JP5167512B2 - Tread rubber composition and pneumatic tire using the same - Google Patents
Tread rubber composition and pneumatic tire using the same Download PDFInfo
- Publication number
- JP5167512B2 JP5167512B2 JP2007169066A JP2007169066A JP5167512B2 JP 5167512 B2 JP5167512 B2 JP 5167512B2 JP 2007169066 A JP2007169066 A JP 2007169066A JP 2007169066 A JP2007169066 A JP 2007169066A JP 5167512 B2 JP5167512 B2 JP 5167512B2
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- rubber
- resin
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- 229920001971 elastomer Polymers 0.000 title claims description 52
- 239000005060 rubber Substances 0.000 title claims description 52
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- 229920003052 natural elastomer Polymers 0.000 claims description 36
- 229920001194 natural rubber Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 35
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- 238000009826 distribution Methods 0.000 claims description 19
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- 238000000034 method Methods 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
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- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 4
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 4
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- 239000011787 zinc oxide Substances 0.000 description 3
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 2
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
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- 241000254043 Melolonthinae Species 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
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- ZDWGXBPVPXVXMQ-UHFFFAOYSA-N bis(2-ethylhexyl) nonanedioate Chemical compound CCCCC(CC)COC(=O)CCCCCCCC(=O)OCC(CC)CCCC ZDWGXBPVPXVXMQ-UHFFFAOYSA-N 0.000 description 2
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- PUFGCEQWYLJYNJ-UHFFFAOYSA-N didodecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCC PUFGCEQWYLJYNJ-UHFFFAOYSA-N 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
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Images
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)
Description
本発明はトレッドゴム組成物及びそれをトレッド部に用いた空気入りタイヤ、特に、天然資源を材料に用いたゴム組成物をトレッド部に採用して制動性を改善し、かつ転がり抵抗を低減した空気入りタイヤに関する。 The present invention employs a tread rubber composition and a pneumatic tire using the same in the tread portion, particularly a rubber composition using natural resources as a tread portion to improve braking performance and reduce rolling resistance. Related to pneumatic tires.
近年、石油資源の枯渇が問題とされている。石油原料の供給量が年々減少しているこのことから、将来的に石油価格の高騰が予測され、スチレンーブタジエンゴム等の合成ゴムやカーボンブラックなどの石油資源からなる原材料の供給は将来、不足することが予測される。将来、石油資源の供給不足を想定すると、天然ゴムやシリカ、炭酸カルシウム等の白色充填剤のような天然資源の原材料を使用していくことが必要となる。 In recent years, exhaustion of petroleum resources has been a problem. As the supply of petroleum raw materials has been decreasing year by year, oil prices are expected to rise in the future, and supply of raw materials consisting of petroleum resources such as synthetic rubber such as styrene-butadiene rubber and carbon black will be insufficient in the future. Is expected to. In the future, assuming short supply of petroleum resources, it will be necessary to use raw materials of natural resources such as natural rubber, white fillers such as silica and calcium carbonate.
従来、天然ゴムを主体としたトレッドゴム配合では、ウェット路面およびドライ路面における走行性能は、通常使用されるスチレンーブタジエンゴムに対して劣る。そこで、充填剤としてシリカ、炭酸カルシウム、水酸化アルミニウムなどの白色充填剤を使用することでウェット路面における走行性能を改善する方法があるが、その場合、ドライ路面における走行性能が不充分となる。 Conventionally, with a tread rubber compound mainly composed of natural rubber, the running performance on wet road surfaces and dry road surfaces is inferior to that of the commonly used styrene-butadiene rubber. Therefore, there is a method of improving the running performance on the wet road surface by using a white filler such as silica, calcium carbonate, aluminum hydroxide as the filler, but in that case, the running performance on the dry road surface becomes insufficient.
特許文献1には、石油が枯渇したときを想定したタイヤ用原材料を示す技術が開示されているが、ウェット路面およびドライ路面において充分な走行性能を示すトレッド用ゴム組成物については開示されていない。 Patent Document 1 discloses a technique that shows a tire raw material that assumes when oil is depleted, but does not disclose a tread rubber composition that exhibits sufficient running performance on wet and dry road surfaces. .
また特許文献2には、石油外資源の含有比率を高めることで、地球に優しく、将来の石油の供給量の減少に備え、ウェット路面およびドライ路面において充分な走行性能を示すタイヤのトレッド用ゴム組成物が開示されている。
本発明は石油資源の原材料に代えて天然資源の原材料を用いるものであり、特に天然ゴム及び/または改質天然ゴムを用い、さらにレジンを所定量配合し、その分子量分布を調整することで、制動性を改善し転がり抵抗を低減したトレッドゴム組成物及びそれを用いた空気入りタイヤを提案する。 The present invention uses natural resource raw materials instead of petroleum resource raw materials, in particular, using natural rubber and / or modified natural rubber, further blending a predetermined amount of resin, and adjusting its molecular weight distribution, A tread rubber composition having improved braking performance and reduced rolling resistance and a pneumatic tire using the tread rubber composition are proposed.
本発明は、天然ゴムおよび/または改質天然ゴムを50質量%以上含むゴム成分100質量部に対して、分子量分布のピークを少なくとも2つ含むレジンであって、前記ピークのうち低分子量側の最大ピーク(P1)のピーク高さ(H1)と高分子側の最大ピーク(
P2)のピーク高さ(H2)の比が以下の関係にある前記レジンを5質量部以上、および
0.5≦(H2/H1)≦2.0
白色充填剤を80質量%以上を含む充填剤を30〜150質量部含有するトレッドゴム組成物である。前記レジンがテルペン系重合体またはテルペン系共重合体であることが望ましい。
The present invention relates to a resin containing at least two peaks of molecular weight distribution with respect to 100 parts by mass of a rubber component containing 50% by mass or more of natural rubber and / or modified natural rubber, which is on the low molecular weight side of the peak. Peak height (H1) of the maximum peak (P1) and maximum peak on the polymer side (
5 parts by mass or more of the resin having a peak height (H2) ratio of P2) in the following relationship, and 0.5 ≦ (H2 / H1) ≦ 2.0
It is a tread rubber composition containing 30 to 150 parts by mass of a filler containing 80% by mass or more of a white filler. The resin is preferably a terpene polymer or a terpene copolymer.
