JP2014065799A - Tread rubber composition and pneumatic tire - Google Patents
Tread rubber composition and pneumatic tire Download PDFInfo
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- JP2014065799A JP2014065799A JP2012211087A JP2012211087A JP2014065799A JP 2014065799 A JP2014065799 A JP 2014065799A JP 2012211087 A JP2012211087 A JP 2012211087A JP 2012211087 A JP2012211087 A JP 2012211087A JP 2014065799 A JP2014065799 A JP 2014065799A
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- 241000589158 Agrobacterium Species 0.000 description 2
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- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 description 2
- 244000188595 Brassica sinapistrum Species 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
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- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
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- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
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- NDMBIXHWJKTSRM-UHFFFAOYSA-N triethoxy-[1-(2-triethoxysilylpropyltetrasulfanyl)propan-2-yl]silane Chemical compound CCO[Si](OCC)(OCC)C(C)CSSSSCC(C)[Si](OCC)(OCC)OCC NDMBIXHWJKTSRM-UHFFFAOYSA-N 0.000 description 1
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- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、トレッド用ゴム組成物、及びそれを用いて作製したトレッドを有する空気入りタイヤに関するものである。 The present invention relates to a rubber composition for a tread and a pneumatic tire having a tread produced using the rubber composition.
ゴム用の可塑剤又は軟化剤として、配合物性に優れる芳香族系オイルが一般的に用いられている。しかしながら、芳香族系オイルは多環芳香族成分を含み、発がん性の問題がある。また、将来の化石資源枯渇の問題や、環境へ与える負荷が大きいという問題もある。 As a plasticizer or softener for rubber, aromatic oils excellent in compounding properties are generally used. However, aromatic oils contain a polycyclic aromatic component and have a carcinogenic problem. In addition, there are problems of fossil resource depletion in the future and a heavy load on the environment.
そこで、芳香族系オイルの代替品として、植物油を配合した例が提案されている（特許文献１参照）。しかしながら、芳香族系オイルと同等以上の配合物性を示すには至っていないという点で改善の余地がある。 Then, the example which mix | blended vegetable oil is proposed as a substitute of aromatic oil (refer patent document 1). However, there is room for improvement in that it does not show the same or better blending properties as aromatic oils.
本発明は、前記課題を解決し、石油資源に由来する成分の使用量を低減しながら、低燃費性、耐摩耗性及びフィラー分散性をバランスよく改善できるトレッド用ゴム組成物、及び該ゴム組成物を用いて作製したトレッドを有する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 reduces the amount of components derived from petroleum resources while reducing fuel consumption, wear resistance and filler dispersibility in a balanced manner, and the rubber composition It aims at providing the pneumatic tire which has the tread produced using the thing.
本発明は、ゴム成分と、遺伝的に改変された植物によって生産された植物油とを含有するトレッド用ゴム組成物に関する。 The present invention relates to a rubber composition for a tread containing a rubber component and a vegetable oil produced by a genetically modified plant.
上記植物油の構成脂肪酸１００質量％中のオレイン酸の含有量が８５質量％以上であることが好ましい。 The content of oleic acid in 100% by mass of the constituent fatty acid of the vegetable oil is preferably 85% by mass or more.
本発明はまた、上記ゴム組成物を用いて作製したトレッド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 a tread produced using the rubber composition.
本発明によれば、ゴム成分と、遺伝的に改変された植物によって生産された植物油とを含有するトレッド用ゴム組成物であるので、石油資源に由来する成分である芳香族系オイルの使用量を低減しながら、低燃費性、耐摩耗性及びフィラー分散性がバランスよく改善された空気入りタイヤを提供できる。 According to the present invention, since it is a rubber composition for a tread containing a rubber component and a vegetable oil produced by a genetically modified plant, the amount of aromatic oil used as a component derived from petroleum resources It is possible to provide a pneumatic tire with improved fuel economy, wear resistance, and filler dispersibility in a well-balanced manner while reducing fuel consumption.
