JP5497254B2 - Rubber composition and pneumatic tire using the same - Google Patents
Rubber composition and pneumatic tire using the same Download PDFInfo
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- JP5497254B2 JP5497254B2 JP2007003451A JP2007003451A JP5497254B2 JP 5497254 B2 JP5497254 B2 JP 5497254B2 JP 2007003451 A JP2007003451 A JP 2007003451A JP 2007003451 A JP2007003451 A JP 2007003451A JP 5497254 B2 JP5497254 B2 JP 5497254B2
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- rubber composition
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- rubber
- softening point
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- 229920001971 elastomer Polymers 0.000 title claims description 123
- 239000005060 rubber Substances 0.000 title claims description 123
- 239000000203 mixture Substances 0.000 title claims description 84
- 239000011347 resin Substances 0.000 claims description 70
- 229920005989 resin Polymers 0.000 claims description 70
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 26
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 150000003505 terpenes Chemical class 0.000 claims description 16
- 235000007586 terpenes Nutrition 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 12
- 239000005011 phenolic resin Substances 0.000 claims description 12
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 10
- 229920006026 co-polymeric resin Polymers 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 238000004898 kneading Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 9
- -1 α-methylstyrene-vinyltoluene-indene Chemical compound 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 3
- 239000010692 aromatic oil Substances 0.000 description 3
- 229920003244 diene elastomer Polymers 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- NVKGGJAQTOIZJM-UHFFFAOYSA-N 1h-indene;prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.C1=CC=C2CC=CC2=C1 NVKGGJAQTOIZJM-UHFFFAOYSA-N 0.000 description 1
- HDXNORRCXXMICJ-UHFFFAOYSA-N 1h-indene;prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1.C1=CC=C2CC=CC2=C1 HDXNORRCXXMICJ-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VXPSQDAMFATNNG-UHFFFAOYSA-N 3-[2-(2,5-dioxopyrrol-3-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C(=CC=CC=2)C=2C(NC(=O)C=2)=O)=C1 VXPSQDAMFATNNG-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
- GZGUQZYXGXWGMT-UHFFFAOYSA-N C(N)(SCCCCCC)=S.[Zn] Chemical compound C(N)(SCCCCCC)=S.[Zn] GZGUQZYXGXWGMT-UHFFFAOYSA-N 0.000 description 1
- 102100024452 DNA-directed RNA polymerase III subunit RPC1 Human genes 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 208000025599 Heat Stress disease Diseases 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 101000689002 Homo sapiens DNA-directed RNA polymerase III subunit RPC1 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical compound CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- OBMHSNXMHVKVSA-UHFFFAOYSA-L zinc;n-benzylcarbamodithioate Chemical compound [Zn+2].[S-]C(=S)NCC1=CC=CC=C1.[S-]C(=S)NCC1=CC=CC=C1 OBMHSNXMHVKVSA-UHFFFAOYSA-L 0.000 description 1
- JEKSRZRYVJGNOY-UHFFFAOYSA-L zinc;n-dodecylcarbamodithioate Chemical compound [Zn+2].CCCCCCCCCCCCNC([S-])=S.CCCCCCCCCCCCNC([S-])=S JEKSRZRYVJGNOY-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、タイヤのトレッドゴムに使用することにより、タイヤの初期グリップ性能と走行安定性の両方を、従来のタイヤよりも向上させることが可能なゴム組成物、及び該ゴム組成物をトレッドゴムに用いた空気入りタイヤに関する。 The present invention relates to a rubber composition capable of improving both the initial grip performance and running stability of a tire as compared with a conventional tire by using the tread rubber for a tire, and the tread rubber. It relates to a pneumatic tire used in the above.
競技等に使用される高性能タイヤのトレッドは、乾燥路面上において走行初期から走行終了まで優れた操縦安定性（ＤＲＹグリップ性）を保つことが望まれる。そのため、従来から、タイヤが比較的低温である走行初期のＤＲＹグリップ性（初期グリップ性能）を向上させる目的で、トレッドゴムに用いるゴム組成物に低軟化点の樹脂及び液状ポリマーを含めたオイル成分並びに低温で効果を発揮する軟化剤等を配合することが検討されている。 It is desired that a high-performance tire tread used for competitions or the like maintains excellent handling stability (DRY grip performance) from the initial driving to the end of driving on a dry road surface. Therefore, conventionally, for the purpose of improving the DRY grip property (initial grip performance) at the beginning of running when the tire is relatively low in temperature, an oil component including a low softening point resin and a liquid polymer in a rubber composition used for tread rubber. In addition, it has been studied to add a softener or the like that exhibits an effect at a low temperature.
例えば、Ｃ9 芳香族系樹脂等を配合したゴム組成物が特許文献１に記載されているが、樹脂の混練り中での分散性を考慮し、該ゴム組成物には軟化点が１４０℃以下のＣ9 芳香族系樹脂を配合している。 For example, although a rubber composition containing a C 9 aromatic resin or the like is described in Patent Document 1, in consideration of dispersibility during resin kneading, the rubber composition has a softening point of 140 ° C. It is blended with the following C 9 aromatic resin.
また、低軟化点の水添テルペンフェノール樹脂を配合したゴム組成物が特許文献２に記載されており、樹脂を水素添加するとポリマーとの相溶性が特によくなるために、通常のテルペンフェノール樹脂よりも低温からの弾性率を下げて初期グリップを向上させる効果が高いことが明らかになっている。 Further, a rubber composition containing a hydrogenated terpene phenol resin having a low softening point is described in Patent Document 2, and when the resin is hydrogenated, the compatibility with the polymer is particularly improved. It has become clear that the effect of improving the initial grip by lowering the elastic modulus from low temperatures is high.
しかしながら、前記の様に低軟化点の樹脂を配合してゴム組成物を調製し、該ゴム組成物をトレッドゴムに使用して製造したタイヤは、初期グリップ性能が向上するものの、走行中、タイヤトレッドの温度が上昇するにつれてグリップ性能が低下する。一方、走行中にタイヤ温度が上昇した際のタイヤのグリップ性能（走行安定性）を向上させるためにＣ9 系樹脂等の高軟化点樹脂を単独でゴム組成物に配合すると、低温路面上でのタイヤの初期グリップ性能が大きく低下する。 However, a tire produced by blending a resin with a low softening point as described above and using the rubber composition for a tread rubber improves the initial grip performance. As the tread temperature rises, grip performance decreases. On the other hand, when compounded in the rubber composition alone high softening point resin such as C 9 resins for tire temperature improves the grip performance of the tire at the time of rise (running stability) while traveling on the low road surface The initial grip performance of the tire is greatly reduced.
