JP5868250B2 - Rubber composition for tread of high performance tire and pneumatic tire using the same - Google Patents
Rubber composition for tread of high performance tire and pneumatic tire using the same Download PDFInfo
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- JP5868250B2 JP5868250B2 JP2012091240A JP2012091240A JP5868250B2 JP 5868250 B2 JP5868250 B2 JP 5868250B2 JP 2012091240 A JP2012091240 A JP 2012091240A JP 2012091240 A JP2012091240 A JP 2012091240A JP 5868250 B2 JP5868250 B2 JP 5868250B2
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- 229920001971 elastomer Polymers 0.000 title claims description 68
- 239000005060 rubber Substances 0.000 title claims description 68
- 239000000203 mixture Substances 0.000 title claims description 48
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 68
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 61
- 239000007788 liquid Substances 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 5
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 45
- 238000012360 testing method Methods 0.000 description 19
- 230000020169 heat generation Effects 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229920003049 isoprene rubber Polymers 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000012763 reinforcing filler Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 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 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 239000010692 aromatic oil Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- ZUBNXRHITOZMOO-UHFFFAOYSA-N zinc;octadecanoic acid;oxygen(2-) Chemical compound [O-2].[Zn+2].CCCCCCCCCCCCCCCCCC(O)=O ZUBNXRHITOZMOO-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Description
本発明は高性能タイヤのトレッド用ゴム組成物およびそれを用いたトレッドを有する空気入りタイヤに関する。 The present invention relates to a rubber composition for a tread of a high-performance tire and a pneumatic tire having a tread using the same.
競技用タイヤなどの高性能タイヤのトレッド用ゴム組成物には、グリップ性能、耐摩耗性能、耐ブロー性能など、種々の性能において優れることが要求され、これらの性能を向上させるために従来から様々な工夫がなされている。 Rubber compositions for treads of high-performance tires such as competition tires are required to be excellent in various performances such as grip performance, wear resistance performance, and blow resistance performance. Have been devised.
例えば、グリップ性能を向上させるために、トレッド用ゴム組成物にスチレン含有率の高いスチレンブタジエンゴムを用いることが知られている。しかし、このトレッド用ゴム組成物は、最適な高温条件下では優れたグリップ性能を示すが、低温条件下ではゴム組成物の硬度が高いためにゴム組成物の温度上昇が遅く、最適な高温条件下に到達し難いという問題がある。さらに、このゴム組成物は発熱による最終到達温度が高く、温度が上昇し過ぎ、耐摩耗性能および耐ブロー性能が低下するという問題がある。 For example, in order to improve grip performance, it is known to use a styrene butadiene rubber having a high styrene content in the tread rubber composition. However, this tread rubber composition shows excellent grip performance under optimum high temperature conditions, but under low temperature conditions, the rubber composition has high hardness, so the temperature rise of the rubber composition is slow, and optimum high temperature conditions There is a problem that it is difficult to reach below. Further, this rubber composition has a problem that the ultimate temperature due to heat generation is high, the temperature is excessively increased, and the wear resistance and blow resistance are lowered.
特許文献１には、スチレン含量の異なる２種のスチレンブタジエンゴムを含有するゴム組成物であって所定の製造方法により得られるタイヤ用ゴム組成物が記載されているが、グリップ性能、耐ブロー性能および耐摩耗性能を向上させることについては考慮されておらず、さらに液状スチレンブタジエンゴムを含有することの開示はない。 Patent Document 1 describes a rubber composition for tires containing two types of styrene butadiene rubbers having different styrene contents and obtained by a predetermined production method. Further, there is no consideration of improving wear resistance performance, and there is no disclosure of containing liquid styrene butadiene rubber.
特許文献２には、液状スチレンブタジエンゴムおよび芳香族石油樹脂を含有するタイヤトレッド用ゴム組成物とすることで、低温および高温条件下でのグリップ性能、持続性ならびに耐摩耗性を向上させる発明が記載されているが、グリップ性能、耐ブロー性能および耐摩耗性能を向上させるという点では改善の余地がある。 Patent Document 2 discloses an invention for improving grip performance, durability and wear resistance under low and high temperature conditions by using a rubber composition for a tire tread containing a liquid styrene butadiene rubber and an aromatic petroleum resin. Although described, there is room for improvement in terms of improving grip performance, blow resistance performance and wear resistance performance.
本発明は、低温条件下での発熱速度を維持し、発熱による最終到達温度でのグリップ性能、耐ブロー性能および耐摩耗性能において優れる高性能タイヤのトレッド用ゴム組成物およびこのゴム組成物を用いたトレッドを有する空気入りタイヤを提供することを目的とする。 The present invention uses a rubber composition for a tread of a high-performance tire that maintains a heat generation rate under a low temperature condition and is excellent in grip performance, blow resistance performance and wear resistance performance at a final temperature due to heat generation, and the rubber composition. An object of the present invention is to provide a pneumatic tire having a tread.
