CN101314652B - Rubber composition for coating tire cord - Google Patents
Rubber composition for coating tire cord Download PDFInfo
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- CN101314652B CN101314652B CN2008101098482A CN200810109848A CN101314652B CN 101314652 B CN101314652 B CN 101314652B CN 2008101098482 A CN2008101098482 A CN 2008101098482A CN 200810109848 A CN200810109848 A CN 200810109848A CN 101314652 B CN101314652 B CN 101314652B
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- rubber
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- weight parts
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- tire
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 71
- 239000005060 rubber Substances 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 239000011248 coating agent Substances 0.000 title claims abstract description 16
- 238000000576 coating method Methods 0.000 title claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 11
- 229920001194 natural rubber Polymers 0.000 claims abstract description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- GPNLWUFFWOYKLP-UHFFFAOYSA-N s-(1,3-benzothiazol-2-yl)thiohydroxylamine Chemical compound C1=CC=C2SC(SN)=NC2=C1 GPNLWUFFWOYKLP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000470 constituent Substances 0.000 claims description 13
- 239000005864 Sulphur Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- 238000005987 sulfurization reaction Methods 0.000 claims description 10
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 8
- 229930003836 cresol Natural products 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 7
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical group [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229920003051 synthetic elastomer Polymers 0.000 claims description 5
- 238000004073 vulcanization Methods 0.000 abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- SDYMYAFSQACTQP-UHFFFAOYSA-N 1,3-benzothiazole-2-sulfonamide Chemical compound C1=CC=C2SC(S(=O)(=O)N)=NC2=C1 SDYMYAFSQACTQP-UHFFFAOYSA-N 0.000 abstract 1
- WHCIAGVVOCLXFV-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-ylsulfanyl)-1,3-benzothiazole Chemical group C1=CC=C2SC(SC=3SC4=CC=CC=C4N=3)=NC2=C1 WHCIAGVVOCLXFV-UHFFFAOYSA-N 0.000 abstract 1
- 230000032683 aging Effects 0.000 abstract 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 abstract 1
- 229920003049 isoprene rubber Polymers 0.000 abstract 1
- 235000013495 cobalt Nutrition 0.000 description 12
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- -1 2-ethylhexyl Chemical group 0.000 description 7
- 239000005062 Polybutadiene Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 5
- 230000003712 anti-aging effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 229920005683 SIBR Polymers 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group 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
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VILGDADBAQFRJE-UHFFFAOYSA-N n,n-bis(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SN(SC=3SC4=CC=CC=C4N=3)C(C)(C)C)=NC2=C1 VILGDADBAQFRJE-UHFFFAOYSA-N 0.000 description 2
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229920013649 Paracril Polymers 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- CTIHZTFULZJBGQ-UHFFFAOYSA-L cobalt(2+);decanoate Chemical compound [Co+2].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O CTIHZTFULZJBGQ-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- QXYKBSYRGILOTK-UHFFFAOYSA-L disodium;1,6-bis(sulfonatosulfanyl)hexane Chemical compound [Na+].[Na+].[O-]S(=O)(=O)SCCCCCCSS([O-])(=O)=O QXYKBSYRGILOTK-UHFFFAOYSA-L 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
The object of the present invention is provide a rubber composition for coating a tire cord, which improves adhesion with a tire cord and has an effect of recovering adhesion with a tire cord at hygrothermal aging with maintaining the initial vulcanization rate. The present invention relates to a rubber composition for coating a tire cord comprising 0.7 to 3 parts by weight of benzothiazolyl sulfonamide or benzothiazolyl sulfenimide represented by the chemical formula (1), and is relative to 100 parts by weight of NR and/or IR, comprising 0.05-0.2 parts by weight of organic cobalt : (wherein R1 is a linear alkyl group having a branched structure of 3 to 16 carbon atoms, and R2 is a linear alkyl group having a branched structure of 3 to 16 carbon atoms or a benzothiazolyl sulfide group) and 3 to 7 parts by weight of sulfur based on 100 parts by weight of a rubber component containing at least 60% by weight of a natural rubber and/or an isoprene rubber.
Description
Technical field
The tyre cord that the present invention relates to rubber composition for coating tire cord and coated by this rubber combination.
