JP7620183B2 - Rubber composition for tires and tire using same - Google Patents
Rubber composition for tires and tire using same Download PDFInfo
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- JP7620183B2 JP7620183B2 JP2021010784A JP2021010784A JP7620183B2 JP 7620183 B2 JP7620183 B2 JP 7620183B2 JP 2021010784 A JP2021010784 A JP 2021010784A JP 2021010784 A JP2021010784 A JP 2021010784A JP 7620183 B2 JP7620183 B2 JP 7620183B2
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- 239000000203 mixture Substances 0.000 title claims description 31
- 229920001971 elastomer Polymers 0.000 title claims description 30
- 239000005060 rubber Substances 0.000 title claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 22
- 229920003244 diene elastomer Polymers 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 244000043261 Hevea brasiliensis Species 0.000 claims description 17
- 229920003052 natural elastomer Polymers 0.000 claims description 17
- 229920001194 natural rubber Polymers 0.000 claims description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- -1 acetylene compound Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 10
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 229920003049 isoprene rubber Polymers 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 238000005299 abrasion Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical compound OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 238000000034 method Methods 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
- 239000011787 zinc oxide Substances 0.000 description 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- YRVRZDIWEXCJSX-UHFFFAOYSA-N 2-methyl-3-(3-triethoxysilylpropyl)thiirane-2-carboxylic acid Chemical compound CCO[Si](OCC)(OCC)CCCC1SC1(C)C(O)=O YRVRZDIWEXCJSX-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- MFNWUMRYUYUAAV-UHFFFAOYSA-N 4-(3-trimethoxysilylpropyl)-3H-1,3-benzothiazole-2-thione Chemical compound CO[Si](OC)(OC)CCCC1=CC=CC2=C1N=C(S2)S MFNWUMRYUYUAAV-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
- ZZOXWBGGPBLVNQ-UHFFFAOYSA-N CN(C)C(SSSSC(N(C)C)=[S+]CCC[SiH2]C(OC)OC)=[S+]CCC[SiH2]C(OC)OC Chemical compound CN(C)C(SSSSC(N(C)C)=[S+]CCC[SiH2]C(OC)OC)=[S+]CCC[SiH2]C(OC)OC ZZOXWBGGPBLVNQ-UHFFFAOYSA-N 0.000 description 1
- SKFGZHGVWONCTD-UHFFFAOYSA-N CN(C)C(SSSSC(N(C)C)=[S+]CCC[Si](OC)(OC)OC)=[S+]CCC[Si](OC)(OC)OC Chemical compound CN(C)C(SSSSC(N(C)C)=[S+]CCC[Si](OC)(OC)OC)=[S+]CCC[Si](OC)(OC)OC SKFGZHGVWONCTD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101100434170 Oryza sativa subsp. japonica ACR2.1 gene Proteins 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Description
本発明は、タイヤ用ゴム組成物およびそれを用いたタイヤに関するものであり、詳しくは、天然ゴムを配合した場合であっても耐摩耗性に優れ、モジュラスが向上し、かつ低発熱性を有するタイヤ用ゴム組成物およびそれを用いたタイヤに関するものである。 The present invention relates to a rubber composition for tires and a tire using the same, and more specifically, to a rubber composition for tires that has excellent abrasion resistance, improved modulus, and low heat buildup even when natural rubber is blended, and a tire using the same.
近年、重荷重用または建設車両用の空気入りタイヤにおいて、天然ゴムにシリカを配合する事例が増加している（例えば特許文献１参照）。しかし、天然ゴム中にシリカを良好に分散させるのは極めて困難であり、例えばシランカップリング剤を使用しても所望の分散性を得るのは難しい。
一方、タイヤ用ゴム組成物は、高モジュラスであるとともに、低転がり抵抗性を獲得して環境負荷を低減するという観点から、低発熱性であることも要求される。
In recent years, there has been an increase in the number of cases in which silica is blended with natural rubber in pneumatic tires for heavy loads or construction vehicles (see, for example, Patent Document 1). However, it is extremely difficult to disperse silica well in natural rubber, and even if a silane coupling agent is used, it is difficult to obtain the desired dispersibility.
