CN101423628B - Rubber composition containing cyclic polysulfide as vulcanizer - Google Patents
Rubber composition containing cyclic polysulfide as vulcanizer Download PDFInfo
- Publication number
- CN101423628B CN101423628B CN2008102135563A CN200810213556A CN101423628B CN 101423628 B CN101423628 B CN 101423628B CN 2008102135563 A CN2008102135563 A CN 2008102135563A CN 200810213556 A CN200810213556 A CN 200810213556A CN 101423628 B CN101423628 B CN 101423628B
- Authority
- CN
- China
- Prior art keywords
- rubber
- formula
- cyclic polysulfide
- polysulfide
- sulphur
- 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.)
- Expired - Fee Related
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 324
- 239000005060 rubber Substances 0.000 title claims abstract description 300
- 229920001021 polysulfide Polymers 0.000 title claims abstract description 157
- 239000005077 polysulfide Substances 0.000 title claims abstract description 150
- 150000008117 polysulfides Polymers 0.000 title claims abstract description 150
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 138
- 239000000203 mixture Substances 0.000 title abstract description 67
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 78
- 239000005864 Sulphur Substances 0.000 claims description 72
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
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- 238000006243 chemical reaction Methods 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
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- 239000000806 elastomer Substances 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- 229960001866 silicon dioxide Drugs 0.000 claims description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims description 22
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
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- VTEKOFXDMRILGB-UHFFFAOYSA-N bis(2-ethylhexyl)carbamothioylsulfanyl n,n-bis(2-ethylhexyl)carbamodithioate Chemical compound CCCCC(CC)CN(CC(CC)CCCC)C(=S)SSC(=S)N(CC(CC)CCCC)CC(CC)CCCC VTEKOFXDMRILGB-UHFFFAOYSA-N 0.000 description 4
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- 229920000877 Melamine resin Polymers 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- XHZJVGWVDZZFII-UHFFFAOYSA-N OC(O)(O)CCC(=O)OC(=O)C=CC Chemical compound OC(O)(O)CCC(=O)OC(=O)C=CC XHZJVGWVDZZFII-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- WEZJBAOYGIDDLB-UHFFFAOYSA-N cobalt(3+);borate Chemical compound [Co+3].[O-]B([O-])[O-] WEZJBAOYGIDDLB-UHFFFAOYSA-N 0.000 description 1
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- ZLCCLBKPLLUIJC-UHFFFAOYSA-L disodium tetrasulfane-1,4-diide Chemical compound [Na+].[Na+].[S-]SS[S-] ZLCCLBKPLLUIJC-UHFFFAOYSA-L 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920001821 foam rubber Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 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 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A rubber composition containing 100 parts by weight a sulfur-vulcanizable rubber (A) and 0.1 to 30 parts by weight of a vulcanization agent of a cyclic polysulfide (B) having the formula (I): wherein R is a substituted or uhsubstituted C2 to C20 alkylene group, substituted or unsubstituted C2 to C20 oxyalkylene group or alkylene group having an aromatic ring, n is an integer of 1 to 20, x is a number of 2 to 6 on average.
Description
The application be submitted on October 13rd, 2004, application number is 200480007072.3, denomination of invention is divided an application for the Chinese invention patent application of " containing cyclic polysulfide as the rubber combination of vulcanizing agent and by the pneumatic tyre of its preparation ".
Technical field
The present invention relates to a kind of rubber combination and reach pneumatic tyre by its preparation; But said compsn contain cyclic polysulfide as vulcanizing agent and have the sulphur vulcanized rubber multiple improvement curability (for example; Combine other specific components in some cases, resistance to heat aging, heat generation, fracture characteristics, resistance to fatigue, wet and slippery property, adhesion property, ice and snow road braking quality, high speed weather resistance, rolling resistance, lateral stability, high firmness, HS, high elongation rate etc.).
Background technology
Because the cross-linked rubber that obtains through sulfur cross-linking comprises polysulfidic bond, so its thermotolerance and overcure-reversion are poor.In order to improve the problem of thermotolerance and overcure-reversion; Known vulcanizing agent for example tetrasulfide polymkeric substance or cyclic polysulfide is effective (Sho Yamazaki; Deng: The Society ofRubber industry, Japan, 1981Research Presentation Conference Abstract; P.532-17, and open (Kokai) No.10-120788 of japanese unexamined patent publication No.).Especially; Cyclic polysulfide is preferred with regard to cross-linking efficiency; But there are some problems in the method for preparing cyclic polysulfide of report so far; As prepare process long, use expensive material etc., but thereby shortage practicality (being open (Kokai) No.58-122944 of japanese patent and japanese unexamined patent publication No. (Kokai) No.2002-293783).
In recent years, pneumatic tyre improves in many aspects.In these improved, in order to improve the resistant to thermal aging performance, japanese unexamined patent publication No. open (Kokai) No.6-57040 had proposed the crosslinked method (promptly sneaking into a large amount of vulcanization accelerators to reduce the ratio of polysulfidic bond) of EV, but it has the relatively poor problem of dynamic resistance to fatigue.Therefore in open (Kokai) No.2002-293783 of japanese unexamined patent publication No., disclose a kind of method that solves this balance between resistance to heat aging and the dynamic resistance to fatigue, but situation can not be satisfied the demand still.
In addition, the tire tread glue of using as pneumatic tyre owing to improve wear resistance or adhesion property is essential, has found the rubber combination with high tensile or elongation at break.On the other hand, tire tread glue is degraded easily.Be accompanied by agingly, sclerosis and loss of adhesion takes place in tyre surface.Moreover, under some situation, even danger such as separation of tread are arranged.For improving the sticking power persistence of high-performance tire; For example making of vulcanizing agent or vulcanization accelerator has been used as research; But particularly in having the rubber combination of mass filler, can not satisfy sticking power and its persistence (referring to open (Kokai) No.2001-348461 of japanese unexamined patent publication No. and open (Kokai) No.10-151906 of japanese unexamined patent publication No.) simultaneously with gratifying level.
For impact plies rubber,, the rubber combination of high tensile and elongation at break is provided in searching in order to improve the high speed weather resistance.On the other hand, the high firmness impact plies rubber and the low tan δ impact plies rubber that is used to improve fuel efficiency of control stability also have been used to improve in searching.These physical propertiess are in the balance state.Consider the rubber combination that high firmness, HS and elongation is provided and can caused tan δ to raise in searching from this angle.
In addition; In in recent years to airtyred multiple improvement; For bead filler rubber,, the rubber combination (for example referring to open (Kokai) No.2002-105249 of japanese unexamined patent publication No.) of high tensile and elongation at break is provided in searching in order to improve resistance to fatigue.On the other hand, the high firmness impact plies rubber and the low tan δ impact plies rubber that is used to improve fuel efficiency (for example referring to open (Kokai) No.5-51487 of japanese unexamined patent publication No.) of control stability also have been used to improve in searching.These physical propertiess are in the balance state.Consider the rubber combination that high firmness, HS and elongation is provided and can caused tan δ to raise in searching from this angle.
Existence is to the airtyred demand of drivable in emergency circumstances, and this tire can make it even be used for being pierced during automobile etc., going under the situation such as burning certain distance and reduce internal pressure rapidly, i.e. run flat tire.For satisfying this demand, multiple suggestion has been proposed.As a kind of suggestion, for example open (Kokai) No.10-297226 of japanese unexamined patent publication No. and open (Tokuhyo) No.2001-519279 of japanese national disclose the upholder (center ring) and use its to support the pneumatic tyre that pierces through or alternate manner damages so that can run flat operation of running flat have been installed on the wheel rim of airtyred cavity.The rubber that is used for the side enhancement layer of this run flat tire requires to have low heating property and high firmness characteristic, and has sneaked into a large amount of polybutadiene rubbers (BR) thus or used the high crosslink density prescription.Yet; Said sidewall Reinforced Rubber requires to have strong thermotolerance and resistance to fatigue characteristic, therefore if attempt crosslinked thermotolerance (just sneaking into vulcanization accelerator that its amount Duos than the sulphur ratio with raising monosulfidic bond and disulfide linkage), then the bending fatigue strength meeting variation of improving through EV; And conversely; If use conventional crosslinked (that is to say that the amount that improves sulphur surpasses said promotor and the ratio that improves polysulfide), then can improve bending fatigue strength; But thermotolerance or aging resistance meeting variation that is to say that this is a self-contradictory problem.
In addition, the prescription of sidewall Reinforced Rubber comprises a large amount of polybutadiene rubbers, even therefore new product (before aging) also only has low elongation at break, thereby (aging back) its persistence that runs flat is limited behind the life-time service.In addition, because run flat tire has thick side members, therefore when sulfuration, the heat conduction of inside tires is difficult.When high temperature vulcanized, will produce huge difference near surface and internal physical character, and when cryogenic vulcanization, have the problem of producing rate variance.
The center ring 1 that runs flat as shown in Figure 1 is placed in the inner chamber 3 of pneumatic tyre 2, and it is made up of endless metal shell 4 and resilient ring 5 and is supported on the wheel rim 6.The resilient ring of the said center ring that runs flat need have low heat generation and high firmness; If but hardness increases (cross-linking density increase) and keeps low heat generation simultaneously; Then elongation at break can diminish, thereby can be restricted in the persistence of the operating period that runs flat.In addition, the resilient ring of center ring 1 contacts with said wheel rim all the time, and the heat that produces because of braking during normal running is sent to said wheel rim, thereby wheel rim is exposed under the quite high temperature for a long time.If therefore the resistance to heat aging of rubber is poor, then can exist in the problem that can not embody estimated performance under the state of running flat.
In addition; Airtyred air retaining wall often uses butyl type rubber; Like butyl rubber or halogenated butyl rubber (as referring to open (Kokai) No.10-87884 of japanese unexamined patent publication No.); But the poor performance of reinforcement such as butyl rubber carbon black, so the mechanical property of the compsn of butyl rubber is relatively poor and in application, be restricted.
In addition, require airtyred belt mixture that high rigidity is provided, if but attempt to improve rigidity through the sulfur consumption that increases carbon black loading or increase as vulcanizing agent or vulcanization accelerator, then elongation can descend and resistance to fatigue can reduce.The result can take place to separate and in tire, have problems at the end of said belt, thereby guarantees that high rigidity and elongation are necessary (japanese unexamined patent publication No. open (KoKai) No.2001-226528).In addition,, proposed to sneak into a large amount of sulphur (japanese unexamined patent publication No. open (Kokai) No.2000-233603), but this can cause resistance to heat aging to descend in order to obtain strong keying action.In order to improve resistance to heat aging, can increase inhibitor, but this can cause being easy to the keying action of infringement and wire (metal).
Detailed Description Of The Invention
So the objective of the invention is to solve the various problems that exists in the conventional pneumatic industry, and provide the rubber combination of multiple improvement physical properties to reach pneumatic tyre by its preparation with vulcanized rubber through the sulfur vulcanizing agent effect of using cyclic polysulfide to replace at least partly using always.
According to the present invention, but a kind of sulphur vulcanized rubber (A) that contains 100 weight parts is provided and as the rubber combination of formula (I) cyclic polysulfide (B) of 0.1～30 weight part of vulcanizing agent:
Wherein R is for replacing or unsubstituted C
2-C
20Alkylidene group, replacement or unsubstituted C
2-C
20Alkylidene oxide or have the alkylidene group of aromatic ring, n is 1～20 integer, x is average 2～6 number.
The accompanying drawing summary
Will be with reference to description of drawings the present invention, wherein Fig. 1 is the cross-sectional view along warp-wise, it has shown the major portion of an embodiment of tire center ring of the present invention.In Fig. 1, label 1 is the center ring that runs flat; 2 is pneumatic tyre; 3 is cavity; 4 is the endless metal shell; 5 is resilient ring; 6 is wheel rim.
Optimum implementation of the present invention
In specification sheets of the present invention and Rights attached thereto claim, used singulative is to be understood that to comprising plural form, is not like this only if from context, obviously can confirm.
In the present invention, as the vulcanizing agent in the said rubber combination, part sulphur (whole in some cases) commonly used replaces with the cyclic polysulfide that (B) has formula (I) at least.Said cyclic polysulfide can be by for example following manner preparation.Just, said dihalide and the alkali metals polysulfide M-S of cyclic polysulfide through having formula X-R-X with formula (I)
xAs the two-phase system reaction and reaction makes, X representes fluorine, chlorine, bromine or iodine respectively to-M in X-R-X, preferably representes the chlorine or bromine halogen atom in the non-conforming mixed solvent of hydrophilic solvent or hydrophilic and lipophilic solvent, and R representes to replace or unsubstituted C
2-C
20Alkylidene group, replacement or unsubstituted C
2-C
20Alkylidene oxide or contain the alkylidene group of aromatic ring, preferred expression replaces or unsubstituted C
2-C
18Alkylidene group is more preferably represented C
4-C
10Alkylidene group can be mentioned phenyl, benzyl, vinyl, silyl, epoxy group(ing), NCO etc. as these substituting groups; At M-S
xAmong-the M, M is a basic metal, for example sodium, potassium, lithium etc., and x is 2～6 integer, is preferably 3～5 integer, perhaps through at M-S
x-M solution (can make water or C as solvent
1-C
4Fatty alcohol most preferably makes water) in so that M-S
x-M and X-R-X add X-R-X and make (referring to open (Kokai) No.2002-293783 of japanese unexamined patent publication No.) in its speed of reacting at the interface.It should be noted that the concentration of X-R-X can become bigger so if the interpolation speed of X-R-X is too fast in one method of back, the place of reaction beyond also can be at said interface takes place, and intermolecular reaction preferentially forms linear chain, and this is not preferred.Therefore, in order to obtain cyclic polysulfide, make M-S
x-M and X-R-X are preferred in said reacting at the interface in nonhomogeneous system as far as possible just.
Radicals R as in said general formula X-R-X and the formula (I) can be mentioned for example line style or sub-branched alkyl, like ethylidene, propylidene, butylidene, pentylidene, hexylidene, octylene, nonamethylene, inferior decyl, propylene.Said alkylidene group also can be used such as phenyl, benzyl substituting group and replace.In addition,, can use the alkylidene group that comprises alkylidene oxide, for example freely be connected with group (CH on it as radicals R
2CH
2O) p and (CH
2) alkylidene group that comprises alkylidene oxide of q, wherein p is 1～5 integer, q is 0～2 integer.Preferred R group comprises CH
2CH
2OCH
2CH
2-, (CH
2CH
2O)
2CH
2CH
2-, (CH
2CH
2O)
3CH-CH
2-, (CH
2CH
2O)
4CH
2CH
2-, (CH
2CH
2O)
5CH
2CH
2-, (CH
2CH
2O)
2CH
2-,-CH
2CH
2OCH
2OCH
2CH
2-, wherein x is preferably MV especially, and more preferably 3～5,3.5～4.5.N is preferably 1～15 integer, more preferably 1～10 integer, more preferably 1～5 integer.
