JP5436953B2 - Rubber composition and pneumatic tire - Google Patents
Rubber composition and pneumatic tire Download PDFInfo
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- JP5436953B2 JP5436953B2 JP2009155443A JP2009155443A JP5436953B2 JP 5436953 B2 JP5436953 B2 JP 5436953B2 JP 2009155443 A JP2009155443 A JP 2009155443A JP 2009155443 A JP2009155443 A JP 2009155443A JP 5436953 B2 JP5436953 B2 JP 5436953B2
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Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ゴム組成物に関し、より詳細には、例としてスタッドレスタイヤやスノータイヤなどの冬用タイヤ（ウインタータイヤ）のトレッドに好適に用いることのできるゴム組成物、及び、同ゴム組成物を用いてな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, and more specifically, as an example, a rubber composition that can be suitably used for a tread of a winter tire (winter tire) such as a studless tire or a snow tire, and the rubber composition The present invention relates to a pneumatic tire used.
氷雪路面では一般路面に比べて著しく摩擦係数が低下し滑りやすくなる。そのため、スタッドレスタイヤ等の冬用タイヤのトレッドに用いられるゴム組成物においては、氷上路面での接地性を高めるために、ガラス転移点の低いブタジエンゴム等の使用や軟化剤の配合により、低温でのゴム硬度を低く維持することがなされている。また、氷上摩擦力を高めるために、トレッドに発泡ゴムを使用したり、中空粒子や、ガラス繊維、植物性粒状体等の硬質材料を配合することがなされている。 On snowy and snowy roads, the friction coefficient is significantly lower than that on ordinary roads, making it easier to slip. Therefore, in rubber compositions used for winter tire treads such as studless tires, the use of butadiene rubber with a low glass transition point or blending of a softening agent at low temperatures in order to improve the ground contact on the road surface on ice. The rubber hardness is kept low. In addition, in order to increase the frictional force on ice, foamed rubber is used for the tread, or hard materials such as hollow particles, glass fibers, and vegetable granules are blended.
例えば、下記特許文献１には、もみ殻の粉砕物のようなセルロース物質を含有する平均粒径２０〜６００μｍの粉体加工品をゴム組成物に配合することが開示されている。同文では、高硬度である上記粉体加工品が氷表面を引っ掻くことによりスパイク効果を発揮し、更に摩耗の進行によりトレッド表面から粉体が脱落したときに生じるトレッド表面の空隙、凹凸及びエッジが氷表面との摩擦を高め、氷上グリップ性能を大幅に向上させるとある。 For example, Patent Literature 1 below discloses blending a rubber composition with a powder processed product having an average particle size of 20 to 600 μm containing a cellulose substance such as a crushed rice husk. In the same sentence, the above-mentioned powder processed product with high hardness exerts a spike effect by scratching the ice surface, and further, there are voids, irregularities and edges on the tread surface that occur when the powder falls off the tread surface due to the progress of wear. It increases friction with the ice surface and greatly improves the grip performance on ice.
また、下記特許文献２には、種子の殻又は果実の核を粉砕してなる植物性粒状体などの引っ掻き効果のある粒子をゴム成分に添加して、引っ掻き効果により氷上摩擦性能を向上させることが開示されている。同文献では特に、レゾルシン・ホルマリン樹脂初期縮合物とラテックスの混合物を主成分とするゴム接着性改良剤で植物性粒状体を表面処理し、これによりトレッドゴムと化学的に結合させて、引っ掻き効果を向上する点が提案されている。 Further, in Patent Document 2 below, particles having a scratching effect such as plant granules obtained by pulverizing seed shells or fruit nuclei are added to the rubber component to improve the friction performance on ice by the scratching effect. Is disclosed. In particular, in this document, the plant granule is surface-treated with a rubber adhesion improver mainly composed of a mixture of resorcin / formalin resin initial condensate and latex, thereby chemically bonding to the tread rubber and scratching effect. The point which improves is proposed.
このように氷上性能を向上させるために、セルロース粒子をゴム組成物に配合することは知られているが、従来一般にセルロース粒子は主としてその引っ掻き効果を利用するものであり、氷上の水膜を効果的に除去する空隙率の高い多孔性セルロース粒子の使用は試みられていなかった。 In order to improve the performance on ice in this way, it is known that cellulose particles are blended into a rubber composition, but conventionally cellulose particles mainly utilize the scratching effect, and the water film on ice is effective. No attempt has been made to use porous cellulose particles having a high porosity to be removed.
一方、下記特許文献３には、氷上の水膜を更に効果的に除去するために、平均粒径１０〜５００μｍの竹炭の粉砕物をゴム組成物に配合することが提案されている。 On the other hand, Patent Document 3 below proposes blending a pulverized bamboo charcoal having an average particle size of 10 to 500 μm with a rubber composition in order to more effectively remove a water film on ice.
また、下記特許文献４には、同様に氷上の水膜を除去するために、平均粒径が１００μｍ以下のセルロース微粉末をゴム組成物に配合することが提案されている。しかしながら、この文献においてセルロース微粉末として用いられているのはパルプの粉砕物であり、パルプを粉砕するだけでは、空隙率の高い多孔性セルロース粒子は得られないことから、氷上性能の改良効果が十分とは言えず、更なる改良が求められる。 Further, Patent Document 4 below proposes to blend a fine cellulose powder having an average particle size of 100 μm or less into a rubber composition in order to remove the water film on ice. However, the cellulose fine powder used in this document is a pulverized product of pulp, and porous cellulose particles having a high porosity cannot be obtained simply by pulverizing the pulp. It is not enough and further improvement is required.
