JP5483367B2 - Rubber composition for inner liner and pneumatic tire - Google Patents
Rubber composition for inner liner and pneumatic tire Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims description 68
- 239000005060 rubber Substances 0.000 title claims description 68
- 239000000203 mixture Substances 0.000 title claims description 51
- 239000002802 bituminous coal Substances 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 16
- 239000011787 zinc oxide Substances 0.000 claims description 10
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 8
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 claims description 7
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 claims description 5
- 229920005555 halobutyl Polymers 0.000 claims description 4
- 239000000446 fuel Substances 0.000 description 27
- 238000000465 moulding Methods 0.000 description 23
- 244000043261 Hevea brasiliensis Species 0.000 description 15
- 229920005549 butyl rubber Polymers 0.000 description 15
- 229920003052 natural elastomer Polymers 0.000 description 15
- 229920001194 natural rubber Polymers 0.000 description 15
- 239000006229 carbon black Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002156 mixing Methods 0.000 description 10
- 238000004898 kneading Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 229920003049 isoprene rubber Polymers 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920005556 chlorobutyl Polymers 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- -1 C 8 Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920005683 SIBR Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000006237 Intermediate SAF Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical compound C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Description
本発明は、インナーライナー用ゴム組成物、及びこれを用いた空気入りタイヤに関する。 The present invention relates to a rubber composition for an inner liner and a pneumatic tire using the same.
従来より、タイヤの転がり抵抗を低減（転がり抵抗性能を向上）させることにより、車の低燃費化が行なわれてきた。近年、車の低燃費化への要求がますます強くなってきており、タイヤ部材のゴム組成物に対して、優れた低発熱性が要求されてきている。そのため、例えば、トレッド部やサイドウォール部に、ｔａｎδの低い低発熱ゴムが使用されるようになってきた。 Conventionally, vehicle fuel efficiency has been reduced by reducing the rolling resistance of tires (improving rolling resistance performance). In recent years, there has been an increasing demand for lower fuel consumption of vehicles, and an excellent low heat generation property has been required for rubber compositions for tire members. Therefore, for example, low heat-generating rubber having a low tan δ has been used for the tread part and the sidewall part.
一方、タイヤ内側のインナーライナー部では、空気を保持する目的で、空気透過性の低いブチル系ゴムを使用するのが一般的となっている。しかし、ブチル系ゴムは、トレッド部やサイドウォール部で使用されるジエン系ゴムに比べ、ヒステリシスロスが大きく、容易にｔａｎδの低いインナーライナー用ゴム組成物とすることは困難であった。 On the other hand, in the inner liner part inside the tire, it is common to use a butyl rubber having low air permeability for the purpose of holding air. However, butyl rubber has a large hysteresis loss compared to diene rubber used in the tread portion and sidewall portion, and it has been difficult to easily form a rubber composition for an inner liner having a low tan δ.
インナーライナー用ゴム組成物において、カーボンブラックを減量することにより、ｔａｎδを低減できるが、未加硫ゴムの粘度も低下してしまい、成形加工時のゴムの厚みの制御が困難になる。すなわち、成形加工性が悪化してしまう。それに対して、特許文献１では、カーボンブラックの一部を瀝青炭粉砕物に置換することにより、ｔａｎδの低減と成形加工性のバランスが改善されることが開示されている。一方、特許文献２では、天然ゴムを多量に含むゴム成分に瀝青炭粉砕物を配合したゴム組成物をインスレーションに使用することにより、タイヤの水分バリア性が向上することが開示されている。しかし、特許文献１，２では、耐空気透過性、低燃費性、成形加工性をバランスよく向上する点については、改善の余地がある。 In the rubber composition for the inner liner, tan δ can be reduced by reducing the amount of carbon black, but the viscosity of the unvulcanized rubber also decreases, and it becomes difficult to control the thickness of the rubber during the molding process. That is, the moldability is deteriorated. On the other hand, Patent Document 1 discloses that the balance between the reduction of tan δ and the moldability is improved by replacing a part of carbon black with a bituminous coal pulverized product. On the other hand, Patent Document 2 discloses that the moisture barrier property of a tire is improved by using a rubber composition in which a bituminous coal pulverized product is blended in a rubber component containing a large amount of natural rubber for the installation. However, in Patent Documents 1 and 2, there is room for improvement in terms of improving the air permeation resistance, fuel efficiency and molding processability in a balanced manner.
本発明は、前記課題を解決し、耐空気透過性、低燃費性、成形加工性をバランスよく向上できるインナーライナー用ゴム組成物、及び該インナーライナー用ゴム組成物をタイヤのインナーライナーに用いた空気入りタイヤを提供することを目的とする。 The present invention solves the above problems and uses a rubber composition for an inner liner capable of improving the air permeation resistance, fuel efficiency and molding processability in a well-balanced manner, and the rubber composition for an inner liner used for a tire inner liner. An object is to provide a pneumatic tire.