Reaction between said dihalide and the alkali metals polysulfide is an equivalent reaction.In the practice, said two kinds of compounds are preferably 50～120 ℃, more preferably 70～100 ℃ of reactions down with 0.95:1.0～1.0:0.95 (equivalence ratio) in temperature.
Non-conforming mixed solvent to being used for hydrophilic solvent of the present invention or hydrophilic solvent has no particular limits.In the reaction system of reality, can use hydrophilic solvent separately or use the mixed solvent system that forms any non-conforming of biphase.Particularly, for example as hydrophilic solvent, except water, also can mention methyl alcohol, ethanol, terepthaloyl moietie, glycol ether or other alcohol.They can use with any form of mixtures.In addition, as mix the lipophilic solvent that uses with said hydrophilic solvent, can mention toluene, YLENE, benzene and other aromatic hydrocarbons, pentane, hexane and other aliphatic hydrocrbon 、 diox, dibutyl ether or other ethers, ETHYLE ACETATE or other ester class etc.They can use with any form of mixtures.
In hydrophilic solvent or in dihalide described in the mixed solvent system of non-conforming and alkali metals polysulfide is equivalent reaction at the interface reaction.In the practice, said two kinds of compounds react with 0.95:1～1:0.95 (equivalence ratio).Temperature of reaction is preferably 50～120 ℃, more preferably 70～100 ℃.The dihalide of question response preferably is made up of two kinds or more kinds of dihalide.Therefore, as dihalide, for example the mixture of Dichloroethyl formal and ethylene dichloride is preferred, and as metallic sulfide, for example sodium polysulphide is preferred.
In above-mentioned reaction, do not need catalyzer, but under some situation, can use quaternary ammonium salt 、 phosphonium salt, crown ether etc. as catalyzer.For example can use (CH
3)
4N
+Cl
-, (CH
3)
4N
+BR
-, (C
4H
9)
4N
+Cl
-, (C
4H
9)
4N
+BR
-, C
12H
25N
+(CH
3)
3BR
-, (C
4H
9)
4P
+BR
-, CH
3P
+(C
6H
5)
3I
-, C
16H
33P
+(C
4H
9)
3BR
-, 15-crown ether-5, hexaoxacyclooctadecane-6-6, phendioxin 8-crown ether-6 etc.Especially, when preparing the cyclic polysulfide (B) of alkylidene group skeleton, preferably use catalyzer.
The cyclic polysulfide (B) that the present invention uses is with 0.1～20 weight part, preferably sneak in the diene rubber of 100 weight parts with 0.5～20 weight part.If mixed volume very little, its effect as vulcanizing agent can not show so, and the intensity of vulcanized rubber can reduce etc.; Therefore this is not preferred, if opposite mixed volume is too much, state of vulcanization increases too many so; Viscosity degradation is too much, thereby this is not preferred.
As in the present invention as composition (A) but the sulphur vulcanized rubber; Can mention any rubber that is generally used for tire or other purposes over; Diene rubber for example is like dissimilar tree elastomer (NR), dissimilar polyisoprene rubber (IR), dissimilar polybutadiene rubber (BR), dissimilar styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene copolymer rubber, X 050 (CR) and their partially hydrogenated thing perhaps (halogenation) butyl rubber (IIR), ethylene-propylene-diene copolymer rubber (EPDM), acrylic elastomer (ACM) etc.They can use separately or use with the form of any mixture.
In first aspect of the present invention; Resistance to heat aging and the outstanding rubber combination of heat generation for the development vulcanized rubber; A kind of rubber combination is provided; But it comprises 100 weight parts as the tree elastomer of said sulphur vulcanized rubber and/or polyisoprene rubber and 1～30 weight part cyclic polysulfide as the formula (I) of vulcanizing agent, and wherein R is-(CH
2)
m-, m is 2～20 integer, and n is 1～15 integer, and preferred 1～10 integer, more preferably 1～5 integer, x are on average greater than 4 to 6 number.
In first aspect of the present invention, shown in the following embodiment, a kind of resistance to heat aging and outstanding rubber combination of heat generation that uses tree elastomer and/or TR 301 is provided as in addition.
As explained above, cyclic polysulfide is for example through having formula X-(CH
2)
nThe dihalide of-X and alkali metals polysulfide M-S
xAs the two-phase system reaction and reaction makes, wherein X representes fluorine, chlorine, bromine or iodine respectively to-M, is preferably the chlorine or bromine halogen atom in the non-conforming mixed solvent of hydrophilic solvent or hydrophilic and lipophilic solvent; N is 2～20, and is preferred 4～12, and M is the element of periodic table of elements IA family; For example sodium, potassium, lithium or other basic metal; X is on average greater than 4 to 6 number, and preferred average about number of 4.5 to 5.5 is perhaps through at M-S
x-M solution (can make water or C as solvent
1-C
4Fatty alcohol most preferably makes water) in so that the speed of reacting at the interface at solvent adds X-(CH
2)
n-X reacts and makes.It should be noted that in one method of back, if X-is (CH
2)
nThe interpolation speed of-X is too fast, then X-(CH
2)
nThe concentration of-X increases, and the place of reaction beyond also can be at said interface takes place, and intermolecular reaction preferentially forms linear chain, so this is not preferred.Therefore, in order to obtain cyclic polysulfide, make M-S
x-M and X-(CH
2)
nIt is preferred that-X reacts in solvent in nonhomogeneous system as far as possible just at the interface.
In a preferred embodiment of the invention; Through in the non-conforming mixed solvent of hydrophilic solvent or hydrophilic solvent and lipophilic solvent, under 50～150 ℃, preferred 50～120 ℃, reacting the cyclic polysulfide that obtains formula (I) at the metal polysulfide that exists or do not exist the dihalide that makes at least two types of formulas (II) under the phase-transfer catalyst with formula (III)
X-(CH
2)
n-X (II)
M-S
x-M (III)
Wherein n R representes to replace or unsubstituted C independently in formula (I)
2-C
20Alkylidene group, replacement or unsubstituted C
2-C
20Alkylidene oxide, or contain the alkylidene group of aromatic ring, x is preferably 3～5 MV, and n is preferably 1～15, and more preferably 1～10; X representes halogen atom in formula (II), and n is 2～20 integer, and this dihalide for example is Dichloroethyl formal or ethylene dichloride; In formula (III), M is the metal of periodic table of elements IA family, and x is on average greater than 3 to 6 number (for example sodium polysulphide).With the contrast of using one type of dihalide, this cyclic polysulfide provides LV, the high vulcanizing agent that vulcanizes efficient.
Among the present invention, above-mentioned reaction is preferably carried out under 50～150 ℃, preferred 50～120 ℃ in the presence of suitable phase-transfer catalyst.As the instance of phase-transfer catalyst, can use quaternary ammonium salt 、 phosphonium salt, crown ether, aliphatic acid metal-salt etc.For example can mention (CH
3)
4N
+Cl
-, (CH
3)
4N
+BR
-, (C
4H
9)
4N
+Cl
-, (C
4H
9)
4N
+BR
-, C
12H
25N
+(CH
3)
3BR
-, (C
4H
9)
4P
+BR
-, CH
3P
+(C
6H
5)
3I
-, C
16H
33P
+(C
4H
9)
3BR
-, 15-crown ether-5, hexaoxacyclooctadecane-6-6, phendioxin 8-crown ether-6 or RCOO
-Na
+, RSO
3 -Na
+, (RO)
2PO
2 -Na
+Deng, wherein R representes alkyl.
Rubber combination in the first aspect present invention contains 100 parts by weight of natural rubber and/or TR 301, wherein sneaks into formula (I) cyclic polysulfide (B) of 0.5～30 weight part, preferred 0.5～10 weight part.Vulcanizer of the present invention can use with vulcanizing agent sulphur for example commonly used.If the amount of cyclic polysulfide (B) very little, then can not obtain sufficient cure efficiency, and sulfuration reduces as the intensity of glue, so this is not preferred, if its amount is too big, then vulcanize as the glue hardening, so this is not preferred conversely.
Except above-mentioned neccessary composition; The rubber combination of first aspect present invention can also contain and is mixed for polytype additive that tire applications or other conventional rubber are used usually, for example filler such as carbon black or silicon-dioxide, vulcanization accelerator, dissimilar oil, inhibitor, plasticized agent.These additives can be mixed be generally used for vulcanizing or crosslinked compsn obtaining with sulfuration.The amount of these additives can be the general quantity of using in the past, only otherwise can have a negative impact to the object of the invention.
In second aspect of the present invention; For improving fracture property and providing resistance to fatigue the outstanding and further improved rubber combination of ageing-resistant performance; The pneumatic tyre that a kind of rubber combination is provided and has used this rubber combination; But said rubber combination contains formula (I) cyclic polysulfide (B) and its amount of sulphur vulcanized rubber (A), 0.5～5 weight part of 100 weight parts makes that the weight ratio of (C)/(B) is 1 or bigger vulcanization accelerator (C); Wherein be average 2～6 number at formula (I) x, n is 1～15, preferred 1～10, more preferably 1～5 integer, and R is for replacing or unsubstituted C
2-C
20Alkylidene group, replacement or unsubstituted C
2-C
20Alkylidene oxide perhaps contains the alkylidene group of aromatic ring.
Rubber combination according to second aspect present invention uses said cyclic polysulfide as vulcanizing agent; Therefore can before aging with after wearing out, all obtain high fracture property; Even when high temperature vulcanized, also can show high fracture property and further improve viscoelastic property.
The cyclic polysulfide (B) that can be used for formula of the present invention (I) through method for preparing.
Based on the rubber of 100 weight parts, rubber combination of the present invention contains 0.5～5, the cyclic polysulfide (B) of preferred 0.8～3 weight part.If its amount is very little, then can not obtain required effect, if its amount is too big, then occur scorching and cost easily and can improve yet, so this not preferred conversely.
Rubber combination of the present invention contains the vulcanization accelerator as component (C), and its amount makes that it is 1 and bigger that the weight ratio (C)/(B) with component (B) is provided, and is preferably 1～5.If its amount is very little, then can not obtain required effect, if its amount is too big, then can not carry out tight cure conversely, rubber performance is impaired, so this is not preferred.
As the vulcanization accelerator component (C) of sneaking in the rubber combination of the present invention; Can use over any compound that in rubber industry, is used as vulcanization accelerator, but preferably based on sulphenamide, based on thiuram, based on benzothiazole, based on dithiocarbamate, based on the vulcanization accelerator of guanidine.
Rubber combination of the present invention can use any sulphur that is used as vulcanizing agent in the past usually with cyclic polysulfide (B).When using sulphur (D) with component (B), preferably its consumption makes that (D)/(B) (weight ratio) is 5 and littler, is preferably 2 or littler.If this ratio is too big, then often be difficult to obtain effect required for the present invention, so this not preferred.
Can rubber combination moulding of the present invention be used for pneumatic tyre crown, belt, bead filler rubber, sidewall, undertread, body piles, tyre bead pad, covering with paint through the method for routine; Perhaps except pneumatic tyre; As polytype other application products, like rubber hose, pipe peculiar to vessel, baffle plate, crawler belt, travelling belt.
In the third aspect of the invention; In order to eliminate prior art problems and to provide the rubber combination with property to reach the pneumatic tyre by its preparation, said rubber combination has HS and elongation, can keep performance for a long time and is used as airtyred tread portion.According to first mode; A kind of tread rubber composition is provided; But it contains the sulphur vulcanized rubber of mainly being made up of aromatic vinyl-diene copolymers rubber of 100 weight parts and the cyclic polysulfide with formula (I) of 0.1～10 weight part; Wherein be average 2～6 number at formula (I) x, n is 1～20 integer, and R is for replacing or unsubstituted C
2-C
20Alkylidene group, replacement or unsubstituted C
2-C
20Alkylidene oxide or have the alkylidene group of aromatic ring.
In addition; According to second mode, a kind of tread rubber composition is provided, it contains the diene rubber composition of 100 weight parts, carbon black that total amount is 100～200 weight parts and/or silicon-dioxide, total amount is the cyclic polysulfide and the sulphur with formula (I) of 0.5～5 weight part; And the ratio of the gross weight of the weight of cyclic polysulfide and cyclic polysulfide and sulphur is 0.1～2 (weight ratio); X is average 2～6 number in formula (I), and n is 1～20 integer, and R is for replacing or unsubstituted C
2-C
20Alkylidene group, replacement or unsubstituted C
2-C
20Alkylidene oxide or contain the alkylidene group of aromatic ring.
In addition; According to Third Way; A kind of tread rubber composition that is suitable for ice and snow road is provided; But its weight-average molecular weight that converts PS into of the cyclic polysulfide with formula (I) and 10～100 weight parts that contains the sulphur vulcanized rubber of mainly being made up of tree elastomer and/or polybutadiene rubber, 0.1～10 weight part of 100 weight parts is 100,000 or littler tenderizer, and wherein x is average 2～6 number in formula (I); N is 1～20 integer, and R is for replacing or unsubstituted C2-C20 alkylidene group, replacement or unsubstituted C
2-C
20Alkylidene oxide or contain the alkylidene group of aromatic ring.
In addition; According to cubic formula; A kind of pneumatic tyre is provided; Its tyre surface has by forms two-layer of the crown that contacts with the road surface and its inner base portion or multiwalled structure more, and this pneumatic tyre uses and contains the base portion of the rubber combination of following composition as tyre surface: but the cyclic polysulfide composition with formula (I) of the silicon-dioxide of the sulphur vulcanized rubber of 100 weight parts, 30～100 weight parts and/or carbon black and 0.1～10 weight part, and x is average 2～6 number in formula (I); N is 1～20 integer, and R is for replacing or unsubstituted C
2-C
20Alkylidene group, replacement or unsubstituted C
2-C
20Alkylidene oxide or contain the alkylidene group of aromatic ring.
Each rubber combination in the third aspect of the invention all uses said cyclic polysulfide as vulcanizing agent, thereby can improve adhesion property, breaking tenacity, adheres to persistence, weather resistance and control stability.
The cyclic polysulfide with formula (I) of sneaking in the rubber combination of first to fourth mode of third aspect present invention can pass through method for preparing.
