JP2008291147A - Rubber composition for tire - Google Patents
Rubber composition for tire Download PDFInfo
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- JP2008291147A JP2008291147A JP2007139377A JP2007139377A JP2008291147A JP 2008291147 A JP2008291147 A JP 2008291147A JP 2007139377 A JP2007139377 A JP 2007139377A JP 2007139377 A JP2007139377 A JP 2007139377A JP 2008291147 A JP2008291147 A JP 2008291147A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 42
- 239000005060 rubber Substances 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 28
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 10
- 150000001993 dienes Chemical class 0.000 claims abstract description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 4
- 229920003244 diene elastomer Polymers 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 12
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000005299 abrasion Methods 0.000 abstract description 4
- 239000006229 carbon black Substances 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 5
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229960000834 vinyl ether Drugs 0.000 description 3
- -1 vinyl ether compound Chemical class 0.000 description 3
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000012669 compression test Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- DQNSRQYYCSXZDF-UHFFFAOYSA-N 1,4-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1CCC(COC=C)CC1 DQNSRQYYCSXZDF-UHFFFAOYSA-N 0.000 description 1
- DLYDGDHLODCOQF-UHFFFAOYSA-N 1-ethenoxyethenylcyclohexane Chemical compound C=COC(=C)C1CCCCC1 DLYDGDHLODCOQF-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明はタイヤ用ゴム組成物に関し、更に詳しくはジエン系ゴム及びシリカ、カーボンブラック等の充填剤を含み、耐フラットスポット性能及び耐摩耗性能に優れたタイヤ用ゴム組成物並びにそれを用いた空気入りタイヤに関する。 TECHNICAL FIELD The present invention relates to a rubber composition for tires, and more particularly, a rubber composition for tires which contains a diene rubber and a filler such as silica and carbon black and has excellent flat spot resistance and wear resistance, and air using the same. Related to tires.
近年、空気入りタイヤの補強性充填剤として、シリカを用いることによって、燃費、ウェット性能、転がり抵抗などに優れたゴム組成物が実用化されている。しかしながら、シリカはゴム組成物中における分散性に難点があり、そのため強度や耐摩耗性に問題がある。
かかる問題を解決すべく種々の提案がなされており、例えば特許文献１にはゴムの末端にシリカと相互作用する変性基を修飾することにより、シリカとの相溶性を高め、シリカの分散性を向上させる提案がなされている。
しかしながら、ゴム組成物中のシリカの分散性を高めることは依然として望まれている。
In recent years, a rubber composition excellent in fuel consumption, wet performance, rolling resistance, and the like has been put into practical use by using silica as a reinforcing filler for a pneumatic tire. However, silica has a difficulty in dispersibility in the rubber composition, and therefore has a problem in strength and wear resistance.
Various proposals have been made to solve such problems. For example, Patent Document 1 modifies a modifying group that interacts with silica at the end of rubber, thereby improving compatibility with silica and increasing dispersibility of silica. Proposals for improvement have been made.
However, it remains desirable to increase the dispersibility of silica in rubber compositions.
従って、本発明の目的は、ジエン系ゴム及びシリカを含む、補強性充填剤を含有するゴム組成物の耐フラットスポット性能及び耐摩耗性能を改良することにある。 Accordingly, an object of the present invention is to improve the flat spot resistance and wear resistance of a rubber composition containing a reinforcing filler, including a diene rubber and silica.
本発明に従えば、ジエン系ゴム１００重量部、シリカを含む補強性充填剤６０〜１２０重量部及びシリカ重量に対して２〜１５重量％のシランカップリング剤を含んでなり、前記ジエン系ゴムが下記式（Ｉ）〜（III）から選ばれる少なくとも１種のジエン系ゴム１０重量部以上を含むタイヤ用ゴム組成物。
本発明によれば、ジエン系ゴム及びシリカ、カーボンブラック等の充填剤を含有するゴム組成物に特殊なジエン系ゴムを配合することにより、従来のゴム組成物よりシリカ分散性に優れ、耐フラットスポット性能及び耐摩耗性能に優れたタイヤ用ゴム組成物を得ることができる。 According to the present invention, by blending a special diene rubber with a diene rubber and a rubber composition containing a filler such as silica and carbon black, the silica dispersibility is superior to that of a conventional rubber composition, and flat resistance is improved. A rubber composition for tires excellent in spot performance and wear resistance performance can be obtained.
