JP5309501B2 - Rubber composition for tire - Google Patents
Rubber composition for tire Download PDFInfo
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- JP5309501B2 JP5309501B2 JP2007223016A JP2007223016A JP5309501B2 JP 5309501 B2 JP5309501 B2 JP 5309501B2 JP 2007223016 A JP2007223016 A JP 2007223016A JP 2007223016 A JP2007223016 A JP 2007223016A JP 5309501 B2 JP5309501 B2 JP 5309501B2
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- polysiloxane
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 29
- 239000005060 rubber Substances 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- -1 polysiloxane Polymers 0.000 claims abstract description 24
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 22
- 125000002252 acyl group Chemical group 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 229920006164 aromatic vinyl copolymer Polymers 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 229920003244 diene elastomer Polymers 0.000 claims description 7
- 238000013329 compounding Methods 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 abstract description 11
- 150000001993 dienes Chemical class 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920006978 SSBR Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 238000011191 terminal modification Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-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
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000000396 limonene group Chemical group 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide 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
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- JBCJMTUHAXHILC-UHFFFAOYSA-N zinc;octanoic acid Chemical compound [Zn+2].CCCCCCCC(O)=O JBCJMTUHAXHILC-UHFFFAOYSA-N 0.000 description 1
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
Abstract
Description
本発明はタイヤ用ゴム組成物に関し、更に詳しくはウェット性能と低転がり抵抗を維持しつつ、硬度の低下を抑制し、更に加工性を改善したタイヤ用ゴム組成物に関する。 The present invention relates to a rubber composition for tires, and more particularly to a rubber composition for tires that suppresses a decrease in hardness and further improves processability while maintaining wet performance and low rolling resistance.
トレッド用ゴム組成物において、ウェット性能と転がり抵抗の両立を図るため、シリカ及びカップリング剤を組合わせて使用する技術が知られており（特許文献１）、両者の高度な両立を図るためにはシリカ及びカップリング剤を多量に配合して対応している。一方、ウェット性能と低転がり抵抗の更なる改善の要求があり、シリカと親和性の高い官能基で末端変性したＳＢＲの開発が行なわれている。しかし、この末端変性ポリマーの適用時に、シリカの配合量がカーボンブラックの配合量よりも極端に大きくなると、ウェット性能や転がり抵抗は改善されるが、シリカ分散性の向上により硬度が低下するという問題がある。 In the tread rubber composition, in order to achieve both wet performance and rolling resistance, a technique using a combination of silica and a coupling agent is known (Patent Document 1). Corresponds to a large amount of silica and coupling agent. On the other hand, there is a demand for further improvement of wet performance and low rolling resistance, and development of SBR having a terminal modified with a functional group having a high affinity with silica has been performed. However, when this terminal-modified polymer is applied, if the blending amount of silica becomes extremely larger than the blending amount of carbon black, the wet performance and rolling resistance are improved, but the problem is that the hardness decreases due to the improvement in silica dispersibility. There is.
また、ゴム組成物中のシリカの配合量がカーボンブラックの配合量より極端に大きくなると、シラノール基とシリカの反応時間を十分に確保する為に混合時間を長くとる必要があり、この混合時間の増大はポリマー分子量低下による加工性（設備への密着：混合機へのゴム密着＆ロールへのゴム密着）が悪化するという問題が生じる。 In addition, when the amount of silica in the rubber composition is extremely larger than the amount of carbon black, it is necessary to increase the mixing time in order to ensure sufficient reaction time between the silanol groups and silica. The increase causes a problem that processability (adhesion to equipment: rubber adhesion to a mixer & rubber adhesion to a roll) is deteriorated due to a decrease in polymer molecular weight.
従って、本発明の目的は、前述の従来技術の問題点を克服して、ウェット性能と転がり抵抗を維持しつつ、硬度の低下を抑制し、更に加工性を改善したタイヤ用ゴム組成物を提供することにある。 Accordingly, an object of the present invention is to provide a tire rubber composition that overcomes the problems of the prior art described above, suppresses a decrease in hardness, and further improves processability while maintaining wet performance and rolling resistance. There is to do.