本発明のゴム組成物は、ゴム成分と、遺伝的に改変された植物によって生産された植物油とを含有する。 The rubber composition of the present invention contains a rubber component and a vegetable oil produced by a genetically modified plant.
（ゴム成分）
ゴム成分としては特に限定されないが、天然ゴム（ＮＲ）、エポキシ化天然ゴム（ＥＮＲ）などの石油外資源由来のゴムを好適に使用できる。
(Rubber component)
Although it does not specifically limit as a rubber component, Rubber | gum derived from resources other than petroleum, such as natural rubber (NR) and epoxidized natural rubber (ENR), can be used conveniently.
本発明のゴム組成物がＮＲを含有する場合、ゴム成分１００質量％中のＮＲ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、耐摩耗性が悪化したり、脆化温度が高くなる傾向がある。ＮＲの含有量は、好ましくは７０質量％以下、より好ましくは６０質量％以下である。７０質量％をこえると、グリップ性能が低下する傾向がある。 When the rubber composition of the present invention contains NR, the content of NR 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, the wear resistance tends to deteriorate or the embrittlement temperature tends to increase. The content of NR is preferably 70% by mass or less, more preferably 60% by mass or less. When it exceeds 70% by mass, grip performance tends to be lowered.
ＥＮＲのエポキシ化率は、好ましくは５モル％以上、より好ましくは１０モル％以上である。５モル％未満であると、ゴム組成物に対する改質効果が小さい傾向がある。ＥＮＲのエポキシ化率は、好ましくは８０モル％以下、より好ましくは６０モル％以下である。８０モル％をこえると、ポリマー成分がゲル化し易くなる傾向がある。
なお、エポキシ化率とは、エポキシ化前の天然ゴム成分中の炭素間二重結合の全数のうちエポキシ化された数の割合の平均値を意味し、例えば、滴定分析や核磁気共鳴（ＮＭＲ）分析などにより求められる。
The epoxidation rate of ENR is preferably 5 mol% or more, more preferably 10 mol% or more. If it is less than 5 mol%, the modification effect on the rubber composition tends to be small. The epoxidation rate of ENR is preferably 80 mol% or less, more preferably 60 mol% or less. If it exceeds 80 mol%, the polymer component tends to gel easily.
The epoxidation rate means an average value of the ratio of the number of epoxidized out of the total number of carbon-carbon double bonds in the natural rubber component before epoxidation. For example, titration analysis or nuclear magnetic resonance (NMR) ) Required by analysis.
本発明のゴム組成物がＥＮＲを含有する場合、ゴム成分１００質量％中のＥＮＲ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、耐摩耗性が低下する傾向がある。ＥＮＲの含有量は、好ましくは７０質量％以下、より好ましくは６０質量％以下である。７０質量％をこえると、グリップ性能が低下する傾向がある。 When the rubber composition of the present invention contains ENR, the content of ENR 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, the wear resistance tends to decrease. The content of ENR is preferably 70% by mass or less, more preferably 60% by mass or less. When it exceeds 70% by mass, grip performance tends to be lowered.
また、所望に応じて、スチレンブタジエンゴム（ＳＢＲ）、ブタジエンゴム（ＢＲ）、イソプレンゴム（ＩＲ）、ブチルゴム（ＩＩＲ）、アクリロニトリルブタジエンゴム（ＮＢＲ）、エチレンプロピレンジエンゴム（ＥＰＤＭ）、クロロプレンゴム（ＣＲ）などの合成ゴムも使用できる。低燃費性、耐摩耗性及びフィラー分散性をバランスよく改善できるという理由から、合成ゴムとしては、ＢＲ及びＳＢＲからなる群から選ばれる少なくとも１種が好ましく、ＢＲがより好ましい。 If desired, styrene butadiene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), butyl rubber (IIR), acrylonitrile butadiene rubber (NBR), ethylene propylene diene rubber (EPDM), chloroprene rubber (CR Synthetic rubber such as) can also be used. The synthetic rubber is preferably at least one selected from the group consisting of BR and SBR, more preferably BR because the fuel efficiency, wear resistance and filler dispersibility can be improved in a balanced manner.