本発明者は、耐空気透過性、低燃費性、成形加工性をバランスよく向上させるに当り、瀝青炭粉砕物を配合した場合に、耐空気透過性が悪化することに着目した。そこで、耐空気透過性が悪化する原因について、検討した結果、瀝青炭粉砕物を配合すると、ゴム組成物の混練り加工性が悪化し、ゴム組成物の均質性が不充分となることが原因であるとの仮説に想到した。そして、瀝青炭粉砕物と共に混合樹脂を配合することにより、瀝青炭粉砕物を配合したゴム組成物の混練り加工性を改善でき、耐空気透過性、低燃費性、成形加工性をバランスよく向上できることを見出し、本発明を完成させた。
すなわち、本発明は、ゴム成分１００質量部に対して、平均粒径が０．１ｍｍ以下の瀝青炭粉砕物を５〜７０質量部、混合樹脂を１〜２０質量部含むインナーライナー用ゴム組成物に関する。
In order to improve the air permeation resistance, low fuel consumption and molding processability in a well-balanced manner, the present inventor has focused on the fact that the air permeation resistance deteriorates when blended with bituminous coal. Therefore, as a result of examining the cause of the deterioration of the air permeation resistance, when the bituminous coal pulverized product is blended, the kneading processability of the rubber composition is deteriorated, and the homogeneity of the rubber composition is insufficient. I came up with the hypothesis that there is. And by blending the mixed resin with the bituminous coal pulverized product, the kneading processability of the rubber composition blended with the bituminous coal pulverized product can be improved, and the air permeation resistance, fuel efficiency and molding processability can be improved in a balanced manner. The headline and the present invention were completed.
That is, the present invention relates to a rubber composition for an inner liner containing 5 to 70 parts by mass of a pulverized bituminous coal having an average particle size of 0.1 mm or less and 1 to 20 parts by mass of a mixed resin with respect to 100 parts by mass of a rubber component. .
上記インナーライナー用ゴム組成物は、ゴム成分１００質量％中のハロゲン化ブチルゴムの含有量が７０質量％以上であることが好ましい。上記混合樹脂が芳香族炭化水素系樹脂と脂肪族炭化水素系樹脂の混合物であることが好ましい。上記インナーライナー用ゴム組成物は、ゴム成分１００質量部に対して、酸化亜鉛を０．５〜１．５質量部含むことが好ましい。 In the rubber composition for an inner liner, the content of halogenated butyl rubber in 100% by mass of the rubber component is preferably 70% by mass or more. The mixed resin is preferably a mixture of an aromatic hydrocarbon resin and an aliphatic hydrocarbon resin. It is preferable that the said rubber composition for inner liners contains 0.5-1.5 mass parts of zinc oxide with respect to 100 mass parts of rubber components.
本発明はまた、上記インナーライナー用ゴム組成物を用いて作製したインナーライナーを有する空気入りタイヤに関する。 The present invention also relates to a pneumatic tire having an inner liner produced using the rubber composition for an inner liner.
本発明によれば、特定量の平均粒径が０．１ｍｍ以下の瀝青炭粉砕物と、所定量の混合樹脂を含むインナーライナー用ゴム組成物であるので、耐空気透過性、低燃費性、成形加工性をバランスよく向上できる。よって、該ゴム組成物をタイヤのインナーライナーに使用することにより、耐空気透過性、低燃費性のバランスに優れた空気入りタイヤを提供することができる。 According to the present invention, since it is a rubber composition for an inner liner containing a specific amount of pulverized bituminous coal having an average particle size of 0.1 mm or less and a predetermined amount of a mixed resin, air permeation resistance, low fuel consumption, molding Workability can be improved in a well-balanced manner. Therefore, a pneumatic tire excellent in the balance of air permeation resistance and fuel efficiency can be provided by using the rubber composition for the inner liner of the tire.
本発明のインナーライナー用ゴム組成物は、特定量の平均粒径が０．１ｍｍ以下の瀝青炭粉砕物と、所定量の混合樹脂を含む。 The rubber composition for an inner liner of the present invention contains a specific amount of a pulverized bituminous coal having an average particle size of 0.1 mm or less and a predetermined amount of a mixed resin.
特定量の平均粒径が０．１ｍｍ以下の瀝青炭粉砕物を配合すると、低燃費性、成形加工性を向上できるものの、耐空気透過性が低下してしまう。しかし、本発明では、この瀝青炭粉砕物と共に所定量の混合樹脂を配合することにより、ゴム組成物の混練り加工性を改善でき、ゴム組成物の均質性を向上できるため、耐空気透過性を向上できる。そのため、瀝青炭粉砕物による耐空気透過性の低下を抑制しつつ、低燃費性、成形加工性を向上できる。すなわち、これらの成分を併用することにより、瀝青炭粉砕物を配合したことによる低燃費性、成形加工性の向上効果を維持しつつ、瀝青炭粉砕物を配合せずに混合樹脂のみを配合した場合よりも優れた耐空気透過性が得られ、耐空気透過性、低燃費性、成形加工性をバランスよく向上できる。 When a specific amount of a bituminous coal pulverized product having an average particle size of 0.1 mm or less is blended, the fuel economy and molding processability can be improved, but the air permeation resistance is lowered. However, in the present invention, by blending a predetermined amount of the mixed resin with the bituminous coal pulverized product, the kneading processability of the rubber composition can be improved and the homogeneity of the rubber composition can be improved. It can be improved. Therefore, low fuel consumption and molding processability can be improved while suppressing a decrease in air permeation resistance due to the bituminous coal pulverized product. In other words, by using these components in combination, while maintaining the improvement in fuel economy and molding processability by blending bituminous coal pulverized material, compared to blending only mixed resin without blending bituminous coal pulverized material. Excellent air permeation resistance can be obtained, and the air permeation resistance, fuel efficiency and molding processability can be improved in a balanced manner.