Based on the rubber (A) of 100 weight parts, the rubber combination of third aspect present invention contains the cyclic polysulfide (B) of 0.1～10 weight part, preferred 0.2～8 weight part.If it is measured very little, then can not get a desired effect, if opposite its amount is too many, then be prone to generation scorching and cost and can raise yet, thereby this not preferred.But; In second mode of the present invention; Its mixed volume makes the total amount of said cyclic polysulfide and sulphur become 0.5～5 weight part, preferred 0.6～4.8 weight part, and makes the ratio of total amount of amount and cyclic polysulfide and sulphur of cyclic polysulfide become 0.1～2 (weight ratio), preferred 0.2～1.9 (weight ratio).
As the copolymer rubber that is used for first mode, can use for example dissimilar styrene-butadiene copolymer rubber (SBR), styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber etc. based on aromatic vinyl-diene.Preferred use second-order transition temperature (Tg) is-40 ℃～0 ℃ a rubber.Preferably will be based on the multipolymer of aromatic vinyl-diene with 40～100wt%, more preferably the amount of 45～100wt% is sneaked in the said rubber combination.Can mention for example tree elastomer (NR), polyisoprene rubber (IR), polybutadiene rubber (BR), acrylonitrile butadiene copolymer rubber (NBR), butyl rubber, halogenated butyl rubber etc. as other rubber components.
The rubber combination of first mode can also contain silicon-dioxide and/or the carbon black (based on the rubber components of 100 weight parts, their total amount is preferably 55 weight parts extremely less than 100 weight parts, more preferably 60 to 98 weight parts) that is used for rubber combination in the past.As carbon black, nitrogen specific surface area (N
2SA measures according to ASTM D3037) be preferably 80m
2/ g is extremely less than 150m
2/ g, more preferably 82 to 148m
2/ g.
In second mode; As the diene rubber that is comprised; With cyclic polysulfide; Can use copolymer rubber (SBR), styrene-isoprene copolymer rubber and the acrylonitrile butadiene copolymer rubber of any diene rubber, particularly tree elastomer (NR) that is used for rubber composition for tyre, multiple polyisoprene rubber (IR), dissimilar polybutadiene rubber (BR), dissimilar styrene-based-divinyl over.They can use separately or use with the form of any mixture.Wherein, preferably use SBR with the 70wt% or the more amount of rubber components.
In second mode, can further contain any carbon black and/or the silicon-dioxide that are used for tire in the past, based on the diene rubber component of 100 weight parts, their total amount is preferably 100～200 weight parts, more preferably 102～190 weight parts.If the amount of said filler very little, then adhesion property is not enough, if opposite its amount is too many, then miscibility and operability reduce, thereby this is not preferred.Should be noted in the discussion above that and consider high adhesion property,, have N as carbon black
2SA is 150～300m
2Those of/g are preferred.
As stated in second mode; A kind of tread rubber composition that contains the cyclic polysulfide of formula (I) is provided, and the amount of said cyclic polysulfide makes that the total amount of cyclic polysulfide and sulphur is 0.5～5 weight part, the ratio of total amount that is preferably amount and the cyclic polysulfide and the sulphur of 0.6～4.8 weight part and cyclic polysulfide is 0.1～2 (weight ratio), is preferably 0.2～1.9 (weight ratio).If the total amount of cyclic polysulfide and sulphur is very little, then adhere to persistence and reduce, if opposite too many, adhesion property is bad, thereby this is not preferred.In addition, if the amount of cyclic polysulfide very little, the improvement degree of then adhering to persistence diminishes, thereby this is not preferred.
In second mode, through sneaking into based on preferred 0.2～5 weight part of 100 parts by weight of rubber components, the more preferably promotor based on thiuram with formula (IV) of 0.3～4.8 weight part, resistance to fatigue and resistance to heat aging are further enhanced in addition,
R wherein
1-R
4Represent C respectively
1-C
10Alkyl or C
1-C
20Alkyl with aromatic ring, y are 1～4 integer.Based on the promotor of thiuram, can mention for example tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, single sulfuration tetra methylthiuram, curing four (2-ethylhexyl) thiuram, tetra-benzyl thiram disulfide as preferably.
In Third Way; A kind of tread rubber composition that is suitable for ice and snow road is provided; It comprises with said cyclic polysulfide mainly by tree elastomer (NR) and/or polybutadiene rubber (BR) but the tenderizer of sulphur vulcanized rubber of forming and 10～100 weight parts, preferred 12～90 weight parts; The weight-average molecular weight that said tenderizer converts PS into is 100,000 or littler, is preferably 5000～90000.
As tire tread rubber,, show the rubber combination of high tensile and elongation at break in searching in order to improve wear resistance or to improve sticking power always.In addition, the quality of tread-rubber descends easily and tyre surface As time goes on can hardening.For snow tyre, because the influence of tyre surface, the ice and snow performance can reduce greatly.Consider from this point; The rubber combination that need have HS and elongation and can keep said performance for a long time; But according to the present invention, in order to realize the enough sticking power of snowfield with tyre surface, preferred said rubber mainly by tree elastomer (NR) form with and Tg be-100 ℃ to-50 ℃.In addition, preferably sneaking into based on the rubber mass of 100 weight parts is the carbon black and/or the silicon-dioxide of 40～100 weight parts.Especially, said carbon black N preferably
2SA is 80m
2/ g is extremely less than 150m
2Those of/g.According to the present invention, based on the rubber of 100 weight parts, the thermoplastic resin or the expansible black lead of the heat-swellable through sneaking into 1～15 weight part, the ice and snow performance preferably improves.
The thermoplastic resin of heat-swellable is for through adding the thermoplastic resin of heat-swellable that thermal expansion forms the inflation thermoplastic resin, and based on the diene rubber of 100 weight parts, and its consumption is 1～15 weight part, be preferably 2～10 weight parts.If its consumption is lower than 1 weight part, then can not obtain the ice and snow performance of needs, if its consumption is more than 15 weight parts on the contrary, then the wear resistance of this rubber combination obviously reduces, thereby this is not preferred.
The particle size of thermoplastic resin before expansion to said heat-swellable do not have special qualification, but before expansion, is preferably 5～300 μ m, and more preferably particle size is those of 10～200 μ m.
Said thermal expansion resin is made up of the thermoplastic resin particle of heat-swellable; Said particle contains the liquid that when heating, can evaporate and produce gas in thermoplastic resin; That is to say the expanded thermoplastic resin particle that the shell that is made up of thermoplastic resin is formed, wherein be filled with gas, under expansion start temperature or higher temperature; Normally temperature is 130～190 ℃, and heating makes said grain expansion.
Thermoplastic resin as above-mentioned heat-swellable; For example; " Expancel091DU-80 " that uses always, " Expancel 092DU-120 " etc. can buy from Sweden ' s Expancel Co., and " Matsumoto Microsphere F-85 ", " Matsumoto Microsphere F-100 " etc. can buy from Matsumoto Yushi K.K.
As the thermoplastic resin of the outer shell component that forms the inflation thermoplastic resin particle, preferably using the expansion start temperature is that 100 ℃ or higher, preferred 120 ℃ or higher and the highest expansion temperature are 150 ℃ or higher, preferred 160 ℃ or higher those.As said thermoplastic resin, preferred for example (methyl) acrylonitrile polymer and the other multipolymer of using with height (methyl) acrylonitrile content.Can use ethylene halide base, halogenation pyridine, styrene-based monomers, (methyl) acrylate-based monomer, vinyl acetate, divinyl, vinyl pyridine, chloroprene or other monomer as other monomer in the multipolymer situation (comonomer just).It should be noted that said thermoplastic resin also can carry out crosslinked through Vinylstyrene, two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid triethyleneglycol ester, three (methyl) vinylformic acid trihydroxymethylpropanyl ester, two (methyl) vinylformic acid 1,3 butylene glycol ester, (methyl) vinylformic acid allyl ester, triacryl formal, isocyanuric acid triallyl ester or other linking agent.About crosslinking method, preferred uncrosslinked, but can not damage the partial cross-linked of thermoplastic resin performance for crosslinking degree yet.
Evaporation produces the liquid of gas during as heating; Can mention for example hydro carbons; Like Skellysolve A, iso-pentane, neopentane, butane, Trimethylmethane, hexane, sherwood oil, chlorinated hydrocarbons such as methyl chloride, methylene dichloride, Ethylene Dichloride, trichloroethane, trieline or other liquid.
The content that is used for expansible black lead of the present invention is 1～15 weight part based on the diene rubber of 100 weight parts, preferred 2～8 weight parts, and can use with the thermoplastic resin of heat-swellable.If its amount is very little, then can not obtain said ice and snow road performance, thereby this not preferred, if opposite its amount is too many, the contact area of small level reduces between the rubber surface, so the rubbing effect on the ice face reduces, thereby this is not preferred.In addition, if its amount is too many, the wear resistance of rubber combination and physical strength can reduce, thereby this is not preferred.
The expansible black lead powder mass that the bed of graphite particles that contains transpirable material of when heating is therebetween formed of serving as reasons, particle size is 30～600 μ m, is preferably 100～350 μ m.But heating expansible expansible black lead is preferred when sulfuration.
Expansible black lead is made up of the overlapping stratiform that is of sheet that carbon atom forms, and through obtain (being intercalation) with s.t. such as sulfuric acid or nitric acid.Said expansible black lead for example can make its expansion to obtain expansible graphite (perhaps expandable graphite) when the heating evaporation through the interlayer material.Because this material is hard before expansion, therefore can resists because of mixing and reduce quality.In addition, because its irreversibly expansion at a certain temperature, thereby the sulfuration of tire can cause following the rubber matrix volume inside easily and form foreign matter.Use the tire tread of this rubber when wearing and tearing, can form concave-convex surface.Through remove effectively ice and tire between surface in contact on moisture film, thereby the frictional force of improving on the ice face is played effect.
Expansible black lead is known substance and can makes through known preparation method.Usually, through in the mixing solutions that graphite granule is immersed strongly-acid material and oxygenant and between bed of graphite particles, insert said acid through intercalation and prepare expansible black lead.For example, with the vitriol oil as the strongly-acid material, and with nitric acid as oxygenant.Therefore, obtain by inserting the expansible black lead that the vitriolic bed of graphite particles constitutes therebetween.Expansible black lead is opened said layer through the volatilization of interlayer compound under thermal treatment and is expanded.Use sulfuric acid as the expansible black lead of interlayer material usually through expanding 300 ℃ or higher temperature thermal treatment down, but initial expansion temperature to 300 ℃ or lower expansible black lead with reduction make and sell through changing interlayer material or use or uniting other lower boiling acidic cpd of use (for example nitric acid).The processing temperature of the rubber combination of mainly being made up of diene rubber that the present invention relates to is 200 ℃ or lower.In the present invention, be that 190 ℃ or lower expansible black lead show expected effect through using the expansion start temperature.
As the expansion start temperature is 190 ℃ or lower expansible black lead, and for example " Graphguard160-50 " of the UCARGraphtech of U.S. preparation, " Graphguard160-80 " etc. can commercially available acquisitions and can be obtained by Tomoe Corporation.
" expansible black lead " is being meant still unexpanded goods after s.t. just on the term, but also refers to the expanded form after thermal treatment sometimes.The expansible black lead of sneaking in the rubber combination of the present invention is a still unexpanded form before thermal treatment.
Among the present invention, preferably make said expansible black lead in the mixing of rubber combination and extrusion step, not expand, and it is expanded in vulcanisation step.Use the expansion start temperature to be preferably 120～190 ℃, more preferably 140～170 ℃ expansible black lead.If the expansion start temperature is lower than 120 ℃, then expansible black lead can expand when mixing or extruding, and the proportion of said rubber can change in this process, so processibility is easy to suffer damage.In addition, if the expansion start temperature is higher than 190 ℃, the processing temperature when then vulcanizing must be set in 190 ℃ or higher, and the thermal degradation performance based on diene rubber that therefore forms said rubber combination main ingredient tends to remarkable reduction.
On the other hand, expansible black lead has the skeleton structure that is made up of carbon atom, and is therefore good with said rubber matrix or sooty affinity.It is advantageous that even sneak in the rubber, the wear resistance decline degree of said vulcanized rubber is little.
According to the 4th kind of mode; Provide a kind of and had crown and to the pneumatic tyre of the double-layer structure at least of its inboard base portion; Wherein tyre surface contacts with the road surface in the crown part office, and said pneumatic tyre uses the rubber combination that contains following composition to be used for the base portion of said tyre surface: 100 weight part sulfur vulcanized rubbers, gross weight are the cyclic polysulfide of the formula (I) of silicon-dioxide and/or carbon black and 0.1～10 weight part of 30～100 weight parts, preferred 35～95 weight parts, preferred 0.2～8 weight part.This rubber combination that is used for base portion also can be used for the rubber combination combination of crown and is used for tyre surface with above-mentioned.Here; But as said vulcanized rubber; Can mention any rubber that is generally used for tire and other purposes over, for example dissimilar tree elastomer (NR), dissimilar polyisoprene rubber (IR), dissimilar polybutadiene rubber (BR), dissimilar styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene copolymer rubber X 050 (CR) and other diene rubber and their partially hydrogenated thing be (halogenation) butyl rubber (IIR), ethylene-propylene-diene copolymer rubber (EPDM), acrylic elastomer (ACM) etc. perhaps.They can use separately or use with the form of any mixture.
Can process rubber combination of the present invention through the domestic method that is used for airtyred tyre surface, tread base etc. and other multiple application and goods etc.
Except said necessary component; The rubber combination of third aspect present invention can also contain the polytype additive that is generally used for tire or the application of other conventional rubber, like other filler, sulfuration or crosslinking accelerator, polytype oil, anti-aging agent, softening agent.Mix and vulcanize this prescription and vulcanize or crosslinked compsn being can be used for subsequently through general method.Can use these additives with the past amount of using with commonly used, as long as the present invention satisfies the purpose of energy storage elasticity in said scope and can not affect adversely.