上記のように従来、氷上性能を改良するために種々の方策が提案されているものの、最近益々厳しくなる市場の要求に対し、必ずしも十分なレベルに達しているとは言えない。 As described above, various measures have been proposed in order to improve the performance on ice. However, it cannot be said that the level is sufficiently high to meet the increasingly demanding market demands recently.
本発明は、以上の点に鑑みてなされたものであり、優れた氷上性能を発揮することができるゴム組成物、及び空気入りタイヤを提供することを目的とする。 This invention is made | formed in view of the above point, and it aims at providing the rubber composition and pneumatic tire which can exhibit the outstanding performance on ice.
本発明者は、上記課題に鑑み、鋭意検討していく中で、空隙率の高い多孔性セルロース粒子を配合することで氷上性能が著しく向上することを見い出し、本発明を完成するに至った。 In view of the above problems, the present inventor has found that the performance on ice is remarkably improved by blending porous cellulose particles having a high porosity, and has completed the present invention.
すなわち、本発明に係るタイヤトレッド用ゴム組成物は、ジエン系ゴム１００重量部に対し、空隙率が７５〜９５％で平均粒径が１０００μｍ以下の多孔性セルロース粒子を０．３〜２０重量部配合してなるものである。 That is, the tire tread rubber composition according to the present invention has 0.3 to 20 parts by weight of porous cellulose particles having a porosity of 75 to 95% and an average particle size of 1000 μm or less with respect to 100 parts by weight of the diene rubber. It is a blended product.
また、本発明に係る空気入りタイヤは、かかるゴム組成物からなるトレッドを備えるものである。 Moreover, the pneumatic tire according to the present invention includes a tread made of such a rubber composition.
本発明によれば、耐摩耗性の低下を抑えながら、氷上性能を著しく向上することができる。 According to the present invention, the performance on ice can be remarkably improved while suppressing a decrease in wear resistance.
以下、本発明の実施に関連する事項について詳細に説明する。 Hereinafter, matters related to the implementation of the present invention will be described in detail.
本発明のゴム組成物において、ゴム成分として用いられるジエン系ゴムとしては、例えば、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、スチレン−イソプレン共重合体ゴム、ブタジエン−イソプレン共重合体ゴム、スチレン−イソプレン−ブタジエン共重合体ゴムなど、タイヤトレッド用ゴム組成物において通常使用される各種ジエン系ゴムが挙げられる。これらジエン系ゴムは、いずれか１種単独で、又は２種以上ブレンドして用いることができる。 Examples of the diene rubber used as the rubber component in the rubber composition of the present invention include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), and styrene-isoprene. Examples include various diene rubbers that are usually used in rubber compositions for tire treads such as polymer rubber, butadiene-isoprene copolymer rubber, and styrene-isoprene-butadiene copolymer rubber. These diene rubbers can be used alone or in a blend of two or more.
上記ゴム成分として、好ましくは、天然ゴムと他のジエン系ゴムとのブレンドを用いることであり、特に好ましくは、天然ゴム（ＮＲ）とブタジエンゴム（ＢＲ）とのブレンドゴムを用いることである。その場合、ＢＲの比率が少なすぎるとゴム組成物の低温特性が得難くなり、逆に多くなりすぎると加工性の悪化や耐引き裂き抵抗性が低下する傾向になるので、ＮＲ／ＢＲの比率は重量比で３０／７０〜８０／２０、更には４０／６０〜７０／３０程度であることが好ましい。 As the rubber component, a blend of natural rubber and another diene rubber is preferably used, and a blend rubber of natural rubber (NR) and butadiene rubber (BR) is particularly preferably used. In that case, if the ratio of BR is too small, it is difficult to obtain low temperature characteristics of the rubber composition. Conversely, if the ratio is too large, the processability tends to deteriorate and the tear resistance tends to decrease, so the ratio of NR / BR is The weight ratio is preferably about 30/70 to 80/20, more preferably about 40/60 to 70/30.
本発明のゴム組成物には、空隙率７５〜９５％で平均粒径が１０００μｍ以下の多孔性セルロース粒子が配合される。多孔性セルロース粒子は、天然素材で生分解性があり、多孔質構造及び高い化学安定性を持つ特徴から、消臭剤、生ごみ処理基材、タバコフィルター基材などに用いられている。本発明では、かかる空隙率の高い多孔性セルロース粒子をゴム組成物に配合するものであり、例えばスタッドレスタイヤなどの空気入りタイヤのトレッドゴムに用いることにより、氷上性能を著しく向上させることができる。その理由は必ずしも明らかではないが、多孔性セルロース粒子の細孔が氷上路面の水膜を効果的に吸水および除水し、更に、砕けた粒子や細孔壁のエッジにより氷上路面を引っ掻く効果が発揮されるためと推測される。 The rubber composition of the present invention is blended with porous cellulose particles having a porosity of 75 to 95% and an average particle size of 1000 μm or less. Porous cellulose particles are natural materials that are biodegradable, have a porous structure and high chemical stability, and are used in deodorants, garbage treatment substrates, tobacco filter substrates, and the like. In the present invention, porous cellulose particles having such a high porosity are blended in a rubber composition. For example, the performance on ice can be remarkably improved by using for a tread rubber of a pneumatic tire such as a studless tire. The reason for this is not necessarily clear, but the pores of the porous cellulose particles effectively absorb and remove the water film on the ice road surface, and further, the effect of scratching the ice surface by the broken particles and the edge of the pore wall is effective. It is presumed to be demonstrated.
