JP2008208309A - Tire rubber composition - Google Patents
Tire rubber composition Download PDFInfo
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- JP2008208309A JP2008208309A JP2007049044A JP2007049044A JP2008208309A JP 2008208309 A JP2008208309 A JP 2008208309A JP 2007049044 A JP2007049044 A JP 2007049044A JP 2007049044 A JP2007049044 A JP 2007049044A JP 2008208309 A JP2008208309 A JP 2008208309A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 44
- 239000005060 rubber Substances 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 22
- 239000002174 Styrene-butadiene Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 14
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 14
- 229920001194 natural rubber Polymers 0.000 claims abstract description 14
- 239000003208 petroleum Substances 0.000 claims abstract description 14
- 150000003505 terpenes Chemical class 0.000 claims abstract description 11
- 235000007586 terpenes Nutrition 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 2
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 2
- 229920006164 aromatic vinyl copolymer Polymers 0.000 description 2
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000005445 natural material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- -1 N-substituted amino group Chemical group 0.000 description 1
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 229930006739 camphene Natural products 0.000 description 1
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002950 monocyclic group Chemical group 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
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明はタイヤ用ゴム組成物に関し、更に詳しくは転がり抵抗とウェット性能とをともに向上させ、地球環境に配慮したタイヤ用ゴム組成物及びそれを用いた空気入りタイヤに関する。 The present invention relates to a rubber composition for tires, and more particularly relates to a rubber composition for tires that improves both rolling resistance and wet performance and is environmentally friendly, and a pneumatic tire using the same.
近年、地球環境の悪化を懸念する風潮から、環境に配慮した製品が求められるようになっており、タイヤもその例外ではなくなってきている。しかしながら、使用する原材料を単に天然系素材に置き換えるだけでは現行製品と同等以上の性能を出すこと、特に転がり抵抗とウェット性能を両立させることは難しいため、種々の原材料の選択が検討されている。 In recent years, environmentally conscious products have been required due to the trend of fear of deterioration of the global environment, and tires are no longer an exception. However, simply replacing the raw materials to be used with natural materials makes it difficult to achieve performance equal to or higher than that of the current product, and in particular, to achieve both rolling resistance and wet performance, so selection of various raw materials has been studied.
上記観点から種々検討開発が行われており、例えば特許文献１には、タイヤの転動抵抗を悪化させることなく、ウェットグリップを向上させるべく、ジエン系ゴムに対し、テルペン類の芳香族ビニル共重合体及びその水素添加物を配合することが提案されているが、この提案にはシリカを配合することについては触れられていない。特許文献２には耐ブローアウト性を損なうことなく、タイヤのグリップ力を向上させることができる高性能タイヤトレッド用ゴム組成物として、ガラス転移点（Ｔｇ）が−３５℃〜０℃のＳＢＲを７０重量部以上含む原料ゴム１００重量部に対し、充填剤８０〜１８０重量部、軟化点が６０℃〜１００℃のジペンテン芳香族ビニル共重合体樹脂又はα−ピネン樹脂５〜６０重量部を配合することが提案されているが、この配合では高い非石油系原料比率のゴム組成物は得られず、また転がり抵抗とウェット性能のバランスも十分ではない。 Various studies and developments have been made from the above viewpoint. For example, Patent Document 1 discloses that a terpene aromatic vinyl copolymer is used for diene rubber in order to improve wet grip without deteriorating rolling resistance of a tire. Although it has been proposed to blend a polymer and its hydrogenated product, this proposal does not mention blending silica. Patent Document 2 discloses SBR having a glass transition point (Tg) of −35 ° C. to 0 ° C. as a rubber composition for a high-performance tire tread that can improve the grip force of a tire without impairing blowout resistance. 80 to 180 parts by weight of filler and 5 to 60 parts by weight of dipentene aromatic vinyl copolymer resin or α-pinene resin having a softening point of 60 to 100 ° C. are added to 100 parts by weight of raw rubber containing 70 parts by weight or more. However, with this blending, a rubber composition with a high non-petroleum raw material ratio cannot be obtained, and the balance between rolling resistance and wet performance is not sufficient.
