JP2008163209A - Rubber composition for tire tread - Google Patents
Rubber composition for tire tread Download PDFInfo
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- JP2008163209A JP2008163209A JP2006354914A JP2006354914A JP2008163209A JP 2008163209 A JP2008163209 A JP 2008163209A JP 2006354914 A JP2006354914 A JP 2006354914A JP 2006354914 A JP2006354914 A JP 2006354914A JP 2008163209 A JP2008163209 A JP 2008163209A
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- rubber composition
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- tire tread
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 48
- 239000005060 rubber Substances 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 35
- 238000004073 vulcanization Methods 0.000 claims abstract description 18
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229960002447 thiram Drugs 0.000 claims abstract description 14
- -1 unsaturated fatty acid alkali metal salt Chemical class 0.000 claims abstract description 12
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 5
- 229920003244 diene elastomer Polymers 0.000 claims description 8
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 10
- 150000001993 dienes Chemical class 0.000 abstract 1
- 238000013329 compounding Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 2
- 229940096818 dipentamethylenethiuram disulfide Drugs 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- OFHMODDLBXETIK-UHFFFAOYSA-N methyl 2,3-dichloropropanoate Chemical compound COC(=O)C(Cl)CCl OFHMODDLBXETIK-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- PFOWLPUJPOQMAL-UHFFFAOYSA-N piperidine-1-carbothioyl piperidine-1-carbodithioate Chemical compound C1CCCCN1C(=S)SC(=S)N1CCCCC1 PFOWLPUJPOQMAL-UHFFFAOYSA-N 0.000 description 2
- KNBRWWCHBRQLNY-UHFFFAOYSA-N piperidine-1-carbothioylsulfanyl piperidine-1-carbodithioate Chemical compound C1CCCCN1C(=S)SSC(=S)N1CCCCC1 KNBRWWCHBRQLNY-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- TXLINXBIWJYFNR-UHFFFAOYSA-N 4-phenylpyridine-2-carbonitrile Chemical compound C1=NC(C#N)=CC(C=2C=CC=CC=2)=C1 TXLINXBIWJYFNR-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 239000004636 vulcanized rubber 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、タイヤトレッド用ゴム組成物に関し、更に詳細には、シリカの分散性を高め、特に転がり抵抗性をより向上させたタイヤトレッド用ゴム組成物に関する。 The present invention relates to a rubber composition for tire treads, and more particularly, to a rubber composition for tire treads having improved dispersibility of silica and particularly improved rolling resistance.
従来、シリカ多量配合系のキャップコンパウンドについては、シリカ自体の凝集性の高さを回避して、加硫ゴムの各種物性（特に、ウェット性能や転がり抵抗など）をより向上させることが課題となっている。これに対し、従来より、各種加工助剤の提案がなされてきたが、昨今の地球環境保護、安全性の強化といった点で、更なる物性向上が期待されている。 Conventionally, for cap compounds with a large amount of silica, it has been a challenge to improve various physical properties of vulcanized rubber (especially wet performance and rolling resistance) by avoiding the high cohesiveness of silica itself. ing. On the other hand, various processing aids have been proposed in the past, but further improvements in physical properties are expected in terms of recent global environmental protection and safety enhancement.
以下の特許文献１には、優れた氷上性能とともに高度な耐摩耗性を有するシリカ配合系のタイヤトレッド用ゴム組成物として、ＮＲを４０〜７０重量部含有するジエン系ゴム１００重量部に対して、窒素吸着比表面積が１００〜１６５ｍ2／ｇ、ＤＢＰ吸油量が９０〜１３０ｍｌ／１００ｇのカーボンブラック１５〜４０重量部とＢＥＴ比表面積が１５０〜２００ｍ2／ｇの沈降シリカ２０〜６０重量部を、その合計量で４０〜９０重量部であり、かつカーボンブラック／シリカの比が０．２５〜１．０となるように配合したゴム組成物が提案されている。しかしながら、当該ゴム組成物においても、依然として、転がり抵抗性の低減といった問題がある。 In the following Patent Document 1, as a rubber composition for a tire tread of a silica compound system having excellent wear resistance with excellent on-ice performance, 100 parts by weight of a diene rubber containing 40 to 70 parts by weight of NR. 15 to 40 parts by weight of carbon black having a nitrogen adsorption specific surface area of 100 to 165 m 2 / g, DBP oil absorption of 90 to 130 ml / 100 g, and 20 to 60 parts by weight of precipitated silica having a BET specific surface area of 150 to 200 m 2 / g. A rubber composition has been proposed in which the total amount is 40 to 90 parts by weight and the carbon black / silica ratio is 0.25 to 1.0. However, the rubber composition still has a problem of reduction in rolling resistance.