こうした問題を解決する方法として高軟化点樹脂と低軟化点樹脂の両方をゴム組成物に配合する方法が考えられる。しかしながら、配合する総樹脂量がゴム組成物の温度特性に影響を与えるため、ゴム組成物に配合可能な樹脂の量が制限される。そのため、該方法によって得られるタイヤは初期グリップ性能及び走行安定性の両方が中庸であった。従って、タイヤの初期グリップ性能と走行安定性を高いレベルで両立することが可能な、タイヤのトレッドゴムに使用するためのゴム組成物を提供することが必要である。 As a method for solving such a problem, a method is conceivable in which both a high softening point resin and a low softening point resin are blended in a rubber composition. However, since the total resin amount to be blended affects the temperature characteristics of the rubber composition, the amount of resin that can be blended in the rubber composition is limited. Therefore, the tire obtained by this method has a moderate initial grip performance and running stability. Therefore, it is necessary to provide a rubber composition for use in a tread rubber of a tire that can achieve both high initial grip performance and running stability of the tire.
本発明者は、低軟化点樹脂が配合され初期グリップ性能が良好であるゴム組成物をトレッドゴムとして用いたタイヤは、走行中のどのような状況でグリップ性能が低下するかについて鋭意検討したところ、同じコース上であっても、その路面温度によってグリップ性の低下の度合いが大きく変化することを見出した。すなわち、路面温度が１０℃以下の状況ではタイヤの走行安定性がほとんど低下しないのに対し、路面温度が４０℃を超える状況ではタイヤの走行安定性が低下しやすいことが判った。 The present inventor has intensively studied under which conditions the grip performance of a tire using a rubber composition containing a low softening point resin and good initial grip performance as a tread rubber is deteriorated. It was found that even on the same course, the degree of decrease in grip performance greatly changes depending on the road surface temperature. That is, it was found that the running stability of the tire hardly decreases when the road surface temperature is 10 ° C. or lower, whereas the running stability of the tire tends to decrease when the road surface temperature exceeds 40 ° C.
また、路面温度が４２℃のサーキットにおいて、該ゴム組成物をトレッドゴムに使用したタイヤを装着した車両を走行させ、走行中の該タイヤの内部温度を測定したところ、１０ラップ程度走行した後に該タイヤの内部温度が１００℃〜１１０℃まで上昇していることが見出された。タイヤの内部温度の測定は車輌がガレージに戻ってきた後に行うため、走行中の該内部温度は更に高いことが予想される。低軟化点樹脂を配合したゴム組成物は１００℃以上での動的弾性率（Ｅ’）の低下が大きいので、該ゴム組成物をトレッドゴムに用いたタイヤは、タイヤ内部が高温になった際に樹脂と共にゴム組成物が軟化し、走行安定性が低下することが懸念される。 Further, in a circuit where the road surface temperature is 42 ° C., a vehicle equipped with a tire using the rubber composition as a tread rubber was run, and the internal temperature of the tire during running was measured. It has been found that the internal temperature of the tire has increased from 100 ° C to 110 ° C. Since the internal temperature of the tire is measured after the vehicle returns to the garage, the internal temperature during driving is expected to be higher. Since the rubber composition containing the low softening point resin has a large decrease in the dynamic elastic modulus (E ′) at 100 ° C. or higher, the tire using the rubber composition as a tread rubber has a high temperature inside the tire. At that time, there is a concern that the rubber composition is softened together with the resin and the running stability is lowered.
そこで、本発明は、タイヤのトレッドゴムに使用することにより、タイヤの初期グリップ性能と走行安定性の両方を、従来のタイヤよりも向上させることが可能なゴム組成物、及び該ゴム組成物をトレッドゴムに用いた空気入りタイヤを堤供することを目的とする。 Accordingly, the present invention provides a rubber composition capable of improving both the initial grip performance and running stability of a tire as compared with a conventional tire by using the tread rubber of a tire, and the rubber composition. The purpose is to provide a pneumatic tire used for tread rubber.
本発明者は、上記目的を達成するために、室温においてＥ’を下げる効果を有し且つ高温でのＥ’を確保できる樹脂及び該樹脂を２種以上組み合わせて配合したゴム組成物に関して鋭意検討したところ、これまでゴム組成物への配合例がなかった高軟化点を有する芳香族ビニル樹脂を単独で、又はこれに加えて更に高軟化点を有する樹脂をゴム組成物に配合することによって、従来のタイヤよりも高い初期グリップ性能と走行安定性を併せ持つタイヤを製造できるトレッドゴム用のゴム組成物が調製できることを見出し、本発明を完成するに至った。 In order to achieve the above object, the present inventor has intensively studied a resin that has an effect of lowering E ′ at room temperature and can secure E ′ at a high temperature, and a rubber composition containing a combination of two or more of the resins. As a result, by adding an aromatic vinyl resin having a high softening point alone, or in addition to this, a resin having a higher softening point to the rubber composition, which has not been incorporated in rubber compositions so far, The present inventors have found that a rubber composition for tread rubber capable of producing a tire having both initial grip performance and running stability higher than those of conventional tires can be prepared, and the present invention has been completed.
即ち、本発明のゴム組成物は、ゴム成分１００質量部に対して、テルペンフェノール樹脂を部分的に又は完全に水素添加した軟化点が１３０℃以上の水添テルペンフェノール樹脂から選択される少なくとも１種を１０〜６０質量部、軟化点が１３０℃以上１９０℃以下でありインデンを含有するＣ９樹脂から選択される少なくとも１種を５〜６０質量部配合してなり、前記ゴム成分が、ブタジエン部のビニル結合量が１０％以上であるブタジエン系共重合体を７０質量％以上含むことを特徴とする。 That is, the rubber composition of the present invention is at least one selected from hydrogenated terpene phenol resins having a softening point of 130 ° C. or higher, obtained by partially or completely hydrogenating the terpene phenol resin with respect to 100 parts by mass of the rubber component. 10-60 parts by weight of the seed, the softening point becomes at least one member selected from C 9 resins containing and indene at 130 ° C. or higher 190 ° C. or less and 5 to 60 parts by mass, the rubber component, butadiene 70% by mass or more of a butadiene-based copolymer having a vinyl bond content of 10% or more by weight is included.
本発明のゴム組成物は、前記水添テルペンフェノール樹脂の軟化点が１４０℃以上、及び前記インデンを含有するＣ9 樹脂の軟化点が１４０℃以上１８０℃以下であることが好適である。 In the rubber composition of the present invention, the hydrogenated terpene phenol resin preferably has a softening point of 140 ° C. or higher, and the C 9 resin containing indene has a softening point of 140 ° C. or higher and 180 ° C. or lower.
更に、前記ブタジエン系共重合体がスチレン−ブタジエン共重合体（ＳＢＲ）を含むことが好ましい。 Furthermore, it is preferable that the butadiene-based copolymer contains a styrene-butadiene copolymer (SBR).
また、前記スチレン−ブタジエン共重合体は、スチレン含有率が２０〜６０質量％であることが好適である。 The styrene-butadiene copolymer preferably has a styrene content of 20 to 60% by mass.