Background technology
Usually, tyre cord is configured in inside tires mostly, due near rubber tyre cord be located at stow away from heat in tire curing procedure place, therefore be not easy to cure, in order to promote sulfuration, use N, N-dicyclohexyl-2-[4-morpholinodithio sulphenamide (DCBS) etc.(patent documentation 1).
With other sulphenamide, be that promotor, thiazole are that promotor etc. replaces above-mentioned DCBS also known.Such vulcanization accelerator, insufficient with the initial stage tackiness of steel cord, and recover little with the effect of the adhesion of steel cord when deteriorated damp and hot, so, also attempted adding Resorcinol, mixed cross-linker or a large amount of cobalts and improved (patent documentation 2).
But these trials exist: can not obtain good tackiness under the high temperature vulcanized condition when producing doughnut, compare inadequate problem with DCBS.Such problem is also arranged: if use a large amount of cobalts, because thermooxidizing is deteriorated, the breaking tenacity of rubber is low, uses Resorcinol, and the breaking tenacity of rubber reduces.
[patent documentation 1] Japanese Laid-Open Patent JP 2005-239874
[patent documentation 2] Japanese Laid-Open Patent JP 2006-328194
Summary of the invention
The problem that invention will solve
The purpose of this invention is to provide a kind of rubber composition for coating tire cord, it can improve the tackiness of rubber cord when maintaining vulcanization rate, though damp and hot also have when deteriorated recover and tyre cord between adhesive effect.
Solve the method for problem
The present invention relates to a kind of rubber combination, the rubber constituent that contains 60 % by weight natural rubbers and/or synthetic polyisoprene with respect to 100 weight parts, the sulphur with the benzothiazole sulphenamide shown in chemical formula (1) or benzothiazole sulfenamide (ス Le Off ェ Application イ ミ De) and 3～7 weight parts that also contains 0.7～3 weight part, with respect to 100 weight part NR and/or IR, contain and be converted into the organic acid cobalt that cobalt is 0.05～0.2 weight part.
(wherein, R
1the straight chained alkyl with branched structure that carbonatoms is 3-16, R
2the straight chained alkyl with branched structure or the sulfuration benzothiazole group that carbonatoms is 3-16.)
Be preferably in rubber combination and do not contain resorcinol resin and cresol resin.
Tyre cord is tire steel cord preferably.
The present invention relates to the tyre cord by above-mentioned rubber composition for coating tire cord coating again.
The effect of invention
According to the present invention, by using specific vulcanization accelerator, can improve and consider environment, the damp and hot tackiness of improvement and tyre cord, improve breaking tenacity.
Embodiment
Rubber composition for coating tire cord of the present invention, the rubber constituent that contains 60 % by weight natural rubbers and/or synthetic polyisoprene with respect to 100 weight parts, the sulphur with the benzothiazole sulphenamide shown in chemical formula (1) or benzothiazole sulfenamide and 3～7 weight parts that also contains 0.7～3 weight part, with respect to 100 weight part NR and/or IR, contain and be converted into the organic acid cobalt that cobalt is 0.05～0.2 weight part.
(wherein, R
1the straight chained alkyl with branched structure that carbonatoms is 3-16, R
2the straight chained alkyl with branched structure or the sulfuration benzothiazole group that carbonatoms is 3-16.)
Here, as the object lesson of tyre cord, can enumerate tire steel cord and tire fiber cord.
Not only contain natural rubber itself in natural rubber, also contain epoxy natural rubber (ENR), deproteinized natural rubber (DPNR).Natural rubber (NR) and/or synthetic polyisoprene (IR) can mix and use with other rubber constituent.Other rubber constituent can exemplify styrene-butadiene rubber(SBR) (SBR), styrene isoprene butadiene rubber (SIBR) (SIBR), divinyl rubber (BR), terpolymer EP rubber (EPDM), chloroprene rubber (CR), isoprene-isobutylene rubber (IIR), paracril (NBR) etc.Wherein, be preferably cis-rich polybutadiene rubber (BR), modification BR, modification SBR.As modification BR, as Japanese Laid-Open Patent Application JP 2006-124503 communique and JP 2006-63143 communique, put down in writing, can exemplify the polybutadiene rubber (a) (BR (A)) that contains the crystallization of 1,2-syndiotactic polybutadiene, tin modification polybutadiene rubber (b) (BR (b)) etc.