本発明者らは、前記課題を解決すべく研究を進めた結果、前記した特殊な変性ジエン系ゴム（Ｉ）、（II）又は（III）をゴム組成物に配合することにより、従来のゴム組成物よりシリカ分散性に優れ、特に耐フラットスポット性能及び耐摩耗性能に優れたタイヤ用ゴム組成物が得られることを見出した。 As a result of researches to solve the above-mentioned problems, the present inventors have blended the above-mentioned special modified diene rubber (I), (II) or (III) into a rubber composition, thereby producing a conventional rubber. It has been found that a rubber composition for a tire is obtained which is superior in silica dispersibility than the composition, and particularly excellent in flat spot resistance and abrasion resistance.
即ち、本発明によれば、例えば天然ゴム（ＮＲ）、ポリイソプレンゴム（ＩＲ）、ポリブタジエンゴム（ＢＲ）、スチレンブタジエン共重合体ゴム（ＳＢＲ）、ブチルゴム（ＩＩＲ）、エポキシ化天然ゴムなどのジエン系ゴムが１００重量部に対し、シリカを含む補強性充填剤６０〜１２０重量部、好ましくは６０〜１００重量部及びシリカ重量に対して２〜１５重量％、好ましくは４〜１２重量％のシランカップリング剤などを配合したゴム組成物であって、前記ジエン系ゴムに前記式（Ｉ）〜（III）から選ばれる少なくとも１種の変性ジエン系ゴムを１０重量部以上配合する。 That is, according to the present invention, dienes such as natural rubber (NR), polyisoprene rubber (IR), polybutadiene rubber (BR), styrene butadiene copolymer rubber (SBR), butyl rubber (IIR), epoxidized natural rubber, etc. 60 to 120 parts by weight, preferably 60 to 100 parts by weight of a reinforcing filler containing silica, and 2 to 15% by weight, preferably 4 to 12% by weight, of silica based on 100 parts by weight of the rubber A rubber composition containing a coupling agent or the like, wherein 10 parts by weight or more of at least one modified diene rubber selected from the formulas (I) to (III) is added to the diene rubber.
前記式（Ｉ）〜（III）において、Ｒ１〜Ｒ６はそれぞれ独立にクロマトグラフィー法で測定した重量平均分子量（Ｍｗ）が１０００以上の、好ましくは１００００以上のジエン系重合体、好ましくはＳＢＲ、ＢＲ、ＩＲから構成される部分を示し、またＲは炭素数１〜８、好ましくは１〜２の最も好ましくは炭素数２のアルキル基又は水素を示す。この変性ジエン系ゴムの配合量が少ないと、所望の効果が無いので好ましくない。 In the formulas (I) to (III), R 1 to R 6 are each a diene polymer having a weight average molecular weight (Mw) measured by a chromatography method of 1000 or more, preferably 10,000 or more, preferably SBR. , BR and IR, and R represents an alkyl group having 1 to 8 carbon atoms, preferably 1 to 2 carbon atoms, and most preferably 2 having 2 carbon atoms. If the amount of the modified diene rubber is too small, there is no desired effect, which is not preferable.