本発明に使用されるゴム成分としては、例えば、イソプレン系ゴム、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、スチレンイソプレンブタジエンゴム（ＳＩＢＲ）、クロロプレンゴム（ＣＲ）、アクリロニトリルブタジエンゴム（ＮＢＲ）等のジエン系ゴムやブチル系ゴムが挙げられる。ゴム成分は、単独で用いてもよく、２種以上を併用してもよい。 Examples of the rubber component used in the present invention include isoprene rubber, butadiene rubber (BR), styrene butadiene rubber (SBR), styrene isoprene butadiene rubber (SIBR), chloroprene rubber (CR), and acrylonitrile butadiene rubber (NBR). And diene rubbers and butyl rubbers. A rubber component may be used independently and may use 2 or more types together.
ブチル系ゴムとしては、例えば、臭素化ブチルゴム（Ｂｒ−ＩＩＲ）、塩素化ブチルゴム（Ｃｌ−ＩＩＲ）などのハロゲン化ブチルゴム（Ｘ−ＩＩＲ）、ブチルゴム（ＩＩＲ）などが挙げられる。 Examples of the butyl rubber include halogenated butyl rubber (X-IIR) such as brominated butyl rubber (Br-IIR) and chlorinated butyl rubber (Cl-IIR), and butyl rubber (IIR).
イソプレン系ゴムとしては、イソプレンゴム（ＩＲ）、天然ゴム（ＮＲ）、改質天然ゴム等が挙げられる。ＮＲには、脱タンパク質天然ゴム（ＤＰＮＲ）、高純度天然ゴム（ＨＰＮＲ）も含まれ、改質天然ゴムとしては、エポキシ化天然ゴム（ＥＮＲ）、水素添加天然ゴム（ＨＮＲ）、グラフト化天然ゴム等が挙げられる。また、ＮＲとしては、例えば、ＳＩＲ２０、ＲＳＳ♯３、ＴＳＲ２０等、タイヤ工業において一般的なものを使用できる。 Examples of the isoprene-based rubber include isoprene rubber (IR), natural rubber (NR), and modified natural rubber. NR includes deproteinized natural rubber (DPNR) and high-purity natural rubber (HPNR). Modified natural rubber includes epoxidized natural rubber (ENR), hydrogenated natural rubber (HNR), and grafted natural rubber. Etc. Moreover, as NR, what is common in tire industry, such as SIR20, RSS # 3, TSR20, can be used, for example.
上記ゴム成分のなかでも、耐空気透過性に優れるという理由から、ブチル系ゴム（好ましくはＸ−ＩＩＲ）が好ましく、イソプレン系ゴム（好ましくはＮＲ）及びブチル系ゴム（好ましくはＸ−ＩＩＲ）を併用することがより好ましい。特に、ＮＲとＸ−ＩＩＲを併用した場合に、耐空気透過性、低燃費性、成形加工性をよりバランスよく向上できる。 Among the rubber components, a butyl rubber (preferably X-IIR) is preferable because of excellent air permeation resistance, and isoprene rubber (preferably NR) and butyl rubber (preferably X-IIR) are preferable. It is more preferable to use together. In particular, when NR and X-IIR are used in combination, air permeation resistance, low fuel consumption, and moldability can be improved in a more balanced manner.
ゴム成分１００質量％中のブチル系ゴムの含有量は、好ましくは７０質量％以上、より好ましくは７５質量％以上である。７０質量％未満であると、耐空気透過性が充分に得られない傾向がある。該ブチル系ゴムの含有量は、１００質量％であってもよいが、好ましくは９０質量％以下、より好ましくは８５質量％以下である。９０質量％を超えると、低燃費性、成形加工性が低下する傾向がある。 The content of butyl rubber in 100% by mass of the rubber component is preferably 70% by mass or more, more preferably 75% by mass or more. If it is less than 70% by mass, the air permeation resistance tends to be insufficient. The content of the butyl rubber may be 100% by mass, but is preferably 90% by mass or less, more preferably 85% by mass or less. If it exceeds 90% by mass, fuel economy and molding processability tend to decrease.