On the other hand, rubber compositions for tires are required to have a high modulus and also to have low heat build-up from the viewpoint of achieving low rolling resistance and reducing the environmental load.
したがって本発明の目的は、天然ゴムを配合した場合であっても耐摩耗性に優れ、モジュラスが向上し、かつ低発熱性を有するタイヤ用ゴム組成物およびそれを用いたタイヤを提供することにある。 The object of the present invention is therefore to provide a rubber composition for tires that has excellent abrasion resistance, improved modulus, and low heat build-up even when natural rubber is blended, and a tire using the same.
本発明者らは鋭意研究を重ねた結果、天然ゴム、シリカおよびシランカップリング剤を特定量で配合するとともに、特定の構造を有するアセチレン系化合物を特定量でもって配合したゴム組成物が、上記課題を解決できることを見出し、本発明を完成することができた。 As a result of extensive research, the inventors discovered that a rubber composition containing specific amounts of natural rubber, silica, and a silane coupling agent, as well as a specific amount of an acetylene-based compound having a specific structure, can solve the above problems, and thus completed the present invention.
すなわち本発明は、天然ゴムを５０質量部以上含むジエン系ゴム１００質量部に対し、
下記式（１）で表されるアセチレン系化合物を０．１～２０質量部、
シリカを２０～１２０質量部、および
シランカップリング剤を１～１５質量部
配合してなることを特徴とするタイヤ用ゴム組成物を提供するものである。
That is, the present invention provides a composition comprising, for 100 parts by mass of a diene rubber containing 50 parts by mass or more of a natural rubber,
0.1 to 20 parts by mass of an acetylene-based compound represented by the following formula (1),
The rubber composition for tires is characterized by comprising 20 to 120 parts by mass of silica and 1 to 15 parts by mass of a silane coupling agent.
（式（１）中、ｍ＋ｎは０～２０である） (In formula (1), m+n is 0 to 20)
本発明のゴム組成物は、天然ゴム、シリカおよびシランカップリング剤を特定量で配合するとともに、前記式（１）で表される特定の構造を有するアセチレン系化合物を特定量でもって配合したので、耐摩耗性に優れ、モジュラスが向上し、かつ低発熱性を有するタイヤ用ゴム組成物およびそれを用いたタイヤを提供することができる。
一般的に、天然ゴムとカーボンブラックとは親和性を有することが知られている。一方、本発明における前記式（１）で表されるアセチレン系化合物は、カーボンブラックとシリカとの親和性を高めることができ、結果として天然ゴム中にシリカを良好に分散させることができる。このように、本発明のゴム組成物がとくにカーボンブラックを含有する場合、優れた効果を奏することができる。
The rubber composition of the present invention contains specific amounts of natural rubber, silica, and a silane coupling agent, as well as a specific amount of an acetylene-based compound having the specific structure represented by formula (1). Therefore, it is possible to provide a rubber composition for tires that has excellent abrasion resistance, improved modulus, and low heat build-up, and a tire using the same.
It is generally known that natural rubber and carbon black have an affinity. On the other hand, the acetylene-based compound represented by the formula (1) in the present invention can increase the affinity between carbon black and silica, and as a result, the silica can be well dispersed in the natural rubber. Thus, when the rubber composition of the present invention contains carbon black, it can exert an excellent effect.