補強性充填剤の配合量が６０重量部未満では、補強性が低く、タイヤ用として実用的でなくなるので好ましくない。１２０重量部を超えると混合性が悪化し、ゴム組成物の物性が低下するので好ましくない。前記補強性充填剤のうちシリカ含量は、５０〜１００重量部であるのが好ましく、更に好ましくは、５５〜１００重量部、更に一層好ましくは、６０〜９５重量部であるのが好ましく、７０〜９５重量部であるのが更に好ましい。シリカの配合量は基本的には多ければ多いほど良いが、多すぎるとゴムの破断強度を逆に低くしてしまい、耐摩耗性が悪化する傾向にあるので好ましくない。 When the blending amount of the reinforcing filler is less than 60 parts by weight, the reinforcing property is low and it is not practical for tires, which is not preferable. If it exceeds 120 parts by weight, the mixing property is deteriorated and the physical properties of the rubber composition are lowered, which is not preferable. The silica content in the reinforcing filler is preferably 50 to 100 parts by weight, more preferably 55 to 100 parts by weight, still more preferably 60 to 95 parts by weight, and preferably 70 to 95 parts by weight. More preferred is 95 parts by weight. Basically, the larger the amount of silica, the better. However, if the amount is too large, the breaking strength of the rubber is lowered, and the wear resistance tends to deteriorate.
シランカップリング剤の量はシリカに対し、２重量％未満ではシリカ凝集を十分抑えることができず、ゴム組成物の破断強度を落としてしまい好ましくなく、逆に１５重量％を超えると混合中にヤケが発生し加工性が悪化するので好ましくない。 If the amount of the silane coupling agent is less than 2% by weight with respect to silica, silica aggregation cannot be sufficiently suppressed, and the breaking strength of the rubber composition is lowered. Discoloration occurs and processability deteriorates, which is not preferable.
前記変性ジエン系ゴムの配合量がジエン系ゴム１００重量部中、１０重量部未満では所望の改良効果が得にくい。好ましくは１５重量部以上、更に好ましくは２０重量部以上で、上限は特にないが、コストと物性とのバランスを考慮すれば３０重量部であるのが好ましい。 If the amount of the modified diene rubber is less than 10 parts by weight in 100 parts by weight of the diene rubber, it is difficult to obtain a desired improvement effect. Preferably it is 15 parts by weight or more, more preferably 20 parts by weight or more, and there is no particular upper limit, but it is preferably 30 parts by weight considering the balance between cost and physical properties.
前記式（Ｉ）〜（III）において、Ｒ１〜Ｒ６はそれぞれ同じであっても異なっても良く、Ｒ１〜Ｒ６はそれぞれＭｗが７５，０００〜５００，０００のスチレンブタジエン共重合体であるのが好ましく、１，４結合が５〜２０％，１，２結合が４０〜７２％、スチレン量が１２〜４５重量％であり、示差熱分析計（ＤＳＣ）で測定したガラス転移温度が−４５℃〜−１０℃であるのが好ましい。変性ジエン系ゴムの重量平均分子量が小さいと変性ジエン系ゴムのせん断力が小さく好ましくない。なお、変性ジエン系ゴムの重量平均分子量が高すぎると原料ゴムの粘度が高く、混合性が悪化する。変性ＳＢＲの重量平均分子量は、好ましくは１００，０００〜５００，０００、更に好ましくは、１５０，０００〜５００，０００である。スチレン量が１２重量％未満ではポリマーの強度が低くなって、せん断力が小さくなるおそれがあり、逆に４５重量％を超えると発熱が高くなりすぎてしまいコンプレッションセット値が悪化するおそれがあるので好ましくない。ガラス転移温度が−４５℃未満ではグリップ力が低くなるおそれがあり、逆に−１０℃より高いと転がり抵抗が悪化するおそれがある。 In the formulas (I) to (III), R 1 to R 6 may be the same or different, and R 1 to R 6 are styrene butadiene copolymers each having Mw of 75,000 to 500,000. The glass transition temperature is preferably 5 to 20% for 1,4 bonds, 40 to 72% for 1,2 bonds, 12 to 45% by weight of styrene, and measured by a differential thermal analyzer (DSC). Is preferably −45 ° C. to −10 ° C. If the weight average molecular weight of the modified diene rubber is small, the shear force of the modified diene rubber is small, which is not preferable. If the weight average molecular weight of the modified diene rubber is too high, the viscosity of the raw rubber is high and the mixing property is deteriorated. The weight average molecular weight of the modified SBR is preferably 100,000 to 500,000, more preferably 150,000 to 500,000. If the amount of styrene is less than 12% by weight, the strength of the polymer may be reduced and the shearing force may be reduced. Conversely, if the amount exceeds 45% by weight, the heat generation becomes too high and the compression set value may deteriorate. It is not preferable. If the glass transition temperature is less than −45 ° C., the gripping power may be lowered. Conversely, if the glass transition temperature is higher than −10 ° C., rolling resistance may be deteriorated.
