WO2011096399A1 - Composition de caoutchouc - Google Patents

Composition de caoutchouc Download PDF

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Publication number
WO2011096399A1
WO2011096399A1 PCT/JP2011/052044 JP2011052044W WO2011096399A1 WO 2011096399 A1 WO2011096399 A1 WO 2011096399A1 JP 2011052044 W JP2011052044 W JP 2011052044W WO 2011096399 A1 WO2011096399 A1 WO 2011096399A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber
weight
rubber composition
pulp
lignin
Prior art date
Application number
PCT/JP2011/052044
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English (en)
Japanese (ja)
Inventor
浩之 矢野
丈史 中谷
行夫 磯部
直哉 市川
Original Assignee
国立大学法人京都大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人京都大学 filed Critical 国立大学法人京都大学
Priority to JP2011552786A priority Critical patent/JP5717656B2/ja
Publication of WO2011096399A1 publication Critical patent/WO2011096399A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • B60C11/14—Anti-skid inserts, e.g. vulcanised into the tread band
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers

Definitions

  • the present invention relates to a rubber composition containing microfibrillated plant fibers.
  • cellulose fibers as a filler to be blended in the rubber component
  • cellulose fibers include microfibrillated cellulose.
  • microfibrillated cellulose reduces bleaching and the binding strength between microfibril units, and fibrillates into microfibril units.
  • wood pulp from which lignin has been chemically removed is used as a raw material, and microfibrillated cellulose produced from wood pulp from which lignin has been removed has hydrophilicity mainly derived from cellulose. Therefore, it is not compatible with the hydrophobic rubber component.
  • An object of the present invention is to provide a rubber composition in which microfibrillated plant fibers are well dispersed in a rubber component.
  • the present inventors mainly derived from cellulose by containing microfibrillated plant fibers containing a relatively large amount of lignin as a filler in the rubber composition. It has been found that hydrophilicity can be excluded and the rubber component that is hydrophobic is better and the dispersibility of the microfibrillated plant fiber can be improved.
  • the present invention has been completed based on such knowledge.
  • Item 1 A rubber composition containing (A) a rubber component and (B) microfibrillated plant fibers obtained by mechanically defibrating pulp containing 2 to 70% by weight of lignin with respect to the weight of cellulose.
  • Item 2. The rubber composition according to Item 1, wherein the content of the microfibrillated plant fiber (B) is 1 to 50 parts by weight with respect to 100 parts by weight of the rubber component (A).
  • Item 3. The rubber composition according to Item 1 or 2, wherein the mechanical fibrillation treatment is a grinding treatment.
  • Item 4. The rubber composition according to any one of Items 1 to 3, wherein the microfibrillated plant fiber has a structure in which cellulose microfibrils and / or cellulose microfibril bundles are covered with hemicellulose and / or lignin.
  • Item 5. The rubber composition according to any one of Items 1 to 4, which is used for tires.
  • Item 6. A pneumatic tire using the rubber composition according to any one of Items 1 to 5.
  • the rubber composition of the present invention comprises (A) a rubber component, and (B) a microfibrillated plant fiber obtained by mechanical defibrating pulp containing 2 to 70% by weight of lignin with respect to the weight of cellulose. contains.
  • Examples of the rubber component (A) include diene rubber components. Specifically, natural rubber (NR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), isoprene rubber (IR) ), Butyl rubber (IIR), acrylonitrile-butadiene rubber (NBR), acrylonitrile-styrene-butadiene copolymer rubber, chloroprene rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer Examples thereof include modified natural rubber such as polymer rubber, chlorosulfonated polyethylene, epoxidized natural rubber (ENR), hydrogenated natural rubber, and deproteinized natural rubber.