本発明に従えば、水酸基含有共役ジエン−芳香族ビニル共重合体３０〜７０重量部を含むジエン系ゴム１００重量部、シリカ６０〜８０重量部及び式（Ｉ）： According to the present invention, 100 parts by weight of a diene rubber containing 30 to 70 parts by weight of a hydroxyl group-containing conjugated diene-aromatic vinyl copolymer, 60 to 80 parts by weight of silica, and formula (I):
（式中、Ｒ1は独立にメチル基、エチル基又はフェニル基を示し、Ｒ2は独立に水素又は有機基を示し、Ｒ3は独立にアルキル基又はアシル基を示し、ｍは０又は１以上の整数であり、ｎは１以上の整数である）の繰り返し単位を有する数平均分子量が２００〜１００，０００のポリシロキサン０．５〜２．５重量部を含んでなるタイヤ用ゴム組成物が提供される。 (In the formula, R 1 independently represents a methyl group, an ethyl group or a phenyl group, R 2 independently represents hydrogen or an organic group, R 3 independently represents an alkyl group or an acyl group, and m represents 0 or 1) A rubber composition for tires comprising 0.5 to 2.5 parts by weight of a polysiloxane having a number average molecular weight of 200 to 100,000 having a repeating unit of the above integers and n being an integer of 1 or more. Is provided.
本発明によれば、水酸基含有共役ジエン−芳香族ビニル共重合体で代表される変性共役ジエンに、前記式（Ｉ）のポリシロキサンを配合することによって、ウェット性能と転がり抵抗を維持しつつ、硬度の低下を抑制し、更に加工性を改善することができる。本発明では水酸基含有共役ジエン−芳香族ビニル共重合体の水酸基と式（Ｉ）のポリシロキサンの反応により、ジエン系ゴムの末端変性をより大きくしてシリカとの反応を促進させることができるものと想定される。なお、式（Ｉ）のポリシロキサンはシリカ表面の余分な水酸基を疎水化してシリカの再凝集を防ぐために、結果としてシリカの分散が良くなり、加工性を改善するという効果もある。 According to the present invention, by blending the polysiloxane of the formula (I) with a modified conjugated diene represented by a hydroxyl group-containing conjugated diene-aromatic vinyl copolymer, while maintaining wet performance and rolling resistance, It is possible to suppress a decrease in hardness and further improve workability. In the present invention, by the reaction of the hydroxyl group of the hydroxyl group-containing conjugated diene-aromatic vinyl copolymer with the polysiloxane of formula (I), the terminal modification of the diene rubber can be further increased to promote the reaction with silica. It is assumed. The polysiloxane of formula (I) hydrophobizes excess hydroxyl groups on the silica surface to prevent silica re-aggregation, resulting in improved silica dispersion and improved workability.
本発明者らは、前記課題を解決すべく研究を進めた結果、水酸基含有共役ジエン−芳香族ビニル共重合体の水酸基と式（Ｉ）のポリシロキサンとの反応により、末端変性をより大きくしてシリカとの反応を促進させることができる。 As a result of researches to solve the above-mentioned problems, the present inventors have increased terminal modification by the reaction of the hydroxyl group of the hydroxyl group-containing conjugated diene-aromatic vinyl copolymer with the polysiloxane of formula (I). Reaction with silica can be promoted.
本発明によれば、水酸基含有共役ジエン−芳香族ビニル共重合体３０〜７０重量部を含むジエン系ゴム１００重量部に、前記式（Ｉ）のポリシロキサンを０．５〜２．５重量部、好ましくは０．７〜２．３重量部配合することにより、前記目的を達成したゴム組成物を得ることができ、空気入りタイヤのタイヤトレッド用ゴム組成物として有用である。前記水酸基含有共役ジエン−芳香族ビニル共重合体の配合量が少ないと、ウェット性能が不十分なので好ましくなく、逆に多過ぎても、ゴムの硬度が高くなり過ぎて、ウェット性能がかえって悪化するので好ましくない。 According to the present invention, 0.5 to 2.5 parts by weight of the polysiloxane of the formula (I) is added to 100 parts by weight of a diene rubber containing 30 to 70 parts by weight of a hydroxyl group-containing conjugated diene-aromatic vinyl copolymer. In addition, preferably by blending 0.7 to 2.3 parts by weight, a rubber composition that achieves the above-mentioned object can be obtained, which is useful as a rubber composition for a tire tread of a pneumatic tire. When the blending amount of the hydroxyl group-containing conjugated diene-aromatic vinyl copolymer is small, it is not preferable because the wet performance is insufficient, and conversely too much, the hardness of the rubber becomes too high and the wet performance is deteriorated. Therefore, it is not preferable.