上記合成ゴムを使用する場合、将来の石油枯渇や環境への配慮から、再生可能な生物由来原料をモノマーとして製造された合成ゴムを使用することが好ましい。このような生物由来原料から製造された合成ゴムは、例えばＢＲの場合、バイオエタノールに触媒を作用させてブタジエンを得て、それを重合するなどの方法により得ることができる。 When the synthetic rubber is used, it is preferable to use a synthetic rubber produced using a renewable bio-derived raw material as a monomer in consideration of future oil depletion and environmental considerations. For example, in the case of BR, a synthetic rubber produced from such a bio-derived raw material can be obtained by a method in which a catalyst is allowed to act on bioethanol to obtain butadiene, which is then polymerized.
本発明のゴム組成物がＢＲを含有する場合、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１５質量％以上である。１０質量％未満であると、耐摩耗性が低下する傾向がある。ＢＲの含有量は、好ましくは７０質量％以下、より好ましくは６０質量％以下である。７０質量％をこえると、低燃費性が低下する傾向がある。 When the rubber composition of the present invention contains BR, the content of BR 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, the wear resistance tends to decrease. The BR content is preferably 70% by mass or less, more preferably 60% by mass or less. If it exceeds 70% by mass, the fuel efficiency tends to decrease.
（植物油）
本発明のゴム組成物は、遺伝的に改変された植物（トランスジェニック植物）によって生産された植物油を含有する。
(Vegetable oil)
The rubber composition of the present invention contains a vegetable oil produced by a genetically modified plant (transgenic plant).
植物油は基本的にトリアシルグリセロール（ＴＡＧ）分子で構成されており、ＴＡＧ分子はグリセロール骨格にエステル化された３本の脂肪酸鎖から構成されている。植物油は、主に食用油として使用されており、栄養上の要請から高不飽和脂肪酸を減らすという目的で、オレイン酸に富むものが求められている。そこで、植物中のオレイン酸合成に関する代謝経路及びこれらの経路のための酵素をコードする遺伝子についての研究がなされてきた。その結果、遺伝子Ｆａｄ２がコードするΔ１２−デサチュラーゼの働きを抑制する事によりオレイン酸の含有量が上昇するという事が、幾つかの植物において認められた。この成果に基づき、遺伝的に改変された植物によりオレイン酸を高含有率で含むヒマワリ油やダイズ油が開発され、既に市販されている。 Vegetable oils are basically composed of triacylglycerol (TAG) molecules, which are composed of three fatty acid chains esterified to the glycerol skeleton. Vegetable oils are mainly used as edible oils, and those rich in oleic acid are required for the purpose of reducing highly unsaturated fatty acids due to nutritional requirements. Thus, studies have been conducted on metabolic pathways for oleic acid synthesis in plants and genes encoding enzymes for these pathways. As a result, it was observed in some plants that the content of oleic acid was increased by suppressing the action of Δ12-desaturase encoded by the gene Fad2. Based on this result, sunflower oil and soybean oil containing oleic acid at a high content have been developed by genetically modified plants and are already on the market.
このように、遺伝的に改変された植物から生産された植物油（以下、遺伝子改変植物油ともいう。）は、通常の植物から得られる植物油とは異なる特性を有する。遺伝子改変植物油を配合することで、低燃費性、耐摩耗性及びフィラー分散性を芳香族系オイルと同等以上に改善することができる。 Thus, a vegetable oil produced from a genetically modified plant (hereinafter also referred to as a genetically modified vegetable oil) has different characteristics from a vegetable oil obtained from a normal plant. By blending the genetically modified vegetable oil, the fuel efficiency, wear resistance and filler dispersibility can be improved to the same or better level as the aromatic oil.