While mixing with other rubber constituent, NR and/or IR account for more than 60 % by weight better in rubber constituent, and 70 % by weight are above better, and 100% is best.Less than 60 % by weight, breaking tenacity has the tendency of step-down.
In the present invention, use and to using the represented benzothiazole sulphenamide of chemical formula (1) or benzothiazole sulfenamide as vulcanization accelerator.In chemical formula (1), R
1the straight chained alkyl with branched structure that carbonatoms is 3-16, R
2the straight chained alkyl with branched structure or the sulfide group that carbonatoms is 3-16.Straight chained alkyl forms by carbon atom 3-16, is preferably 4-16, is more preferably 6-12.Carbonatoms is below 2, and incipient cure speed is fast, the tackiness variation, and more than 17, incipient cure speed is too slow, the rubber hardness step-down.As R
1and R
2middle desirable alkyl can exemplify: the tertiary butyl, 2-ethylhexyl, 2-methyl hexyl, 3-ethylhexyl, 3-methyl hexyl, 2-ethyl propyl, 2-ethyl-butyl, 2-ethyl pentyl group, 2-ethyl heptyl, 2-ethyl octyl group etc.Again, manufacture raw material based on reducing, improve the reason of manufacturing yield, improving purity, reduce the cost, be preferably R
1and R
2identical.
R in chemical formula (1)
2also can exemplify the sulfuration benzothiazole group represented with following formula.Work as R
2while being sulfuration benzothiazole group, with the represented compound of chemical formula (1), be exactly the benzothiazole sulfenamide.R
1while being the tertiary butyl, R
2that sulfuration benzothiazole group is better.
Represented benzothiazole sulphenamide or the benzothiazole sulfenamide with chemical formula (1), can exemplify the BEHZ (N that chemical industry Co., Ltd. of Kawaguchi produces, N-bis-(2-ethylhexyl)-2-[4-morpholinodithio sulphenamide), the SANTOCURE TBSI (the N-tertiary butyl-2-[4-morpholinodithio sulfenamide) that the BMHZ (N, N-bis-(2-methyl hexyl)-2-[4-morpholinodithio sulphenamide) that chemical industry Co., Ltd. of Kawaguchi produces, FLEXSYS Co., Ltd. produce etc.
With respect to the rubber constituent that contains the above NR of 60 % by weight and/or IR of 100 weight parts, with chemical formula (1) combined amount of represented benzothiazole sulphenamide or benzothiazole sulfenamide under be limited to 0.7 weight part above, be preferably 0.8 weight part more than.Combined amount less than 0.7 weight part, the hardness of rubber is low, the breaking tenacity step-down.Again, be limited on combined amount below 3 weight parts, be preferably below 2.7 weight parts.Combined amount surpasses 2.7 weight parts, with the tackiness of cord, reduces.
With respect to NR and/or IR100 weight part, the combined amount of sulphur is more than 3 weight parts, is preferably 3.5 weight parts.Combined amount less than 3 weight parts of sulphur, the rubber stock obtained and the tackiness of cord are insufficient.Again, the combined amount of sulphur (B) is below 7 weight parts, is preferably below 6.5 weight parts.The combined amount of sulphur surpasses 7 weight parts, and due to the tackiness deterioration of frosting and adjacent component, the concentration of sulphur becomes inhomogeneous.
In order to improve breaking tenacity, be preferably rubber composition for coating tire cord of the present invention and do not contain resorcinol resin and cresol resin.Owing to containing the modification resorcinol resin in resorcinol resin, contain the modification cresol resin in cresol resin, do not refer to all not containing resorcinol resin, modification resorcinol resin, cresol resin, modification cresol resin containing resorcinol resin and cresol resin so said here.
In rubber combination of the present invention, except above-mentioned rubber constituent, sulphur and vulcanization accelerator, weighting agents such as mixed carbon black, silicon-dioxide, calcium carbonate as required, the additive of softening agent, zinc oxide, vulcanization aid, whipping agent, anti-aging agent, wax etc.