本発明において配合される水酸基含有共役ジエン−芳香族ビニル共重合体は公知のゴムであり、例えば第１級、第２級又は第３級水酸基を有する芳香族ビニル単量体と共役ジエン系単量体及びその他の共重合可能な単量体を共重合させて、分子中の活性金属を有するジエン系重合体を製造し、次いでケトン類、エステル類、アルデヒド類及びエポキシ類などの変性剤を反応させて、第１級、第２級又は第３級水酸基をジエン系重合体に導入することで得られる。このように、本発明で使用される水酸基含有共役ジエン−芳香族ビニル共重合体は分子中に少なくとも１つの水酸基を有する共役ジエン系ゴムである。 The hydroxyl group-containing conjugated diene-aromatic vinyl copolymer blended in the present invention is a known rubber, for example, an aromatic vinyl monomer having a primary, secondary or tertiary hydroxyl group and a conjugated diene monomer. A diene polymer having an active metal in the molecule is prepared by copolymerizing a monomer and other copolymerizable monomers, and then a modifying agent such as ketones, esters, aldehydes and epoxies is added. It is obtained by reacting and introducing a primary, secondary or tertiary hydroxyl group into the diene polymer. Thus, the hydroxyl group-containing conjugated diene-aromatic vinyl copolymer used in the present invention is a conjugated diene rubber having at least one hydroxyl group in the molecule.
本発明において使用する前記式（Ｉ）のポリシロキサンにおいて、Ｒ1は独立にメチル基、エチル基又はフェニル基を示し、Ｒ2は独立に水素又は有機基を示し、Ｒ3は独立にアルキル基又はアシル基を示し、ｍは０又は１以上の整数であり、ｎは１以上の整数であり、数平均分子量は２００〜１００，０００、好ましくは５００〜５０，０００である。なお、前記式（Ｉ）において、Ｒ2の有機基としては、例えばＣＨ3，Ｃ2Ｈ5、スチレン残基、ジビニルベンゼン残基、リモネン残基、ブタジエン残基、イソプレン残基などをあげることができ、Ｒ3としてはＣＨ3，Ｃ2Ｈ5などの炭素数１〜３６のアルキル基、炭素数１〜３６のアシル基などをあげることができる。 In the polysiloxane of the formula (I) used in the present invention, R 1 independently represents a methyl group, an ethyl group or a phenyl group, R 2 independently represents hydrogen or an organic group, and R 3 independently represents an alkyl group. Or an acyl group, m is 0 or an integer of 1 or more, n is an integer of 1 or more, and the number average molecular weight is 200 to 100,000, preferably 500 to 50,000. In the formula (I), examples of the organic group represented by R 2 include CH 3 , C 2 H 5 , styrene residue, divinylbenzene residue, limonene residue, butadiene residue, and isoprene residue. R 3 may be an alkyl group having 1 to 36 carbon atoms such as CH 3 or C 2 H 5 , an acyl group having 1 to 36 carbon atoms, or the like.
本発明の好ましい態様に従えば、前記シリカ及びポリシロキサンと共に、シランカップリング剤を配合し、その量はウェット性能及びゴムの混合加工性の観点から、以下の範囲のタイヤ用キャップトレッドゴム組成物が提供される。
０．５≦（ＷPS／ＷSC）≦７
シリカ配合量×１重量％≦ＷPS＋ＷSC≦シリカ配合量×４０重量％
（式中、ＷPS：ポリシロキサンの配合量（重量部）、
ＷSC：シランカップリング剤の配合量（重量部））
According to a preferred embodiment of the present invention, a silane coupling agent is blended together with the silica and polysiloxane, and the amount thereof is in the following range from the viewpoint of wet performance and mixed processability of rubber. Is provided.