In fourth aspect of the present invention; In order to be provided for the rubber combination that high firmness, HS and elongation and tan δ do not raise that has of airtyred bead filler rubber; Provide a kind of use to contain the pneumatic tyre of the rubber combination of following composition: but its amount that comprises of 100 weight parts is that vulcanized rubber, the total amount of 65 weight % or more aromatic vinyl-conjugated diene copolymer rubber and tree elastomer is the silicon-dioxide of 50～120 weight parts and/or the (ii) cyclic polysulfide of the said formula (I) of carbon black and 0.1～10 weight part; X is the number of average out to 2～6 in formula (I); N is 1～15 integer, and R is for replacing or unsubstituted C
2～C
20Alkylidene group, replacement or unsubstituted C
2～C
20Alkylidene oxide or contain the alkylidene group of aromatic ring, thus the inside that is formed on sidewall extends to the high firmness Reinforced Rubber (bead filler rubber) of sidewall from tyre bead.But said pneumatic tyre contains the sulphur vulcanized rubber that mainly is made up of tree elastomer, and silicon-dioxide and/or carbon black, and uses said cyclic polysulfide as vulcanizing agent, to obtain high firmness, HS and elongation, low febrifacient rubber combination.Through using it, can improve airtyred weather resistance and control stability, and can not cause rolling resistance to descend as airtyred bead filler rubber.
But as being used for vulcanized rubber of the present invention; Can mention and contain 65 weight % or more, as to be preferably 70 weight % or more aromatic vinyl-conjugated diene copolymer rubber rubber like (i) tree elastomer and (ii) those of styrene-butadiene copolymer (SBR); Can mention any rubber that is usually used in tire or other application in addition over, like dissimilar polyisoprene rubber (IR), dissimilar polybutadiene rubber (BR), acrylonitrile butadiene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber and other diene rubber or butyl rubber, halogenated butyl rubber, ethylene-propylene-diene copolymer rubber etc.These can use separately or with the form of its any mixture.
Based on the rubber of 100 weight parts, will can be used for fourth aspect present invention rubber combination (i) silicon-dioxide and (ii) carbon black be that the amount of 50～120 weight parts, preferred 55～115 weight parts is mixed with (i) and total amount (ii).If this amount is too little, then the hardness of rubber is not enough and can not obtain high control stability, so this is not preferred, conversely if its amount is too big, then the heat generation change greatly and rolling resistance or weather resistance variation, so this is not preferred.Component (i) and blending ratio are not (ii) had particular restriction, but consider that from hardness and febrifacient angle ratio (i)/(ii) is preferably 0～90/100～10.
As can be used for silicon-dioxide of the present invention, can use any silicon-dioxide that is used for tire etc. in the past, for example native silicon dioxide, synthetic silica, more particularly precipitated silica, dry type silicon-dioxide and wet silicon dioxide.On the other hand, for any carbon black that can be used for carbon black of the present invention, can use over being used for tire or other application, but preferably use the nitrogen specific surface area to be 20m
2/ g or bigger those, more preferably using the nitrogen specific surface area is 20～150m
2Those of/g.
Except said necessary component; Based on 100 parts by weight of rubber, the rubber combination of fourth aspect present invention can also contain preferred 1～30 weight part, more preferably heat reactive resin and preferred 0.01～10 weight part, the more preferably solidifying agent of the said heat reactive resin of 0.1～8 weight part of 3～25 weight parts.If its its amount is too little, then can not obtain required effect (promptly improving control stability), conversely if its amount is too big, then weather resistance decline, so this is not preferred.
Type to said heat reactive resin does not have particular restriction; But can mention resin or the YLENE, 1 of the phenolic varnish type of rosinol, Yatall MA, cashew nut oil, octadecadienoic acid, oleic acid, linolic acid or other oily modification based on phenol; 3,5-Three methyl Benzene or other aromatic modified phenolic varnish type are based on the phenolic varnish type of the resin of phenol and paracril or other modified rubber resin based on phenol.
The methylene radical that can be used as the solidifying agent of above-mentioned heat reactive resin comprises vulkacit H and methylolated melamine derivative to body.That for example can give an example has hexamethylolmelamine, six (ethoxyl methyl) trimeric cyanamide, six (methoxymethyl) trimeric cyanamide, N, N ', a N "-trimethylammonium-N; N ', N "-trimethylol melamine, N, N '; N "-trimethylol melamine, N-melamine methylol, N, N '-two (methoxymethyl) trimeric cyanamide, N, N '; N "-tributyl-N, N ', N "-trimethylol melamine etc.
The cyclic polysulfide of sneaking into the formula (I) in the rubber combination of the present invention for example can pass through method for preparing.
Based on the rubber of 100 weight parts, the rubber combination of fourth aspect present invention contains the cyclic polysulfide (C) of 0.1～10 weight part, preferred 0.2～8 weight part.If its amount is too little, then can not obtain required effect, if opposite its amount is too big, weather resistance variation then, thereby these are not preferred.
Rubber combination according to the present invention can use over any sulphur of making vulcanizing agent commonly used with cyclic polysulfide (B) as vulcanizing agent.When using sulphur (D) with component (B), preferably its amount makes that (D)/(B) (weight ratio) is 8 or lower, is preferably 6 or lower.If this ratio is too big, then often be difficult to obtain effect required for the present invention, thereby this not preferred.
Except above-mentioned necessary component, rubber combination of the present invention can also contain filler such as carbon black and silicon-dioxide, polytype oil, inhibitor, softening agent, polytype vulcanization accelerator, perhaps other is generally used for polytype additive of tire or the application of other conventional rubber to silane coupling agent.Mix this mixture to obtain to can be used for subsequently the sulfurized compsn through general method.If the object of the invention can not affect adversely, also can use these additives with the general quantity of using in the past.
In aspect the of the present invention the 5th, the present invention can improve the defective of the sidewall Reinforced Rubber of run flat tire greatly, promptly hangs down elongation at break and obtains thermotolerance and resistance to fatigue simultaneously.In addition; In order to improve resistance to deterioration simultaneously; A kind of sidewall Reinforced Rubber compsn of run flat tire is provided, and its second-order transition temperature that comprises at least 50 weight parts (Tg) that contains (i) 100 weight parts is the rubber of-80 ℃ or lower polybutadiene rubber, the (ii) nitrogen specific surface area (N of 20～70 weight parts
2SA) be 70m
2/ g or lower carbon black and the (iii) cyclic polysulfide with formula (I) of 2～15 weight parts, in formula (I), x is average 2～6 number, and n is 1～15 integer, and R is for replacing or unsubstituted C
2-C
20Alkylidene group replaces or unsubstituted C
2-C
20Alkylidene oxide perhaps contains the alkylidene group of aromatic ring, and it obtains through dihalide with formula X-R-X and the alkali metals polysulfide reaction with formula M-Sx-M, and in X-R-X, X representes halogen atom respectively, and R representes to replace or unsubstituted C
2-C
20Alkylidene group, replacement or unsubstituted C
2-C
20Alkylidene oxide or contain the alkylidene group of aromatic ring is at M-S
xAmong-the M, M is a basic metal, and x is 2～6 integer.In addition, a kind of pneumatic tyre with the performance of running flat is provided, bead filler rubber and/or sidewall Reinforced Rubber that it uses said rubber combination to insert with the crescent shape xsect as the partial interior on the sidewall.
According to a fifth aspect of the invention; Through using said cyclic polysulfide as vulcanizing agent; The existing shortcoming of sidewall Reinforced Rubber (promptly low elongation at break) can reduce significantly; And through when reducing the polysulfidic bond ratio, giving crosslinked snappiness, can obtain thermotolerance and resistance to fatigue simultaneously, and can improve resistance to deterioration.
Based on total amount is the rubber of 100 weight parts, and the Tg that the rubber components that can be used for fifth aspect present invention must comprise 50 weight parts or more, preferred 55～80 weight parts is-80 ℃ or lower, preferred-85 ℃～-110 ℃ polybutadiene rubber (BR).If the consumption of BR very little, then can not satisfy low heat generation, thereby this not preferred.
As the available rubber components; Except polybutadiene rubber (BR); What can mention among the present invention is any diene rubber that is usually used in tire or other application in the past, for example tree elastomer (NR), polyisoprene rubber (IR), dissimilar styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene copolymer rubber (NBR) and their partially hydrogenated thing and modified form, ethylene-propylene rubber (EPDM) etc.They can use separately or use with the form of any mixture.
The carbon black that can be used for the fifth aspect present invention rubber combination can comprise any carbon black that is usually used in tire etc. in the past, but its nitrogen specific surface area (N
2SA) (measure) and be necessary for 70m according to JIS K6217-2
2/ g or lower, preferred 20～65m
2/ g.If the nitrogen specific surface area is too big, then the heat generation of said rubber becomes big and the weather resistance that runs flat can reduce, thereby this is not preferred.Based on the said rubber components of 100 weight parts, sneaking into said sooty amount is 20～70 weight parts, preferred 30～60 weight parts.If its amount is very little, then said rubber can become too soft and run into when piercing through can not support vehicle weight, thereby this is not preferred, if opposite its amount is too many, then heat generation becomes bigger, thereby this is not preferred.
The cyclic polysulfide with formula (I) of sneaking in the rubber combination of the present invention can for example prepare in the following manner.
(for example can use if desired according to the rubber combination of fifth aspect present invention based on the vulcanization accelerator of sulphenamide; N-cyclohexyl-2-[4-morpholinodithio base sulphenamide, the N-tertiary butyl-2-[4-morpholinodithio base sulphenamide, N-oxydiethylene-2-[4-morpholinodithio base sulphenamide, N; N '-dicyclohexyl-2-[4-morpholinodithio base sulphenamide) or based on the vulcanization accelerator of thiuram (for example tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetra-benzyl thiram disulfide, curing four (2-ethylhexyl) thiuram, single sulfuration tetra methylthiuram or dipentamethylene thiuram tetrasulfide) as vulcanization accelerator; Based on 100 parts by weight of rubber; Its amount is preferably 1～5 weight part, more preferably 1.5～4 weight parts, increases and improves thermotolerance and resistance to fatigue simultaneously so that improve cross-linking efficiency.
Can be used on the sidewall of run flat tire partial interior with the bead filler rubber and/or the sidewall Reinforced Rubber of the transversal planar insertion of crescent moon according to usual method according to rubber combination of the present invention.In addition, the cyclic polysulfide crosslinked action can be resisted and reverted, and therefore when tyre vulcanization, even at high temperature vulcanize sidewall inner (being the capsule side) at least, also can reduce the variation of internal physical character and improve sulfuration productivity.
Except above-mentioned necessary component, can also comprise carbon black, silicon-dioxide or other filler, vulcanization accelerator, polytype oil, anti-aging agent, softening agent, silane coupling agent or other is generally used for polytype additive of tire or other rubber applications according to rubber combination of the present invention.Said prescription can obtain can be used for the sulfurized compsn with the domestic method mixing.The object of the invention can use these additives with past general mixed volume commonly used, as long as can not affect adversely.
In aspect the 6th of the present invention; In order to improve the performance that runs flat (for example weather resistance, resistance to fatigue and resistance to heat aging) of the resilient ring that forms the run flat tire center ring, a kind of center ring of run flat tire is provided, the resilient ring that it is included in film, the rigid metal shell in the tire/wheel edge cavity and supports wheel rim; Wherein use the rubber combination contain following composition to form said resilient ring: but the sulphur vulcanized rubber (A) of 100 weight parts and have cyclic polysulfide (B) and the sulphur (D) of formula (I); Its amount makes that (D)/(B) (weight ratio) is 0～2, and in formula (I), x is average 2～6 number; N is 1～15 integer, and R is for replacing or unsubstituted C
2-C
20Alkylidene group, replacement or unsubstituted C
2-C
20Alkylidene oxide or contain the alkylidene group of aromatic ring.
According to a sixth aspect of the invention; Owing to can improve the elongation at break of resilient ring; Therefore providing when piercing through, when particularly turning down in the high firmness of support vehicle weight, can improve the weather resistance that runs flat when operating greatly on said resilient ring contact road surface.In addition, be used for the preferred embodiment bonding,, also can not peel off and can further improve weather resistance even under the operational condition of harshness with said shell at associating organic acid cobalt salt and a resole type alkyl phenol resin.
The resilient ring that forms the run flat tire center ring need have high firmness, but elongation is low and finally can rupture running flat to encircle described in the operation like this.By way of parenthesis, in the present invention, the rubber that contains cyclic polysulfide through use is used for resilient ring, can improve to run flat weather resistance or reduce weight, even and for high temperature vulcanized, also reversion can not take place, thereby improved productivity.Through sneaking into bonding composition, the direct bonding possibility that becomes.
As the run flat rubber components of rubber combination of center ring of according to a sixth aspect of the invention formation, can mention for example dissimilar tree elastomer (NR), polyisoprene rubber (IR), dissimilar polybutadiene rubbers (BR), dissimilar styrene-butadiene copolymer rubber (SBR), ethylene-propylene-diene terpolymer rubber (EPDM), paracril (NBR) and their partially hydrogenated thing and modified form etc.They can use separately or use with the form of any mixture.
According to a sixth aspect of the invention, said cyclic polysulfide (B) with formula (I) and any sulphur commonly used (D) mix as vulcanizing agent, and based on the rubber components of 100 weight parts, their total amount is preferably 1～20 weight part, more preferably 2.5～10 weight parts.If its amount very little, then is difficult to obtain required physical properties and can reduces, thereby this not preferred that if opposite its amount is too many, the physical properties (being stability to aging) after then aging can descend, thereby this is not preferred with the bonding force of metal casing.According to the present invention, must use vulcanizing agent (B) and (D) with (D)/(B)=0～2, preferred 0～1 weight ratio in addition.If this ratio is too high, the effect of the resistance to heat aging that then can not improve, thereby this is not preferred.
According to a sixth aspect of the invention; Said rubber combination preferably contains its amount and is 0.1～5 times of the gross weight of said cyclic polysulfide (B) and any sulphur (D), preferred 0.5～4 times vulcanization accelerator, particularly based on sulphenamide and/or based on the vulcanization accelerator of thiuram.If sneak into said vulcanization accelerator, then can further improve resistant to thermal aging performance and fracture property, thereby this is preferred.
The cyclic polysulfide with formula (I) of sneaking in the rubber combination of the present invention can for example can prepare in the above described manner.
An optimal way as the rubber combination of sixth aspect present invention; In order to improve bonding between said rubber combination and the metal; Based on the rubber of 100 weight parts, can sneak into its amount and be 0.1～5 weight part, more preferably organic acid cobalt salt and/or its amount of 0.5～4 weight part are 1～6 weight part, the more preferably resole type alkyl phenol resin of 2～5 weight parts.As the organic acid cobalt salt, can mention for example cobalt naphthenate, cobalt stearate, neodecanoic acid cobalt borate, resin acid cobalt, acetylacetone cobalt etc.If the amount of organic acid cobalt salt is very little, then can not obtain required improvement effect, if opposite consumption is too many, then rubber performance worsens, thereby this is not preferred.