本発明では、顕著なシリカ分散性と転がり抵抗性を併せ有するシリカ配合系のタイヤトレッド用ゴム組成物を提供することを目的とする。 An object of the present invention is to provide a rubber composition for a tire tread of a silica compound system having both remarkable silica dispersibility and rolling resistance.
本発明によれば、ジエン系ゴム１００重量部に対して、ＢＥＴ比表面積１００〜３００ｍ2／ｇのシリカを１０重量部以上含む補強性充填剤３０〜１００重量部を配合してなるシリカ配合系タイヤトレッド用ゴム組成物において、不飽和脂肪酸のアルカリ金属塩を０．１〜５．０重量部とチウラム系加硫促進剤を０．０５〜２．００重量部配合したことを特徴とするタイヤトレッド用ゴム組成物が提供される。 According to the present invention, a silica compounding system comprising 100 to 100 parts by weight of a diene rubber and 30 to 100 parts by weight of a reinforcing filler containing 10 parts by weight or more of silica having a BET specific surface area of 100 to 300 m 2 / g. In a tire tread rubber composition, 0.1 to 5.0 parts by weight of an alkali metal salt of an unsaturated fatty acid and 0.05 to 2.00 parts by weight of a thiuram vulcanization accelerator are blended. A tread rubber composition is provided.
また、本発明によれば、前記チウラム系加硫促進剤をシリカの投入工程時に添加してなるタイヤトレッド用ゴム組成物が提供される。 Moreover, according to this invention, the rubber composition for tire treads which adds the said thiuram type vulcanization accelerator at the time of the injection | throwing-in process of a silica is provided.
本発明では、シリカ配合系のタイヤトレッド用ゴム組成物について、高シリカ配合時におけるシリカの分散性と、特に転がり抵抗性の点で改良することを目指して、鋭意好適な配合剤を探索していたところ、この度、かかる配合剤として、不飽和脂肪酸のアルカリ金属塩とチウラム系加硫促進剤を併用すること、特にこれら配合剤をシリカの配合時に添加することによって、これらの特性の点において顕著な効果が得られることを見出したものである。 In the present invention, a rubber compound for a tire tread of a silica compound system is eagerly searching for a suitable compounding agent with the aim of improving the dispersibility of silica at the time of compounding high silica and particularly in terms of rolling resistance. However, this time, as such a compounding agent, an alkali metal salt of an unsaturated fatty acid and a thiuram vulcanization accelerator are used in combination, and particularly by adding these compounding agents at the time of compounding silica, it is remarkable in terms of these characteristics. It has been found that various effects can be obtained.
本発明のタイヤトレッド用ゴム組成物に用いられるジエン系ゴムとしては、例えば、天然ゴム（ＮＲ）、各種ブタジエンゴム（ＢＲ）、各種スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、ポリイソプレンゴム（ＩＲ）、アクリロニトリル−ブタジエン共重合体ゴム（ＮＢＲ）、クロロプレンゴム、エチレン−プロピレン−ジエン共重合体ゴム、スチレン−イソプレン共重合体ゴム、スチレン−イソプレン−ブタジエン共重合体ゴム、イソプレン−ブタジエン共重合体ゴムなどが挙げられる。これらのジエン系ゴムは、単独又は二種以上のブレンドゴムとして使用されてよい。 Examples of the diene rubber used in the rubber composition for a tire tread of the present invention include natural rubber (NR), various butadiene rubbers (BR), various styrene-butadiene copolymer rubbers (SBR), and polyisoprene rubber (IR ), Acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer Examples include rubber. These diene rubbers may be used alone or as a blend rubber of two or more.