0.5 ≦ (W PS / W SC ) ≦ 7
Silica compounding amount × 1 wt% ≦ W PS + W SC ≦ Silica compounding amount × 40 wt%
( WPS : blending amount of polysiloxane (parts by weight)
W SC : Amount of silane coupling agent (parts by weight))
本発明において使用するシランカップリング剤の種類には特に限定はなく、タイヤ用ゴム組成物にシリカと共に配合される任意のシランカップリング剤とすることができる。 There is no limitation in particular in the kind of silane coupling agent used in this invention, It can be set as the arbitrary silane coupling agents mix | blended with a silica with the rubber composition for tires.
前記式（Ｉ）のポリシロキサンは公知物質であり、例えば一般的には特開平９−１１１０４４号公報に記載のようにして製造することができ、簡単に言えば式（Ｉ）のシロキサン構造を有する化合物は相当するポリアルキルハイドロジェンシロキサンとアルコール又はカルボン酸とを触媒の存在下に反応させることより合成される。ポリアルキルハイドロジェンシロキサンとしては、例えば特開平９−１１１０４４号公報の段落〔００１２〕に記載されている。前記アルコールとしては、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘプタノール、オクタノール、オクタデカノール、フェノール、ベンジルアルコール、の他に、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテルなど酸素原子を有するアルコールを例示することができる。カルボン酸としては酢酸、プロピオン酸、パルミチン酸、ステアリン酸、ミリスチン酸などを例示することができる。触媒としては、塩化白金酸、白金−エーテル錯体、白金−オレフィン錯体、ＰｄＣｌ2（ＰＰｈ3）2，ＲｈＣｌ2（ＰＰｈ3）2オクチル酸錫、オクチル酸亜鉛、又は酸、塩基触媒が使用できる。 The polysiloxane of the formula (I) is a known substance, and can be generally produced, for example, as described in JP-A-9-1111044. In brief, the siloxane structure of the formula (I) The compound having is synthesized by reacting the corresponding polyalkylhydrogensiloxane with an alcohol or carboxylic acid in the presence of a catalyst. Examples of the polyalkyl hydrogen siloxane are described in paragraph [0012] of JP-A-9-1111044. Examples of the alcohol include methanol, ethanol, propanol, butanol, pentanol, heptanol, octanol, octadecanol, phenol, benzyl alcohol, and alcohols having oxygen atoms such as ethylene glycol monomethyl ether and diethylene glycol monomethyl ether. be able to. Examples of the carboxylic acid include acetic acid, propionic acid, palmitic acid, stearic acid, myristic acid and the like. As the catalyst, chloroplatinic acid, platinum-ether complex, platinum-olefin complex, PdCl 2 (PPh 3 ) 2 , RhCl 2 (PPh 3 ) 2 tin octylate, zinc octylate, or acid, base catalyst can be used.
本発明に用いるジエン系ゴムは、空気入りタイヤ用として使用することができる任意のジエン系ゴム、例えば天然ゴム（ＮＲ）、ポリイソプレン（ＩＲ）、ポリブタジエン（ＢＲ）、スチレンブタジエン共重合体ゴム（ＳＢＲ）、エチレン・プロピレンゴム（ＥＰＤＭ）などをあげることができ、これらは単独又は任意のブレンドとして使用することができる。 The diene rubber used in the present invention may be any diene rubber that can be used for pneumatic tires, such as natural rubber (NR), polyisoprene (IR), polybutadiene (BR), styrene butadiene copolymer rubber ( SBR), ethylene-propylene rubber (EPDM) and the like can be mentioned, and these can be used alone or as any blend.
本発明に係るゴム組成物には、前記した成分に加えて、カーボンブラックなどの補強剤（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 above-described components, the rubber composition according to the present invention includes a reinforcing agent (filler) such as carbon black, a vulcanization or crosslinking agent, a vulcanization or crosslinking accelerator, various oils, an antiaging agent, a plasticizer, and the like. Various additives generally blended for tires and other rubber compositions can be blended, and such additives are kneaded by a general method to form a composition and vulcanized or crosslinked. Can be used for 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.
