JP6267444B2 - Pneumatic tire - Google Patents
Pneumatic tire Download PDFInfo
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- JP6267444B2 JP6267444B2 JP2013118554A JP2013118554A JP6267444B2 JP 6267444 B2 JP6267444 B2 JP 6267444B2 JP 2013118554 A JP2013118554 A JP 2013118554A JP 2013118554 A JP2013118554 A JP 2013118554A JP 6267444 B2 JP6267444 B2 JP 6267444B2
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- 229920001971 elastomer Polymers 0.000 claims description 29
- 239000005060 rubber Substances 0.000 claims description 29
- 239000004088 foaming agent Substances 0.000 claims description 22
- 238000005187 foaming Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000004156 Azodicarbonamide Substances 0.000 claims description 3
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 claims description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical group NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 3
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 239000003094 microcapsule Substances 0.000 claims 2
- 238000004381 surface treatment Methods 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000005062 Polybutadiene Substances 0.000 description 9
- 229920002857 polybutadiene Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- 239000002174 Styrene-butadiene Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000013585 weight reducing agent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001821 foam rubber Polymers 0.000 description 4
- -1 4,4'-oxobisbenzenesulfonyl Chemical group 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000034 method Methods 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
- 239000008117 stearic acid Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 239000011787 zinc oxide Substances 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
- IGFAHOKFJJCIHD-UHFFFAOYSA-N 4-n-butyl-1-n,1-n-dimethyl-4-n-phenylbenzene-1,4-diamine Chemical compound C=1C=C(N(C)C)C=CC=1N(CCCC)C1=CC=CC=C1 IGFAHOKFJJCIHD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920005683 SIBR Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 239000007822 coupling agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Tires In General (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
本発明は、発泡ゴム層をトレッド部に有する空気入りタイヤに関する。 The present invention relates to a pneumatic tire having a foam rubber layer in a tread portion.
近年、自動車の低燃費化のため、タイヤの軽量化を行うことが要求されているため、タイヤの軽量化の手段として、トレッド部に発泡ゴム層を有する空気入りタイヤが製造、市販されている。トレッド部に使用した発泡ゴムの気泡が、水の膜を取り除き、路面との接地を安定化させる。この発泡ゴムは、ソリッドゴムに熱分解型発泡剤を添加し、加硫することで得ることができる(特許文献1)。 In recent years, there has been a demand for reducing the weight of tires in order to reduce the fuel consumption of automobiles. As a means for reducing the weight of tires, pneumatic tires having a foamed rubber layer in the tread portion have been manufactured and marketed. . The foamed rubber bubbles used in the tread remove the water film and stabilize the contact with the road surface. This foamed rubber can be obtained by adding a pyrolytic foaming agent to solid rubber and vulcanizing it (Patent Document 1).
しかしながら、平均粒径が10μmを超える汎用の大粒径発泡剤を使用すると、発泡剤の粒内の熱分布が不均一となり、発泡剤の熱分解が不均一に起こるため、円形率が低下する。その結果、発泡の角になった部分が破壊起点となり、タイヤに必要とされる耐摩耗性を確保できないという問題が生じる。 However, when a general-purpose large particle size foaming agent having an average particle size exceeding 10 μm is used, the heat distribution in the particles of the foaming agent becomes non-uniform and the thermal decomposition of the foaming agent occurs non-uniformly. . As a result, the foamed corner becomes the starting point of breakage, resulting in a problem that the wear resistance required for the tire cannot be ensured.
本発明は、発泡による軽量化効果を損なうことなく、吸水によるウエット制動性能、操縦安定性を高度に両立できる空気入りタイヤを提供することを目的とする。 An object of the present invention is to provide a pneumatic tire that can achieve both high wet braking performance and water handling stability due to water absorption without impairing the weight reduction effect due to foaming.
すなわち、本発明は、発泡ゴム層をトレッド部に用いた空気入りタイヤであって、下記式
で定義される気泡の円形率が0.8〜1.0を満たすことを特徴とする空気入りタイヤに関する。
That is, the present invention is a pneumatic tire using a foamed rubber layer in the tread portion,
It relates to a pneumatic tire characterized in that the circularity of the bubbles defined by the above satisfies 0.8 to 1.0.
