JP2012140545A - Rubber composition and pneumatic tire - Google Patents
Rubber composition and pneumatic tire Download PDFInfo
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- JP2012140545A JP2012140545A JP2010294546A JP2010294546A JP2012140545A JP 2012140545 A JP2012140545 A JP 2012140545A JP 2010294546 A JP2010294546 A JP 2010294546A JP 2010294546 A JP2010294546 A JP 2010294546A JP 2012140545 A JP2012140545 A JP 2012140545A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 74
- 239000005060 rubber Substances 0.000 title claims abstract description 74
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 146
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 135
- 239000002245 particle Substances 0.000 claims abstract description 57
- 230000008961 swelling Effects 0.000 claims abstract description 14
- 230000009477 glass transition Effects 0.000 claims abstract description 13
- 150000001993 dienes Chemical class 0.000 claims description 32
- -1 diene compounds Chemical class 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 229920003244 diene elastomer Polymers 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 3
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- 230000000379 polymerizing effect Effects 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 7
- 230000006872 improvement Effects 0.000 abstract description 5
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 16
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- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
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- 238000004073 vulcanization Methods 0.000 description 9
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
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- 238000000034 method Methods 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
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- 239000011593 sulfur Substances 0.000 description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 6
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- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920003052 natural elastomer Polymers 0.000 description 5
- 229920001194 natural rubber Polymers 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229920003049 isoprene rubber Polymers 0.000 description 4
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- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
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- 239000000463 material Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- 230000003712 anti-aging effect Effects 0.000 description 2
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
Description
本発明は、ゴム組成物、及び、それを用いた空気入りタイヤに関するものである。 The present invention relates to a rubber composition and a pneumatic tire using the same.
ゴム材料の低発熱化や加工性改善といった問題は、各種材料の最適化等で改善はされるものの、その要求は年々高くなっている。例えば、ゴム製品であるタイヤの転がり抵抗と、湿潤路面でのグリップ性能（ｗｅｔμ）の改良にあたっては、両者がトレードオフの関係にあることから、そのバランス改善の技術的ハードルは高い。また、近年、低燃費タイヤなどの環境に対応した商品へのニーズが大きいことから、その要求に対して大幅な改良が必要になっている。そのようなゴム製品に対する要求特性を満たすためには、何かしらのブレークスルーが必要である。 Although problems such as low heat generation and improved workability of rubber materials can be improved by optimizing various materials, the demand is increasing year by year. For example, in improving the rolling resistance of a tire, which is a rubber product, and the grip performance (wetμ) on a wet road surface, the technical hurdle for improving the balance is high because the two are in a trade-off relationship. In recent years, there has been a great need for products corresponding to the environment, such as fuel-efficient tires, and therefore, there has been a need for significant improvements in response to such demands. In order to satisfy the required properties for such rubber products, some breakthrough is necessary.
上記要求性能に対応するために、架橋されたポリマー粒子であるゴムゲル（ポリマーゲル）をゴム組成物に配合することが提案されている（例えば、下記特許文献１〜３参照）。しかしながら、これらのポリマーゲルはナノゲルとも称されるようにナノサイズの微粒子状のゲルであるため、ゴム組成物中で凝集しやすく、分散性については未だ改良の余地があり、更なる物性の改良が求められる。 In order to cope with the required performance, it has been proposed to blend a rubber gel (polymer gel), which is a crosslinked polymer particle, into a rubber composition (for example, see Patent Documents 1 to 3 below). However, since these polymer gels are nano-sized fine-particle gels, also called nanogels, they tend to aggregate in the rubber composition, and there is still room for improvement in dispersibility. Is required.
なお、下記特許文献４には、ポリスチレンからなるコアとスチレン−ブタジエン共重合体からなる表面層とを備えたポリマーナノ粒子を、スチレンブタジエンゴムに配合したゴム組成物が開示されている。しかしながら、該ポリマーナノ粒子は、コアのガラス転移温度が１５０〜６００℃と高いものであるため、ヒステリシスロスが大きく、ゴム組成物の低発熱化を図ることはできない。 Patent Document 4 listed below discloses a rubber composition in which polymer nanoparticles having a core made of polystyrene and a surface layer made of styrene-butadiene copolymer are blended with styrene butadiene rubber. However, since the polymer nanoparticles have a high glass transition temperature of 150 to 600 ° C. in the core, the hysteresis loss is large and the heat generation of the rubber composition cannot be reduced.
本発明は、以上の点に鑑み、ポリマーゲルの粒子表面にグラフト鎖を設けることにより、ポリマーゲルの分散性を向上させて、物性バランスの更なる向上を図ることができるゴム組成物を提供することを目的とする。 In view of the above points, the present invention provides a rubber composition capable of improving the dispersibility of a polymer gel and further improving the balance of physical properties by providing a graft chain on the particle surface of the polymer gel. For the purpose.
本発明に係るゴム組成物は、ジエン系ゴムからなるゴム成分と、ポリマーゲルとを含み、該ポリマーゲルが、トルエン膨潤指数Ｑｉが１０以下かつガラス転移温度が−１００〜０℃の架橋されたジエン系ポリマー粒子の粒子表面に、グラフト鎖を設けてなるものであって、グラフト変性前のポリマーゲルの５質量％トルエン溶液粘度ηｏに対するグラフト変性後のポリマーゲルの５質量％トルエン溶液粘度ηの比（η／ηｏ）が２〜３０であることを特徴とする。本発明に係る空気入りタイヤは、該ゴム組成物を用いてなるゴム部分を有するものである。 The rubber composition according to the present invention includes a rubber component composed of a diene rubber and a polymer gel, and the polymer gel is crosslinked with a toluene swelling index Qi of 10 or less and a glass transition temperature of −100 to 0 ° C. A graft chain is provided on the particle surface of the diene polymer particle, and the 5% toluene solution viscosity η of the polymer gel after graft modification with respect to the 5% toluene solution viscosity η o of the polymer gel before graft modification. The ratio (η / η o ) is 2 to 30. The pneumatic tire according to the present invention has a rubber portion using the rubber composition.
本発明によれば、架橋されたジエン系ポリマー粒子であるポリマーゲルの表面に上記グラフト鎖を設けたことにより、ポリマーゲルの凝集を抑えて分散性を向上することができ、硬度や強度を維持しつつ、低発熱化などの物性向上を図ることができる。 According to the present invention, by providing the graft chain on the surface of the polymer gel, which is a crosslinked diene polymer particle, the dispersibility can be improved by suppressing the aggregation of the polymer gel, and the hardness and strength are maintained. However, physical properties such as low heat generation can be improved.
以下、本発明の実施に関連する事項について詳細に説明する。 Hereinafter, matters related to the implementation of the present invention will be described in detail.
実施形態に係るゴム組成物は、（Ａ）ジエン系ゴムからなるゴム成分（但し、下記ポリマーゲルは除く。）と、（Ｂ）ポリマーゲルと、を含有するものであり、マトリックスとしてのゴム成分（Ａ）に、分散相としてのポリマーゲル（Ｂ）が分散したものである。 The rubber composition according to the embodiment contains (A) a rubber component composed of a diene rubber (excluding the following polymer gel) and (B) a polymer gel, and the rubber component as a matrix The polymer gel (B) as a dispersed phase is dispersed in (A).
上記（Ａ）のジエン系ゴムとしては、例えば、天然ゴム（ＮＲ）、ポリイソプレンゴム（ＩＲ）、スチレン−ブタジエンゴム（ＳＢＲ）、ポリブタジエンゴム（ＢＲ）、スチレン−イソプレンゴム、ブタジエン−イソプレンゴム、スチレン−イソプレン−ブタジエン共重合体ゴム、ニトリルゴムなどが挙げられ、これらはそれぞれ単独で用いても２種以上併用してもよい。上記の中でも、タイヤ用に用いる場合、天然ゴム、スチレン−ブタジエンゴム、ポリブタジエンゴムが好ましい。 Examples of the diene rubber (A) include natural rubber (NR), polyisoprene rubber (IR), styrene-butadiene rubber (SBR), polybutadiene rubber (BR), styrene-isoprene rubber, butadiene-isoprene rubber, Examples thereof include styrene-isoprene-butadiene copolymer rubber and nitrile rubber, and these may be used alone or in combination of two or more. Among these, when used for tires, natural rubber, styrene-butadiene rubber, and polybutadiene rubber are preferable.
