU AUTOGRAPH AGS-J (trade name, the load manufactured by Shimadzu Corporation
5KN) temperature, elongation speed at 23 DEG C are to measure under 50mm/min.Test is carried out 2 times, and its meansigma methods is as evaluation
Value.Evaluation of estimate is the biggest, represents that the cohesiveness between covering mixture and tyre framework body is the most excellent.Result the most following table institute
Show.
<fluidity evaluating [MFR (g/10 divides, 200 DEG C)]>
Above-mentioned various granules, use the semi-automatic melt index manufactured by Toyo Seiki Seisaku-sho, Ltd.
Analyzer MODEL 2A (trade name), measures mobility (MFR: single according to ASTM A1238 (method B) under the load of 98.07N
Position g/10 divides).The numerical value of measured value is the biggest, represents that the ease for operation of mixture is the most excellent.Result is as shown in following table.
<extracting experiment>
First, the monofilament of a diameter of 0.8mm is arranged in the ring-type columnar mould of a length of 60mm of a diameter of 10mm
The heart.
Secondly, each resin (covering mixture) cavity portion filling table 1 below and the table 2 of ring-type columnar mould listed
And injection moulding.The resin cooling that will obtain, and the ring-type column test specimen of pyrite plate wire is obtained at the center of resin portion.
To each test specimen obtained, the AG-5KNK (trade name) that use is manufactured by Shimadzu Corporation will
Steel wire is extracted with the speed of 50mm/min from resin portion, measures pulling capacity (unit: N) in withdrawal process.Based on measured value,
The resistance to pull out of each test specimen is evaluated according to following standard.The resistance to pull out of pulling capacity the biggest expression metal reinforcement cord component
The most excellent.
[table 1]
[table 2]
Abbreviation in table is as follows.
Amide 12:3024U, is manufactured by Ube Industries Ltd.
ET680: thermoplastic polyurethanes elastomer (ELASTOLLAN ET680 (esters), BASF manufacture)
ET690: thermoplastic polyurethanes elastomer (ELASTOLLAN ET690 (esters), BASF manufacture)
ET890: thermoplastic polyurethanes elastomer (ELASTOLLAN ET890 (esters), BASF manufacture)
Unmodified SEBS: thermoplastic polystyrene class elastomer (H1052, by Asahi Kasei
Chemicals Corporation manufactures, styrene-content: 20 mass %)
Modified SEBS: the thermoplastic polystyrene class elastomer of acid (M1943 is by Asahi Kasei
Chemicals Corporation manufactures, styrene-content: 20 mass %)
Nylon 12 (thermoplastic resin) (1:1 (mass ratio)-3014U and3024U's is mixed
Compound, is manufactured by Ube Industries Ltd.)
The modified thermoplastic olefin class elastomer of TAFMER MH 7007: specific acid (MH7007, by
Mitsui Chemicals, Inc. manufacture)
The modified thermoplastic olefin class elastomer of TAFMER MH 7010: specific acid (MH7010, by
Mitsui Chemicals, Inc. manufacture)
The modified thermoplastic olefin class elastomer of TAFMER MH 7020: specific acid (MH7020, by
Mitsui Chemicals, Inc. manufacture)
The modified thermoplastic olefin class elastomer of TAFMER MA 8510: specific acid (MH8510, by
Mitsui Chemicals, Inc. manufacture)
TAFMER A1050S: the specific not thermoplastic olefin class elastomer that acid is modified (A1050S, by
Mitsui Chemicals, Inc. manufacture)
Rubber components: rubber components is obtained as following.
By each component listed by table 2 at initial temperature is 40 DEG C seal banbury mixers in mix 3 minutes with
Produce rubber composition.After using roll to seal the rubber composition of gained, rubber comminutor is used to carry out pelletize to obtain
Rubber grain.
[table 4]
It should be noted that the acid number of the thermoplastic polyolefin-like elastomer of specific acid modification is carried out according to calculating formula (1)
Calculate.