前記式（Ｉ）〜（III）の変性ジエン系ゴムは一般的には以下のようにして製造することができる。炭化水素溶媒中にて、スチレン、ブタジエンをモノマーとして、有機リチウム化合物及びエーテルやアミン等の極性化合物を触媒として、リチウムアニオン重合を行う。反応停止剤として、予め合成したビニルエーテル化合物を適量投入し、重合完了後、回収、洗浄、乾燥することにより得ることができる。 The modified diene rubbers of the above formulas (I) to (III) can generally be produced as follows. Lithium anion polymerization is carried out in a hydrocarbon solvent using styrene and butadiene as monomers and using an organic lithium compound and a polar compound such as ether or amine as a catalyst. As a reaction terminator, an appropriate amount of a pre-synthesized vinyl ether compound is added, and it can be obtained by collecting, washing and drying after completion of polymerization.
本発明に係るゴム組成物には、前記した成分に加えて、シリカやカーボンブラック以外他の補強剤（フィラー）、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、可塑剤などのタイヤ用、その他のゴム組成物用に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量は本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 In addition to the components described above, the rubber composition according to the present invention includes other reinforcing agents (fillers) other than silica and carbon black, vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, anti-aging agents, Various additives generally blended for tires such as plasticizers and other rubber compositions can be blended, and such additives are kneaded into a composition by a general method to be vulcanized or Can be used to crosslink. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used.
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
合成例
合成例に用いた試薬は以下の通りである。
・シクロヘキサン、スチレンは関東化学（株）製のものを、モレキュラーシーブス４Ａにより脱水し、窒素バブリングして用いた。
・ブタジエンは、新日本石油化学（株）製、純度９９．３％のブタジエンを前記モレキュラーシーブス４Ａにより脱水して用いた。
・ｎ−ブチルリチウムは、関東化学（株）製のｎ−ヘキサン溶液（１．５８mol／Ｌ）のものを用いた。
・１，１，４，４−テトラメチルエチレンジアミン（ＴＭＥＤＡ）は、前記モレキュラーシーブス４Ａにより脱水し、窒素バブリングして用いた。
・トルエンは関東化学（株）製の脱水グレード品をそのまま用いた。
・メルカプトシランは東レダウコーニングシリコーン（株）製Ｚ６９１１をそのまま用いた。
・シクロヘキシルビニルエーテルは日本カーバイド工業（株）製ＣＨＶＥをそのまま用いた。
Synthesis Examples The reagents used in the synthesis examples are as follows.
Cyclohexane and styrene were manufactured by Kanto Chemical Co., Ltd., dehydrated with molecular sieves 4A, and used after bubbling with nitrogen.
-Butadiene was manufactured by Shin Nippon Petrochemical Co., Ltd., and butadiene having a purity of 99.3% was dehydrated with the molecular sieves 4A.
-The n-butyllithium used was an n-hexane solution (1.58 mol / L) manufactured by Kanto Chemical Co., Inc.
-1,1,4,4-tetramethylethylenediamine (TMEDA) was dehydrated with the molecular sieve 4A and used after bubbling with nitrogen.
-Toluene used the dehydration grade product made from Kanto Chemical Co., Ltd. as it was.
-Z6911 manufactured by Toray Dow Corning Silicone Co., Ltd. was used as the mercaptosilane.