ゴム成分１００質量％中のイソプレン系ゴムの含有量は、好ましくは１０質量％以上、より好ましくは１５質量％以上である。１０質量％未満であると、低燃費性、成形加工性が低下する傾向がある。該イソプレン系ゴムの含有量は、好ましくは３０質量％以下、より好ましくは２５質量％以下である。３０質量％を超えると、耐空気透過性が充分に得られない傾向がある。 The content of the isoprene-based rubber in 100% by mass of the rubber component is preferably 10% by mass or more, more preferably 15% by mass or more. If it is less than 10% by mass, fuel economy and molding processability tend to decrease. The content of the isoprene-based rubber is preferably 30% by mass or less, more preferably 25% by mass or less. When it exceeds 30% by mass, there is a tendency that sufficient air permeation resistance cannot be obtained.
本発明のインナーライナー用ゴム組成物中に含有される瀝青炭（ｂｉｔｕｍｉｏｕｓ ｃｏａｌ）は、石炭一般を含む。このような瀝青炭は、粉砕物としてインナーライナー用ゴム組成物に含有される。 The bituminous coal contained in the rubber composition for an inner liner of the present invention includes coal in general. Such bituminous coal is contained in the rubber composition for an inner liner as a pulverized product.
瀝青炭粉砕物の平均粒径は、０．１ｍｍ以下であり、好ましくは０．０５ｍｍ以下、より好ましくは０．０１ｍｍ以下である。０．１ｍｍを超えると、ゴム組成物のヒステリシスロスが充分に低減されず、低燃費性を充分に向上できない。また、耐空気透過性も充分に向上できない。瀝青炭粉砕物の平均粒径の下限は特に限定されないが、好ましくは０．００１ｍｍ以上である。０．００１ｍｍ未満では、コストが高くなる傾向がある。
なお、瀝青炭粉砕物の平均粒径は、ＪＩＳ Ｚ ８８１５−１９９４に準拠して測定される粒度分布から算出された質量基準の平均粒径である。
The average particle size of the bituminous coal pulverized product is 0.1 mm or less, preferably 0.05 mm or less, more preferably 0.01 mm or less. If it exceeds 0.1 mm, the hysteresis loss of the rubber composition is not sufficiently reduced, and the fuel efficiency cannot be sufficiently improved. Further, the air permeation resistance cannot be sufficiently improved. Although the minimum of the average particle diameter of a bituminous coal ground material is not specifically limited, Preferably it is 0.001 mm or more. If it is less than 0.001 mm, the cost tends to increase.
The average particle size of the pulverized bituminous coal is a mass-based average particle size calculated from a particle size distribution measured according to JIS Z 8815-1994.
瀝青炭粉砕物の比重は、１．６以下が好ましく、１．５以下がより好ましく、１．３以下が更に好ましい。１．６を超えると、ゴム組成物全体の比重が増加し、タイヤの低燃費性向上が充分に図れないおそれがある。瀝青炭粉砕物の比重は、０．５以上が好ましく、１．０以上がより好ましい。０．５未満であると、混練時の加工性が悪化するおそれがある。 The specific gravity of the pulverized bituminous coal is preferably 1.6 or less, more preferably 1.5 or less, and even more preferably 1.3 or less. When it exceeds 1.6, the specific gravity of the whole rubber composition increases, and there is a possibility that the fuel efficiency of the tire cannot be sufficiently improved. The specific gravity of the pulverized bituminous coal is preferably 0.5 or more, and more preferably 1.0 or more. If it is less than 0.5, the workability during kneading may be deteriorated.
瀝青炭粉砕物の含有量は、ゴム成分１００質量部に対して、５質量部以上、好ましくは１０質量部以上である。５質量部未満であると、瀝青炭粉砕物配合による充分な効果が得られない。上記瀝青炭粉砕物の含有量は、７０質量部以下、好ましくは６０質量部以下である。７０質量部を超えると、混練時の加工性が悪化するおそれがある。 The content of the bituminous coal pulverized product is 5 parts by mass or more, preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 5 parts by mass, a sufficient effect by blending the bituminous coal pulverized product cannot be obtained. Content of the said bituminous coal ground material is 70 mass parts or less, Preferably it is 60 mass parts or less. When it exceeds 70 mass parts, there exists a possibility that the workability at the time of kneading | mixing may deteriorate.
本発明では、混合樹脂が使用される。混合樹脂とは、２種以上の樹脂の混合物のことをいう。混合樹脂に使用する樹脂としては、たとえば、フェノール性粘着樹脂、クロマン樹脂、インデン樹脂、クロマンインデン樹脂などの芳香族炭化水素系樹脂、Ｃ５、Ｃ８、Ｃ９などの脂肪族炭化水素系樹脂などがあげられ、これらのなかから２種以上を選択して混合したものを使用することができる。なかでも、芳香族炭化水素系樹脂と脂肪族炭化水素系樹脂との組み合わせが好ましい。 In the present invention, a mixed resin is used. A mixed resin refers to a mixture of two or more resins. The resin used for the mixed resin, e.g., phenolic tackifier resins, chroman resins, indene resins, Black aromatic hydrocarbon resins such as indene resins, C 5, C 8, aliphatic hydrocarbon resins such as C 9 A mixture of two or more selected from these can be used. Among these, a combination of an aromatic hydrocarbon resin and an aliphatic hydrocarbon resin is preferable.