上記（Ｂ）のポリマーゲルとしては、トルエン膨潤指数Ｑｉが１０以下かつガラス転移温度が−１００〜０℃の架橋されたジエン系ポリマー粒子の粒子表面に、グラフト鎖を結合させてなるものが用いられる。 As the polymer gel (B), a gel obtained by bonding a graft chain to the surface of a crosslinked diene polymer particle having a toluene swelling index Qi of 10 or less and a glass transition temperature of −100 to 0 ° C. is used. It is done.
かかるポリマーゲルは、その低いトルエン膨潤指数によりフィラーとしての性質を持つものであるが、それ自体はジエン系ポリマーからなり、上記（Ａ）のジエン系ゴムと共通ないし類似しているので、従来のカーボンブラックやシリカ等のフィラーとは異なる優れた物性をゴム組成物に付与することができる。例えば、従来のフィラーに置換して配合することにより、硬度や強度を維持しつつ、低発熱化を図ることができ、また低温性能の改良や加工性の改良などを図ることができる。また、ポリマーゲルは、カーボンブラックやシリカに比べて比重が小さいので、ゴム製品の軽量化を図ることができる。また、ポリマーゲルは、通常ナノサイズの微粒子状ゲルであることからゴム組成物中で凝集しやすいが、その粒子表面をグラフト化することにより、分散性を向上させることができ、更なるゴム物性の改良を図ることができる。詳細には、ポリマーゲル表面に設けられたグラフト鎖により、立体構造的にポリマーゲルの凝集が抑えられ（ポリマーゲル同士が近づくのをグラフト鎖が立体的に妨げる。）、更にはゴム成分としてジエン系ゴムとの相溶性も良くなることから、物性の改良が図られるものと考えられる。 Such a polymer gel has properties as a filler due to its low toluene swelling index, but it itself comprises a diene polymer and is similar to or similar to the diene rubber of the above (A). Excellent physical properties different from fillers such as carbon black and silica can be imparted to the rubber composition. For example, by substituting and blending with conventional fillers, it is possible to reduce heat generation while maintaining hardness and strength, and to improve low temperature performance and workability. In addition, since the polymer gel has a specific gravity smaller than that of carbon black or silica, the weight of the rubber product can be reduced. In addition, polymer gels are usually nano-sized fine-particle gels, so they easily aggregate in the rubber composition. However, by dispersing the surface of the particles, the dispersibility can be improved and further rubber properties can be obtained. Can be improved. Specifically, the graft chains provided on the surface of the polymer gel suppress the aggregation of the polymer gel sterically (the graft chain sterically hinders the polymer gels from approaching each other), and diene as a rubber component. Since the compatibility with the rubber is improved, it is considered that the physical properties are improved.
該ポリマーゲルを構成するジエン系ポリマー粒子は、ゴム分散液を架橋することにより製造することができる。ゴム分散液としては、懸濁重合により製造されるゴムラテックス、溶液重合されたゴムを水中に乳化させて得られるゴム分散液などが挙げられ、また、架橋剤としては、有機ペルオキシド、硫黄系架橋剤など挙げられる。また、ゴム粒子の架橋は、ゴムの乳化重合中に、架橋作用を持つ多官能化合物との共重合によっても行うことができる。具体的には、例えば、特開平１０−２０４２２５号公報、特表２００４−５０４４６５号公報、特表２００４−５０６０５８号公報、特表２００４−５３０７６０号公報などに開示の方法を用いることができる。 The diene polymer particles constituting the polymer gel can be produced by crosslinking the rubber dispersion. Examples of the rubber dispersion include rubber latex produced by suspension polymerization, rubber dispersion obtained by emulsifying solution-polymerized rubber in water, and examples of the crosslinking agent include organic peroxides and sulfur-based crosslinking. Agents and the like. The rubber particles can also be crosslinked by copolymerization with a polyfunctional compound having a crosslinking action during the emulsion polymerization of the rubber. Specifically, for example, methods disclosed in JP-A-10-204225, JP-T 2004-504465, JP-T 2004-506058, JP-T 2004-530760, and the like can be used.
該ポリマーゲルを構成するジエン系ポリマーとしては、例えば、天然ゴム、ポリイソプレンゴム、スチレン−ブタジエンゴム、ポリブタジエンゴム、スチレン−イソプレンゴム、ブタジエン−イソプレンゴム、スチレン−イソプレン−ブタジエン共重合体ゴム、ニトリルゴムなどが挙げられ、これらはそれぞれ単独で用いても２種以上併用してもよい。好ましくは、ポリブタジエンゴム、スチレンブタジエンゴムを主成分とするものである。 Examples of the diene polymer constituting the polymer gel include natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, styrene-isoprene rubber, butadiene-isoprene rubber, styrene-isoprene-butadiene copolymer rubber, and nitrile. Examples thereof include rubbers, and these may be used alone or in combination of two or more. Preferably, polybutadiene rubber or styrene butadiene rubber is the main component.
該ジエン系ポリマー粒子のガラス転移温度（Ｔｇ）は−１００〜０℃である。このようなガラス転移温度の低いポリマー粒子を用いることで損失係数（ｔａｎδ）を低くして低発熱性を改良することができる。ガラス転移温度が０℃よりも高いと、低発熱性を改良することは困難である。ガラス転移温度は、より好ましくは、−９０〜−２０℃であり、更に好ましくは−８０〜−４０℃である。該ジエン系ポリマー粒子のガラス転移温度は、ベースとなるジエン系ポリマーの種類と、その架橋度により調整することができる。ガラス転移温度は、ＪＩＳ Ｋ７１２１に準拠して示差走査熱量測定（ＤＳＣ）を用いて測定される値（昇温速度２０℃／分）である。 The glass transition temperature (Tg) of the diene polymer particles is −100 to 0 ° C. By using such polymer particles having a low glass transition temperature, the loss factor (tan δ) can be lowered to improve the low heat generation. If the glass transition temperature is higher than 0 ° C., it is difficult to improve the low exothermic property. The glass transition temperature is more preferably −90 to −20 ° C., still more preferably −80 to −40 ° C. The glass transition temperature of the diene polymer particles can be adjusted by the type of the diene polymer used as a base and the degree of crosslinking thereof. The glass transition temperature is a value (temperature increase rate 20 ° C./min) measured using differential scanning calorimetry (DSC) in accordance with JIS K7121.
該ジエン系ポリマー粒子のトルエン膨潤指数Ｑｉは１０以下である。このようなトルエン膨潤指数Ｑｉの小さいポリマー粒子を用いることにより、フィラーとしての補強効果を発揮することができる。すなわち、トルエン膨潤指数が大きすぎると、ポリマー粒子が柔らかくなり、補強効果が失われる。トルエン膨潤指数Ｑｉは、より好ましくは１〜９であり、更に好ましくは２〜６である。トルエン膨潤指数Ｑｉは、例えば、ジエン系ポリマー粒子の架橋度により調整することができる。 The toluene swelling index Qi of the diene polymer particles is 10 or less. By using such polymer particles having a small toluene swelling index Qi, a reinforcing effect as a filler can be exhibited. That is, if the toluene swelling index is too large, the polymer particles become soft and the reinforcing effect is lost. The toluene swelling index Qi is more preferably 1 to 9, and further preferably 2 to 6. The toluene swelling index Qi can be adjusted by, for example, the degree of crosslinking of the diene polymer particles.
ここで、トルエン膨潤指数Ｑｉは、ジエン系ポリマー粒子をトルエンに膨潤させた後、乾燥させることにより測定される。すなわち、ジエン系ポリマー粒子２５０ｍｇを、トルエン２５ｍＬ中で、２４時間、振とう下に膨潤させ、２００００ｒｐｍで遠心分離してから、濡れ質量を秤量し、次いで７０℃で質量一定まで乾燥させてから、乾燥質量を秤量する。トルエン膨潤指数は、Ｑｉ＝（ポリマー粒子の濡れ質量）／（ポリマー粒子の乾燥質量）により求められる。 Here, the toluene swelling index Qi is measured by allowing the diene polymer particles to swell in toluene and then drying. That is, 250 mg of diene polymer particles were swollen under shaking in 25 mL of toluene for 24 hours, centrifuged at 20000 rpm, weighed mass, then dried to constant mass at 70 ° C., Weigh dry mass. The toluene swelling index is determined by Qi = (wet mass of polymer particles) / (dry mass of polymer particles).
該ジエン系ポリマー粒子の粒径は、平均粒子径（ＤＩＮ ５３ ２０６によるＤＶＮ値）が５〜２０００ｎｍであることが好ましく、より好ましくは１０〜５００ｎｍであり、更に好ましくは２０〜２００ｎｍである。 The average particle diameter (DVN value according to DIN 53 206) of the diene polymer particles is preferably 5 to 2000 nm, more preferably 10 to 500 nm, and still more preferably 20 to 200 nm.