発泡ゴム層の発泡が、平均粒径0.5〜12μmの熱分解型発泡剤を使用して形成されたものであることが好ましい。 It is preferable that foaming of the foamed rubber layer is formed using a pyrolytic foaming agent having an average particle size of 0.5 to 12 μm.
熱分解型発泡剤が、アゾジカルボンアミド、N,N’−ジニトロソペンタメチレンテトラミン、4,4’−オキソビスベンゼンスルホニルヒドラジド、または炭酸水素ナトリウムであることが好ましい。 The pyrolytic foaming agent is preferably azodicarbonamide, N, N'-dinitrosopentamethylenetetramine, 4,4'-oxobisbenzenesulfonyl hydrazide, or sodium bicarbonate.
発泡率が10〜50%であることが好ましい。 The foaming rate is preferably 10 to 50%.
本発明の空気入りタイヤであれば、気泡の円形率が0.8〜1.0を満たすため、破壊の開始を防止し、耐摩耗性を確保することができる。よって、発泡による軽量化効果を損なうことなく、吸水によるウエット制動性能、操縦安定性を高度に両立することができ、冬用タイヤだけでなく、一般タイヤにも発泡ゴムをトレッド部に使用することが可能となって、発泡ゴムの吸水効果により、多少の雪道であれば走行できるようになる。 If it is the pneumatic tire of this invention, since the circularity of a bubble satisfy | fills 0.8-1.0, the start of destruction can be prevented and abrasion resistance can be ensured. Therefore, the wet braking performance by water absorption and handling stability can be highly compatible without impairing the weight reduction effect by foaming, and foam rubber should be used for the tread part not only for winter tires but also for general tires. It becomes possible to run on some snowy roads due to the water absorption effect of the foam rubber.
本発明の空気入りタイヤは、下記式
で定義される気泡の円形率が0.8〜1.0を満たすことを特徴とする。
The pneumatic tire of the present invention has the following formula:
It is characterized in that the circularity of the bubbles defined by the above satisfies 0.8 to 1.0.
気泡の円形率は、0.8〜1.0であるが、0.85〜1.0が好ましい。円形率が0.8未満であると、角になっている部分が破壊起点となり、耐摩耗性が低下し、一般タイヤとして必要な耐摩耗性能を確保することが困難となる傾向がある。 The circularity of the bubbles is 0.8 to 1.0, preferably 0.85 to 1.0. If the circularity is less than 0.8, the cornered portion becomes the starting point of fracture, the wear resistance is lowered, and it tends to be difficult to ensure the wear resistance required for a general tire.
発泡ゴム層は、熱分解型発泡剤を用いて製造することが好ましい。熱分解型発泡剤は、マイクロセルラーなどの発泡剤と比べ、加硫後のゴム組成物の物性に影響を与える残滓を生じ難いので、物性に悪影響を与え難くいという特徴がある。 The foamed rubber layer is preferably produced using a pyrolytic foaming agent. Compared with microcellular foaming agents, pyrolytic foaming agents are less likely to produce residues that affect the physical properties of the rubber composition after vulcanization, and are therefore less likely to adversely affect physical properties.
熱分解型化学発泡剤は、平均粒径が0.5〜12μmであることが好ましく、0.5〜10mであることがより好ましく、0.5〜5μmであることがさらに好ましい。発泡剤の平均粒径が12μmを超えると、発泡剤の粒内の熱分布が不均一となり、前記発泡剤の熱分解が不均一に起こり、円形率の低い気泡が生成する傾向がある。また、発泡剤の平均粒径が0.5μm未満であると、粉塵爆発などの危険性があり、発泡剤のハンドリングが困難となり、作業性が著しく低下する傾向がある。 The thermal decomposable chemical foaming agent preferably has an average particle size of 0.5 to 12 μm, more preferably 0.5 to 10 m, and even more preferably 0.5 to 5 μm. When the average particle diameter of the foaming agent exceeds 12 μm, the heat distribution within the foaming agent particles becomes non-uniform, the thermal decomposition of the foaming agent occurs non-uniformly, and there is a tendency that bubbles with a low circularity are generated. If the average particle size of the foaming agent is less than 0.5 μm, there is a risk of dust explosion, handling of the foaming agent becomes difficult, and workability tends to be significantly reduced.