実施例１〜２及び比較例１〜４
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１．７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。
Examples 1-2 and Comparative Examples 1-4
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 1.7 liter closed mixer, and when the temperature reached 150 ° C, a master batch was obtained. A vulcanization accelerator and sulfur were kneaded with this master batch with an open roll to obtain a rubber composition.
次に得られたゴム組成物を１５×１５×０．２cmの金型中で１６０℃で２０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、比較例１の値を１００として指数表示して、表Ｉに示す。 Next, the obtained rubber composition was vulcanized in a 15 × 15 × 0.2 cm mold at 160 ° C. for 20 minutes to prepare a vulcanized rubber sheet. The physical properties of the vulcanized rubber were measured by the following test methods. It was measured. The results are shown in Table I as an index with the value of Comparative Example 1 being 100.
ゴム物性評価試験法
ｔａｎδ（６０℃）：ＪＩＳ Ｋ ６３９４準拠し、粘弾性スペクトロメーター（東洋製機製作所製）を用いて測定し、その結果を比較例１の値を１００として指数表示した。この値が小さいほど、低発熱性（即ち低燃費性）に優れることを示す。
ｔａｎδ（０℃）：ＪＩＳ Ｋ ６３９４に準拠し、粘弾性スペクトロメーター（東洋製機製作所製）を用いて測定し、その結果を比較例１の値を１００として指数表示した。この値が大きいほど、ウェット性能に優れることを示す。
Rubber physical property evaluation test method tan δ (60 ° C.): Measured using a viscoelastic spectrometer (manufactured by Toyo Seisakusho Co., Ltd.) in accordance with JIS K 6394. It shows that it is excellent in low heat generation property (namely, low fuel consumption), so that this value is small.
tan δ (0 ° C.): Measured using a viscoelastic spectrometer (manufactured by Toyo Seisakusho) in accordance with JIS K 6394, and the result was indicated as an index with the value of Comparative Example 1 being 100. It shows that it is excellent in wet performance, so that this value is large.
ウェット制動：上記ゴム組成物をＣａｐコンパウンドに使用した試作タイヤを排気量２０００ｃｃクラスの車に装着し、テストコースにおけるウェット制動テストを５回実施し、その制動距離の平均値を求めた。結果を比較例１の値を１００として指数表示した。この値が小さいほど、ウェット制動距離が短いことを示す。
転がり抵抗：転がり抵抗試験機を用いて試験タイヤの転がり抵抗を測定し、その結果を比較例１の値を１００として指数表示した。この値が小さいほど、低燃費性であることを示す。
Wet braking: A prototype tire using the rubber composition as a cap compound was mounted on a vehicle with a displacement of 2000 cc, and a wet braking test on a test course was conducted five times, and the average value of the braking distance was obtained. The results were expressed as an index with the value of Comparative Example 1 being 100. The smaller this value, the shorter the wet braking distance.
Rolling resistance: The rolling resistance of the test tire was measured using a rolling resistance tester, and the result was shown as an index with the value of Comparative Example 1 being 100. The smaller this value, the lower the fuel consumption.
加工性：ロール加工性について、目視にて以下の基準に従って判別した。
×…ロールへの密着が酷く、シート取上げが困難。
△…ロールへの密着が酷いが、シート取上げ可能。
○…ロールへやや密着するが、シート取上げ可能。
◎…ロールへの密着はあまりなく、きれいに剥がれる。
Processability: The roll processability was visually determined according to the following criteria.
X: The adhesion to the roll is so severe that it is difficult to pick up the sheet.
Δ: The adhesion to the roll is severe, but the sheet can be taken up.
○: Slightly adheres to the roll, but the sheet can be taken up.
◎… There is not much adhesion to the roll and it peels cleanly.