以下、本発明をさらに詳細に説明する。
（ジエン系ゴム）
本発明で使用されるジエン系ゴムは、天然ゴム（ＮＲ）を必須成分とする。ＮＲの配合量は、ジエン系ゴム全体を１００質量部としたときに、５０質量部以上が好ましく、７０質量部以上がさらに好ましい。
また、本発明の効果向上の観点から、ジエン系ゴム１００質量部中、天然ゴムが７０質量部以上を占め、残部がスチレン－ブタジエン共重合体ゴム（ＳＢＲ）、ブタジエンゴム（ＢＲ）および合成イソプレンゴム（ＩＲ）から選択された１種以上であることが好ましい。
また、本発明で使用されるジエン系ゴムは、上記以外にも、ゴム組成物に配合することができる任意のジエン系ゴムを用いることができ、例えば、アクリロニトリル－ブタジエン共重合体ゴム（ＮＢＲ）、エチレン－プロピレン－ジエンターポリマー（ＥＰＤＭ）等を使用できる。これらは、単独で用いてもよく、２種以上を併用してもよい。また、その分子量やミクロ構造はとくに制限されず、アミン、アミド、シリル、アルコキシシリル、カルボキシル、ヒドロキシル基等で末端変性されていても、エポキシ化されていてもよい。
The present invention will now be described in further detail.
(Diene rubber)
The diene rubber used in the present invention contains natural rubber (NR) as an essential component. The amount of NR is preferably 50 parts by mass or more, and more preferably 70 parts by mass or more, based on 100 parts by mass of the total diene rubber.
From the viewpoint of improving the effects of the present invention, it is preferable that, per 100 parts by mass of diene rubber, natural rubber accounts for 70 parts by mass or more, with the remainder being one or more types selected from styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR) and synthetic isoprene rubber (IR).
In addition to the above, the diene rubber used in the present invention may be any diene rubber that can be blended in a rubber composition, such as acrylonitrile-butadiene copolymer rubber (NBR) or ethylene-propylene-diene terpolymer (EPDM). These may be used alone or in combination of two or more. There are no particular limitations on the molecular weight or microstructure, and the diene rubber may be terminally modified with an amine, amide, silyl, alkoxysilyl, carboxyl, or hydroxyl group, or may be epoxidized.
（アセチレン系化合物）
本発明で使用されるアセチレン系化合物は、下記式（１）で表される。
(Acetylene compounds)
The acetylene compound used in the present invention is represented by the following formula (1).
式（１）中、ｍ＋ｎは０～２０であり、好ましくは１～２０であり、さらに好ましくは２～１２である。ｍ＋ｎが１以上、すなわちエチレンオキサイド基を含有するアセチレン系化合物は、シリカの分散性をさらに良好にすることができる。
本発明で使用されるアセチレン系化合物は、市販されているものを利用することができ、例えば川研ファインケミカル株式会社製商品名アセチレノール、エボニックインダストリーズ社製商品名サーフィノール等が挙げられる。
In formula (1), m+n is 0 to 20, preferably 1 to 20, and more preferably 2 to 12. An acetylene compound in which m+n is 1 or more, i.e., an ethylene oxide group-containing acetylene compound, can further improve the dispersibility of silica.
The acetylene compound used in the present invention may be a commercially available product, for example, Acetylenol (trade name) manufactured by Kawaken Fine Chemicals Co., Ltd., Surfynol (trade name) manufactured by Evonik Industries Ltd., and the like.
（シリカ）
本発明で使用されるシリカとしては、本発明の効果向上の観点から、ＣＴＡＢ吸着比表面積が１００～２４０ｍ２／ｇであるのが好ましく、１２０～２２０ｍ２／ｇであるのがさらに好ましい。
なお、ＣＴＡＢ吸着比表面積は、シリカ表面への臭化ｎ－ヘキサデシルトリメチルアンモニウムの吸着量をＪＩＳ Ｋ６２１７－３：２００１「第３部：比表面積の求め方－ＣＴＡＢ吸着法」にしたがって測定した値である。
(silica)
From the viewpoint of improving the effects of the present invention, the silica used in the present invention preferably has a CTAB adsorption specific surface area of 100 to 240 m 2 /g, and more preferably 120 to 220 m 2 /g.
The CTAB adsorption specific surface area is a value obtained by measuring the amount of n-hexadecyltrimethylammonium bromide adsorbed on the silica surface in accordance with JIS K6217-3:2001 "Part 3: Determination of specific surface area - CTAB adsorption method."