本発明は、５０〜８０質量％の（Ａ−１）スチレン含有率が３０質量％以下のスチレンブタジエンゴム、および２０〜５０質量％の（Ａ−２）スチレン含有率が４５質量％以上のスチレンブタジエンゴムのみからなる（Ａ）ゴム成分１００質量部に対し、（Ｂ）スチレン含有率が３０質量％以下、質量平均分子量が２０００〜１５０００の液状スチレンブタジエンゴムを２０質量部以上含有する高性能タイヤのトレッド用ゴム組成物に関する。 The present invention includes 50 to 80% by mass of (A-1) styrene butadiene rubber having a styrene content of 30% by mass or less, and 20 to 50% by mass of (A-2) styrene having a styrene content of 45% by mass or more. (A) A high-performance tire containing 20 parts by mass or more of a liquid styrene butadiene rubber having a styrene content of 30% by mass or less and a mass average molecular weight of 2000 to 15000 with respect to 100 parts by mass of the rubber component (A) comprising only butadiene rubber. It relates to the rubber composition for treads.
また、本発明は前記の高性能タイヤのトレッド用ゴム組成物を用いたトレッドを有する空気入りタイヤに関する。 The present invention also relates to a pneumatic tire having a tread using the rubber composition for a tread of the high performance tire.
本発明によれば、スチレン含有率の異なるスチレンブタジエンゴムを所定の比率で混合したゴム成分および所定の液状スチレンブタジエンゴムを含有する高性能タイヤのトレッド用ゴム組成物とすることで、低温条件下での発熱速度を犠牲にすることなく、最終到達温度でのグリップ性能、耐ブロー性能および耐摩耗性能において優れた高性能タイヤのトレッド用ゴム組成物、および該ゴム組成物を用いたトレッドを有する空気入りタイヤを提供することができる。 According to the present invention, a rubber composition for a tread of a high-performance tire containing a rubber component in which styrene butadiene rubbers having different styrene contents are mixed at a predetermined ratio and a predetermined liquid styrene butadiene rubber is used. A rubber composition for a tread of a high-performance tire excellent in grip performance at the ultimate temperature, blow resistance and wear resistance without sacrificing the heat generation rate in the tire, and a tread using the rubber composition A pneumatic tire can be provided.
本発明の高性能タイヤのトレッド用ゴム組成物は、スチレン含有率の異なるスチレンブタジエンゴム（ＳＢＲ）を所定の比率で混合したゴム成分（Ａ）を含有する。 The rubber composition for a tread of the high performance tire of the present invention contains a rubber component (A) in which styrene butadiene rubbers (SBR) having different styrene contents are mixed at a predetermined ratio.
ゴム成分（Ａ）は、スチレン含有率の異なるＳＢＲ（Ａ−１）およびＳＢＲ（Ａ−２）のみからなるゴム成分である。ＳＢＲ（Ａ−１）およびＳＢＲ（Ａ−２）は、スチレン含有率が異なることにより相溶性が低く、ゴム組成物中においても完全には相溶せずに混在する。その結果、ＳＢＲ（Ａ−１）およびＳＢＲ（Ａ−２）のそれぞれの特徴を併せ持つゴム組成物を得ることができる。特に、ＳＢＲ（Ａ−１）が海（マトリックス）、ＳＢＲ（Ａ−２）が島の海島構造を形成することで、低温条件下における温度上昇速度、耐ブロー性能および耐摩耗性能を維持し、グリップ性能に優れたトレッド用ゴム組成物とすることができる。 The rubber component (A) is a rubber component composed only of SBR (A-1) and SBR (A-2) having different styrene contents. SBR (A-1) and SBR (A-2) have low compatibility due to different styrene contents, and are not completely compatible in the rubber composition. As a result, a rubber composition having both the characteristics of SBR (A-1) and SBR (A-2) can be obtained. In particular, SBR (A-1) forms the sea-island structure of the sea (matrix) and SBR (A-2) forms the island structure, maintaining the temperature rise rate, blow resistance and wear resistance under low temperature conditions, A rubber composition for a tread excellent in grip performance can be obtained.
また、前記ゴム成分は、ＳＢＲ（Ａ−１）およびＳＢＲ（Ａ−２）以外のゴム成分として天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、エポキシ化天然ゴム（ＥＮＲ）およびブタジエンゴム（ＢＲ）などのタイヤ工業で一般的に用いられるゴム成分を含有する場合より、特にグリップ性能および耐ブロー性能において優れるという点から、ＳＢＲ（Ａ−１）およびＳＢＲ（Ａ−２）のみからなるゴム成分とする。 The rubber component includes natural rubber (NR), isoprene rubber (IR), epoxidized natural rubber (ENR) and butadiene rubber (BR) as rubber components other than SBR (A-1) and SBR (A-2). The rubber component consisting only of SBR (A-1) and SBR (A-2) from the point of being particularly excellent in grip performance and blow resistance performance than the case of containing a rubber component generally used in the tire industry such as To do.