前記レジンの分子量分布のピークは、いずれも3000以下であり、少なくとも1つの分子量分布のピークは1000以上であり、少なくとも1つの分子量分布は1000未満であることが望ましい。また改質天然ゴムは、エポキシ化天然ゴムであり、そのエポキシ化率が12モル%以上であることが望ましい。 The molecular weight distribution peak of the resin is preferably 3000 or less, at least one molecular weight distribution peak is 1000 or more, and at least one molecular weight distribution is preferably less than 1000. The modified natural rubber is an epoxidized natural rubber, and the epoxidation rate is desirably 12 mol% or more.
さらに本発明は、前記トレッドゴム組成物を用いた空気入りタイヤである。 Furthermore, the present invention is a pneumatic tire using the tread rubber composition.
本発明によれば、天然資源の原材料を用いることで地球に優しく、将来の石油の供給量の減少に備えたタイヤに用いるトレッドゴム組成物を提供することができ、さらに本発明のトレッドゴム組成物から得られる空気入りタイヤは、ウェット路面およびドライ路面において優れた制動性能を有し、転がり抵抗も低減される。 According to the present invention, it is possible to provide a tread rubber composition used for a tire that is gentle to the earth by using raw materials of natural resources and is prepared for a future reduction in the supply of petroleum, and further, the tread rubber composition of the present invention. A pneumatic tire obtained from an object has excellent braking performance on wet and dry road surfaces, and rolling resistance is also reduced.
本発明は、天然ゴムおよび/または改質天然ゴムを50質量%以上含むゴム成分100質量部に対して、分子量分布のピークを少なくとも2つ含んでいるレジンを5質量部以上、および白色充填剤を80質量%以上を含む充填剤を30〜150質量部含有するトレッドゴム組成物である。 The present invention relates to 100 parts by mass of a rubber component containing 50% by mass or more of natural rubber and / or modified natural rubber, 5 parts by mass or more of a resin containing at least two peaks of molecular weight distribution, and a white filler Is a tread rubber composition containing 30 to 150 parts by mass of a filler containing 80% by mass or more.
<ゴム成分>
本発明のトレッド用ゴム組成物におけるゴム成分は、天然ゴム(NR)および/または改質天然ゴムが用いられる。
<Rubber component>
As the rubber component in the rubber composition for a tread of the present invention, natural rubber (NR) and / or modified natural rubber is used.
天然ゴムは、シス1、4ポリイソプレンが使用されるが、トランス1、4ポリイソプレンを適宜混合することもできる。 As the natural rubber, cis 1,4 polyisoprene is used, but trans 1,4 polyisoprene can be appropriately mixed.
改質天然ゴムは、エポキシ化天然ゴム(ENR)または脱蛋白天然ゴムが使用される。エポキシ化天然ゴムは、天然ゴムの二重結合をエポキシ化したものをいう。エポキシ化天然ゴムは市販品としても入手できる。天然ゴムをエポキシ化する方法としては、クロルヒドリン法、直接酸化法、過酸化水素法、アルキルヒドロペルオキシド法、過酸法などの方法を用いて行なうことができる。たとえば、天然ゴムに過酢酸や過ギ酸などの有機過酸を反応させる方法などがあげられる。 As the modified natural rubber, epoxidized natural rubber (ENR) or deproteinized natural rubber is used. Epoxidized natural rubber refers to an epoxidized natural rubber double bond. Epoxidized natural rubber is also available as a commercial product. As a method for epoxidizing natural rubber, a chlorohydrin method, a direct oxidation method, a hydrogen peroxide method, an alkyl hydroperoxide method, a peracid method, or the like can be used. Examples thereof include a method of reacting natural rubber with an organic peracid such as peracetic acid or performic acid.
エポキシ化天然ゴムのエポキシ化率の平均は12モル%以上であることが好ましく、15モル%以上であることがより好ましい。エポキシ化率の平均が12モル%未満では、トレッドゴム組成物のウェットおよびドライ路面における摩擦係数が低くなり制動性能が改善できない。また、エポキシ化率の平均は80モル%以下であることが好ましく、60モル%以下であることがより好ましい。エポキシ化率の平均が80モル%を超えるとゴム成分のゲル化が生じる。 The average epoxidation rate of the epoxidized natural rubber is preferably 12 mol% or more, more preferably 15 mol% or more. If the average of the epoxidation rate is less than 12 mol%, the coefficient of friction on the wet and dry road surfaces of the tread rubber composition becomes low and the braking performance cannot be improved. The average epoxidation rate is preferably 80 mol% or less, and more preferably 60 mol% or less. When the average of the epoxidation rate exceeds 80 mol%, gelation of the rubber component occurs.
ゴム成分中における天然ゴムおよび/または改質天然ゴムの含有率は50質量%以上、好ましくは80質量%以上である。含有率が50質量%未満では、石油外資源の比率が小さくなる。ゴム成分中における天然ゴムおよび/または改質天然ゴムの含有率は、特に100質量%にすることで、制動特性の改善と転がり抵抗の低減の両立を図ることができる。 The content of natural rubber and / or modified natural rubber in the rubber component is 50% by mass or more, preferably 80% by mass or more. When the content is less than 50% by mass, the ratio of non-petroleum resources becomes small. By setting the content of the natural rubber and / or modified natural rubber in the rubber component to 100% by mass in particular, it is possible to achieve both improvement in braking characteristics and reduction in rolling resistance.
<その他のゴム成分>
本発明ではゴム成分として、天然ゴム、エポキシ化天然ゴムまたは脱蛋白天然ゴム以外に使用されるゴム成分として次のものがある。例えば、スチレン−ブタジエンゴム(SBR)、ポリブタジエンゴム(BR)、ポリイソプレンゴム(IR)、エチレン−プロピレン−ジエンゴム(EPDM)、クロロプレンゴム(CR)、イソブチレンとp−メチルスチレンとの共重合体のハロゲン化物、アクリロニトリル−ブタジエンゴム(NBR)、ブチルゴム(IIR)等が挙げられる。なお、エチレン−プロピレン−ジエンゴム(EPDM)とは、エチレン−プロピレンゴム(EPM)に第三ジエン成分を含むものである。ここで第三ジエン成分としては、たとえば炭素数5〜20の非共役ジエンが挙げられ、1,4−ペンタジエン、1,4−ヘキサジエン、1,5−ヘキサジエン、2,5−ジメチル−1,5−ヘキサジエンおよび1,4−オクタジエン、または1,4−シクロヘキサジエン、シクロオクタジエン、ジシクロペンタジエンなどの環状ジエン、5−エチリデン−2−ノルボルネン、5−ブチリデン−2−ノルボルネン、2−メタリル−5−ノルボルネンおよび2−イソプロペニル−5−ノルボルネンなどのアルケニルノルボルネン等が例示できる。特に、ジシクロペンタジエン、5−エチリデン−2−ノルボルネン等が使用できる。
<Other rubber components>
In the present invention, as rubber components, there are the following rubber components used in addition to natural rubber, epoxidized natural rubber or deproteinized natural rubber. For example, styrene-butadiene rubber (SBR), polybutadiene rubber (BR), polyisoprene rubber (IR), ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), a copolymer of isobutylene and p-methylstyrene. Halides, acrylonitrile-butadiene rubber (NBR), butyl rubber (IIR) and the like can be mentioned. The ethylene-propylene-diene rubber (EPDM) is an ethylene-propylene rubber (EPM) containing a third diene component. Examples of the third diene component include non-conjugated dienes having 5 to 20 carbon atoms such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, and 2,5-dimethyl-1,5. -Hexadiene and 1,4-octadiene, or cyclic dienes such as 1,4-cyclohexadiene, cyclooctadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5 Examples thereof include alkenyl norbornene such as -norbornene and 2-isopropenyl-5-norbornene. In particular, dicyclopentadiene, 5-ethylidene-2-norbornene and the like can be used.