遺伝子の改変には、細胞に遺伝子を導入する際に用いられる公知の形質転換法を採用でき、例えば、目的の遺伝子（標的遺伝子）を構成するＤＮＡを含むプラスミドなどのベクターを導入したアグロバクテリウム属菌を植物細胞に感染させて遺伝子を導入する方法（アグロバクテリウム法）、標的遺伝子を構成するＤＮＡを担持させた金粒子をパーティクルガンにより細胞内に撃ち込む方法（パーティクルガン法）、標的遺伝子を組み込んだベクターを含む溶液中で電圧により細胞膜に孔を開け、そこから当該ベクターを導入する方法（エレクトロポレーション法）などが挙げられる。 For gene modification, a known transformation method used when a gene is introduced into a cell can be employed. For example, Agrobacterium into which a vector such as a plasmid containing a DNA constituting a target gene (target gene) is introduced A method of introducing a gene by infecting a genus fungus into a plant cell (Agrobacterium method), a method of shooting a gold particle carrying a DNA constituting a target gene into a cell by a particle gun (particle gun method), a target gene Examples include a method (electroporation method) in which a hole is made in a cell membrane by a voltage in a solution containing a vector into which is incorporated, and the vector is introduced therefrom.
植物の種類は特に問わないが、生産性が高いという点から、菜種（キャノーラ）、コーン、大豆、ヒマワリ及びコットンが好ましく、キャノーラがより好ましい。 The type of plant is not particularly limited, but rapeseed (canola), corn, soybean, sunflower and cotton are preferable, and canola is more preferable because of high productivity.
植物中の遺伝子の改変箇所についても特に問わないが、オレイン酸の含有量を多く、かつリノール酸及びリノレン酸の含有量を少なくできるという点から、Ｆａｄ２でコードされたΔ１２−デサチュラーゼ及びΔ６−デサチュラーゼからなる群より選択される少なくとも一種の酵素の働きを抑制したものであることが好ましい。 There are no particular restrictions on the gene modification sites in the plant, but Δ12-desaturase and Δ6-desaturase encoded by Fad2 can be used because the content of oleic acid is high and the content of linoleic acid and linolenic acid can be reduced. It is preferable that the action of at least one enzyme selected from the group consisting of is suppressed.
遺伝子改変植物油の構成脂肪酸１００質量％中のオレイン酸の含有量は、好ましくは８５質量％以上である。８５質量％未満であると、低燃費性、耐摩耗性及びフィラー分散性の改善効果が低い傾向がある。オレイン酸の含有量は、好ましくは９５質量％以下、より好ましくは９０質量％以下である。９５質量％を超えると、耐加硫戻り性が悪化する傾向がある。 The content of oleic acid in 100% by mass of the constituent fatty acid of the genetically modified vegetable oil is preferably 85% by mass or more. If it is less than 85% by mass, the effect of improving fuel economy, wear resistance and filler dispersibility tends to be low. The content of oleic acid is preferably 95% by mass or less, more preferably 90% by mass or less. When it exceeds 95% by mass, the reversion resistance is liable to deteriorate.
遺伝子改変植物油の構成脂肪酸１００質量％中のリノール酸の含有量は、好ましくは１５質量％以下、より好ましくは８質量％以下である。１５質量％を超えると、加工性及び耐加硫戻り性が悪化する傾向がある。リノール酸の含有量の下限は特に限定されないが、好ましくは１質量％以上である。 The content of linoleic acid in 100% by mass of the constituent fatty acid of the genetically modified vegetable oil is preferably 15% by mass or less, more preferably 8% by mass or less. When it exceeds 15 mass%, there exists a tendency for workability and vulcanization-resistant return property to deteriorate. Although the minimum of content of linoleic acid is not specifically limited, Preferably it is 1 mass% or more.
遺伝子改変植物油の構成脂肪酸１００質量％中のリノレン酸の含有量は、好ましくは１０質量％以下、より好ましくは５質量％以下である。１０質量％を超えると、加工性及び耐加硫戻り性が悪化する傾向がある。リノレン酸の含有量の下限は特に限定されないが、好ましくは１質量％以上である。 The content of linolenic acid in 100% by mass of the constituent fatty acid of the genetically modified vegetable oil is preferably 10% by mass or less, more preferably 5% by mass or less. If it exceeds 10% by mass, the workability and vulcanization resistance tend to deteriorate. Although the minimum of content of linolenic acid is not specifically limited, Preferably it is 1 mass% or more.