このような多孔性セルロース粒子としては、レンゴー株式会社から「ビスコパール」として市販されており、また、特開２００１−３２３０９５号公報や特開２００４−１１５２８４号公報に記載されており、それらを好適に用いることができる。 Such porous cellulose particles are commercially available as “Viscopar” from Rengo Co., Ltd., and also described in JP-A Nos. 2001-323095 and 2004-115284. Can be used.
詳細には、ビスコース等のアルカリ型セルロース溶液に多孔化剤を加え、セルロースの凝固・再生と多孔化剤による発泡とを同時進行させて得られたセルロース粒子を用いることが好ましい。多孔化剤としては、炭酸カルシウム等の炭酸塩が挙げられ、炭酸塩をアルカリ型セルロース溶液に均一に混合分散し、得られた分散液の液滴を塩酸等の酸性溶液と接触させることにより、酸によってセルロースの凝固・再生と炭酸塩の発泡・分解が同時に進行して、上記のような高い空隙率を持つ多孔性セルロース粒子が得られる。 Specifically, it is preferable to use cellulose particles obtained by adding a porosifying agent to an alkaline type cellulose solution such as viscose and simultaneously coagulating / regenerating cellulose and foaming with the porogen. Examples of the porosifying agent include carbonates such as calcium carbonate. The carbonate is uniformly mixed and dispersed in an alkaline cellulose solution, and droplets of the obtained dispersion are brought into contact with an acidic solution such as hydrochloric acid. By the acid, coagulation / regeneration of cellulose and foaming / decomposition of carbonate proceed simultaneously to obtain porous cellulose particles having a high porosity as described above.
多孔性セルロース粒子の空隙率が７５％未満では、氷上性能の向上効果が不十分である。逆に、多孔性セルロース粒子の空隙率が９５％を超えると、粒子の強度が弱くなり、ゴム成分との混合時に変形したり、破砕しやすくなる。該空隙率は、より好ましくは８５〜９５％である。 When the porosity of the porous cellulose particles is less than 75%, the effect on improving the performance on ice is insufficient. On the contrary, when the porosity of the porous cellulose particles exceeds 95%, the strength of the particles becomes weak, and the porous cellulose particles are easily deformed or crushed when mixed with the rubber component. The porosity is more preferably 85 to 95%.
多孔性セルロース粒子の空隙率は、一定重量の試料（即ち、多孔性セルロース粒子）の体積をメスシリンダーで測定し、嵩比重を求めて、下記式から求めることができる。 The porosity of the porous cellulose particles can be obtained from the following formula by measuring the volume of a sample having a constant weight (that is, porous cellulose particles) with a graduated cylinder and determining the bulk specific gravity.
空隙率［％］＝（空隙体積[ml]）／（試料の嵩体積[ml]）×100
＝｛（試料の嵩体積[ml]）−（試料の実体積[ml]）｝／（試料の嵩体積[ml]）×100
＝｛１−（試料の実体積[ml]）／（試料の嵩体積[ml]）｝×100
＝｛１−（試料の嵩比重[g/ml]）／（試料の真比重[g/ml]）｝×100
ここで、セルロースの真比重は１．５である。
Porosity [%] = (void volume [ml]) / (sample bulk volume [ml]) × 100
= {(Bulk volume of sample [ml])-(Actual volume of sample [ml])} / (Bulk volume of sample [ml]) × 100
= {1- (actual volume of sample [ml]) / (bulk volume of sample [ml])} × 100
= {1- (Sample Bulk Specific Gravity [g / ml]) / (Sample True Specific Gravity [g / ml])} × 100
Here, the true specific gravity of cellulose is 1.5.
多孔性セルロース粒子の粒径は、上記のように平均粒径が１０００μｍ以下のものが用いられ、平均粒径が１０００μｍを超える大粒径のセルロース粒子では、耐摩耗性に劣る。平均粒径の下限は、特に限定されないが、５μｍ以上であることが好ましい。平均粒径は、より好ましくは１００〜８００μｍであり、更に好ましくは２００〜８００μｍである。 As described above, the porous cellulose particles having an average particle size of 1000 μm or less are used, and cellulose particles having a large particle size exceeding 1000 μm have poor wear resistance. Although the minimum of an average particle diameter is not specifically limited, It is preferable that it is 5 micrometers or more. The average particle diameter is more preferably 100 to 800 μm, and further preferably 200 to 800 μm.
多孔性セルロース粒子としては、長径／短径の比が１〜２である球状粒子が好ましく用いられる。このような球状構造の粒子を用いることにより、ゴム組成物中への分散性を向上して、氷上性能の向上や耐摩耗性の維持に寄与することができる。長径／短径の比は、より好ましくは１〜１．５である。 As the porous cellulose particles, spherical particles having a major axis / minor axis ratio of 1 to 2 are preferably used. By using particles having such a spherical structure, it is possible to improve the dispersibility in the rubber composition and contribute to improvement of performance on ice and maintenance of wear resistance. The ratio of major axis / minor axis is more preferably 1 to 1.5.