On the other hand, if the amount of resole type alkylphenol or resole type alkyl phenol resin very little, then can not obtain required improvement effect; And if its amount is too many; Scorching can take place mediating or add man-hour rubber then, easily can not moulding, thereby this is not preferred.
Will explain the 6th aspect of the present invention particularly with reference to the embodiment of Fig. 1.Fig. 1 is the cross-sectional view along warp-wise, and it has shown the major parts of a typical embodiments of tire center ring of the present invention.
Turn round not like Fig. 1, run flat tire center ring 1 according to the present invention is formed by endless metal shell in the cavity 3 that inserts pneumatic tyre 24 and caoutchouc elasticity ring 5.Said run flat tire center ring 1 moulding makes external diameter less than the internal diameter of cavity 3, thereby keeps apart from the internal surface certain distance of the cavity 3 of pneumatic tyre 2.Said internal diameter forms has the size identical substantially with the internal diameter of airtyred tyre surface.The inside that said run flat tire center ring 1 inserts pneumatic tyre 2, it is assembled together at wheel rim 6 places of said tire with pneumatic tyre 2 under this state, thus formation tire center ring.If the tire center ring is connected that automobile etc. is gone up and in operation pneumatic tyre be pierced, the flat 2 that then pierces through is by the peripheral support of run flat tire center ring 1, thereby the operation that runs flat in this state becomes possibility.
As stated, form by endless metal shell and resilient ring according to the run flat tire center ring of tyre assembly of the present invention.Said endless metal shell 4 its outside form tire that successive stayed surface pierces through in order to support and within it portion form a left side and right two sidewalls as holder part.External support surface is moulding in many ways.For example; As shown in fig. 1; With the shape of the vertical level cross-sectionn of circumferential direction can be shape with outwardly-bent surface, also can be straight or have three or the more a plurality of curved surface of arranging along tire axial, perhaps two or more curved surfaces.Can in recess, discharge resilient ring and alleviate ballistic effect and/or the endless metal shell is separated with rubber elastomer so that in the operating process that runs flat, give with ring section; The sidewall of said metal casing is directly contacted with wheel rim and keeps stable engagement state (referring to Japanese patent application No.2002-271795).Like this, even form stayed surface,, so also can increase the operating distance that runs flat of this tire if improve bonding between metal and the rubber elastomer of the present invention with this mode.
Said resilient ring is bonded to the end of two holder part of endless metal shell.Through near left and right sides wheel rim, this endless metal shell is able to support.Said rubber-like elasticity ring is made up of rubber, can alleviate from piercing through or the vibrations or the vibration of the endless metal shell of other tire, stops the slip with respect to wheel rim, and stably on wheel rim, supports annular metal casing.
The run flat endless metal shell 4 of center ring 1 of formation has strong bonding force with rubber-like elasticity ring 5, but preferably should guarantee the bond area be scheduled to.Become nondimensional in the wheel rim work or the load in when operation of running flat through tip diameter R (inch).When bond area is S (cm
2) time, the ratio of S/R should be 4.5cm
2/ inch or bigger is preferably 8～20cm
2/ inch.At this; Said " bond area " refers at an end place rubber-like elastic body of endless metal shell and the bond area between the metal; The end face of the metal casing that just contacts with rubber-like elastic body and total bond area on preceding/surface, back in the end of endless metal shape (in case along peripheral direction, then at place, level cross-sectionn) perpendicular to circumferential direction.
In addition, the gluing of surfaces between endless metal shell 4 and the rubber-like elasticity ring 5 can be through axially with radially forming.More preferably the two equates basically.In this way, form the structure of the power that when running flat operation, can bear vertically and radially produce.
In Fig. 1, the center ring 1 that runs flat, pneumatic tyre 2 and wheel rim 6 be the coaxial Cheng Huan about wheel shaft (not shown) place greatly.Should be noted that the size to metal casing 4 does not have special limitation, preferred thickness is 0.5～3.0mm, and width is the distance between the tire bead front end of the left and right sides.
Tire center ring of the present invention supports the weight of automobile etc. through flat, so endless metal shell 4 is processed by metallic substance.As said metal, can mention iron, stainless steel, aluminium, titanium, their alloy etc.
Form in through xsect recessed or breach when promoting the wheel rim assembling, be easy to generate local pressure and concentrate at resilient ring.If can guarantee the elongation characteristic, when wheel rim assembles, can not damage said resilient ring more so, thereby this is preferred the utilization.But, according to the present invention, owing to sneak into cyclic polysulfide, even for the resilient ring that has recessed or breach, owing to can guarantee elongation, thereby can prevent the damage when wheel rim assembles, so this is preferred.
According to a sixth aspect of the invention; Except above-mentioned necessary component, said rubber combination can also comprise filler (for example carbon black, silicon-dioxide), vulcanization accelerator, polytype oil, inhibitor, softening agent, silane coupling agent or other and be usually used in polytype additive that tire or other conventional rubber are used.Can mix this prescription to obtain being used for the sulfurized compsn through general method.The mixed volume of said additive is conventional general quantity, only otherwise can have a negative impact to the object of the invention.
In aspect the of the present invention the 7th; For mechanical property, the particularly fracture characteristics that improves butyl rubber composition; With the further resistance to deterioration of improving, a kind of rubber combination is provided, it comprises gross weight is the rubber (A) that contains 70 weight parts or more butyl rubber or halogenated butyl rubber of 100 weight parts and the (ii) cyclic polysulfide with formula (I) (B) of 0.1～10 weight part; In formula (I); X is average 2～6 number, and n is 1～15 integer, and R replaces or unsubstituted C for comprising
2-C
18Alkylidene group, replacement or unsubstituted C
2-C
18Alkylidene oxide is at interior alkylidene group, the dihalide of formula (I) material through having formula X-R-X with have formula M-S
xThe alkali metals polysulfide of-M is reacted with two-phase system in the non-conforming mixed solvent of hydrophilic and lipophilic solvent and is obtained, and wherein in X-R-X, X representes halogen atom respectively, and R representes to comprise and replaces or unsubstituted C
2-C
18Alkylidene group, replacement or unsubstituted C
2-C
18Alkylidene oxide is at interior alkylidene group, at M-S
xAmong-the M, M is a basic metal, and x is 2～6 integer.
According to a seventh aspect of the invention, through using cyclic polysulfide (B), can improve the fracture characteristics of butyl rubber significantly and further improve resistance to deterioration as vulcanizing agent.
As the rubber components according to the rubber combination of seventh aspect present invention, in the rubber components of 100 weight parts, the consumption of butyl rubber or halogenated butyl rubber is 70 weight parts or more, preferred 75～100 weight parts.Said butyl rubber or halogenated butyl rubber refer to iso-butylene and isoprene copolymer and halogenide, iso-butylene and p-methylstyrene multipolymer and halogenide thereof etc. in the present invention.
In addition, said butyl rubber or halogenated butyl rubber have the temperature limit of brittleness that is higher than general diene rubber,, are about-35 ℃ perhaps according to prescription.Thereby when being used for tire liner etc., in the low especially area of temperature, air retaining wall can reach temperature limit of brittleness sometimes, and said rubber finally ftractures.In the past, in order to reduce temperature limit of brittleness, use the method for sneaking into tree elastomer or other diene rubber, but can cause sacrificing butyl rubber inherent low gas permeability like this.
According to a seventh aspect of the invention, the inventor finds that the temperature limit of brittleness of said butyl rubber is minimized through using said cyclic polysulfide as vulcanizing agent.According to thinking that this gets in the cross linked chain owing to long alkylidene group of said cyclic polysulfide or alkylidene oxide, thus make crosslink part the entropy increase and bigger snappiness is provided.
In aspect the of the present invention the 7th; As rubber; Except butyl rubber or the halogenated butyl rubber, can mention for example dissimilar tree elastomer (NR), polyisoprene rubber (IR), dissimilar polybutadiene rubber (BR), dissimilar styrene-butadiene copolymer rubber (SBR), ethylene-propylene-diene terpolymer rubber (EPDM) etc.They can use separately or use with the form of any mixture.If the butyl rubber in the used rubber components of the present invention or the amount of halogenated butyl rubber are lower than 70 weight parts, then will damage butyl rubber or halogenated butyl rubber inherent low gas permeability and high hysteresis loss etc., thereby this not preferred.
According to a seventh aspect of the invention, based on the rubber constituent of 100 weight parts, the cyclic polysulfide with formula (I) is sneaked into the amount of 0.1～10 weight part, preferred 0.1～5 weight part as vulcanizing agent.If its amount is very little, the effect of fracture property or the ageing resistance of then can not being improved, thereby this is not preferred; If opposite its amount is too many; Then this vulcanizing agent is excessive for the diene rubber of butyl rubber, thereby not only said effect becomes saturated, moreover; Also can not cause viscosity when vulcanizing, thereby this not preferred.Butyl rubber is crosslinked through zinc white (zinc oxide), but is known that said physical properties can improve through therewith using sulphur.Through using cyclic polysulfide (I) instead of part or whole sulphur, can improve the performance of rubber significantly.Preferably use its amount to be 0.5～5 times vulcanization accelerator of said cyclic polysulfide weight according to rubber combination of the present invention, be preferably based on thiazole or based on sulphenamide, based on thiuram or other vulcanization accelerator.
The cyclic polysulfide with formula (I) of sneaking into the rubber combination of seventh aspect present invention can for example pass through method for preparing.
Except above-mentioned necessary component, said rubber combination can also comprise filler (for example carbon black, silicon-dioxide), vulcanization accelerator, polytype oil, inhibitor, softening agent, silane coupling agent or other and be usually used in polytype additive that tire or other conventional rubber are used.Can mix this prescription can be used for the sulfurized compsn subsequently through general method.The mixed volume of said additive is conventional general quantity, only otherwise can have a negative impact to the object of the invention.
In eight aspect of the present invention; For fracture property and the ageing resistance of improving said rubber combination; A kind of rubber combination is provided, and it contains the diene rubber of 100 weight parts, the aliphatic acid of 0.05～1 weight part or the cyclic polysulfide (C) of alicyclic acid family cobalt salt (in cobalt element) and 0.1～20 weight part.
In eight aspect of the present invention, as said cyclic polysulfide (C), use cyclic polysulfide with formula (I), x is average 2～6 number in formula (I), and n is 1～20 integer, and R is for replacing or unsubstituted C
2-C
20Alkylidene group, replacement or unsubstituted C
2-C
20Alkylidene oxide, or contain the alkylidene group of aromatic ring.Said cyclic polysulfide can for example pass through method for preparing.
In eight aspect of the present invention,, use cyclic polysulfide with formula (I) as vulcanizing agent.Through instead of part or whole sulphur, can improve modulus and the variation of the back physical properties that suppresses to wear out.
The diene rubber that is used for eighth aspect present invention can be for being usually used in any diene rubber of tire and other purposes in the past, can mention tree elastomer (NR) for example, polyisoprene rubber (IR), dissimilar polybutadiene rubber (BR), dissimilar styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene copolymer rubber, hydrogenated nbr etc.They can use separately or use with the form of any mixture.
Sneak into the aliphatic carboxylic acid of rubber combination of the present invention or the cobalt salt of alicyclic carboxylic acid and serve as the acvator that promotes the vulcanization of rubber.As the organic acid that forms said cobalt salt, can mention for example neodecanoic acid, Triple Pressed Stearic Acid, naphthenic acid, sylvic acid, tall oil acid, palmitinic acid, oleic acid, octadecadienoic acid and linolic acid.In addition, said organic acid also can be the acid of boracic.For example, can mention three new decane borates etc.
Based on the diene rubber component of 100 weight parts, the amount of the cobalt salt of aliphatic carboxylic acid or alicyclic carboxylic acid is 0.05～1 weight part (converting cobalt element into), preferred 0.1～0.3 weight part.If its amount is very little, then be difficult to the purpose that reaches required, if opposite its amount is too big, then processing characteristics reduces and the physical properties decline of vulcanized rubber, thereby this is not preferred.
Based on the diene rubber of 100 weight parts, the cyclic polysulfide (I) that is used for eighth aspect present invention is sneaked into the amount of 0.1～20 weight part, preferred 0.5～20 weight part.If consumption is very little, then the effect of vulcanizing agent can not show, and the intensity of said vulcanized rubber can be descended degradation, thereby this is not preferred, if opposite consumption is too big, then state of vulcanization increase too many and viscosity degradation too many, thereby this is not preferred.
Rubber combination according to eighth aspect present invention can use sulphur or other vulcanizing agent commonly used in the past if desired.When using sulphur, can instead of part or 60% said cyclic polysulfide use at the most.
Except said necessary component, can also comprise filler (for example carbon black, silicon-dioxide), polytype oil, inhibitor, softening agent, vulcanization accelerator, silane coupling agent or other according to the rubber combination of eighth aspect present invention and be usually used in polytype additive that tire or other conventional rubber are used.Can mix this prescription to obtain can be used for the sulfurized compsn through general method.The mixed volume of said additive is conventional general quantity, only otherwise can have a negative impact to the object of the invention.
Embodiment
To further specify the present invention with embodiment below, but scope of the present invention is not limited to these embodiment.
Preparation example I-1
Sodium polysulphide (Na to 89.76 gram (0.15mol) 30%
2S
4) add 80 gram water, 2.4 gram (0.075mol) sulphur and 1.16 grams (0.0045mol) Tetrabutyl amonium bromide in the aqueous solution as catalyzer; Reacted 2 hours down at 80 ℃; Add 100 gram toluene then and in 1 hour, splashing into 23.3 gram (0.15mol) 1 under 90 ℃; 6-dioxy hexane further reacted 4 hours.After reaction finishes, separate organic phase and, obtain the cyclic polysulfide that 32.2 grams (productive rate 94%) have formula (II) concentrated under the pressure that reduces under 90 ℃.
1HNMR(270MHz，CDCl
3)δ(ppm)：1.4-1.9(8H，-CH
2-)，2.9-3.3(4H，-S-CH
2-)。
Wherein the MV of x is 4.5, and n is 1～4 numerical value.
Preparation example I-2
Sodium polysulphide (Na to 89.76 gram (0.15mol) 30%
2S
4) add 80 gram water, 4.8 gram (0.15mol) sulphur and 1.16 grams (0.0045mol) Tetrabutyl amonium bromide in the aqueous solution as catalyzer; Reacted 2 hours down at 80 ℃; Add 100 gram toluene then and in 1 hour, splashing into 23.3 gram (0.15mol) 1 under 90 ℃; The 6-dichloro hexane further reacted 4 hours.After reaction finishes, separate organic phase and, obtain the cyclic polysulfide that 35.2 grams (productive rate 95%) have formula (VI) concentrated under the pressure that reduces under 90 ℃.