（シランカップリング剤）
本発明で使用されるシランカップリング剤としては、とくに制限されないが、含硫黄シランカップリング剤が好ましく、例えばビス（３－トリエトキシシリルプロピル）テトラスルフィド、ビス（３－トリエトキシシリルプロピル）ジスルフィド、ビス（３－トリメトキシシリルプロピル）テトラスルフィド、メルカプトプロピルトリメトキシシラン、メルカプトプロピルトリエトキシシラン、３－トリメトキシシリルプロピル－Ｎ，Ｎ－ジメチルチオカルバモイル－テトラスルフィド、トリメトキシシリルプロピル－メルカプトベンゾチアゾールテトラスルフィド、トリエトキシシリルプロピル－メタクリレート－モノスルフィド、ジメトキシメチルシリルプロピル－Ｎ，Ｎ－ジメチルチオカルバモイル－テトラスルフィド、γ－メルカプトプロピルトリエトキシシラン、３－オクタノイルチオプロピルトリエトキシシラン等を例示することができる。シランカップリング剤は、１種または２種以上を併用してもよい。
(Silane coupling agent)
The silane coupling agent used in the present invention is not particularly limited, but is preferably a sulfur-containing silane coupling agent, such as bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)disulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl-tetrasulfide, trimethoxysilylpropyl-mercaptobenzothiazole tetrasulfide, triethoxysilylpropyl-methacrylate-monosulfide, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl-tetrasulfide, γ-mercaptopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, etc. Silane coupling agents may be used alone or in combination of two or more.
（カーボンブラック）
本発明のゴム組成物は、カーボンブラックを配合することができる。カーボンブラックは、本発明の効果向上の観点から、窒素吸着比表面積（Ｎ２ＳＡ）が３０～１８０ｍ２／ｇであるのが好ましく、４０～１４０ｍ２／ｇであるのがさらに好ましい。
なお窒素吸着比表面積（Ｎ２ＳＡ）は、ＪＩＳ Ｋ ６２１７－２：２００１「第２部：比表面積の求め方－窒素吸着法－単点法」にしたがって測定した値である。
(Carbon Black)
The rubber composition of the present invention may contain carbon black. From the viewpoint of improving the effects of the present invention, the carbon black preferably has a nitrogen adsorption specific surface area (N 2 SA) of 30 to 180 m 2 /g, more preferably 40 to 140 m 2 /g.
The nitrogen adsorption specific surface area (N 2 SA) is a value measured in accordance with JIS K 6217-2:2001 "Part 2: Determination of specific surface area - Nitrogen adsorption method - Single point method".
（ゴム組成物の配合割合）
本発明のゴム組成物は、ジエン系ゴム１００質量部に対し、前記式（１）で表されるアセチレン系化合物を０．１～２０質量部、シリカを２０～１２０質量部、およびシランカップリング剤を１～１５質量部配合してなることを特徴とする。
ジエン系ゴム１００質量部に対し、アセチレン系化合物の配合量が０．１質量部未満では、配合量が少なすぎて本発明の効果を奏することができず、逆に２０質量部を超えると耐摩耗性が悪化する。
シリカの前記配合量が２０質量部未満では、ゴム組成物の機械的特性や耐摩耗性が悪化し、逆に１２０質量部を超えると破断物性が悪化する。
シランカップリング剤の前記配合量が１質量部未満では、配合量が少なすぎて本発明の効果を奏することができず、逆に１５質量部を超えると破断物性が悪化する。
(Rubber composition blending ratio)
The rubber composition of the present invention is characterized in that it is obtained by compounding, per 100 parts by mass of diene rubber, 0.1 to 20 parts by mass of the acetylene compound represented by the formula (1), 20 to 120 parts by mass of silica, and 1 to 15 parts by mass of a silane coupling agent.
If the amount of the acetylene compound is less than 0.1 parts by mass per 100 parts by mass of diene rubber, the amount is too small to achieve the effects of the present invention, whereas if it exceeds 20 parts by mass, the abrasion resistance deteriorates.
If the amount of silica is less than 20 parts by mass, the mechanical properties and abrasion resistance of the rubber composition deteriorate, whereas if it exceeds 120 parts by mass, the breaking properties deteriorate.