また、本発明のゴム組成物は、更に前記ゴム成分１００質量部に対してカーボンブラックを６０〜２００質量部配合してなることが好適である。 Moreover, it is preferable that the rubber composition of the present invention further comprises 60 to 200 parts by mass of carbon black with respect to 100 parts by mass of the rubber component.
更に、本発明の好適例において、前記Ｃ9 樹脂が軟化点１５５℃以上１８０℃以下のα-メチルスチレン−ビニルトルエン−インデン共重合体樹脂である。 Furthermore, in a preferred embodiment of the present invention, the C 9 resin is an α-methylstyrene-vinyltoluene-indene copolymer resin having a softening point of 155 ° C. or higher and 180 ° C. or lower.
本発明の空気入りタイヤは、前記ゴム組成物をトレッドゴムに使用して製造することが好適である。 The pneumatic tire of the present invention is preferably produced using the rubber composition as a tread rubber.
本発明によれば、タイヤのトレッドゴムに使用することにより、タイヤの初期グリップ性能と走行安定性の両方を、従来のタイヤよりも向上させることが可能なゴム組成物、及び該ゴム組成物をトレッドゴムに用いた空気入りタイヤを堤供することができる。 According to the present invention, a rubber composition capable of improving both the initial grip performance and running stability of a tire as compared with a conventional tire by using the tire tread rubber, and the rubber composition. A pneumatic tire used for tread rubber can be provided.
本発明のゴム組成物は、ゴム成分１００質量部に対して、テルペンフェノール樹脂を部分的に又は完全に水素添加した軟化点が１３０℃以上の水添テルペンフェノール樹脂から選択される少なくとも１種を１０〜６０質量部、軟化点が１３０℃以上１９０℃以下でありインデンを含有するＣ9 樹脂から選択される少なくとも１種を５〜６０質量部配合してなる。ここで、軟化点が１３０℃未満の水添テルペンフェノール樹脂を配合すると、タイヤの初期グリップ性能は向上するものの走行安定性が損なわれる。該走行安定性の観点から、前記水添テルペンフェノール樹脂の軟化点は１４０℃以上が好ましい。該樹脂の配合量は、ゴム組成物に該樹脂の特性を付与するため、ゴム成分１００質量部に対して１０質量部以上配合することが必要であるが、６０質量部を超えると低温においてゴム組成物が硬化する。 The rubber composition of the present invention comprises at least one selected from hydrogenated terpene phenol resins having a softening point of 130 ° C. or higher, obtained by partially or completely hydrogenating a terpene phenol resin with respect to 100 parts by mass of the rubber component. 10 to 60 parts by mass, 5 to 60 parts by mass of at least one selected from C 9 resins having a softening point of 130 ° C. or higher and 190 ° C. or lower and containing indene. Here, when a hydrogenated terpene phenol resin having a softening point of less than 130 ° C. is blended, the initial grip performance of the tire is improved, but the running stability is impaired. From the viewpoint of running stability, the softening point of the hydrogenated terpene phenol resin is preferably 140 ° C. or higher. In order to give the rubber composition the properties of the resin, the amount of the resin needs to be 10 parts by mass or more with respect to 100 parts by mass of the rubber component. The composition is cured.
本発明のゴム組成物は、更に、ゴム成分１００質量部に対して、軟化点が１３０℃以上１９０℃以下でありインデンを含有するＣ9 樹脂から選択される少なくとも１種を５〜６０質量部配合する。前記水添テルペンフェノール樹脂を単独でゴム組成物に配合しても一定の効果は得られるが、更にインデンを含有するＣ9 樹脂を配合することでタイヤの走行安定性を改善する効果を大幅に向上させることができる。なお、軟化点が１３０℃未満のインデンを含有するＣ9 樹脂をゴム組成物に配合すると、タイヤの走行安定性を改善できない。また、混練り中での樹脂の分散性を考慮すると、軟化点は１９０℃以下が好ましい。タイヤの走行安定性向上の観点から、前記インデンを含有するＣ9 樹脂の軟化点は１４０℃以上１８０℃以下であることが好ましい。該樹脂のゴム組成物への配合量は、ゴム組成物に該樹脂の特性を付与するために、ゴム成分１００質量部に対して５質量部以上配合することが必要であるが、６０質量部を超えると低温においてゴム組成物が硬化する。前記インデンを含有するＣ9 樹脂とは、インデンの単独重合体、及びＣ9 芳香族系モノマーの共重合体樹脂のうち、原料のモノマーにインデンが含まれる樹脂のことをいい、該Ｃ9芳香族系モノマーとしては、ビニルトルエン、α-メチルスチレン、クマロン等が挙げられる。即ち、前記Ｃ9 樹脂としては、ビニルトルエン−α-メチルスチレン−インデン樹脂、ビニルトルエン−インデン樹脂、α-メチルスチレン−インデン樹脂、クマロン−インデン樹脂等が挙げられる。 The rubber composition of the present invention further has 5 to 60 parts by mass of at least one selected from C 9 resins having a softening point of 130 ° C. or higher and 190 ° C. or lower and containing indene with respect to 100 parts by mass of the rubber component. Blend. Even if the hydrogenated terpene phenol resin is blended with the rubber composition alone, a certain effect can be obtained, but further, the effect of improving the running stability of the tire can be greatly improved by blending a C 9 resin containing indene. Can be improved. Incidentally, the C 9 resin having a softening point contains indene below 130 ° C. is blended in the rubber composition can not improve the running stability of the tire. In consideration of the dispersibility of the resin during kneading, the softening point is preferably 190 ° C. or lower. From the viewpoint of improving the running stability of the tire, the softening point of the C 9 resin containing indene is preferably 140 ° C. or higher and 180 ° C. or lower. The compounding amount of the resin in the rubber composition needs to be 5 parts by mass or more with respect to 100 parts by mass of the rubber component in order to give the rubber composition the characteristics of the resin. If it exceeds, the rubber composition is cured at a low temperature. The C 9 resin containing the indene, homopolymers of indene, and C 9 of the copolymer resin of an aromatic monomer, refers to a resin that contains indene in the monomer raw material, the C 9 aromatic Examples of the group-based monomer include vinyltoluene, α-methylstyrene, coumarone, and the like. That is, examples of the C 9 resin include vinyltoluene-α-methylstyrene-indene resin, vinyltoluene-indene resin, α-methylstyrene-indene resin, coumarone-indene resin, and the like.
また、前記Ｃ9 樹脂としては、軟化点１５５℃以上１８０℃以下のα-メチルスチレン−ビニルトルエン−インデン共重合体樹脂が更に一層好適である。前記Ｃ9 樹脂が、α-メチルスチレン−ビニルトルエン−インデン共重合体樹脂であると
高温での走行安定性が十分に確保されるからであり、かかる軟化点が１５５℃未満であると高温での十分な走行安定性が得られず、１８０℃を超えると樹脂はゴム成分との混練りで十分な分散がとれなくなる。
As the C 9 resin, an α-methylstyrene-vinyltoluene-indene copolymer resin having a softening point of 155 ° C. or higher and 180 ° C. or lower is even more preferable. If the C 9 resin is an α-methylstyrene-vinyltoluene-indene copolymer resin, sufficient running stability at high temperature is ensured. If the softening point is less than 155 ° C., the temperature is high. If the temperature exceeds 180 ° C., the resin cannot be sufficiently dispersed by kneading with the rubber component.