特許文献３は、単環式又は二環式の不飽和テルペンの重合で得られる単位を７０〜１００質量％の分率で含み且つＴｇが５０〜１２０℃で数平均分子量が４００〜２０００ｇ／molの可塑化用樹脂を含む、耐摩耗性が改善されたトレッドキャップ用ゴム組成物及びこのトレッドを含むタイヤを提案している。しかしながら、この提案も、本発明のようにシリカ及びＮＲとの相溶性が良い末端変性ＳＢＲを用いることは記載されておらず、高い非石油系原料比率を達成するものではない。特許文献４には、石油外資源の含有比率を高め、ウェット路面及びドライ路面において充分な走行性能を示すタイヤのトレッド用ゴム組成物を開発することを目的に、天然ゴム及び／又はエポキシ化天然ゴムを８０重量％以上含むゴム成分１００重量部に対して、８重量部以上のレジン及び白色充填剤８０重量％以上からなる充填剤を含有するトレッド用ゴム組成物が提案されている。しかし、この提案も上記特許文献３の提案と同様に、シリカ及びＮＲとの相溶性が良い末端変性ＳＢＲを用いることについて言及していない。 Patent Document 3 includes a unit obtained by polymerization of a monocyclic or bicyclic unsaturated terpene in a fraction of 70 to 100% by mass, a Tg of 50 to 120 ° C., and a number average molecular weight of 400 to 2000 g / mol. A rubber composition for a tread cap with improved wear resistance and a tire including the tread are proposed. However, this proposal also does not describe the use of terminal-modified SBR having good compatibility with silica and NR as in the present invention, and does not achieve a high ratio of non-petroleum raw materials. In Patent Document 4, natural rubber and / or epoxidized natural are used for the purpose of developing a rubber composition for a tire tread that increases the content ratio of non-petroleum resources and exhibits sufficient running performance on wet and dry road surfaces. A rubber composition for a tread has been proposed which contains 8 parts by weight or more of a resin and 80% by weight or more of a white filler with respect to 100 parts by weight of a rubber component containing 80% by weight or more of rubber. However, this proposal does not mention the use of terminal-modified SBR having good compatibility with silica and NR, similarly to the proposal of Patent Document 3 above.
従って、本発明の目的は、可能な限り原材料に天然系素材を使用することによって環境に配慮すると同時に、転がり抵抗とウェット性能をともに向上させたゴム組成物を提供することにある。 Accordingly, it is an object of the present invention to provide a rubber composition in which both the rolling resistance and the wet performance are improved while considering the environment by using a natural material as a raw material as much as possible.
本発明に従えば、７０重量部以上の天然ゴム（ＮＲ）及び３０重量部以下の末端変性スチレン−ブタジエン共重合体ゴム（ＳＢＲ）からなるジエン系ゴム１００重量部、ＢＥＴ比表面積が１４０ｍ2／ｇ以下のシリカ５０〜１００重量部、軟化点が１００℃を超える芳香族ビニル変性テルペン樹脂１０〜５０重量部を含んでなり、ゴム組成物中に使用される非石油系原料の比率が８０重量％以上であるタイヤ用ゴム組成物並びにそれを用いた空気入りタイヤが提供される。 According to the present invention, 100 parts by weight of a diene rubber comprising 70 parts by weight or more of natural rubber (NR) and 30 parts by weight or less of a terminal-modified styrene-butadiene copolymer rubber (SBR), and a BET specific surface area of 140 m 2 / 50 to 100 parts by weight of silica having a g or less, 10 to 50 parts by weight of an aromatic vinyl-modified terpene resin having a softening point exceeding 100 ° C., and the ratio of the non-petroleum raw material used in the rubber composition is 80% by weight % Or more of a rubber composition for a tire and a pneumatic tire using the same.
本発明によれば天然ゴムに末端変性ＳＢＲ、特定のシリカ及び芳香族ビニル変性テルペン樹脂を配合することにより、可能な限り原材料に天然系素材を使用して環境に配慮すると同時に、転がり抵抗とウェット性能をともに向上させたゴム組成物を開発することに成功した。 According to the present invention, by blending natural rubber with terminal-modified SBR, specific silica and aromatic vinyl-modified terpene resin, natural materials are used as raw materials as much as possible, and at the same time rolling resistance and wet We have succeeded in developing a rubber composition with improved performance.