ＳＢＲとしては、例えば、乳化重合スチレンブタジエンゴム（Ｅ−ＳＢＲ）、溶液重合スチレンブタジエンゴム（Ｓ−ＳＢＲ）が挙げられるが、ＳＢＲ（Ａ−１）およびＳＢＲ（Ａ−２）は、それぞれ乳化重合ＳＢＲ（Ｅ−ＳＢＲ）とすることも、溶液重合ＳＢＲ（Ｓ−ＳＢＲ）とすることもできる。 Examples of SBR include emulsion polymerization styrene butadiene rubber (E-SBR) and solution polymerization styrene butadiene rubber (S-SBR). SBR (A-1) and SBR (A-2) are emulsion polymerizations, respectively. It can be SBR (E-SBR) or solution polymerization SBR (S-SBR).
ＳＢＲ（Ａ−１）のスチレン含有率は、３０質量％以下であり、２７質量％以下であることが好ましい。スチレン含有率が３０質量％を超える場合は、ＳＢＲ（Ａ−２）のスチレン含有率との差が小さく、相溶性が高くなり、グリップ性能、耐ブロー性能および耐摩耗性能を向上させることができなくなる傾向がある。また、ＳＢＲ（Ａ−１）のスチレン含有率は、２３質量％以上であることが、グリップ性能において優れるという点から好ましい。 The styrene content of SBR (A-1) is 30% by mass or less, and preferably 27% by mass or less. When the styrene content exceeds 30% by mass, the difference from the styrene content of SBR (A-2) is small, the compatibility becomes high, and the grip performance, blow resistance and wear resistance can be improved. There is a tendency to disappear. Further, the styrene content of SBR (A-1) is preferably 23% by mass or more from the viewpoint of excellent grip performance.
ゴム成分中のＳＢＲ（Ａ−１）の含有率は、５０質量％以上であり、６０質量％以上であることが好ましい。含有率が５０質量％未満である場合は、ＳＢＲ（Ａ−１）が海、ＳＢＲ（Ａ−２）が島の海島構造を形成することができず、低温条件での発熱速度、耐摩耗性能および耐ブロー性能が低下する傾向がある。また、ＳＢＲ（Ａ−１）の含有率は、８０質量％以下であり、７５質量％以下であることが好ましい。含有率が８０質量％を超える場合は、充分なグリップ性能が得られない傾向がある。 The content of SBR (A-1) in the rubber component is 50% by mass or more, and preferably 60% by mass or more. When the content is less than 50% by mass, SBR (A-1) cannot form a sea-island structure with sea and SBR (A-2) with island, and heat generation rate and wear resistance performance under low temperature conditions. And there is a tendency for the blow-proof performance to decrease. Moreover, the content rate of SBR (A-1) is 80 mass% or less, and it is preferable that it is 75 mass% or less. When the content exceeds 80% by mass, sufficient grip performance tends to be not obtained.
ＳＢＲ（Ａ−２）のスチレン含有率は、４５質量％以上であり、４７質量％以上であることが好ましい。スチレン含有率が４５質量％未満である場合は、ＳＢＲ（Ａ−１）のスチレン含有率との差が小さく、相溶性が高くなり、グリップ性能、耐ブロー性能および耐摩耗性能を向上させることができなくなる傾向がある。また、ＳＢＲ（Ａ−２）のスチレン含有率は、６０質量％以下であることが、低温条件下での発熱速度において優れるという点から好ましい。 The styrene content of SBR (A-2) is 45% by mass or more, and preferably 47% by mass or more. When the styrene content is less than 45% by mass, the difference from the styrene content of SBR (A-1) is small, the compatibility becomes high, and the grip performance, blow resistance and wear resistance can be improved. There is a tendency to become impossible. Moreover, it is preferable that the styrene content rate of SBR (A-2) is 60 mass% or less from the point of being excellent in the heat_generation | fever rate under low temperature conditions.
ゴム成分中のＳＢＲ（Ａ−２）の含有率は、２０質量％以上であり、２５質量％以上であることが好ましい。含有率が２０質量％未満である場合は、充分なグリップ性能が得られない傾向がある。また、ＳＢＲ（Ａ−２）の含有量は、５０質量％以下であり、４０質量％以下であることが好ましい。含有率が５０質量％を超える場合は、ＳＢＲ（Ａ−１）が海、ＳＢＲ（Ａ−２）が島の海島構造を形成することができず、低温条件での発熱速度、耐摩耗性能および耐ブロー性能が低下する傾向がある。 The content of SBR (A-2) in the rubber component is 20% by mass or more, and preferably 25% by mass or more. When the content is less than 20% by mass, sufficient grip performance tends not to be obtained. Moreover, content of SBR (A-2) is 50 mass% or less, and it is preferable that it is 40 mass% or less. When the content exceeds 50% by mass, the SBR (A-1) cannot form a sea-island structure where the sea and SBR (A-2) are islands, and the heat generation rate, wear resistance performance under low temperature conditions and Blow resistance tends to decrease.