本発明のゴム組成物において、前記ゴム成分はブタジエン部のビニル結合量が１０％以上であるブタジエン系共重合体を７０質量％以上含むことが好適である。ブタジエン部のビニル結合量が１０％未満であるとゴム組成物の高温域での剛性が低下して所望の効果が得られず、該ブタジエン系共重合体のゴム成分中での含有率が７０質量％未満であるとゴム組成物の基本的な耐熱性が大きく低下する。 In the rubber composition of the present invention, it is preferable that the rubber component contains 70% by mass or more of a butadiene-based copolymer having a vinyl bond amount in the butadiene portion of 10% or more. If the vinyl bond content of the butadiene part is less than 10%, the rigidity of the rubber composition at a high temperature range is lowered and a desired effect cannot be obtained, and the content of the butadiene copolymer in the rubber component is 70. If it is less than mass%, the basic heat resistance of the rubber composition is greatly reduced.
なお、本発明のゴム組成物のゴム成分は、特に限定されず、上記ブタジエン系共重合体の他、天然ゴム、ポリブタジエンゴム、ポリイソプレンゴム、エチレン−プロピレン共重合体、イソブチレン−イソプレン共重合体、ポリクロロプレン等のジエン系ゴムを含んでもよい。 The rubber component of the rubber composition of the present invention is not particularly limited, and in addition to the above butadiene copolymer, natural rubber, polybutadiene rubber, polyisoprene rubber, ethylene-propylene copolymer, isobutylene-isoprene copolymer. Further, a diene rubber such as polychloroprene may be included.
また、本発明のゴム組成物において、前記ブタジエン系共重合体がスチレン−ブタジエン共重合体を含むことが好ましい。ブタジエン系共重合体がスチレン−ブタジエン共重合体を含むと、ゴム組成物はヒステリシスロスが向上するため基本的なグリップ性能が向上する。スチレン−ブタジエン共重合体は、乳化重合や溶液重合等の如何なる合成法で合成してもよい。スチレン−ブタジエン共重合体以外のブタジエン系共重合体としてはアクリロニトリル−ブタジエン共重合体等が挙げられる。 In the rubber composition of the present invention, the butadiene copolymer preferably contains a styrene-butadiene copolymer. When the butadiene-based copolymer contains a styrene-butadiene copolymer, the rubber composition has improved hysteresis loss, and thus the basic grip performance is improved. The styrene-butadiene copolymer may be synthesized by any synthesis method such as emulsion polymerization or solution polymerization. Examples of the butadiene-based copolymer other than the styrene-butadiene copolymer include acrylonitrile-butadiene copolymer.
また、前記スチレン−ブタジエン共重合体のスチレン含有率は２０〜６０質量％であることが好ましい。スチレン含有率が２０質量％未満であると、低温及び高温においてタイヤが所望のグリップ性能を得ることができず、スチレン含有率が６０質量％を超えると、ブロック剛性が必要以上に高くなり路面へのゴムの食い込みが少なくなるため、タイヤが所望のグリップ性能を得ることができない。更に、タイヤのグリップ性能が顕著に高くなることから、前記スチレン−ブタジエン共重合体のスチレン含有率は２０〜４５質量％であることがより好ましい。 Moreover, it is preferable that the styrene content rate of the said styrene-butadiene copolymer is 20-60 mass%. If the styrene content is less than 20% by mass, the tire cannot obtain a desired grip performance at low and high temperatures, and if the styrene content exceeds 60% by mass, the block rigidity becomes higher than necessary and the road surface is increased. Therefore, the tire cannot obtain a desired grip performance. Further, since the grip performance of the tire is remarkably enhanced, the styrene content of the styrene-butadiene copolymer is more preferably 20 to 45% by mass.
本発明のゴム組成物は、更にカーボンブラックを上記ゴム成分１００質量部に対して６０〜２００質量部配合してなることが好ましく、６０〜１６０質量部配合してなることが更に好ましい。ここで、前記ゴム組成物へのカーボンブラックの配合量が６０質量部未満であると、タイヤのＤＲＹグリップ性向上への寄与が十分ではなく、２００質量部を超えるとタイヤの耐摩耗性を低下させ、更に加工性が極端に悪化する。また、前記ゴム組成物へのカーボンブラックの配合量は７０〜１４０質量部であることがより一層好ましい。前記カーボンブラックは、窒素吸着比表面積が約８０〜２８０ｍ２／ｇであることが好ましい。カーボンブラックの窒素吸着比表面積が８０ｍ２／ｇ未満では十分な弾性率が得られず耐摩耗性が悪化し、２８０ｍ２／ｇを超えるとグリップ力、耐摩耗性の向上が望めない一方で混練作業性が悪化する。前記カーボンブラックの例としては、ＨＡＦ、ＩＳＡＦ、及びＳＡＦ等が挙げられ、耐摩耗性能とグリップ性能の両立という点からＳＡＦが好ましい。カーボンブラックは、１種単独で使用しても２種以上を併用してもよく、市販品を好適に使用できる。 The rubber composition of the present invention preferably further comprises 60 to 200 parts by mass of carbon black and more preferably 60 to 160 parts by mass with respect to 100 parts by mass of the rubber component. Here, if the blending amount of carbon black in the rubber composition is less than 60 parts by mass, the contribution to improving the DRY grip property of the tire is not sufficient, and if it exceeds 200 parts by mass, the wear resistance of the tire is reduced. Further, the workability is extremely deteriorated. The amount of carbon black added to the rubber composition is more preferably 70 to 140 parts by mass. The carbon black preferably has a nitrogen adsorption specific surface area of about 80 to 280 m 2 / g. When the nitrogen adsorption specific surface area of carbon black is less than 80 m 2 / g, sufficient elastic modulus cannot be obtained and wear resistance deteriorates, and when it exceeds 280 m 2 / g, improvement in grip strength and wear resistance cannot be expected, but kneading Workability deteriorates. Examples of the carbon black include HAF, ISAF, and SAF, and SAF is preferable from the viewpoint of achieving both wear resistance and grip performance. Carbon black may be used individually by 1 type, or may use 2 or more types together, and a commercial item can be used conveniently.
