JP2006143818A - Rubber composition - Google Patents
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- JP2006143818A JP2006143818A JP2004333438A JP2004333438A JP2006143818A JP 2006143818 A JP2006143818 A JP 2006143818A JP 2004333438 A JP2004333438 A JP 2004333438A JP 2004333438 A JP2004333438 A JP 2004333438A JP 2006143818 A JP2006143818 A JP 2006143818A
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- rubber
- butadiene
- isoprene
- aromatic vinyl
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 52
- 239000005060 rubber Substances 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 26
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 239000007822 coupling agent Substances 0.000 claims abstract description 5
- -1 diene compound Chemical class 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 229920003244 diene elastomer Polymers 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 abstract description 5
- 230000000379 polymerizing effect Effects 0.000 abstract 3
- 239000011369 resultant mixture Substances 0.000 abstract 2
- 238000005299 abrasion Methods 0.000 abstract 1
- 230000002123 temporal effect Effects 0.000 abstract 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 11
- 239000002174 Styrene-butadiene Substances 0.000 description 9
- 239000005062 Polybutadiene Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method 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
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920006978 SSBR Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- GPNLWUFFWOYKLP-UHFFFAOYSA-N s-(1,3-benzothiazol-2-yl)thiohydroxylamine Chemical compound C1=CC=C2SC(SN)=NC2=C1 GPNLWUFFWOYKLP-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明はゴム組成物に関し、更に詳しくは湿潤面でのグリップ力に優れ、耐摩耗性及び転がり抵抗が改良され、かつ耐経時変化に優れたゴム組成物に関する。この組成物はタイヤ用、特にタイヤトレッド用として使用するのに適している。 The present invention relates to a rubber composition, and more particularly to a rubber composition having excellent gripping force on a wet surface, improved wear resistance and rolling resistance, and excellent change with time. This composition is suitable for use as a tire, particularly as a tire tread.
特許文献１には末端にＳｉ基を化学結合させたＳＢＲを用いてシリカとの反応性に優れ、空気入りタイヤとしても低燃費性とグリップ性に優れるゴム組成物が開示されているが、この提案にはポリマー自身が水分との反応性が高く、経時の安定性も良好でないという問題がある。また、グリーンタイヤとしてすでに認知され、ポリマーとして、ハイビニル含有スチレン−ブタジエン共重合体（ＳＳＢＲ）とポリブタジエンゴム（ＢＲ）とを組み合わせたものもあるが、これはグリップ性が十分でないという問題がある。更に特許文献２には特定のイソプレンを含有する共役ジエン系ゴムについて記載されているが、これにはシリカとの相互作用が低いという問題がある。 Patent Document 1 discloses a rubber composition that is excellent in reactivity with silica using SBR having a Si group chemically bonded to the terminal, and excellent in fuel efficiency and grip as a pneumatic tire. The proposal has a problem that the polymer itself is highly reactive with moisture and is not stable over time. Further, there is a combination of high vinyl-containing styrene-butadiene copolymer (SSBR) and polybutadiene rubber (BR) as a polymer already recognized as a green tire, but this has a problem that grip properties are not sufficient. Furthermore, Patent Document 2 describes a conjugated diene rubber containing a specific isoprene, but this has a problem of low interaction with silica.
従って、本発明は、例えばタイヤ用として用いた場合に、ウェットグリップ、耐摩耗性及び転がり抵抗に優れ、しかも経時安定性に優れたゴム組成物を提供することを目的とする。 Accordingly, an object of the present invention is to provide a rubber composition which is excellent in wet grip, wear resistance and rolling resistance when used for tires, for example, and excellent in stability with time.