該ジエン系ポリマー粒子としては、官能基を有する変性ポリマー粒子を用いてもよい。官能基としては、例えば、カルボキシル基などのカルボン酸誘導体、ヒドロキシル基などのヒドロキシ系官能基、アミノ基、チオール基、スルホ基などのヘテロ原子を含むものが挙げられる。このような官能基は、ジエン系ポリマーの重合時に、官能基が導入されたモノマーを用いて合成してもよく、また重合後の活性末端に官能基を導入してなる末端変性ポリマーを用いることもできる。また、上記架橋によりポリマー粒子を作製した後に、その粒子表面のＣ＝Ｃ二重結合に対して官能基を有する化合物を反応させることにより、粒子表面に官能基を組み込むこともできる。 As the diene polymer particles, modified polymer particles having a functional group may be used. Examples of the functional group include those containing a hetero atom such as a carboxylic acid derivative such as a carboxyl group, a hydroxy functional group such as a hydroxyl group, an amino group, a thiol group, and a sulfo group. Such a functional group may be synthesized using a monomer into which a functional group is introduced during polymerization of a diene polymer, or a terminal-modified polymer in which a functional group is introduced into an active terminal after polymerization is used. You can also. Moreover, after producing polymer particles by the above crosslinking, a functional group can be incorporated into the particle surface by reacting a compound having a functional group with the C═C double bond on the particle surface.
該ジエン系ポリマー粒子の粒子表面にグラフト鎖を設けてなるポリマーゲルは、グラフト鎖を設けることにより、元のジエン系ポリマー粒子に対して５質量％トルエン溶液粘度が高くなる。すなわち、ポリマー粒子は上記のようにトルエン中で溶解せず膨潤しており、グラフト変性したものも膨潤しているが、トルエンとグラフト鎖との作用により、グラフト変性したものは未変性のものに比べて溶液粘度が上昇する。そのため、かかるグラフト変性前後のトルエン溶液粘度を比較することにより、グラフト鎖のジエン系ゴムに及ぼす影響を捉えることができる。より詳細には、上記粒子表面に設けるグラフト鎖は、その分子量と組成によりポリマーゲルの物性に与える影響が大きいので、グラフト鎖の分子量と組成の影響を反映したトルエン溶液粘度を用いて、変性前後で比較することにより、物性改善につながるポリマーゲルの特定が可能となる。 The polymer gel in which the graft chain is provided on the particle surface of the diene polymer particle has a 5 mass% toluene solution viscosity higher than that of the original diene polymer particle by providing the graft chain. That is, the polymer particles are swollen without dissolving in toluene as described above, and the graft-modified ones are also swollen, but the graft-modified ones are unmodified by the action of toluene and graft chains. Compared with the solution viscosity increases. Therefore, by comparing the toluene solution viscosities before and after the graft modification, the influence of the graft chain on the diene rubber can be grasped. More specifically, since the graft chain provided on the particle surface has a large influence on the physical properties of the polymer gel due to its molecular weight and composition, the viscosity of the toluene solution reflecting the influence of the molecular weight and composition of the graft chain is used before and after modification. By comparing the above, it is possible to identify a polymer gel that leads to improvement of physical properties.
すなわち、ポリマーゲルとしては、グラフト変性前の５質量％トルエン溶液粘度ηｏに対するグラフト変性後の５質量％トルエン溶液粘度ηの比（η／ηｏ）が２〜３０の範囲内にあるものを用いることが好ましい。この比η／ηｏは、より好ましくは上限が２０以下、更に好ましくは１５以下、特に好ましくは１０以下であり、また、下限がより好ましくは４以上である。この比が低すぎるとポリマーゲルの分散に十分でなく、逆に高すぎるとゴム組成物の発熱が高くなる傾向にある。この比は、グラフト鎖を構成する重合体の種類（組成）や分子量などにより調整することができる。 That is, the polymer gel has a ratio (η / η o ) of 5 mass% toluene solution viscosity η after graft modification to 5 mass% toluene solution viscosity η o before graft modification in the range of 2-30. It is preferable to use it. This ratio η / η o has an upper limit of preferably 20 or less, more preferably 15 or less, particularly preferably 10 or less, and a lower limit of 4 or more. If this ratio is too low, it is not sufficient for dispersing the polymer gel. Conversely, if it is too high, the heat generation of the rubber composition tends to increase. This ratio can be adjusted by the type (composition) of the polymer constituting the graft chain, the molecular weight, and the like.
ここで、トルエン溶液粘度は、ＪＩＳ Ｚ８８０３に従い測定される。詳細には、グラフト変性前後のポリマーゲルのそれぞれについて、トルエン中５質量％に調整した溶液を２４時間放置した後、Ｂ型回転粘度計（Ｂｒｏｏｋｆｉｅｌｄ ＤＶ−ＩＩ ＋ｐｒｏ、スピンドル形状Ｎｏ．４）を用いて、温度２５℃、回転速度２０ｒｐｍにより、１分後の値を測定する。 Here, the toluene solution viscosity is measured according to JIS Z8803. Specifically, for each of the polymer gels before and after graft modification, a solution adjusted to 5% by mass in toluene was allowed to stand for 24 hours, and then a B-type rotational viscometer (Brookfield DV-II + pro, spindle shape No. 4) was used. Then, the value after 1 minute is measured at a temperature of 25 ° C. and a rotation speed of 20 rpm.
なお、グラフト変性後のポリマーゲルの５質量％トルエン溶液粘度ηは、特に限定するものではないが、１０００〜１００００ｍＰａ・ｓであることが好ましく、より好ましくは１５００〜５０００ｍＰａ・ｓである。 In addition, although the 5 mass% toluene solution viscosity (eta) of the polymer gel after graft modification is not specifically limited, It is preferable that it is 1000-10000 mPa * s, More preferably, it is 1500-5000 mPa * s.
該グラフト鎖を構成する単量体としては、ビニル系単量体が好ましく用いられる。ビニル系単量体としては、（メタ）アクリル酸エステル、芳香族アルケニル化合物、共役ジエン系化合物、オレフィン化合物、多官能ビニル化合物などが挙げられる。（メタ）アクリル酸エステルとしては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸ヘキシル、アクリル酸オクチル、アクリル酸エチルヘキシル、アクリル酸デシル、アクリル酸ステアリル、及びこれらのメタクリル酸化合物などの炭素数１〜１８のアルキル基を持つアクリル酸又はメタクリル酸脂肪族炭化水素が挙げられる。芳香族アルケニル化合物としては、例えば、スチレン、α−メチルスチレン、ｐ−メチルスチレンなどが挙げられる。共役ジエン系化合物としては、例えば、ブタジエン、イソプレンなどが挙げられる。オレフィン化合物としては、例えば、エチレン、プロピレン、イソブチレンなどが挙げられる。多官能ビニル化合物としては、例えば、ポリエチレングリコールジメタクリレート、トリメチロールプロパントリアクリレートなどが挙げられる。これらは、それぞれ１種単独で用いても、２種以上を組みあわせて用いてもよい。これらの中でも、好ましくは（メタ）アクリル酸エステルを用いることであり、より好ましくは炭素数１〜４のアルキル基を持つ（メタ）アクリル酸エステルを用いることである。 As the monomer constituting the graft chain, a vinyl monomer is preferably used. Examples of vinyl monomers include (meth) acrylic acid esters, aromatic alkenyl compounds, conjugated diene compounds, olefin compounds, polyfunctional vinyl compounds, and the like. Examples of (meth) acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, octyl acrylate, ethyl hexyl acrylate, and decyl acrylate. , Stearyl acrylate, and acrylic acid or methacrylic acid aliphatic hydrocarbons having an alkyl group having 1 to 18 carbon atoms such as methacrylic acid compounds. Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, p-methylstyrene, and the like. Examples of the conjugated diene compound include butadiene and isoprene. Examples of the olefin compound include ethylene, propylene, isobutylene and the like. Examples of the polyfunctional vinyl compound include polyethylene glycol dimethacrylate and trimethylolpropane triacrylate. Each of these may be used alone or in combination of two or more. Among these, Preferably it is using (meth) acrylic acid ester, More preferably, it is using (meth) acrylic acid ester which has a C1-C4 alkyl group.