前記ゴム組成物には、この他にゴム業界で使用されるアルキルフェノール系樹脂を用いることができる。該アルキルフェノール系樹脂としては、ｐ-ｔ-ブチルフェノール−アセチレン等のアルキルフェノール−アセチレン系樹脂、及びクレゾール類、キシレノール類、p-ｔ-ブチルフェノール、及びp-ｔ-オクテルフェノール類を含むアルキルフェノール−ホルムアルテヒド系樹脂等が挙げられる。これらの樹脂の軟化点としては１３０〜１６０℃が好ましい。軟化点が１３０℃未満では走行安定性が低下し、また１６０℃を超えると樹脂の極性が高いため混練の際に樹脂が均一に分散せず、耐摩耗性が著しく低下する。これらのアルキルフェノール系樹脂は単独で使用しても、２種以上を使用してもよい。該樹脂の配合量はゴム成分１００質量部に対して１０〜１００質量部であることが好ましい。該樹脂の配合量が１０質量部未満の場合には樹脂によるグリップ性能が向上せず、１００質量部を超えると混練作業性を著しく悪化させる。また、これらの効果が顕著であることから、該樹脂の配合量は２０〜８０質量部であることがより好ましい。 In addition to this, the phenolic resin used in the rubber industry can be used for the rubber composition. Examples of the alkylphenol resins include alkylphenol-acetylene resins such as pt-butylphenol-acetylene, and alkylphenol-formartenes including cresols, xylenols, pt-butylphenol, and pt-octylphenols. Examples thereof include hydride resins. The softening point of these resins is preferably 130 to 160 ° C. When the softening point is less than 130 ° C., running stability is lowered, and when it exceeds 160 ° C., the polarity of the resin is high, so that the resin is not uniformly dispersed during kneading, and the wear resistance is significantly lowered. These alkylphenol resins may be used alone or in combination of two or more. It is preferable that the compounding quantity of this resin is 10-100 mass parts with respect to 100 mass parts of rubber components. When the amount of the resin is less than 10 parts by mass, the grip performance by the resin is not improved, and when it exceeds 100 parts by mass, the kneading workability is remarkably deteriorated. Moreover, since these effects are remarkable, it is more preferable that the compounding quantity of this resin is 20-80 mass parts.
前記ゴム組成物には、ゴム成分、樹脂成分、カーボンブラックの他、プロセスオイル等の油分、加硫剤、加硫促進剤、老化防止剤、軟化剤、酸化亜鉛、無機充填剤、オゾン劣化防止剤、着色剤、帯電防止剤、滑剤、酸化防止剤、カップリング剤、発泡剤、発泡助剤及びステアリン酸等のゴム業界で通常使用される配合剤を、本発明の目的を害しない範囲内で適宜選択し配合することができる。これら配合剤は、市販品を好適に使用できる。 The rubber composition includes rubber components, resin components, carbon black, oils such as process oils, vulcanizing agents, vulcanization accelerators, anti-aging agents, softening agents, zinc oxide, inorganic fillers, and ozone deterioration prevention. Additives, colorants, antistatic agents, lubricants, antioxidants, coupling agents, foaming agents, foaming aids, and compounding agents commonly used in the rubber industry such as stearic acid are within the range that does not impair the purpose of the present invention. Can be appropriately selected and blended. As these compounding agents, commercially available products can be suitably used.
前記プロセスオイル等の油分としては、特に制限はなく、目的に応じて適宜選択して使用可能である。前記油分としては、アロマティックオイル、ナフテン系オイル、パラフィン系オイル、エステル系オイル、溶液状共役ジエンゴム、及び溶液状水素添加共役ジエンゴム等が挙げられる。油分がゴム組成物に含まれていると該ゴム組成物の流動性をコントロールできるため、加硫前のゴム組成物の粘度を低下させて流動性を高めることにより、極めて良好にゴム組成物の押出を行うことができる点で有利である。 There is no restriction | limiting in particular as oils, such as the said process oil, According to the objective, it can select suitably and can be used. Examples of the oil include aromatic oils, naphthenic oils, paraffinic oils, ester oils, solution conjugated diene rubbers, solution hydrogenated conjugated diene rubbers, and the like. When the oil component is contained in the rubber composition, the fluidity of the rubber composition can be controlled. Therefore, by reducing the viscosity of the rubber composition before vulcanization and increasing the fluidity, the rubber composition can be improved very well. This is advantageous in that it can be extruded.
前記油分の前記ゴム組成物における含有量は、ゴム成分１００質量部に対して、ゴム成分が油展されている場合はこれらの油展分も含めて３５〜２００質量部が好ましく、４０〜１５０質量部がより好ましい。ゴム成分１００質量部に対して油分の含有量が３５質量部未満であると、未加硫ゴムのムーニー粘度が極端に高くなって加工性が悪化し、更にタイヤのＤＲＹグリップ性も悪化する場合があり、２００質量部を超えるとムーニー粘度が極端に低くなって加工性が悪化し、更にトレッドが柔らかくなり過ぎて耐摩耗性が悪化する場合がある。 The content of the oil in the rubber composition is preferably 35 to 200 parts by mass, including these oils, when the rubber component is oil-extended with respect to 100 parts by mass of the rubber component. Part by mass is more preferable. When the oil content is less than 35 parts by mass with respect to 100 parts by mass of the rubber component, the Mooney viscosity of the unvulcanized rubber becomes extremely high and the workability deteriorates, and further, the DRY grip property of the tire also deteriorates. When the amount exceeds 200 parts by mass, the Mooney viscosity becomes extremely low and workability is deteriorated. Further, the tread becomes too soft and wear resistance may be deteriorated.
また、上記加硫剤として、従来の硫黄に加えて、有機チオスルフェート化合物（例えば１，６−ヘキサメチレンジチオ硫酸ナトリウム・２水和物）、ビスマレイミド化合物（例えばフェニレンビスマレイミド）の少なくとも1種を併用することができる。 Further, as the vulcanizing agent, in addition to conventional sulfur, at least one of an organic thiosulfate compound (for example, sodium 1,6-hexamethylenedithiosulfate dihydrate) and a bismaleimide compound (for example, phenylene bismaleimide) Seeds can be used in combination.
また、上記加硫促進剤としては、テトラキス−２−エチルへキシルチウラムジスルフィド、テトラキス−２−イソプロピルチウラムジスルフィド、テトラキス−ドデシルチウラムジスルフィド、及びテトラキス−ベンジルチウラムジスルフィド等のチウラム化合物、ジ−２−エチルへキシルジチオカルバメート亜鉛、ドデシルジチオカルバメート亜鉛、及びベンジルジチオカルバメート亜鉛等のジチオカルバミン酸塩類化合物、並びにジベンゾチアジルジスルフィド、４，４’−ジメチルジベンゾチアジルジスルフィド、Ｎ-シクロへキシル−２−ベンソチアジル−スルフェンアミド、Ｎ-ｔ-ブチル−２−ベンゾチアジル−スルフェンアミド、Ｎ-ｔ-ブチル−２−ベンゾチアジル−スルフェンイミド、Ｎ-オキシジエチレン−ベンゾチアジル−スルフェンアミド、及びＮ，Ｎ’-ジシクロへキシル−２−ベンゾチアジル−スルフェンアミド等のベンゾチアゾリル加硫促進剤等が挙げられる。 Examples of the vulcanization accelerator include tetrakis-2-ethylhexyl thiuram disulfide, tetrakis-2-isopropyl thiuram disulfide, tetrakis-dodecyl thiuram disulfide, and thiuram compounds such as tetrakis-benzyl thiuram disulfide, di-2-ethyl Dithiocarbamate compounds such as zinc hexyl dithiocarbamate, zinc dodecyldithiocarbamate, and zinc benzyldithiocarbamate, and dibenzothiazyl disulfide, 4,4′-dimethyldibenzothiazyl disulfide, N-cyclohexyl-2-benzothiazyl- Sulfenamide, Nt-butyl-2-benzothiazyl-sulfenamide, Nt-butyl-2-benzothiazyl-sulfenimide, N-oxydiethylene-benzothiazyl Fen'amido, and N, hexyl N'- dicyclohexyl-2-benzothiazyl - benzothiazolyl vulcanization accelerator such as sulfenamide and the like.