If the amount of the silane coupling agent is less than 1 part by mass, the amount is too small to achieve the effects of the present invention, whereas if it exceeds 15 parts by mass, the breaking properties deteriorate.
アセチレン系化合物の配合量は、ジエン系ゴム１００質量部に対し、０．５～１５質量部が好ましく、１～１０質量部がさらに好ましい。
シリカの配合量の配合量は、ジエン系ゴム１００質量部に対し、４０～８０質量部が好ましい。
シランカップリング剤の配合量の配合量は、ジエン系ゴム１００質量部に対し、１～１０質量部が好ましい。
カーボンブラックを配合する場合、その配合量は、ジエン系ゴム１００質量部に対し、５～６０質量部が好ましく、１０～５０質量部がさらに好ましい。
The amount of the acetylene compound is preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the diene rubber.
The compounding amount of silica is preferably 40 to 80 parts by mass based on 100 parts by mass of the diene rubber.
The amount of the silane coupling agent is preferably 1 to 10 parts by mass based on 100 parts by mass of the diene rubber.
When carbon black is compounded, the compounding amount is preferably from 5 to 60 parts by mass, and more preferably from 10 to 50 parts by mass, per 100 parts by mass of the diene rubber.
（その他成分）
本発明におけるゴム組成物には、前記した成分に加えて、加硫又は架橋剤；加硫又は架橋促進剤；酸化亜鉛；老化防止剤；可塑剤などのゴム組成物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も、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。
(Other ingredients)
In addition to the above-mentioned components, the rubber composition of the present invention may contain various additives that are generally incorporated in rubber compositions, such as vulcanizing or crosslinking agents, vulcanizing or crosslinking accelerators, zinc oxide, antioxidants, and plasticizers, and these additives can be kneaded in a general manner to form a composition, which can be used for vulcanization or crosslinking. The amounts of these additives may be conventional amounts, provided that they do not violate the object of the present invention.
また本発明のタイヤは、本発明のゴム組成物を使用して調製することができ、空気入りタイヤであることが好ましく、空気、窒素等の不活性ガス及びその他の気体を充填することができる。また本発明のタイヤは、トレッド、とくに重荷重用または建設車両用タイヤのキャップトレッドに適用するのがよい。 The tire of the present invention can be prepared using the rubber composition of the present invention, and is preferably a pneumatic tire, which can be filled with air, an inert gas such as nitrogen, or other gases. The tire of the present invention is preferably applied to a tread, particularly a cap tread of a tire for heavy loads or a tire for a construction vehicle.
以下、本発明を実施例および比較例によりさらに説明するが、本発明は下記例に制限されるものではない。 The present invention will be further explained below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
実施例１～１５、比較例１～２
表１、２に示す配合（質量部）において、加硫系（加硫促進剤、硫黄）と硬化剤を除く成分を１．７リットルの密閉式バンバリーミキサーで５分間混練した後、ミキサー外に放出させて室温冷却した。続いて、該組成物を同バンバリーミキサーに再度入れ、加硫系を加えて混練し、ゴム組成物を得た。得られたゴム組成物を１６０℃、２０分の条件でプレス加硫し、以下に示す試験法で物性を測定した。
Examples 1 to 15, Comparative Examples 1 to 2
In the formulation (parts by mass) shown in Tables 1 and 2, the components other than the vulcanization system (vulcanization accelerator, sulfur) and the curing agent were mixed in a 1.7-liter closed Banbury mixer for 5 minutes, then discharged from the mixer and cooled at room temperature. The composition was then placed in the same Banbury mixer again, and the vulcanization system was added and mixed to obtain a rubber composition. The obtained rubber composition was press-vulcanized at 160°C for 20 minutes, and the physical properties were measured using the test methods shown below.