表Ｉ脚注
＊１：ＮＲ（天然ゴム）
＊２：ＳＳＢＲ（ＮＳ１１６Ｒ）（日本ゼオン製 カーボンブラック用末端変性ポリマー（ＳＢＲ））
以下の方法で合成した水酸基含有共役ジエン−芳香族ビニル共重合体撹拌機付帯のオートクレープにシクロヘキサン８０００ｇ、スチレン４６０ｇ、ブタジエン７００ｇを入れ、更にＴＭＥＤＡ３．５ミリｍｏｌ及びｎ−ブチルリチウム１１ミリｍｏｌを入れ、５０℃で重合した、重合開始１０分後に残部のブタジエン８４０ｇを連続的に添加。重合添加率１００％になった事を確認後、活性末端（Ｌｉ）に対して等モルのメタノールを添加して重合を停止。この溶液にｓｅｃ−ブチルリチウム６０ミリｍｏｌ及びＴＭＥＤＡ６０ミリｍｏｌを添加して７０℃で１時間反応させ、エチレンオキシド（ＥＯ）６０ミリｍｏｌを添加し、更に２０分撹拌した。メタノール１２０ミリｍｏｌを添加して反応を停止後スチームストッピング法により重合体を回収した。
＊３：ＳＳＢＲ（溶液重合ＳＢＲ）
Table I footnotes
* 1: NR (natural rubber)
* 2: SSBR (NS116R) ( manufactured by Nippon Zeon, terminal-modified polymer for carbon black (SBR) )
8000 g of cyclohexane, 460 g of styrene and 700 g of butadiene were put into an autoclave attached with a stirrer of a hydroxyl group-containing conjugated diene-aromatic vinyl copolymer synthesized by the following method. The remaining 840 g of butadiene was continuously added 10 minutes after the start of polymerization. After confirming that the polymerization addition rate was 100%, equimolar methanol was added to the active terminal (Li) to terminate the polymerization. To this solution, 60 mmol of sec-butyllithium and 60 mmol of TMEDA were added and reacted at 70 ° C. for 1 hour, 60 mmol of ethylene oxide (EO) was added, and the mixture was further stirred for 20 minutes. After stopping the reaction by adding 120 mmol of methanol, the polymer was recovered by a steam stopping method.
* 3: SSBR (Solution Polymerization SBR)
＊４：ＳｉＯ2 （ローディア製 シリカＺｅｏｓｉｌ １１６５ＭＰ）
＊５：カーボンブラック（東海カーボン製 カーボンブラックシーストＨ）
＊６：亜鉛華（正同化学製 酸化亜鉛３種）
＊７：ステアリン酸（日本油脂製 ビーズステアリン酸）
＊８：老化防止剤６ＰＰＤ（フレキシス製 老化防止剤６ＰＰＤ）
＊９：Ｓｉ６９（Ｄｅｇｕｓｓａ製 シランカップリング剤Ｓｉ６９）
＊１０：アロマオイル（ジャパンエナジー製 プロセスＸ−１４０）
＊１１：ポリシロキサン（日本ユニカー製 ポリシロキサンＫＩ−９０Ｅ）
＊１２：硫黄（鶴見化学工業製 油処理硫黄）
＊１３：ＣＺ（大内新興化学製 加硫促進剤ノクセラーＣＺ−Ｇ）
＊１４：ＤＰＧ（大内新興化学製 加硫促進剤ノクセラーＤ）
* 4: SiO 2 ( Silica Zeosil 1165MP manufactured by Rhodia )
* 5: Carbon black ( Carbon black seast H made by Tokai Carbon )
* 6: Zinc Hana ( Zinc Oxide manufactured by Zodo Chemical )
* 7: Stearic acid ( beef stearic acid made by Nippon Oil & Fats )
* 8: Anti-aging agent 6PPD ( Anti-aging agent 6PPD manufactured by Flexis )
* 9: Si69 ( Degussa silane coupling agent Si69 )
* 10: Aroma oil ( Process X-140 manufactured by Japan Energy )
* 11: Polysiloxane ( Nihon Unicar Polysiloxane KI-90E )
* 12: Sulfur ( Tsurumi Chemical Industries oil-treated sulfur )
* 13: CZ ( Ouchi Shinsei Chemical Vulcanization Accelerator Noxeller CZ-G )
* 14: DPG ( Ouchi Shinsei Chemical Vulcanization Accelerator Noxeller D )
比較例１は従来の標準例（ＮＳ１１６Ｒ＋シリカ系）であり、これを基準として他の例の物性を指数表示した。比較例２（水酸基含有共役ジエン−芳香族ビニル共重合体＋シリカ系）は燃費及びウェット性能は向上するが、加工性悪化する。これに対し、実施例１はポリシロキサンの添加によりウェット性能を悪化させることなく、硬度が良好になる。これはポリシロキサンがポリマーの余分な官能基を潰すためロールへの密着性がややよくなるためと思われる。実施例２はポリシロキサン（添加量を増大させることによりウェット性能を維持しつつ、更に加工性も良好となる。しかしながら、比較例３（ＮＳ１１６Ｒ＋シリカ＋ポリシロキサン）のように、ＮＳ１１６Ｒの多い系では、密着性向上の効果がなく、比較例４（水酸基含有共役ジエン−芳香族ビニル共重合体の配合量減＋シリカ＋ポリシロキサン）の燃費とウェット性能の改善は見られない。 