熱分解型化学発泡剤としては、とくに限定されず、たとえばアゾジカルボンアミド、N,N’−ジニトロソペンタメチレンテトラミン、4,4’−オキソビスベンゼンスルホニルヒドラジド、および、炭酸水素ナトリウムが挙げられる。これらの発泡剤は単独でも、複数のものを組み合わせて使用することもできる。 The pyrolytic chemical foaming agent is not particularly limited, and examples thereof include azodicarbonamide, N, N′-dinitrosopentamethylenetetramine, 4,4′-oxobisbenzenesulfonylhydrazide, and sodium hydrogen carbonate. These foaming agents can be used alone or in combination.
熱分解型発泡剤の配合量は、とくに限定されないが、ゴム成分100質量部に対して3〜8質量部が好ましく、4〜7質量部がより好ましい。8質量部を超えると、発泡倍率が大きくなりすぎて、操縦安定性、摩耗性能などを確保できなくなり、3質量部未満では、発泡しなくなり、軽量化、吸水効果を発揮できなくなる傾向がある。 Although the compounding quantity of a thermal decomposition type foaming agent is not specifically limited, 3-8 mass parts is preferable with respect to 100 mass parts of rubber components, and 4-7 mass parts is more preferable. When the amount exceeds 8 parts by mass, the expansion ratio becomes too large, and the steering stability and wear performance cannot be ensured. When the amount is less than 3 parts by mass, foaming does not occur, and there is a tendency that the weight reduction and water absorption effect cannot be exhibited.
本発明のタイヤにおける発泡層において、下記式で定義される発泡率
本発明で使用するゴム組成物が含有するゴム成分としては特に限定されず、例えば、天然ゴム(NR)、イソプレンゴム(IR)、スチレンブタジエンゴム(SBR)、ブタジエンゴム(BR)、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)などのジエン系ゴムが挙げられる。これらは単独で用いてもよいし、2種以上を併用してもよい。なかでも、耐亀裂成長性の改善効果が高いという点から、SBR、BRが好ましく、SBR及びBRの併用がより好ましい。 The rubber component contained in the rubber composition used in the present invention is not particularly limited. For example, natural rubber (NR), isoprene rubber (IR), styrene butadiene rubber (SBR), butadiene rubber (BR), styrene isoprene butadiene. Examples include diene rubbers such as rubber (SIBR), chloroprene rubber (CR), and acrylonitrile butadiene rubber (NBR). These may be used alone or in combination of two or more. Among these, SBR and BR are preferable because the effect of improving crack growth resistance is high, and the combined use of SBR and BR is more preferable.
SBR、BRとしては特に限定されず、タイヤ工業において一般的なものを使用できる。 SBR and BR are not particularly limited, and those common in the tire industry can be used.
ゴム成分100質量%中のSBRの含有量は、好ましくは30質量%以上、より好ましくは45質量%以上、更に好ましくは55質量%以上である。また、SBR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75質量%以下、更に好ましくは65質量%以下である。上記範囲内であれば、本発明の効果が良好に得られる。 The content of SBR in 100% by mass of the rubber component is preferably 30% by mass or more, more preferably 45% by mass or more, and further preferably 55% by mass or more. The SBR content may be 100% by mass, preferably 90% by mass or less, more preferably 75% by mass or less, and still more preferably 65% by mass or less. If it is in the said range, the effect of this invention will be acquired favorably.
ゴム成分100質量%中のBRの含有量は、好ましくは10質量%以上、より好ましくは25質量%以上、更に好ましくは35質量%以上である。また、BRの含有量は、好ましくは70質量%以下、より好ましくは55質量%以下、更に好ましくは45質量%以下である。上記範囲内であれば、本発明の効果が良好に得られる。 The content of BR in 100% by mass of the rubber component is preferably 10% by mass or more, more preferably 25% by mass or more, and further preferably 35% by mass or more. The BR content is preferably 70% by mass or less, more preferably 55% by mass or less, and still more preferably 45% by mass or less. If it is in the said range, the effect of this invention will be acquired favorably.