<レジン>
本発明のトレッド用ゴム組成物はレジンがゴム成分100質量部に対して、5質量部以上、50質量部以下配合される。
<Resin>
In the rubber composition for a tread of the present invention, the resin is blended in an amount of 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the rubber component.
レジンとしては、芳香族系石油樹脂(C9留分による樹脂)、クマロンインデン樹脂(石炭クマロンインデン樹脂など)、テルペン系樹脂、芳香族変性テルペン樹脂(天然芳香族テルペンなど)、ロジン樹脂、フェノール系樹脂、石油系レジン(C5留分による樹脂)などがあげられる。なかでも、天然芳香族テルペン、石炭クマロンインデン樹脂などの石油以外の天然資源をもとに得られる天然由来のレジンが好ましい。 Examples of the resin include aromatic petroleum resins (resin using C9 fraction), coumarone indene resin (coal coumarone indene resin, etc.), terpene resin, aromatic modified terpene resin (natural aromatic terpene, etc.), rosin resin, Examples thereof include phenolic resins and petroleum resins (resins using C5 fraction). Of these, natural resins obtained from natural resources other than petroleum such as natural aromatic terpenes and coal coumarone indene resins are preferred.
例えば、リモネンなどのジペンテン、α−ピネン、β−ピネン、3−カレン、ターピノーレン、ミルセンなどのモノテルペン、ロンギフォーレン、カリオフィレンなどのセスキテルペンなどのテルペン類をモノマーとして単独重合または共重合したテルペン系(共)重合体が優れている。テルペン系(共)重合体は、テルペン類のモノマーのみの単独重合または共重合体とすることもできるが、テルペン類のモノマーとテルペン類以外のモノマーを用いた共重合体とすることもできる。 For example, a terpene system obtained by homopolymerization or copolymerization of terpenes such as dipentene such as limonene, monoterpenes such as α-pinene, β-pinene, 3-carene, terpinolene and myrcene, and sesquiterpenes such as longifolene and caryophyllene as monomers. The (co) polymer is excellent. The terpene-based (co) polymer can be a homopolymer or a copolymer of only the terpene monomer, but can also be a copolymer using a terpene monomer and a monomer other than the terpene.
テルペン系(共)重合体におけるテルペン類の単独重合体または共重合体の含量は、50質量%以上が好ましく、70質量%以上、特に80質量%以上がより好ましい。テルペン類の(共)重合体が50質量%未満では、充填剤の分散性向上、耐摩耗性の改善の効果が期待できない。 The content of the terpene homopolymer or copolymer in the terpene (co) polymer is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. When the (co) polymer of terpenes is less than 50% by mass, the effect of improving the dispersibility of the filler and improving the wear resistance cannot be expected.
テルペン系(共)重合体として、リモネン、α−ピネン、β−ピネンおよびターピノーレンの群から選択される1種以上のモノマーの単独重合体、または共重合体は天然ゴム、ENRなどの改質天然ゴム、さらにSBRなどの合成ゴムとの相溶性に優れ、好適に使用される。特に、β−ピネン及び/またはリモネンの(共)重合体は、ガラス転位温度が−30℃〜−45℃であり前記ゴム成分との相溶性に優れている。なおテルペン系(共)重合体は、耐熱老化性、耐候性、耐オゾン性を改善するため水素添加処理することができる。 As the terpene-based (co) polymer, a homopolymer of one or more monomers selected from the group of limonene, α-pinene, β-pinene and terpinolene, or a copolymer is a modified natural such as natural rubber or ENR It is excellent in compatibility with rubber and synthetic rubber such as SBR, and is preferably used. In particular, the (co) polymer of β-pinene and / or limonene has a glass transition temperature of −30 ° C. to −45 ° C. and is excellent in compatibility with the rubber component. The terpene (co) polymer can be subjected to a hydrogenation treatment in order to improve heat aging resistance, weather resistance, and ozone resistance.
なおレジンは、テルペン類以外にロジンなどの天然由来のモノマー、イソプレンやフェノールなどの石油資源由来のモノマー、クマロンなどの石炭由来のモノマーも使用できる。なかでも環境に配慮する観点から石油資源由来のモノマー及び石炭資源由来のモノマーの使用は避けた方が好ましい。 In addition to terpenes, natural resins such as rosin, monomers derived from petroleum resources such as isoprene and phenol, and monomers derived from coal such as coumarone can be used as the resin. In particular, it is preferable to avoid the use of monomers derived from petroleum resources and monomers derived from coal resources from the viewpoint of environmental considerations.
前記レジンのゲルパーミエーション・クロマトグラムの測定条件は次のとおりである。
カラム:東ソー(株)製のTSKgerG2000H8(60cm×2(120cm))、
検出器:東ソー(株)製RI(40℃)、
流速:1ml/min THF、
圧力:22〜23kg/cm2、
移動相:1%THF、
装置:東ソー(株)製TOYOSODA HLC−801A。
The measurement conditions of the gel permeation chromatogram of the resin are as follows.
Column: TSKgerG2000H8 (60 cm × 2 (120 cm)) manufactured by Tosoh Corporation
Detector: RI (40 ° C) manufactured by Tosoh Corporation
Flow rate: 1 ml / min THF,
Pressure: 22-23 kg / cm 2 ,
Mobile phase: 1% THF,
Apparatus: TOYOSODA HLC-801A manufactured by Tosoh Corporation.