該グラフト鎖としては、ジエン系ポリマー粒子の粒子表面に存在するジエン系ポリマーの主鎖に対して枝状に分岐して結合した構造を持つ重合体鎖であれば特に限定されず、例えば、予め重合した重合体をジエン系ポリマー粒子の粒子表面に結合させて形成されたものでもよく、あるいはまた、ジエン系ポリマー粒子の粒子表面から重合を開始させるグラフト重合により形成されたものでもよい。予め重合した重合体をジエン系ポリマー粒子の表面に結合させる場合、例えば、上記のように官能基を導入した変性ポリマー粒子を用いるとともに、グラフト鎖となる重合体に該官能基と反応できる官能基を導入しておいて、両者の反応により、該重合体を変性ポリマーゲルに結合させてもよい。一方、グラフト重合による場合、ジエン系ポリマー粒子の粒子表面の炭素−炭素二重結合などに対してグラフト重合可能なビニル系単量体を重合させることができる。グラフト重合方法としては、アゾ系開始剤などのラジカル重合開始剤を用いた溶液重合法や乳化重合法など、公知のラジカル重合法を適用することができる。 The graft chain is not particularly limited as long as it is a polymer chain having a structure in which the main chain of the diene polymer existing on the particle surface of the diene polymer particle is branched and bonded. The polymer may be formed by bonding the polymer to the particle surface of the diene polymer particle, or may be formed by graft polymerization that initiates polymerization from the particle surface of the diene polymer particle. When a polymer that has been polymerized in advance is bonded to the surface of a diene polymer particle, for example, a modified polymer particle into which a functional group is introduced as described above is used, and a functional group that can react with the functional group on a polymer that becomes a graft chain. The polymer may be bound to the modified polymer gel by the reaction of both. On the other hand, in the case of graft polymerization, a vinyl monomer that can be graft-polymerized to the carbon-carbon double bond on the particle surface of the diene polymer particles can be polymerized. As the graft polymerization method, a known radical polymerization method such as a solution polymerization method or an emulsion polymerization method using a radical polymerization initiator such as an azo initiator can be applied.
該グラフト鎖としては、変性されたものであってもよい。例えば、ゴム成分であるジエン系ゴムと相互作用するチオール基などの官能基をグラフト鎖に導入しておけば、グラフト鎖とジエン系ゴムとが反応して結合することにより、ポリマーゲルとジエン系ゴムとの結合による補強性を高めることができる。 The graft chain may be modified. For example, if a functional group such as a thiol group that interacts with a diene rubber, which is a rubber component, is introduced into the graft chain, the graft chain reacts with the diene rubber so that the polymer gel and the diene system are bonded. Reinforcing property by bonding with rubber can be enhanced.
該グラフト鎖の含有量（グラフト率）は、特に限定されないが、ベースとなるジエン系ポリマー粒子に対して、０．１〜３０質量％であることが好ましく、より好ましくは１〜２０質量％である。 The content (graft ratio) of the graft chain is not particularly limited, but is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass with respect to the diene polymer particles as a base. is there.
該グラフト鎖を持つポリマーゲルの配合量は、上記ゴム成分１００質量部に対して、１〜１００質量部であることが好ましく、より好ましくは５〜７０質量部であり、更に好ましくは５〜５０質量部である。ポリマーゲルの配合量が少なすぎると、その添加効果が不十分となるおそれがある。逆に配合量が多すぎると、局所的な凝集塊に起因して、強度が低下し、低発熱性が損なわれるおそれがある。 The blending amount of the polymer gel having a graft chain is preferably 1 to 100 parts by mass, more preferably 5 to 70 parts by mass, and further preferably 5 to 50 parts by mass with respect to 100 parts by mass of the rubber component. Part by mass. If the amount of the polymer gel is too small, the effect of addition may be insufficient. On the other hand, if the amount is too large, the strength is lowered due to local agglomerates and the low heat build-up may be impaired.
本発明に係るゴム組成物には、カーボンブラックやシリカなどの無機充填剤を配合してもよい。かかる無機充填剤の配合量は、特に限定されないが、前記ゴム成分１００質量部に対して、例えば、５〜１００質量部であることが好ましく、より好ましくは１０〜５０質量部である。 You may mix | blend inorganic fillers, such as carbon black and a silica, with the rubber composition which concerns on this invention. Although the compounding quantity of this inorganic filler is not specifically limited, It is preferable that it is 5-100 mass parts with respect to 100 mass parts of said rubber components, More preferably, it is 10-50 mass parts.
カーボンブラックとしては、特に限定されず、例えば、ＳＡＦクラス（Ｎ１００番台）、ＩＳＡＦクラス（Ｎ２００番台）、ＨＡＦクラス（Ｎ３００番台）、ＦＥＦ（Ｎ５００番台）、ＧＰＦ（Ｎ６００番台）（ともにＡＳＴＭグレード）のものなどが挙げられる。また、シリカとしても、特に限定されず、湿式シリカ、乾式シリカ、コロイダルシリカ、沈降シリカなどが挙げられ、そのうち含水珪酸を主成分とする湿式シリカを用いることが好ましい。なお、無機充填剤としてシリカを配合する場合、スルフィドシランやメルカプトシランなどのシランカップリング剤を併用することが好ましく、シランカップリング剤は、通常、シリカ１００質量部に対して２〜２５質量部にて用いることができる。 The carbon black is not particularly limited. For example, SAF class (N100 series), ISAF class (N200 series), HAF class (N300 series), FEF (N500 series), GPF (N600 series) (both ASTM grade) Things. Further, the silica is not particularly limited, and examples thereof include wet silica, dry silica, colloidal silica, and precipitated silica. Of these, wet silica containing hydrous silicic acid as a main component is preferably used. In addition, when mix | blending a silica as an inorganic filler, it is preferable to use together silane coupling agents, such as sulfide silane and mercaptosilane, and a silane coupling agent is 2-25 mass parts normally with respect to 100 mass parts of silica. Can be used.
カーボンブラック及びシリカ以外の無機充填剤としては、例えば、酸化チタン、クレー、タルク、炭酸カルシウムなどが挙げられる。なお、以上挙げたカーボンブラックやシリカ、更にはその他の無機充填剤は、いずれか一種を単独で用いてもよく、あるいはまた複数種の無機充填剤を組み合わせて用いてもよい。 Examples of inorganic fillers other than carbon black and silica include titanium oxide, clay, talc, and calcium carbonate. In addition, any one of the above-mentioned carbon black, silica, and other inorganic fillers may be used alone, or a plurality of inorganic fillers may be used in combination.
本発明に係るゴム組成物には、上記の成分の他に、軟化剤、可塑剤、老化防止剤、亜鉛華、ステアリン酸、加硫剤、加硫促進剤など、ゴム組成物において一般に使用される種々の添加剤を任意に配合することができる。特に限定するものではないが、加硫剤の配合量は、上記ゴム成分１００質量部に対して０．１〜１０質量部であることが好ましく、より好ましくは０．５〜５質量部である。また、加硫促進剤の配合量は、上記ゴム成分１００質量部に対して０．１〜７質量部であることが好ましく、より好ましくは０．５〜５質量部である。 In addition to the above components, the rubber composition according to the present invention is generally used in rubber compositions such as softeners, plasticizers, anti-aging agents, zinc white, stearic acid, vulcanizing agents, and vulcanization accelerators. Various additives can be arbitrarily blended. Although it does not specifically limit, it is preferable that the compounding quantity of a vulcanizing agent is 0.1-10 mass parts with respect to 100 mass parts of said rubber components, More preferably, it is 0.5-5 mass parts. . Moreover, it is preferable that the compounding quantity of a vulcanization accelerator is 0.1-7 mass parts with respect to 100 mass parts of said rubber components, More preferably, it is 0.5-5 mass parts.
上記ゴム組成物の調製方法は、特に限定されず、通常に用いられるバンバリーミキサーやロール、ニーダー等の混合機を用いて混練することで調製され、所定形状に成形し加硫することで、タイヤ、防振ゴム、ベルトなどの各種ゴム製品を得ることができる。好ましくは、タイヤ用ゴム組成物して用いることであり、常法に従い、例えば１４０〜１８０℃で加硫成形することにより、空気入りタイヤのトレッドゴムやサイドウォールゴムなどの様々なゴム部分を形成することができる。 The method for preparing the rubber composition is not particularly limited. The rubber composition is prepared by kneading using a commonly used Banbury mixer, roll, kneader, or other such mixer, molded into a predetermined shape, and vulcanized to produce a tire. Various rubber products such as anti-vibration rubber and belt can be obtained. Preferably, it is used as a rubber composition for tires, and various rubber parts such as tread rubber and sidewall rubber of a pneumatic tire are formed by vulcanization molding at 140 to 180 ° C. according to a conventional method. can do.