  • NBR acrylonitrile-butadiene rubber
  • modified natural rubber such as polymer rubber, chlorosulfonated polyethylene, epoxid
  • the rubber component other than the diene rubber component examples include ethylene-propylene copolymer rubber, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine rubber, urethane rubber, and the like. These rubber components may be used alone or in combination of two or more. What is necessary is just to mix
  • microfibrillated plant fiber (B) Since the microfibrillated plant fiber (B) does not completely remove lignin chemically, the matrix portion composed of lignin and hemicellulose that fills the space between the microfibrillated cellulose is broken to form microfibrils (microfibrillation). Presumed to be. Therefore, the microfibrillated plant fiber (B) obtained by mechanical fibrillation treatment is composed of cellulose, hemicellulose and protolignin (lignin in a state existing in the plant tissue) inherent in the plant material. It is presumed that this structure is retained.
  • the microfibrillated plant fiber (B) has a structure in which hemicellulose and / or lignin coats part or all of the periphery of cellulose microfibrils and / or cellulose microfibril bundles, in particular, cellulose microfibrils and / or Alternatively, it is presumed that hemicellulose covers a cellulose microfibril bundle and further has a structure in which this is covered with lignin. However, it is presumed that there will also be a portion where hemicellulose and / or lignin is removed and the hemicellulose or cellulose fiber length is exposed on the surface.
  • the average fiber diameter of the microfibrillated plant fiber (B) (hereinafter also referred to as average fiber diameter) is preferably 4 nm to 10 ⁇ m, more preferably 4 nm to 1 ⁇ m, and more preferably 4 nm to 200 nm. Is more preferable. Further, the microfibrillated plant fiber (B) has intricately intertwined fibers.
  • the relationship between the lignin content and the cellulose content in the microfibrillated plant fiber (B) is that the lignin is 2 to 70% by weight, preferably 5 to 60% by weight, more preferably 10 to 50% by weight, based on the cellulose weight. is there.
  • the content of lignin in the microfibrillated plant fiber (B) is preferably 1 to 40% by weight, more preferably 3 to 35% by weight, and still more preferably 5 to 35% by weight.
  • the fibrillated plant fiber (B) does not remove the lignin in the pulp which is the raw material, the lignin content in the pulp and the lignin content in the microfibrillated plant fiber are almost the same.
  • the relationship between the cellulose content and the lignin content in the pulp and the relationship between the cellulose content and the lignin content in the microfibrillated plant fiber are almost the same.
  • this composition is different from the microfibrillated plant fiber (B) used in the present invention in that it is not microfibrillated and protolignin is not present. Is different.
  • the pulp used when producing the microfibrillated plant fiber (B) is different from the pulp used in the production of the conventional microfibrillated cellulose, and it is necessary that the lignin is not completely removed.
  • the lignin content in the pulp is 1 to 40% by weight, preferably 3 to 35% by weight, more preferably 5 to 35% by weight. Further, regarding the relationship between the lignin content and the cellulose content in the pulp, lignin is 2 to 70% by weight, preferably 5 to 65% by weight, more preferably 10 to 60% by weight, based on the weight of cellulose.
  • a plant raw material for supplying pulp used in producing the microfibrillated plant fiber (B) a wide variety of plant raw materials for supplying pulp used in the production of conventional microfibrillated cellulose are used.
  • wood, bamboo, hemp, jute, kenaf, crop waste, cloth, recycled pulp, and waste paper Preferred are wood, bamboo, hemp, jute, kenaf, and crop residue.
  • Any method for pulping a plant material is not limited as long as the lignin in the plant material is not completely removed and the pulp content is about 2 to 70% by weight based on the cellulose content in the pulp. Applicable.
  • a mechanical pulping method for mechanically pulping plant materials can be applied.
  • the mechanical pulp (MP) obtained by the mechanical pulping method include groundwood pulp (GP), refiner mechanical pulp (RMP), thermomechanical pulp (TMP), and chemithermomechanical pulp (CTMP).
  • chemical pulp obtained by pulverizing plant raw materials chemically or chemically and mechanically by chlorination, alkali treatment, oxygen oxidation treatment, sodium hypochlorite treatment, sulfite treatment, etc.