多孔性セルロース粒子の平均粒径と、長径／短径の比は、次のようにして求められる。すなわち、多孔性セルロース粒子を顕微鏡で観察して画像を得て、この画像を用いて、粒子の長径と短径（長径と短径が同じ場合には、ある軸方向の長さとこれに直交する軸方向の長さ）を１００個の粒子について測定し、その平均値を算出することで平均粒径が得られ、また、長径を短径で割った値の平均値により長径／短径の比が得られる。 The average particle diameter of the porous cellulose particles and the ratio of major axis / minor axis are obtained as follows. That is, an image is obtained by observing the porous cellulose particles with a microscope, and using this image, the major axis and minor axis of the particle (if the major axis and minor axis are the same, the length in a certain axial direction is orthogonal to this. (Length in the axial direction) is measured for 100 particles, and the average value is obtained by calculating the average value, and the ratio of major axis / minor axis is determined by the average value obtained by dividing the major axis by the minor axis. Is obtained.
多孔性セルロース粒子は、ジエン系ゴム１００重量部に対して、０．３〜２０重量部の範囲内で配合することができる。該配合量が０．３重量部未満では、添加効果が不十分であり、逆に２０重量部を超えると、耐摩耗性が悪化する。該配合量は、より好ましくは１〜１５重量部である。 The porous cellulose particles can be blended within a range of 0.3 to 20 parts by weight with respect to 100 parts by weight of the diene rubber. When the blending amount is less than 0.3 parts by weight, the effect of addition is insufficient, and when it exceeds 20 parts by weight, the wear resistance is deteriorated. The blending amount is more preferably 1 to 15 parts by weight.
本発明のゴム組成物には、多孔性セルロース粒子とともに、種子の殻又は果実の核を粉砕してなる植物性粒状体、及び／又は、植物の多孔質性炭化物の粉砕物を更に配合してもよい。これらの植物性粒状体や多孔質性炭化物の粉砕物を併用することにより、氷上性能を更に向上することができる。 The rubber composition of the present invention further contains, together with porous cellulose particles, plant granules obtained by pulverizing seed shells or fruit nuclei and / or pulverized products of plant porous carbides. Also good. The performance on ice can be further improved by using these plant granules and porous carbide pulverized material in combination.
上記植物性粒状体としては、胡桃（クルミ）、椿などの種子の殻、あるいは桃、梅などの果実の核を公知の方法で粉砕してなる粉砕品を用いることができる。これらはモース硬度が２〜５程度であり、氷よりも硬いので、氷上路面に対して引っ掻き効果を発揮することができる。 As the plant granular material, a pulverized product obtained by pulverizing seed husks such as walnuts and persimmons or fruit nuclei such as peaches and plums by a known method can be used. Since these have a Mohs hardness of about 2 to 5 and are harder than ice, they can exhibit a scratching effect on the road surface on ice.
植物性粒状体は、ゴムとのなじみを良くして脱落を防ぐために、ゴム接着性改良剤で表面処理されたものを用いることが好ましい。ゴム接着性改良剤としては、例えば、レゾルシン・ホルマリン樹脂初期縮合物とラテックスの混合物を主成分とするもの（ＲＦＬ液）が挙げられる。 In order to improve the familiarity with rubber and prevent dropping, it is preferable to use a plant granule that has been surface-treated with a rubber adhesion improver. As the rubber adhesion improver, for example, one having a mixture of resorcin / formalin resin initial condensate and latex as a main component (RFL solution) can be mentioned.
植物性粒状体の平均粒径は、特に限定されないが、引っ掻き効果を発揮するとともにトレッドからの脱落を防止するため、１００〜６００μｍであることが好ましい。なお、平均粒径は、レーザ回折・散乱法により測定される値であり、例えば、光源として赤色半導体レーザ（波長６８０ｎｍ）を用いる島津製作所製のレーザ回折式粒度分布測定装置「ＳＡＬＤ−２２００」を用いて測定することができる。 The average particle size of the plant-based granular material is not particularly limited, but is preferably 100 to 600 μm in order to exhibit a scratching effect and prevent the flakes from falling off the tread. The average particle diameter is a value measured by a laser diffraction / scattering method. For example, a laser diffraction particle size distribution measuring apparatus “SALD-2200” manufactured by Shimadzu Corporation using a red semiconductor laser (wavelength 680 nm) as a light source is used. Can be measured.
上記多孔性炭化物の粉砕物は、木、竹などの植物を材料として炭化して得られる炭素を主成分とする固体生成物からなる多孔質性物質を粉砕してなるものであり、中でも竹炭の粉砕物（竹炭粉末）はその特有の多孔質性により優れた吸着性を発揮することから、氷上路面に発生する水膜を効果的に吸水、除去することができる。 The pulverized product of the porous carbide is obtained by pulverizing a porous material composed of a solid product mainly composed of carbon obtained by carbonizing a plant such as wood or bamboo. Since the pulverized product (bamboo charcoal powder) exhibits excellent adsorptivity due to its unique porosity, the water film generated on the road surface on ice can be effectively absorbed and removed.