発熱性：（株）東洋精機製作所製の粘弾性スペクトロメーターを用いて、初期歪＝１０％、振幅＝±２％、周波数＝２０Ｈｚの条件下でｔａｎδ（６０℃）を測定し、この値をもって発熱性を評価した。結果は、比較例１または２の値を１００として指数で示した。指数が小さいほど、低発熱性であることを示す。
１００％モジュラス（Ｍ１００）：ＪＩＳ Ｋ６２５１に従い、２３℃にて引張試験を実施し、伸び１００％時の引張応力を測定した。結果は、比較例１または２を１００として指数で示した。指数が大きいほど、高モジュラスであることを示す。
耐摩耗性：ＪＩＳ Ｋ６２６４－２に準拠して、岩本製作所社製ランボーン摩耗試験機を使用し、荷重４９Ｎ、スリップ率２５％、時間４分、室温の条件で測定した。結果は、比較例１または２の値を１００として指数で示した。指数が大きいほど耐摩耗性に優れることを意味する。
結果を表１、２に示す。なお、比較例１は、実施例１～７と比較され、比較例２は、実施例８～１５と比較される。
Heat generation: Using a viscoelasticity spectrometer manufactured by Toyo Seiki Seisakusho Co., Ltd., tan δ (60°C) was measured under the conditions of initial strain = 10%, amplitude = ±2%, and frequency = 20 Hz, and the heat generation was evaluated based on this value. The results were expressed as an index, with the value of Comparative Example 1 or 2 being 100. The smaller the index, the lower the heat generation.
100% modulus (M100): A tensile test was carried out at 23° C. in accordance with JIS K6251 to measure the tensile stress at 100% elongation. The results are expressed as an index, with Comparative Example 1 or 2 being set at 100. A larger index indicates a higher modulus.
Abrasion resistance: According to JIS K6264-2, a Lambourn abrasion tester manufactured by Iwamoto Seisakusho Co., Ltd. was used to measure under the conditions of a load of 49 N, a slip rate of 25%, a time of 4 minutes, and room temperature. The results are expressed as an index, with the value of Comparative Example 1 or 2 being 100. A larger index indicates better abrasion resistance.
The results are shown in Tables 1 and 2. Comparative Example 1 is compared with Examples 1 to 7, and Comparative Example 2 is compared with Examples 8 to 15.
＊１：ＮＲ（ＳＴＲ２０）
＊２：ＳＢＲ（日本ゼオン株式会社製Ｎｉｐｏｌ １５０２）
＊３：シリカ（UNITED SILICA INDUSTRIAL社製ULTRASIL VN-3G、ＣＴＡＢ比表面積＝１４７ｍ２／ｇ）
＊４：カーボンブラック（東海カーボン株式会社製シーストＫＨ、Ｎ２ＳＡ＝９２ｍ２／ｇ）
＊５：酸化亜鉛（正同化学工業（株）製酸化亜鉛３種）
＊６：ステアリン酸（日油(株)製ビーズステアリン酸）
＊７：老化防止剤（フレキシス社製サントフレックス６ＰＰＤ）
＊８：シランカップリング剤（エボニックデグッサジャパン社製Ｓｉ６９）
＊９：硫黄（四国化成工業株式会社製ミュークロンＯＴ－２０）
＊１０：加硫促進剤（大内新興化学工業（株）製ノクセラーＣＺ－Ｇ）
＊１１：アセチレン系化合物１（川研ファインケミカル株式会社製商品名アセチレノールＥ６０、式（１）で表されるアセチレン系化合物において、ｍ＝３、ｎ＝３の化合物）
＊１２：アセチレン系化合物２（川研ファインケミカル株式会社製商品名アセチレノールＥ１００、式（１）で表されるアセチレン系化合物において、ｍ＝５、ｎ＝５の化合物）
＊１３：アセチレン系化合物３（川研ファインケミカル株式会社製商品名アセチレノールＥ００、式（１）で表されるアセチレン系化合物において、ｍ＝０、ｎ＝０の化合物）
*1: NR (STR20)
*2: SBR (Nipol 1502 manufactured by Nippon Zeon Co., Ltd.)