なお、上記脂肪酸組成（オレイン酸、リノール酸、リノレン酸の含有量）は、ＧＬＣ（気−液クロマトグラフィー）により測定できる。 The fatty acid composition (contents of oleic acid, linoleic acid, and linolenic acid) can be measured by GLC (gas-liquid chromatography).
遺伝子改変植物油の含有量は、ゴム成分１００質量部に対して、好ましくは５〜８０質量部である。５質量部未満では充分な軟化効果が得られない傾向があり、また、８０質量部を超えると、加工性が悪化する傾向がある。 The content of the genetically modified vegetable oil is preferably 5 to 80 parts by mass with respect to 100 parts by mass of the rubber component. If the amount is less than 5 parts by mass, a sufficient softening effect tends not to be obtained, and if it exceeds 80 parts by mass, the workability tends to deteriorate.
本発明のゴム組成物は、遺伝子改変植物油を使用しているため、良好な配合物性を確保しながら、芳香族系オイルなどの石油資源に由来するオイルの使用量を低減することができる。全オイル１００質量％中、遺伝子改変植物油の含有量は、好ましくは９５質量％以上、より好ましくは９９質量％以上、更に好ましくは１００質量％である。また、全オイル１００質量％中、石油資源に由来するオイルの含有量は、好ましくは５質量％以下、より好ましくは１質量％以下、更に好ましくは０質量％（実質的に含有しない）である。 Since the rubber composition of the present invention uses genetically modified vegetable oil, the amount of oil derived from petroleum resources such as aromatic oils can be reduced while ensuring good compounding properties. The content of the genetically modified vegetable oil in 100% by mass of the total oil is preferably 95% by mass or more, more preferably 99% by mass or more, and further preferably 100% by mass. The content of oil derived from petroleum resources is preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably 0% by mass (substantially not contained) in 100% by mass of total oil. .
（フィラー）
本発明のゴム組成物は、更に、補強剤（フィラー）を含有してもよい。フィラーとしては特に限定されず、シリカ、カーボンブラックなどが挙げられるが、シリカを使用することが好ましい。シリカとしては、特に制限はなく、例えば、湿式法又は乾式法により調製されたものを使用できる。
(Filler)
The rubber composition of the present invention may further contain a reinforcing agent (filler). The filler is not particularly limited, and examples thereof include silica and carbon black, but it is preferable to use silica. There is no restriction | limiting in particular as a silica, For example, what was prepared by the wet method or the dry process can be used.
本発明のゴム組成物がシリカを含有する場合、シリカの含有量は、ゴム成分１００質量部に対して、好ましくは１５質量部以上、より好ましくは４５質量部以上であり、また、好ましくは１５０質量部以下、より好ましくは１００質量部以下である。上記範囲内であれば、低燃費性、耐摩耗性及びフィラー分散性を高次元でバランスよく改善することができる。 When the rubber composition of the present invention contains silica, the content of silica is preferably 15 parts by mass or more, more preferably 45 parts by mass or more, and preferably 150 parts by mass with respect to 100 parts by mass of the rubber component. It is 100 parts by mass or less, more preferably 100 parts by mass or less. If it is in the said range, low-fuel-consumption property, abrasion resistance, and filler dispersibility can be improved with a high dimension in a well-balanced manner.