本発明の高性能タイヤのトレッド用ゴム組成物は、液状ＳＢＲ（Ｂ）を含有する。 The rubber composition for a tread of the high performance tire of the present invention contains liquid SBR (B).
液状ＳＢＲ（Ｂ）のスチレン含有率は、３０質量％以下であり、２７質量％以下であることが好ましい。スチレン含有率が３０質量％を超える場合は、低温条件下での発熱速度が低下する傾向がある。また、液状ＳＢＲ（Ｂ）のスチレン含有率は、２０質量％以上であることが好ましく、２３質量％以上であることがより好ましい。スチレン含有率が２０質量％未満である場合は、充分なグリップ性能が得られない傾向がある。 The styrene content rate of liquid SBR (B) is 30 mass% or less, and it is preferable that it is 27 mass% or less. When the styrene content exceeds 30% by mass, the heat generation rate under low temperature conditions tends to decrease. Moreover, it is preferable that the styrene content rate of liquid SBR (B) is 20 mass% or more, and it is more preferable that it is 23 mass% or more. When the styrene content is less than 20% by mass, there is a tendency that sufficient grip performance cannot be obtained.
液状ＳＢＲ（Ｂ）の質量平均分子量は、２０００〜１５０００であり、４０００〜１２０００であることが好ましい。質量平均分子量が２０００未満である場合は、充分なグリップ性能や、耐摩耗性能が得られない傾向がある。また、質量平均分子量が１５０００を超える場合は、低温条件下での発熱速度が低下する傾向がある。なお、本発明における液状ＳＢＲの質量平均分子量はゲル浸透クロマトグラフィー（ＧＰＣ）で測定したポリスチレン換算質量平均分子量である。 The mass average molecular weight of liquid SBR (B) is 2000-15000, and it is preferable that it is 4000-12000. When the mass average molecular weight is less than 2000, there is a tendency that sufficient grip performance and wear resistance performance cannot be obtained. On the other hand, when the mass average molecular weight exceeds 15000, the heat generation rate under low temperature conditions tends to decrease. In addition, the mass mean molecular weight of liquid SBR in this invention is a polystyrene conversion mass mean molecular weight measured by gel permeation chromatography (GPC).
液状ＳＢＲ（Ｂ）の含有量は、ゴム成分（Ａ）１００質量部に対して２０質量部以上であり、３０質量部以上であることが好ましい。含有量が２０質量部未満である場合は、充分なグリップ性能が得られない傾向がある。また、液状ＳＢＲ（Ｂ）の含有量は、ゴム成分１００質量部に対して１００質量部以下であることが好ましく、８０質量部以下であることがより好ましい。含有量が１００質量部を超える場合は、耐ブロー性能、耐摩耗性能が低下する傾向がある。 Content of liquid SBR (B) is 20 mass parts or more with respect to 100 mass parts of rubber components (A), and it is preferable that it is 30 mass parts or more. When the content is less than 20 parts by mass, sufficient grip performance tends not to be obtained. Moreover, it is preferable that it is 100 mass parts or less with respect to 100 mass parts of rubber components, and, as for content of liquid SBR (B), it is more preferable that it is 80 mass parts or less. When content exceeds 100 mass parts, there exists a tendency for blow-proof performance and abrasion-proof performance to fall.
本発明の高性能タイヤのトレッド用ゴム組成物は、補強用充填剤を含有することが好ましい。 The rubber composition for a tread of the high performance tire of the present invention preferably contains a reinforcing filler.
補強用充填剤としては、カーボンブラック、シリカ、炭酸カルシウム、アルミナ、クレー、タルクなど、従来からタイヤ用ゴム組成物において用いられているもののなかから任意に選択して用いることができるが、主にカーボンブラックを含有することが好ましい。 As the reinforcing filler, carbon black, silica, calcium carbonate, alumina, clay, talc, etc., which can be arbitrarily selected from those conventionally used in tire rubber compositions, are mainly used. It is preferable to contain carbon black.