*3: Silica (ULTRASIL VN-3G manufactured by UNITED SILICA INDUSTRIAL, CTAB specific surface area = 147 m2 /g)
*4: Carbon black (Seest KH, manufactured by Tokai Carbon Co., Ltd., N 2 SA = 92 m 2 /g)
*5: Zinc oxide (3 types of zinc oxide manufactured by Seido Chemical Industry Co., Ltd.)
*6: Stearic acid (beads stearic acid manufactured by NOF Corp.)
*7: Anti-aging agent (Santoflex 6PPD manufactured by Flexis)
*8: Silane coupling agent (Si69 manufactured by Evonik Degussa Japan)
*9: Sulfur (Mu-Clon OT-20 manufactured by Shikoku Chemical Industry Co., Ltd.)
*10: Vulcanization accelerator (Noccela CZ-G manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)
*11: Acetylene-based compound 1 (product name Acetylenol E60 manufactured by Kawaken Fine Chemical Co., Ltd., a compound in which m = 3 and n = 3 in the acetylene-based compound represented by formula (1))
*12: Acetylene-based compound 2 (product name Acetylenol E100 manufactured by Kawaken Fine Chemical Co., Ltd., a compound in which m = 5 and n = 5 in the acetylene-based compound represented by formula (1))
*13: Acetylene-based compound 3 (product name Acetylenol E00 manufactured by Kawaken Fine Chemical Co., Ltd., a compound in which m = 0 and n = 0 in the acetylene-based compound represented by formula (1))
表１、２の結果から、各実施例のゴム組成物は、天然ゴムを５０質量部以上含むジエン系ゴム１００質量部に対し、前記式（１）で表されるアセチレン系化合物を０．１～２０質量部、シリカを２０～１２０質量部、およびシランカップリング剤を１～１５質量部配合してなるものであるので、比較例１または２に比べて、耐摩耗性に優れ、モジュラスが向上し、かつ低発熱性を有する。
なお、比較例１、２は、前記式（１）で表されるアセチレン系化合物を配合していない例である。
From the results in Tables 1 and 2, it can be seen that the rubber composition of each Example is prepared by compounding 0.1 to 20 parts by mass of the acetylene compound represented by formula (1), 20 to 120 parts by mass of silica, and 1 to 15 parts by mass of a silane coupling agent with 100 parts by mass of diene rubber containing 50 parts by mass or more of natural rubber, and therefore has superior abrasion resistance, improved modulus, and low heat build-up properties compared to Comparative Examples 1 and 2.
Comparative Examples 1 and 2 are examples in which the acetylene compound represented by the formula (1) was not blended.
Claims (5)
下記式（１）で表されるアセチレン系化合物を０．１～２０質量部、
シリカを２０～１２０質量部、および
シランカップリング剤を１～１５質量部
配合してなるタイヤ用ゴム組成物であって、
前記タイヤ用ゴム組成物はさらにカーボンブラックを含有することを特徴とするタイヤ用ゴム組成物。
0.1 to 20 parts by mass of an acetylene-based compound represented by the following formula (1),
A rubber composition for tires , comprising 20 to 120 parts by mass of silica and 1 to 15 parts by mass of a silane coupling agent,
The rubber composition for tires further comprises carbon black.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011140547A (en) | 2010-01-06 | 2011-07-21 | Sumitomo Rubber Ind Ltd | Tire rubber composition and studless tire |
| JP2016113473A (en) | 2014-12-11 | 2016-06-23 | 横浜ゴム株式会社 | Rubber composition for tire tread |
| JP2018188567A (en) | 2017-05-09 | 2018-11-29 | 住友ゴム工業株式会社 | Tire tread and tire |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011140547A (en) | 2010-01-06 | 2011-07-21 | Sumitomo Rubber Ind Ltd | Tire rubber composition and studless tire |
| JP2016113473A (en) | 2014-12-11 | 2016-06-23 | 横浜ゴム株式会社 | Rubber composition for tire tread |
| JP2018188567A (en) | 2017-05-09 | 2018-11-29 | 住友ゴム工業株式会社 | Tire tread and tire |
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