-As cyclohexyl vinyl ether, CHVE manufactured by Nippon Carbide Industry Co., Ltd. was used as it was.
合成例１：ＳＢＲ−ＭＳ０１の合成
ブロック化メルカプトシラン（α）の合成法
メルカプトシラン１１９．２ｇ（０．５mol）とシクロヘキシルビニルエーテル６３．１ｇ（０．５mol）を、リン酸エステル触媒存在下、室温で１時間反応させ、メルカプト基をビニルエーテルによりブロックしたブロック化メルカプトシラン（α）を得た。
Synthesis Example 1: Synthesis of SBR-MS01
Synthesis Method of Blocked Mercaptosilane (α) Mercaptosilane ( 119.2 g, 0.5 mol) and cyclohexyl vinyl ether (63.1 g, 0.5 mol) were reacted in the presence of a phosphate ester catalyst at room temperature for 1 hour to form a mercapto group. A blocked mercaptosilane (α) blocked with vinyl ether was obtained.
ＳＢＲ−ＭＳ０１の合成
窒素置換された内容量１０Ｌのオートクレーブ反応器に、シクロヘキサン４５３３ｇ、スチレン１６７．４ｇ（１．６０７mol）、ブタジエン６３４．４ｇ（１１．７３mol）及びＴＭＥＤＡ１．０３０mL（７．１９６mmol）を仕込み、攪拌を開始した。反応容器内の内容物の温度を５０℃にした後、ｎ−ブチルリチウム３．８８３mL（６．９１５mmol）を添加した。重合転化率が１００％に到達した後、ブロック化メルカプトシラン（α）を１．４２８ｇ（３．９２０mmol）を添加し、１時間攪拌した。更に、メタノール０．５mLを添加して３０分間攪拌した。得られたポリマー溶液に老化防止剤（イルガノックス１５２０）を少量添加し、減圧濃縮して溶媒を取り除いた。メタノール中でポリマーを凝固、洗浄した後に、乾燥することにより固形状のポリマーを得た。1Ｈ−ＮＭＲの測定から、得られたポリマーのミクロ構造は、スチレン量２２．０wt％、ビニル量６４．３％であった。ＧＰＣ（ポリスチレン換算、溶出液：ＴＨＦ）による測定から、分子量は、Ｍｎ３４７０００，Ｍｗ４７１０００，Ｍｗ／Ｍｎ１．３６であった。
Synthesis of SBR-MS01 Into an autoclave reactor having a nitrogen content of 10 L, 4533 g of cyclohexane, 167.4 g (1.607 mol) of styrene, 634.4 g (11.73 mol) of butadiene and 1.030 mL (7.196 mmol) of TMEDA were added. Charge and start stirring. After the temperature of the contents in the reaction vessel was 50 ° C., 3.883 mL (6.915 mmol) of n-butyllithium was added. After the polymerization conversion rate reached 100%, 1.428 g (3.920 mmol) of blocked mercaptosilane (α) was added and stirred for 1 hour. Further, 0.5 mL of methanol was added and stirred for 30 minutes. A small amount of an antioxidant (Irganox 1520) was added to the resulting polymer solution, and the solvent was removed by concentration under reduced pressure. The polymer was coagulated and washed in methanol, and then dried to obtain a solid polymer. From the measurement of 1 H-NMR, the microstructure of the polymer obtained was 22.0 wt% styrene and 64.3% vinyl. From the measurement by GPC (polystyrene conversion, eluent: THF), the molecular weight was Mn347000, Mw471000, Mw / Mn1.36.