また、シリカは、シランカップリング剤と併用することが好ましい。シランカップリング剤としては、従来からタイヤの分野において用いられているものであれば特に制限はないが、例えば、ビス（３−トリエトキシシリルプロピル）テトラスルフィド、ビス（３−トリメトキシシリルプロピル）テトラスルフィド、ビス（２−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エトキシシラン、２−メルカプトエチルトリメトキシシランなどがあげられ、これらをそれぞれ単独で、又は任意に組み合わせて用いることができる。なかでも、シランカップリング剤の補強性効果と加工性が良好であるという点から、ビス（３−トリエトキシシリルプロピル）ジスルフィド、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エトキシシランを用いることが好ましく、更に、加工性が特に良好であるという点から、ビス（３−トリエトキシシリルプロピル）ジスルフィドを用いることがより好ましい。
シランカップリング剤の含有量は、シリカ１００質量部に対して、好ましくは４〜１２質量部である。
Silica is preferably used in combination with a silane coupling agent. The silane coupling agent is not particularly limited as long as it is conventionally used in the tire field. For example, bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) Examples thereof include tetrasulfide, bis (2-triethoxysilylpropyl) tetrasulfide, 3-mercaptopropyltriethoxysilane, and 2-mercaptoethyltrimethoxysilane, and these can be used alone or in any combination. . Among these, bis (3-triethoxysilylpropyl) disulfide, bis (3-triethoxysilylpropyl) tetrasulfide, 3-mercaptopropyltrimethyl are preferred because the reinforcing effect and processability of the silane coupling agent are good. It is preferable to use ethoxysilane, and it is more preferable to use bis (3-triethoxysilylpropyl) disulfide from the viewpoint that processability is particularly good.
The content of the silane coupling agent is preferably 4 to 12 parts by mass with respect to 100 parts by mass of silica.
（その他材料）
本発明のゴム組成物には、前記成分以外にも、従来タイヤ工業で使用される配合剤、例えば、ワックス、老化防止剤、硫黄、加硫促進剤、酸化亜鉛、ステアリン酸などを必要に応じて適宜配合することができる。
(Other materials)
In addition to the above components, the rubber composition of the present invention may contain compounding agents conventionally used in the tire industry, such as waxes, anti-aging agents, sulfur, vulcanization accelerators, zinc oxide, stearic acid and the like as necessary. Can be appropriately blended.
本発明のゴム組成物は、一般的な方法で製造される。すなわち、バンバリーミキサーやニーダー、オープンロールなどで前記各成分を混練りし、その後加硫する方法などにより製造できる。 The rubber composition of the present invention is produced by a general method. That is, it can be produced by a method of kneading the above components with a Banbury mixer, kneader, open roll or the like and then vulcanizing.
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される。すなわち、必要に応じて各種添加剤を配合したゴム組成物を、未加硫の段階で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した後、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 is produced by a usual method using the rubber composition. That is, a rubber composition containing various additives as necessary is extruded in accordance with the shape of the tread at an unvulcanized stage, molded by a normal method on a tire molding machine, and other tires. After bonding together with the members to form an unvulcanized tire, the tire can be manufactured by heating and pressing in a vulcanizer.
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、実施例及び比較例で用いた各種薬品について説明する。
ＮＲ：ＳＩＲ２０
ＥＮＲ：クンプーランガスリー社製のＥＮＲ５０（エポキシ化率：５０モル％）
ＢＲ：宇部興産（株）製のＢＲ１５０Ｂ
ワックス：日本精鑞（株）製のオゾエース０３５５
シリカ：デグッサ社製のＵｌｔｒａｓｉｌ ＶＮ３
シランカップリング剤：デグッサ社製のＳｉ２６６（ビス（３−トリエトキシシリルプロピル）ジスルフィド）
植物油１：Ｄｏｗ ＡｇｒｏＳｃｉｅｎｃｅｓ社製のＮａｔｒｅｏｎキャノーラ油（遺伝子改変植物油、オレイン酸の含有量：７０質量％、リノール酸の含有量：１８質量％、リノレン酸の含有量：７質量％）
植物油２：Ｄｏｗ ＡｇｒｏＳｃｉｅｎｃｅｓ社製のＮａｔｒｅｏｎキャノーラ油（遺伝子改変植物油、オレイン酸の含有量：８５質量％、リノール酸の含有量：８質量％、リノレン酸の含有量：４質量％）
プロセス油：ＪＸ日鉱日石エネルギー（株）製のアロマオイル
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）製の椿
硫黄：鶴見化学（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ＣＺ−Ｇ（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）
老化防止剤：住友化学（株）製のアンチゲン６Ｃ
Hereinafter, various chemicals used in Examples and Comparative Examples will be described.