前記カーボンブラックの窒素吸着比表面積（Ｎ2ＳＡ）は１００ｍ2／ｇ以上であることが好ましく、１５０ｍ2／ｇ以上であることがより好ましい。Ｎ2ＳＡが１００ｍ2／ｇ未満である場合はグリップ性能において劣る傾向がある。また、カーボンブラックのＮ2ＳＡは、３００ｍ2／ｇ以下であることが好ましく、２５０ｍ2／ｇ以下であることがより好ましい。３００ｍ2／ｇを超える場合は良好な分散が得られ難くなり、耐摩耗性能が悪化する傾向がある。 The carbon black has a nitrogen adsorption specific surface area (N 2 SA) of preferably 100 m 2 / g or more, and more preferably 150 m 2 / g or more. When N 2 SA is less than 100 m 2 / g, grip performance tends to be inferior. Further, N 2 SA of carbon black is preferably 300 m 2 / g or less, and more preferably 250 m 2 / g or less. When it exceeds 300 m 2 / g, it becomes difficult to obtain good dispersion, and the wear resistance tends to deteriorate.
前記カーボンブラックを含有する場合の含有量は、ゴム成分（Ａ）１００質量部に対して６０〜１８０質量部であることが好ましく、８０〜１００質量部であることがより好ましい。含有量が６０質量部未満の場合は十分なグリップ性能を維持できない恐れがある。また、含有量が１８０質量部を超える場合は、加工性が悪化し、本発明のゴム組成物を得ることが困難となる恐れがある。 When the carbon black is contained, the content is preferably 60 to 180 parts by mass and more preferably 80 to 100 parts by mass with respect to 100 parts by mass of the rubber component (A). If the content is less than 60 parts by mass, sufficient grip performance may not be maintained. Moreover, when content exceeds 180 mass parts, workability may deteriorate and it may become difficult to obtain the rubber composition of this invention.
本発明の高性能タイヤのトレッド用ゴム組成物は、軟化剤を含有することが好ましい。 The rubber composition for a tread of the high performance tire of the present invention preferably contains a softening agent.
軟化剤としては、従来からタイヤ用ゴム組成物に用いられているものであれば特に限定されないが、例えばアロマチックオイル、プロセスオイル、パラフィンオイル等の鉱物油などのオイル、クマロンインデンレジン、石油系レジンなどのレジン、液状ブタジエンゴム、液状イソプレンゴム、液状スチレンイソプレンゴムなどの低分子量の液状ポリマーが挙げられる。なお、本発明における液状ポリマーは液状ＳＢＲ（Ｂ）を含まないものとする。 The softening agent is not particularly limited as long as it is conventionally used in tire rubber compositions. For example, oils such as aromatic oils, process oils, paraffin oils and other mineral oils, coumarone indene resins, petroleum Examples thereof include low molecular weight liquid polymers such as resins such as resin, liquid butadiene rubber, liquid isoprene rubber, and liquid styrene isoprene rubber. In addition, the liquid polymer in this invention shall not contain liquid SBR (B).
前記低分子量の液状ポリマーは、ゲル浸透クロマトグラフィー（ＧＰＣ）で測定したポリスチレン換算質量平均分子量が１０００〜２０００００であることが好ましい。ポリスチレン換算質量平均分子量が１０００未満の場合は、耐久性の向上効果が劣る傾向がある。また、ポリスチレン換算質量平均分子量が２０００００を超える場合は粘度が高く生産性が悪化する傾向がある。 The low molecular weight liquid polymer preferably has a polystyrene-reduced mass average molecular weight of 1,000 to 200,000 as measured by gel permeation chromatography (GPC). When the polystyrene-equivalent mass average molecular weight is less than 1000, the durability improving effect tends to be inferior. Moreover, when the polystyrene conversion mass average molecular weight exceeds 200000, the viscosity tends to be high and the productivity tends to deteriorate.
本発明の高性能タイヤのトレッド用ゴム組成物は、前記のゴム成分、液状ＳＢＲ（Ｂ）、補強用充填剤および軟化剤以外にも、通常ゴム工業で使用される配合剤、例えば、硫黄、シランカップリング剤、各種老化防止剤、酸化亜鉛、ステアリン酸、各種加硫促進剤などを好適に含有することができる。 The rubber composition for a tread of the high-performance tire of the present invention contains, other than the rubber component, liquid SBR (B), reinforcing filler and softener, a compounding agent usually used in the rubber industry, such as sulfur, A silane coupling agent, various anti-aging agents, zinc oxide, stearic acid, various vulcanization accelerators and the like can be suitably contained.
本発明のゴム組成物は、競技用タイヤなどの高性能タイヤのトレッド用ゴム組成物に用いられ、特に、競技用ドライタイヤのトレッド部に用いられることが好ましい。 The rubber composition of the present invention is used for a rubber composition for a tread of a high performance tire such as a competition tire, and is particularly preferably used for a tread portion of a dry tire for competition.
本発明の高性能タイヤのトレッド用ゴム組成物は、一般的な方法で製造される。すなわち、バンバリーミキサーやニーダー、オープンロールなどで前記ゴム成分、および必要に応じてその他の配合剤を混練りし、その後加硫することにより、本発明の高性能タイヤのトレッド用ゴム組成物を製造することができる。 The rubber composition for a tread of a high performance tire of the present invention is produced by a general method. That is, the rubber composition for a tread of the high-performance tire of the present invention is manufactured by kneading the rubber component and other compounding agents as necessary with a Banbury mixer, kneader, open roll, etc., and then vulcanizing. can do.