以下、本発明の実施例を示すが、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
［ポリマーゲル１の作製］（比較例）
日本ゼオン（株）製ＳＢＲラテックス「Ｎｉｐｏｌ Ｌｘ１１０」１７７．８ｇと蒸留水１８２．２ｇを、攪拌手段を備えた反応器へ注ぎ、次いで、ｔ−ブチルペルオキシラウレート１．４４ｇを添加した。反応器内を２時間窒素置換した後、８０℃で４時間攪拌し、反応器を室温に戻し、貧溶媒に注ぎ洗浄した。３回洗浄後、乾燥することでポリマーゲルを得た。得られたポリマーゲル１は、Ｔｇ＝−５０℃、Ｑｉ＝３、平均粒子径＝８０ｎｍ、比重＝０．９４であった。
[Production of Polymer Gel 1] (Comparative Example)
177.8 g of SBR latex “Nipol Lx110” manufactured by Nippon Zeon Co., Ltd. and 182.2 g of distilled water were poured into a reactor equipped with stirring means, and then 1.44 g of t-butylperoxylaurate was added. The inside of the reactor was purged with nitrogen for 2 hours, and then stirred at 80 ° C. for 4 hours. The reactor was returned to room temperature, poured into a poor solvent and washed. After washing three times, the polymer gel was obtained by drying. The obtained polymer gel 1 had Tg = −50 ° C., Qi = 3, average particle diameter = 80 nm, and specific gravity = 0.94.
［ポリマーゲル２の作製］
日本ゼオン（株）製ＳＢＲラテックス「Ｎｉｐｏｌ Ｌｘ１１０」１７７．８ｇと蒸留水１８２．２ｇを、攪拌手段を備えた反応器へ注ぎ、次いで、ｔ−ブチルペルオキシラウレート１．４４ｇを添加した。反応器内を２時間窒素置換した後、８０℃で４時間攪拌し、反応器を室温に戻し、ポリマーゲルを得た。得られたポリマーゲルは、Ｔｇ＝−５０℃、Ｑｉ＝３、平均粒子径＝８０ｎｍ、比重＝０．９４、５質量％トルエン溶液粘度ηｏ＝３８６ｍＰａ・ｓであった。更に、該ポリマーゲルに対してグラフト重合を実施した。すなわち、上記水分を含むポリマーゲル２００ｇ、ドデシル硫酸ナトリウム０．６ｇを反応器に添加、窒素置換と攪拌を実施しながら昇温を開始し、６０℃の時点で、メチルアクリレート１０．２ｇ、エチルアクリレート１．３ｇ、ｔ−ブチルハイドロパーオキサイド０．３６ｇをゆっくりと添加し、その後８０℃へ昇温、そのまま２時間保持した。終了後、反応溶液を貧溶媒へ注ぎ、３回洗浄後乾燥させ、所望のポリマーゲルを得た。得られたポリマーゲル２は、比重＝０．９６、グラフト率が１１．５質量％、５質量％トルエン溶液粘度η＝２１２０ｍＰａ・ｓであり、従って、溶液粘度の比η／ηｏ＝５．５であった。
[Preparation of polymer gel 2]
177.8 g of SBR latex “Nipol Lx110” manufactured by Nippon Zeon Co., Ltd. and 182.2 g of distilled water were poured into a reactor equipped with stirring means, and then 1.44 g of t-butylperoxylaurate was added. After the inside of the reactor was purged with nitrogen for 2 hours, the reactor was stirred at 80 ° C. for 4 hours, and the reactor was returned to room temperature to obtain a polymer gel. The obtained polymer gel had Tg = −50 ° C., Qi = 3, average particle diameter = 80 nm, specific gravity = 0.94, 5 mass% toluene solution viscosity η o = 386 mPa · s. Further, graft polymerization was performed on the polymer gel. That is, 200 g of the above polymer gel containing water and 0.6 g of sodium dodecyl sulfate were added to the reactor, and the temperature was raised while performing nitrogen substitution and stirring. At 60 ° C., 10.2 g of methyl acrylate, ethyl acrylate 1.3 g and 0.36 g of t-butyl hydroperoxide were slowly added, and then the temperature was raised to 80 ° C. and maintained for 2 hours. After completion, the reaction solution was poured into a poor solvent, washed 3 times and dried to obtain a desired polymer gel. The obtained polymer gel 2 has a specific gravity = 0.96, a graft ratio of 11.5% by mass, and a 5% by mass toluene solution viscosity η = 2120 mPa · s, and thus the solution viscosity ratio η / η o = 5. It was 5.
［ポリマーゲル３の作製］（比較例）
日本ゼオン（株）製ＳＢＲラテックス「Ｎｉｐｏｌ Ｌｘ１１０」１７７．８ｇと蒸留水１８２．２ｇを、攪拌手段を備えた反応器へ注ぎ、次いで、ｔ−ブチルペルオキシラウレート１．４４ｇを添加した。反応器内を２時間窒素置換した後、８０℃で４時間攪拌し、反応器を室温に戻し、ポリマーゲルを得た。得られたポリマーゲルは、Ｔｇ＝−５０℃、Ｑｉ＝３、平均粒子径＝８０ｎｍ、比重＝０．９４、５質量％トルエン溶液粘度ηｏ＝３８６ｍＰａ・ｓであった。更に、該ポリマーゲルに対してグラフト重合を実施した。すなわち、上記水分を含むポリマーゲル２００ｇ、ドデシル硫酸ナトリウム０．６ｇを反応器に添加、窒素置換と攪拌を実施しながら昇温を開始し、６０℃の時点で、メチルアクリレート２０．４ｇ、エチルアクリレート２．６ｇ、ｔ−ブチルハイドロパーオキサイド０．７３ｇをゆっくりと添加し、その後８０℃へ昇温、そのまま４時間保持した。終了後、反応溶液を貧溶媒へ注ぎ、３回洗浄後乾燥させ、所望のポリマーゲルを得た。得られたポリマーゲル３は、比重＝０．９８、グラフト率が４４．０質量％、５質量％トルエン溶液粘度η＝１５４７７ｍＰａ・ｓであり、従って、溶液粘度の比η／ηｏ＝４０．１であった。
[Production of Polymer Gel 3] (Comparative Example)
177.8 g of SBR latex “Nipol Lx110” manufactured by Nippon Zeon Co., Ltd. and 182.2 g of distilled water were poured into a reactor equipped with stirring means, and then 1.44 g of t-butylperoxylaurate was added. The inside of the reactor was purged with nitrogen for 2 hours, and then stirred at 80 ° C. for 4 hours, and the reactor was returned to room temperature to obtain a polymer gel. The obtained polymer gel had Tg = −50 ° C., Qi = 3, average particle diameter = 80 nm, specific gravity = 0.94, 5 mass% toluene solution viscosity η o = 386 mPa · s. Further, graft polymerization was performed on the polymer gel. That is, 200 g of the above polymer gel containing water and 0.6 g of sodium dodecyl sulfate were added to the reactor, and the temperature was raised while performing nitrogen substitution and stirring. At 60 ° C., 20.4 g of methyl acrylate, ethyl acrylate 2.6 g and 0.73 g of t-butyl hydroperoxide were slowly added, and then the temperature was raised to 80 ° C. and maintained for 4 hours. After completion, the reaction solution was poured into a poor solvent, washed 3 times and dried to obtain a desired polymer gel. The obtained polymer gel 3 has a specific gravity = 0.98, a grafting ratio of 44.0% by mass, and a 5% by mass toluene solution viscosity η = 15477 mPa · s. Therefore, the solution viscosity ratio η / η o = 40. 1
［ポリマーゲル４の作製］（比較例）
日本ゼオン（株）製ＳＢＲラテックス「Ｎｉｐｏｌ Ｌｘ４１５Ｍ」１８６．０ｇと蒸留水２１３．９ｇを、攪拌手段を備えた反応器へ注ぎ、次いで、ｔ−ブチルペルオキシラウレート１．４４ｇを添加した。反応器内を２時間窒素置換した後、８０℃で４時間攪拌し、反応器を室温に戻し、ポリマーゲルを得た。得られたポリマーゲルは、Ｔｇ＝２７℃、Ｑｉ＝３、平均粒子径＝１１０ｎｍ、比重＝０．９３、５質量％トルエン溶液粘度ηｏ＝４４１ｍＰａ・ｓであった。更に、該ポリマーゲルに対してグラフト重合を実施した。すなわち、上記水分を含むポリマーゲル２００ｇ、ドデシル硫酸ナトリウム０．５ｇを反応器に添加、窒素置換と攪拌を実施しながら昇温を開始し、６０℃の時点で、メチルアクリレート１０．２ｇ、エチルアクリレート１．３ｇ、ｔ−ブチルハイドロパーオキサイド０．３７ｇをゆっくりと添加し、その後８０℃へ昇温、そのまま２時間保持した。終了後、反応溶液を貧溶媒へ注ぎ、３回洗浄後乾燥させ、所望のポリマーゲルを得た。得られたポリマーゲル４は、比重＝０．９４、グラフト率が１３．２質量％、５質量％トルエン溶液粘度η＝２７７５ｍＰａ・ｓであり、従って、溶液粘度の比η／ηｏ＝６．３であった。
[Production of Polymer Gel 4] (Comparative Example)
186.0 g of SBR latex “Nipol Lx415M” manufactured by Nippon Zeon Co., Ltd. and 213.9 g of distilled water were poured into a reactor equipped with a stirring means, and then 1.44 g of t-butyl peroxylaurate was added. After the inside of the reactor was purged with nitrogen for 2 hours, the reactor was stirred at 80 ° C. for 4 hours, and the reactor was returned to room temperature to obtain a polymer gel. The obtained polymer gel had Tg = 27 ° C., Qi = 3, average particle size = 110 nm, specific gravity = 0.93, and 5 mass% toluene solution viscosity η o = 441 mPa · s. Further, graft polymerization was performed on the polymer gel. That is, 200 g of the above polymer gel containing water and 0.5 g of sodium dodecyl sulfate were added to the reactor, and the temperature was raised while performing nitrogen substitution and stirring. At 60 ° C., 10.2 g of methyl acrylate, ethyl acrylate 1.3 g and 0.37 g of t-butyl hydroperoxide were slowly added, and then the temperature was raised to 80 ° C. and maintained for 2 hours. After completion, the reaction solution was poured into a poor solvent, washed 3 times and dried to obtain a desired polymer gel. The obtained polymer gel 4 has a specific gravity = 0.94, a graft ratio of 13.2% by mass, and a 5% by mass toluene solution viscosity η = 2775 mPa · s. Therefore, the solution viscosity ratio η / η o = 6. 3.