Comparative Example 1 is a conventional standard example (NS116R + silica type), and the physical properties of other examples are indicated by an index based on this. Comparative Example 2 (hydroxyl group-containing conjugated diene-aromatic vinyl copolymer + silica system) improves fuel efficiency and wet performance but deteriorates processability. On the other hand, Example 1 has good hardness without deteriorating wet performance due to the addition of polysiloxane. This seems to be because the polysiloxane crushes excess functional groups of the polymer, so that the adhesion to the roll is slightly improved. Example 2 is a polysiloxane (maintaining wet performance by increasing the addition amount, and further improves the workability. However, as in Comparative Example 3 (NS116R + silica + polysiloxane), a system with a lot of NS116R is used. There is no effect of improving adhesion, and improvement in fuel efficiency and wet performance of Comparative Example 4 (reduction in the amount of hydroxyl group-containing conjugated diene-aromatic vinyl copolymer + silica + polysiloxane) is not observed.
本発明では、共役ジエン系重合体が水酸基含有共役ジエン−芳香族ビニル共重合体に特定のポリシロキサンを配合することによってウェット性能と転がり抵抗を維持しつつ、硬度の低下を抑制し、更に加工性を改善することが可能となり、タイヤトレッド用などとして有用である。 In the present invention, a conjugated diene polymer suppresses a decrease in hardness while maintaining wet performance and rolling resistance by blending a specific polysiloxane with a hydroxyl group-containing conjugated diene-aromatic vinyl copolymer, and further processing. This is useful for tire treads and the like.
Claims (3)
０．５≦（ＷPS／ＷSC）≦７
シリカ配合量×１重量％≦ＷPS＋ＷSC≦シリカ配合量×４０重量％
（式中、ＷPS：ポリシロキサンの配合量（重量部）、ＷSC：シランカップリング剤の配合量（重量部））にある請求項１に記載のタイヤ用ゴム組成物。 The rubber composition further comprises a silane coupling agent, and the amount of the polysiloxane of the formula (I) and the silane coupling agent is in the following range:
0.5 ≦ (W PS / W SC ) ≦ 7
Silica compounding amount × 1 wt% ≦ W PS + W SC ≦ Silica compounding amount × 40 wt%
The rubber composition for tires according to claim 1, which is in the formula (W PS : blending amount of polysiloxane (part by weight), W SC : blending amount of silane coupling agent (part by weight)).
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| JP5415787B2 (en) * | 2009-03-04 | 2014-02-12 | 住友ゴム工業株式会社 | Rubber composition for tread and pneumatic tire |
| JP5493548B2 (en) * | 2009-07-29 | 2014-05-14 | 横浜ゴム株式会社 | Rubber composition for bearing |
| US9499009B2 (en) | 2012-06-27 | 2016-11-22 | The Yokohama Rubber Co., Ltd. | Rubber composition for tire treads and pneumatic tire using same |
| CN105073873B (en) * | 2013-02-25 | 2017-06-09 | 横滨橡胶株式会社 | Rubber composition for tire tread and pneumatic tire |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6057397A (en) * | 1995-01-23 | 2000-05-02 | Nippon Zeon Co., Ltd. | Rubber composition and process for preparing the same |
| JP2002212340A (en) * | 2001-01-19 | 2002-07-31 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP2002220491A (en) * | 2001-01-24 | 2002-08-09 | Yokohama Rubber Co Ltd:The | Production method of rubber composition for tire |
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