  • KP sulfite pulp
  • SP sulfite pulp
  • SCP semi-chemical pulp
  • CGP chemi-ground pulp
  • CMP chemi-mechanical pulp
  • the pulp may be subjected to chemical modification treatment commonly used in the pulp field as necessary, for example, esterification treatment, etherification treatment, acetalization treatment, pulp treated with an aromatic ring of lignin, etc.
  • the applied pulp is illustrated.
  • the esterification treatment, etherification treatment, and acetalization treatment mainly include esterification, etherification, and acetalization treatment of hydroxyl groups present in cellulose, hemicellulose, and lignin.
  • the treatment of the lignin aromatic ring includes introducing a desired substituent into the lignin aromatic ring.
  • Lignin-containing pulp is not mechanically ground by refiner, twin screw kneader (double screw extruder), twin screw kneader, high pressure homogenizer, medium stirring mill, stone mill, grinder, vibration mill, sand grinder, etc. It is defibrated or refined by beating to make microfibrillated plant fibers.
  • a preferred temperature in the defibrating treatment is 0 to 99 ° C, more preferably 0 to 90 ° C. It is desirable that the pulp that is the raw material for the defibrating process has a shape (for example, a powder form) suitable for such a defibrating process.
  • a preferred defibration method is grinding treatment, and it is preferable to use a stone mill type grinding machine or a twin-screw kneading extruder.
  • the grinding may be performed until the fiber diameter reaches a desired size.
  • the amount of the rubber component (A) is preferably in the range of 1 to 50 parts by weight, more preferably in the range of 2 to 35 parts by weight, and still more preferably in the range of 3 to 20 parts by weight.
  • the rubber component (A) and the microfibrillated plant fiber (B) are blended and dispersed in water, and then the obtained dispersion is coagulated with an acid, washed with water, and then dried. It is manufactured as a master batch obtained by this.
  • the solid content concentration of the rubber component (A) in the dispersion is preferably 0.5% by weight or more, preferably 1.0% by weight or more in the dispersion from the viewpoint that the yield of each material during solidification is good. Is more preferable, and 1.5% by weight or more is more preferable. Further, the rubber component (A) is preferably 30% by weight or less, more preferably 20% by weight or less, more preferably 10% by weight in the dispersion from the viewpoint of good mixing efficiency with the microfibrillated plant fiber (B). % Or less is more preferable.
  • the solid content concentration of the microfibrillated plant fiber (B) in the dispersion is preferably 0.1% by weight or more in the dispersion from the viewpoint that the yield of each material during solidification is good. % By weight or more is more preferable, and 0.5% by weight or more is more preferable. Further, the microfibrillated plant fiber (B) is preferably 10% by weight or less, more preferably 5% by weight or less, more preferably 2% by weight in the dispersion from the viewpoint of good mixing efficiency with the rubber component (A). % Or less is more preferable.
  • the acid for solidifying the solid content in the dispersion is not particularly limited, and examples thereof include formic acid, acetic acid, hydrochloric acid, and sulfuric acid.
  • the rubber composition (masterbatch) obtained by the above method further comprises reinforcing fillers such as carbon black and silica; silane compounds such as silane coupling agents; process oils; waxes; anti-aging agents; sulfur and vulcanization.
  • Vulcanizing agents such as accelerators; vulcanizing aids such as zinc oxide and stearic acid can be appropriately blended.
  • the microfibrillated plant fiber (B) is well dispersed in the rubber component (A), the breaking characteristics and rigidity are improved. Therefore, it is suitably used for tires, and when used for tires, it is possible to improve steering stability without deteriorating low fuel consumption characteristics.
  • the rubber composition of the present invention When using the rubber composition of the present invention for tires, the rubber composition containing the rubber component (A) and the microfibrillated plant fiber (B) prepared above with a Banbury mixer, kneader, open roll, etc., A rubber composition can be produced by kneading a desired additive and then vulcanizing.