竹炭の原料となる竹材としては、孟宗竹、苦竹、淡竹、紋竹などの各種の竹のほか、千鳥笹、仙台笹などの笹も含まれる。竹炭粉砕物は、竹材を窯を用いて蒸し焼きにして炭化して得られた竹炭を、公知の粉砕機（例えば、ボールミル）を用いて粉末状に粉砕することにより得ることができる。 Bamboo materials that are used as raw materials for bamboo charcoal include various kinds of bamboo such as 孟 mune bamboo, maitake, pale bamboo, and crested bamboo, as well as bamboo such as chidori and Sendai. The bamboo charcoal pulverized product can be obtained by pulverizing bamboo charcoal obtained by steaming and baking bamboo material using a kiln into a powder using a known pulverizer (for example, a ball mill).
上記多孔性炭化物の粉砕物の平均粒径は、特に限定されないが、１０〜５００μｍであることが好ましい。なお、平均粒径は、植物性粒状体と同様、レーザ回折・散乱法により測定される値である。 The average particle size of the pulverized product of the porous carbide is not particularly limited, but is preferably 10 to 500 μm. The average particle diameter is a value measured by a laser diffraction / scattering method, as in the case of plant granules.
これら植物性粒状体と多孔性炭化物の粉砕物を配合する場合、その配合量は、両者の合計量で、ジエン系ゴム１００重量部に対して、０．３〜２０重量部であることが好ましく、より好ましくは１〜１０重量部である。 When blending the pulverized product of these plant granules and porous carbide, the blending amount of both is preferably 0.3 to 20 parts by weight with respect to 100 parts by weight of the diene rubber. More preferably, it is 1 to 10 parts by weight.
本発明のゴム組成物は、上記した各成分に加え、通常のゴム工業で使用されているカーボンブラックやシリカなどの補強剤や充填剤、プロセスオイル、亜鉛華、ステアリン酸、軟化剤、可塑剤、老化防止剤（アミン−ケトン系、芳香族第２アミン系、フェノール系、イミダゾール系等）、加硫剤、加硫促進剤（グアニジン系、チアゾール系、スルフェンアミド系、チウラム系等）などの配合薬品類を通常の範囲内で適宜配合することができる。 The rubber composition of the present invention comprises, in addition to the above-mentioned components, reinforcing agents and fillers such as carbon black and silica, process oil, zinc white, stearic acid, softener, and plasticizer that are used in ordinary rubber industry. , Anti-aging agent (amine-ketone, aromatic secondary amine, phenol, imidazole, etc.), vulcanizing agent, vulcanization accelerator (guanidine, thiazole, sulfenamide, thiuram, etc.), etc. These compounding chemicals can be appropriately blended within a normal range.
ここで、カーボンブラックとしては、スタッドレスタイヤのトレッド部に用いる場合は、ゴム組成物の低温性能、耐摩耗性やゴムの補強性などの観点から、窒素吸着比表面積（Ｎ２ＳＡ）（ＪＩＳ Ｋ６２１７−２）が７０〜１５０ｍ２／ｇであり、かつＤＢＰ吸油量（ＪＩＳ Ｋ６２１７−４）が１００〜１５０ｍｌ／１００ｇであるものが好ましく用いられる。具体的にはＳＡＦ，ＩＳＡＦ，ＨＡＦ級のカーボンブラックが例示され、配合量としてはジエン系ゴム１００重量部に対して１０〜８０重量部程度の範囲で使用されることが好ましい。 Here, as carbon black, when used in a tread portion of a studless tire, nitrogen adsorption specific surface area (N 2 SA) (JIS K6217) is considered from the viewpoint of low temperature performance, abrasion resistance, rubber reinforcement, and the like of the rubber composition. -2) is 70 to 150 m 2 / g and DBP oil absorption (JIS K6217-4) is preferably 100 to 150 ml / 100 g. Specifically, SAF, ISAF, and HAF grade carbon black are exemplified, and the blending amount is preferably in the range of about 10 to 80 parts by weight with respect to 100 parts by weight of the diene rubber.
また、シリカを用いる場合は、湿式シリカ、乾式シリカ或いは表面処理シリカなどが使用され、配合量はゴムのｔａｎδのバランスや補強性、電気伝導度の観点からジエン系ゴム１００重量部に対して５０重量部未満が好ましく、カーボンブラックとの合計量では１０〜１２０重量部程度が好ましい。また、シリカを配合する場合、シランカップリング剤を併用することが好ましい。 In addition, when silica is used, wet silica, dry silica, surface-treated silica or the like is used, and the blending amount is 50 with respect to 100 parts by weight of diene rubber from the viewpoint of balance of tan δ of rubber, reinforcing property, and electrical conductivity. The amount is preferably less than parts by weight, and is preferably about 10 to 120 parts by weight in total with carbon black. Moreover, when mix | blending a silica, it is preferable to use a silane coupling agent together.
本発明のゴム組成物は、通常に用いられるバンバリーミキサーやニーダなどの混合機を用いて混練し作製することができる。該ゴム組成物は、スタッドレスタイヤ、スノータイヤなどの冬用タイヤ（ウインタータイヤ）のトレッド部のためのゴム組成物として好適に用いられる。 The rubber composition of the present invention can be prepared by kneading using a commonly used mixer such as a Banbury mixer or a kneader. The rubber composition is suitably used as a rubber composition for a tread portion of a winter tire (winter tire) such as a studless tire or a snow tire.