本発明のゴム組成物は、ゴム成分、樹脂、及び必要に応じて適宜選択した前記その他の配合剤等を、混練り、熱入れ、押出、及び加硫等することにより製造できる。 The rubber composition of the present invention can be produced by kneading, heating, extruding, vulcanizing, etc., a rubber component, a resin, and the above-described other compounding agents appropriately selected as necessary.
混練りの条件としては、特に制限はなく、混練り装置への各成分の投入量、ローターの回転速度、ラム圧、混練り温度、混練り時間、混練り装置の種類等の諸条件によって適宜選択できる。前記混練り装置としては、一般にゴム組成物の混練りに用いるバンバリーミキサー、インターミックス、及びニーダー等が挙げられる。 The kneading conditions are not particularly limited, and are appropriately determined according to various conditions such as the amount of each component charged into the kneading apparatus, the rotational speed of the rotor, the ram pressure, the kneading temperature, the kneading time, and the type of the kneading apparatus. You can choose. Examples of the kneading apparatus include Banbury mixers, intermixes, and kneaders that are generally used for kneading rubber compositions.
熱入れの条件は、特に制限はなく、熱入れ温度、熱入れ時間、熱入れ装置等の諸条件について目的に応じて適宜選択することができる。前記熱入れ装置としては、通常ゴム組成物の熱入れに用いるロール機等が挙げられる。 The conditions for the heating are not particularly limited, and various conditions such as the heating temperature, the heating time, and the heating apparatus can be appropriately selected according to the purpose. Examples of the heating apparatus include a roll machine that is usually used for heating a rubber composition.
押出の条件は、特に制限はなく、押出時間、押出速度、押出装置、及び押出温度等の諸条件に応じて適宜選択できる。前記押出装置としては、一般にタイヤ用ゴム組成物の押出に用いる押出機等が挙げられる。前記押出温度は、適宜決定することができる。 The conditions for extrusion are not particularly limited, and can be appropriately selected according to various conditions such as extrusion time, extrusion speed, extrusion apparatus, and extrusion temperature. As said extrusion apparatus, the extruder etc. which are generally used for extrusion of the rubber composition for tires are mentioned. The extrusion temperature can be appropriately determined.
加硫を行う装置、方式、条件等については、特に制限はなく、目的に応じて適宜選択することができる。加硫を行う装置としては、一般にタイヤ用ゴム組成物の加硫に用いる金型による成形加硫機等が挙げられる。加硫する温度は通常約１００〜約１９０℃である。 There is no restriction | limiting in particular about the apparatus, system, conditions, etc. which perform a vulcanization | cure, According to the objective, it can select suitably. Examples of the vulcanizing apparatus include a molding vulcanizer using a mold generally used for vulcanizing a tire rubber composition. The vulcanization temperature is usually about 100 to about 190 ° C.
本発明のゴム組成物は、空気入りタイヤのトレッドゴム、特にサーキット走行等に使用する高速競技車用タイヤのトレッドゴムに用いることが好適である。なお、トレッドゴム以外のタイヤ部材としては、公知の部材を使用することができる。また、該空気入りタイヤに充填する気体としては、通常の或いは酸素分圧を調整した空気の他、窒素、アルゴン、ヘリウム等の不活性ガスを用いることができる。 The rubber composition of the present invention is preferably used for a tread rubber of a pneumatic tire, particularly a tread rubber of a tire for a high-speed competition vehicle used for circuit running or the like. In addition, as a tire member other than the tread rubber, a known member can be used. Further, as the gas filled in the pneumatic tire, an inert gas such as nitrogen, argon, helium, or the like can be used in addition to normal or air whose oxygen partial pressure is adjusted.
本発明の空気入りタイヤは、前記ゴム組成物を少なくとも用いてなり、好ましくは少なくともトレッドに用いてなる。本発明のタイヤは、前記本発明のゴム組成物を用いること以外は、特に限定はなく、公知のタイヤの構成をそのまま採用することができる。 The pneumatic tire of the present invention comprises at least the rubber composition, preferably at least for a tread. The tire of the present invention is not particularly limited except that the rubber composition of the present invention is used, and a known tire configuration can be employed as it is.
本発明の空気入りタイヤの構成の一例としては、該空気入りタイヤが、1対のビード部、該ビード部にトロイド状をなして連なるカーカス、該カーカスのクラウン部をたが締めするベルト及びトレッドを有してなるタイヤであることが挙げられる。本発明のタイヤは、ラジアル構造を有していてもよいし、バイアス構造を有していてもよい。 As an example of the configuration of the pneumatic tire of the present invention, the pneumatic tire includes a pair of bead portions, a carcass connected to the bead portion in a toroid shape, a belt and a tread for tightening a crown portion of the carcass It is mentioned that it is a tire which has. The tire of the present invention may have a radial structure or a bias structure.
本発明の空気入りタイヤのトレッドの構造としては、特に制限はなく、1層構造であってもよいし、多層構造であってもよく、また、直接路面に接地する上層のキャップ部と、該キャップ部のタイヤの内側に隣接して配置される下層のベース部とから構成される、いわゆるキャップ・ベース構造を有していてもよい。本発明においては、少なくとも前記キャップ部が前記ゴム組成物で形成されていることが好ましい。 The structure of the tread of the pneumatic tire of the present invention is not particularly limited, and may be a one-layer structure or a multilayer structure, and an upper cap portion that directly contacts the road surface; You may have what is called a cap base structure comprised from the base part of the lower layer arrange | positioned adjacent to the inner side of the tire of a cap part. In the present invention, it is preferable that at least the cap portion is formed of the rubber composition.
本発明のタイヤは、その製造方法につき特に制限はないが、例えば、以下のようにして製造することができる。即ち、まず、本発明のゴム組成物を調製し、該ゴム組成物を生タイヤケースのクラウン部に予め貼り付けられた未加硫のベース部の上に貼り付ける。その後、所定のモールドで所定温度、所定圧力の下で加硫成形することにより製造することができる。 Although there is no restriction | limiting in particular about the tire of this invention, For example, it can manufacture as follows. That is, first, the rubber composition of the present invention is prepared, and the rubber composition is pasted on an unvulcanized base portion that is preliminarily pasted on the crown portion of the raw tire case. Thereafter, it can be produced by vulcanization molding with a predetermined mold at a predetermined temperature and a predetermined pressure.