With respect to the rubber constituent that contains the above NR of 60 % by weight and/or IR of 100 weight parts, more than the lower limit of the combined amount of carbon black is preferably 40 weight parts, more than being more preferably 45 weight parts.Combined amount less than 40 weight parts, have the hardness step-down of rubber, the trend of breaking tenacity deficiency.Again, the upper limit of combined amount is preferably below 70 weight parts, is more preferably below 65 weight parts.Combined amount surpasses 70 weight parts, has that heat generation uprises, the weather resistance downward trend.
With respect to the rubber constituent that contains the above NR of 60 % by weight and/or IR of 100 weight parts, more than the lower limit of the combined amount of silicon-dioxide is preferably 4 weight parts, more than being more preferably 5 weight parts.Combined amount less than 4 weight parts, the raising effect of elongation at break EB has the trend diminished.Again, the upper limit of combined amount is preferably below 20 weight parts, is more preferably below 15 weight parts.Combined amount surpasses 20 weight parts, and the trend that vulcanization rate is slack-off, the cord tackiness reduces and rubber hardness Hs reduces is arranged.
As silane coupling agent, be not particularly limited, can use known coupling agent.With respect to the silicon-dioxide of 100 weight parts, the lower limit of the combined amount of silane coupling agent is preferably 4 weight parts, more than being more preferably 6 weight parts.Combined amount less than 4 weight parts, tan δ has the trend uprised.Again, the upper limit of combined amount is preferably below 10 weight parts, is more preferably below 8 weight parts.Combined amount surpasses 10 weight parts, from the economy cost uprise, elongation at break has a declining tendency.
Vulcanization aid can exemplify the organic acid cobalt, in order to realize the crosslinked purpose between cord and rubber, by the mixed organic acid cobalt, can improve the tackiness between cord and rubber.The organic acid cobalt can exemplify cobalt stearate, cobalt naphthenate, new cobalt decanoate etc., is preferably cobalt stearate.With respect to 100 weight part NR and/or IR, it is more than 0.05 weight part that the content of organic acid cobalt is converted into cobalt, is preferably 0.1 weight part.Should be containing quantity not sufficient 0.05 weight part, the coating of steel cord and the tackiness of rubber are insufficient.Again, this content is below 0.8 weight part, is preferably below 0.2 weight part.This content surpasses 0.8 weight part, and the autothermic cracking of rubber becomes significantly, and fracture characteristics worsens.
Adhesion to tyre cord in new tire is important, and therefore, incipient cure speed is important factor.Rubber combination of the present invention, owing to having used specific vulcanization accelerator, incipient cure speed appropriateness, in sulfuration, the copper on the coatingsurface of tyre cord, the sulphur in rubber and cobalt etc. move under appropriate mobility, may combine.Again, because reversion is also little, the combination of the copper-sulphur of formation-rubber can not ruptured, and for example, can be suppressed at the reduction of elongation at break while only using natural rubber as rubber constituent, the weather resistance of raising rubber.
The rubber combination of invention, after coating tyre cord formation belt with this rubber combination, form unvulcanized rubber with other tyre element laminating, by sulfuration, can obtain pneumatic tyre (radial etc.).Here, belt refers in buffer layer also for the belt of radial, is the effect that tightly to hitch carcass in order bringing into play, to improve the tyre surface rigidity.Large from the tension force produced due to tire pressure, and in abutting connection with and other 1 band bundle of angular cross between produce the large viewpoint that should become while rotating, be preferably rubber combination of the present invention at belt Cladding Steel cord.
Rubber composition for coating tire cord of the present invention can be for top, edge strip of a slab and the thermofin etc. of tyre cord.The configuration of edge strip of a slab and thermofin is and the cord adjacency, identical with the top rubber of cord or show similar physical properties.
The present invention relates to the tyre cord with the rubber composition for coating tire cord coating again.Tyre cord can exemplify body cord, weighting material, adhesive tape, buffer layer (band bundle) etc.Steel can exemplify steel cord for tire, 2+2/0.23 (2 of wire diameter 0.23mm become cord with 2 cords twisted together), brass-plating high tensile cord etc.
Embodiment
Followingly according to embodiment, describe the present invention in detail, but the present invention is not limited to these.