本発明の空気入りタイヤは、上記ゴム組成物を用いてゴム用押し出し機などによりタイヤのトレッド部を作製し未加硫タイヤを成型した後、常法に従い加硫工程を経ることで製造することができる。キャップベース構造のスタッドレスタイヤに適用される場合は、接地面側のキャップトレッドにのみに本発明のゴム組成物を適用すればよい。 The pneumatic tire of the present invention is manufactured by producing a tread portion of a tire using a rubber extruder or the like and molding an unvulcanized tire using the rubber composition, followed by a vulcanization process according to a conventional method. Can do. When applied to a studless tire having a cap base structure, the rubber composition of the present invention may be applied only to the cap tread on the ground contact surface side.
このようにして得られた空気入りタイヤは、トレッドゴムに配合した多孔性セルロース粒子がトレッド表面に露出することで、上述した水膜除去効果や引っ掻き効果等により、トレッドゴムと路面との摩擦係数を高めて氷上性能を向上することができる。また、耐摩耗性を低下を抑えることができる。また、クルミ殻の粉砕物等の植物性粒状体や、竹炭粉砕物等の多孔性炭化物の粉砕物を併用することで、更なる氷上性能の向上を実現することができる。しかも、道路の損傷やアスファルトの粉塵を発生させることなく、天然素材を使用することにより、多孔性セルロース粒子の飛散によっても健康や環境に悪影響を及ぼさない。 In the pneumatic tire thus obtained, the porous cellulose particles blended in the tread rubber are exposed on the tread surface, and the friction coefficient between the tread rubber and the road surface due to the water film removing effect and the scratching effect described above. Can improve the performance on ice. In addition, it is possible to suppress a decrease in wear resistance. Further, the use of vegetable granules such as pulverized walnut shells and porous carbide pulverized products such as bamboo charcoal pulverized products can further improve the performance on ice. In addition, the use of natural materials without causing road damage or asphalt dust does not adversely affect health or the environment due to the scattering of porous cellulose particles.
以下、本発明の実施例を示すが、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
バンバリーミキサーを使用し、下記表１に示す配合に従い、スタッドレスタイヤ用トレッドゴム組成物を調製した。表１中の各成分は以下の通りである。なお、下記の竹炭粉砕物、植物性粒状体、ジルコンビーズおよびセルロース微粉末の空隙率は、上記の多孔性セルロース粒子の空隙率の算出式によるものであり、真比重については、竹炭粉砕物は１．４、植物性粒状体は１．１５、ジルコンビーズは６．０、セルロース微粉末は１．５とした。 Using a Banbury mixer, a tread rubber composition for studless tires was prepared according to the formulation shown in Table 1 below. Each component in Table 1 is as follows. In addition, the porosity of the following bamboo charcoal pulverized product, vegetable granule, zircon beads and cellulose fine powder is based on the above formula for calculating the porosity of the porous cellulose particles. 1.4, vegetable granules were 1.15, zircon beads were 6.0, and cellulose fine powder was 1.5.
・天然ゴム：ＲＳＳ＃３
・ブタジエンゴム：ＪＳＲ株式会社製ハイシスブタジエンゴム「ＢＲ０１」
・カーボンブラック：東海カーボン株式会社製「シーストＫＨ」（Ｎ３３９、ＨＡＦ）
・シリカ：東ソー・シリカ株式会社製「ニップシールＡＱ」
・シランカップリング剤：デグサ社製「Ｓｉ７５」
・パラフィンオイル：株式会社ジャパンエナジー製「ＪＯＭＯプロセスＰ２００」。
・ Natural rubber: RSS # 3
・ Butadiene rubber: High butadiene rubber “BR01” manufactured by JSR Corporation
Carbon black: “Seast KH” (N339, HAF) manufactured by Tokai Carbon Co., Ltd.
・ Silica: “Nip Seal AQ” manufactured by Tosoh Silica Co., Ltd.
Silane coupling agent: “Si75” manufactured by Degussa
Paraffin oil: “JOMO Process P200” manufactured by Japan Energy Corporation.