上記測定条件で得られる分子量分布において、少なくとも2つのピークを有している。図1は本発明で使用されるレジンA、レジンBの2種類のレジンの分子量分布を示す。例えば、レジンAはこの分子量分布において、GPC測定におけるポリスチレン換算の分子量が1000以上の高分子量側と、ポリスチレン換算の分子量が1000未満の低分子量側に、それぞれピークP1、P2を有している。低分子量側のピーク(P1)の位置が分子量1000以上の場合、転がり抵抗の低減を図ることが困難であり、高分子量側のピーク(P2)の位置が分子量1000以下の場合、制動性を向上することができない。 The molecular weight distribution obtained under the above measurement conditions has at least two peaks. FIG. 1 shows the molecular weight distribution of two types of resins, resin A and resin B, used in the present invention. For example, the resin A has peaks P1 and P2 in the molecular weight distribution, on the high molecular weight side having a polystyrene equivalent molecular weight of 1000 or more in GPC measurement and on the low molecular weight side having a polystyrene equivalent molecular weight of less than 1000, respectively. When the position of the low molecular weight peak (P1) is 1000 or more, it is difficult to reduce the rolling resistance, and when the position of the high molecular weight peak (P2) is 1000 or less, the braking performance is improved. Can not do it.
また、分子量分布においてピークを1つ有する従来のレジンを使用すると、そのピークを示す分子量の位置に従って、転がり抵抗の低減またはグルップ性能の向上のいずれかの特性に偏り、両特性のバランスを図ることが困難である。なお分子量分布におけるピークは、少なくとも2つ必要であるが、低分子量側の最大ピーク(P1)と高分子量側の最大ピーク(P2)の間に1つ以上の更なる中間分子量のピーク(Pm)を有することができる。また、低分子量側の最大ピーク(P1)より低分子側あるいは高分子量側の最大ピーク(P2)よりも高分子側にもピークを有することもできる。 In addition, when a conventional resin having one peak in the molecular weight distribution is used, depending on the position of the molecular weight that shows the peak, it is biased toward either the reduction of rolling resistance or the improvement of the group performance, and the balance between the two characteristics is achieved. Is difficult. It should be noted that at least two peaks in the molecular weight distribution are required, but one or more additional intermediate molecular weight peaks (Pm) between the maximum peak (P1) on the low molecular weight side and the maximum peak (P2) on the high molecular weight side. Can have. Moreover, it can also have a peak on the high molecular weight side from the low molecular weight side maximum peak (P1) or the high molecular weight side maximum peak (P2).
ここで、低分子量側の最大ピーク(P1)とは、低分子量側で最大のピーク高さ(H1)を有するピークをいい、高分子量側の最大ピーク(P2)とは、高分子量側で最大のピーク高さ(H2)を有するピークをいう。 Here, the maximum peak (P1) on the low molecular weight side means a peak having the maximum peak height (H1) on the low molecular weight side, and the maximum peak (P2) on the high molecular weight side is the maximum on the high molecular weight side. A peak having a peak height (H2) of.
本発明では、低分子量側の最大ピーク(P1)と高分子量側の最大ピーク(P2)の、それぞれのピーク高さの比(H2/H1)は、0.5以上で2.0以下の範囲、好ましくは0.8以上で1.5以下の範囲である。ピーク高さの比(H2/H1)が0.5未満の場合、グリップ性が低下する傾向があり、一方2.0を超えると転がり抵抗が悪化する傾向がある。 In the present invention, the ratio (H2 / H1) of the peak heights of the maximum peak (P1) on the low molecular weight side and the maximum peak (P2) on the high molecular weight side is in the range of 0.5 to 2.0. The range is preferably 0.8 or more and 1.5 or less. When the ratio of peak heights (H2 / H1) is less than 0.5, grip properties tend to decrease, while when it exceeds 2.0, rolling resistance tends to deteriorate.
ここでピーク高さの比は、図1に示すようにGPC測定で得られた分子量とピーク強度の関係を示すグラフにおいて、低分子量側の最大ピーク(P1)のピーク高さ(H1)の高分子量側の最大ピーク(P2)のピーク高さ(H2)に対する比(H2/H1)として定義される。図1において高分子量側の最大ピーク(P2)は、分子量が3000以下であることが好ましい。分子量が3000を超えた領域にピークが存在すると、ゴム組成物の硬度が高くなり、制動性が低下する傾向にある。 Here, the ratio of the peak height is the height of the peak height (H1) of the maximum peak (P1) on the low molecular weight side in the graph showing the relationship between the molecular weight and the peak intensity obtained by GPC measurement as shown in FIG. It is defined as the ratio (H2 / H1) of the maximum peak (P2) on the molecular weight side to the peak height (H2). In FIG. 1, the maximum peak (P2) on the high molecular weight side preferably has a molecular weight of 3000 or less. When a peak exists in the region where the molecular weight exceeds 3000, the hardness of the rubber composition increases and the braking performance tends to decrease.
本発明において、レジンの軟化点は50℃以上であることが好ましく、80℃以上であることがより好ましい。軟化点が50℃未満では、製造工程での粘着性が強くなり、タイヤの製造における作業が困難である傾向がある。また、レジンの軟化点は150℃以下であることが好ましく、140℃以下であることがより好ましい。軟化点が150℃をこえると、ウェット制動性能が不充分となり、レジンを配合する効果がなくなる傾向がある。 In the present invention, the softening point of the resin is preferably 50 ° C. or higher, and more preferably 80 ° C. or higher. When the softening point is less than 50 ° C., the tackiness in the manufacturing process becomes strong, and the work in manufacturing the tire tends to be difficult. The softening point of the resin is preferably 150 ° C. or less, and more preferably 140 ° C. or less. When the softening point exceeds 150 ° C., the wet braking performance becomes insufficient and the effect of blending the resin tends to be lost.
レジンの含有量は、ゴム成分100質量部に対して5質量部以上、好ましくは8質量部以上である。含有量が5質量部未満では、制動性能の改善効果が小さくなる。また、含有量は50質量部以下、好ましくは35質量部以下である。含有量が50質量部をこえると、硬度が増大する。 The content of the resin is 5 parts by mass or more, preferably 8 parts by mass or more with respect to 100 parts by mass of the rubber component. When the content is less than 5 parts by mass, the effect of improving the braking performance is reduced. Moreover, content is 50 mass parts or less, Preferably it is 35 mass parts or less. When the content exceeds 50 parts by mass, the hardness increases.