本発明の空気入りタイヤは、本発明の高性能タイヤのトレッド用ゴム組成物を用いてトレッドを製造し、このトレッドを用いて通常の方法により製造される。すなわち、本発明の高性能タイヤのトレッド用ゴム組成物を未加硫の段階でタイヤのトレッドの形状に押出し加工し、タイヤ成形機上で、通常の方法により、他のタイヤ部材とともに貼り合わせて未加硫タイヤを成形する。該未加硫タイヤを加硫機中で加熱・加圧し、本発明の空気入りタイヤを得る。 The pneumatic tire of the present invention is manufactured by a normal method using a tread produced by using the rubber composition for a tread of the high performance tire of the present invention. That is, the rubber composition for a tread of the high-performance tire of the present invention is extruded into a tire tread shape at an unvulcanized stage, and pasted together with other tire members by a normal method on a tire molding machine. Form an unvulcanized tire. The unvulcanized tire is heated and pressurized in a vulcanizer to obtain the pneumatic tire of the present invention.
本発明を実施例に基づいて説明するが、本発明は、実施例にのみ限定されるものではない。 The present invention will be described based on examples, but the present invention is not limited to the examples.
以下に実施例および比較例において用いた各種薬品をまとめて示す。
ＳＢＲ１：Ｄｏｗ Ｃｈｅｍｉｃａｌ Ｃｏｍｐａｎｙ社製のＳＥ ＳＬＲ４６３０（スチレン含有率：２５質量％、ＳＢＲ固形分１００質量部に対しオイル３７．５質量部含有）
ＳＢＲ２：試作品（スチレン含有率：３０質量％、ＳＢＲ固形分１００質量部に対しオイル３７．５質量部含有）
ＳＢＲ３：日本ゼオン（株）製のＮｉｐｏｌ ９５４１（スチレン含有率：４５質量％、ＳＢＲ固形分１００質量部に対しオイル３７．５質量部含有）
ＳＢＲ４：試作品（スチレン含有率：５０質量％、ＳＢＲ固形分１００質量部に対しオイル３７．５質量部含有）
カーボンブラック：東海カーボン（株）製のシースト９（Ｎ１１０、Ｎ2ＳＡ：１４２ｍ2／ｇ）
ＮＲ：ＴＳＲ２０
液状ＳＢＲ１：サートマー社製のＲＩＣＯＮ１００（スチレン含有率：２５質量％、質量平均分子量：５０００）
液状ＳＢＲ２：試作品（スチレン含有率：１５質量％、質量平均分子量：６０００）
液状ＳＢＲ３：試作品（スチレン含有率：４０質量％、質量平均分子量：８０００）
液状ＳＢＲ４：試作品（スチレン含有率：２５質量％、質量平均分子量：２００００）
液状ＢＲ：サートマー社製のＲＩＣＯＮ１３１（質量平均分子量：４５００）
レジン：日塗化学（株）製のエスクロンＧ−９０（クマロンインデンレジン、軟化点：９０℃）
可塑剤：田岡化学工業（株）製のＤＯＳ（セバシン酸ジ２−エチルヘキシル）
酸化亜鉛：三井金属鉱業（株）製の酸化亜鉛
ステアリン酸：日本油脂（株）製の椿
老化防止剤：住友化学（株）製のアンチゲン６Ｃ
ワックス：大内新興化学工業（株）製のサンノックＮ
硫黄：軽井沢硫黄（株）製の粉末硫黄
加硫促進剤：大内新興化学工業（株）製のノクセラーＣＺ（Ｎ−シクロヘキシル−２−ベンゾチアジルスルフェンアミド）
The various chemicals used in the examples and comparative examples are summarized below.
SBR1: SE SLR4630 manufactured by Dow Chemical Company (styrene content: 25% by mass, containing 37.5 parts by mass of oil with respect to 100 parts by mass of SBR solid content)
SBR2: prototype (styrene content: 30% by mass, 37.5 parts by mass of oil with respect to 100 parts by mass of SBR solid content)
SBR3: Nipol 9541 manufactured by Nippon Zeon Co., Ltd. (styrene content: 45% by mass, containing 37.5 parts by mass of oil with respect to 100 parts by mass of SBR solid content)
SBR4: Prototype (styrene content: 50% by mass, 37.5 parts by mass of oil with respect to 100 parts by mass of SBR solid content)
Carbon Black: Seast 9 (N110, N 2 SA: 142 m 2 / g) manufactured by Tokai Carbon Co., Ltd.