本発明のタイヤトレッド用ゴム組成物に配合使用される補強性充填剤としては、シリカが単独で、あるいはシリカとカーボンブラックが併用されて、総量で３０〜１００重量部の量で使用される。そして、本発明のタイヤトレッド用ゴム組成物に配合して用いられるシリカとしては、特に、ＢＥＴ比表面積が１００〜３００ｍ2／ｇ（ＩＳＯ５７９４に従って測定）である、微細なシリカが好適に使用される。また、当該シリカの配合量としては、当該ジエン系ゴム１００重量部に対して、前記補強性充填剤量の３０〜１００重量部のうち１０〜１００重量部、好ましくは２０〜１００重量部の量で配合される。かかるシリカの配合量が１０重量部未満であると、本発明における所期の効果が発揮されず、逆に１００重量部を超えると、混合加工性が劣り、本発明の所期の効果が低減されるので好ましくない。 As the reinforcing filler blended and used in the tire tread rubber composition of the present invention, silica is used alone, or silica and carbon black are used in combination, and the total amount is 30 to 100 parts by weight. And especially as a silica mix | blended and used for the rubber composition for tire treads of this invention, the fine silica whose BET specific surface area is 100-300 m < 2 > / g (measured according to ISO5794) is used suitably. . The amount of silica is 10 to 100 parts by weight, preferably 20 to 100 parts by weight, of 30 to 100 parts by weight of the reinforcing filler, based on 100 parts by weight of the diene rubber. It is blended with. If the amount of silica is less than 10 parts by weight, the desired effect in the present invention is not exhibited. Conversely, if it exceeds 100 parts by weight, the mixing processability is inferior, and the expected effect of the present invention is reduced. This is not preferable.
本発明のタイヤトレッド用ゴム組成物に配合使用される不飽和脂肪酸のアルカリ金属塩としては、例えば、アクリル酸、クロトン酸、イソクロトン酸、ウンデシレン酸、オレイン酸、エライジン酸、セトレイン酸、エルカ酸、ブラシジン酸、ソルビン酸、リノール酸、リノレイン酸、アラキドン酸などの不飽和脂肪酸のカリウム塩、ナトリウム塩などが挙げられる。当該不飽和脂肪酸のアルカリ金属塩の配合量としては、ジエン系ゴム１００重量部に対して、０．１〜５．０重量部、好ましくは２．０〜４．０重量部の量で配合される。この配合量が０．１重量部未満では、所期の効果が発揮されず、逆に５．０重量部を超えるとゴム組成物の破断強度が低下するので好ましくない。 Examples of the alkali metal salt of an unsaturated fatty acid used in the rubber composition for a tire tread of the present invention include acrylic acid, crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, cetreic acid, erucic acid, Examples include potassium salts and sodium salts of unsaturated fatty acids such as brassic acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid. The amount of the alkali metal salt of the unsaturated fatty acid is 0.1 to 5.0 parts by weight, preferably 2.0 to 4.0 parts by weight, based on 100 parts by weight of the diene rubber. The If the blending amount is less than 0.1 parts by weight, the desired effect is not exhibited. Conversely, if the blending amount exceeds 5.0 parts by weight, the breaking strength of the rubber composition decreases, which is not preferable.
また、本発明のタイヤトレッド用ゴム組成物に前記不飽和脂肪酸のアルカリ金属塩と併用配合されるチウラム系加硫促進剤としては、例えば、テトラメチルチウラムモノスルフィド（ＴＭＴＭ）、テトラメチルチウラムジスルフィド（ＴＭＴＤ）、テトラエチルチウラムジスルフィド（ＴＥＴＤ）、テトラブチルチウラムジスルフィド（ＴＢＴＤ）、ペンタメチレンチウラムテトラスルフィド（ＰＴＴ）、ジペンタメチレンチウラムモノスルフィド（ＤＰＴＭ）、ジペンタメチレンチウラムジスルフィド（ＤＰＴＤ）、ジペンタメチレンチウラムテトラスルフィド（ＤＰＴＴ）、ジペンタメチレンチウラムヘキサスルフィド（ＤＰＨＴ）などが挙げられる。当該チウラム系加硫促進剤の配合量としては、ジエン系ゴム１００重量部に対して、０．０５〜２．００重量部、好ましくは０．３〜０．６重量部の量で配合される。この配合量が０．０５重量部未満では、所期の効果が発揮されず、逆に２．００重量部を超えると焼けのコントロールが難しく、加工上問題となる。 Examples of the thiuram-based vulcanization accelerator that is used in combination with the alkali metal salt of the unsaturated fatty acid in the tire tread rubber composition of the present invention include, for example, tetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide ( TMTD), tetraethyl thiuram disulfide (TETD), tetrabutyl thiuram disulfide (TBTD), pentamethylene thiuram tetrasulfide (PTT), dipentamethylene thiuram monosulfide (DPTM), dipentamethylene thiuram disulfide (DPTD), dipentamethylene thiuram Examples thereof include tetrasulfide (DPTT) and dipentamethylene thiuram hexasulfide (DPHT). The amount of the thiuram vulcanization accelerator is 0.05 to 2.00 parts by weight, preferably 0.3 to 0.6 parts by weight, based on 100 parts by weight of the diene rubber. . If the blending amount is less than 0.05 parts by weight, the desired effect is not exhibited. Conversely, if the blending amount exceeds 2.00 parts by weight, it is difficult to control the burning, which causes a problem in processing.