The thermoplastic polyolefin-like elastomer modified for specific acid and the specific thermoplastic polyolefin-like bullet that acid is not modified
Gonosome, is similar to specific covering mixture, and thermoplastic polyolefin-like elastomer that specific acid is modified and specific acid are modified
The dumb-bell shape test sample of thermoplastic polyolefin-like elastomer by use SHIMADZU AUTOGRAPH AGS-J (load:
5KN) it is set under 200mm/min measure in elongation speed, and finds each there is tensile modulus of elasticity less than 140MPa.
For the test specimen formed with mixture by the covering of embodiment 1-1 to 1-4,2-1 to 2-5 and 3-1 to 3-9,
Can be by checking that the image viewing using SEM capture is to each having the island that thermoplastic resin is marine facies and elastomer is island phase
Structure.
Shown in result from table 1, the covering mixture of embodiment has higher than the covering mixture of comparative example
Resistance to pull out, and also have excellence to the thermoplastic elastomer (TPE) (thermoplastic polyurethanes elastomer) forming tyre framework body
Cohesiveness.Therefore use the covering steel wire of the covering mixture of embodiment, and use these to be supplied to use as protection band
The tire of the tyre framework body gained of resin material has shielded metal cords component (steel wire) and the tyre framework of excellence
Adhesion durability between body.The tire using the material of embodiment and comparative example to be formed carries out field test, knot
Fruit, with like above, uses the tire of embodiment material to have the adhesion durability of excellence.
The exemplary of the present invention is as follows, but the scope of the present invention is not limited to this.
<1-1>tire, comprising:
The ring-type tyre framework body formed by resin material；With
The metal reinforcement cord component being wound on tyre framework external week, at least some of metal reinforcement cord component quilt
Covering mixture covers, and this covering mixture includes thermoplastic resin and thermoplastic polyurethanes elastomer.
The tire of<1-2><1-1>, wherein covering mixture has the marine facies included containing thermoplastic resin and containing heat
The island structure of the island phase of plastic polyurethane class elastomer.
<1-3><1-1>or the tire of<1-2>, the wherein thermoplastic resin (p) in covering mixture and thermoplastic poly ammonia
The mass ratio (p/e) of esters elastomer (e) is 95/5 to 55/45.
<1-4><1-1>, to arbitrary tire in<1-3>, the wherein tensile modulus of elasticity (x1) of tyre framework body, covering is with mixed
The tensile modulus of elasticity (x2) of compound, and the tensile modulus of elasticity (x3) of metal reinforcement cord component meets relation x1 < x2 < x3.
<1-5><1-1>, to arbitrary tire in<1-4>, wherein fracture rate elongation (y1) of tyre framework body, covering mixes
The fracture rate of thing extends (y2), and the elongation at break (y3) of metal reinforcement cord component meets relation y1 > y2 > y3.
<1-6><1-1>, to arbitrary tire in<1-5>, wherein forms the resin material of tyre framework body and is contained in covering
Resin by the thermoplastic resin of mixture identical type each other.
<1-7><1-1>, to arbitrary tire in<1-6>, the thermoplastic resin being wherein contained in covering mixture is thermoplastic
Property polyamide-based resin.
<1-8><1-1>includes thermoplastic poly to arbitrary tire in<1-7>, the resin material wherein forming tyre framework body
Amide-type elastomer.
<2-1>tire, comprising:
The ring-type tyre framework body formed by resin material；With
The metal reinforcement cord component being wound on tyre framework external week, at least some of metal reinforcement cord component quilt
Covering mixture covers, and this covering mixture includes thermoplastic resin and thermoplastic polystyrene class elastomer.
The tire of<2-2><2-1>, wherein covering mixture has the marine facies included containing thermoplastic resin and containing heat
The island structure of the island phase of plasticity polystyrene type elastomer.
<2-3><2-1>or the tire of<2-2>, the wherein thermoplastic resin (p) in covering mixture and thermoplasticity polyphenyl
The mass ratio (p/e) of vinyl elastomer (e) is 95/5 to 55/45.
<2-4><2-1>, to arbitrary tire in<2-3>, the wherein tensile modulus of elasticity (x1) of tyre framework body, covering is with mixed
The tensile modulus of elasticity (x2) of compound, and the tensile modulus of elasticity (x3) of metal reinforcement cord component meets relation x1 < x2 < x3.