Embodiment 1-11 and comparative example 1-10
(material)
NR:TSR20 (Thailand's product)
BR1250H: the polybutadiene rubber that Zeon Corp produces (using lithium as the initiator polymerization)
Carbon black N330: the clear carbon black N330 produced with CABOT Co., Ltd.
Carbon black N326: the clear carbon black N326 produced with CABOT Co., Ltd.
The Z115Gr that silicon-dioxide Z115G:Rhodia company produces
Silane coupling agent: the Si69 that Deggusa company produces
Cobalt stearate: the cobalt stearate that Dainippon Ink. & Chemicals Inc produces
Oil treatment insoluble sulfur: the Crystex that Flexsys company produces (contain insoluble sulfur 80% and oil 20%, put down in writing the combined amount of the full oil treatment insoluble sulfur that contains oil in table)
Accelerator D CBS: the Accel DZ-G (N, N-dicyclohexyl benzothiazole sulphenamide) that chemical industry Co., Ltd. of Kawaguchi produces
Vulcanization accelerator BEHZ: the BEHZ (N, N-bis-(2-ethylhexyl) benzothiazole sulphenamide) that chemical industry Co., Ltd. of Kawaguchi produces
Vulcanization accelerator TBBS: the Nocceler NS that the emerging chemical industry of imperial palace Co., Ltd. produces
Accelerator DM: the Nocceler DM that the emerging chemical industry of imperial palace Co., Ltd. produces
The SANTOCURE TBSI (the N-tertiary butyl-2-[4-morpholinodithio sulfenamide) that vulcanization accelerator TBSI:Flexsys Co., Ltd. produces
Sumikanol620: the modification resorcinol resin that Sumitomo Chemical Co produces
Sumikanol507A: the HMMPME ((hexamethylolmelamine) five methyl esters) that Sumitomo Chemical Co produces
The Duralink HTS (hexa-methylene dithio sulfuric acid disodium dihydrate) that HTS:Flexsysy Co., Ltd. produces
Perfume oil: the Process X-140 that Japan energy company produces
Antiaging agent: the Noclac6C that the emerging chemical industry of imperial palace Co., Ltd. produces
Zinc oxide: zinc Co., Ltd. of eastern nation produces Yin ridge R
(manufacture method)
By each medicine in the mixed content except sulphur and vulcanization accelerator shown in table 1 and table 2, mixing in Banbury mixer, add oil treatment insoluble sulfur and various vulcanization accelerator in the mixing thing obtained thus, the mixing unvulcanized rubber composition that obtains in mill.This unvulcanized rubber composition, 150 ℃ of press vulcanizations 30 minutes, is obtained to the vulcanized rubber sample.About perfume oil, antiaging agent and zinc oxide, although not record of table 1 mixes in all embodiment and comparative example with 2 weight parts, 1 weight part, 10 weight parts respectively, vulcanization accelerator is to mix with the equimolar amount of DCBS.
(test method)
<sulfuration test >
Use the oscillatory type vulcanzing tester (curelastometer:JSR type vulkameter) of putting down in writing in JIS K6300,160 ℃ of mensuration temperature, vulcanize test, with time and moment of torsion mapping, obtain the vulcanization rate curve.The minimum value that makes the moment of torsion of vulcanization rate curve is that ML, maximum value are MH, its difference (MH-ML) during for ME, reads the time T that arrives ML+0.1ME
10(dividing).
<tension test (fracture resistance and elongation at break) >
According to JIS K6251, use No. 3 dumbbells to carry out tension test, measure the elongation at break (%) under room temperature.
<adherence test >
Carry out adherence test, measure respectively the rubber coated rate (%) of rubber combination.The rubber coated rate is the rubber coated ratio exponential representation of release surface when peeling off between steel cord and rubber.5 mean that 100% coats, and 0 means there is no the state coated fully.Again, under the condition in 80 ℃ of temperature, humidity 95%, by rubber combination, the rubber combination after damp and hot deteriorated 150 hours similarly carries out rubber coated rate mensuration.
<test for viscoelastic >
The test film for preparing specific dimensions from above-mentioned vulcanizate compositions, the determination of viscoelasticity instrument VES that uses Co., Ltd.'s this making of rock to produce, under the condition of initial strain 10%, dynamic strain 2% and frequency 10Hz, the complex elastic-modulus (E of rubber test sheet while measuring 70 ℃
*) and loss tangent (tan6).E
*larger rigidity is better.