<充填剤>
本発明のトレッド用ゴム組成物に使用される充填剤としては、シリカ、炭酸カルシウム、セリサイト、カーボンブラック、水酸化アルミニウム、クレーなどが挙げられる。本発明のトレッド用ゴム組成物としては、シリカ、炭酸カルシウム、セリサイトなどの白色充填剤を用いることが好ましい。これらの白色充填剤を用いることで、カーボンブラックなどの充填剤の場合と異なり、転がり抵抗が低減し、石油外資源の比率が上昇するという効果が得られる。
<Filler>
Examples of the filler used in the rubber composition for a tread of the present invention include silica, calcium carbonate, sericite, carbon black, aluminum hydroxide, and clay. As the tread rubber composition of the present invention, it is preferable to use a white filler such as silica, calcium carbonate or sericite. By using these white fillers, unlike the case of fillers such as carbon black, the effect of reducing rolling resistance and increasing the ratio of non-petroleum resources can be obtained.
充填剤中の白色充填剤の含有率は80質量%以上、好ましくは90質量%以上である。含有率が80質量%未満では、石油外資源の比率が低下し、好ましくない。白色充填剤の含有率は100質量%であることが好ましい。 The content of the white filler in the filler is 80% by mass or more, preferably 90% by mass or more. If the content is less than 80% by mass, the ratio of non-petroleum resources decreases, which is not preferable. The content of the white filler is preferably 100% by mass.
本発明でカーボンブラックを用いる場合、該カーボンブラックの窒素吸着比表面積は、100m2/g以上1500m2/g以下が好ましい。該窒素吸着比表面積が100m2/g以上である場合、ゴム組成物の機械的強度が改善され、1500m2/g以下である場合製造時の加工性を確保する点で好ましい。該窒素吸着比表面積は、105m2/g以上がより好ましく、また、1300m2/g以下、さらに1000m2/g以下がより好ましい。 When carbon black is used in the present invention, the nitrogen adsorption specific surface area of the carbon black is preferably 100 m 2 / g or more and 1500 m 2 / g or less. When the nitrogen adsorption specific surface area is 100 m 2 / g or more, the mechanical strength of the rubber composition is improved, and when the nitrogen adsorption specific surface area is 1500 m 2 / g or less, it is preferable from the viewpoint of ensuring processability during production. The nitrogen adsorption specific surface area is more preferably 105 m 2 / g or more, more preferably 1300 m 2 / g or less, and still more preferably 1000 m 2 / g or less.
また、シリカを用いる場合、シリカの窒素吸着比表面積(BET法)は、たとえば100〜300m2/g、さらに150〜250m2/gの範囲内であることが好ましい。シリカの窒素吸着比表面積が100m2/g以上である場合、補強効果が十分得られることによりタイヤの耐摩耗性が良好に向上する。一方、該窒素吸着比表面積が300m2/g以下である場合、それぞれのゴムの製造時の加工性が良好であり、タイヤの操縦安定性も良好に確保される。なお、窒素吸着比表面積は、ASTM D3037−81に準じてBET法で測定される。 Moreover, when using silica, it is preferable that the nitrogen adsorption specific surface area (BET method) of a silica exists in the range of 100-300 m < 2 > / g, for example, and also 150-250 m < 2 > / g. When the nitrogen adsorption specific surface area of silica is 100 m 2 / g or more, the abrasion resistance of the tire is improved satisfactorily by obtaining a sufficient reinforcing effect. On the other hand, when the nitrogen adsorption specific surface area is 300 m 2 / g or less, the processability during production of each rubber is good, and the steering stability of the tire is also ensured. The nitrogen adsorption specific surface area is measured by the BET method according to ASTM D3037-81.
<シランカプリング剤>
白色充填剤としてシリカを使用する場合、シランカップリング剤を併用することが好ましい。シランカップリング剤の配合量は、シリカ100質量部に対して1〜20質量部とすることが好ましい。配合量が1質量部未満では、耐摩耗性が悪くなる傾向があり、一方シランカップリング剤の配合量が20質量%以上の場合、ゴムの混練、押出工程での焼け(スコーチ)が生じる可能性がある。
<Silane coupling agent>
When silica is used as the white filler, it is preferable to use a silane coupling agent in combination. It is preferable that the compounding quantity of a silane coupling agent shall be 1-20 mass parts with respect to 100 mass parts of silica. If the blending amount is less than 1 part by mass, the wear resistance tends to deteriorate. On the other hand, if the blending amount of the silane coupling agent is 20% by mass or more, scorching may occur in the rubber kneading and extrusion processes. There is sex.
含硫黄シランカップリング剤としては、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、ビス−[3−(トリエトキシシリル)−プロピル]テトラスルフィド、3−メルカプトプロピルトリメトキシシラン等が例示される。その他のシラン系カップリング剤としては、ビニルトリクロロシラン、ビニルトリス(2−メトキシエトキシ)シラン、γ−グリシドキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−(2−アミノエチル)アミノプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン等を使用することができる。 As sulfur-containing silane coupling agents, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl-tetrasulfide, trimethoxysilylpropyl-mercaptobenzothiazole tetrasulfide, triethoxysilylpropyl-methacrylate-monosulfide, dimethoxymethyl Examples include silylpropyl-N, N-dimethylthiocarbamoyl-tetrasulfide, bis- [3- (triethoxysilyl) -propyl] tetrasulfide, 3-mercaptopropyltrimethoxysilane and the like. Other silane coupling agents include vinyltrichlorosilane, vinyltris (2-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- (2-aminoethyl) Aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like can be used.
<その他の配合剤>
ゴム組成物には、上記の他に、加硫剤、加硫促進剤、軟化剤、可塑剤、老化防止剤およびスコーチ防止剤等を添加することが可能である。
<Other ingredients>
In addition to the above, it is possible to add a vulcanizing agent, a vulcanization accelerator, a softening agent, a plasticizer, an anti-aging agent, an anti-scorch agent, and the like to the rubber composition.