本発明のタイヤトレッド用ゴム組成物では、前記したチウラム系加硫促進剤を他の加硫促進剤とは別にして、ゴム組成物の混合工程におけるマスターバッチの混合工程で、シリカ投入工程時にシリカと一緒に配合すると、格段の所期の効果が発揮されるので、かかる態様で得られるゴム組成物を使用することが一層望ましい。 In the tire tread rubber composition of the present invention, apart from the above-mentioned thiuram vulcanization accelerator, other than the vulcanization accelerator, in the master batch mixing step in the rubber composition mixing step, the silica charging step When blended together with silica, a remarkable effect is exhibited, so that it is more desirable to use a rubber composition obtained in such an embodiment.
本発明に係るタイヤトレッド用ゴム組成物には、更に、通常の加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、充填材、可塑剤、その他タイヤゴム用に配合されている各種配合剤を配合することができ、かかる配合剤は、一般的な方法で混練、加硫してゴム組成物とし、加硫または架橋することができる。これら配合剤の配合量も、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。 The rubber composition for tire treads according to the present invention is further blended for ordinary vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, anti-aging agents, fillers, plasticizers, and other tire rubbers. Various compounding agents can be blended, and these compounding agents can be kneaded and vulcanized by a general method to obtain a rubber composition, which can be vulcanized or crosslinked. The compounding amounts of these compounding agents can be set to conventional general compounding amounts as long as the object of the present invention is not violated.
以下、実施例及び比較例によって本発明を更に説明するが、本発明の技術的範囲をこれらの実施例に限定するものでないことは言うまでもない。 EXAMPLES Hereinafter, although this invention is further demonstrated by an Example and a comparative example, it cannot be overemphasized that the technical scope of this invention is not limited to these Examples.
サンプルの調製
表１に示す配合（重量部）に従って、１）の態様（実施例１及び２の態様）では、硫黄並びにチウラム系加硫促進剤、及び加硫促進剤１及び２を除くゴム、シリカなどの各配合成分を、また２）の態様（比較例４、実施例３及び４の態様）では、硫黄及び加硫促進剤１及び２を除くゴム、シリカなどの各配合成分を、それぞれ１.７Ｌの密閉式バンバリーミキサーに装填して５分間混合し、当該ゴムを混合機外に放出して室温まで冷却したマスターバッチを、再度同バンバリーミキサーに投入し、これに前記除外した１）又は２）の態様の硫黄と加硫促進剤を配合、混合してゴム組成物を得た。次いで、この未加硫ゴム組成物を所定の金型中で、１６０℃、２０分間プレス加硫して試験サンプル（ゴムシート）を作製し、以下の転がり抵抗性試験及びシリカ分散性試験に供した。
Sample Preparation According to the formulation (parts by weight) shown in Table 1, in 1) embodiment (embodiments of Examples 1 and 2), sulfur and thiuram vulcanization accelerator, and rubber excluding vulcanization accelerators 1 and 2, Each compounding component, such as silica, and each of the compounding components, such as rubber and silica, excluding sulfur and vulcanization accelerators 1 and 2, are added in the embodiment of 2) (embodiments of Comparative Example 4, Examples 3 and 4). A master batch which was loaded into a 1.7-liter closed Banbury mixer and mixed for 5 minutes, the rubber was discharged to the outside of the mixer and cooled to room temperature, was charged again into the Banbury mixer, and the above was excluded 1) Alternatively, the rubber composition was obtained by blending and mixing the sulfur of the aspect 2) and the vulcanization accelerator. Next, this unvulcanized rubber composition was press vulcanized in a predetermined mold at 160 ° C. for 20 minutes to prepare a test sample (rubber sheet), which was subjected to the following rolling resistance test and silica dispersibility test. did.