  • the present invention also relates to a pneumatic tire using the rubber composition.
  • a pneumatic tire is manufactured by a normal method using the rubber composition of the present invention. That is, the rubber composition of the present invention is further mixed with a desired compounding agent and kneaded, and the resulting kneaded product is extruded in accordance with the shape of various members of the tire at an unvulcanized stage.
  • An unvulcanized tire is formed by molding in the usual manner. A tire can be obtained by heating and pressurizing this unvulcanized tire in a vulcanizer.
  • the rubber composition of the present invention contains microfibrillated plant fibers using wood pulp from which lignin has not been removed or from which part of lignin has been removed as a raw material, interfacial interaction between cellulose and rubber components And the dispersibility of the microfibrillated plant fiber in the rubber component is improved. Therefore, the breaking characteristics of the rubber composition are improved. When such a rubber composition is used for a tire, it is possible to improve steering stability by improving rigidity without reducing fuel efficiency.
  • microfibrillated plant fiber 1 (solid content: 30% by weight) was prepared.
  • microfibrillated plant fiber 2 (solid) was prepared in the same manner as the preparation of the microfibrillated plant fiber 1 except that unbleached kraft pulp derived from conifers (containing 5 to 7% by weight of lignin) was used as the wood pulp. A partial concentration: 30% by weight) was prepared.
  • Microfibrillated plant fiber 1 (solid content: 30% by weight) was submerged in water using a high-speed homogenizer (batch homogenizer T65D Ultra Turrax (Ultraturrax T25) manufactured by IKA) at 14,000 rpm, 1 After stirring and dispersing for a time, natural rubber latex (HYTEX-HA manufactured by Golden Hope Plantations, solid content concentration: 60% by weight) was added, and the mixture was further stirred and dispersed at 24,000 rpm for 30 minutes. The obtained mixed solution was coagulated with a 5% by weight aqueous formic acid solution, washed with water, and then dried in a heating oven at 40 ° C. to obtain master batches 1 to 3.
  • a high-speed homogenizer batch homogenizer T65D Ultra Turrax (Ultraturrax T25) manufactured by IKA
  • natural rubber latex (HYTEX-HA manufactured by Golden Hope Plantations, solid content concentration: 60% by weight) was added, and the mixture was further stirred and dispersed at 24,000
  • Master batches 4 to 6 were prepared in the same manner as master batches 1 to 3, except that microfibrillated plant fiber 2 was used.
  • Table 1 shows the content of microfibrillated plant fibers, natural rubber latex and water in the dispersion before coagulation and washing with water when preparing master batches 1 to 6.
  • Anti-aging agent NOCRACK 6C (Ouchi Shinsei Chemical Co., Ltd.)
  • Stearic acid Bead stearic acid Tsubaki (manufactured by NOF Corporation)
  • Zinc oxide 2 types of zinc oxide (Mitsui Metal Mining Co., Ltd.)
  • Sulfur Powdered sulfur (manufactured by Tsurumi Chemical Co., Ltd.)
  • Vulcanization accelerator Noxeller DM (Ouchi Shinsei Chemical Co., Ltd.)
  • a test specimen for measurement was cut out from a 2 mm rubber slab sheet of the vulcanized rubber composition prepared by the above-described method, and the temperature was 70 ° C. and the initial strain was 10% using a viscoelastic spectrometer VES (manufactured by Iwamoto Seisakusho).
  • VES viscoelastic spectrometer
  • E * (complex elastic modulus) and tan ⁇ (loss tangent) of each test specimen were measured under the conditions of dynamic strain 2% and frequency 10 Hz.
  • Steering stability index (E * for each formulation) ⁇ (E * for standard formulation) x 100
  • Rolling resistance index (tan ⁇ of each formulation) ⁇ (tan ⁇ of standard formulation) ⁇ 100 The steering stability index and rolling resistance index were calculated.