Test-results separately as shown in Tables 1 and 2.
[table 1]
[table 2]
From the evaluation result of table 1 and table 2, while using vulcanization accelerator BEHZ, compare elongation at break and cord tackiness excellence with the DCBS of comparative example 1.
Embodiment 12～21 and comparative example 11～19
(manufacture method)
By each medicine in the mixed content except sulphur and vulcanization accelerator shown in table 3 and table 4, mixing in Banbury mixer, add oil treatment insoluble sulfur and various vulcanization accelerator in the mixing thing obtained thus, the mixing unvulcanized rubber composition that obtains in mill.This unvulcanized rubber composition, 150 ℃ of press vulcanizations 30 minutes, is obtained to the vulcanized rubber sample.About perfume oil, antiaging agent and zinc oxide, although the not record of table 3 and table 4 mixes in all embodiment and comparative example with 2 weight parts, 1 weight part, 10 weight parts respectively, vulcanization accelerator is to mix with the equimolar amount of DCBS.
By the method same with above-mentioned test method, embodiment 12～21 and the resulting composition of comparative example 11～19 are estimated.Test-results separately as shown in Table 3 and Table 4.
[table 3]
[table 4]
Can find out from the evaluation result of table 3 and table 4, while using vulcanization accelerator TBSI, compare elongation at break and cord tackiness excellence with the DCBS of comparative example 11.
Claims (4)
1. a tire, there is the tyre cord coated by rubber composition for coating tire cord, this rubber combination is with respect to the rubber constituent that contains the above natural rubber of 60 % by weight and/or synthetic polyisoprene of 100 weight parts, also contain the benzothiazole sulphenamide shown in the chemical formula (1) of 0.7～3 weight part or the sulphur of benzothiazole sulfenamide and 3～7 weight parts, with respect to 100 weight part natural rubber and/or synthetic polyisoprenes, contain and be converted into the organic acid cobalt that cobalt is 0.05～0.2 weight part
Wherein, R
1the straight chained alkyl with branched structure that carbonatoms is 3-16, R
2the straight chained alkyl with branched structure or the sulfuration benzothiazole group that carbonatoms is 3-16,
Wherein said rubber combination is not containing resorcinol resin and cresol resin.
2. the tire of putting down in writing according to claim 1, wherein tyre cord is tire steel cord.
3. the tire of putting down in writing according to claim 1, described organic acid cobalt is cobalt stearate.
4. the tire of putting down in writing according to claim 1, with respect to the rubber constituent of 100 weight parts, rubber combination also contains the carbon black of 45～70 weight parts or the silicon-dioxide of 4～20 weight parts.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007147078 | 2007-06-01 | ||
| JP2007-147078 | 2007-06-01 | ||
| JP2007147078 | 2007-06-01 | ||
| JP2008067292A JP4431618B2 (en) | 2007-06-01 | 2008-03-17 | Rubber composition for covering tire cord |
| JP2008-067292 | 2008-03-17 | ||
| JP2008067292 | 2008-03-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101314652A CN101314652A (en) | 2008-12-03 |
| CN101314652B true CN101314652B (en) | 2013-12-11 |
Family
ID=40105806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101098482A Expired - Fee Related CN101314652B (en) | 2007-06-01 | 2008-05-30 | Rubber composition for coating tire cord |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4431618B2 (en) |