以下、実施例により本発明を更に具体的に説明するが、本発明はこれらの実施例によって何ら限定されるものではなく、その要旨を変更しない範囲において適宜変更可能である。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples, and can be appropriately changed without departing from the scope of the present invention.
（比較例１〜４及び実施例１〜９）
下記の表１に示す配合（単位は質量部）に従い、バンバリーミキサーを用いて各ゴム組成物を混練して調製した。また、該ゴム組成物を用いて乗用車タイヤ（サイズ：２２５／４０Ｒ１８）のトレッドを形成し、試作タイヤを製造した。その後、該ゴム組成物及び該試作タイヤについて、ＤＲＹグリップ性等を以下の方法に従って評価した。結果を表1に示す。
(Comparative Examples 1-4 and Examples 1-9)
Each rubber composition was kneaded and prepared using a Banbury mixer in accordance with the formulation shown in Table 1 below (unit: parts by mass). Further, a tread of a passenger car tire (size: 225 / 40R18) was formed using the rubber composition, and a prototype tire was manufactured. Thereafter, the DRY grip properties and the like of the rubber composition and the prototype tire were evaluated according to the following methods. The results are shown in Table 1.
＜動的弾性率 Ｅ’（ＭＰａ）＞
得られたゴム組成物を１４５℃、４５分で加硫した後、ＪＩＳ Ｋ６２６５に記されるフレクソメーターによる定応力測定を行いサンプル内部に亀裂が発生するまでの時間を耐熱疲労時間とし測定を行った。データは比較例1を１００として指数化した値を示す。
<Dynamic elastic modulus E '(MPa)>
After the obtained rubber composition is vulcanized at 145 ° C. for 45 minutes, a constant stress measurement is performed with a flexometer described in JIS K6265, and the time until a crack occurs inside the sample is measured as a heat fatigue time. went. The data shows values indexed with Comparative Example 1 as 100.
＜ＤＲＹグリップ性＞
試作タイヤを最高時速３００ｋｍ／ｈで走行可能な高性能車両に装備させて、サーキットで走行させ、計測１周目の走行初期グリップ（初期グリップ性能）と計測１２周目の走行末期グリップ（走行安定性）におけるテストドライバーのフィーリングを下記の基準にて評価した。数値が正の値で大きくなる程、ＤＲＹグリップ性に優れることを意味する。
＋３・・・運転頻度の低い一般ドライバーが明確に差を認識できる程度
＋２・・・運転頻度の高い一般ドライバーが差を認識できる程度
＋１・・・プロのドライバーが差を認識できる程度
０ ・・・コントロール
−１・・・プロのドライバーが差を認識できる程度
−２・・・運転頻度の高い一般ドライバーが差を認識できる程度
−３・・・運転頻度の低い一般ドライバーが明確に差を認識できる程度
<DRY grip>
Equipped with a high-performance vehicle that can run a prototype tire at a maximum speed of 300 km / h and run on a circuit, the initial grip (initial grip performance) of the first lap of measurement and the final grip of the last lap of measurement (running stability) The feeling of the test driver in the property was evaluated according to the following criteria. It means that it is excellent in DRY grip property, so that a numerical value becomes large with a positive value.
+3: To the extent that a general driver with low driving frequency can clearly recognize the difference +2: To the extent that a general driver with high driving frequency can recognize the difference +1: To the extent that a professional driver can recognize the difference 0・ Control-1: To the extent that a professional driver can recognize the difference-2 ... To the extent that a general driver with high driving frequency can recognize the difference-3 ... With a general driver with low driving frequency clearly seeing the difference As much as possible
＊１ 日本合成ゴム（株）社製、０１２０（スチレン含有率３５％、ビニル結合量１６％、３５％アロマティックオイル油添）
＊２ 旭化成（株）社製、タフデン４３５０（スチレン含有率３９％、ビニル結合量３８％、５０％アロマティックオイル油添）
＊３ ＳＡＦ（Ｎ２ＳＡ １５０ｍ２／ｇ）
＊４ 富士興産（株）社製、フコール アロマックス＃３
＊５ 精工化学（株）社製、マイクロクリスタリンワックス
＊６ 大内新興化学工業（株）社製、Ｎ−（１，３−ジメチルブチル）−Ｎ’−フェニル−ｐ−フェニレンジアミン
＊７ ヤスハラケミカル（株）社製、クリアロンＰ１２５、水添テルペン樹脂、軟化点１２５℃
＊８ ヤスハラケミカル（株）社製、クリアロンＰ１５０、水添テルペン樹脂、軟化点１５０℃
＊９ 新日本石油化学（株）社製、ネオポリマー１７０Ｓ、α-メチルスチレン−ビニルトルエン−インデン共重合体樹脂、軟化点１６０℃
＊１０ Ｒｕｔｇｅｒｓ Ｃｈｅｍｉｃａｌｓ社製、 ＮＯＢＡＲＥＳ Ｃ１６０、クマロンインデン樹脂、軟化点１６０℃
＊１１ 住友化学工業（株）社製、ジフェニルグアニジン
＊１２ 三進化学工業（株）社製、ビス（４−メチルジベンゾチアゾリル−２）−ジスルフィド
・ １３ 大内新興化学工業（株）社製、Ｎ−シクロヘキシル−２−ベンゾチアジルスルフェンアミド
* 1 Made by Nippon Synthetic Rubber Co., Ltd., 0120 (styrene content 35%, vinyl bond 16%, 35% aromatic oil)
* 2 Toughden 4350 manufactured by Asahi Kasei Corporation (styrene content 39%, vinyl bond 38%, 50% aromatic oil oiled)
* 3 SAF (N2SA 150m 2 / g)
* 4 Fucor Aromax # 3, manufactured by Fuji Kosan Co., Ltd.