試験方法
１）転がり抵抗性： ＪＩＳ Ｋ６３９４に準拠して、（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、この値をもって転がり抵抗性を評価した。結果は、比較例１を１００として指数で示した。指数が大きい程、転がり抵抗性が良好であることを示す。
２）シリカ分散性： アルファーテクノロジー社製ＲＰＡ２０００を用いて、測定温度１１０℃（予熱１分）、周波数６ｃｐｍ、振幅０．２８〜１０％の条件で、貯蔵弾性率の歪依存性を測定し、歪量０．５６％時の貯蔵弾性率の値を求めた。比較例１を１００とした指数で表示した。数値が大きい程、分散不良塊が少なく、分散性が良好であることを示す。
Test Method 1) Rolling Resistance: In accordance with JIS K6394, using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho Co., Ltd. under conditions of initial strain = 10%, amplitude = ± 2%, frequency = 20 Hz. Tan δ (60 ° C.) was measured, and the rolling resistance was evaluated with this value. The results are shown as an index with Comparative Example 1 as 100. The larger the index, the better the rolling resistance.
2) Silica dispersibility: Using RPA2000 manufactured by Alpha Technology, the strain dependence of the storage modulus was measured under the conditions of a measurement temperature of 110 ° C. (preheating 1 minute), a frequency of 6 cpm, and an amplitude of 0.28 to 10%. The value of the storage elastic modulus when the strain amount was 0.56% was determined. The index was expressed as an index with Comparative Example 1 as 100. The larger the value, the smaller the number of defective dispersion and the better the dispersibility.
実施例１〜４及び比較例１〜４
結果を、以下の表１に示す。
The results are shown in Table 1 below.
表１の結果から、シリカ配合系ゴム組成物に所定配合量の不飽和脂肪酸のアルカリ金属塩とチウラム系加硫促進剤とを併用配合した実施例１〜４のゴム組成物では、転がり抵抗性及びシリカの分散性が極めて良好であることが分る。更に、当該チウラム系加硫促進剤をシリカの投入工程時に添加した実施例３及び４では、これらの特性がより向上していることが示されている。 From the results shown in Table 1, in the rubber compositions of Examples 1 to 4 in which a silica compounded rubber composition was used in combination with a predetermined compounding amount of an alkali metal salt of an unsaturated fatty acid and a thiuram vulcanization accelerator, rolling resistance was obtained. It can be seen that the dispersibility of the silica is very good. Furthermore, in Examples 3 and 4 in which the thiuram vulcanization accelerator was added during the silica charging step, it was shown that these characteristics were further improved.
よって、本発明のゴム組成物は、これをタイヤトレッド用ゴム組成物として利用すれば極めて有用である。 Therefore, the rubber composition of the present invention is extremely useful when used as a rubber composition for tire treads.
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| KR101351804B1 (en) * | 2012-05-15 | 2014-02-05 | 한국신발피혁연구원 | Rubber composition styrene-butadiene based for outsole having excellent hardness change property |
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| US10179479B2 (en) | 2015-05-19 | 2019-01-15 | Bridgestone Americas Tire Operations, Llc | Plant oil-containing rubber compositions, tread thereof and race tires containing the tread |
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| JP2002097304A (en) * | 2000-09-21 | 2002-04-02 | Ohtsu Tire & Rubber Co Ltd :The | Tire tread rubber composition |
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| JP2002097304A (en) * | 2000-09-21 | 2002-04-02 | Ohtsu Tire & Rubber Co Ltd :The | Tire tread rubber composition |
| JP2003107932A (en) * | 2001-07-18 | 2003-04-11 | Mitsuboshi Belting Ltd | Transfer belt and rubber composition for transfer belt |
| JP2004051754A (en) * | 2002-07-18 | 2004-02-19 | Yokohama Rubber Co Ltd:The | Tire tread rubber composition for iced or snowy road |
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