  • Table 3 shows the evaluation of each physical property of each vulcanized rubber composition.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de caoutchouc qui contient (A) un composant de caoutchouc, et (B) des fibres végétales microfibrillées obtenues par fibrillation mécanique d'une pâte à papier qui contient 2 à 70 % en poids de lignine par rapport à la masse en poids de cellulose.
PCT/JP2011/052044 2010-02-02 2011-02-01 Composition de caoutchouc WO2011096399A1 (fr)

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JP2010-020896 2010-02-02

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2620296A1 (fr) * 2012-01-30 2013-07-31 Sumitomo Rubber Industries Limited Composition de caoutchouc pour pneu, son procédé de préparation et bande pneumatique
US20130197131A1 (en) * 2012-01-30 2013-08-01 Sumitomo Rubber Industries, Ltd. Rubber composition for tire, method of producing the same, and pneumatic tire
JP2013194088A (ja) * 2012-03-16 2013-09-30 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物、その製造方法及び空気入りタイヤ
JP2014129509A (ja) * 2012-11-29 2014-07-10 Nishikawa Rubber Co Ltd エラストマー組成物およびその製造方法
JP2014227484A (ja) * 2013-05-23 2014-12-08 住友ゴム工業株式会社 マスターバッチ、製造方法、ゴム組成物及び空気入りタイヤ
US9012541B2 (en) 2012-09-03 2015-04-21 Sumitomo Rubber Industries, Ltd. Rubber composition and pneumatic tire
US9068060B2 (en) 2013-01-10 2015-06-30 Sumitomo Rubber Industries, Ltd. Composite and method for producing the same, rubber composition, and pneumatic tire
US9181355B2 (en) 2010-06-10 2015-11-10 Sumitomo Rubber Industries, Ltd. Modified natural rubber, method for producing same, rubber composition, and pneumatic tire
US9217075B2 (en) 2012-01-24 2015-12-22 Sumitomo Rubber Industries, Ltd. Rubber composition for tire, and pneumatic tire
US9410033B2 (en) 2011-11-11 2016-08-09 Sumitomo Rubber Industries, Ltd. Rubber composition for undertread, and pneumatic tire
US20170183483A1 (en) * 2014-05-22 2017-06-29 The Yokohama Rubber Co., Ltd. Rubber Composition for Tire and Studless Tire
WO2017169787A1 (fr) * 2016-03-31 2017-10-05 住友ゴム工業株式会社 Composition de caoutchouc et pneumatique
US10336890B2 (en) 2014-03-17 2019-07-02 Sumitomo Rubber Industries, Ltd. Rubber composition for studless winter tires, and studless winter tire
JP2019203108A (ja) * 2018-05-25 2019-11-28 旭化成株式会社 微細セルロース含有樹脂組成物
JP7118167B2 (ja) 2019-10-28 2022-08-15 バンドー化学株式会社 伝動ベルト及びその製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11149134B2 (en) 2017-06-23 2021-10-19 Rengo Co., Ltd. Resin composition containing cellulose xanthate fine fibers

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JPH11157303A (ja) * 1997-09-24 1999-06-15 Goodyear Tire & Rubber Co:The アイストラクションのためのタイヤトレッド
JP2005075856A (ja) * 2003-08-28 2005-03-24 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物
JP2006206864A (ja) * 2004-12-27 2006-08-10 Yokohama Rubber Co Ltd:The ゴム／短繊維マスターバッチ及びその製造方法並びにそれらのマスターバッチを用いた空気入りタイヤ
JP2007177112A (ja) * 2005-12-28 2007-07-12 Sumitomo Rubber Ind Ltd インナーライナー用ゴム組成物