ゴム成分100質量%中のSBR及びBRの合計含有量は、好ましくは60質量%以上、より好ましくは80質量%以上、更に好ましくは90質量%以上であり、100質量%であってもよい。上記範囲内であれば、本発明の効果が良好に得られる。 The total content of SBR and BR in 100% by mass of the rubber component is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and may be 100% by mass. If it is in the said range, the effect of this invention will be acquired favorably.
本発明に使用するゴム組成物は、ゴム成分以外にゴム組成物の製造に一般に使用される添加剤を適宜配合することができる。添加剤としては、公知のものを用いることができ、硫黄などの加硫剤;チアゾール系加硫促進剤、チウラム系加硫促進剤、スルフェンアミド系加硫促進剤、グアニジン系加硫促進剤などの加硫促進剤;ステアリン酸、酸化亜鉛などの加硫活性化剤;有機過酸化物;カーボンブラック、シリカ、炭酸カルシウム、タルク、アルミナ、クレー、水酸化アルミニウム、マイカなどの充填剤;伸展油、滑剤などの加工助剤;老化防止剤;カップリング剤を例示することができる。 In addition to the rubber component, the rubber composition used in the present invention can be appropriately blended with additives generally used in the production of rubber compositions. Known additives can be used, such as sulfur vulcanizing agents; thiazole vulcanization accelerators, thiuram vulcanization accelerators, sulfenamide vulcanization accelerators, guanidine vulcanization accelerators. Vulcanization accelerators such as stearic acid and zinc oxide; organic peroxides; fillers such as carbon black, silica, calcium carbonate, talc, alumina, clay, aluminum hydroxide, mica; Examples thereof include processing aids such as oils and lubricants; anti-aging agents; and coupling agents.
発泡の形状については、とくに限定されるものではない。発泡ゴム層のトレッド内部の平均気泡径が、トレッド表面部よりも小さいことによって、操縦安定性が要求される夏用タイヤにも適用することができるようになり、また、発泡の吸水効果により、多少の雪道であれば走行可能となる。 The shape of the foam is not particularly limited. Since the average cell diameter inside the tread of the foam rubber layer is smaller than the tread surface part, it can be applied to summer tires that require steering stability, and due to the water absorption effect of foaming, It can be run on some snowy roads.
本発明の空気入りタイヤは、ゴム組成物を用いて通常の方法によって製造される。すなわち、必要に応じてゴム成分に各種添加剤を配合したゴム組成物を、未加硫の段階でタイヤのトレッドの形状に合わせて押し出し加工し、タイヤ成型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発泡させ、本発明の空気入りタイヤを製造することができる。 The pneumatic tire of the present invention is produced by a usual method using a rubber composition. That is, if necessary, a rubber composition in which various additives are blended with a rubber component is extruded in accordance with the shape of the tread of the tire at an unvulcanized stage, and molded by a normal method on a tire molding machine. And it bonds together with another tire member, and forms an unvulcanized tire. This unvulcanized tire can be heated and pressurized in a vulcanizer to be foamed to produce the pneumatic tire of the present invention.
タイヤ用ゴム組成物の加硫工程における加硫圧力はとくに限定されないが、1.0〜5.0MPaが好ましく、1.4〜3.0MPaがより好ましい。また、加硫温度もとくに限定されないが、140〜180℃が好ましく、150〜180℃がより好ましい。 The vulcanization pressure in the vulcanization step of the tire rubber composition is not particularly limited, but is preferably 1.0 to 5.0 MPa, and more preferably 1.4 to 3.0 MPa. The vulcanization temperature is not particularly limited, but is preferably 140 to 180 ° C, and more preferably 150 to 180 ° C.
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.