・多孔性セルロース粒子１：レンゴー株式会社製「ビスコパールミニ」（平均粒径＝４００μｍ、粒子の長径／短径の比＝１．１１、空隙率＝８７％）
・多孔性セルロース粒子２：レンゴー株式会社製「ビスコパールミニ」（平均粒径＝７００μｍ、粒子の長径／短径の比＝１．０９、空隙率＝８０％）
・多孔性セルロース粒子３：レンゴー株式会社製「ビスコパールＡ」（平均粒径＝２０００μｍ、粒子の長径／短径の比＝１．０５、空隙率＝９３％）
・竹炭粉砕物：孟宗竹の竹炭（宮崎土晃株式会社製「１号炭」）をハンマーミルで粉砕し、得られた粉砕物をふるいにより分級した竹炭粉末（平均粒径＝１００μｍ、空隙率＝４６％）
・植物性粒状体：クルミ殻粉砕物（株式会社日本ウォルナット製「ソフトグリップ＃４６」）に対し、特開平１０−７８４１号公報に記載に方法に準じてＲＦＬ処理液で表面処理を施したもの（処理後の植物性粒状体の平均粒径＝３００μｍ、空隙率＝４８％）
・ジルコンビーズ：東レ株式会社製「トレセラム」（平均粒径＝４００μｍ、空隙率＝４％）
・セルロース微粉末：特開２００５−２９７０８号公報に開示の方法によりパルプをボールミルで粉砕した後ふるい分けしたセルロースパウダー（平均粒径＝３００μｍ、空隙率＝３４％）。
Porous cellulose particles 1: “Visco Pearl Mini” manufactured by Rengo Co., Ltd. (average particle size = 400 μm, ratio of major axis / minor axis of particle = 1.11, porosity = 87%)
Porous cellulose particles 2: “Visco Pearl Mini” manufactured by Rengo Co., Ltd. (average particle size = 700 μm, ratio of major axis / minor axis of particle = 1.09, porosity = 80%)
Porous cellulose particles 3: “Visco Pearl A” manufactured by Rengo Co., Ltd. (average particle size = 2000 μm, ratio of major axis / minor axis of particle = 1.05, porosity = 93%)
・ Bamboo charcoal pulverized product: Bamboo charcoal powder obtained by crushing bamboo charcoal from Somune bamboo (“No. 1 charcoal” manufactured by Miyazaki Dogo Co., Ltd.) with a hammer mill and classifying the resulting pulverized product with a sieve (average particle size = 100 μm, porosity = 46%)
・ Plant granules: crushed walnut shell ("Soft Grip # 46" manufactured by Japan Walnut Co., Ltd.) subjected to surface treatment with an RFL treatment solution according to the method described in JP-A-10-7841 (Average particle size of the treated plant granules = 300 μm, porosity = 48%)
・ Zircon beads: “Traceram” manufactured by Toray Industries, Inc. (average particle size = 400 μm, porosity = 4%)
Cellulose fine powder: Cellulose powder (average particle size = 300 μm, porosity = 34%) obtained by pulverizing pulp with a ball mill by the method disclosed in JP-A-2005-29708 and then sieving.
各ゴム組成物には、共通配合として、ジエン系ゴム１００重量部に対し、ステアリン酸（花王株式会社製「ルナックＳ−２０」）２重量部、亜鉛華（三井金属鉱業株式会社製「亜鉛華１種」）２重量部、老化防止剤（住友化学株式会社製「アンチゲン６Ｃ」）２重量部、ワックス（日本精鑞株式会社製「ＯＺＯＡＣＥ０３５５」）２重量部、加硫促進剤（住友化学株式会社製「ソクシノールＣＺ」）１．５重量部、及び、硫黄（鶴見化学工業株式会社製「粉末硫黄」）２．１重量部を配合した。 In each rubber composition, 2 parts by weight of stearic acid ("Lunac S-20" manufactured by Kao Corporation) and zinc white ("Zinc Flower" manufactured by Mitsui Mining & Smelting Co., Ltd.) are used as a common compound. 1 type)) 2 parts by weight, anti-aging agent (“Antigen 6C” manufactured by Sumitomo Chemical Co., Ltd.) 2 parts by weight, wax (“OZOACE0355” manufactured by Nippon Seiki Co., Ltd.) 2 parts by weight, vulcanization accelerator (Sumitomo Chemical Co., Ltd.) 1.5 parts by weight of company "Soccinol CZ") and 2.1 parts by weight of sulfur ("powder sulfur" manufactured by Tsurumi Chemical Co., Ltd.) were blended.
得られた各ゴム組成物について、硬度（２３℃）を測定した。また、各ゴム組成物を用いてスタッドレスタイヤを作製し、耐摩耗性と、氷上路面における制動性能（氷上制動性能）を評価した。タイヤサイズは１８５／６５Ｒ１４として、そのトレッドに各ゴム組成物を適用し、常法に従い加硫成形することにより製造した。各使用リムは１４×５．５ＪＪとした。各測定・評価方法は次の通りである。 About each obtained rubber composition, hardness (23 degreeC) was measured. Also, studless tires were prepared using each rubber composition, and the wear resistance and braking performance on the road surface on ice (on-ice braking performance) were evaluated. The tire size was 185 / 65R14, and each rubber composition was applied to the tread and vulcanized and molded according to a conventional method. Each rim used was 14 × 5.5 JJ. Each measurement / evaluation method is as follows.
・硬度：ＪＩＳ Ｋ６２５３に準拠して、１６０℃×２０分で加硫したサンプル（厚みが１２ｍｍ以上のもの）について、２３℃での硬度を、タイプＡデュロメータを用いて測定した。 Hardness: Based on JIS K6253, the hardness at 23 ° C. of a sample vulcanized at 160 ° C. for 20 minutes (thickness of 12 mm or more) was measured using a type A durometer.
・耐摩耗性：上記タイヤを２０００ｃｃの４ＷＤ車に装着し、２５００ｋｍ毎に左右ローテーションして、１００００ｋｍ走行後の残溝（４本のタイヤの残溝の平均値）を測定し、比較例２の値を１００とした指数で表示した。指数が大きいほど耐摩耗性が良好であることを示す。 ・ Abrasion resistance: The above tire was mounted on a 2000 cc 4WD vehicle, rotated left and right every 2500 km, and the remaining grooves after running 10,000 km (average value of remaining grooves of four tires) were measured. The value was expressed as an index with a value of 100. A larger index indicates better wear resistance.