| CN (1) | CN101314652B (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5085231B2 (en) * | 2007-08-24 | 2012-11-28 | 東洋ゴム工業株式会社 | Rubber composition for covering steel cord and pneumatic tire |
| JP4493712B2 (en) | 2007-12-05 | 2010-06-30 | 住友ゴム工業株式会社 | Rubber composition for tire |
| BRPI0821841B1 (en) * | 2007-12-27 | 2019-07-02 | Bridgestone Corporation | RUBBER COMPOSITION |
| JP5458508B2 (en) * | 2008-05-28 | 2014-04-02 | 横浜ゴム株式会社 | Adhesive rubber composition |
| JP5242247B2 (en) * | 2008-06-05 | 2013-07-24 | 東洋ゴム工業株式会社 | Rubber composition for covering steel cord and pneumatic tire |
| JP5524522B2 (en) | 2008-08-19 | 2014-06-18 | 株式会社ブリヂストン | Rubber composition |
| JP5632592B2 (en) * | 2008-08-19 | 2014-11-26 | 株式会社ブリヂストン | Rubber composition |
| JP5270395B2 (en) * | 2009-02-12 | 2013-08-21 | 東洋ゴム工業株式会社 | Rubber composition for covering steel cord and pneumatic tire |
| JP5312978B2 (en) * | 2009-02-23 | 2013-10-09 | 東洋ゴム工業株式会社 | Rubber composition for covering steel cord and pneumatic tire |
| JP5420300B2 (en) * | 2009-04-13 | 2014-02-19 | 株式会社ブリヂストン | Rubber composition and pneumatic tire using the same |
| JP5362429B2 (en) * | 2009-04-24 | 2013-12-11 | 東洋ゴム工業株式会社 | Rubber composition for covering steel cord and pneumatic tire |
| JP2011006039A (en) * | 2009-05-29 | 2011-01-13 | Bridgestone Corp | Pneumatic tire |
| JP5383351B2 (en) * | 2009-06-02 | 2014-01-08 | 株式会社ブリヂストン | Pneumatic tire |
| JP2011006590A (en) * | 2009-06-26 | 2011-01-13 | Bridgestone Corp | Rubber crawler |
| JP5579179B2 (en) * | 2009-07-01 | 2014-08-27 | 株式会社ブリヂストン | Rubber-steel cord composite |
| JP2011012164A (en) * | 2009-07-01 | 2011-01-20 | Bridgestone Corp | Pneumatic tire |
| JP4811506B2 (en) * | 2009-08-03 | 2011-11-09 | 横浜ゴム株式会社 | Rubber composition for coating steel wire |
| DE102011007010B4 (en) * | 2010-04-23 | 2017-04-06 | The Yokohama Rubber Co., Ltd. | Rubber-metal composite, vulcanized product thereof and its use in a pneumatic tire |
| JP5377454B2 (en) * | 2010-10-21 | 2013-12-25 | 住友ゴム工業株式会社 | Rubber composition for band topping, rubber composition for breaker edge strip, and pneumatic tire |
| JP5395113B2 (en) * | 2011-05-13 | 2014-01-22 | 住友ゴム工業株式会社 | Rubber composition for breaker topping and pneumatic tire |
| JP5249449B2 (en) * | 2011-08-26 | 2013-07-31 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire |
| JP5406964B2 (en) * | 2011-11-08 | 2014-02-05 | 住友ゴム工業株式会社 | Rubber composition for tire cord covering, breaker edge strip, breaker cushion or cord adjacent strip, and pneumatic tire |
| FR2996230B1 (en) * | 2012-09-28 | 2014-10-31 | Michelin & Cie | IN SITU GUM CABLE COMPRISING A COMPOSITION COMPRISING AN ORGANIC POLYSULFIDE. |
| FR3000748B1 (en) * | 2013-01-08 | 2015-03-13 | Michelin & Cie | SEMI-FINISHED PNEUMATIC PRODUCT COMPRISING A COMPOSITION COMPRISING A CORROSION INHIBITOR |
| CN111205522A (en) * | 2020-02-23 | 2020-05-29 | 湖北玲珑轮胎有限公司 | Rubber coating composition for steel wire carcass cords of all-steel radial tires |
| JP7567291B2 (en) * | 2020-08-28 | 2024-10-16 | 住友ゴム工業株式会社 | Rubber composition for fiber coating and tire |
-
2008
- 2008-03-17 JP JP2008067292A patent/JP4431618B2/en active Active
- 2008-05-30 CN CN2008101098482A patent/CN101314652B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
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| Nicolaas Maria Huntink.DURABILITY OF RUBBER PRODUCTS.《DURABILITY OF RUBBER PRODUCTS》.Twente University Press,2003,第159页最后1段到第169页第2段. * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009007549A (en) | 2009-01-15 |
| JP4431618B2 (en) | 2010-03-17 |
| CN101314652A (en) | 2008-12-03 |
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