本発明に従えば、（Ａ）１，３−ブタジエン単位３０〜９９．９重量％、イソプレン単位０．１〜１０重量％及び芳香族ビニル単量体単位０〜６０重量％からなる共役ジエン系ゴム並びに（Ｂ）シス含量が５〜９５重量％で重量平均分子量が６，０００〜６０，０００のジエン化合物の重合体を含む、シス含量が８０〜９９重量％で重量平均分子量が５００，０００〜１，０００，０００のジエン系ゴム含有ゴム組成物であって、前記共役ジエン系ゴム（Ａ）が、重合に使用する単量体のうち、１，３−ブタジエンの８０重量％以上、イソプレンの８０重量％以下及び芳香族ビニル単量体の８０重量％以上からなる単量体混合物を先ず重合し、次にこれに残りのイソプレンを添加して重合し、更に残りの１，３−ブタジエン及び芳香族ビニル単量体を添加して重合し、そして得られたポリマーにカップリング剤を反応させて得られるゴム組成物が提供される。 According to the present invention, (A) a conjugated diene system comprising 30 to 99.9% by weight of 1,3-butadiene units, 0.1 to 10% by weight of isoprene units and 0 to 60% by weight of aromatic vinyl monomer units. Rubber and (B) a polymer of a diene compound having a cis content of 5 to 95% by weight and a weight average molecular weight of 6,000 to 60,000, and having a cis content of 80 to 99% by weight and a weight average molecular weight of 500,000 -1,000,000 diene rubber-containing rubber composition, wherein the conjugated diene rubber (A) is 80% by weight or more of 1,3-butadiene among monomers used for polymerization, isoprene A monomer mixture comprising 80% by weight or less of the above and 80% by weight or more of the aromatic vinyl monomer is polymerized first, and then the remaining isoprene is added thereto to polymerize, followed by the remaining 1,3-butadiene. And aromatic vinyl Polymerization with the addition of dimers, and the resulting rubber composition obtained by reacting a coupling agent polymer.
表Ｉの結果からも明らかなように、本発明に従えば、湿潤面でのグリップ力の増加、耐摩耗性の向上及び転がり抵抗の低減を図ることができる。 As is apparent from the results in Table I, according to the present invention, it is possible to increase the grip force on the wet surface, improve the wear resistance, and reduce the rolling resistance.
本発明に係るゴム組成物は、前述の如く、特定量の１，３−ブタジエン単位、イソプレン単位及び芳香族ビニル単量体単位からなる共役ジエン系ゴム（Ａ）に、低分子量のジエン成分を含むジエン系ゴム（Ｂ）を配合してなるゴム組成物である。 As described above, the rubber composition according to the present invention has a low molecular weight diene component added to the conjugated diene rubber (A) comprising a specific amount of 1,3-butadiene unit, isoprene unit and aromatic vinyl monomer unit. It is a rubber composition formed by blending the diene rubber (B) containing.
本発明のゴム組成物に配合される共役ジエン系ゴム（Ａ）は１，３−ブタジエン単位３０〜９９．９重量％、好ましくは６０〜８５重量％、イソプレン単位０．１〜１０重量％、好ましくは０．２〜５重量％、及び芳香族ビニル単量体単位０〜６０重量％、好ましくは０〜４０重量％からなり、これは、１，３−ブタジエンの８０重量％以上、イソプレン８０重量％以下及び芳香族ビニル単量体（例えばスチレン）８０重量％以上からなる単量体混合物を先ず重合した後、これに残りのイソプレンを添加して重合し、更に残りの１，３−ブタジエン及び芳香族ビニル単量体を添加して重合し、そして得られたポリマーの活性末端とカップリング剤とを反応させて得られる重合体である。 Conjugated diene rubber (A) blended in the rubber composition of the present invention is 30 to 99.9% by weight of 1,3-butadiene units, preferably 60 to 85% by weight, 0.1 to 10% by weight of isoprene units, Preferably 0.2 to 5% by weight and 0 to 60% by weight, preferably 0 to 40% by weight of aromatic vinyl monomer units, which is 80% by weight or more of 1,3-butadiene, isoprene 80 First, a monomer mixture composed of 80% by weight or less of an aromatic vinyl monomer (for example, styrene) is polymerized, and then the remaining isoprene is added thereto for polymerization, and the remaining 1,3-butadiene is further polymerized. And an aromatic vinyl monomer and polymerized, and a polymer obtained by reacting the active terminal of the obtained polymer with a coupling agent.