・氷上制動性能：上記タイヤを２０００ｃｃの４ＷＤ車に装着し、−３±３℃の氷盤路上で４０ｋｍ／ｈ走行からＡＢＳ作動させて制動距離を測定し（ｎ＝１０の平均値）、制動距離の逆数について、比較例２の値を１００とした指数で表示した。指数が大きいほど制動距離が短く、制動性能に優れることを示す。 -On-ice braking performance: The above tire is mounted on a 2000 cc 4WD vehicle, and the braking distance is measured by running an ABS from 40 km / h on an icing road at -3 ± 3 ° C (average value of n = 10). The reciprocal of the distance was displayed as an index with the value of Comparative Example 2 as 100. The larger the index, the shorter the braking distance and the better the braking performance.
結果は表１に示す通りであり、多孔性セルロース粒子を配合した実施例１〜５であると、竹炭粉砕物やジルコンビーズを配合した比較例２，３に対して、耐摩耗性を大幅に悪化させることなく、氷上制動性能が大幅に向上していた。また、代表的なセルロース粒子である植物性粒状体を配合した比較例７やセルロース微粉末を配合した比較例８に対しても、氷上制動性能が大幅に向上していた。 A result is as showing in Table 1, and it is Example 1-5 which mix | blended the porous cellulose particle, and compared with Comparative Examples 2 and 3 which mix | blended the bamboo charcoal ground material and the zircon bead, abrasion resistance is greatly improved. The braking performance on ice was greatly improved without deteriorating. In addition, braking performance on ice was greatly improved as compared with Comparative Example 7 in which vegetable granules as typical cellulose particles were blended and Comparative Example 8 in which cellulose fine powder was blended.
また、多孔性セルロース粒子と植物性粒状体を併用した実施例６、多孔性セルロース粒子と竹炭粉砕物と植物性粒状体の三者を組み合わせた実施例７，８では、氷上制動性能の更なる向上効果が得られた。 Further, in Example 6 in which porous cellulose particles and vegetable granules are used in combination, and in Examples 7 and 8 in which the porous cellulose particles, bamboo charcoal pulverized material, and plant granules are combined, braking performance on ice is further increased. Improvement effect was obtained.
なお、比較例４は、多孔性セルロース粒子であるが、平均粒径が大きいものであったため、耐摩耗性が大きく悪化した。また、多孔性セルロース粒子の配合量が少なすぎる比較例５では、氷上制動性能の改良効果が不十分であり、また、その配合量が多すぎる比較例６では、耐摩耗性が大幅に悪化していた。 In addition, although the comparative example 4 is a porous cellulose particle, since the average particle diameter was large, abrasion resistance deteriorated greatly. In Comparative Example 5 in which the blending amount of the porous cellulose particles is too small, the effect of improving the braking performance on ice is insufficient, and in Comparative Example 6 in which the blending amount is too large, the wear resistance is greatly deteriorated. It was.
本発明に係るゴム組成物は、スタッドレスタイヤ、スノータイヤなどの冬用タイヤ、産業車両用タイヤなどの各種空気入りタイヤを始めとして、靴底、マット類、床材等の防滑性が要求されるゴム製品に広く利用することができる。 The rubber composition according to the present invention is required to have anti-slip properties such as shoe soles, mats, floor materials, and the like, including various pneumatic tires such as winter tires such as studless tires and snow tires, and tires for industrial vehicles. Can be widely used for rubber products.
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| JP6099871B2 (en) * | 2012-03-13 | 2017-03-22 | 東洋ゴム工業株式会社 | Pneumatic tire |
| JP6113419B2 (en) * | 2012-05-16 | 2017-04-12 | 東洋ゴム工業株式会社 | Rubber composition for tire tread and pneumatic tire |
| WO2015016390A1 (en) * | 2013-07-31 | 2015-02-05 | Compagnie Generale Des Etablissements Michelin | A pneumatic tire having a tread comprising milliparticles |
| EP3027431B1 (en) * | 2013-07-31 | 2020-05-27 | Compagnie Générale des Etablissements Michelin | A pneumatic tire having a tread comprising milliparticles |
| JP6173870B2 (en) * | 2013-10-17 | 2017-08-02 | 東洋ゴム工業株式会社 | Rubber composition for tire tread and pneumatic tire |
| JP6584773B2 (en) * | 2014-12-16 | 2019-10-02 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition for tire and pneumatic tire |
| JP6427596B2 (en) * | 2014-12-19 | 2018-11-28 | 株式会社アシックス | Shoe forming rubber composition, shoe forming member, and shoe |
| JP6437391B2 (en) | 2015-07-07 | 2018-12-12 | 東洋ゴム工業株式会社 | Rubber composition for tire, tire and method for producing the same |
| JP6456791B2 (en) * | 2015-07-30 | 2019-01-23 | 東洋ゴム工業株式会社 | Rubber composition for studless tire tread, studless tire, and method for producing the rubber composition |
| JP6732420B2 (en) * | 2015-09-28 | 2020-07-29 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition for tire tread and method for producing the same |
| JP6929641B2 (en) * | 2016-12-20 | 2021-09-01 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber compositions for tires, tires and their manufacturing methods |
| JP7255299B2 (en) * | 2019-04-01 | 2023-04-11 | 横浜ゴム株式会社 | Rubber composition and studless tire using the same |
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