NR: SIR20
ENR: ENR50 (epoxidation rate: 50 mol%) manufactured by Kungpu Langurs
BR: BR150B manufactured by Ube Industries, Ltd.
Wax: Ozoace 0355 manufactured by Nippon Seiki Co., Ltd.
Silica: Ultrasil VN3 manufactured by Degussa
Silane coupling agent: Si266 (bis (3-triethoxysilylpropyl) disulfide) manufactured by Degussa
Vegetable oil 1: Natreon canola oil manufactured by Dow AgroSciences (genetically modified vegetable oil, oleic acid content: 70 mass%, linoleic acid content: 18 mass%, linolenic acid content: 7 mass%)
Vegetable oil 2: Natreon canola oil manufactured by Dow AgroSciences (genetically modified vegetable oil, oleic acid content: 85 mass%, linoleic acid content: 8 mass%, linolenic acid content: 4 mass%)
Process oil: Aroma oil manufactured by JX Nippon Oil & Energy Co., Ltd. Zinc oxide: Zinc Hua No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Stearic acid: Sulfur manufactured by NOF Corporation: Tsurumi Chemical Co., Ltd. Powder sulfur vulcanization accelerator: Noxeller CZ-G (N-cyclohexyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Anti-aging agent: Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.
＜実施例及び比較例＞
（株）神戸製鋼所製の１．７Ｌのバンバリーミキサーを用いて、表１に示した配合量の薬品のうち、硫黄及び加硫促進剤以外を充填率が５８％になるように投入して、回転数８０ｒｐｍの条件下で、混練機の表示温度が１４０℃になるまで３〜８分間混練りした。なお、シリカについては２回にわけて投入した。この混合物に対して硫黄及び加硫促進剤を加え、オープンロールを用いて、５０℃の条件下で３分間混練りして、未加硫ゴム組成物を得た。得られた未加硫ゴム組成物を、下記の評価に必要なサイズに成形し、１６０℃で２０分間プレス加硫することで、各実施例及び比較例の加硫ゴム組成物を得た。
<Examples and Comparative Examples>
Using a 1.7-L Banbury mixer manufactured by Kobe Steel, Inc., out of the chemicals in the blending amounts shown in Table 1, other than sulfur and vulcanization accelerator were charged so that the filling rate was 58%. The mixture was kneaded for 3 to 8 minutes under the condition of a rotational speed of 80 rpm until the indicated temperature of the kneader reached 140 ° C. Silica was added in two portions. Sulfur and a vulcanization accelerator were added to this mixture and kneaded for 3 minutes at 50 ° C. using an open roll to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was molded into a size necessary for the following evaluation, and press vulcanized at 160 ° C. for 20 minutes to obtain vulcanized rubber compositions of Examples and Comparative Examples.
（転がり抵抗の測定）
加硫ゴム組成物からなる２ｍｍ×１３０ｍｍ×１３０ｍｍのゴムスラブシートを作製し、そこから測定用試験片を切り出し、粘弾性スペクトロメーターＶＥＳ（（株）岩本製作所製）を用いて、温度７０℃、初期歪１０％、動歪２％、周波数１０Ｈｚの条件下で、各測定用試験片のｔａｎδを測定し、比較例１のｔａｎδを１００として、各配合のｔａｎδを指数表示した。指数が大きいほど転がり抵抗が低く、低燃費性に優れることを示す。
(Measurement of rolling resistance)
A rubber slab sheet of 2 mm × 130 mm × 130 mm made of a vulcanized rubber composition was prepared, and a test piece for measurement was cut out from the rubber slab sheet, using a viscoelastic spectrometer VES (manufactured by Iwamoto Seisakusho), at a temperature of 70 ° C., Under the conditions of an initial strain of 10%, a dynamic strain of 2%, and a frequency of 10 Hz, tan δ of each test specimen was measured, and tan δ of each formulation was indicated as an index, with tan δ of Comparative Example 1 being 100. A larger index indicates lower rolling resistance and better fuel efficiency.