本発明のゴム組成物に配合されるジエン系ゴム（Ｂ）は、シス含量が５〜９５重量％、好ましくは６０〜９０重量％で、重量平均分子量が６，０００〜６０，０００、好ましくは７，０００〜３０，０００のジエン化合物の重合体を含有する、シス含量が８０〜９９重量％、好ましくは９５〜９９重量％で重量平均分子量が５００，０００〜１，０００，０００、好ましくは６００，０００〜９００，０００のジエン化合物の重合体で、本発明のゴム組成物は少なくともかかるゴム成分（Ａ）及び（Ｂ）から構成される。ゴム成分（Ａ）はシリカとの相互作用がすぐれ、シリカの分散が向上し、湿潤面でのグリップや、転がり抵抗、耐摩耗性を改良する作用をする。一方ゴム成分（Ｂ）は低分子成分が可塑剤と同様に作用し、しかも、経時での変化が少なく、安定した性能を維持でき、特に耐摩耗性を改良する作用を有する本発明のゴム組成物は、好ましくはゴム成分（Ａ）６０〜９５重量部、更に好ましくは７０〜９０重量部及びゴム成分（Ｂ）５〜４０重量部、更に好ましくは１０〜３０重量部を配合する。この範囲を外れると、耐摩耗性や経時変化性に劣るおそれがある。 The diene rubber (B) blended in the rubber composition of the present invention has a cis content of 5 to 95% by weight, preferably 60 to 90% by weight, and a weight average molecular weight of 6,000 to 60,000, preferably Containing a polymer of diene compounds of 7,000 to 30,000, cis content of 80 to 99% by weight, preferably 95 to 99% by weight and weight average molecular weight of 500,000 to 1,000,000, preferably The rubber composition of the present invention is a polymer of diene compounds of 600,000 to 900,000 and is composed of at least such rubber components (A) and (B). The rubber component (A) has an excellent interaction with the silica, improves the dispersion of the silica, and acts to improve grip on the wet surface, rolling resistance, and wear resistance. On the other hand, the rubber component (B) has a low molecular component that acts in the same manner as a plasticizer, and has little change over time, can maintain stable performance, and particularly has a function of improving wear resistance. The product preferably contains 60 to 95 parts by weight of the rubber component (A), more preferably 70 to 90 parts by weight, and 5 to 40 parts by weight of the rubber component (B), more preferably 10 to 30 parts by weight. If it is out of this range, there is a possibility that the wear resistance and the change with time are inferior.
本発明のゴム組成物は、前記共役ジエン系ゴム（Ａ）及び（Ｂ）以外のその他のゴムを含んでいてもよい。そのようなゴムとしては、例えば、天然ゴム（ＮＲ）、ポリイソプレンゴム（ＩＲ）、乳化重合ＳＢＲ（スチレン−ブタジエン共重合ゴム）、溶液重合ランダムＳＢＲ（結合スチレン５〜５０重量％、ブタジエン部分の１，２−結合含有量１０〜８０％）、高トランスＳＢＲ（ブタジエン部のトランス結合含有量７０〜９５％）、低シスＢＲ（ポリブタジエンゴム）、高シスＢＲ、高トランスＢＲ（ブタジエン部のトランス結合含有量７０〜９５％）、スチレン−イソプレン共重合体ゴム、ブタジエン−イソプレン共重合体ゴム、乳化重合スチレン−アクリロニトリル−ブタジエン共重合体ゴム、アクリロニトリル−ブタジエン共重合体ゴム、高ビニルＳＢＲ−低ビニルＳＢＲブロック共重合体ゴム、ポリイソプレン−ＳＢＲブロック共重合体ゴム、ポリスチレン−ポリブタジエン−ポリスチレンブロック共重合体ゴム、アクリルゴム、エピクロロヒドリンゴム、フッ素ゴム、シリコンゴム、エチレン−プロピレン共重合体ゴム、ウレタンゴムなどが挙げられる。なかでも、ＮＲ，ＢＲ，ＩＲ，ＳＢＲが好ましく用いられる。これらのゴムは、それぞれ、単独又は任意の２種以上を組合せて使用することができる。 The rubber composition of the present invention may contain other rubbers other than the conjugated diene rubbers (A) and (B). Examples of such rubber include natural rubber (NR), polyisoprene rubber (IR), emulsion polymerization SBR (styrene-butadiene copolymer rubber), solution polymerization random SBR (bonded styrene 5 to 50% by weight, butadiene portion). 1,2-bond content 10-80%), high trans SBR (trans bond content of butadiene part 70-95%), low cis BR (polybutadiene rubber), high cis BR, high trans BR (trans of butadiene part) Bond content 70-95%), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, emulsion polymerized styrene-acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, high vinyl SBR-low Vinyl SBR block copolymer rubber, polyisoprene-SBR block copolymer Rubber, polystyrene - polybutadiene - polystyrene block copolymer rubber, acrylic rubber, epichlorohydrin rubber, fluorine rubber, silicone rubber, ethylene - propylene copolymer rubber, and urethane rubber. Of these, NR, BR, IR, and SBR are preferably used. Each of these rubbers can be used alone or in combination of two or more.