合成例２Synthesis example 2
ブロック化メルカプトシラン（β）の合成法
メルカプトシラン ２３８．４ｇ（１．０mol）とシクロヘキシルジビニルエーテル９８．２ｇ（０．５mol）をリン酸エステル触媒下、室温で、１時間反応させ、メルカプト基をビニルエーテルによりブロックしたブロック化メルカプトシラン（β）を得た。
Synthesis Method of Blocked Mercaptosilane (β) Mercaptosilane ( 238.4 g, 1.0 mol) and cyclohexyl divinyl ether (98.2 g, 0.5 mol) were reacted at room temperature for 1 hour in the presence of a phosphate ester catalyst to form a mercapto group. A blocked mercaptosilane (β) blocked with vinyl ether was obtained.
ＳＢＲ−ＭＳ０２の合成
窒素置換された内容量１０Ｌのオートクレーブ反応器に、シクロヘキサン４５３３ｇ、スチレン１６７．４ｇ（１．６０７mol）、ブタジエン６３４．４ｇ（１１．７３mol）及びＴＭＥＤＡ１．０３０mL（７．１９６mmol）を仕込み、攪拌を開始した。反応容器内の内容物の温度を５０℃にした後、ｎ−ブチルリチウム３．８８３mL（６．９１５mmol）を添加した。重合転化率が１００％に到達した後、ブロック化メルカプトシラン（β）を１．０５５ｇ（１．５６８mmol）を添加し、１時間攪拌した。更に、メタノール０．５mLを添加して３０分間攪拌した。得られたポリマー溶液に老化防止剤（イルガノックス１５２０）を少量添加し、減圧濃縮して溶媒を取り除いた。メタノール中でポリマーを凝固、洗浄した後に、乾燥することにより固形状のポリマーを得た。1Ｈ−ＮＭＲの測定から、得られたポリマーのミクロ構造は、スチレン量２３．２wt％、ビニル量６５．７％であった。ＧＰＣ（ポリスチレン換算、溶出液：ＴＨＦ）による測定から、分子量は、Ｍｎ３８９０００，Ｍｗ５１３０００，Ｍｗ／Ｍｎ１．３２であった。
Synthesis of SBR-MS02 Into an autoclave reactor with a nitrogen content of 10 L, 4533 g of cyclohexane, 167.4 g (1.607 mol) of styrene, 634.4 g (11.73 mol) of butadiene and 1.030 mL (7.196 mmol) of TMEDA were added. Charge and start stirring. After the temperature of the contents in the reaction vessel was 50 ° C., 3.883 mL (6.915 mmol) of n-butyllithium was added. After the polymerization conversion rate reached 100%, 1.055 g (1.568 mmol) of blocked mercaptosilane (β) was added and stirred for 1 hour. Further, 0.5 mL of methanol was added and stirred for 30 minutes. A small amount of an antioxidant (Irganox 1520) was added to the resulting polymer solution, and the solvent was removed by concentration under reduced pressure. The polymer was coagulated and washed in methanol, and then dried to obtain a solid polymer. From the measurement of 1 H-NMR, the microstructure of the obtained polymer had a styrene content of 23.2 wt% and a vinyl content of 65.7%. From the measurement by GPC (polystyrene conversion, eluent: THF), the molecular weight was Mn389000, Mw513000, Mw / Mn1.32.
実施例１〜４及び比較例１〜２
サンプルの調製
表Ｉに示す配合において、加硫促進剤と硫黄を除く成分を１．８リットルの密閉型ミキサーで６分間混練し、１５０℃に達したときに放出してマスターバッチを得た。このマスターバッチに加硫促進剤と硫黄をオープンロールで混練し、ゴム組成物を得た。次に得られたゴム組成物を１５×１５×０．２cmの金型及びコンプレッション試験用金型（厚さ１２．７mm、直径２９．０mmの円柱状）、ランボーン摩耗用金型（直径６３．５mm、厚さ５mmの円板状）中で１６０℃で２５分間加硫して加硫ゴムシートを調製し、以下に示す試験法で加硫ゴムの物性を測定した。結果は、実施例１では比較例１の値を１００として、実施例２〜４では比較例２の値を１００として、それぞれ、指数表示した。
Examples 1-4 and Comparative Examples 1-2
Sample preparation In the formulation shown in Table I, the components other than the vulcanization accelerator and sulfur were kneaded for 6 minutes in a 1.8 liter closed mixer and released when the temperature reached 150 ° C to obtain a master batch. A vulcanization accelerator and sulfur were kneaded with this masterbatch with an open roll to obtain a rubber composition. Next, the rubber composition thus obtained was molded into a 15 × 15 × 0.2 cm mold and a compression test mold (thickness 12.7 mm, a cylindrical shape with a diameter of 29.0 mm), a Lambourn wear mold (diameter 63. A vulcanized rubber sheet was prepared by vulcanization at 160 ° C. for 25 minutes in a disk shape having a thickness of 5 mm and a thickness of 5 mm, and the physical properties of the vulcanized rubber were measured by the following test methods. The results are shown as indices in Example 1 with the value of Comparative Example 1 as 100 and in Examples 2 to 4 with the value of Comparative Example 2 as 100.