* 5 Seiko Chemical Co., Ltd., microcrystalline wax * 6 Ouchi Shinsei Chemical Co., Ltd., N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine * 7 Yasuhara Chemical ( Co., Ltd., Clearon P125, hydrogenated terpene resin, softening point 125 ° C
* 8 Yashara Chemical Co., Ltd., Clearon P150, hydrogenated terpene resin, softening point 150 ° C
* 9 Made by Nippon Petrochemical Co., Ltd., Neopolymer 170S, α-methylstyrene-vinyltoluene-indene copolymer resin, softening point 160 ° C
* 10 Ruggers Chemicals, NOBARES C160, coumarone indene resin, softening point 160 ° C
* 11 Sumitomo Chemical Co., Ltd., diphenyl guanidine * 12 Sanshin Chemical Industry Co., Ltd., bis (4-methyldibenzothiazolyl-2) -disulfide 13 Ouchi Shinsei Chemical Co., Ltd. N-cyclohexyl-2-benzothiazylsulfenamide
軟化点１２５℃の水添テルペン樹脂のみをゴム組成物に配合した比較例1では、初期グリップ性能は非常に良好だが、走行中のグリップ低下が大きいため走行安定性が低い。軟化点１５０℃の水添テルペン樹脂をゴム組成物に配合した比較例２でも同様の結果である。これは、樹脂に水素添加するとポリマーとの相溶性が高くなるため、該樹脂を配合したゴム組成物の弾性率が低下するためであると考えられる。更に、軟化点１６０℃のＣ9 樹脂をゴム組成物に配合した比較例３では、１２０℃のＥ’が１６０となり走行安定性は著しく改良されるが、初期グリップ性能は大きく低下する。また、上記２つの樹脂を組み合わせて配合した比較例４は１２０℃のＥ’が増加しない。これは低軟化点の樹脂を配合しているためであると思われる。 In Comparative Example 1 in which only the hydrogenated terpene resin having a softening point of 125 ° C. is blended in the rubber composition, the initial grip performance is very good, but the running stability is low due to the large reduction in grip during running. The same result was obtained in Comparative Example 2 in which a hydrogenated terpene resin having a softening point of 150 ° C. was blended in the rubber composition. This is considered to be because, when hydrogenation is added to the resin, the compatibility with the polymer is increased, so that the elastic modulus of the rubber composition containing the resin is decreased. Furthermore, in Comparative Example 3 in which a C 9 resin having a softening point of 160 ° C. was blended in the rubber composition, E ′ at 120 ° C. was 160, and running stability was significantly improved, but initial grip performance was greatly reduced. In Comparative Example 4 in which the above two resins are combined and combined, E ′ at 120 ° C. does not increase. This seems to be because a resin with a low softening point is blended.
これらに対して、軟化点１５０℃の水添テルペン樹脂と軟化点１６０℃のα-メチルスチレン−ビニルトルエン−インデン共重合体樹脂を組み合わせてゴム組成物に配合した実施例1〜３及び５〜９は、１２０℃のＥ’が改善され(実施例1〜３及び５〜９)、初期グリップ性能を維持しつつ走行安定性が改善される（実施例1、２、３、５、６、７及び９）。こうした効果は、軟化点１６０℃のクマロンインデン樹脂を配合した場合にも確認できる（実施例４）。 On the other hand, Examples 1-3 and 5 in which a hydrogenated terpene resin having a softening point of 150 ° C. and an α-methylstyrene-vinyltoluene-indene copolymer resin having a softening point of 160 ° C. were combined in a rubber composition. 9, E ′ at 120 ° C. is improved (Examples 1 to 3 and 5 to 9), and running stability is improved while maintaining initial grip performance (Examples 1, 2, 3, 5, 6, 7 and 9). Such an effect can also be confirmed when a coumarone indene resin having a softening point of 160 ° C. is blended (Example 4).
Claims (7)
前記ゴム成分が、ブタジエン部のビニル結合量が１０％以上であるブタジエン系共重合体を７０質量％以上含むことを特徴とするゴム組成物。 10 to 60 parts by mass of a softening point of at least one selected from hydrogenated terpene phenolic resins having a softening point of 130 ° C. or higher with respect to 100 parts by mass of the rubber component partially or completely hydrogenated Is 130 ° C. or higher and 190 ° C. or lower, and contains 5 to 60 parts by mass of at least one selected from C 9 resin containing indene,
The rubber composition, wherein the rubber component contains 70% by mass or more of a butadiene-based copolymer having a butadiene portion having a vinyl bond amount of 10% or more.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007003451A JP5497254B2 (en) | 2007-01-11 | 2007-01-11 | Rubber composition and pneumatic tire using the same |
| EP08703163A EP2103650B1 (en) | 2007-01-11 | 2008-01-11 | Rubber composition and tire using the same |
| US12/522,424 US8318861B2 (en) | 2007-01-11 | 2008-01-11 | Rubber composition and tire using the same |
| PCT/JP2008/050299 WO2008084860A1 (en) | 2007-01-11 | 2008-01-11 | Rubber composition and tire using the same |
| CN200880002192.2A CN101589100B (en) | 2007-01-11 | 2008-01-11 | Rubber composition and tire using the same |
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| JP2007003451A JP5497254B2 (en) | 2007-01-11 | 2007-01-11 | Rubber composition and pneumatic tire using the same |
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| JP2008169296A JP2008169296A (en) | 2008-07-24 |
| JP5497254B2 true JP5497254B2 (en) | 2014-05-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4752957B2 (en) * | 2009-06-17 | 2011-08-17 | 横浜ゴム株式会社 | Rubber composition for tire tread |
| WO2011078859A1 (en) * | 2009-12-23 | 2011-06-30 | Michelin Recherche Et Technique S.A. | Rubber composition for aircraft tire treads |
| FR2968006B1 (en) | 2010-11-26 | 2012-12-21 | Michelin Soc Tech | TIRE TREAD TIRE |
| JP5654358B2 (en) * | 2011-01-06 | 2015-01-14 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire |
| JP6412775B2 (en) * | 2014-02-06 | 2018-10-24 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire |
| JP6743362B2 (en) * | 2015-10-06 | 2020-08-19 | 住友ゴム工業株式会社 | Rubber composition for tires |
| JP6733223B2 (en) * | 2016-03-07 | 2020-07-29 | 住友ゴム工業株式会社 | High performance tires |
| KR102208967B1 (en) * | 2016-09-30 | 2021-01-28 | 코오롱인더스트리 주식회사 | Composition for tire tread comprising resin alternative to process oil |
| JP7119329B2 (en) * | 2017-10-12 | 2022-08-17 | 住友ゴム工業株式会社 | Rubber composition for tire |
| CN115667410A (en) * | 2020-06-08 | 2023-01-31 | 哈利玛化成株式会社 | Rubber modifier for tire and rubber composition for tire |
| CN114381053A (en) * | 2022-02-08 | 2022-04-22 | 徐州徐轮橡胶有限公司 | Self-cleaning type tread rubber material for mold |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0912784A (en) * | 1995-06-29 | 1997-01-14 | Toyo Tire & Rubber Co Ltd | Rubber composition |
| JP3714750B2 (en) * | 1997-01-10 | 2005-11-09 | 横浜ゴム株式会社 | Tire tread rubber composition for competition |
| JPH10195242A (en) * | 1997-01-14 | 1998-07-28 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP4037744B2 (en) * | 2001-12-28 | 2008-01-23 | 株式会社ブリヂストン | Rubber composition and tire using the same |
| WO2004000931A1 (en) * | 2002-06-19 | 2003-12-31 | Bridgestone Corporation | Rubber composition for tire and tire made therefrom |
| JP2006249230A (en) * | 2005-03-10 | 2006-09-21 | Bridgestone Corp | Rubber composition for tread and pneumatic tire using the same |
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