混合樹脂としては、具体的には、ストラクトール社製のストラクトール４０ＭＳ、ラインケミー社（Ｒｈｅｉｎ Ｃｈｅｍｉｅ Ｃｏｒｐ．）製のレノジン１４５Ａ、フローポリマー社（Ｆｌｏｗ Ｐｏｌｙｍｅｒｓ Ｉｎｃ．）製のプロミックス４００などがあげられる。 Specific examples of the mixed resin include STRACTOL 40MS manufactured by STRECTOL, RENODIN 145A manufactured by RHEIN CHEMIE CORP, and PROMIX 400 manufactured by FLOW POLYMERS INC. .
混合樹脂の含有量は、ゴム成分１００質量部に対して、１質量部以上、好ましくは２質量部以上である。１質量部未満であると、混合樹脂配合による充分な効果が得られない。上記混合樹脂の含有量は、２０質量部以下、好ましくは１８質量部以下である。２０質量部を超えると、混練ゴムの粘度が著しく低下し、成形加工性が悪化するおそれがある。 Content of mixed resin is 1 mass part or more with respect to 100 mass parts of rubber components, Preferably it is 2 mass parts or more. If it is less than 1 part by mass, a sufficient effect due to the blended resin cannot be obtained. Content of the said mixed resin is 20 mass parts or less, Preferably it is 18 mass parts or less. When it exceeds 20 parts by mass, the viscosity of the kneaded rubber is remarkably lowered, and the moldability may be deteriorated.
本発明では、カーボンブラックを使用することが好ましい。使用できるカーボンブラックとしては、ＧＰＦ、ＦＥＦ、ＨＡＦ、ＩＳＡＦ、ＳＡＦなどが挙げられるが、特に限定されない。カーボンブラックを配合することにより、補強性を高めることができ、耐破壊強度を向上できる。 In the present invention, it is preferable to use carbon black. Examples of carbon black that can be used include GPF, FEF, HAF, ISAF, and SAF, but are not particularly limited. By blending carbon black, the reinforcing property can be enhanced and the fracture resistance can be improved.
カーボンブラックのチッ素吸着比表面積（Ｎ２ＳＡ）は、耐亀裂成長性に優れるという理由から、１０ｍ２／ｇ以上が好ましく、２０ｍ２／ｇ以上がより好ましい。また、カーボンブラックのチッ素吸着比表面積は、低発熱性に優れるという理由から、５０ｍ２／ｇ以下が好ましく、４０ｍ２／ｇ以下がより好ましい。
なお、カーボンブラックのチッ素吸着比表面積は、ＪＩＳ Ｋ６２１７のＡ法によって求められる。
The nitrogen adsorption specific surface area (N 2 SA) of carbon black is preferably 10 m 2 / g or more, more preferably 20 m 2 / g or more, because it has excellent crack growth resistance. Further, the nitrogen adsorption specific surface area of carbon black, for the reason that low heat build-up property is superior, preferably 50 m 2 / g or less, 40 m 2 / g or less is more preferable.
In addition, the nitrogen adsorption specific surface area of carbon black is calculated | required by A method of JISK6217.
本発明のゴム組成物がカーボンブラックを含有する場合、カーボンブラックの含有量は、ゴム成分１００質量部に対して、好ましくは２０質量部以上、より好ましくは３０質量部以上である。２０質量部未満であると、充分な補強性が得られない傾向がある。また、ムーニー粘度が低くなり、加硫中にゴムがプライコード間に流出する現象が生じやすく、成形加工性が悪化するおそれがある。また、該カーボンブラックの含有量は、好ましくは６０質量部以下、より好ましくは５０質量部以下である。６０質量部を超えると、発熱が大きくなる傾向がある。 When the rubber composition of the present invention contains carbon black, the content of carbon black is preferably 20 parts by mass or more, more preferably 30 parts by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 20 parts by mass, sufficient reinforcing properties tend not to be obtained. In addition, the Mooney viscosity becomes low, and a phenomenon that rubber flows out between the ply cords during vulcanization tends to occur, which may deteriorate the molding processability. Further, the carbon black content is preferably 60 parts by mass or less, more preferably 50 parts by mass or less. When it exceeds 60 parts by mass, the heat generation tends to increase.
瀝青炭粉砕物とカーボンブラックの合計含有量は、ゴム成分１００質量部に対して、好ましくは４０質量部以上、より好ましくは５５質量部以上である。４０質量部未満であると、補強性が低下し、耐久性が悪化してしまうおそれがある。また、該合計含有量は、好ましくは１００質量部以下、より好ましくは９０質量部以下、更に好ましくは８０質量部以下である。１００質量部を超えると、混練加工性が悪化し、分散性が悪化するおそれがある。 The total content of the bituminous coal pulverized product and carbon black is preferably 40 parts by mass or more, and more preferably 55 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 40 parts by mass, the reinforcing property may be lowered and the durability may be deteriorated. The total content is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and still more preferably 80 parts by mass or less. If it exceeds 100 parts by mass, the kneading processability is deteriorated and the dispersibility may be deteriorated.