ゴム物性評価試験法
コンプレッション試験：ＪＩＳ Ｋ６２６２−１９９３に従って、７０℃×２２時間、初期歪２５％の条件で測定した。
ｔａｎδ（６０℃）：（株）東洋精機製作所製、粘弾性スペクトロメータを用いて、初期静歪１０％、動歪２％、周波数２０Ｈｚ、雰囲気温度６０℃で測定した。
Ｅ’（６０℃）：上記条件にて、貯蔵弾性率Ｅ’を測定した。
耐摩耗性：ランボーン摩耗試験機（岩本製作所（株）製）を使して、荷重５kgスリップ率２５％の条件にて測定し、試料の摩耗量を計測した。数字が大きいもの程、優れることを示す。
Rubber physical property evaluation test method Compression test: Measured in accordance with JIS K6262-1993 under conditions of 70C x 22 hours and initial strain of 25%.
tan δ (60 ° C.): Measured at an initial static strain of 10%, dynamic strain of 2%, frequency of 20 Hz, and ambient temperature of 60 ° C. using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho.
E ′ (60 ° C.): The storage elastic modulus E ′ was measured under the above conditions.
Abrasion resistance: Using a Lambourn abrasion tester (manufactured by Iwamoto Seisakusho Co., Ltd.), the load was measured under the condition of a 5 kg slip rate of 25%, and the amount of wear of the sample was measured. The larger the number, the better.
表Ｉ脚注
＊１：日本ゼオン（株）製ＮＳ１１６（ＮＭＰ（Ｎ−メチルピロリドン）末端変性ＳＢＲ）
＊２：メルカプトシリル変性ＳＢＲＭＳ０１（合成例１）
＊３：メルカプトシリル変性ＳＢＲＭＳ０２（合成例２）
＊４：日本ゼオン（株）製Ｎｉｐｏｌ１７２１（３７．５重量部油展）
＊５：日本ゼオン（株）製ＮｉｐｏｌＢＲ１２２０
＊６：Ｒｈｏｄｉａ製Ｚｅｏｓｉｌ１１６５ＭＰ
＊７：東レ・ダウコーニングシリコーン社製Ｚ−６９１１
＊８：東海カーボン（株）製Ｎ２３４級 シーストＭ
＊９：正同化学（株）製酸化亜鉛３種
＊１０：日本油脂工業（株）製ビーズステアリン酸
＊１１：フレキシス社製ＳＡＮＴＯＦＬＥＸ ６ＰＰＤ
＊１２：大内新興化学工業（株）製サンノック
＊１３：（株）ジャパンエナジー製プロセスＸ−１４０
＊１４：細井化学工業（株）製油処理硫黄
＊１５：大内新興化学工業（株）製ＣＺ−Ｇ
＊１６：大内新興化学工業（株）製Ｄ−Ｇ
Table I footnote * 1: NS116 (NMP (N-methylpyrrolidone) terminal-modified SBR) manufactured by Nippon Zeon Co., Ltd.