［ポリマーゲル５の作製］（比較例）
日本ゼオン（株）製ＳＢＲラテックス「Ｎｉｐｏｌ Ｌｘ１１０」１７７．８ｇと蒸留水１８２．２ｇを、攪拌手段を備えた反応器へ注ぎ、次いで、ｔ−ブチルペルオキシラウレート０．７２ｇを添加した。反応器内を２時間窒素置換した後、８０℃で１時間攪拌し、反応器を室温に戻し、ポリマーゲルを得た。得られたポリマーゲルは、Ｔｇ＝−５０℃、Ｑｉ＝２４、平均粒子径＝１００ｎｍ、比重＝０．９３、５質量％トルエン溶液粘度ηｏ＝６４４ｍＰａ・ｓであった。更に、該ポリマーゲルに対してグラフト重合を実施した。すなわち、上記水分を含むポリマーゲル２００ｇ、ドデシル硫酸ナトリウム０．６ｇを反応器に添加、窒素置換と攪拌を実施しながら昇温を開始し、６０℃の時点で、メチルアクリレート１０．２ｇ、エチルアクリレート１．３ｇ、ｔ−ブチルハイドロパーオキサイド０．３６ｇをゆっくりと添加し、その後８０℃へ昇温、そのまま２時間保持した。終了後、反応溶液を貧溶媒へ注ぎ、３回洗浄後乾燥させ、所望のポリマーゲルを得た。得られたポリマーゲル５は、比重＝０．９４、グラフト率が２１．５質量％、５質量％トルエン溶液粘度η＝８０５１ｍＰａ・ｓであり、従って、溶液粘度の比η／ηｏ＝１２．５であった。
[Production of Polymer Gel 5] (Comparative Example)
177.8 g of SBR latex “Nipol Lx110” manufactured by Nippon Zeon Co., Ltd. and 182.2 g of distilled water were poured into a reactor equipped with stirring means, and then 0.72 g of t-butyl peroxylaurate was added. The inside of the reactor was purged with nitrogen for 2 hours, and then stirred at 80 ° C. for 1 hour, and the reactor was returned to room temperature to obtain a polymer gel. The obtained polymer gel had Tg = −50 ° C., Qi = 24, average particle size = 100 nm, specific gravity = 0.93, 5 mass% toluene solution viscosity η o = 644 mPa · s. Further, graft polymerization was performed on the polymer gel. That is, 200 g of the above polymer gel containing water and 0.6 g of sodium dodecyl sulfate were added to the reactor, and the temperature was raised while performing nitrogen substitution and stirring. At 60 ° C., 10.2 g of methyl acrylate, ethyl acrylate 1.3 g and 0.36 g of t-butyl hydroperoxide were slowly added, and then the temperature was raised to 80 ° C. and maintained for 2 hours. After completion, the reaction solution was poured into a poor solvent, washed 3 times and dried to obtain a desired polymer gel. The obtained polymer gel 5 has a specific gravity = 0.94, a graft ratio of 21.5% by mass, and a 5% by mass toluene solution viscosity η = 8051 mPa · s, and thus the solution viscosity ratio η / η o = 12. It was 5.
［ポリマーゲル６の作製］
日本ゼオン（株）製ＳＢＲラテックス「Ｎｉｐｏｌ Ｌｘ１１０」１７７．８ｇと蒸留水１８２．２ｇを、攪拌手段を備えた反応器へ注ぎ、次いで、ｔ−ブチルペルオキシラウレート１．４４ｇを添加した。反応器内を２時間窒素置換した後、８０℃で４時間攪拌し、反応器を室温に戻し、ポリマーゲルを得た。得られたポリマーゲルは、Ｔｇ＝−５０℃、Ｑｉ＝３、平均粒子径＝８０ｎｍ、比重＝０．９４、５質量％トルエン溶液粘度ηｏ＝３８６ｍＰａ・ｓであった。更に、該ポリマーゲルに対してグラフト重合を実施した。すなわち、上記水分を含むポリマーゲル２００ｇ、ドデシル硫酸ナトリウム０．６ｇを反応器に添加、窒素置換と攪拌を実施しながら昇温を開始し、６０℃の時点で、メチルメタクリレート１２．１ｇ、ｔ−ブチルハイドロパーオキサイド０．４１ｇをゆっくりと添加し、その後８０℃へ昇温、そのまま２時間保持した。終了後、反応溶液を貧溶媒へ注ぎ、３回洗浄後乾燥させ、所望のポリマーゲルを得た。得られたポリマーゲル６は、比重＝０．９４、グラフト率が１８．１質量％、５質量％トルエン溶液粘度η＝３５１２ｍＰａ・ｓであり、従って、溶液粘度の比η／ηｏ＝９．１であった。
[Preparation of polymer gel 6]
177.8 g of SBR latex “Nipol Lx110” manufactured by Nippon Zeon Co., Ltd. and 182.2 g of distilled water were poured into a reactor equipped with stirring means, and then 1.44 g of t-butylperoxylaurate was added. The inside of the reactor was purged with nitrogen for 2 hours, and then stirred at 80 ° C. for 4 hours, and the reactor was returned to room temperature to obtain a polymer gel. The obtained polymer gel had Tg = −50 ° C., Qi = 3, average particle diameter = 80 nm, specific gravity = 0.94, 5 mass% toluene solution viscosity η o = 386 mPa · s. Further, graft polymerization was performed on the polymer gel. That is, 200 g of the above polymer gel containing water and 0.6 g of sodium dodecyl sulfate were added to the reactor, and the temperature was increased while performing nitrogen substitution and stirring. At 60 ° C., 12.1 g of methyl methacrylate, t- 0.41 g of butyl hydroperoxide was slowly added, and then the temperature was raised to 80 ° C. and held there for 2 hours. After completion, the reaction solution was poured into a poor solvent, washed 3 times and dried to obtain a desired polymer gel. The obtained polymer gel 6 has a specific gravity = 0.94, a graft ratio of 18.1% by mass, and a 5% by mass toluene solution viscosity η = 3512 mPa · s. Therefore, the solution viscosity ratio η / η o = 9. 1
［ポリマーゲル７の作製］
日本ゼオン（株）製ＳＢＲラテックス「Ｎｉｐｏｌ Ｌｘ１１０」１７７．８ｇと蒸留水１８２．２ｇを、攪拌手段を備えた反応器へ注ぎ、次いで、ｔ−ブチルペルオキシラウレート１．４４ｇを添加した。反応器内を２時間窒素置換した後、８０℃で４時間攪拌し、反応器を室温に戻し、ポリマーゲルを得た。得られたポリマーゲルは、Ｔｇ＝−５０℃、Ｑｉ＝３、平均粒子径＝８０ｎｍ、比重＝０．９４、５質量％トルエン溶液粘度ηｏ＝３８６ｍＰａ・ｓであった。更に、該ポリマーゲルに対してグラフト重合を実施した。すなわち、上記水分を含むポリマーゲル２００ｇ、ドデシル硫酸ナトリウム０．６ｇを反応器に添加、窒素置換と攪拌を実施しながら昇温を開始し、６０℃の時点で、スチレン１２．４ｇ、ｔ−ブチルハイドロパーオキサイド０．４２ｇをゆっくりと添加し、その後８０℃へ昇温、そのまま２時間保持した。終了後、反応溶液を貧溶媒へ注ぎ、３回洗浄後乾燥させ、所望のポリマーゲルを得た。得られたポリマーゲル７は、比重＝０．９５、グラフト率が１９．９質量％、５質量％トルエン溶液粘度η＝４０１２ｍＰａ・ｓであり、従って、溶液粘度の比η／ηｏ＝１０．４であった。
[Preparation of polymer gel 7]
177.8 g of SBR latex “Nipol Lx110” manufactured by Nippon Zeon Co., Ltd. and 182.2 g of distilled water were poured into a reactor equipped with stirring means, and then 1.44 g of t-butylperoxylaurate was added. The inside of the reactor was purged with nitrogen for 2 hours, and then stirred at 80 ° C. for 4 hours, and the reactor was returned to room temperature to obtain a polymer gel. The obtained polymer gel had Tg = −50 ° C., Qi = 3, average particle diameter = 80 nm, specific gravity = 0.94, 5 mass% toluene solution viscosity η o = 386 mPa · s. Further, graft polymerization was performed on the polymer gel. That is, 200 g of the polymer gel containing water and 0.6 g of sodium dodecyl sulfate were added to the reactor, and the temperature was raised while performing nitrogen substitution and stirring. At 60 ° C., 12.4 g of styrene, t-butyl Hydroperoxide (0.42 g) was slowly added, and then the temperature was raised to 80 ° C. and held there for 2 hours. After completion, the reaction solution was poured into a poor solvent, washed 3 times and dried to obtain a desired polymer gel. The obtained polymer gel 7 has a specific gravity = 0.95, a grafting ratio of 19.9% by mass, and a 5% by mass toluene solution viscosity η = 4012 mPa · s. Therefore, the solution viscosity ratio η / η o = 10. 4.