本発明のゴム組成物が、前記共役ジエン系ゴム（Ａ）及び（Ｂ）以外のその他のゴムを含む場合には、前記の共役ジエン系ゴムの割合を、ゴム成分の全量に対して、１０重量％以上とすることが好ましく、２０〜９０重量％の範囲とすることがより好ましく、３０〜８０重量％の範囲とすることが特に好ましい。この割合が低すぎると、十分な改善効果を得ることができなくなる。 When the rubber composition of the present invention contains other rubbers other than the conjugated diene rubbers (A) and (B), the ratio of the conjugated diene rubber is 10 to the total amount of the rubber component. It is preferable to set it as weight% or more, It is more preferable to set it as the range of 20 to 90 weight%, It is especially preferable to set it as the range of 30 to 80 weight%. If this ratio is too low, a sufficient improvement effect cannot be obtained.
本発明に従えば、前記ゴム成分１００重量部に対し、カーボンブラック及び／又はシリカ３０〜１２０重量部、更に好ましくは５０〜９５重量部を配合する。カーボンブラックの配合量は、好ましくは１〜１１０重量部、更に好ましくは５〜５０重量部であり、シリカの配合量は、好ましくは１０〜１１０重量部、更に好ましくは３０〜９５重量部である。カーボンブラック及び／又はシリカを３０〜１２０重量部配合することにより、本発明の目的を好ましく達成することができる。 According to the present invention, 30 to 120 parts by weight, more preferably 50 to 95 parts by weight of carbon black and / or silica are added to 100 parts by weight of the rubber component. The compounding amount of carbon black is preferably 1-110 parts by weight, more preferably 5-50 parts by weight, and the compounding amount of silica is preferably 10-110 parts by weight, more preferably 30-95 parts by weight. . By blending 30 to 120 parts by weight of carbon black and / or silica, the object of the present invention can be preferably achieved.
本発明において配合するカーボンブラック及びシリカは従来からタイヤ用などのゴム組成物に配合されている従来のカーボンブラックやシリカを配合することができるが、本発明で使用するのに好ましいカーボンブラックとしては、窒素吸着比表面積（Ｎ2ＳＡ）が５０〜２００ｍ2／ｇ、更に好ましくは８０〜１８０ｍ2／ｇであり、シリカとしては、窒素吸着比表面積（Ｎ2ＳＡ）が１００〜３００ｍ2／ｇ、更に好ましくは１３０〜２５０ｍ2／ｇである。なお、ここで窒素吸着比表面積（Ｎ2ＳＡ）はＪＩＳ Ｋ６２２１に準拠して測定したものである。 Carbon black and silica to be blended in the present invention can be blended with conventional carbon black and silica that have been blended in rubber compositions for tires and the like, but as carbon black preferred for use in the present invention, The nitrogen adsorption specific surface area (N 2 SA) is 50 to 200 m 2 / g, more preferably 80 to 180 m 2 / g, and the silica has a nitrogen adsorption specific surface area (N 2 SA) of 100 to 300 m 2 / g. More preferably, it is 130-250 m < 2 > / g. Here, the nitrogen adsorption specific surface area (N 2 SA) is measured in accordance with JIS K6221.
本発明に係るゴム組成物には、前記した必須成分に加えて、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、可塑性剤などのタイヤ用、その他一般ゴム用に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量は本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 In addition to the above-mentioned essential components, the rubber composition according to the present invention is used for tires such as vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, anti-aging agents, plasticizers, and other general rubbers. Various additives that are generally blended can be blended, and such additives can be kneaded by a general method to form a composition, which can be used for vulcanization or crosslinking. The blending amounts of these additives may be conventional conventional blending amounts as long as the object of the present invention is not adversely affected.