以下に実施例及び比較例で用いた各種薬品について、まとめて説明する。
SBR::日本ゼオン(株)製のNipol 1502(スチレン量:23.5質量%) 80質量部
BR:宇部興産(株)製のハイシスBR150B 20質量部
カーボンブラック:キャボットジャパン(株)製のショウブラックN220(チッ素吸着比表面積(N2SA):125m2/g) 20質量部
シリカ:デグッサ社製のウルトラシルVN3(チッ素吸着比表面積(N2SA):175m2/g) 80質量部
シランカップリング剤:デグッサ社製のSi69(ビス(3−トリエトキシシリルプロピル)テトラスルフィド) 5質量部
老化防止剤:大内新興化学工業(株)製のノクラック6C(N−1,3−ジメチルブチル−N’−フェニル−p−フェニレンジアミン) 3質量部
ステアリン酸:日油(株)製のステアリン酸 5質量部
オイル:出光興産(株)製のミネラルオイルPW−380 10質量部
酸化亜鉛:三井金属鉱業(株)製の亜鉛華1号 2質量部
ワックス:大内新興化学工業(株)製のサンノックワックス 2質量部
硫黄:鶴見化学工業(株)製の粉末硫黄 2質量部
加硫促進剤1:大内新興化学工業(株)製のノクセラーD(1,3−ジフェニルグアニジン) 0.5質量部
加硫促進剤2:大内新興化学工業(株)製のノクセラーCZ(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) 2質量部
発泡剤1:永和化成工業(株)製のネオセルボンN#1000SW(4,4’−オキソビスベンゼンスルホニルヒドラジド、平均粒径14μm) 5質量部
発泡剤2:永和化成工業(株)製のネオセルボンN#1000M(4,4’−オキソビスベンゼンスルホニルヒドラジド、平均粒径4μm) 5質量部
発泡剤3:永和化成工業(株)製のネオセルボンN#5000(4,4’−オキソビスベンゼンスルホニルヒドラジド、平均粒径12μm) 5質量部
Hereinafter, various chemicals used in Examples and Comparative Examples will be described together.
SBR :: Nipol 1502 manufactured by Nippon Zeon Co., Ltd. (styrene amount: 23.5% by mass) 80 parts by mass BR: Hisys BR150B manufactured by Ube Industries, Ltd. 20 parts by mass Carbon black: Showa manufactured by Cabot Japan Co., Ltd. Black N220 (nitrogen adsorption specific surface area (N 2 SA): 125 m 2 / g) 20 parts by mass Silica: Ultrasil VN3 (nitrogen adsorption specific surface area (N 2 SA): 175 m 2 / g) manufactured by Degussa 80 mass Part Silane coupling agent: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Degussa, Inc. 5 parts by mass anti-aging agent: NOCRACK 6C (N-1,3-made by Ouchi Shinsei Chemical Co., Ltd.) Dimethylbutyl-N′-phenyl-p-phenylenediamine) 3 parts by mass Stearic acid: 5 masses of stearic acid manufactured by NOF Corporation Oil: Mineral oil PW-380 manufactured by Idemitsu Kosan Co., Ltd. 10 parts by mass Zinc oxide: Zinc Hana No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. 2 parts by weight Wax: Sunnock wax manufactured by Ouchi Shinsei Chemical Co., Ltd. 2 parts by mass sulfur: powdered sulfur produced by Tsurumi Chemical Industry Co., Ltd. 2 parts by mass vulcanization accelerator 1: Noxeller D (1,3-diphenylguanidine) produced by Ouchi Shinsei Chemical Industry Co., Ltd. 0.5 parts by mass Sulfur accelerator 2: Noxeller CZ (N-cyclohexyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinsei Chemical Co., Ltd. 2 parts by mass blowing agent 1: Neocerbon N # 1000SW manufactured by Eiwa Kasei Kogyo Co., Ltd. (4,4′-oxobisbenzenesulfonyl hydrazide, average particle size 14 μm) 5 parts by mass blowing agent 2: Neocerbon N # 1000M (4,4′-oxobisbenzenes) manufactured by Eiwa Kasei Kogyo Co., Ltd. E hydrazide, an average particle diameter of 4 [mu] m) 5 parts by weight foaming agent 3: Eiwa Chemical Industry Co., Ltd. Neoserubon N # 5000 (4,4'-oxo-bis benzenesulfonyl hydrazide, average particle size 12 [mu] m) 5 parts by weight
(実施例1、2および比較例1)
表1に示す発泡剤を、ゴム成分100質量部に対して5質量部使用し、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3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、50℃の条件下で5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トレッド形状に成形して、他のタイヤ部材と貼り合わせ、170℃で15分間加硫することにより、各実施例および比較例のタイヤ(タイヤサイズ 195/65R15)を作製した。得られたタイヤを用いて、以下の評価を行った。評価結果を表1に示す。
(Examples 1 and 2 and Comparative Example 1)
5 parts by mass of the foaming agent shown in Table 1 is used with respect to 100 parts by mass of the rubber component, and materials other than sulfur and a vulcanization accelerator are mixed for 3 minutes at 150 ° C. using a 1.7 L Banbury mixer. A kneaded product was obtained by kneading. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded for 5 minutes at 50 ° C. using an open roll to obtain an unvulcanized rubber composition.