近年、地球環境の悪化を懸念する風潮から、環境に配慮した製品が求められるようになっており、タイヤ業界もその例外でなくなってきていることは前述の通りである。そこで、本発明者らは、できるだけ多量の天然系素材をゴム組成物に配合することで環境に配慮すると同時に、転がり抵抗とウェット性能をともに向上させたゴム組成物を開発すべく研究を進めた結果、天然ゴム７０重量部以上、好ましくは７５重量部以上、末端変性ＳＢＲを３０重量部以下、好ましくは２５重量部以下からなるジエン系ゴム１００重量部に対し、ＡＳＴＭ Ｄ１９９３−０３に準じて測定したＢＥＴ比表面積が１４０ｍ2／ｇ以下、好ましくは２０〜１３５ｍ2／ｇのシリカを５０〜１００重量部、好ましくは５０〜９５重量部、ＪＩＳ Ｋ６２２０−１に準じて測定した、軟化点が１００℃より高い、好ましくは１０５〜１６０℃の芳香族ビニル変性テルペン樹脂を１０〜５０重量部、好ましくは１５〜５０重量部、含む原料がゴム組成物中に使用され、非石油系原料の比率が８０重量％以上でありながら、前記従来技術の問題点であった転がり抵抗とウェット性能をともに改良したタイヤ用ゴム組成物を得ることに成功した。 In recent years, environmentally conscious products have been required due to the trend of fear of deterioration of the global environment, and the tire industry is no longer an exception, as described above. Accordingly, the present inventors conducted research to develop a rubber composition in which both the rolling resistance and the wet performance were improved while considering the environment by incorporating as much natural material as possible into the rubber composition. As a result, it is measured according to ASTM D1993-03 with respect to 100 parts by weight of diene rubber comprising 70 parts by weight or more of natural rubber, preferably 75 parts by weight or more and terminal-modified SBR of 30 parts by weight or less, preferably 25 parts by weight or less. The BET specific surface area of 140 m 2 / g or less, preferably 20 to 135 m 2 / g of silica is 50 to 100 parts by weight, preferably 50 to 95 parts by weight, and the softening point is 100 according to JIS K6220-1. 10 to 50 parts by weight, preferably 15 to 50 parts by weight, of an aromatic vinyl-modified terpene resin having a temperature higher than ° C., preferably 105 to 160 ° C. A rubber composition for a tire having improved rolling resistance and wet performance, both of which is a problem of the prior art, is obtained while the material is used in the rubber composition and the ratio of the non-petroleum raw material is 80% by weight or more. Succeeded.
本発明において使用する末端変性ＳＢＲには特に限定はなく、例えば末端部分にＮ−置換アミノ基や水酸基などを有するＳＢＲが挙げられるが、その中でも特に水酸基をＳＢＲの分子末端部分に含む末端変性ＳＢＲを配合する。末端部分に水酸基を含むことにより、ＮＲ／シリカ配合系においてシリカの分散性を更に向上させ、性能も向上させることができる。かかる末端変性ＳＢＲは知られており、例えば特許公報第３４８８９２６号などに記載された方法で製造することができ、日本ゼオン（株）製Ｎｉｐｏｌ ＮＳ６１６などの市販品を用いることもできる。本発明によれば、末端変性ＳＢＲを配合することで、ゴム組成物のウェット性能をより向上させることができる。ただし末端変性ＳＢＲの配合量が多いとゴム組成物中の非石油系原料比率が低下するので好ましくない。 The terminal-modified SBR used in the present invention is not particularly limited, and examples thereof include SBR having an N-substituted amino group or a hydroxyl group at the terminal portion. Among them, a terminal-modified SBR containing a hydroxyl group at the molecular terminal portion of SBR is particularly preferable. Is blended. By including a hydroxyl group at the terminal portion, it is possible to further improve the dispersibility of the silica and improve the performance in the NR / silica blend system. Such a terminal-modified SBR is known and can be produced by, for example, a method described in Japanese Patent Publication No. 3488926, and a commercial product such as Nipol NS616 manufactured by Nippon Zeon Co., Ltd. can also be used. According to this invention, the wet performance of a rubber composition can be improved more by mix | blending terminal modified SBR. However, a large amount of terminal-modified SBR is not preferable because the ratio of non-petroleum raw materials in the rubber composition is lowered.