本発明のゴム組成物には、前記成分以外にも、ゴム組成物の製造に一般に使用される配合剤、例えば、シリカ、炭酸カルシウム、クレー等の補強用充填剤、酸化亜鉛、ステアリン酸、各種老化防止剤、オイル等の軟化剤、ワックス、硫黄等の加硫剤、加硫促進剤などを適宜配合することができる。 In addition to the above components, the rubber composition of the present invention includes compounding agents generally used in the production of rubber compositions, for example, reinforcing fillers such as silica, calcium carbonate, clay, zinc oxide, stearic acid, various Anti-aging agents, softeners such as oil, vulcanizing agents such as wax and sulfur, vulcanization accelerators, and the like can be appropriately blended.
酸化亜鉛の含有量は、ゴム成分１００質量部に対して、好ましくは０．５質量部以上、より好ましくは０．７質量部以上である。０．５質量部未満であると、耐空気透過性は向上するものの、シート押出時の平坦性と低燃費性が悪化する傾向がある。上記酸化亜鉛の含有量は、好ましくは１．５質量部以下、より好ましくは１．３質量部以下である。１．５質量部を超えると、架橋密度が上がり、低燃費性が向上する傾向がある。その一方で、酸化亜鉛の量が多いために酸化亜鉛の未分散塊が多く存在し、練り時の焼けが発生しやすく、焼け部は凹凸の原因となり、シートの平坦性を悪化させる傾向がある。更に、酸化亜鉛の大きな未分散塊の周囲には空隙が存在しやすく空気が流動しやすいため、耐空気透過性も低下する傾向がある。
酸化亜鉛の含有量が上記範囲内であると、耐空気透過性、低燃費性、成形加工性をよりバランスよく向上できる。
The content of zinc oxide is preferably 0.5 parts by mass or more, more preferably 0.7 parts by mass or more with respect to 100 parts by mass of the rubber component. When the content is less than 0.5 parts by mass, the air permeation resistance is improved, but the flatness and low fuel consumption during sheet extrusion tend to deteriorate. The zinc oxide content is preferably 1.5 parts by mass or less, more preferably 1.3 parts by mass or less. When it exceeds 1.5 parts by mass, the crosslinking density increases and the fuel efficiency tends to be improved. On the other hand, since there is a large amount of zinc oxide, there are many undispersed lumps of zinc oxide, which tends to cause burning at the time of kneading, and the burned portion tends to cause unevenness and tends to deteriorate the flatness of the sheet. . Furthermore, since air gaps are likely to exist around the large undispersed mass of zinc oxide and air easily flows, the air permeation resistance tends to be lowered.
When the content of zinc oxide is within the above range, the air permeation resistance, the fuel efficiency and the moldability can be improved in a balanced manner.
本発明のゴム組成物の製造方法としては、公知の方法を用いることができ、例えば、前記各成分をオープンロール、バンバリーミキサーなどのゴム混練装置を用いて混練し、その後加硫する方法等により製造できる。 As a method for producing the rubber composition of the present invention, a known method can be used. For example, the above components are kneaded using a rubber kneader such as an open roll or a Banbury mixer, and then vulcanized. Can be manufactured.
本発明のゴム組成物は、インナーライナーに好適に使用できる。
インナーライナーとは、タイヤ内腔面をなすように形成される部材であり、この部材により、空気透過量を低減して、タイヤ内圧を保持することができる。具体的には、特開２００８−２９１０９１号公報の図１、特開２００７−１６０９８０号公報の図１〜２などに示される部材である。
The rubber composition of the present invention can be suitably used for an inner liner.
The inner liner is a member formed so as to form a tire lumen surface, and by this member, the air permeation amount can be reduced and the tire internal pressure can be maintained. Specifically, it is a member shown in FIG. 1 of JP 2008-291091 A, FIGS. 1-2 of JP 2007-160980 A, and the like.
本発明の空気入りタイヤは、上記ゴム組成物を用いて通常の方法によって製造できる。すなわち、ゴム組成物を未加硫の段階でインナーライナーの形状に合わせて押し出し加工し、タイヤ成形機上にて通常の方法にて成形し、他のタイヤ部材とともに貼り合わせ、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してタイヤを製造できる。 The pneumatic tire of the present invention can be produced by a usual method using the rubber composition. That is, the rubber composition is extruded in accordance with the shape of the inner liner at an unvulcanized stage, molded by a normal method on a tire molding machine, and bonded together with other tire members to form an unvulcanized tire. Form. This unvulcanized tire can be heated and pressurized in a vulcanizer to produce a tire.
実施例に基づいて、本発明を具体的に説明するが、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 specifically described based on examples, but the present invention is not limited to these examples.