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
実施例１〜４及び比較例１〜３
共役ジエン系ゴム（Ａ）の調製
特願２００２−３３８７４１号公報の段落［００１９］〜［００４６］に記載の方法、特に実施例１に従って製造した。
Examples 1-4 and Comparative Examples 1-3
Preparation of Conjugated Diene Rubber (A) The conjugated diene rubber (A) was prepared according to the method described in paragraphs [0019] to [0046] of Japanese Patent Application No. 2002-338741, particularly according to Example 1.
サンプルの調製
表Ｉに示す配合において、加硫促進剤と硫黄を除く成分を３リットルの密閉型ミキサーで５分間混練し、１５０℃に達したときに放出してマスターバッチを得た。このマスターバッチに加硫促進剤と硫黄をオープンロールで混練し、ゴム組成物を得た。
Sample preparation In the formulation shown in Table I, components other than the vulcanization accelerator and sulfur were kneaded in a 3 liter closed mixer for 5 minutes and released when the temperature reached 150 ° C to obtain a master batch. A vulcanization accelerator and sulfur were kneaded with this master batch with an open roll to obtain a rubber composition.
次に得られたゴム組成物を１５×１５×０．２cmの金型中で１６０℃で２０分間加硫して加硫ゴムシートを調製し、以下に示す試験法でゴム物性測定した。結果は表Ｉに示す。 Next, the obtained rubber composition was vulcanized in a 15 × 15 × 0.2 cm mold at 160 ° C. for 20 minutes to prepare a vulcanized rubber sheet, and the physical properties of the rubber were measured by the following test methods. The results are shown in Table I.
表Ｉ脚注
＊１：日本ゼオン（株）製ＳＢＲ（Ｎｉｐｏｌ ＳＢＲ１７２１）
＊２：ＳＢＲ（Ｓｔ ２０／Ｖｎ ６０、イソプレン０．９重量％ 分子量４９万 ＭＬ1+4 ５５）
＊３：日本ゼオン（株）製ＢＲ（Ｎｉｐｏｌ ＢＲ１２２０）
＊４：天然ゴム（ＴＳＲ２０）
＊５：日本ゼオン（株）製ＢＲ（ＢＲＸ５０００、低分子量分４０phr （シス８８重量％、分子量２５，０００）を含むポリブタジエンゴム、分子量６２万、シス９６重量％）
＊６：Ｒｈｏｄｉａ（株）製シリカ（Ｎ2ＳＡ：１６５ｍ2／ｇ）
＊７：デグッサ社製シランカップリング剤
＊８：正同化学工業（株）製酸化亜鉛３種
＊９：昭和キャボット（株）製Ｎ２３４（Ｎ2ＳＡ：１１９ｍ2／ｇ）
＊１０：昭和キャボット（株）製Ｎ３３９（Ｎ2ＳＡ：７２ｍ2／ｇ）
＊１１：日本油脂（株）製工業用ステアリン酸
＊１２：フレキシス社製ＳＡＮＴＯＦＬＥＸ ６ＰＰＤ
＊１３：フレキシス社製ＦＬＥＣＴＯＬ ＴＭＱ
＊１４：日本精蝋（株）製パラフィンワックス
＊１５：昭和シェル石油（株）製アロマオイル
＊１６：鶴見化学工業（株）製５％油入微粉硫黄
＊１７：フレキシス社製Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド
＊１８：フレキシス社製ジフェニルグアニジン
Table I Footnote * 1: SBR manufactured by Nippon Zeon Co., Ltd. (Nipol SBR1721)
* 2: SBR (St 20 / Vn 60, 0.9% by weight of isoprene, molecular weight 490,000 ML 1 + 4 55)
* 3: BR made by Nippon Zeon Co., Ltd. (Nipol BR1220)
* 4: Natural rubber (TSR20)
* 5: BR made by Nippon Zeon Co., Ltd. (BRX5000, polybutadiene rubber containing 40 phr low molecular weight (cis 88% by weight, molecular weight 25,000), molecular weight 620,000, cis 96% by weight)
* 6: Silica manufactured silica (N 2 SA: 165 m 2 / g)
* 7: Sinus coupling agent manufactured by Degussa * 8: Zinc oxide 3 types manufactured by Shodo Chemical Co., Ltd. * 9: N234 manufactured by Showa Cabot Corporation (N 2 SA: 119 m 2 / g)
* 10: N339 manufactured by Showa Cabot Co., Ltd. (N 2 SA: 72 m 2 / g)
* 11: Industrial stearic acid manufactured by NOF Corporation * 12: SANTOFLEX 6PPD manufactured by Flexis
* 13: FLECTOL TMQ manufactured by Flexis