本発明によれば、前述の如く、ＢＥＴ比表面積が１４０ｍ2／ｇ以下、好ましくは２０〜１３５ｍ2／ｇのシリカを用いることによってゴム組成物の転がり抵抗を低減させることができる。シリカとしては上記比表面積を満足する限り、任意のシリカを用いることができる。 According to the present invention, as described above, BET specific surface area of 140 m 2 / g or less, preferably it is possible to reduce the rolling resistance of the rubber composition by the use of silica 20~135m 2 / g. Any silica can be used as long as the above specific surface area is satisfied.
本発明のゴム組成物には、更に、芳香族ビニル変性テルペン樹脂を用いることによってウェット性能の向上が可能となる。ここで用いる芳香族ビニル変性テルペン樹脂は、例えばα−ピネン、β−ピネン、ジペンテン、リモネン、カンフェン等のテルペン類と、スチレン、α−メチルスチレン、ビニルトルエン等の芳香族ビニル化合物とを共重合させることによって得られる公知の樹脂であり、例えばヤスハラケミカル（株）製ＹＳレジン ＴＯ−１２５，ＴＯ−１１５，ＴＲ−１０５などの市販品を用いることもできる。この配合量が少ないとウェット性能が十分に向上しないので好ましくなく、逆に多いとゴム組成物がやわらかくなりすぎてしまい、所定の性能が得られないので好ましくない。 The rubber composition of the present invention can further improve wet performance by using an aromatic vinyl-modified terpene resin. The aromatic vinyl-modified terpene resin used here is a copolymer of, for example, terpenes such as α-pinene, β-pinene, dipentene, limonene, and camphene, and aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene. For example, commercially available products such as YS resin TO-125, TO-115, TR-105 manufactured by Yasuhara Chemical Co., Ltd. can be used. If the blending amount is small, the wet performance is not sufficiently improved, which is not preferable. Conversely, if the blending amount is large, the rubber composition becomes too soft and the predetermined performance cannot be obtained.
以上の通り、本発明に従えば、以上の構成で非石油系原料を８０重量％以上配合したゴム組成物が所望の物性を有するのでタイヤとしての非石油系原料比率を高めることが可能となる。好ましくは非石油系原料の比率はゴム組成物重量の８１重量％以上である。 As described above, according to the present invention, it is possible to increase the ratio of non-petroleum raw material as a tire because a rubber composition containing 80% by weight or more of non-petroleum raw material having the above configuration has desired physical properties. . Preferably, the ratio of the non-petroleum-based raw material is 81% by weight or more of the weight of the rubber composition.
本発明に係るゴム組成物には、前記した成分に加えて、カーボンブラックなどのその他の補強剤（フィラー）、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、可塑剤などのタイヤ用、その他のゴム組成物用に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量は本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 In addition to the components described above, the rubber composition according to the present invention includes other reinforcing agents (fillers) such as carbon black, vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, anti-aging agents, plastics Various additives generally blended for tires such as additives and other rubber compositions can be blended, and these additives are kneaded by a general method to form a composition, which is then vulcanized or crosslinked. Can be used to do. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used.
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
実施例１〜５及び比較例１〜５
サンプルの調製
表Ｉに示す配合において、加硫促進剤と硫黄を除く成分を１．８リットルの密閉型ミキサーで５分間混練し、１４０℃に達したときに放出してマスターバッチを得た。このマスターバッチに加硫促進剤と硫黄をオープンロールで混練し、ゴム組成物を得た。このゴム組成物の非石油系原料比率（％）を表Ｉに示す。
Examples 1-5 and Comparative Examples 1-5
Sample preparation In the formulation shown in Table I, components other than the vulcanization accelerator and sulfur were kneaded for 5 minutes in a 1.8 liter closed mixer, and released when the temperature reached 140 ° C to obtain a master batch. A vulcanization accelerator and sulfur were kneaded with this masterbatch with an open roll to obtain a rubber composition. Table I shows the non-petroleum raw material ratio (%) of this rubber composition.
次に得られたゴム組成物を１５×１５×０．２cmの金型中で１６０℃で１５分間加硫して加硫ゴムシートを調製し、以下に示す試験法で加硫ゴムの物性を測定した。結果は表Ｉに示す。 Next, the obtained rubber composition was vulcanized in a 15 × 15 × 0.2 cm mold at 160 ° C. for 15 minutes to prepare a vulcanized rubber sheet. The physical properties of the vulcanized rubber were measured by the following test methods. It was measured. The results are shown in Table I.