以下、参考例、実施例及び比較例で使用した各種薬品について、まとめて説明する。
ハロゲン化ブチルゴム：エクソン化学（株）製のクロロブチルゴム１０６６（塩素化ブチルゴム）
ＮＲ：ＴＳＲ２０
カーボンブラック：三菱化学（株）製のダイアブラックＮ６６０（Ｎ２ＳＡ：２８ｍ２／ｇ、ＤＢＰ：８４ｍｌ／１００ｇ）
瀝青炭粉砕物１：Ｃｏａｌ Ｆｉｌｌｅｒｓ Ｉｎｃ社製のオースチンブラック３２５（平均粒径：０．００５ｍｍ、比重：１．３）
瀝青炭粉砕物２：Ｃｏａｌ Ｆｉｌｌｅｒｓ Ｉｎｃ社製のオースチンブラック３２５（平均粒径：０．１０ｍｍ、比重：１．３）
瀝青炭粉砕物３：Ｃｏａｌ Ｆｉｌｌｅｒｓ Ｉｎｃ社製のオースチンブラック３２５（平均粒径：０．２０ｍｍ、比重：１．３）
混合樹脂：シルアンドザイラリー社製のストラクトール４０ＭＳ（芳香族炭化水素系樹脂と脂肪族炭化水素系樹脂の混合物）
Ｃ５樹脂：丸善石油化学（株）製のマルカレッツＴ−１００ＡＳ（Ｃ５単一樹脂）
酸化亜鉛：三井金属鉱業（株）製の亜鉛華１号
ステアリン酸：日油（株）製のステアリン酸「椿」
プロセスオイル：出光興産（株）製のダイアナプロセスＰＡ３２
硫黄：軽井沢硫黄（株）製の粉末硫黄
加硫促進剤：大内新興化学工業（株）製のノクセラーＭＢＴＳ
Hereinafter, various chemicals used in Reference Examples, Examples and Comparative Examples will be described together.
Halogenated butyl rubber: Chlorobutyl rubber 1066 (chlorinated butyl rubber) manufactured by Exxon Chemical Co., Ltd.
NR: TSR20
Carbon Black: Dia Black N660 manufactured by Mitsubishi Chemical Corporation (N 2 SA: 28 m 2 / g, DBP: 84 ml / 100 g)
Bituminous coal pulverized product 1: Austin Black 325 (average particle size: 0.005 mm, specific gravity: 1.3) manufactured by Coal Fillers Inc.
Bituminous coal pulverized product 2: Austin Black 325 manufactured by Coal Fillers Inc (average particle size: 0.10 mm, specific gravity: 1.3)
Bituminous coal pulverized product 3: Austin Black 325 (average particle size: 0.20 mm, specific gravity: 1.3) manufactured by Coal Fillers Inc.
Mixed resin: Stractol 40MS (mixture of aromatic hydrocarbon resin and aliphatic hydrocarbon resin) manufactured by Sil and Zylary
C5 resin: Marukaretsu T-100AS (C5 single resin) manufactured by Maruzen Petrochemical Co., Ltd.
Zinc oxide: Zinc Hana No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Stearic acid: Stearic acid “Kashiwa” manufactured by NOF Corporation
Process oil: Diana process PA32 manufactured by Idemitsu Kosan Co., Ltd.
Sulfur: Powder sulfur vulcanization accelerator manufactured by Karuizawa Sulfur Co., Ltd .: Noxeller MBTS manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
参考例１〜７、実施例７、９及び比較例１〜８
表１に示す配合処方にしたがい、１．７Ｌバンバリーミキサーを用いて、硫黄及び加硫促進剤以外の材料を１５０℃の条件下で４分間混練りし、混練り物を得た。次に、得られた混練り物に硫黄及び加硫促進剤を添加し、オープンロールを用いて、８０℃の条件下で３分間練り込み、未加硫ゴム組成物を得た。得られた未加硫ゴム組成物を１５０℃で３０分間加硫し、加硫ゴム組成物を得た。
また、得られた未加硫ゴム組成物をインナーライナーの形状に成形した後、他のタイヤ部材と貼り合わせて、１６０℃で２０分間加硫することにより、試験用タイヤ（空気入りタイヤ）（タイヤサイズ：１９５／６５Ｒ１５）を製造した。
Reference Examples 1-7, Examples 7, 9 and Comparative Examples 1-8
In accordance with the formulation shown in Table 1, materials other than sulfur and a vulcanization accelerator were kneaded for 4 minutes at 150 ° C. using a 1.7 L Banbury mixer to obtain a kneaded product. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded for 3 minutes at 80 ° C. using an open roll to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was vulcanized at 150 ° C. for 30 minutes to obtain a vulcanized rubber composition.
Moreover, after molding the obtained unvulcanized rubber composition into the shape of an inner liner, it is bonded to another tire member, and vulcanized at 160 ° C. for 20 minutes, whereby a test tire (pneumatic tire) ( Tire size: 195 / 65R15) was produced.
得られた未加硫ゴム組成物、加硫ゴム組成物、試験用タイヤについて下記の評価を行った。結果を表１に示す。 The following evaluation was performed about the obtained unvulcanized rubber composition, the vulcanized rubber composition, and the test tire. The results are shown in Table 1.