加硫剤としては、有機過酸化物もしくは硫黄系加硫剤を使用できる。有機過酸化物としては、たとえば、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ジ−t−ブチルパーオキサイド、t−ブチルクミルパーオキサイド、メチルエチルケトンパーオキサイド、クメンハイドロパーオキサイド、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキサン、2,5−ジメチル−2,5−ジ(ベンゾイルパーオキシ)ヘキサン、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキシン−3あるいは1,3−ビス(t−ブチルパーオキシプロピル)ベンゼン、ジ−t−ブチルパーオキシ−ジイソプロピールベンゼン、t−ブチルパーオキシベンゼン、2,4−ジクロロベンゾイルパーオキサイド、1,1−ジ−t−ブチルパーオキシ−3,3,5−トリメチルシロキサン、n−ブチル−4,4−ジ−t−ブチルパーオキシバレレートなどを使用することができる。これらの中で、ジクミルパーオキサイド、t−ブチルパーオキシベンゼンおよびジ−t−ブチルパーオキシ−ジイソプロピルベンゼンが好ましい。また、硫黄系加硫剤としては、たとえば、硫黄、モルホリンジスルフィドなどを使用することができる。これらの中では硫黄が好ましい。 As the vulcanizing agent, an organic peroxide or a sulfur vulcanizing agent can be used. Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, 2,5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne- 3 or 1,3-bis (t-butylperoxypropyl) benzene, di-t-butylperoxy-diisopropylbenzene, t-butylperoxybenzene, 2,4-dichlorobenzoyl peroxide, 1,1- Di-t-butylperoxy-3,3,5-trimethylsiloxane, n-butyl-4, - it can be used such as di -t- butyl peroxy valerate. Of these, dicumyl peroxide, t-butylperoxybenzene and di-t-butylperoxy-diisopropylbenzene are preferred. Moreover, as a sulfur type vulcanizing agent, sulfur, morpholine disulfide, etc. can be used, for example. Of these, sulfur is preferred.
加硫促進剤としては、スルフェンアミド系、チアゾール系、チウラム系、チオウレア系、グアニジン系、ジチオカルバミン酸系、アルデヒド−アミン系またはアルデヒド−アンモニア系、イミダゾリン系、もしくは、キサンテート系加硫促進剤のうち少なくとも一つを含有するものを使用することが可能である。 Vulcanization accelerators include sulfenamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamic acid, aldehyde-amine or aldehyde-ammonia, imidazoline, or xanthate vulcanization accelerators. Those containing at least one of them can be used.
老化防止剤としては、アミン系、フェノール系、イミダゾール系の化合物や、カルバミン酸金属塩、ワックスなどを適宜選択して使用することが可能である。 As the anti-aging agent, amine-based, phenol-based, and imidazole-based compounds, carbamic acid metal salts, waxes, and the like can be appropriately selected and used.
本発明では練り加工性を一層向上させるために軟化剤を併用しても良い。軟化剤としては、プロセスオイル、潤滑油、パラフィン、流動パラフィン、石油アスファルト、ワセリンなどの石油系軟化剤、ヒマシ油、アマニ油、ナタネ油、ヤシ油などの脂肪油系軟化剤、トール油、サブ、蜜ロウ、カルナバロウ、ラノリンなどのワックス類、リノール酸、パルミチン酸、ステアリン酸、ラウリン酸などの脂肪酸、等が挙げられる。 In the present invention, a softener may be used in combination in order to further improve kneading processability. Softeners include process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petroleum jelly such as petroleum jelly, fatty oil softener such as castor oil, linseed oil, rapeseed oil, coconut oil, tall oil, , Waxes such as beeswax, carnauba wax and lanolin, and fatty acids such as linoleic acid, palmitic acid, stearic acid and lauric acid.
可塑剤としては、DMP(フタル酸ジメチル)、DEP(フタル酸ジエチル)、DBP(フタル酸ジブチル)、DHP(フタル酸ジヘプチル)、DOP(フタル酸ジオクチル)、DINP(フタル酸ジイソノニル)、DIDP(フタル酸ジイソデシル)、BBP(フタル酸ブチルベンジル)、DLP(フタル酸ジラウリル)、DCHP(フタル酸ジシクロヘキシル)、無水ヒドロフタル酸エステル、DOZ(アゼライン酸ジ−2−エチルヘキシル)、DBS(セバシン酸ジブチル)、DOS(セバシン酸ジオクチル)、クエン酸アセチルトリエチル、クエン酸アセチルトリブチル、DBM(マレイン酸ジブチル)、DOM(マレイン酸−2−エチルヘキシル)、DBF(フマル酸ジブチル)等が挙げられる。 As plasticizers, DMP (dimethyl phthalate), DEP (diethyl phthalate), DBP (dibutyl phthalate), DHP (diheptyl phthalate), DOP (dioctyl phthalate), DINP (diisononyl phthalate), DIDP (phthalate) Acid diisodecyl), BBP (butylbenzyl phthalate), DLP (dilauryl phthalate), DCHP (dicyclohexyl phthalate), hydrophthalic anhydride ester, DOZ (di-2-ethylhexyl azelate), DBS (dibutyl sebacate), DOS (Dioctyl sebacate), acetyl triethyl citrate, acetyl tributyl citrate, DBM (dibutyl maleate), DOM (2-ethylhexyl maleate), DBF (dibutyl fumarate) and the like.
スコーチを防止または遅延させるためのスコーチ防止剤としては、たとえば無水フタル酸、サリチル酸、安息香酸などの有機酸、N−ニトロソジフェニルアミンなどのニトロソ化合物、N−シクロヘキシルチオフタルイミド等を使用することができる。 As the scorch preventing agent for preventing or delaying scorch, for example, organic acids such as phthalic anhydride, salicylic acid and benzoic acid, nitroso compounds such as N-nitrosodiphenylamine, N-cyclohexylthiophthalimide and the like can be used.
<タイヤ構造>
本発明の空気入りタイヤの構造は、たとえば図2のタイヤ断面の右上半分に例示されるものである。タイヤ1は、トレッド部を構成するトレッドゴム7と、その両端からタイヤ半径方向内方にのびる一対のサイドウォール部8と、各サイドウォール部の内方端に位置するクリンチ部3およびリム上部に位置するチェーファー部2とを備える。また一対のビードコア4の間にはカーカス10が架け渡されるとともに、このカーカス10のタイヤ半径方向外側にブレーカー部9が配置される。前記カーカス10は、カーカスコードを配列する1枚以上のカーカスプライから形成され、このカーカスプライは、トレッド部からサイドウォール部を経て、ビードコア4と、該ビードコア4の上端からサイドウォール方向に延びるビードエーペックス5との廻りをタイヤ軸方向の内側から外側に折返され、折返し部によって係止される。ブレーカー部は、ブレーカーコードを配列した2枚以上のブレーカープライからなり、各ブレーカーコードがブレーカープライ間で交差して配置される。
<Tire structure>
The structure of the pneumatic tire of the present invention is exemplified in the upper right half of the tire cross section of FIG. The tire 1 includes a
本発明のトレッド用ゴム組成物を用いて、通常の方法により、該ゴム組成物からなるトレッドを含有するタイヤを製造することができる。すなわち、必要に応じて前記薬品を配合した本発明のトレッド用ゴム組成物を、未加硫の段階でタイヤのトレッドの形状にあわせて押出し加工し、タイヤ成型機上にて通常の方法で成形することにより、未加硫タイヤを形成する。この未加硫タイヤを加硫機中で加熱加圧することによりタイヤを得る。 By using the rubber composition for a tread of the present invention, a tire containing a tread composed of the rubber composition can be produced by a usual method. That is, the rubber composition for a tread of the present invention, which is blended with the chemicals as necessary, is extruded according to the shape of the tread of the tire at an unvulcanized stage, and molded by a normal method on a tire molding machine. By doing so, an unvulcanized tire is formed. The unvulcanized tire is heated and pressurized in a vulcanizer to obtain a tire.