1HNMR(270MHz，CDCl
3)δ(ppm)：1.4-1.9(8H，-CH
2-)，2.9-3.3(4H，?-S-CH
2-)。
Wherein the MV of x is 5, and n is 1～4 numerical value.
Example I-1 is to I-4 and comparative example I-1 to I-4 specimen preparation
With the prescription (weight part) shown in the Table I-1, will in 1.5 liters of Laboratary type Banbury Banbury mixeies, mix 7.5 minutes except other composition of vulcanization system with 60rpm speed, mix in order to sulfuration through 8 inches mills then, sulfuration is 20 minutes under 160 ℃.The result sees Table I-1.
Table I-1
The note of Table I-1
＊1：Nippon?Zeon?Nipol?IR-2200
＊2：Tokai?Carbon?SeastN
*3:Karuizawa Refinery oil fills sulphur
＊4：Ouchi?Shinko?Chemical?Industrial?Noccelar?NS-F
*5: the embodiment 3 synthetic cyclic polysulfides of japanese unexamined patent publication No. open (Kokai) No.2002-293783 (average x=4)
*6: preparation example I-1 synthetic cyclic polysulfide (average x=4.5)
*7: preparation example I-2 synthetic cyclic polysulfide (average x=5)
*8: measure (No. 3 dumbbells) based on JIS K6251
*9: measure (No. 3 dumbbells) based on JIS K6251
*10: be 10% in the initial elongation rate, dynamic strain be 2% and frequency be under the 20Hz, measure (the sample width is 5mm) through Toyo Seiki Seisakusho Rheograph Solid
Can be clear that from the conclusion of Table I-1; Use the rubber combination of the example I-1 of cyclic polysulfide of the present invention to I-4; Compare with the rubber combination of comparative example I-3 and I-4, can keep breaking tenacity and elongation at break and the tan δ under 60 ℃ to become lower after the thermal ageing.
Wherein n is the numerical value of 1-4.
Example II-1 is to II-3 and comparative example II-1
Rubber combination with each prescription (weight part) that Table II-1 lists mix through 8 inches mills and said rubber 190 ℃ of sulfurations 10 minutes.The result sees Table I.Testing method is following.
100% and 300% modulus: measure (No. 3 dumbbells) according to JIS K6251.
Breaking tenacity TB: measure according to JIS K6251.
Elongation at break EB: measure according to JIS K6251.
Tan δ (60 ℃): be 10% in the initial elongation rate, dynamic strain be 2% and frequency be under the 20Hz, measure (the sample width is 5mm) through Toyo Seiki Seisakusho Rheograph Solid.
Table II-1
The note of Table II-1
*1: tree elastomer (TSR-20)
*2: carbon black (Shoblack N335, Showa Cabot)
*3: zinc oxide (Ginrei R, Toho Zinc)
*4: Triple Pressed Stearic Acid (Beads Stearic Acid YR, NOF Corporation)
*5: inhibitor (Santoflex 6PPD, Flexsys)
*6: vulcanization accelerator (Noccelar NS-P, Ouchi Shinko Chemical Industrial)
*7: sulphur (oil fills sulphur, Karuizawa Refinery)
*8: cyclic polysulfide (using preparation example I-2 synthetic)
Be clear that from the conclusion of Table II-1 example II-1 is only used the polysulfide of 1 weight part, all show excellent fracture property and low tan δ in the starting stage with after wearing out.Example II-2 is the cyclic polysulfide of 1:1 and the instance of sulphur for usage ratio.Even use, also can obtain similar effect with sulphur.Example II-3 shows excellent physical properties for using the instance of 0.5 weight part cyclic polysulfide after aging.
EXAMPLE III-1 to III-4 and Comparative Example III-1 prepares sample to III-3
Each prescription with table HI-1 will mix 5 minutes in 16 liters of Banbury Banbury mixeies except other composition (weight part) of vulcanization system, and discharging obtains master batch when reaching 160 ± 2 ℃.To said master batch add vulcanization system through mill to obtain rubber combination.
Then, the gained rubber combination in the mould of 15 * 15 * 0.2cm in 160 ℃ of sulfurations 30 minutes and preparation vulcanized rubber sheet, the rubber performance through following this sheet rubber of test determines subsequently.The result sees Table III-1.
The testing method that rubber performance is estimated
The wetland braking quality: preparation uses every kind of mixture to be of a size of the tire of 195/65R15 as tyre surface; It is attached on the vehicle of 2000cc discharge capacity; On urban road, go and reached about 20 in about 6 months; 000 km, in spilling the asphalt surface test section of 1mm deep water, measuring starting velocity is the braking distance of 100km then.The numeric indicia of Comparative Example III-1 is an index 100.Numerical value is big more, and then braking distance is short approximately and braking quality is good more.
The note of Table III-1
Nipol9526:Nippon Zeon styrene-butadiene copolymer rubber (styrene content: 35%, 50phr, oil fills, Tg=-35 ℃)
Nipol1712:Nippon Zeon styrene-butadiene copolymer rubber (styrene content: 23.5%, 37.5phr, oil fills, Tg=-51 ℃)
Nipol1220:Nippon Zeon polybutadiene rubber (non-oil fills, Tg=-100 ℃)
DIA I:Mitsubishi Chemical carbon black (N
2SA=114m
2/ g)
Nipsil AQ:Nippon Silica Industry wet silicon dioxide
The Si-69:Degussa silane coupling agent
The Santoflex6PPD:Flexsys inhibitor
Zinc oxide #3:Seido Chemical Industry
Bead Triple Pressed Stearic Acid: NOF Corporation Triple Pressed Stearic Acid
Desolex No.3:Showa Shell Oil treated oil
Santocure CBS:Flexsys vulcanization accelerator
" Gold Flower " oil treatment sulphur powder: Tsurumi Chemical sulphur
Cyclic polysulfide III-1: according to the method for the embodiment 3 of open (Kokai) No.2002-293783 of japanese unexamined patent publication No., synthetic has the cyclic polysulfide of formula (I) structure, wherein R=(CH
2)
6, x (on average)=4, n=1～5.
Cyclic polysulfide III-2: have the cyclic polysulfide of formula (I), wherein R=(CH according to the method synthetic of the embodiment 2 of open (Kokai) No.2002-293783 of japanese unexamined patent publication No.
2)
2O (CH
2) O (CH
2)
2, x (on average)=4, n=1～2.
EXAMPLE III-5 to III-9 and Comparative Example III-4 is to III-7
Each prescription with Table III-2 will mix 5 minutes in 16 liters of Banbury Banbury mixeies except other composition (weight part) of vulcanization system, and discharging obtains master batch when reaching 150 ℃.To said master batch add vulcanization system and through mill to obtain rubber combination.
Then, said rubber combination in the mould of 15 * 15 * 0.2cm in 150 ℃ of sulfurations 40 minutes with preparation 2mm thick vulcanized rubber sheet, the rubber performance through following this sheet rubber of test determines subsequently.The result sees Table III-2.
The testing method that rubber performance is estimated
The velocity of variation of M300: before the thermal ageing and at the velocity of variation of 300% modulus of 100 ℃ of following thermal ageings after 24 hours.If velocity of variation is 10% or lower, then adhesion property is stable good.
The evaluation of adhesion property: the laboratory vehicle road segment segment of every kind of rubber combination as the 195/55R15 tire and the 4.41km that goes of tyre surface used in preparation.Adhesion property is divided into 5 grades through sensory evaluation.Numerical value is big more, and adhesion property is good more.It should be noted that each embodiment all shows the velocity of variation of 300% good modulus and good adhesion property in Table III-2.
The note of Table III-2
SBR:Zeon Nipol9526 (styrene content: 35%)
Charcoal SAF:Mitsubishi Chemical Diablack A
Silicon-dioxide: Degussa Ultrasil7000GR
Accelerator CBS: Ouchi Shinko Chemical Industrial Noccelar CZ-G
Promotor TOT-N:Ouchi Shinko Chemical Industrial Noccelar TOT-N
Sulphur: Tsurumi Chemical
Cyclic polysulfide III-3: identical with above-mentioned cyclic polysulfide III-1
EXAMPLE III-10 is to III-14 and comparative example 1II-8 to III-10
Each prescription to show in the Table III-3 will mix 5 minutes in 16 liters of Banbury Banbury mixeies except other composition (weight part) of vulcanization system, and discharging obtains master batch when reaching 160 ℃.To said master batch add vulcanization system and through mill to obtain rubber combination.
Then, said rubber combination in the mould of 15 * 15 * 0.2cm in 160 ℃ of sulfurations 30 minutes with preparation 2mm thick vulcanized rubber sheet, the rubber performance through following this sheet rubber of test determines subsequently.The result sees Table III-3.
The testing method that rubber performance is estimated
Ice face braking quality: use each mixture to come the tire of preparation size as 195/65R15 as tyre surface; It is attached on the vehicle of discharge capacity of 2000cc; On urban road, go and reached about 20 in about 6 months; 000km, then at ice temperature for being that 40km measures braking distance on-5 ℃ the ice face test section from starting velocity.The numeric indicia of comparative example 1II-8 is 100.Numerical value is big more, and braking distance is short more, and braking quality is good more.
The note of Table III-3
Tree elastomer TSR20:SIR (Tg=-70 ℃)
Nipol1441:Nipon Zeon polybutadiene rubber (37.5phr, oil fills, Tg=-101 ℃)
DIA I:Mitsubishi Chemical carbon black (N
2SA=114m
2/ g)
Nipsil AQ:Nippon Silica Industry wet silicon dioxide
The Si-69:Degussa silane coupling agent
The Santoflex6PPD:Flexsys inhibitor
Zinc oxide #3:Seido Chemical Industry
Bead Triple Pressed Stearic Acid: NOF Corporation Triple Pressed Stearic Acid
Desolex No.3:Showa Shell Oil treated oil
Santocure CBS:Flexsys vulcanization accelerator
" Gold Flower " oil treatment sulphur powder: Tsurumi Chemical sulphur
Cyclic polysulfide III-1: identical with above-mentioned cyclic polysulfide III-1
Cyclic polysulfide III-2: identical with above-mentioned cyclic polysulfide III-2
EXAMPLE III-15 to III-18 and Comparative Example III-11 is to III-12
With each prescription that shows in the Table III-4, will in 16 liters of Banbury Banbury mixeies, mediate 5 minutes except other composition (weight part) of vulcanization system, discharging obtains master batch when reaching 160 ℃.To said master batch add vulcanization system and through mill to obtain rubber combination.
Then, said rubber combination in the mould of 15 * 15 * 0.2cm in 160 ℃ of sulfurations 30 minutes with preparation 2mm thick vulcanized rubber sheet, the rubber performance through following this sheet rubber of test determines subsequently.The result sees Table III-4.
The testing method that rubber performance is estimated
Use the tire with double-layer structure tyre surface of every kind of mixture as base portion preparation size 195/65R15, the maximum ga(u)ge of crown is 7mm, and the thickness of base portion is 2mm.Said tire is used for following test.
The high speed weather resistance: JIS D4230JIS high speed durability test is that the rotating cylinder of 1707mm carries out through diameter, improves speed 10km/hr in per then 30 minutes.Continue to test to bulging of tyre.The numeric indicia of Comparative Example III-11 is an index 100.Numerical value is big more, and operating range is longer and performance is good more.
Rolling resistance: through the rotating cylinder diameter is that the indoor rotating cylinder type tire detector of anti-rolling resistance of 1707mm is measured.The used test condition is a JATMA Y/B2003 version.Numerical value is big more, and rolling resistance is more little and performance is good more.
Control stability: vehicle goes in the obstacle test segment that is provided with mark post with fixed spacing.Use V-bar to estimate control stability.The numeric indicia of Comparative Example III-11 is an index 100.Numerical value is big more, and then control stability is good more.
The note of Table III-4
Tree elastomer TSR20:SIR20
Nipol1520:Nipon Zeon styrene-butadiene copolymer rubber (styrene content: 23.5%)
Dia E:Mitsubishi Chemical carbon black (N
2SA=41m
2/ g)
The Santoflex6PPD:Flexsys inhibitor
Zinc oxide #3:Seido Chemical Industry
Bead Triple Pressed Stearic Acid: NOF Corporation Triple Pressed Stearic Acid
Desolex No.3:Showa ShellOil treated oil
Santocure NS:Flexsys vulcanization accelerator
" Gold Flower " oil treatment sulphur powder: Tsurumi Chemical sulphur
Cyclic polysulfide III-6: identical with above-mentioned cyclic polysulfide III-1
Cyclic polysulfide III-7: identical with above-mentioned cyclic polysulfide III-2
EXAMPLE IV-1 to IV-4 and Comparative Example IV-1 is to IV-2
Each prescription to show in the Table IV-1 will mix 5 minutes in the Banbury Banbury mixer except other composition of sulphur and crosslinking accelerator.Then, the compound that obtains, sulphur and crosslinking accelerator are mixed to obtain rubber combination through mill.The rubber combination of gained is crosslinked 160 ℃ of dip molds 20 minutes, and as the evaluation of physical properties.Testing method is following.
Testing method
Rupke JIS hardness Hs (20 ℃): based on the Durometer A hardness of JIS K6253.
100% and 300% modulus: test based on JIS K6251.
Breaking tenacity TB (MPa): test based on JIS K6251.
Elongation at break EB (%): test based on JIS K6251.
Tan δ (60 ℃): through Toyo Seiki Seisakusho viscoelastic spectrometer be 10% in initial strain, amplitude is to test 20Hz under for ± 2% with frequency.
On using in the table every kind of mixture be used as the tire of high firmness Reinforced Rubber preparation size as 195/65R15, its in the inside of sidewall from base portion extend to sidewall height be 50mm, said tire is used for following test.
The load durability test
Through diameter is the load durability test that the rotating cylinder of 1707mm carries out JIS D4230, JATMA Y/B2003 version, increases by 20% load in per then 5 hours.Continue to test to bulging of tyre.The result queue of Comparative Example IV-1 is an index 100.Numerical value is big more, and operating range is longer and performance is good more.
Rolling resistance
Through having the rotating cylinder diameter is that the indoor rotating cylinder type tire drag tstr of 1707mm is tested.Said test condition is seen JATMA Y/B2003 version.Numerical value is big more, and rolling resistance is more little and performance is good more.