ゴム物性評価試験法
粘弾性測定（０℃及び６０℃のｔａｎδ）にてウェット性能及び転がり抵抗を評価した。粘弾性測定は以下のようにして実施した。
東洋精機製の粘弾性スペクトロメーターを用い、伸長変形歪率１０±２％、振動数２０Hzの条件で測定した。
性能は比較例１を基準に指数表示した。なお、ウェット性能については、指数の値が高いほど０℃のｔａｎδの値が大きい（性能良好である）ことを示している。また転がり抵抗については、指数の値が高いほど６０℃のｔａｎδの値が小さい（性能良好である）ことを示しており、どちらの性能も、この指数の値が高いほど性能良好であることを示す。
Rubber physical property evaluation test method Wet performance and rolling resistance were evaluated by viscoelasticity measurement (tan δ at 0 ° C. and 60 ° C.). The viscoelasticity measurement was performed as follows.
Using a viscoelastic spectrometer manufactured by Toyo Seiki, measurement was performed under the conditions of an elongation deformation strain rate of 10 ± 2% and a frequency of 20 Hz.
The performance was expressed as an index based on Comparative Example 1. As for the wet performance, the higher the index value, the larger the tan δ value at 0 ° C. (the better the performance). As for rolling resistance, the higher the index value, the smaller the tan δ value at 60 ° C. (the better the performance). Both performances indicate that the higher the index value, the better the performance. Show.
表Ｉ脚注
＊１：天然ゴム ＴＳＲ−２０
＊２：日本ゼオン（株）製Ｎｉｐｏｌ ＮＳ６１６
＊３：日本ゼオン（株）製Ｎｉｐｏｌ ＮＳ１１６Ｒ
＊４：日本ゼオン（株）製Ｎｉｐｏｌ １５０２
＊５：東海カーボン（株）製シースト ＫＨ
＊６：ローディアジャパン（株）製Ｚｅｏｓｉｌ １１５ＧＲ
＊７：東ソー・シリカ（株）製Ｎｉｐｓｉｌ ＡＱ
＊８：ヤスハラケミカル（株）製ＹＳレジン ＴＯ１２５
＊９：ヤスハラケミカル（株）製ＹＳレジン ＰＸ２００（変性なし）
＊１０：正同化学工業（株）製酸化亜鉛３種
＊１１：日本油脂（株）製ビーズステアリン酸 ＹＲ
＊１２：フレキシス社製サントフレックス ６ＰＰＤ
＊１３：大内新興化学工業（株）製サンノック
＊１４：デグサ社製Ｓｉ６９
＊１５：鶴見化学工業（株）製金華印油入微粉硫黄
＊１６：大内新興化学工業（株）製ノクセラー ＣＺ−Ｇ
Table I Footnote * 1: Natural rubber TSR-20
* 2: Nipol NS616 manufactured by Nippon Zeon Co., Ltd.
* 3: Nipol NS116R manufactured by Nippon Zeon Co., Ltd.
* 4: Nipol 1502 manufactured by Nippon Zeon Co., Ltd.
* 5: Toast Carbon Co., Ltd. Seest KH
* 6: Rhodia Japan Co., Ltd. Zeosil 115GR
* 7: Nippon Sil AQ manufactured by Tosoh Silica Corporation
* 8: YS resin TO125 manufactured by Yasuhara Chemical Co., Ltd.
* 9: YS resin PX200 (no modification) manufactured by Yasuhara Chemical Co., Ltd.
* 10: Three types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd. * 11: Bead stearic acid YR manufactured by NOF Corporation
* 12: Santoflex 6PPD manufactured by Flexis
* 13: Sunnock manufactured by Ouchi Shinsei Chemical Co., Ltd. * 14: Si69 manufactured by Degussa
* 15: Fine powdered sulfur with Jinhua seal oil manufactured by Tsurumi Chemical Industry Co., Ltd. * 16: Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Industries
比較例２は末端変性していないＳＢＲを使用した例で転がり抵抗に劣る。比較例３はＢＥＴ比表面積の大きいシリカを使用した例で転がり抵抗に劣る。比較例４は樹脂に芳香族変性していないポリテルペン（液状）を使用した例で、ウェット性能に劣る。比較例５はＳＢＲ比率が高いため転がり抵抗に劣り、非石油系原料比率も８０％を割って好ましくない。 Comparative Example 2 is an example using SBR that is not terminal-modified, and is inferior in rolling resistance. Comparative Example 3 is an example using silica having a large BET specific surface area and is inferior in rolling resistance. Comparative Example 4 is an example in which a polyterpene (liquid) that is not aromatically modified is used for the resin and is inferior in wet performance. Since Comparative Example 5 has a high SBR ratio, the rolling resistance is inferior, and the non-petroleum raw material ratio is also less than 80%.