JP2009019200A (ja) * 2007-06-11 2009-01-29 Kyoto Univ リグニン含有ミクロフィブリル化植物繊維及びその製造方法
JP2009191198A (ja) * 2008-02-15 2009-08-27 Bridgestone Corp ゴム組成物及びその製造方法

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Publication number Priority date Publication date Assignee Title
JPH11157303A (ja) * 1997-09-24 1999-06-15 Goodyear Tire & Rubber Co:The アイストラクションのためのタイヤトレッド
JP2005075856A (ja) * 2003-08-28 2005-03-24 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物
JP2006206864A (ja) * 2004-12-27 2006-08-10 Yokohama Rubber Co Ltd:The ゴム／短繊維マスターバッチ及びその製造方法並びにそれらのマスターバッチを用いた空気入りタイヤ
JP2007177112A (ja) * 2005-12-28 2007-07-12 Sumitomo Rubber Ind Ltd インナーライナー用ゴム組成物
JP2009019200A (ja) * 2007-06-11 2009-01-29 Kyoto Univ リグニン含有ミクロフィブリル化植物繊維及びその製造方法
JP2009191198A (ja) * 2008-02-15 2009-08-27 Bridgestone Corp ゴム組成物及びその製造方法

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9181355B2 (en) 2010-06-10 2015-11-10 Sumitomo Rubber Industries, Ltd. Modified natural rubber, method for producing same, rubber composition, and pneumatic tire
US9410033B2 (en) 2011-11-11 2016-08-09 Sumitomo Rubber Industries, Ltd. Rubber composition for undertread, and pneumatic tire
US9217075B2 (en) 2012-01-24 2015-12-22 Sumitomo Rubber Industries, Ltd. Rubber composition for tire, and pneumatic tire
US20130197131A1 (en) * 2012-01-30 2013-08-01 Sumitomo Rubber Industries, Ltd. Rubber composition for tire, method of producing the same, and pneumatic tire
JP2013155303A (ja) * 2012-01-30 2013-08-15 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物、その製造方法及び空気入りタイヤ
EP2620296A1 (fr) * 2012-01-30 2013-07-31 Sumitomo Rubber Industries Limited Composition de caoutchouc pour pneu, son procédé de préparation et bande pneumatique
JP2013194088A (ja) * 2012-03-16 2013-09-30 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物、その製造方法及び空気入りタイヤ
US9012541B2 (en) 2012-09-03 2015-04-21 Sumitomo Rubber Industries, Ltd. Rubber composition and pneumatic tire
JP2014129509A (ja) * 2012-11-29 2014-07-10 Nishikawa Rubber Co Ltd エラストマー組成物およびその製造方法
US9068060B2 (en) 2013-01-10 2015-06-30 Sumitomo Rubber Industries, Ltd. Composite and method for producing the same, rubber composition, and pneumatic tire
JP2014227484A (ja) * 2013-05-23 2014-12-08 住友ゴム工業株式会社 マスターバッチ、製造方法、ゴム組成物及び空気入りタイヤ
US10336890B2 (en) 2014-03-17 2019-07-02 Sumitomo Rubber Industries, Ltd. Rubber composition for studless winter tires, and studless winter tire
US20170183483A1 (en) * 2014-05-22 2017-06-29 The Yokohama Rubber Co., Ltd. Rubber Composition for Tire and Studless Tire
US10570274B2 (en) * 2014-05-22 2020-02-25 The Yokohama Rubber Co., Ltd. Rubber composition for tire and studless tire
WO2017169787A1 (fr) * 2016-03-31 2017-10-05 住友ゴム工業株式会社 Composition de caoutchouc et pneumatique
JPWO2017169787A1 (ja) * 2016-03-31 2018-04-19 住友ゴム工業株式会社 ゴム組成物及び空気入りタイヤ
JP2019203108A (ja) * 2018-05-25 2019-11-28 旭化成株式会社 微細セルロース含有樹脂組成物
JP7118167B2 (ja) 2019-10-28 2022-08-15 バンドー化学株式会社 伝動ベルト及びその製造方法

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