* 14: Paraffin wax manufactured by Nippon Seiwa Co., Ltd. * 15: Aroma oil manufactured by Showa Shell Sekiyu K.K. * 16: Fine powdered sulfur containing 5% oil manufactured by Tsurumi Chemical Co., Ltd. * 17: N-cyclohexyl manufactured by Flexis Corporation 2-Benzothiazolylsulfenamide * 18: Diphenylguanidine manufactured by Flexis
物性評価試験法
硬度：７０℃×１６８時間の老化試験前後の試験片の硬度をＪＩＳ ６２５３に準拠して測定した。
３００％モジュラス：ＪＩＳ ６２５１に準拠して測定した。
ｔａｎδ（０℃及び６０℃）：粘弾性スペクトロメータ（東洋精機製作所）を用い、０℃及び６０℃でそれぞれ初期歪１０％、動的歪：±２％、周波数２０Ｈｚの条件下で測定した。
ランボーン摩耗：ランボーン試験機（岩本製作所）を用いて、温度２０℃、スリップ率５０％条件下で摩耗減量を測定し、比較例１の値を１００として指数表示した。この数字が大きい程、耐摩耗性が良好であることを示す。
Physical property evaluation test method Hardness: The hardness of a test piece before and after an aging test at 70 ° C. × 168 hours was measured according to JIS 6253.
300% modulus: measured in accordance with JIS 6251.
tan δ (0 ° C. and 60 ° C.): Measured using a viscoelastic spectrometer (Toyo Seiki Seisakusho) at 0 ° C. and 60 ° C. under the conditions of initial strain 10%, dynamic strain: ± 2%, and frequency 20 Hz.
Lambourne wear: wear loss was measured using a Lambourne tester (Iwamoto Seisakusho) under the conditions of a temperature of 20 ° C. and a slip rate of 50%. Larger numbers indicate better wear resistance.
Claims (2)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006143811A (en) * | 2004-11-17 | 2006-06-08 | Yokohama Rubber Co Ltd:The | Rubber composition |
| JP2006152200A (en) * | 2004-12-01 | 2006-06-15 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP2010270207A (en) * | 2009-05-20 | 2010-12-02 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread and pneumatic tire |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002338741A (en) * | 2001-03-16 | 2002-11-27 | Nippon Zeon Co Ltd | Rubber composition |
| JP2002338744A (en) * | 2001-03-16 | 2002-11-27 | Nippon Zeon Co Ltd | Oil-extended rubber and rubber composition |
| JP2004043735A (en) * | 2002-07-15 | 2004-02-12 | Yokohama Rubber Co Ltd:The | Rubber composition for radial tire |
| JP2006143811A (en) * | 2004-11-17 | 2006-06-08 | Yokohama Rubber Co Ltd:The | Rubber composition |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002338741A (en) * | 2001-03-16 | 2002-11-27 | Nippon Zeon Co Ltd | Rubber composition |
| JP2002338744A (en) * | 2001-03-16 | 2002-11-27 | Nippon Zeon Co Ltd | Oil-extended rubber and rubber composition |
| JP2004043735A (en) * | 2002-07-15 | 2004-02-12 | Yokohama Rubber Co Ltd:The | Rubber composition for radial tire |
| JP2006143811A (en) * | 2004-11-17 | 2006-06-08 | Yokohama Rubber Co Ltd:The | Rubber composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006143811A (en) * | 2004-11-17 | 2006-06-08 | Yokohama Rubber Co Ltd:The | Rubber composition |
| JP2006152200A (en) * | 2004-12-01 | 2006-06-15 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP2010270207A (en) * | 2009-05-20 | 2010-12-02 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread and pneumatic tire |
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