* 2: Mercaptosilyl-modified SBRMS01 (Synthesis Example 1)
* 3: Mercaptosilyl-modified SBRMS02 (Synthesis Example 2)
* 4: Nipol 1721 (37.5 parts by weight oil exhibition) manufactured by Nippon Zeon Co., Ltd.
* 5: Nipol BR1220 manufactured by Nippon Zeon Co., Ltd.
* 6: Rhodia Zeosil 1165MP
* 7: Toray Dow Corning Silicone Z-6911
* 8: Tokai Carbon Co., Ltd. N234 grade Seest M
* 9: Three types of zinc oxide manufactured by Shodo Chemical Co., Ltd. * 10: Bead stearic acid manufactured by Nippon Oil & Fats Co., Ltd. * 11: SANTOFLEX 6PPD manufactured by Flexis Corporation
* 12: Sannoch manufactured by Ouchi Shinsei Chemical Co., Ltd. * 13: Process X-140 manufactured by Japan Energy Co., Ltd.
* 14: Hosei Chemical Industries Co., Ltd. oil-treated sulfur * 15: Ouchi Shinsei Chemical Co., Ltd. CZ-G
* 16: DG manufactured by Ouchi Shinsei Chemical Co., Ltd.
表Ｉに示すように、本発明によれば、耐コンプレッション性がよく、ｔａｎδが小さく、Ｅ’６０℃が高く、シリカ分散に優れたタイヤトレッド用ゴム組成物を得ることができる。 As shown in Table I, according to the present invention, it is possible to obtain a rubber composition for a tire tread having good compression resistance, small tan δ, high E′60 ° C. and excellent silica dispersion.
本発明によれば、ジエン系ゴム及びシリカを含む補強性充填剤を含有するゴム組成物であって、耐フラットスポット性能及び耐摩耗性能に優れたタイヤ用ゴム組成物を得ることができ、空気入りタイヤのトレッド用として使用するのに好適である。 According to the present invention, a rubber composition containing a reinforcing filler containing a diene rubber and silica can be obtained, and a rubber composition for a tire excellent in flat spot resistance and wear resistance can be obtained. It is suitable for use as a tread for entering tires.
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| JP2011122057A (en) * | 2009-12-10 | 2011-06-23 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP2011162625A (en) * | 2010-02-08 | 2011-08-25 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire tread and pneumatic tire |
| KR101842086B1 (en) | 2011-02-14 | 2018-03-26 | 제이에스알 가부시끼가이샤 | Rubber composition, method for producing same, and tire |
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| JP2000344954A (en) * | 1999-06-04 | 2000-12-12 | Sumitomo Rubber Ind Ltd | Modified diene-based rubber composition |
| JP2008526577A (en) * | 2005-01-14 | 2008-07-24 | 株式会社ブリヂストン | Tire composition having improved silica reinforcement and vulcanizate thereof |
| JP2006213777A (en) * | 2005-02-01 | 2006-08-17 | Toyo Tire & Rubber Co Ltd | Rubber composition for pneumatic tire |
| WO2007132909A1 (en) * | 2006-05-11 | 2007-11-22 | The Yokohama Rubber Co., Ltd. | Mercaptosilane (coupling agent) blocked with vinyl ether group, rubber composition using the same, and pneumatic tire |
| WO2009004918A1 (en) * | 2007-07-03 | 2009-01-08 | The Yokohama Rubber Co., Ltd. | Sulfur-containing conjugated diolefin copolymer rubber, and rubber composition comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011122057A (en) * | 2009-12-10 | 2011-06-23 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| US8362118B2 (en) | 2009-12-10 | 2013-01-29 | The Yokohama Rubber Co., Ltd. | Rubber composition for use in tires |
| JP2011162625A (en) * | 2010-02-08 | 2011-08-25 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire tread and pneumatic tire |
| KR101842086B1 (en) | 2011-02-14 | 2018-03-26 | 제이에스알 가부시끼가이샤 | Rubber composition, method for producing same, and tire |
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