Control stability
Vehicle goes in the obstacle test segment that is provided with mark post with fixed spacing.Use V-bar to estimate control stability.The numeric indicia of Comparative Example IV-1 is an index 100.Numerical value is big more, and then control stability is good more.
Table IV-1
The note of Table IV-1
*1: tree elastomer TSR20:SIR20
*2:Nippon Zeon styrene-butadiene copolymer rubber Nipol1502
*3:Mitsubishi Chemical carbon black DIA HA (N
2SA=74m
2/ g)
*4：Flexsys?Santoflex6PPD
*5:Seido ChemicalIndustry zinc oxide # 3
*6:NOF Corporation bead Triple Pressed Stearic Acid
*7:Sumitomo Dulles Sumilight resin PR-12687 (cashew nut oil modified phenol resins)
*8:Showa ShellOil Desolex No.3 (treated oil)
＊9：Flexsys?Santocure?NS
*10:Ouchi Shinko Chemical Industrial Noccelar H (resin curing agent vulkacit H)
*11:Tsurumi Chemical " Gold Flower ", oil treatment sulphur powder
*12: the cyclic polysulfide that uses preparation example I-2
*13: the cyclic polysulfide that uses preparation EXAMPLE III-2
Can be clear that from the result of Table IV-1 EXAMPLE IV-1 and IV-2 only use cyclic polysulfide, so weather resistance improves greatly with respect to the Comparative Example IV of only using sulphur-1, the while rolling resistance has identical degree with control stability.EXAMPLE IV-3 is compared with the Comparative Example IV of only using sulphur-1 for uniting the instance that uses cyclic polysulfide and sulphur, and it has improved weather resistance widely, and rolling resistance has identical degree with control stability simultaneously.EXAMPLE IV-4 is compared with the comparative example who uses sulphur for uniting the instance that uses cyclic polysulfide and heat reactive resin, and its weather resistance and control stability are able to improve, and rolling resistance has identical degree simultaneously.
Reference implementation example V-1, EXAMPLE V-1-V-4 and Comparative Example V-1
Following test will be estimated the physical properties of vulcanizer of the present invention.
The prescription of rubber (weight part) is seen Table V-1.
Table V-1
The note of Table V-1
*1：Nipol?BR1220(Tg＝-100℃)(Nippon?Zeon)
*2：TSR20
＊3：Diablack?E(Mitsubishi?Chemical，N
2SA＝33m
2/g)
＊4：Shoblack?N339(Showa?Cabot，N
2SA＝90m
2/g)
*5: zinc white #3 (Seido Chemical Industry)
*6: bead Triple Pressed Stearic Acid (Kao)
*7：Crystex?HSOT20(Flexsys)
*8: use above-mentioned synthetic cyclic polysulfide I-2
*9: use above-mentioned synthetic cyclic polysulfide III-2
*10:Noccelar NS-F (Ouchi Shinko Chemical Industrial is based on sulphenamide)
*11:Noccelar NS-F (Ouchi Shinko Chemical Industrial is based on thiuram)
The rubber combination (weight part) that will have each prescription of Table V-1 demonstration mixes through 8 inches mills, under 160 ℃ of cure conditions, vulcanizes 20 minutes then.The result sees Table V-1.Testing method is following.
100% modulus: based on JIS K6251 test (No. three dumb-bell shapes of JIS)
Breaking tenacity TB: based on JIS K6251 test (No. three dumb-bell shapes of JIS)
Elongation at break EB: based on JIS K6251 test (No. three dumb-bell shapes of JIS)
De Mattia deflects the crack growth test: test through following method according to JIS K6260: clamp the vulcanized rubber testing plate that has breach in advance in the 65mm distance; Stroke (stroke) bending and rate of bending with 20mm are 300rpm, the length of per then 1000 crooked test crack growths.Crooked numerical value when crackle reaches the two ends of sample is seen shown in the table.Crooked numerical value is big more, and opposing crack growth performance is good more.
Rubber heat generation: the heat generation of estimating sidewall Reinforced Rubber when running flat through following test.
With thickness is that 5mm and width are that the vulcanized rubber sheet of 25mm is attached to De Mattia and deflects on the crack growth tstr, is 300rpm with stroke bending and the rate of bending of 40mm.Surface temperature with non-contact thermometer test sample center after 30 minutes.Temperature is high more, because the crooked rubber heat generation that causes is high more.
The reference implementation example is estimated based on the rubber of sidewall Reinforced Rubber instance commonly used.EXAMPLE V-1 shows that compound V-1 has replaced half sulphur approximately, and it is being able to improve aspect resistant to thermal aging and the opposing crack growth.Comparative Example V-1 has shown the situation of carbon black overshoot scope, and because the crooked heat generation that causes is big.EXAMPLE V-2 shows that compound 1 has replaced the situation of whole sulphur, and its resistance to heat aging is able to improve with opposing crack growth ability.EXAMPLE V-3 has shown uses the instance based on the vulcanization accelerator of thiuram, and its resistance to heat aging increases.EXAMPLE V-4 has shown the situation of using compound V-2, and resistance to heat aging further improves and the crack growth characteristic is greatly improved.
Comparative example, example VI-1 are to VI-5 and Comparative Example V I-1
The physical properties of rubber combination of the present invention is estimated in following test.
The prescription of said rubber combination (weight part) is seen shown in the Table VI-1.
*1: the numeric indicia with conventional embodiment is index 100 (numerical value is big more, and weather resistance is good more)
The note of Table VI-1
＊1：TSR20
*2:HTC100 (NSC charcoal)
*3: zinc white #3 (Seido Chemical Industry)
*4: bead Triple Pressed Stearic Acid (Kao)
*5：Nocrac6C(Ouchi?Shinko?Chemical?Industrial)
*6: cobalt naphthenate (cobalt contents 10%) (Dainippon Ink&Chemical)
*7：Hitanol2501Y(Hitachi?Chemical)
*8: oil fills sulphur (Karuizawa Refinery)
*9: preparation example I-2 synthetic cyclic polysulfide
*10:Noccelar DM (based on thiazole) (Ouchi Shinko Chemical Industrial)
*11:Noccelar TOT-N (based on thiuram) (Ouchi Shinko ChemicalIndustrial)
*12:Noccelar NS-F (based on sulphenamide) (Ouchi Shinko ChemicalIndustrial)
＊13：Chemlock205(Lord)
In the rubber combination (weight part) of each prescription with Table VI-1; Other composition mixture in 16 liters of tangent type Banbury mixeies that will be except vulcanizing agent; Mix with vulcanizing agent through 8 inches mills then, then vulcanized rubber 20 minutes under 160 ℃ cure conditions.The result sees Table VI-1.Testing method is following.
100% modulus: according to JIS K6251 test (No. three dumb-bell shapes of JIS)
Breaking tenacity TB: according to JIS K6251 test (No. three dumb-bell shapes of JIS)
Elongation at break EB: according to JIS K6251 test (No. three dumb-bell shapes of JIS)
The persistence that runs flat test: preparation uses the prescription of comparative example and embodiment to be used for the center ring of resilient ring, and is assemblied in 16 * 6.5JJ wheel rim 205/55R16 type inside tires.This tire is assemblied in the right front wheel place of the passenger vehicle of 2.5 liter capacities, and air pressure is 0kPa, and goes along oval distance counterclockwise with the speed of 90km/h.Measurement is felt distance unusual and that stop to drive up to the driver.
The numeric indicia of Comparative Example V I-1 is an index 100.Numerical value is big more, and persistence is good more.
Conventional example has shown typical resilient ring prescription commonly used.Other embodiment estimates with the distance that runs flat based on the physical properties of compsn.Comparative Example V I-1 is the very few instance of vulcanizing agent consumption, and its rubber vulcanizate module is crossed low and the distance that runs flat is short.Example VI-1 is the instance of an amount of blended vulcanizing agent, and it has even is lower than the performance that runs flat under the conventional embodiment in modulus.Example VI-2 is the instance that sulphur and cyclic polysulfide use with suitable proportion together.The performance of the said rubber performance that improves and run flat improves.The ratio that Comparative Example V I-2 has shown sulphur and cyclic polysulfide is greater than 2 situation, and the ageing resistance of its rubber reduces and the performance that runs flat reduces.Example VI-3 has shown uses the situation based on the promotor of thiuram, its performance that runs flat to be able to improve.Example VI-4 has shown the situation that improves the promotor ratio based on the promotor of sulphenamide through using, and its performance that runs flat is further improved.Example VI-5 has shown sneaks into organic acid cobalt and alkyl phenol resin and makes said ring not need the direct and bonding instance of said shell of tackiness agent in the resilient ring rubber combination.
Example VII A-1～4 and Comparative Example V II-1
Following test is used for estimating the physical properties of vulcanizer of the present invention.
The prescription of rubber is seen (weight part) shown in the Table VII-1.
Table VII-1
The note of Table VII-1
*1：TSR20
*2: bromination butyl 2255 (Exxon Mobile Chemical)
＊3：Diablack?E(Mitsubishi?Chemical)
*4: zinc white #3 (Seido Chemical Industry)
*5: bead Triple Pressed Stearic Acid (Kao)
＊6：FR-120(Fujikosan)
＊7：Extract?No.4S(Showa?Shell?Oil)
*8:5% oil fills sulphur (Karuizawa Refinery)
*9: preparation example I-2 synthetic cyclic polysulfide
*10: preparation EXAMPLE III-2 synthetic cyclic polysulfide
*11：Noccelar?DM(Ouchi?Shinko?Chemical?Industrial)
＊12：Noccelar?TOT-N(Ouchi?Shinko?Chemical?Industrial)
＊13：Noccelar?NS-F(Ouchi?Shinko?Chemical?Industrial)
Mix rubber combination (weight part) through 8 inches mills, then vulcanized rubber 20 minutes under 160 ℃ cure conditions with each prescription shown in the Table VII-1.The result sees Table VII-1.Testing method is following.
300% modulus: according to JIS K6251 test (No. three dumbbells of JIS)
Breaking tenacity TB: according to JIS K6251 test (No. three dumbbells of JIS)
Elongation at break EB: according to JIS K6251 test (No. three dumbbells of JIS)
Impact brittleness temperature: according to JIS K6261 test, the temperature limit of brittleness of testing rubber.
It should be noted that Comparative Example V II-1 is the air retaining wall rubber compounding of conventional sulphur prescription, example VII A-1 is half the approximately cyclic polysulfide VII-1 alternate example, and the property retention rate after its elongation and the thermal ageing is able to improve.Example VII A-2 is for substituting the instance of sulphur with cyclic polysulfide VII-1, the performance after further improvement of its elongation and the thermal ageing is improved.Example VII A-3 is for using the instance of the cyclic polysulfide VII-2 with different skeletons, and its fracture physical properties is further improved.Example VII A-4 has shown uses the situation based on the vulcanization accelerator of thiuram, and its modulus and fracture property are improved.Example VII A-5 has shown uses the situation based on the vulcanization accelerator of sulphenamide, and its modulus and fracture property are improved.
Preparation example VII A I-1 (preparation of vulcanizing agent VIII-3)
With the sodium tetrasulfide aqueous solution of 100 gram water dilutions, 89.8 gram (0.15mol) 30wt%, splash into 25.9 gram (0.15mol) 1 at 90 ℃ in following two hours, two (2-chloroethoxy) methane of 2-, and other 3 hours of reaction under this temperature.After reaction finishes, clean this and contain water-insoluble, then under 100 ℃ in the pressure that reduces down drying obtained the cyclic polysulfide that 33.2g (productive rate 96%) has formula (I), wherein R=-CH in 2 hours
2CH
2OCH
2OCH
2CH
2-, x (on average)=4, n=1～5 (vulcanizing agent 3).The number-average molecular weight of the cyclic polysulfide of gained is 600.Its NMR data are following.
1H-NMR
*(δ: 2.9～3.3 (4H, the CH of chloroform-di)
2S), 3.7-4.0 (4H, CH
2O), 4.8 (2H, OCH
2O)
Example VII A I-1 to VIII-3 and Comparative Example V III-1
Mix rubber combination through 8 inches mills, under 170 ℃ of cure conditions, vulcanized 10 minutes then with each prescription (weight part) shown in the Table VIII-1.The result sees Table VIII-1.Testing method is following.
100% modulus: based on JIS K6251 test (No. three dumbbells of JIS, test speed is 500mm/min)
Breaking tenacity TB: based on JIS K6251 test (No. three dumbbells of JIS, test speed is 500mm/min)
Elongation at break EB: based on JIS K6251 test (No. three dumbbells of JIS, test speed is 500mm/min).
Table VIII-1
The note of Table VIII-1
＊1：RSS# 3
＊2：Mitsubishi?Chemical?Diablack?E
*3:Seido ChemicalIndustry zinc oxide # 3
*4:NOF Corporation bead Triple Pressed Stearic Acid
*5：Flexsys?Santoflex?PPD
*7：Rhodia?Manobond?C22.5
*8：Akzo?Nobel?Crystex?HS
*9: preparation EXAMPLE III-1 synthetic cyclic polysulfide
*10: preparation example I-2 synthetic cyclic polysulfide
*11: preparation example VII A I-1 synthetic cyclic polysulfide
＊12：Ouchi?Shinko?Chemical?Industrial?Noccelar?DZ-G
Comparative Example V III-1 is the instance of the belt mixture of routine.This instance is with the reference of the rubber combination of the present invention that judges.Example VII A I-1～VIII-3 shown with cyclic polysulfide (vulcanizing agent VIII-1～VIII-3) replaces the situation of sulphur, its 100% initial modulus with aging after physical properties be improved.
Standard implementation example IX-1
119.7g in 50g toluene (0.2mol) 30% sodium polysulphide (Na
2S
4) add 0.64g (1mol%) Tetrabutyl amonium bromide in the mixed solvent of the aqueous solution, and splash into the Dichloroethyl formal that 34.6g (0.2mol) is dissolved in 30g toluene in following 30 minutes at 90 ℃, reacted 5 hours.After the reaction, separate organic phase and under 90 ℃ in concentrated down 45.0g (productive rate=97.8%) the cyclic polysulfide IX-1 that obtains of the pressure that reduces.The cyclic polysulfide of gained is measured through GPC, and its number-average molecular weight is 570.