以上の通り、本発明に従えば、天然ゴムに、末端変性ＳＢＲ、特定のＢＥＴ比表面積を有するシリカ、特定の軟化点を有する芳香族ビニル変性テルペン樹脂を配合することにより、ゴム組成物に配合する非石油系原料の比率を８０重量％以上としても、転がり抵抗とウェット性能をともに向上させたゴム組成物を得ることができ、環境に配慮した製品を得ることができるので、各種タイヤ用として有用である。 As described above, according to the present invention, blended into a rubber composition by blending natural rubber with terminal-modified SBR, silica having a specific BET specific surface area, and aromatic vinyl-modified terpene resin having a specific softening point. Even if the ratio of non-petroleum-based raw materials is 80% by weight or more, a rubber composition with improved rolling resistance and wet performance can be obtained, and environmentally friendly products can be obtained. Useful.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009072382A1 (en) * | 2007-12-07 | 2009-06-11 | Sumitomo Rubber Industries, Ltd. | Rubber composition for breaker topping |
| JP2009138157A (en) * | 2007-12-10 | 2009-06-25 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP2009155632A (en) * | 2007-12-07 | 2009-07-16 | Sumitomo Rubber Ind Ltd | Rubber composition for breaker topping |
| JP2010254740A (en) * | 2009-04-21 | 2010-11-11 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
| JP2011057965A (en) * | 2009-08-10 | 2011-03-24 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
| JP2012087208A (en) * | 2010-10-19 | 2012-05-10 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire and pneumatic tire |
| JP2014034620A (en) * | 2012-08-08 | 2014-02-24 | Yokohama Rubber Co Ltd:The | Rubber composition for tire and pneumatic tire employing the same |
| US9051451B2 (en) | 2011-05-13 | 2015-06-09 | Sumitomo Rubber Industries, Ltd. | Rubber composition for breaker topping and pneumatic tire |
| JP2019006845A (en) * | 2017-06-20 | 2019-01-17 | 株式会社ブリヂストン | Rubber composition and tire using the same |
| US10696823B2 (en) | 2013-11-27 | 2020-06-30 | Bridgestone Corporation | Rubber composition and tire |
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| RU2660883C1 (en) | 2014-11-27 | 2018-07-10 | Бриджстоун Корпорейшн | Rubber composition, method for its production and tire |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009072382A1 (en) * | 2007-12-07 | 2009-06-11 | Sumitomo Rubber Industries, Ltd. | Rubber composition for breaker topping |
| JP2009155632A (en) * | 2007-12-07 | 2009-07-16 | Sumitomo Rubber Ind Ltd | Rubber composition for breaker topping |
| US8258213B2 (en) | 2007-12-07 | 2012-09-04 | Sumitomo Rubber Industries, Ltd. | Rubber composition for breaker topping |
| JP2009138157A (en) * | 2007-12-10 | 2009-06-25 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP2010254740A (en) * | 2009-04-21 | 2010-11-11 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
| JP2011057965A (en) * | 2009-08-10 | 2011-03-24 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
| DE102010039105B4 (en) * | 2009-08-10 | 2016-12-22 | The Yokohama Rubber Co., Ltd. | A rubber composition for use in tire treads and use of the rubber composition in a tread of a pneumatic tire |
| JP2012087208A (en) * | 2010-10-19 | 2012-05-10 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire and pneumatic tire |
| US9051451B2 (en) | 2011-05-13 | 2015-06-09 | Sumitomo Rubber Industries, Ltd. | Rubber composition for breaker topping and pneumatic tire |
| JP2014034620A (en) * | 2012-08-08 | 2014-02-24 | Yokohama Rubber Co Ltd:The | Rubber composition for tire and pneumatic tire employing the same |
| US10696823B2 (en) | 2013-11-27 | 2020-06-30 | Bridgestone Corporation | Rubber composition and tire |
| JP2019006845A (en) * | 2017-06-20 | 2019-01-17 | 株式会社ブリヂストン | Rubber composition and tire using the same |
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