<2-5><2-1>, to arbitrary tire in<2-4>, the wherein elongation at break (y1) of tyre framework body, covering mixes
The elongation at break (y2) of thing, and the elongation at break (y3) of metal reinforcement cord component meets relation y1 > y2 > y3.
<2-6><2-1>, to arbitrary tire in<2-5>, wherein forms the resin material of tyre framework body and is contained in covering
Resin by the thermoplastic resin of mixture identical type each other.
<2-7><2-1>, to arbitrary tire in<2-6>, wherein thermoplastic polystyrene class elastomer is the thermoplastic that acid is modified
Property polystyrene type elastomer, unmodified thermoplastic polystyrene class elastomer, or the thermoplastic polystyrene class that acid is modified
Elastomer and the combination of unmodified thermoplastic polystyrene class elastomer.
<2-8><2-1>, to arbitrary tire in<2-7>, the thermoplastic resin being wherein contained in covering mixture is thermoplastic
Property polyamide-based resin.
<2-9><2-1>includes thermoplastic poly to arbitrary tire in<2-8>, the resin material wherein forming tyre framework body
Amide-type elastomer.
<3-1>tire, comprising:
The ring-type tyre framework body formed by resin material；With
The metal reinforcement cord component being wound on tyre framework external week, wherein,
At least some of metal reinforcement cord component is capped to be covered with mixture, and this covering mixture includes thermoplasticity
Resin and at least one thermoplastic olefin class elastomer, this thermoplastic olefin class elastomer selects free elastic modelling quantity less than 140MPa
The modified thermoplastic olefin class elastomer of acid, and the thermoplastic olefin class bullet that acid is not modified that elastic modelling quantity is less than 140MPa
The group of gonosome composition.
The tire of<3-2><3-1>, wherein covering mixture has the marine facies included containing thermoplastic resin and containing heat
The island structure of the island phase of plastomeric olefin class elastomer.
<3-3><3-1>or the tire of<3-2>, the wherein thermoplastic resin (p) in covering mixture and thermoplastic olefin
The mass ratio (p/e) of class elastomer (e) is 95/5 to 55/45.
Arbitrary tire in<3-4><3-1>to<3-3>, the wherein tensile modulus of elasticity (x1) of tyre framework body, cover and use
The tensile modulus of elasticity (x2) of mixture, and the tensile modulus of elasticity (x3) of metal reinforcement cord component meet relation x1 < x2 <
x3。
Arbitrary tire in<3-5><3-1>to<3-4>, the wherein elongation at break (y1) of tyre framework body, cover with mixed
The elongation at break (y2) of compound, and the elongation at break (y3) of metal reinforcement cord component meets relation y3 < y2 < y1.
Arbitrary tire in<3-6><3-1>to<3-5>, the resin material wherein forming tyre framework body covers with being contained in
The resin of the thermoplastic resin of lid mixture identical type each other.
Arbitrary tire in<3-7><3-1>to<3-6>, wherein the acid number of the thermoplastic olefin class elastomer that acid is modified is
0.1mg(CH3ONa)/more than g, but less than 20.0mg (CH3ONa)/g。
Arbitrary tire in<3-8><3-1>to<3-7>, the thermoplastic resin being wherein contained in covering mixture is heat
Plastic polyamide resinoid.
Arbitrary tire in<3-9><3-1>to<3-8>, the resin material wherein forming tyre framework body includes thermoplasticity
Polyamide-based elastomer.
Japanese patent application 2012-044594, Japanese patent application 2012-044649 and Japanese patent application
The disclosure of No. 2012-045525 is generally introduced with it has work reference in this.
All publications, patent, patent application and technical instruction described in the present invention is hereby incorporated by reference
Degree is pointed out to be incorporated herein by reference such as single publication, patent, patent application and technical instruction the most individually
Degree.
Claims (24)
1. a tire, comprising:
The ring-type tyre framework body formed by resin material；With
The metal reinforcement cord component being wound on described tyre framework external week,
Described metal reinforcement cord component be included thermoplastic resin and thermoplastic polyurethanes elastomer at least partially
Covering mixture covers,
The elongation at break of wherein said tyre framework body, the elongation at break of described covering mixture, and described metal are mended
The elongation at break of strong cord component meets relation y1 > y2 > y3, wherein y1 is the elongation at break of described tyre framework body, y2
It is the elongation at break of described covering mixture, and y3 is the elongation at break of described metal reinforcement cord component.