［ポリマーゲル８の作製］
日本ゼオン（株）製ＳＢＲラテックス「Ｎｉｐｏｌ Ｌｘ１１０」１７７．８ｇと蒸留水１８２．２ｇを、攪拌手段を備えた反応器へ注ぎ、次いで、ｔ−ブチルペルオキシラウレート１．４４ｇを添加した。反応器内を２時間窒素置換した後、８０℃で２時間攪拌し、反応器を室温に戻し、ポリマーゲルを得た。得られたポリマーゲルは、Ｔｇ＝−５０℃、Ｑｉ＝９、平均粒子径＝９０ｎｍ、比重＝０．９３、５質量％トルエン溶液粘度ηｏ＝４９３ｍＰａ・ｓであった。更に、該ポリマーゲルに対してグラフト重合を実施した。すなわち、上記水分を含むポリマーゲル２００ｇ、ドデシル硫酸ナトリウム０．６ｇを反応器に添加、窒素置換と攪拌を実施しながら昇温を開始し、６０℃の時点で、メチルアクリレート１０．２ｇ、エチルアクリレート１．３ｇ、ｔ−ブチルハイドロパーオキサイド０．３６ｇをゆっくりと添加し、その後８０℃へ昇温、そのまま２時間保持した。終了後、反応溶液を貧溶媒へ注ぎ、３回洗浄後乾燥させ、所望のポリマーゲルを得た。得られたポリマーゲル８は、比重＝０．９３、グラフト率が１４．５質量％、５質量％トルエン溶液粘度η＝３５４０ｍＰａ・ｓであり、従って、溶液粘度の比η／ηｏ＝７．２であった。
[Preparation of polymer gel 8]
177.8 g of SBR latex “Nipol Lx110” manufactured by Nippon Zeon Co., Ltd. and 182.2 g of distilled water were poured into a reactor equipped with stirring means, and then 1.44 g of t-butylperoxylaurate was added. The inside of the reactor was purged with nitrogen for 2 hours, and then stirred at 80 ° C. for 2 hours. The reactor was returned to room temperature to obtain a polymer gel. The obtained polymer gel had Tg = −50 ° C., Qi = 9, average particle diameter = 90 nm, specific gravity = 0.93, 5 mass% toluene solution viscosity η o = 493 mPa · s. Further, graft polymerization was performed on the polymer gel. That is, 200 g of the above polymer gel containing water and 0.6 g of sodium dodecyl sulfate were added to the reactor, and the temperature was raised while performing nitrogen substitution and stirring. At 60 ° C., 10.2 g of methyl acrylate, ethyl acrylate 1.3 g and 0.36 g of t-butyl hydroperoxide were slowly added, and then the temperature was raised to 80 ° C. and maintained for 2 hours. After completion, the reaction solution was poured into a poor solvent, washed 3 times and dried to obtain a desired polymer gel. The obtained polymer gel 8 has a specific gravity = 0.93, a graft ratio of 14.5% by mass, and a 5% by mass toluene solution viscosity η = 3540 mPa · s, and thus a solution viscosity ratio η / η o = 7. 2.
［第１実施例］
バンバリーミキサーを使用し、下記表１に示す配合に従って、タイヤ用ゴム組成物を調製した。詳細には、第一混合段階で、硫黄と加硫促進剤を除く成分を添加混合し、次いで、得られた混合物に、最終混合段階で硫黄と加硫促進剤を添加混合して、ゴム組成物を調製した。表中の各成分、及び共通配合については以下の通りである。
[First embodiment]
Using a Banbury mixer, a tire rubber composition was prepared according to the formulation shown in Table 1 below. Specifically, in the first mixing stage, components other than sulfur and vulcanization accelerator are added and mixed, and then the resulting mixture is added and mixed with sulfur and vulcanization accelerator in the final mixing stage to obtain a rubber composition. A product was prepared. Each component in the table and the common formulation are as follows.
・天然ゴム：ＲＳＳ＃３
・カーボンブラック：Ｎ３３９、三菱化学（株）製（比重＝１．８）
・オイル：株式会社ジャパンエナジー製「プロセスＮＣ−１４０」
・ Natural rubber: RSS # 3
Carbon black: N339, manufactured by Mitsubishi Chemical Corporation (specific gravity = 1.8)
・ Oil: “Process NC-140” manufactured by Japan Energy Co., Ltd.
共通配合は、ゴム成分１００質量部に対して、亜鉛華（三井金属鉱業（株）製「亜鉛華１号」）３質量部、老化防止剤（住友化学（株）製「アンチゲン６Ｃ」）２質量部、ステアリン酸（花王（株）製「ルナックＳ−２０」）２質量部、ワックス（日本精鑞（株）製「ＯＺＯＡＣＥ０３５５」）２質量部、硫黄（鶴見化学工業（株）製「５％油入微粉末硫黄」）１．５質量部、加硫促進剤１（住友化学（株）製「ソクシノールＣＺ」）１．８質量部、加硫促進剤２（大内新興化学工業（株）製「ノクセラーＤ」）２．０質量部とした。 Common blending is 3 parts by weight of zinc white ("Zinc Flower No. 1" manufactured by Mitsui Mining & Smelting Co., Ltd.) and 100% of anti-aging agent ("Antigen 6C" manufactured by Sumitomo Chemical Co., Ltd.). 2 parts by mass of stearic acid (“Lunac S-20” manufactured by Kao Corporation), 2 parts by mass of wax (“OZOACE0355” manufactured by Nippon Seiki Co., Ltd.), sulfur (“5 manufactured by Tsurumi Chemical Co., Ltd.) % Oil-filled fine powder sulfur ") 1.5 parts by mass, vulcanization accelerator 1 (" Soccinol CZ "manufactured by Sumitomo Chemical Co., Ltd.) 1.8 parts by mass, vulcanization accelerator 2 (Ouchi Shinsei Chemical Industry Co., Ltd.) “Noxeller D” manufactured by KK) was 2.0 parts by mass.
得られた各ゴム組成物について、ムーニー粘度を測定するとともに、１６０℃×３０分で加硫して所定形状の試験片を作製し、得られた試験片を用いて、硬度、引張強度、ｔａｎδ、反発弾性率を測定した。各測定方法は以下の通りである。 About each obtained rubber composition, while measuring Mooney viscosity, it vulcanizes | cures at 160 degreeC x 30 minutes, and produces the test piece of a predetermined shape, Hardness, tensile strength, tan (delta) was used for the obtained test piece. The impact resilience was measured. Each measuring method is as follows.