Example I X-1
1.98g in 500g toluene (0.02mol) 1,2-ethylene dichloride and 1197g (2mol) 30% sodium polysulphide (Na
2S
4) add 0.64g (1mol%) Tetrabutyl amonium bromide in the mixed solvent of the aqueous solution, continue 2 hours down at 50 ℃.Then, 311.0g (1.8mol) Dichloroethyl formal is dissolved in the 300g toluene, the temperature of reaction of mixture is risen to 90 ℃, it was splashed in 1 hour, and reacted 5 hours.After the reaction, separate organic phase and under 90 ℃ in concentrated down 405g (productive rate=96.9%) the cyclic polysulfide IX-2 that obtains of the pressure that reduces.The cyclic polysulfide of gained is measured through GPC, and its number-average molecular weight is 530.
Example I X-2
1.98g in 50g toluene (0.02mol) 1,2-ethylene dichloride and 119.7g (0.2mol) 30% sodium polysulphide (Na
2S
4) add 0.64g (1mol%) Tetrabutyl amonium bromide in the mixed solvent of the aqueous solution, continue 2 hours down at 50 ℃.Then, 31.1g (0.18mol) Dichloroethyl formal is dissolved in the 30g toluene, the temperature of reaction of mixture is risen to 90 ℃, it was splashed in 30 minutes, the single step reaction 5 hours of going forward side by side.After the reaction, separate organic phase and under 90 ℃ in concentrated down 43.8g (productive rate=98%) the cyclic polysulfide IX-3 that obtains of the pressure that reduces.The cyclic polysulfide of gained is measured through GPC, and its number-average molecular weight is 630.
Table I X-1
| ? | Viscosity (80 ℃) (Pas) |
| Cyclic polysulfide IX-1 | 272 |
| Cyclic polysulfide IX-2 | 70 |
| Cyclic polysulfide IX-3 | 8.2 |
The preparation of standard implementation example IX-2, example I X-3～IX-4 and comparative example IX-1 sample
Each prescription that shows with Table I X-2 will obtain master batch except vulcanization accelerator and the mixture in inner Banbury mixer of other composition the sulphur.In this master batch, sneak into vulcanization accelerator and sulphur to obtain rubber combination through mill.
Then, the rubber combination of gained in the mould of 15 * 15 * 0.2cm in 150 ℃ of sulfurations 30 minutes with preparation vulcanized rubber sheet, the physical properties through following testing method measurement vulcanized rubber subsequently.The result sees Table I X-2.
The testing method that rubber performance is estimated
100% and 300% modulus (Mpa): test according to JIS K6251
Breaking tenacity TB (Mpa): test according to JIS K6251
Elongation at break EB (%): test according to JIS K6251
Table I X-2
The note of Table I X-2
＊1：RSS# 3
*2：Tokai?Carbon?Seast?N
*3:Seido Chemical Industry zinc white # 3
*4:Kao bead Triple Pressed Stearic Acid
＊5：Ouchi?Shinko?Chemical?Industrial?Nocrac6C
*6：Ouchi?Shinko?Chemical?Industrial?Noccelar?NS-F
*7:Karuizawa Refinery oil fills sulphur
*8: see standard implementation example IX-1
*9: see example I X-1
*10: see example I X-2
According to the present invention; As stated, through the condensation reaction of two kinds of uses or more kinds of dihalide and metal polysulfide in rubber combination, when sneaking into vulcanizing agent; Can obtain having the rubber combination of excellent resistance to heat aging; And the viscosity of rubber combination can aggregative growth and can not be reduced sulfuration efficient, thereby it can be used for inflated wheel crown, band, pipe, travelling belt etc.
Industrial application
Rubber combination according to first aspect present invention; Except resistance to heat aging; It can also through make the have formula mean number of sulphur of cyclic polysulfide of (I) greater than 4 to 6, preferred about 4.5 to 5 suppresses heating, thereby described rubber combination for example goes for pneumatic tyre crown, belt, undertread, sidewall, body piles, bead filler rubber, tyre bead pad, air retaining wall, rubber hose, flexible pipe, travelling belt, rubber shock absorber, rubber roll, pneumatic type baffle plate, shoe plate, rubber packing, vibroshock, latex foam products, rubber window seal etc.
The aging front and back of rubber combination according to second aspect present invention have good fracture characteristics and low tan δ, thereby it is applicable to for example pneumatic tyre crown, belt, sidewall, body piles, undertread bead filler rubber, tyre bead pad etc.
Rubber combination according to third aspect present invention can improve adhesion property, breaking tenacity, adheres to persistence, weather resistance and control stability, thereby it is applicable to the for example crown or the base portion of airtyred tyre surface.
Rubber combination according to a forth aspect of the invention has high firmness, high tensile and elongation at break and good heat generation (tan δ), therefore is applicable to for example airtyred bead filler rubber.
Rubber combination according to a fifth aspect of the invention has the excellent in resistance fatigability (opposing crack growth) of the sidewall Reinforced Rubber needs of run flat tire.Thereby it for example can be used for bead filler rubber or the sidewall Reinforced Rubber inserted with the crescent shape xsect in the inside on the airtyred sidewall with the performance of running flat.
Rubber combination according to a sixth aspect of the invention has excellent run flat performance and resistant to thermal aging performance, thereby can be used for the resilient ring of run flat tire center ring.
Rubber combination according to a seventh aspect of the invention has excellent fracture property and low-temperature performance; Thereby it for example is suitable for, and carries out plate, motor car engine bearing, rubber axle sleeve, flexible pipe, marine hose, curing bag, cable, vibroshock, sound damper etc. in the inner tube of a tyre of airtyred air retaining wall, crown, sidewall, tubed tyre, pneumatic type baffle plate, rubber shock absorber, multilayer rubber vibration isolator, winter.
Rubber combination according to eighth aspect present invention has higher rigidity than conventional mixture, and resistance to heat aging is excellent, thereby it uses the belt mixture applicable to for example pneumatic tyre.
Claims (4)
1. rubber combination that is used for ice and snow road, but sulphur vulcanized rubber (A) and 0.1～10 weight part of 100 weight parts formula (I) cyclic polysulfide (B) contained as vulcanizing agent:
Wherein R is replacement or unsubstituted C in formula (I)
2-C
20Alkylidene group, n are 1～20 integer, x be average 2～6 number and
But wherein said sulphur vulcanized rubber (A) but be the sulphur vulcanized rubber of mainly forming by tree elastomer and/or polybutadiene rubber; Mixed volume with cyclic polysulfide of formula (I) is 0.1～10 weight part; The weight-average molecular weight that converts the PS meter into that wherein said compsn also contains 10～100 weight parts is 100; 000 or lower tenderizer
The dihalide of said cyclic polysulfide through having formula X-R-X with have formula M-S
xAs two-phase system reaction and reaction makes, in X-R-X, X representes halogen atom respectively to the alkali metals polysulfide of-M in the non-conforming mixed solvent of hydrophilic solvent or hydrophilic solvent, and R representes to replace or unsubstituted C
2-C
20Alkylidene group is at M-S
xAmong-the M, M is a basic metal, and x is 2～6 integer,
Wherein said compsn also contains the thermoplastic resin or the heat-swellable graphite of the heat-swellable of 1～15 weight part.
2. according to the rubber combination of claim 1, but wherein said sulphur vulcanized rubber (A) has-100 ℃～-50 ℃ average glass transition temperature (Tg).
3. according to the rubber combination of claim 1 or 2, but wherein based on the sulphur vulcanized rubber (A) of 100 weight parts, said compsn also contains silicon-dioxide and/or the nitrogen specific surface area (N that total amount is 40～100 weight parts
2SA) be 85m
2/ g is extremely less than 150m
2The carbon black of/g.
4. according to the rubber combination of claim 1, wherein said cyclic polysulfide (B) with formula (I) is through at least two types of dihalide with formula (II): X-(CH
2)
m-X (II) and the metal polysulfide with formula (III): M-S
xIn obtaining existing or do not exist to react phase-transfer catalyst under under 50～150 ℃, n R representes unsubstituted C to-M (III) independently in formula (I) in the non-conforming mixed solvent of hydrophilic solvent or hydrophilic solvent and lipophilic solvent
2-C
20Alkylidene group, X representes halogen atom in formula (II), m is 2～20 integer, M is the metal of periodic table of elements IA family in formula (III), x for average greater than 3 to the number that is not more than 6.
Applications Claiming Priority (20)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003353974 | 2003-10-14 | ||
| JP353974/2003 | 2003-10-14 | ||
| JP2003364613 | 2003-10-24 | ||
| JP364613/2003 | 2003-10-24 | ||
| JP2003383849 | 2003-11-13 | ||
| JP2003383808 | 2003-11-13 | ||
| JP383808/2003 | 2003-11-13 | ||
| JP383943/2003 | 2003-11-13 | ||
| JP2003383943 | 2003-11-13 | ||
| JP383849/2003 | 2003-11-13 | ||
| JP385220/2003 | 2003-11-14 | ||
| JP2003385220 | 2003-11-14 | ||
| JP386800/2003 | 2003-11-17 | ||
| JP2003386800 | 2003-11-17 | ||
| JP2003388197 | 2003-11-18 | ||
| JP388197/2003 | 2003-11-18 | ||
| JP2003390979 | 2003-11-20 | ||
| JP390979/2003 | 2003-11-20 | ||
| JP2003397146 | 2003-11-27 | ||
| JP397146/2003 | 2003-11-27 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800070723A Division CN1761709A (en) | 2003-10-14 | 2004-10-13 | Rubber composition containing cyclic polysulfide as vulcanizer and pneumatic tire made therefrom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101423628A CN101423628A (en) | 2009-05-06 |
| CN101423628B true CN101423628B (en) | 2012-01-11 |
Family
ID=36707330
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102135563A Expired - Fee Related CN101423628B (en) | 2003-10-14 | 2004-10-13 | Rubber composition containing cyclic polysulfide as vulcanizer |
| CNA2004800070723A Pending CN1761709A (en) | 2003-10-14 | 2004-10-13 | Rubber composition containing cyclic polysulfide as vulcanizer and pneumatic tire made therefrom |
| CNA2008102135578A Pending CN101423630A (en) | 2003-10-14 | 2004-10-13 | Rubber composition containing cyclic polysulfide as vulcanizer and pneumatic tire made therefrom |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800070723A Pending CN1761709A (en) | 2003-10-14 | 2004-10-13 | Rubber composition containing cyclic polysulfide as vulcanizer and pneumatic tire made therefrom |
| CNA2008102135578A Pending CN101423630A (en) | 2003-10-14 | 2004-10-13 | Rubber composition containing cyclic polysulfide as vulcanizer and pneumatic tire made therefrom |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN101423628B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101796124B (en) * | 2007-09-05 | 2013-04-10 | 住友橡胶工业株式会社 | Rubber composition for studless tire and studless tire utilizing the same |
| JP4915467B2 (en) * | 2010-06-04 | 2012-04-11 | 横浜ゴム株式会社 | Rubber composition for tire |
| US9809899B2 (en) * | 2014-08-07 | 2017-11-07 | Macdermid Acumen, Inc. | Treatment for electroplating racks to avoid rack metallization |
| CN108136826B (en) * | 2015-09-25 | 2021-01-26 | 米其林集团总公司 | High strength rubber composition comprising aromatic polyphenol derivatives |
| US10774199B2 (en) | 2015-12-08 | 2020-09-15 | Sumitomo Seika Chemicals Co., Ltd. | Additive for rubber |
| CN105542235A (en) * | 2015-12-17 | 2016-05-04 | 山东永泰集团有限公司 | Radial tire tread base rubber of wheeled loader and preparation method thereof |
| JP6724377B2 (en) * | 2016-01-19 | 2020-07-15 | 横浜ゴム株式会社 | Pneumatic tire |
| FR3058729A1 (en) * | 2016-11-17 | 2018-05-18 | Compagnie Generale Des Etablissements Michelin | PNEUMATIC COMPRISING A TREAD COMPRISING A THERMOPLASTIC ELASTOMER AND A SULFUR-BASED SULFURING SYSTEM |
| EP3640291A4 (en) * | 2017-06-16 | 2021-03-03 | Bridgestone Corporation | VULCANIZED RUBBER, TIRE AND SELF-SUPPORTING TIRE |
| EP3703956B1 (en) * | 2017-10-30 | 2021-12-08 | Compagnie Générale des Etablissements Michelin | Tire with innerlayer based on at least an isoprene elastomer, reinforcing resin and metallic salt |
| CN110358145B (en) * | 2019-07-09 | 2021-02-09 | 江阴市三良橡塑新材料有限公司 | Cobalt salt adhesion promoter mainly based on cobalt palmitate and preparation method thereof |
| JP7543017B2 (en) * | 2020-07-30 | 2024-09-02 | 住友理工株式会社 | Rubber composition for coating plated wire reinforcing layer and high pressure hose using same |
| CN114196078B (en) * | 2021-12-29 | 2023-03-07 | 太仓市金锚新材料科技有限公司 | Rubber fireproof sealing sleeve and preparation method thereof |
| CN115947881B (en) * | 2023-03-15 | 2023-05-30 | 山东润科化工股份有限公司 | Synthesis method of brominated ethylene propylene diene monomer |
| CN118580584A (en) * | 2024-05-31 | 2024-09-03 | 浙江佳洁塑胶有限公司 | Preparation method of rubber composition bathroom anti-slip mat |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5851321A (en) * | 1995-01-13 | 1998-12-22 | The Yokohama Rubber Co., Ltd. | Pneumatic tire including cap tread portion |
| US20020107338A1 (en) * | 2000-12-08 | 2002-08-08 | The Yokohama Rubber Co., Ltd | Method for production of cyclic polysulfide compound and rubber composition containing the same |
-
2004
- 2004-10-13 CN CN2008102135563A patent/CN101423628B/en not_active Expired - Fee Related
- 2004-10-13 CN CNA2004800070723A patent/CN1761709A/en active Pending
- 2004-10-13 CN CNA2008102135578A patent/CN101423630A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5851321A (en) * | 1995-01-13 | 1998-12-22 | The Yokohama Rubber Co., Ltd. | Pneumatic tire including cap tread portion |
| US20020107338A1 (en) * | 2000-12-08 | 2002-08-08 | The Yokohama Rubber Co., Ltd | Method for production of cyclic polysulfide compound and rubber composition containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1761709A (en) | 2006-04-19 |
| CN101423630A (en) | 2009-05-06 |
| CN101423628A (en) | 2009-05-06 |
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Address after: Kanagawa Prefecture, Japan Patentee after: THE YOKOHAMA RUBBER Co.,Ltd. Country or region after: Japan Address before: Tokyo, Japan Patentee before: THE YOKOHAMA RUBBER Co.,Ltd. Country or region before: Japan |
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Granted publication date: 20120111 |