実施例にもとづいて本発明を詳細に説明するが、本発明はこれらのみに限定されるものではない。 The present invention will be described in detail based on examples, but the present invention is not limited to these examples.
実施例1、参考例2及び比較例1〜3
表1に記載する硫黄および加硫促進剤以外の各種薬品を(株)神戸製鋼所製の1.7Lバンバリーに充填し、77rpmで145℃に到達するまで混練した。得られた混練物に対して、硫黄および加硫促進剤を表1に示す量配合し、オープンロールで80℃で6分間混練して未加硫ゴム組成物を得た。前記未加硫ゴム組成物をタイヤ成型機上でトレッド形状に成形し、他のタイヤ部材と貼りあわせて未加硫タイヤを作製した。それを160℃で20分間加硫することにより、タイヤを製造した。
Example 1, Reference Example 2 and Comparative Examples 1-3
Various chemicals other than sulfur and vulcanization accelerators listed in Table 1 were filled in a 1.7 L Banbury manufactured by Kobe Steel, Ltd., and kneaded at 77 rpm until reaching 145 ° C. To the obtained kneaded product, sulfur and a vulcanization accelerator were blended in the amounts shown in Table 1, and kneaded at 80 ° C. for 6 minutes with an open roll to obtain an unvulcanized rubber composition. The unvulcanized rubber composition was molded into a tread shape on a tire molding machine and bonded to another tire member to produce an unvulcanized tire. A tire was manufactured by vulcanizing it at 160 ° C. for 20 minutes.
表1に示すゴム配合で調整したトレッドゴム組成物を用い、常法にて加硫成形し、図2に示す構造を有するサイズ195/65R15の空気入りタイヤを作製した。ここで、試作タイヤの基本構造は次のとおりである。 Using a tread rubber composition adjusted with the rubber composition shown in Table 1, vulcanization molding was carried out by a conventional method to produce a pneumatic tire of size 195 / 65R15 having the structure shown in FIG. Here, the basic structure of the prototype tire is as follows.
カーカスプライ
コード角度 タイヤ周方向に88度
コード材料 ポリエステル 1670/2 dtex
ブレーカー
コード角度 タイヤ周方向に20度×−20度
コード材料 スチールコード
Carcass ply Cord angle 88 degrees in the tire circumferential direction Cord material Polyester 1670/2 dtex
Breaker Cord angle 20 degrees x -20 degrees in the tire circumferential direction Cord material Steel cord
以下に実施例において使用した各種薬品を詳細に説明する。
(注1)ENR−25:GATHRIE POLYMER SDN. BHD社製のエポキシ化天然ゴム(エポキシ化率:25モル%)
(注2)NR:RSS#1
(注3)カーボンブラック:昭和キャボット(株)製のショウブラックN220
(注4)シリカ:テグッサ社製のウルトラシル VN3(BET比表面積:175m2/g)
(注5)シランカップリング剤:テグッサ社製のSi−69
(注6)オイル:植物油:日清製油(株)製の精製パーム油J(S)
(注7)レジンA:ヤスハラケミカル(株)製のPX300N(β−ピネン重合樹脂、分子量分布:高分子量側のピーク位置がMw=2750、低分子量側のピーク位置がMw=540、ピークの強度比(H2/H1=0.81)
(注8)レジンB:ヤスハラケミカル(株)製のPX1150N(β−ピネン重合樹脂、分子量分布:高分子量側のピーク位置がMw=2600、低分子量側のピーク位置がMw=210、ピークの強度比(H2/H1=2.83)
(注9)ワックス:大内新興化学工業(株)製のサンノックワックス
(注10)老化防止剤:精工化学(株)製のオゾノン6C
(注11)ステアリン酸:日本油脂(株)製のステアリン酸
(注12)酸化亜鉛:三井金属鉱業(株)製の酸化亜鉛2種
(注13)硫黄:軽井沢硫黄(株)製の粉末硫黄
(注14)加硫促進剤TBBS:大内新興化学工業(株)製のノクセラーNS
これら薬品のうち石油外資源は、NR、ENR、シリカ、硫黄、オイル、レジンA、レジンB、ステアリン酸、酸化亜鉛である。
The various chemicals used in the examples are described in detail below.
(Note 1) ENR-25: Epoxidized natural rubber manufactured by GATHRIE POLYMER SDN. BHD (epoxidation rate: 25 mol%)
(Note 2) NR: RSS # 1
(Note 3) Carbon Black: Show Black N220 manufactured by Showa Cabot Corporation
(Note 4) Silica: Ultrasil VN3 (BET specific surface area: 175 m 2 / g) manufactured by Tegussa
(Note 5) Silane coupling agent: Si-69 manufactured by Tegussa
(Note 6) Oil: Vegetable oil: Refined palm oil J (S) manufactured by Nisshin Oil Co., Ltd.
(Note 7) Resin A: PX300N (β-pinene polymer resin, manufactured by Yasuhara Chemical Co., Ltd., molecular weight distribution: high molecular weight side peak position Mw = 2750, low molecular weight side peak position Mw = 540, peak intensity ratio (H2 / H1 = 0.81)
(Note 8) Resin B: PX1150N manufactured by Yasuhara Chemical Co., Ltd. (β-pinene polymer resin, molecular weight distribution: peak position on the high molecular weight side is Mw = 2600, peak position on the low molecular weight side is Mw = 210, peak intensity ratio (H2 / H1 = 2.83)
(Note 9) Wax: Sunnock wax manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. (Note 10) Anti-aging agent: Ozonon 6C manufactured by Seiko Chemical Co., Ltd.
(Note 11) Stearic acid: Stearic acid manufactured by NOF Corporation (Note 12) Zinc oxide: Two types of zinc oxide manufactured by Mitsui Mining & Smelting Co., Ltd. (Note 13) Sulfur: Powdered sulfur manufactured by Karuizawa Sulfur Co., Ltd. (Note 14) Vulcanization accelerator TBBS: Noxeller NS manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Of these chemicals, non-petroleum resources are NR, ENR, silica, sulfur, oil, Resin A, Resin B, stearic acid, and zinc oxide.