Tire the most according to claim 1, wherein said covering mixture has and includes containing described thermoplastic resin
Marine facies and the island structure of island phase containing described thermoplastic polyurethanes elastomer.
Tire the most according to claim 1, in wherein said covering mixture, described thermoplastic resin and described thermoplastic
The mass ratio of property polyurethane elastomer is 95/5 to 55/45.
Tire the most according to claim 1, the tensile modulus of elasticity of wherein said tyre framework body, described covering mixes
The tensile modulus of elasticity of thing, and the tensile modulus of elasticity of described metal reinforcement cord component meets relation x1 < x2 < x3, wherein x1
For the tensile modulus of elasticity of described tyre framework body, x2 is the tensile modulus of elasticity of described covering mixture, and x3 is described
The tensile modulus of elasticity of metal reinforcement cord component.
Tire the most according to claim 1, wherein forms the described resin material of described tyre framework body and is contained in institute
State the resin that described thermoplastic resin is identical type of covering mixture.
Tire the most according to claim 1, the described thermoplastic resin being wherein contained in described covering mixture is heat
Plastic polyamide resinoid.
7., according to the tire described in any one of claim 1 to 6, wherein form the described resin material bag of described tyre framework body
Include polyamide thermoplastic class elastomer.
8. a tire, comprising:
The ring-type tyre framework body formed by resin material；With
The metal reinforcement cord component being wound on described tyre framework external week,
Described metal reinforcement cord component be included thermoplastic resin and thermoplastic polystyrene class elastomer at least partially
Covering with mixture cover,
The elongation at break of wherein said tyre framework body, the elongation at break of described covering mixture, and described metal are mended
The elongation at break of strong cord component meets relation y1 > y2 > y3, wherein y1 is the elongation at break of described tyre framework body, y2
For the elongation at break of described covering mixture, and the elongation at break that y3 is described metal reinforcement cord component.
Tire the most according to claim 8, wherein said covering mixture has and includes containing described thermoplastic resin
Marine facies and the island structure of island phase containing described thermoplastic polystyrene class elastomer.
Tire the most according to claim 8, in wherein said covering mixture, described thermoplastic resin and described heat
The mass ratio of plasticity polystyrene type elastomer is 95/5 to 55/45.
11. tires according to claim 8, the tensile modulus of elasticity of wherein said tyre framework body, described covering is with mixed
The tensile modulus of elasticity of compound, and the tensile modulus of elasticity of described metal reinforcement cord component meet relation x1 < x2 < x3, wherein
X1 is the tensile modulus of elasticity of described tyre framework body, and x2 is the tensile modulus of elasticity of described covering mixture, and x3 is institute
State the tensile modulus of elasticity of metal reinforcement cord component.
12. tires according to claim 8, wherein form the described resin material of described tyre framework body and are contained in institute
State the resin that described thermoplastic resin is identical type of covering mixture.
13. tires according to claim 8, wherein said thermoplastic polystyrene class elastomer is the thermoplasticity that acid is modified
Polystyrene type elastomer, unmodified thermoplastic polystyrene class elastomer, or the thermoplastic polystyrene class bullet that acid is modified
Gonosome and the combination of unmodified thermoplastic polystyrene class elastomer.
14. tires according to claim 8, the described thermoplastic resin being wherein contained in described covering mixture is heat
Plastic polyamide resinoid.
15., according to Claim 8 to the tire described in 14 any one, wherein form the described resin material of described tyre framework body
Including polyamide thermoplastic class elastomer.
16. 1 kinds of tires, comprising:
The ring-type tyre framework body formed by resin material；With
The metal reinforcement cord component being wound on described tyre framework external week, wherein,
Described metal reinforcement cord component be included covering of thermoplastic resin and thermoplastic olefin class elastomer at least partially
Lid mixture covers, and described thermoplastic olefin class elastomer selects the thermoplasticity that free elastic modelling quantity is modified less than the acid of 140MPa
The group of olefin type elastomer and the elastic modelling quantity thermoplastic olefin class elastomer composition that acid is not modified less than 140MPa is at least
A kind of.