（成形加工性指数）
ＪＩＳ Ｋ６３００に準じて、１３０℃における未加硫ゴム組成物のムーニー粘度ＭＬ（１＋４）を測定した。そして、測定したムーニー粘度の値と、シート加工性（シート作成時の焼け性、シートの平坦性）とを総合的に評価した。結果は、比較例１の成形加工性を１００として指数表示した。指数が１００より小さいと、成形時のゲージ（ゴムの厚み）が不安定となり、成形加工性に劣る。
(Molding processability index)
The Mooney viscosity ML (1 + 4) of the unvulcanized rubber composition at 130 ° C. was measured according to JIS K6300. And the value of the measured Mooney viscosity and sheet workability (burnability at the time of sheet preparation, sheet flatness) were evaluated comprehensively. The results are shown as an index with the molding processability of Comparative Example 1 as 100. When the index is smaller than 100, the gauge (rubber thickness) at the time of molding becomes unstable and the molding processability is poor.
（低燃費性指数）
（株）岩本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％、動歪振幅１％および周波数１０Ｈｚの条件下で、７０℃における加硫ゴム組成物のヒステリシスロス（ｔａｎδ）を測定した。比較例１のｔａｎδを１００として、下記計算式により指数表示した。指数が大きいほど転がり抵抗性（低燃費性）が優れる。
（低燃費性指数）＝（比較例１のｔａｎδ）／（各配合のｔａｎδ）×１００
(Low fuel consumption index)
Using a viscoelastic spectrometer manufactured by Iwamoto Seisakusho, the hysteresis loss (tan δ) of the vulcanized rubber composition at 70 ° C. was measured under conditions of an initial strain of 10%, a dynamic strain amplitude of 1% and a frequency of 10 Hz. . The tan δ of Comparative Example 1 was set to 100, and the index was displayed by the following calculation formula. The higher the index, the better the rolling resistance (low fuel consumption).
(Low fuel consumption index) = (tan δ of Comparative Example 1) / (tan δ of each formulation) × 100
（耐空気透過性指数）
得られた試験用タイヤをリム組みしたのち、内圧を２００ｋＰａに設定した。内圧封じ込めの条件で３ヶ月放置し、タイヤの内圧の低下をタイヤ内圧低下率（％／月）として測定した。
比較例１の内圧低下率を１００として、下記計算式により指数表示した。指数が大きいほど空気保持性能（耐空気透過性）が優れる。
（耐空気透過性指数）＝（比較例１の内圧低下率）／（各配合の内圧低下率）×１００
(Air permeability resistance index)
After assembling the rim of the obtained test tire, the internal pressure was set to 200 kPa. The tire was left for 3 months under conditions of internal pressure containment, and the decrease in tire internal pressure was measured as the rate of decrease in tire internal pressure (% / month).
The internal pressure reduction rate of Comparative Example 1 was taken as 100, and the index was expressed by the following formula. The larger the index, the better the air retention performance (air permeability resistance).
(Air permeability resistance index) = (Internal pressure reduction rate of Comparative Example 1) / (Internal pressure reduction rate of each formulation) × 100
特定量の平均粒径が０．１ｍｍ以下の瀝青炭粉砕物と、所定量の混合樹脂を含む参考例、実施例は、耐空気透過性、低燃費性、成形加工性をバランスよく向上できた。 The reference examples and examples containing a specific amount of a bituminous coal pulverized product having an average particle size of 0.1 mm or less and a predetermined amount of mixed resin were able to improve the air permeation resistance, fuel efficiency and molding processability in a balanced manner.
一方、特定量の平均粒径が０．１ｍｍ以下の瀝青炭粉砕物と、所定量の混合樹脂を組み合わせなかった比較例では、参考例、実施例に比べて、性能が劣っていた。 On the other hand, in the comparative example in which the specific amount of the bituminous coal pulverized product having an average particle size of 0.1 mm or less and the predetermined amount of the mixed resin were not combined, the performance was inferior compared to the reference example and the example.
参考例２と、比較例３，４を比較すると、特定量の平均粒径が０．１ｍｍ以下の瀝青炭粉砕物と共に所定量の混合樹脂を併用することにより、瀝青炭粉砕物を配合した場合であっても、瀝青炭粉砕物を配合したことによる低燃費性、成形加工性の向上効果（比較例３）を維持しつつ、瀝青炭粉砕物を配合せずに混合樹脂のみを配合した場合（比較例４）よりも優れた耐空気透過性が得られ、耐空気透過性、低燃費性、成形加工性をバランスよく向上できることが分かる。 Comparing Reference Example 2 with Comparative Examples 3 and 4, it was the case where a predetermined amount of mixed resin was used in combination with a bituminous coal pulverized product having a specific average particle size of 0.1 mm or less. However, in the case where only the mixed resin is blended without blending the bituminous coal pulverized product while maintaining the improvement in fuel efficiency and molding processability (Comparative Example 3) by blending the bituminous coal pulverized product (Comparative Example 4). It can be seen that the air permeation resistance superior to that of) is obtained, and the air permeation resistance, low fuel consumption and molding processability can be improved in a balanced manner.
混合樹脂の代わりにＣ５樹脂を用いた比較例８では、耐空気透過性、低燃費性、成形加工性を向上できなかった。 In Comparative Example 8 in which C5 resin was used instead of the mixed resin, the air permeation resistance, low fuel consumption, and molding processability could not be improved.
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