・ムーニー粘度：混合後におけるゴム組成物の１００℃でのムーニー粘度（ＡＳＴＭ Ｄ１６４６）を測定した。 Mooney viscosity: Mooney viscosity (ASTM D1646) at 100 ° C. of the rubber composition after mixing was measured.
・硬度：ＪＩＳ Ｋ６２５３に準拠したタイプＡデュロメータを使用し、２３℃での硬度を測定した。 Hardness: A hardness at 23 ° C. was measured using a type A durometer according to JIS K6253.
・引張強度：ＪＩＳ Ｋ６２５１に準拠して引張試験を行い（３号形ダンベル使用）、破断時引っ張り強さを測定した。 -Tensile strength: A tensile test was performed in accordance with JIS K6251 (using No. 3 dumbbell), and the tensile strength at break was measured.
・ｔａｎδ：動的粘弾性測定装置（上島製作所（株）製）を使用し、ＪＩＳ Ｋ６３９４に準じて、周波数５０Ｈｚ、静歪み１０％、動歪み１．０％、温度５０℃の条件で損失係数ｔａｎδを測定し、比較例１の値を１００とした指数で表示した。指数が小さいほどｔａｎδが小さく、発熱しにくい（即ち、低発熱性に優れる）ことを示す。 Tan δ: Loss coefficient using a dynamic viscoelasticity measuring device (manufactured by Ueshima Seisakusho Co., Ltd.) under the conditions of frequency 50 Hz, static strain 10%, dynamic strain 1.0%, temperature 50 ° C. Tan δ was measured and displayed as an index with the value of Comparative Example 1 being 100. The smaller the index, the smaller the tan δ, and the less the heat is generated (that is, the low heat buildup is excellent).
・反発弾性率：リュプケ式反発弾性試験機を使用し、ＪＩＳ Ｋ６３０１に準じて、室温雰囲気下での反発弾性率（％）を測定し、反発弾性率の逆数について比較例１の値を１００とした指数で表示した。指数が大きいほど、反発弾性率が低く、ウェットグリップ性に優れることを示す。
結果は表１に示す通りであり、比較例２では、ポリマーゲルを配合したものの、その表面をグラフト化していないものであったため、比較例１に対し、低発熱化の効果は認められたものの、硬度及び引張強度が劣っていた。比較例３では、ポリマーゲルの表面をグラフト化したものの、トルエン溶液粘度の比η／ηｏが高すぎたため、グラフト鎖の絡み合いが高度に生起しており、そのため、低発熱性とウェットグリップ性が悪化しており、加工性も損なわれた。比較例４では、ポリマーゲルの表面をグラフト化したものの、ベースとなるジエン系ポリマー粒子のガラス転移温度が高すぎたため、低発熱性とウェットグリップ性、更には加工性についても改良効果は得られなかった。同様に比較例５では、ベースとなるジエン系ポリマー粒子の膨潤度Ｑｉが高いため、十分な補強性を得ることができなかった。これに対し、実施例１〜６のように特定のガラス転移温度及び膨潤度を持つジエン系ポリマー粒子にグラフト鎖を付加させ、その溶液粘度の比η／ηｏを調整したものでは、補強性を十分に保ちつつ、低発熱性とウェットグリップ性が顕著に改善されており、また、ムーニー粘度が低く、加工性にも優れていた。 The results are as shown in Table 1. In Comparative Example 2, although the polymer gel was blended, the surface was not grafted. The hardness and tensile strength were inferior. In Comparative Example 3, although the surface of the polymer gel was grafted, the η / η o ratio of the toluene solution was too high, so that the entanglement of the graft chain occurred to a high degree. Deteriorated and processability was also impaired. In Comparative Example 4, although the surface of the polymer gel was grafted, the glass transition temperature of the diene polymer particles as the base was too high, so that an improvement effect was obtained with respect to low heat build-up, wet grip, and workability. There wasn't. Similarly, in Comparative Example 5, since the degree of swelling Qi of the diene polymer particles serving as the base is high, sufficient reinforcement could not be obtained. On the other hand, as in Examples 1 to 6, a graft chain is added to a diene polymer particle having a specific glass transition temperature and swelling degree, and the solution viscosity ratio η / η o is adjusted. In addition, the low heat build-up and wet grip properties were remarkably improved, and the Mooney viscosity was low and the processability was excellent.
［第２実施例］
バンバリーミキサーを使用し、下記表２に示す配合に従って、タイヤ用ゴム組成物を調製した。詳細には、第一混合段階で、硫黄と加硫促進剤を除く成分を添加混合し、次いで、得られた混合物に、最終混合段階で硫黄と加硫促進剤を添加混合して、ゴム組成物を調製した。表中のＳＢＲは、スチレンブタジエンゴム（ＪＳＲ（株）製「ＳＢＲ１５０２」）であり、その他は表１と同じである。
[Second Embodiment]
Using a Banbury mixer, a tire rubber composition was prepared according to the formulation shown in Table 2 below. Specifically, in the first mixing stage, components other than sulfur and vulcanization accelerator are added and mixed, and then the resulting mixture is added and mixed with sulfur and vulcanization accelerator in the final mixing stage to obtain a rubber composition. A product was prepared. SBR in the table is styrene butadiene rubber (“SBR1502” manufactured by JSR Corporation), and the others are the same as in Table 1.
得られた各ゴム組成物について、第１実施例と同様に、ムーニー粘度、硬度、引張強度、ｔａｎδ、反発弾性率を測定した。ｔａｎδと反発弾性率については、比較例６の値を１００とした指数で表示した。 About each obtained rubber composition, the Mooney viscosity, hardness, tensile strength, tan-delta, and impact resilience were measured similarly to 1st Example. The tan δ and the rebound resilience were expressed as an index with the value of Comparative Example 6 being 100.
結果は表２に示す通りであり、第１実施例と同様、実施例７〜１１であると、ポリマーゲルのグラフト化による材料の低発熱化とウェットグリップ性のバランス向上、及び加工性の改善を示し、強度も保持されていた。
本発明に係るゴム組成物は、タイヤ、防振ゴム、ベルトなどの各種ゴム製品に用いることができ、好ましくは、空気入りタイヤのトレッドやサイドウォールに用いることができる。 The rubber composition according to the present invention can be used for various rubber products such as tires, anti-vibration rubbers, and belts, and can be preferably used for treads and sidewalls of pneumatic tires.
Claims (5)
トルエン膨潤指数Ｑｉが１０以下かつガラス転移温度が−１００〜０℃の架橋されたジエン系ポリマー粒子の粒子表面に、グラフト鎖を設けてなるポリマーゲルであって、グラフト変性前のポリマーゲルの５質量％トルエン溶液粘度ηｏに対するグラフト変性後のポリマーゲルの５質量％トルエン溶液粘度ηの比（η／ηｏ）が２〜３０であるポリマーゲルと、
を含むゴム組成物。 A rubber component made of diene rubber;
A polymer gel in which a graft chain is provided on the surface of a crosslinked diene polymer particle having a toluene swelling index Qi of 10 or less and a glass transition temperature of −100 to 0 ° C. a polymer gel ratio of 5 wt% toluene solution viscosity of the polymer gel after graft modification η (η / η o) is 2 to 30 relative to the mass% toluene solution viscosity eta o,
A rubber composition comprising:
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019111601A1 (en) * | 2017-12-07 | 2019-06-13 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition for tire and pneumatic tire using same |
| JP2021088624A (en) * | 2019-12-02 | 2021-06-10 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition and pneumatic tire using the same |
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| JP2009051941A (en) * | 2007-08-27 | 2009-03-12 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire tread and pneumatic tire |
| JP2010116553A (en) * | 2008-10-16 | 2010-05-27 | Sumitomo Rubber Ind Ltd | Rubber composition and studless tire using the same |
| JP2010215884A (en) * | 2009-02-17 | 2010-09-30 | Ube Ind Ltd | Rubber composition for tire and tire using the same |
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| WO2019111601A1 (en) * | 2017-12-07 | 2019-06-13 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition for tire and pneumatic tire using same |
| JP2019099765A (en) * | 2017-12-07 | 2019-06-24 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Tire rubber composition, and pneumatic tire including the same |
| JP2021088624A (en) * | 2019-12-02 | 2021-06-10 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition and pneumatic tire using the same |
| JP7365876B2 (en) | 2019-12-02 | 2023-10-20 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition and pneumatic tire using the same |
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