（耐摩耗性の測定）
ランボーン摩耗試験機にて、負荷荷重２．５ｋｇ、温度２０℃、スリップ率４０％、試験時間２分間の条件下で、各加硫ゴム組成物から得られたランボーン摩耗試験用試験片のランボーン摩耗量を測定し、比較例１のランボーン摩耗量を１００として、各配合のランボーン摩耗量を指数表示した。指数が大きいほど耐摩耗性に優れることを示す。
(Measurement of wear resistance)
Lambone wear of test pieces for lambone wear test obtained from each vulcanized rubber composition under the conditions of load load of 2.5 kg, temperature of 20 ° C., slip rate of 40%, test time of 2 minutes with a lambbone wear tester The amount was measured, and the amount of lamborn wear of Comparative Example 1 was set to 100, and the amount of lamborn wear of each formulation was displayed as an index. It shows that it is excellent in abrasion resistance, so that an index | exponent is large.
（フィラー分散性の測定）
加硫ゴム組成物からなる２ｍｍ×１３０ｍｍ×１３０ｍｍのゴムスラブシートを作製し、そこから測定用試験片を切り出し、ＪＩＳ Ｋ６８１２に準じて測定用試験片中のシリカの凝集塊をカウントして、比較例１の分散率（％）を１００として、各配合の分散率を指数表示した。指数が大きいほどフィラーが分散しており、良好であることを示す。
(Measurement of filler dispersibility)
A rubber slab sheet of 2 mm × 130 mm × 130 mm made of a vulcanized rubber composition is prepared, and a test piece for measurement is cut out therefrom, and the aggregates of silica in the test piece for measurement are counted according to JIS K6812 for comparison. The dispersion ratio (%) of Example 1 was set to 100, and the dispersion ratio of each formulation was displayed as an index. The larger the index, the better the dispersion of the filler and the better.
表１から、遺伝子改変植物油（植物油１、２）を配合した実施例は、該遺伝子改変植物油の代わりに芳香族系オイル（プロセス油）を配合した比較例と比較して、低燃費性、耐摩耗性及びフィラー分散性がバランスよく改善された。また、植物油２を配合した実施例４〜６、１０〜１２は、植物油１を配合した実施例１〜３、７〜９よりも各性能の改善効果が大きい傾向があった。 From Table 1, the examples in which the genetically modified vegetable oils (vegetable oils 1 and 2) were blended were compared with the comparative examples in which an aromatic oil (process oil) was blended in place of the genetically modified vegetable oils. Abrasion and filler dispersibility were improved in a well-balanced manner. Moreover, Examples 4-6 and 10-12 which mix | blended the vegetable oil 2 had the tendency for the improvement effect of each performance to be larger than Examples 1-3, 7-9 which mix | blended the vegetable oil 1. FIG.
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| JP2014065798A (en) * | 2012-09-25 | 2014-04-17 | Sumitomo Rubber Ind Ltd | Rubber composition for tread of studless tire and studless tire |
| CN108084529A (en) * | 2016-11-23 | 2018-05-29 | 韩国轮胎株式会社 | Rubber composition for tire tread and the tire using said composition manufacture |
| JP2018090789A (en) * | 2016-11-28 | 2018-06-14 | ザ・グッドイヤー・タイヤ・アンド・ラバー・カンパニー | Rubber composition containing specialized soybean oil, and tire with component thereof |
| KR101914359B1 (en) * | 2017-02-01 | 2018-11-01 | 한국타이어 주식회사 | Rubber composition for tire tread and studded tire manufactured by using the same |
| US10179479B2 (en) | 2015-05-19 | 2019-01-15 | Bridgestone Americas Tire Operations, Llc | Plant oil-containing rubber compositions, tread thereof and race tires containing the tread |
| JP2021107505A (en) * | 2019-12-27 | 2021-07-29 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Modified vegetable oil and method for producing the same, and rubber composition and tire |
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