NR: TSR20
Liquid SBR1: RICON 100 manufactured by Sartomer (styrene content: 25% by mass, mass average molecular weight: 5000)
Liquid SBR2: prototype (styrene content: 15% by mass, mass average molecular weight: 6000)
Liquid SBR3: prototype (styrene content: 40% by mass, mass average molecular weight: 8000)
Liquid SBR4: prototype (styrene content: 25% by mass, mass average molecular weight: 20000)
Liquid BR: RICON 131 manufactured by Sartomer (mass average molecular weight: 4500)
Resin: Escron G-90 (coumarone indene resin, softening point: 90 ° C.) manufactured by Nikko Chemical Co., Ltd.
Plasticizer: DOS (di-2-ethylhexyl sebacate) manufactured by Taoka Chemical Co., Ltd.
Zinc oxide: Zinc oxide stearic acid manufactured by Mitsui Mining & Smelting Co., Ltd .: Anti-aging agent manufactured by NOF Corporation: Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.
Wax: Sunnock N manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Sulfur: Powder sulfur vulcanization accelerator manufactured by Karuizawa Sulfur Co., Ltd .: Noxeller CZ (N-cyclohexyl-2-benzothiazylsulfenamide) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
実施例１〜６および比較例１〜１１
表１および表２に示す配合内容のうち、各種薬品（硫黄ならびに加硫促進剤１および２を除く）を、（株）神戸製鋼製の１．７Ｌバンバリーミキサーにて混練りし、混練り物を得た。次に、オープンロールを用いて、得られた混練り物に硫黄ならびに加硫促進剤を添加して混練りし、未加硫ゴム組成物を得た。さらに、未加硫ゴム組成物を１５０℃で３分間加硫することで試験用ゴム組成物を得た。
Examples 1-6 and Comparative Examples 1-11
Among the contents shown in Tables 1 and 2, various chemicals (excluding sulfur and vulcanization accelerators 1 and 2) were kneaded with a 1.7 L Banbury mixer manufactured by Kobe Steel Co., Ltd. Obtained. Next, using an open roll, sulfur and a vulcanization accelerator were added to the obtained kneaded product and kneaded to obtain an unvulcanized rubber composition. Furthermore, the rubber composition for a test was obtained by vulcanizing the unvulcanized rubber composition at 150 ° C. for 3 minutes.
また、前記未加硫ゴム組成物を所定の形状の口金を備えた押し出し機で押し出し成形し、他のタイヤ部材とともに貼り合わせて未加硫タイヤを形成し、１７０℃の条件下で１２分間プレス加硫することにより、試験用タイヤ（サイズ：１９５／６５Ｒ１５）を製造した。 Further, the unvulcanized rubber composition is extruded by an extruder equipped with a die having a predetermined shape, and is bonded together with other tire members to form an unvulcanized tire, which is pressed at 170 ° C. for 12 minutes. By vulcanization, a test tire (size: 195 / 65R15) was produced.
＜発熱試験＞
各試験用ゴム組成物を用い、下記の試験条件でフレクソメーター（レオ・ラボ（株）製）による繰り返し圧縮変形を与え、ゴム組成物の自己発熱による温度上昇速度と到達温度を計測した。結果は、比較例１におけるゴム組成物の温度上昇速度および到達温度を１００として指数表示した。指数が大きいほど、上昇速度が速いこと、および到達温度が高いことを示す。試験結果を表１および表２に示す。
試験条件
初期温度：４０℃
繰り返し圧縮歪：２０％
周波数：１０Ｈｚ
<Exothermic test>
Each rubber composition for test was subjected to repeated compression deformation by a flexometer (manufactured by Leo Lab.) Under the following test conditions, and the temperature rise rate and the ultimate temperature due to self-heating of the rubber composition were measured. The results are shown as an index with the temperature rise rate and the reached temperature of the rubber composition in Comparative Example 1 as 100. The larger the index, the faster the rising speed and the higher the reached temperature. The test results are shown in Tables 1 and 2.
Test conditions Initial temperature: 40 ° C
Repeated compression strain: 20%
Frequency: 10Hz
＜グリップ性能試験＞
各試験用タイヤを用いて、ドライアスファルト路面のテストコース（１周約５ｋｍ）にて１０周の実車走行を行なった。その際における操舵時のコントロール性をテストドライバーが評価し、比較例１を１００として指数表示した。指数が大きいほど、ドライ路面におけるグリップ性が高いことを示す。試験結果を表１および表２に示す。
<Grip performance test>
Using each test tire, the vehicle traveled 10 laps on a dry asphalt road test course (about 5 km per lap). The test driver evaluated the controllability at the time of steering at that time, and the comparative example 1 was set to 100 and displayed as an index. It shows that the grip property on a dry road surface is so high that an index | exponent is large. The test results are shown in Tables 1 and 2.