得られたタイヤを使用して、以下の試験をおこなった。
<ドライ制動指数、ウエット制動指数>
試験タイヤを車に装着し、ドライアスファルト路面およびウェットアスファルト路面において、時速100kmからの制動停止距離を測定し、その測定値から、摩擦係数μを求めた。比較例1のμを100として指数表示した。指数が大きいほど性能は良好である。
The following tests were performed using the obtained tires.
<Dry braking index, wet braking index>
The test tire was mounted on a vehicle, and the braking stop distance from 100 km / h was measured on the dry asphalt road surface and the wet asphalt road surface, and the friction coefficient μ was obtained from the measured value. The index was displayed with μ in Comparative Example 1 as 100. The larger the index, the better the performance.
<転がり抵抗指数>
試験タイヤを15×6JJリムに装着し、気温25℃、内圧230KPaを充填し、荷重3.43kNで速度80km/hの条件で転がり抵抗試験機を用いて転がり抵抗を測定した。転がり抵抗の測定値を荷重で除した転がり抵抗係数(RRC)につき、実施例1、参考例2、比較例2、3の転がり抵抗を、下記の式により比較例1(基準配合)を100として表示した。値が大きいほど転がり抵抗が小さく性能が良好である。結果を表1に示す。
転がり抵抗指数=基準配合の転がり抵抗/各配合の転がり抵抗係数×100
<性能評価>
表1において、本発明の実施例1、参考例2は分子量分布においてピーク高さの比(H2/H1)が、0.5〜2.0の範囲に含まれる2つのピークを有しているレジンA(H2/H1=0.81)を8質量部配合しており、ドライ制動性能、ウエット制動性能、転がり抵抗指数が総合的に優れている。
<Rolling resistance index>
The test tire was mounted on a 15 × 6 JJ rim, filled with an air temperature of 25 ° C. and an internal pressure of 230 KPa, and the rolling resistance was measured using a rolling resistance tester under a load of 3.43 kN and a speed of 80 km / h. Regarding the rolling resistance coefficient (RRC) obtained by dividing the measured value of rolling resistance by the load, the rolling resistance of Example 1, Reference Example 2 , Comparative Examples 2 and 3 is set to 100 as Comparative Example 1 (reference formulation) by the following formula. displayed. The larger the value, the smaller the rolling resistance and the better the performance. The results are shown in Table 1.
Rolling resistance index = Rolling resistance of standard composition / Rolling resistance coefficient of each composition × 100
<Performance evaluation>
In Table 1, Example 1 and Reference Example 2 of the present invention have two peaks whose ratio of peak height (H2 / H1) is in the range of 0.5 to 2.0 in the molecular weight distribution. 8 parts by mass of resin A (H2 / H1 = 0.81) is blended, and the dry braking performance, wet braking performance, and rolling resistance index are comprehensively excellent.
今回開示された実施の形態および実施例はすべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は上記した説明ではなくて特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。 It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.
1 タイヤ、2 チェーファー、3 クリンチゴム、4 ビードコア、5 ビードエーペックス、7 トレッド部、8 サイドウオール部、9 ブレーカー部、10 カーカス。 1 tire, 2 chafer, 3 clinch rubber, 4 bead core, 5 bead apex, 7 tread part, 8 side wall part, 9 breaker part, 10 carcass.
Claims (4)
分子量分布のピークを少なくとも2つ含み、テルペン系重合体およびテルペン系共重合体の少なくともいずれかよりなるレジンであって、前記ピークのうち低分子量側の最大ピーク(P1)のピーク高さ(H1)と高分子側の最大ピーク(P2)のピーク高さ(H2)の比が以下の関係にある前記レジンを5質量部以上、および
0.5≦(H2/H1)≦2.0
白色充填剤を80質量%以上含む充填剤を30〜150質量部含有するトレッドゴム組成物。 The rubber component 100 parts by mass consisting of epoxidized natural rubber,
Seen at least two free peaks of molecular weight distribution, a more composed resin least one terpene-based polymer and terpene copolymer, the peak height of the maximum peak (P1) of the low molecular weight side of the peak ( 5 parts by mass or more of the resin in which the ratio of the peak height (H2) of the H1) to the maximum peak (P2) on the polymer side is as follows: 0.5 ≦ (H2 / H1) ≦ 2.0
A tread rubber composition containing 30 to 150 parts by mass of a filler containing 80% by mass or more of a white filler.
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CN102947379B (en) * | 2010-06-18 | 2014-04-30 | 横滨橡胶株式会社 | Tire rubber composition and pneumatic tire using same |
CN103221476B (en) * | 2010-12-03 | 2014-11-12 | 横滨橡胶株式会社 | Rubber composition for tire tread |
JP5351220B2 (en) | 2011-07-26 | 2013-11-27 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire |
JP6193577B2 (en) * | 2013-02-01 | 2017-09-06 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire |
JP6084870B2 (en) * | 2013-03-12 | 2017-02-22 | 住友ゴム工業株式会社 | Rubber composition for tread and pneumatic tire |
JP6880551B2 (en) | 2016-02-08 | 2021-06-02 | 住友ゴム工業株式会社 | tire |
JP6878813B2 (en) | 2016-10-03 | 2021-06-02 | 住友ゴム工業株式会社 | Rubber composition for base tread |
JP7069675B2 (en) | 2017-12-08 | 2022-05-18 | 住友ゴム工業株式会社 | Pneumatic tires |
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JP4288460B2 (en) * | 2002-11-18 | 2009-07-01 | Jsr株式会社 | Method for producing rubber composition, and rubber composition |
JP2005002206A (en) * | 2003-06-11 | 2005-01-06 | Yokohama Rubber Co Ltd:The | Rubber composition and pneumatic tire |
JP4012160B2 (en) * | 2004-02-17 | 2007-11-21 | 住友ゴム工業株式会社 | Rubber composition for base tread and pneumatic tire |
JP2005336303A (en) * | 2004-05-26 | 2005-12-08 | Bridgestone Corp | Pneumatic tire |
JP4602716B2 (en) * | 2004-08-24 | 2010-12-22 | 住友ゴム工業株式会社 | Rubber composition for tread |
JP2006160813A (en) * | 2004-12-03 | 2006-06-22 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
JP2006249324A (en) * | 2005-03-11 | 2006-09-21 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
JP5208361B2 (en) * | 2005-10-28 | 2013-06-12 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire using the same |
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