The obtained unvulcanized rubber composition was molded into a tread shape, bonded to another tire member, and vulcanized at 170 ° C. for 15 minutes, whereby tires of each example and comparative example (tire size 195 / 65R15). ) Was produced. The following evaluation was performed using the obtained tire. The evaluation results are shown in Table 1.
<気泡の円形度>
得られたタイヤよりトレッドのブロックを切り出し、厚み方向にスライスしたものを、走査型電子顕微鏡(Scanning Electron Microscope:SEM/フィリップ社製XL30 ESEM)を用いて気泡を観察した。このとき観察した気泡を画像解析ソフトImage Jを用いて、1mm×1mmの範囲内にある全ての気泡について気泡周長と気泡面積を測定し、それぞれの円形率を算出し、平均化した。
<Bubble circularity>
From the obtained tire, a tread block was cut out and sliced in the thickness direction, and bubbles were observed using a scanning electron microscope (Scanning Electron Microscope: SEM / XL 30 ESEM manufactured by Philippe). The bubbles observed at this time were measured by using image analysis software Image J, the bubble circumference and bubble area were measured for all the bubbles in the range of 1 mm × 1 mm, and the circularity was calculated and averaged.
(発泡率)
加硫ゴムの固相部の密度/発泡ゴム全体の密度を測定し、下記式により発泡率(%)を算出した。数値が大きいほど、体積あたりの独立気泡が多いことを示す。
(発泡率)=(加硫ゴムの固相部の密度/発泡ゴム全体の密度−1)×100
(Foaming rate)
The density of the solid phase part of the vulcanized rubber / the density of the entire foamed rubber was measured, and the foaming rate (%) was calculated by the following formula. It shows that there are many closed cells per volume, so that a numerical value is large.
(Foaming rate) = (Density of solid phase part of vulcanized rubber / Density of whole foamed rubber-1) × 100
<耐摩耗性>
得られたタイヤを15x6JJのアルミホイールリムにリム組みし、かつ内圧210kPa(前後同一)を充填して、排気量2000ccの国産FF車の4輪自動車に装着し、一般道を走行した後、6ヶ月後の残溝を計測した。実施例1を100とする100点法で指数にて著した。数値が大きいほど良好である。
<Abrasion resistance>
The resulting tire was assembled on a 15x6 JJ aluminum wheel rim, filled with an internal pressure of 210 kPa (same front and rear), mounted on a 4-wheeled automobile with a 2000cc domestic FF vehicle, The remaining groove after a month was measured. It was written by an index by a 100-point method with Example 1 as 100. The larger the value, the better.
実施例1〜2のタイヤでは比較例1のタイヤと比較して、発泡率が同じであるにもかかわらず、気泡の気泡円形率が高く、タイヤの耐摩耗性に優れている。 In comparison with the tire of Comparative Example 1, the tires of Examples 1 and 2 have a high bubble circularity of the bubbles and excellent tire wear resistance, although the foaming rate is the same.
Claims (4)
で定義される気泡の円形率が0.8〜1.0を満たすことを特徴とする空気入りタイヤ。
(但し、熱膨張性マイクロカプセルを配合すると共に、該熱膨張性マイクロカプセルがアルコキシシラン誘導体にて表面処理を施されたものであることを特徴とするタイヤ用ゴム組成物を用いた空気入りタイヤを除く。) A pneumatic tire using a foamed rubber layer for the tread part,
A pneumatic tire characterized by satisfying a circularity ratio of air bubbles of 0.8 to 1.0.
(However, while Blend the thermally expandable microcapsule, pneumatic of heat expandable microcapsules using the rubber composition for a tire which is characterized in that which has been subjected to a surface treatment with alkoxysilane derivatives (Excluding tires.)
The pneumatic tire according to any one of claims 1 to 3, wherein a foaming rate is 10 to 50%.
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