＜耐摩耗性能試験＞
各試験用タイヤを用いて、ドライアスファルト路面のテストコース（１周約５ｋｍ）にて１０周の実車走行を行なった。走行後のタイヤトレッドゴムの残溝量を計測し（新品時１５ｍｍ）、比較例１の残溝量を１００として指数表示した。指数が大きいほど耐摩耗性能が高いことを示す。試験結果を表１および表２に示す。
<Abrasion resistance test>
Using each test tire, the vehicle traveled 10 laps on a dry asphalt road test course (about 5 km per lap). The remaining groove amount of the tire tread rubber after running was measured (15 mm when new), and the index was displayed with the remaining groove amount of Comparative Example 1 being 100. The larger the index, the higher the wear resistance performance. The test results are shown in Tables 1 and 2.
＜耐ブローアウト性能試験＞
各試験用ゴム組成物を用い、下記の試験条件でフレクソメーター（レオ・ラボ（株）製）による繰り返し圧縮変形を与え、ゴム組成物が自己発熱によりブローアウトするまでの時間を測定した。結果は、比較例１におけるゴム組成物がブローアウトするまでの時間を１００として指数表示した。指数が大きいほど、ブローアウトするまでの時間が長く、耐ブロー性能において優れることを示す。試験結果を表１および表２に示す。
<Blowout resistance test>
Each rubber composition for test was subjected to repeated compression deformation by a flexometer (manufactured by Leo Lab.) Under the following test conditions, and the time until the rubber composition blows out due to self-heating was measured. The results are shown as an index with the time until the rubber composition in Comparative Example 1 blows out as 100. The larger the index, the longer the time until blowout and the better the blow-proof performance. The test results are shown in Tables 1 and 2.
表１および表２の結果より、スチレン含有率の異なるスチレンブタジエンゴムを所定の比率で混合したゴム成分および所定の液状スチレンブタジエンゴムを含有する高性能タイヤのトレッド用ゴム組成物は、低温条件下での発熱速度を犠牲にすることなく、最終到達温度でのグリップ性能、耐ブロー性能および耐摩耗性能において優れることがわかる。 From the results of Tables 1 and 2, the rubber composition for a tread of a high performance tire containing a rubber component in which styrene butadiene rubbers having different styrene contents are mixed at a predetermined ratio and a predetermined liquid styrene butadiene rubber is obtained under low temperature conditions. It can be seen that the grip performance, blow resistance, and wear resistance at the final temperature are excellent without sacrificing the heat generation rate at.
Claims (3)
２０〜５０質量％の（Ａ−２）スチレン含有率が４５質量％以上のスチレンブタジエンゴムのみからなる（Ａ）ゴム成分１００質量部に対し、
（Ｂ）スチレン含有率が２０〜３０質量％、質量平均分子量が２０００〜１５０００の液状スチレンブタジエンゴムを２０質量部以上含有する競技用タイヤのトレッド用ゴム組成物。 Only 50 to 80% by mass of (A-1) solid styrene butadiene rubber having a styrene content of 30% by mass or less, and 20 to 50% by mass of (A-2) styrene butadiene rubber having a styrene content of 45% by mass or more. (A) for 100 parts by mass of rubber component,
(B) A rubber composition for a tread of a racing tire containing 20 parts by mass or more of a liquid styrene butadiene rubber having a styrene content of 20 to 30 % by mass and a mass average molecular weight of 2000 to 15000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012091240A JP5868250B2 (en) | 2012-04-12 | 2012-04-12 | Rubber composition for tread of high performance tire and pneumatic tire using the same |
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| JP2012091240A JP5868250B2 (en) | 2012-04-12 | 2012-04-12 | Rubber composition for tread of high performance tire and pneumatic tire using the same |
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| JP5868250B2 true JP5868250B2 (en) | 2016-02-24 |
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| CN114957820B (en) * | 2022-04-27 | 2023-08-29 | 中策橡胶集团股份有限公司 | Tread rubber composition, mixing method and application thereof, and tire |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS56163908A (en) * | 1980-05-23 | 1981-12-16 | Bridgestone Corp | Pneumatic tyre |
| JP3392456B2 (en) * | 1993-04-14 | 2003-03-31 | 横浜ゴム株式会社 | Rubber composition for tire tread |
| JP4895576B2 (en) * | 2005-11-15 | 2012-03-14 | 住友ゴム工業株式会社 | Rubber composition and high-performance tire using the same |
| JP4964460B2 (en) * | 2005-12-12 | 2012-06-27 | 住友ゴム工業株式会社 | Rubber composition for tire |
| JP2008291087A (en) * | 2007-05-23 | 2008-12-04 | Sumitomo Rubber Ind Ltd | Rubber composition for tire tread, and pneumatic tire having tread using the same |
| JP2009173737A (en) * | 2008-01-23 | 2009-08-06 | Bridgestone Corp | Method for producing rubber composition, rubber composition, and tire using the same |
| JP5616073B2 (en) * | 2010-01-27 | 2014-10-29 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire |
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