17. tires according to claim 16, wherein said covering mixture has and includes containing described thermoplastic resin
The marine facies of fat and the island structure of the island phase containing described thermoplastic olefin class elastomer.
18. tires according to claim 16, in wherein said covering mixture, described thermoplastic resin and described heat
The mass ratio of plastomeric olefin class elastomer is 95/5 to 55/45.
19. tires according to claim 16, the tensile modulus of elasticity of wherein said tyre framework body, described covering is with mixed
The tensile modulus of elasticity of compound, and the tensile modulus of elasticity of described metal reinforcement cord component meet relation x1 < x2 < x3, wherein
X1 is the tensile modulus of elasticity of described tyre framework body, and x2 is the tensile modulus of elasticity of described covering mixture, and x3 is institute
State the tensile modulus of elasticity of metal reinforcement cord component.
20. tires according to claim 16, the elongation at break of wherein said tyre framework body, described covering mixes
The elongation at break of thing, and the elongation at break of described metal reinforcement cord component meets relation y3, and < y2 < y1, wherein y1 is institute
Stating the elongation at break of tyre framework body, y2 is the elongation at break of described covering mixture, and y3 is described metal reinforcement
The elongation at break of cord component.
21. tires according to claim 16, wherein form the described resin material of described tyre framework body and are contained in
The resin that described thermoplastic resin is identical type of described covering mixture.
22. tires according to claim 16, the acid number of the thermoplastic olefin class elastomer that wherein said acid is modified is
0.1mg(CH3ONa)/more than g, but less than 20.0mg (CH3ONa)/g。
23. tires according to claim 16, the described thermoplastic resin being wherein contained in described covering mixture is
Polyamide thermoplastic resinoid.
24., according to the tire described in any one of claim 16 to 23, wherein form the described resinous wood of described tyre framework body
Material includes polyamide thermoplastic class elastomer.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012044649A JP5905298B2 (en) | 2012-02-29 | 2012-02-29 | tire |
| JP2012-044649 | 2012-02-29 | ||
| JP2012044594A JP5840534B2 (en) | 2012-02-29 | 2012-02-29 | tire |
| JP2012-044594 | 2012-02-29 | ||
| JP2012-045525 | 2012-03-01 | ||
| JP2012045525A JP5840535B2 (en) | 2012-03-01 | 2012-03-01 | tire |
| PCT/JP2013/055237 WO2013129525A1 (en) | 2012-02-29 | 2013-02-27 | Tire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104159753A CN104159753A (en) | 2014-11-19 |
| CN104159753B true CN104159753B (en) | 2016-11-30 |
Family
ID=
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103370209A (en) * | 2011-02-15 | 2013-10-23 | 株式会社普利司通 | Tire |
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103370209A (en) * | 2011-02-15 | 2013-10-23 | 株式会社普利司通 | Tire |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105142928B (en) | Tire | |
| CN105163957B (en) | Tire | |
| CN104144798B (en) | Tire | |
| CN107709040B (en) | The manufacturing method of tire and tire | |
| CN104144800B (en) | Tire | |
| WO2013129525A1 (en) | Tire | |
| CN104144801B (en) | Tire | |
| CN108472995B (en) | Tyre for vehicle wheels | |
| CN104245356A (en) | Tire | |
| JP6785193B2 (en) | Resin metal composite members for tires and tires | |
| JP6785245B2 (en) | tire | |
| CN104271363A (en) | Tire | |
| WO2017104214A1 (en) | Tire | |
| CN104159753B (en) | Tire | |
| CN108472993B (en) | Tyre for vehicle wheels | |
| JP6114498B2 (en) | tire | |
| US20210214576A1 (en) | Resin-metal composite member for tire, method of manufacturing the same, and tire | |
| WO2021117427A1 (en) | Tire resin member, bead member, tire belt, tire frame body and tire, and methods for manufacturing same | |
| CN104125887B (en) | Tire | |
| JP2020062935A (en) | Wire-resin composite member for tire, and tire | |
| JP2019001357A (en) | Resin metal composite member for tire and tire | |
| CN104125887A (en) | Tire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |