WO2020122073A1 - Rubber composition, tyre tread, and tyre - Google Patents
Rubber composition, tyre tread, and tyre Download PDFInfo
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- WO2020122073A1 WO2020122073A1 PCT/JP2019/048336 JP2019048336W WO2020122073A1 WO 2020122073 A1 WO2020122073 A1 WO 2020122073A1 JP 2019048336 W JP2019048336 W JP 2019048336W WO 2020122073 A1 WO2020122073 A1 WO 2020122073A1
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- rubber composition
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Classifications
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- 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
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
Definitions
- the present invention relates to a rubber composition, a tire tread, and a tire.
- a tire capable of running on ice represented by the studless tire is required to have performance on ice such as braking performance and starting performance on a polished ice burn.
- a hydrophilic material which is a water-soluble short fiber is added to a rubber composition, the hydrophilicity of the rubber surface is improved. There is a way.
- an object of the present invention is to provide a rubber composition that can maintain high on-ice performance, a tire tread that can maintain high on-ice performance, and a tire that can maintain high on-ice performance when used for a tire. ..
- the gist of the present invention which solves the above problems is as follows.
- the rubber composition according to the present invention comprises a rubber component and a polyester polyol resin having an aromatic ring in an amount of 0.1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the rubber component.
- the above-mentioned rubber composition is used for the tire tread according to the present invention.
- a tire according to the present invention includes the above-mentioned tire tread.
- the present invention it is possible to provide a rubber composition that maintains high on-ice performance when used in a tire.
- ADVANTAGE OF THE INVENTION According to this invention, the tread for tires which maintain high on-ice performance can be provided, when it uses for a tire. According to the present invention, it is possible to provide a tire that maintains high on-ice performance.
- the rubber composition according to the present invention contains a rubber component and a polyester polyol resin having an aromatic ring in an amount of 0.1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the rubber component.
- the polyester polyol resin blended in the rubber composition according to the present invention has an aromatic ring
- the components (mainly the polyester polyol resin etc.) in the rubber composition are reduced from being dissolved in water or Suppress.
- the polyester polyol resin having an aromatic ring is mixed in the rubber composition, the tire surface is appropriately hydrophilized. Therefore, when a rubber composition containing a polyester polyol resin having an aromatic ring is applied to a tire, it is considered that high performance on ice (or also referred to as an effect of improving ⁇ on ice) is maintained even under wet conditions.
- the rubber composition according to the present invention contains a rubber component.
- a rubber component it is preferable to contain a diene rubber from the viewpoint that excellent strength, low rolling resistance, WET performance or steering stability can be obtained, for example.
- the rubber component may be composed of 100% of the diene rubber, but as long as the object of the present invention is not impaired, rubber other than diene rubber (hereinafter, may be referred to as “non-diene rubber”). ) May be contained.
- the diene rubber is not particularly limited, and a known diene rubber can be used.
- a known diene rubber can be used.
- the diene rubber natural rubber (NR), butadiene rubber (BR), synthetic isoprene rubber (IR), styrene-butadiene rubber (SBR), styrene-isoprene-butadiene rubber (SIBR), chloroprene rubber (CR) ), acrylonitrile butadiene rubber (NBR) and modified products thereof.
- the diene rubbers may be used alone or in combination of two or more.
- the rubber composition in the present invention preferably contains natural rubber as the rubber component. Thereby, abrasion resistance can be improved.
- the ratio of the natural rubber in the rubber component is preferably 45% by mass or more and 75% by mass or less, and 48% by mass or more and 70% by mass or less. It is more preferable that the content is 50% by mass or more and 65% by mass or less. Thereby, the wear resistance can be further improved.
- the rubber composition in the present invention preferably contains, as the rubber component, at least one selected from the group consisting of unmodified butadiene rubber and modified butadiene rubber. Thereby, the performance on ice can be improved.
- the upper limit of the compounding amount of the unmodified or modified butadiene rubber in the rubber component is 55% by mass. It is preferably 52 mass% and more preferably.
- the lower limit of the compounding amount of the unmodified or modified butadiene rubber in the rubber component is preferably 25% by mass, and more preferably 30% by mass.
- the blending amount of the butadiene rubber in the rubber component is preferably 25% by mass or more and 55% by mass or less.
- modified rubber The modifying group introduced into the modified styrene-butadiene rubber and the modified butadiene rubber (hereinafter, both rubbers may be collectively referred to as “modified rubber”) is not particularly limited. However, it is preferable that the terminal of the modified rubber is modified with a silane compound from the viewpoint that the dispersibility of the filler can be improved.
- the silane compound include a silane compound having a glycidoxy group, an alkoxysilane compound, a hydrocarbyloxysilane compound, and the like.
- modified rubber obtained by using a conjugated diene compound as a monomer, a polymer or copolymer of the conjugated diene compound, or using a conjugated diene compound and an aromatic vinyl compound as a monomer
- the obtained copolymer of the conjugated diene compound and the aromatic vinyl compound can be used, and those obtained by modifying the molecular end and/or the main chain of these (co)polymers can also be used. ..
- known modified rubbers having modified molecular ends include WO 2003/029299, WO 2003/046020, JP-A 2004-513987, JP-A 11-29603, and JP-A 11-29603.
- modified diene rubbers disclosed in 2003-113202, JP-A 2007-217562, and Japanese Patent Publication No. 6-29338 include known modified rubbers having a modified main chain.
- the modified diene rubbers disclosed in JP 2003-534426 A and JP 2002-201310 A can be exemplified.
- Examples include the modified conjugated diene polymer (A2) described in No. 2018/186367.
- the rubber composition in the present invention contains a polyester polyol resin having an aromatic ring. Since the aromatic ring acts as a hydrophobic site, it can be said that the polyester polyol resin having an aromatic ring is a hydrophilic material having a hydrophobic portion. Due to its chemical structure, the hydrophilic material having such a hydrophobic portion reduces or suppresses the water solubility of the material that makes the rubber surface hydrophilic (such as the polyester polyol resin having the aromatic ring), and therefore improves ⁇ on ice. The effect is considered to be sustained. Therefore, by blending the polyester polyol resin having an aromatic ring with the rubber composition, the hydrophilicity of the tire surface is improved and high performance on ice is maintained.
- the polyester polyol resin having an aromatic ring is preferably a polyester polyol resin containing an aromatic ring in its main chain or side chain, and from the viewpoint of insolubility in water, a polyester polyol having an aromatic ring in its main chain. Resins are more preferred.
- the polyester polyol resin having an aromatic ring is, for example, a polycondensation product of an aromatic polyvalent carboxylic acid and a polyhydric alcohol, which is a resin having two or more hydroxyl groups in one molecule, or a polyvalent carboxylic acid. And a polycondensate of an aromatic polyhydric alcohol, which includes a resin having two or more hydroxyl groups in one molecule.
- the polyester polyol resin having an aromatic ring may be used alone or in combination of two or more.
- aromatic polycarboxylic acid examples include isophthalic acid, phthalic acid, terephthalic acid, furandicarboxylic acid, aromatic dicarboxylic acid such as diphenyldicarboxylic acid or naphthalene dicarboxylic acid, or aromatic tricarboxylic acid such as naphthalene tricarboxylic acid. ..
- the aromatic polycarboxylic acid is preferably an aromatic dicarboxylic acid.
- polyhydric alcohol examples include dialcohol and trialcohol, and specifically, ethylene glycol, diethylene glycol, triethylene glycol, 1,6-hexanediol, methylpentanediol, propylene glycol, dipropylene glycol, 1 , 4-butanediol, trimethylolethane, trimethylolpropane, neopentyl glycol and the like.
- the polyhydric alcohol is preferably dialcohol.
- polycarboxylic acid examples include oxalic acid, malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid and the like.
- aromatic polyhydric alcohol examples include 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, bisphenol A and resorcinol.
- polyester polyol resin having an aromatic ring to be blended with the rubber composition according to the present invention a resin synthesized by a known method may be used, or a commercially available product may be used. Examples of commercially available products include "Zeofine” series manufactured by Nippon Zeon Co., Ltd.
- the weight average molecular weight of the polyester polyol resin having an aromatic ring in the present invention is preferably 20,000 or more and 100,000 or less, and preferably 30,000 or more and 80,000 or less.
- the weight average molecular weight of the above polyester polyol resin having an aromatic ring is 20,000 or more, it is easy to reduce or suppress water solubility due to the molecular weight effect.
- the weight average molecular weight is 100,000 or less, it will be easy to be compatible with other components.
- the weight average molecular weight is measured by GPC (gel permeation chromatography).
- the said weight average molecular weight is a standard polystyrene conversion molecular weight.
- the polyester polyol resin having an aromatic ring in the present invention preferably has a hydroxyl value of 45 to 78 mgKOH/g.
- the number of hydroxyl groups in one molecule in the polyester polyol resin is preferably 3 or more.
- the compounding amount of the polyester polyol resin having an aromatic ring is 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the rubber component.
- the blending amount of the polyester polyol resin is preferably, for example, 0.7 parts by mass or more, 2 parts by mass or more, and 3.6 parts by mass or more with respect to 100 parts by mass of the rubber component.
- the blending amount of the polyester polyol resin is preferably, for example, 18 parts by mass or less, 16 parts by mass or less, and 13 parts by mass or less based on 100 parts by mass of the rubber component.
- the rubber composition according to the present invention may optionally contain a filler in addition to the above rubber component and the above polyester polyol resin having an aromatic group.
- a filler examples include silica, carbon black, aluminum oxide, clay, alumina, talc, mica, kaolin, glass balloons, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, titanium oxide, titanic acid. Examples thereof include potassium and barium sulfate.
- the fillers may be used alone or in combination of two or more. From the viewpoint of reinforcing properties and low rolling resistance, the filler preferably contains silica.
- the silica is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, and aluminum silicate. ..
- the BET specific surface area of silica is not particularly limited and is, for example, preferably 40 to 350 m 2 /g, more preferably 80 to 300 m 2 /g, further preferably 150 to 280 m 2 /g. Yes, even more preferably 180 to 270 m 2 /g, and particularly preferably 200 to 260 m 2 /g.
- the carbon black is not particularly limited, and examples thereof include high, medium or low structure carbon black such as SAF, ISAF, ISAF-HS, IISAF, N339, HAF, FEF, GPF and SRF grade.
- the filler in the present invention preferably contains at least one selected from the group consisting of silica and carbon black, and more preferably contains silica and carbon black.
- at least one selected from the group consisting of silica and carbon black is added to the rubber composition as a filler, the elastic modulus, strength, water removing effect, abrasion resistance, etc. are improved.
- the amount of the filler to be added is not particularly limited and may be appropriately adjusted. For example, 20 parts by mass or more based on 100 parts by mass of the rubber component. It is preferably 120 parts by mass or less. From the viewpoint of performance on ice and workability, the amount of the filler to be blended is more preferably 50 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the rubber component.
- the compounding amount of silica is not particularly limited and can be appropriately adjusted according to the purpose.
- the amount is preferably 60 parts by mass or more and more preferably 25 parts by mass or more and 50 parts by mass or less.
- the compounding amount of carbon black is not particularly limited and may be appropriately adjusted according to the purpose.
- the amount is preferably not less than 60 parts by mass and more preferably not less than 20 parts by mass and not more than 50 parts by mass.
- the total blending amount of carbon black and silica is preferably 50 parts by mass or more and 120 parts by mass or less, and 60 parts by mass with respect to 100 parts by mass of the rubber component. More preferably, it is 90 parts by mass or less.
- the ratio of silica to the total amount of carbon black and silica (100% by mass) is preferably 20 to 78% by mass, and 30 to 72% by mass. Is more preferable, and further preferably 34 to 67% by mass. Silica ratio within the above range
- the rubber composition in the present invention may contain other components in addition to the above-mentioned rubber component, polyester polyol resin, and filler to be blended as necessary, to the extent that the effects of the invention are not impaired.
- the other components for example, other thermoplastic resin (other than polyester polyol resin having an aromatic ring), softening agent, vulcanizing agent, vulcanization accelerator, silane coupling agent, antioxidant, vulcanization accelerating aid
- additives usually used in the rubber industry such as an agent, an antiozonant, and a surfactant, may be appropriately contained.
- the rubber composition according to the present invention may further contain another thermoplastic resin in addition to at least one kind of the polyester polyol resin having an aromatic ring.
- the type of the other thermoplastic resin is not particularly limited, and examples thereof include C 5 resin, C 9 resin, C 5 to C 9 resin, dicyclopentadiene resin, rosin resin, alkylphenol resin. Or a terpene phenolic resin or the like. These may or may not be hydrogenated.
- the thermoplastic resin further contains another thermoplastic resin, the compatibility with the rubber component or the polyester polyol resin having an aromatic ring is improved, so that the rubber composition is easily processed.
- the compounding amount of the other thermoplastic resin is not particularly limited, but is 5 parts by mass or more and 50 parts by mass or more with respect to 100 parts by mass of the rubber component. It is preferably less than or equal to parts by mass.
- the blending amount of the other thermoplastic resin is 5 parts by mass or more and 50 parts by mass or less, braking performance when the rubber composition is used in a tire is further improved.
- the rubber composition according to the present invention may further contain a softening agent.
- a softening agent By including the softening agent in the rubber composition, flexibility can be further imparted, and thus the performance on ice can be further improved.
- softening agent aliphatic ester, phosphate ester, mineral oil derived from minerals, aromatic oil derived from petroleum, paraffin oil, naphthene oil, palm oil derived from natural products, sunflower oil, castor oil, cottonseed oil, Soybean oil and the like can be mentioned.
- the softening agents may be used alone or in combination of two or more.
- the content of the softening agent in the rubber composition of the present invention is preferably 20 parts by mass or less, and 15 parts by mass with respect to 100 parts by mass of the rubber component. It is more preferably not more than part.
- the blending amount of the softening agent satisfies the above range, the performance on ice and the wear performance are easily compatible with each other.
- the rubber composition according to the present invention may further contain a vulcanizing agent.
- the vulcanizing agent is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include sulfur and bismaleimide compounds.
- the vulcanizing agents may be used alone or in combination of two or more.
- the compounding amount of the vulcanizing agent is not particularly limited and can be appropriately adjusted according to the purpose.
- 0.1 part by mass or more and 2.0 parts by mass or less is preferable with respect to 100 parts by mass of the rubber component.
- 1.0 parts by mass or more and 2.0 parts by mass or less are more preferable, and 1.2 parts by mass or more and 1.8 parts by mass or less are particularly preferable.
- the rubber composition according to the present invention may further contain a vulcanization accelerator.
- the vulcanization accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one selected from guanidines, sulfenamides, thiazoles, thiourea and diethylthiourea. Preferably.
- the vulcanization accelerators may be used alone or in combination of two or more.
- the compounding amount of the vulcanization accelerator is not particularly limited and can be appropriately adjusted according to the purpose, and is, for example, 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the rubber component.
- the amount is 0.1 parts by mass or more, the effect of vulcanization is easily obtained, and when the amount is 20 parts by mass or less, excessive progress of vulcanization can be suppressed.
- silane coupling agent When the rubber composition according to the present invention contains silica as a filler, it preferably further contains a silane coupling agent.
- silane coupling agent By using the silane coupling agent, the effects of improving the dispersibility of silica, the workability during rubber processing, or the abrasion resistance can be obtained.
- the silane coupling agent may be used alone or in combination of two or more.
- silane coupling agent examples include bis(3-triethoxysilylpropyl) tetrasulfide (trade name “Si69” manufactured by Evonik Degussa), bis(3-triethoxysilylpropyl) trisulfide, bis(3 -Triethoxysilylpropyl) disulfide, bis(2-triethoxysilylethyl) tetrasulfide, bis(3-trimethoxysilylpropyl) tetrasulfide, bis(2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxy Silane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetras
- the blending amount of the silane coupling agent varies depending on the type of the silane coupling agent and the like, but is preferably in the range of 1% by mass or more and 25% by mass or less with respect to the blending amount of silica, and 2% by mass or more. The range is more preferably 20% by mass or less, and particularly preferably 3% by mass or more and 18% by mass or less.
- the rubber composition according to the present invention may further include an antioxidant.
- an antioxidant known ones can be used and are not particularly limited.
- a phenol anti-aging agent, an imidazole anti-aging agent, an amine anti-aging agent, etc. can be mentioned.
- These antioxidants can be used alone or in combination of two or more.
- the rubber composition according to the present invention may further contain a vulcanization acceleration aid.
- a vulcanization acceleration aid examples include zinc white (ZnO), fatty acids, and the like.
- the fatty acid may be saturated or unsaturated, linear or branched fatty acid, and the number of carbon atoms of the fatty acid is not particularly limited, but for example, the number of carbon atoms is preferably 1 to 30, and preferably 15 to 30.
- fatty acids are more preferable, and more specifically, cyclohexanoic acid (cyclohexanecarboxylic acid), naphthenic acid such as alkylcyclopentane having a side chain; hexanoic acid, octanoic acid, decanoic acid (branched carboxylic acid such as neodecanoic acid Saturated fatty acids such as dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid (stearic acid); unsaturated fatty acids such as methacrylic acid, oleic acid, linoleic acid, linolenic acid; rosin, tall oil acid, abietic acid, etc. Examples thereof include resin acids. These may be used alone or in combination of two or more. In the present invention, zinc white or stearic acid can be preferably used.
- the method for producing the rubber composition according to the present invention is not particularly limited, and each component (rubber component, filler and other components) constituting the rubber composition is blended and kneaded. Can be obtained by
- any rubber member forming the inside of the tire can be applied without limitation.
- the rubber member a belt coating rubber, a carcass coating rubber, a tread (tread base rubber, etc.), a shoulder portion, a sidewall portion, a stiffener rubber in a bead portion, a rubber between belt layers, a tread portion and a belt
- the rubber member examples include cushion rubber, rubber between the belt and the carcass, cushion rubber for recycled tires, and rubber for repairing tires.
- the tire tread according to the present invention is characterized by using the above-mentioned rubber composition. Since the rubber composition of the present invention is used for the tire tread that is a portion that comes into direct contact with the road surface, high performance on ice can be maintained.
- the tire according to the present invention is characterized by using the rubber composition described above. Since the tire of the present invention uses the rubber composition, high tire performance on ice can be maintained.
- a conventional method can be used.
- the manufacturing method a carcass layer containing an unvulcanized rubber on the drum for tire molding, a belt, members used for tire production such as a tread for a tire according to the present invention are sequentially laminated, and the drum is removed to remove green.
- a desired tire for example, a pneumatic tire
- Silane coupling agent bis(3-triethoxysilylpropyl) tetrasulfide, product name "Si69” manufactured by Evonik Degussa (*8)
- Process oil Naphthene type process oil Product name “Diana Process Oil NS-24” manufactured by Idemitsu Kosan Co., Ltd.
- Examples 1-2 and Comparative Examples 1-2> According to the formulation shown in Table 1, the rubber compositions of Examples 1 and 2 and Comparative Example 1 were prepared using a normal Banbury mixer. Then, the obtained vulcanized rubber was evaluated for the performance on ice by the following method. Further, in the same manner as above, a rubber composition of Comparative Example 2 was prepared by using an ordinary Banbury mixer according to the formulation shown in Table 1, and the on-ice performance was evaluated by the following method. Table 1 shows the composition and evaluation data.
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Abstract
Provided are a rubber composition with which it is possible to sustain high on-ice performance when used for a tyre, a tyre tread with which it is possible to sustain high on-ice performance, and a tyre with which it is possible to sustain high on-ice performance. This rubber composition is characterised by containing a rubber component and, in relation to 100 parts by mass of the rubber component, 0.1-20 parts by mass of a polyester polyol resin having an aromatic ring.
Description
本発明は、ゴム組成物、タイヤ用トレッド及びタイヤに関する。
The present invention relates to a rubber composition, a tire tread, and a tire.
スパイクタイヤを装着した自動車が道路を損傷することにより発生する粉（スパイクタイヤ粉塵）に対する環境面の対策として、氷上走行可能なスタッドレスタイヤ等が推奨されている。当該スタッドレスタイヤに代表される氷上走行可能なタイヤには、磨かれたアイスバーン上でのブレーキ性能及び発進性能等の氷上性能が要求される。氷上におけるタイヤの性能を向上させる方法の一つとして、例えば、特許文献１で示すように、ゴム組成物に水溶性短繊維である親水性材料を添加することによりゴム表面の親水性を向上させる方法がある。
➤ Studless tires that can run on ice are recommended as an environmental measure against dust (spike tire dust) generated when a vehicle equipped with spike tires damages the road. A tire capable of running on ice represented by the studless tire is required to have performance on ice such as braking performance and starting performance on a polished ice burn. As one of methods for improving the performance of a tire on ice, for example, as shown in Patent Document 1, by adding a hydrophilic material which is a water-soluble short fiber to a rubber composition, the hydrophilicity of the rubber surface is improved. There is a way.
上記特許文献１の技術では、親水性材料がゴム表面を親水化するため氷上性能は向上する。しかしながら、上記特許文献１のタイヤは、水溶性短繊維を使用しているため、高い氷上性能を長期間持続することが難しくなる虞がある。そこで、本発明は、タイヤに用いた場合に、高い氷上性能を持続できるゴム組成物、並びに高い氷上性能を持続できるタイヤ用トレッド、及び高い氷上性能を持続できるタイヤを提供することを目的とする。
In the technique of Patent Document 1 above, the hydrophilic material hydrophilizes the rubber surface to improve the performance on ice. However, since the tire of Patent Document 1 described above uses water-soluble short fibers, it may be difficult to maintain high performance on ice for a long period of time. Therefore, an object of the present invention is to provide a rubber composition that can maintain high on-ice performance, a tire tread that can maintain high on-ice performance, and a tire that can maintain high on-ice performance when used for a tire. ..
上記課題を解決する本発明の要旨構成は、以下の通りである。
本発明に係るゴム組成物は、ゴム成分と、前記ゴム成分１００質量部に対して、０．１質量部以上２０質量部以下の芳香族環を有するポリエステルポリオール樹脂と、を含有することを特徴とする。
本発明に係るタイヤ用トレッドは、上記ゴム組成物を用いる。
本発明に係るタイヤは、上記タイヤ用トレッドを備える。 The gist of the present invention which solves the above problems is as follows.
The rubber composition according to the present invention comprises a rubber component and a polyester polyol resin having an aromatic ring in an amount of 0.1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the rubber component. And
The above-mentioned rubber composition is used for the tire tread according to the present invention.
A tire according to the present invention includes the above-mentioned tire tread.
本発明に係るゴム組成物は、ゴム成分と、前記ゴム成分１００質量部に対して、０．１質量部以上２０質量部以下の芳香族環を有するポリエステルポリオール樹脂と、を含有することを特徴とする。
本発明に係るタイヤ用トレッドは、上記ゴム組成物を用いる。
本発明に係るタイヤは、上記タイヤ用トレッドを備える。 The gist of the present invention which solves the above problems is as follows.
The rubber composition according to the present invention comprises a rubber component and a polyester polyol resin having an aromatic ring in an amount of 0.1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the rubber component. And
The above-mentioned rubber composition is used for the tire tread according to the present invention.
A tire according to the present invention includes the above-mentioned tire tread.
本発明によれば、タイヤに用いた場合に、高い氷上性能を持続するゴム組成物を提供できる。
本発明によれば、タイヤに用いた場合に、高い氷上性能を持続するタイヤ用トレッドを提供できる。
本発明によれば、高い氷上性能を持続するタイヤを提供できる。 According to the present invention, it is possible to provide a rubber composition that maintains high on-ice performance when used in a tire.
ADVANTAGE OF THE INVENTION According to this invention, the tread for tires which maintain high on-ice performance can be provided, when it uses for a tire.
According to the present invention, it is possible to provide a tire that maintains high on-ice performance.
本発明によれば、タイヤに用いた場合に、高い氷上性能を持続するタイヤ用トレッドを提供できる。
本発明によれば、高い氷上性能を持続するタイヤを提供できる。 According to the present invention, it is possible to provide a rubber composition that maintains high on-ice performance when used in a tire.
ADVANTAGE OF THE INVENTION According to this invention, the tread for tires which maintain high on-ice performance can be provided, when it uses for a tire.
According to the present invention, it is possible to provide a tire that maintains high on-ice performance.
以下、本発明の実施形態について説明する。これらの記載は、本発明の例示を目的とするものであり、本発明を何ら限定するものではない。
An embodiment of the present invention will be described below. These descriptions are for the purpose of illustrating the present invention and are not intended to limit the present invention in any way.
「ゴム組成物」
本発明に係るゴム組成物は、ゴム成分と、前記ゴム成分１００質量部に対して、０．１質量部以上２０質量部以下の芳香族環を有するポリエステルポリオール樹脂と、を含有する。 "Rubber composition"
The rubber composition according to the present invention contains a rubber component and a polyester polyol resin having an aromatic ring in an amount of 0.1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the rubber component.
本発明に係るゴム組成物は、ゴム成分と、前記ゴム成分１００質量部に対して、０．１質量部以上２０質量部以下の芳香族環を有するポリエステルポリオール樹脂と、を含有する。 "Rubber composition"
The rubber composition according to the present invention contains a rubber component and a polyester polyol resin having an aromatic ring in an amount of 0.1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the rubber component.
本発明に係るゴム組成物に配合されたポリエステルポリオール樹脂は、芳香族環を有するため、当該ゴム組成物中の成分（主に当該ポリエステルポリオール樹脂等）が水に対して溶解することを低減又は抑制する。さらには、芳香族環を有するポリエステルポリオール樹脂が、ゴム組成物に配合されているため、適度にタイヤ表面が親水化される。そのため、芳香族環を有するポリエステルポリオール樹脂を含有するゴム組成物をタイヤに適用すると、湿潤条件下においても、高い氷上性能（又は、氷上μ向上効果とも称する）が持続すると考えられる。
Since the polyester polyol resin blended in the rubber composition according to the present invention has an aromatic ring, the components (mainly the polyester polyol resin etc.) in the rubber composition are reduced from being dissolved in water or Suppress. Furthermore, since the polyester polyol resin having an aromatic ring is mixed in the rubber composition, the tire surface is appropriately hydrophilized. Therefore, when a rubber composition containing a polyester polyol resin having an aromatic ring is applied to a tire, it is considered that high performance on ice (or also referred to as an effect of improving μ on ice) is maintained even under wet conditions.
＜ゴム成分＞
本発明に係るゴム組成物は、ゴム成分を含む。当該ゴム成分の構成については、例えば、優れた強度、低転がり抵抗性、ＷＥＴ性能又は操縦安定性を得ることができる観点から、ジエン系ゴムを含有することが好ましい。 <Rubber component>
The rubber composition according to the present invention contains a rubber component. Regarding the constitution of the rubber component, it is preferable to contain a diene rubber from the viewpoint that excellent strength, low rolling resistance, WET performance or steering stability can be obtained, for example.
本発明に係るゴム組成物は、ゴム成分を含む。当該ゴム成分の構成については、例えば、優れた強度、低転がり抵抗性、ＷＥＴ性能又は操縦安定性を得ることができる観点から、ジエン系ゴムを含有することが好ましい。 <Rubber component>
The rubber composition according to the present invention contains a rubber component. Regarding the constitution of the rubber component, it is preferable to contain a diene rubber from the viewpoint that excellent strength, low rolling resistance, WET performance or steering stability can be obtained, for example.
前記ゴム成分は、前記ジエン系ゴム１００％から構成することもできるが、本発明の目的を損なわない範囲であれば、ジエン系以外のゴム（以下、「非ジエン系ゴム」ということがある。）を含有してもよい。
The rubber component may be composed of 100% of the diene rubber, but as long as the object of the present invention is not impaired, rubber other than diene rubber (hereinafter, may be referred to as “non-diene rubber”). ) May be contained.
ここで、前記ジエン系ゴムは、特に限定されず、公知のジエン系ゴムを用いることができる。例えば、前記ジエン系ゴムとしては、天然ゴム（ＮＲ）、ブタジエンゴム（ＢＲ）、合成イソプレンゴム（ＩＲ）、スチレン・ブタジエンゴム（ＳＢＲ）、スチレン・イソプレン・ブタジエンゴム（ＳＩＢＲ）、クロロプレンゴム（ＣＲ）、アクリロニトリルブタジエンゴム（ＮＢＲ）及びこれらの変性体などが挙げられる。ジエン系ゴムは、１種を単独で用いてもよく、２種以上組み合わせて用いてもよい。
Here, the diene rubber is not particularly limited, and a known diene rubber can be used. For example, as the diene rubber, natural rubber (NR), butadiene rubber (BR), synthetic isoprene rubber (IR), styrene-butadiene rubber (SBR), styrene-isoprene-butadiene rubber (SIBR), chloroprene rubber (CR) ), acrylonitrile butadiene rubber (NBR) and modified products thereof. The diene rubbers may be used alone or in combination of two or more.
本発明におけるゴム組成物は、前記ゴム成分として、天然ゴムを含むことが好ましい。これにより、耐摩耗性を向上させることができる。
The rubber composition in the present invention preferably contains natural rubber as the rubber component. Thereby, abrasion resistance can be improved.
本発明におけるゴム組成物に天然ゴムを含む場合において、前記ゴム成分中における前記天然ゴムの割合は、４５質量％以上７５質量％以下であることが好ましく、４８質量％以上７０質量％以下であることがより好ましく、５０質量％以上６５質量％以下であることがさらに好ましい。これにより、耐摩耗性をより向上させることができる。
When the rubber composition of the present invention contains natural rubber, the ratio of the natural rubber in the rubber component is preferably 45% by mass or more and 75% by mass or less, and 48% by mass or more and 70% by mass or less. It is more preferable that the content is 50% by mass or more and 65% by mass or less. Thereby, the wear resistance can be further improved.
本発明におけるゴム組成物は、前記ゴム成分として、未変性のブタジエンゴム及び変性したブタジエンゴムからなる群より選択される１種以上を含むことが好ましい。これにより、氷上性能を向上させることができる。
The rubber composition in the present invention preferably contains, as the rubber component, at least one selected from the group consisting of unmodified butadiene rubber and modified butadiene rubber. Thereby, the performance on ice can be improved.
本発明におけるゴム組成物に未変性のブタジエンゴム又は変性したブタジエンゴムを含む場合において、前記ゴム成分中における前記未変性又は変性のブタジエンゴムの配合量の上限値は、５５質量％であることが好ましく、５２質量％であることがより好ましい。一方、前記ゴム成分中における前記未変性又は変性のブタジエンゴムの配合量の下限値は、２５質量％であることが好ましく、３０質量％であることがより好ましい。例えば、前記ゴム成分中における前記ブタジエンゴムの配合量は、２５質量％以上５５質量％以下であることが好ましい。
When the rubber composition of the present invention contains an unmodified butadiene rubber or a modified butadiene rubber, the upper limit of the compounding amount of the unmodified or modified butadiene rubber in the rubber component is 55% by mass. It is preferably 52 mass% and more preferably. On the other hand, the lower limit of the compounding amount of the unmodified or modified butadiene rubber in the rubber component is preferably 25% by mass, and more preferably 30% by mass. For example, the blending amount of the butadiene rubber in the rubber component is preferably 25% by mass or more and 55% by mass or less.
上記変性したスチレン・ブタジエンゴム及び上記変性したブタジエンゴム（以下、両ゴムを総称して「変性ゴム」ということがある。）に導入される変性基については、特に限定はされない。しかし、当該変性ゴムは、充填剤の分散性を向上させることができる観点から、末端をシラン化合物で変性していることが好ましい。シラン化合物として、例えば、グリシドキシ基を有するシラン化合物、アルコキシシラン化合物、ヒドロカルビルオキシシラン化合物等が挙げられる。
The modifying group introduced into the modified styrene-butadiene rubber and the modified butadiene rubber (hereinafter, both rubbers may be collectively referred to as “modified rubber”) is not particularly limited. However, it is preferable that the terminal of the modified rubber is modified with a silane compound from the viewpoint that the dispersibility of the filler can be improved. Examples of the silane compound include a silane compound having a glycidoxy group, an alkoxysilane compound, a hydrocarbyloxysilane compound, and the like.
前記変性ゴムとしては、単量体として共役ジエン化合物を使用して得た、該共役ジエン化合物の重合体又は共重合体、或いは、単量体として共役ジエン化合物と芳香族ビニル化合物を使用して得た、該共役ジエン化合物と芳香族ビニル化合物との共重合体を使用することができ、また、これら（共）重合体の分子末端及び／又は主鎖を変性したものを使用することもできる。具体的に、分子末端を変性した公知の変性ゴムとしては、国際公開第２００３／０２９２９９号、国際公開第２００３／０４６０２０号、特表２００４－５１３９８７号公報、特開平１１－２９６０３号公報、特開２００３－１１３２０２号公報、特開２００７－２１７５６２号公報、及び、特公平６－２９３３８号公報等に開示の変性ジエン系ゴムを例示することができ、主鎖を変性した公知の変性ゴムとしては、特表２００３－５３４４２６号公報、及び、特開２００２－２０１３１０号公報等に開示の変性ジエン系ゴムを例示できる。
As the modified rubber, obtained by using a conjugated diene compound as a monomer, a polymer or copolymer of the conjugated diene compound, or using a conjugated diene compound and an aromatic vinyl compound as a monomer The obtained copolymer of the conjugated diene compound and the aromatic vinyl compound can be used, and those obtained by modifying the molecular end and/or the main chain of these (co)polymers can also be used. .. Specifically, known modified rubbers having modified molecular ends include WO 2003/029299, WO 2003/046020, JP-A 2004-513987, JP-A 11-29603, and JP-A 11-29603. Examples of the modified diene rubbers disclosed in 2003-113202, JP-A 2007-217562, and Japanese Patent Publication No. 6-29338 include known modified rubbers having a modified main chain. The modified diene rubbers disclosed in JP 2003-534426 A and JP 2002-201310 A can be exemplified.
また、上記変性したスチレン・ブタジエンゴムとしては、国際公開第２０１７／０７７７１２号のポリマー成分Ｐ２としての変性（共）重合体及び実施例に記載の変性重合体Ｃ、変性重合体Ｄ、及び国際公開第２０１８／１８６３６７号に記載されている変性共役ジエン系重合体（Ａ２）などが挙げられる。
As the modified styrene-butadiene rubber, the modified (co)polymer as the polymer component P2 of WO2017/0777712 and the modified polymer C, the modified polymer D described in Examples and the international publication. Examples include the modified conjugated diene polymer (A2) described in No. 2018/186367.
＜芳香族環を有するポリエステルポリオール樹脂＞
本発明におけるゴム組成物は、芳香族環を有するポリエステルポリオール樹脂を含む。芳香族環が疎水性部位として作用するため、前記芳香族環を有するポリエステルポリオール樹脂は、疎水部を備えた親水性材料であるとも言える。このような疎水部を備えた親水性材料は、その化学構造により、ゴム表面を親水化する材料（当該芳香族環を有するポリエステルポリオール樹脂等）の水溶けを低減又は抑制するため、氷上μ向上効果が持続されると考えられる。したがって、芳香族環を有するポリエステルポリオール樹脂をゴム組成物に配合することにより、タイヤ表面の親水性を向上させ、かつ高い氷上性能が持続される。 <Polyester polyol resin having an aromatic ring>
The rubber composition in the present invention contains a polyester polyol resin having an aromatic ring. Since the aromatic ring acts as a hydrophobic site, it can be said that the polyester polyol resin having an aromatic ring is a hydrophilic material having a hydrophobic portion. Due to its chemical structure, the hydrophilic material having such a hydrophobic portion reduces or suppresses the water solubility of the material that makes the rubber surface hydrophilic (such as the polyester polyol resin having the aromatic ring), and therefore improves μ on ice. The effect is considered to be sustained. Therefore, by blending the polyester polyol resin having an aromatic ring with the rubber composition, the hydrophilicity of the tire surface is improved and high performance on ice is maintained.
本発明におけるゴム組成物は、芳香族環を有するポリエステルポリオール樹脂を含む。芳香族環が疎水性部位として作用するため、前記芳香族環を有するポリエステルポリオール樹脂は、疎水部を備えた親水性材料であるとも言える。このような疎水部を備えた親水性材料は、その化学構造により、ゴム表面を親水化する材料（当該芳香族環を有するポリエステルポリオール樹脂等）の水溶けを低減又は抑制するため、氷上μ向上効果が持続されると考えられる。したがって、芳香族環を有するポリエステルポリオール樹脂をゴム組成物に配合することにより、タイヤ表面の親水性を向上させ、かつ高い氷上性能が持続される。 <Polyester polyol resin having an aromatic ring>
The rubber composition in the present invention contains a polyester polyol resin having an aromatic ring. Since the aromatic ring acts as a hydrophobic site, it can be said that the polyester polyol resin having an aromatic ring is a hydrophilic material having a hydrophobic portion. Due to its chemical structure, the hydrophilic material having such a hydrophobic portion reduces or suppresses the water solubility of the material that makes the rubber surface hydrophilic (such as the polyester polyol resin having the aromatic ring), and therefore improves μ on ice. The effect is considered to be sustained. Therefore, by blending the polyester polyol resin having an aromatic ring with the rubber composition, the hydrophilicity of the tire surface is improved and high performance on ice is maintained.
前記芳香族環を有するポリエステルポリオール樹脂は、芳香族環を主鎖又は側鎖に含むポリエステルポリオール樹脂であることが好ましく、水に対する非溶解性の観点から、主鎖に芳香族環を有するポリエステルポリオール樹脂がより好ましい。
The polyester polyol resin having an aromatic ring is preferably a polyester polyol resin containing an aromatic ring in its main chain or side chain, and from the viewpoint of insolubility in water, a polyester polyol having an aromatic ring in its main chain. Resins are more preferred.
前記芳香族環を有するポリエステルポリオール樹脂は、例えば、芳香族多価カルボン酸と多価アルコールとの重縮合物であって、１分子内に水酸基を２個以上有する樹脂、又は、多価カルボン酸と芳香族多価アルコールとの重縮合物であって、１分子内に水酸基を２個以上有する樹脂などが挙げられる。芳香族環を有するポリエステルポリオール樹脂は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
The polyester polyol resin having an aromatic ring is, for example, a polycondensation product of an aromatic polyvalent carboxylic acid and a polyhydric alcohol, which is a resin having two or more hydroxyl groups in one molecule, or a polyvalent carboxylic acid. And a polycondensate of an aromatic polyhydric alcohol, which includes a resin having two or more hydroxyl groups in one molecule. The polyester polyol resin having an aromatic ring may be used alone or in combination of two or more.
上記芳香族多価カルボン酸としては、イソフタル酸、フタル酸、テレフタル酸、フランジカルボン酸、ジフェニルジカルボン酸若しくはナフタレンジカルボン酸等の芳香族ジカルボン酸、又はナフタレントリカルボン酸等の芳香族トリカルボン酸が挙げられる。前記芳香族多価カルボン酸としては、芳香族ジカルボン酸が好ましい。
Examples of the aromatic polycarboxylic acid include isophthalic acid, phthalic acid, terephthalic acid, furandicarboxylic acid, aromatic dicarboxylic acid such as diphenyldicarboxylic acid or naphthalene dicarboxylic acid, or aromatic tricarboxylic acid such as naphthalene tricarboxylic acid. .. The aromatic polycarboxylic acid is preferably an aromatic dicarboxylic acid.
上記多価アルコールとしては、ジアルコール、トリアルコール等が挙げられ、具体的には、エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，６－ヘキサンジオール、メチルペンタンジオール、プロピレングリコール、ジプロピレングリコール、１，４－ブタンジオール、トリメチロールエタン、トリメチロールプロパン、ネオペンチルグリコール等が挙げられる。前記多価アルコールとしては、ジアルコールが好ましい。
Examples of the polyhydric alcohol include dialcohol and trialcohol, and specifically, ethylene glycol, diethylene glycol, triethylene glycol, 1,6-hexanediol, methylpentanediol, propylene glycol, dipropylene glycol, 1 , 4-butanediol, trimethylolethane, trimethylolpropane, neopentyl glycol and the like. The polyhydric alcohol is preferably dialcohol.
上記多価カルボン酸としては、シュウ酸、マロン酸、コハク酸、無水コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、セバシン酸、アゼライン酸等が挙げられる。
Examples of the polycarboxylic acid include oxalic acid, malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid and the like.
上記芳香族多価アルコールとしては、１，２－ベンゼンジメタノール、１，３－ベンゼンジメタノール、１，４－ベンゼンジメタノール、ビスフェノールＡ、レゾルシノール等が挙げられる。
Examples of the aromatic polyhydric alcohol include 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, bisphenol A and resorcinol.
本発明に係るゴム組成物に配合する芳香族環を有するポリエステルポリオール樹脂は、公知の方法で合成した樹脂を使用してもよく、又は市販品を使用してもよい。市販品としては、例えば、日本ゼオン社製 商品名「ゼオファイン」シリーズ等が挙げられる。
As the polyester polyol resin having an aromatic ring to be blended with the rubber composition according to the present invention, a resin synthesized by a known method may be used, or a commercially available product may be used. Examples of commercially available products include "Zeofine" series manufactured by Nippon Zeon Co., Ltd.
本発明における芳香族環を有するポリエステルポリオール樹脂の重量平均分子量は、２００００以上１０００００以下が好ましく、３００００以上８００００以下が好ましい。上記芳香族環を有するポリエステルポリオール樹脂の重量平均分子量が２００００以上であると、分子量効果により、水溶けを低減又は抑制しやすい。また、当該重量平均分子量が１０００００以下であると、他の成分と相溶し易い。なお、本発明において、重量平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によって測定する。また、当該重量平均分子量は、標準ポリスチレン換算分子量である。
The weight average molecular weight of the polyester polyol resin having an aromatic ring in the present invention is preferably 20,000 or more and 100,000 or less, and preferably 30,000 or more and 80,000 or less. When the weight average molecular weight of the above polyester polyol resin having an aromatic ring is 20,000 or more, it is easy to reduce or suppress water solubility due to the molecular weight effect. Moreover, when the said weight average molecular weight is 100,000 or less, it will be easy to be compatible with other components. In the present invention, the weight average molecular weight is measured by GPC (gel permeation chromatography). Moreover, the said weight average molecular weight is a standard polystyrene conversion molecular weight.
本発明における芳香族環を有するポリエステルポリオール樹脂は、水酸基価が４５～７８ｍｇＫＯＨ／ｇが好ましい。当該ポリエステルポリオール樹脂における１分子内の水酸基の数は、３以上が好ましい。
The polyester polyol resin having an aromatic ring in the present invention preferably has a hydroxyl value of 45 to 78 mgKOH/g. The number of hydroxyl groups in one molecule in the polyester polyol resin is preferably 3 or more.
本発明に係るゴム組成物において、前記芳香族環を有するポリエステルポリオール樹脂の配合量は、ゴム成分１００質量部に対して、０．１質量部以上２０質量部以下である。前記配合量が、上記範囲であると、水への溶解が低減され、かつ親水性が向上する。上記ポリエステルポリオール樹脂の配合量は、ゴム成分１００質量部に対して、例えば、０．７質量部以上、２質量部以上、３．６質量部以上であることが好ましい。また、前記ポリエステルポリオール樹脂の配合量は、ゴム成分１００質量部に対して、例えば、１８質量部以下、１６質量部以下、１３質量部以下であることが好ましい。
In the rubber composition according to the present invention, the compounding amount of the polyester polyol resin having an aromatic ring is 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the rubber component. When the blending amount is within the above range, solubility in water is reduced and hydrophilicity is improved. The blending amount of the polyester polyol resin is preferably, for example, 0.7 parts by mass or more, 2 parts by mass or more, and 3.6 parts by mass or more with respect to 100 parts by mass of the rubber component. Further, the blending amount of the polyester polyol resin is preferably, for example, 18 parts by mass or less, 16 parts by mass or less, and 13 parts by mass or less based on 100 parts by mass of the rubber component.
＜充填剤＞
本発明に係るゴム組成物は、上記のゴム成分及び上記の芳香族を有するポリエステルポリオール樹脂に加えて、必要により充填剤を含んでもよい。当該充填剤としては、例えば、シリカ、カーボンブラック、酸化アルミニウム、クレー、アルミナ、タルク、マイカ、カオリン、ガラスバルーン、ガラスビーズ、炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、酸化マグネシウム、酸化チタン、チタン酸カリウム、硫酸バリウムなどが挙げられる。充填剤は、１種を単独で用いてもよく、２種以上組み合わせて用いてもよい。補強性と低転がり抵抗性の観点から、充填剤はシリカを含むことが好ましい。 <Filler>
The rubber composition according to the present invention may optionally contain a filler in addition to the above rubber component and the above polyester polyol resin having an aromatic group. Examples of the filler include silica, carbon black, aluminum oxide, clay, alumina, talc, mica, kaolin, glass balloons, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, titanium oxide, titanic acid. Examples thereof include potassium and barium sulfate. The fillers may be used alone or in combination of two or more. From the viewpoint of reinforcing properties and low rolling resistance, the filler preferably contains silica.
本発明に係るゴム組成物は、上記のゴム成分及び上記の芳香族を有するポリエステルポリオール樹脂に加えて、必要により充填剤を含んでもよい。当該充填剤としては、例えば、シリカ、カーボンブラック、酸化アルミニウム、クレー、アルミナ、タルク、マイカ、カオリン、ガラスバルーン、ガラスビーズ、炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、酸化マグネシウム、酸化チタン、チタン酸カリウム、硫酸バリウムなどが挙げられる。充填剤は、１種を単独で用いてもよく、２種以上組み合わせて用いてもよい。補強性と低転がり抵抗性の観点から、充填剤はシリカを含むことが好ましい。 <Filler>
The rubber composition according to the present invention may optionally contain a filler in addition to the above rubber component and the above polyester polyol resin having an aromatic group. Examples of the filler include silica, carbon black, aluminum oxide, clay, alumina, talc, mica, kaolin, glass balloons, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, titanium oxide, titanic acid. Examples thereof include potassium and barium sulfate. The fillers may be used alone or in combination of two or more. From the viewpoint of reinforcing properties and low rolling resistance, the filler preferably contains silica.
上記シリカとしては、特に限定されず、目的に応じて適宜選択することができ、例えば、湿式シリカ（含水ケイ酸）、乾式シリカ（無水ケイ酸）、ケイ酸カルシウム、ケイ酸アルミニウムなどが挙げられる。
The silica is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, and aluminum silicate. ..
シリカのＢＥＴ比表面積は、特に限定されず、例えば、好ましくは、４０～３５０ｍ２／ｇであり、より好ましくは、８０～３００ｍ２／ｇであり、さらに好ましくは、１５０～２８０ｍ２／ｇであり、よりさらに好ましくは、１８０～２７０ｍ２／ｇであり、特に好ましくは、２００～２６０ｍ２／ｇである。
The BET specific surface area of silica is not particularly limited and is, for example, preferably 40 to 350 m 2 /g, more preferably 80 to 300 m 2 /g, further preferably 150 to 280 m 2 /g. Yes, even more preferably 180 to 270 m 2 /g, and particularly preferably 200 to 260 m 2 /g.
シリカのＢＥＴ比表面積が上記範囲であると、発生した水の除水性をより向上することから、氷上性能がより向上する。
When the BET specific surface area of silica is within the above range, the water removal property of the generated water is further improved, so that the performance on ice is further improved.
カーボンブラックとしては、特に限定されず、例えば高、中又は低ストラクチャーの、ＳＡＦ、ＩＳＡＦ、ＩＳＡＦ－ＨＳ、ＩＩＳＡＦ、Ｎ３３９、ＨＡＦ、ＦＥＦ、ＧＰＦ、ＳＲＦグレードなどのカーボンブラックが挙げられる。
The carbon black is not particularly limited, and examples thereof include high, medium or low structure carbon black such as SAF, ISAF, ISAF-HS, IISAF, N339, HAF, FEF, GPF and SRF grade.
本発明における充填剤は、シリカ及びカーボンブラックからなる群から選択される少なくとも１種を含むことが好ましく、シリカ及びカーボンブラックを含むことがより好ましい。充填剤として、シリカ及びカーボンブラックからなる群から選択される少なくとも１種をゴム組成物に配合すると、弾性率、強度、除水性効果、又は耐摩耗性等が向上する。
The filler in the present invention preferably contains at least one selected from the group consisting of silica and carbon black, and more preferably contains silica and carbon black. When at least one selected from the group consisting of silica and carbon black is added to the rubber composition as a filler, the elastic modulus, strength, water removing effect, abrasion resistance, etc. are improved.
本発明に係るゴム組成物に充填剤を配合する場合において、充填剤の配合量としては、特に限定されず、適宜調節すればよいが、例えば、ゴム成分１００質量部に対して２０質量部以上１２０質量部以下であることが好ましい。充填剤の配合量は、氷上性能と作業性の観点から、ゴム成分１００質量部に対して５０質量部以上１００質量部以下であることがより好ましい。
In the case of adding a filler to the rubber composition according to the present invention, the amount of the filler to be added is not particularly limited and may be appropriately adjusted. For example, 20 parts by mass or more based on 100 parts by mass of the rubber component. It is preferably 120 parts by mass or less. From the viewpoint of performance on ice and workability, the amount of the filler to be blended is more preferably 50 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the rubber component.
本発明に係るゴム組成物にシリカを配合する場合において、シリカの配合量は、特に限定されず、目的に応じて適宜調節できるが、前記ゴム成分１００質量部に対して、例えば、２０質量部以上６０質量部以下であることが好ましく、２５質量部以上５０質量部以下であることがより好ましい。
When silica is compounded in the rubber composition according to the present invention, the compounding amount of silica is not particularly limited and can be appropriately adjusted according to the purpose. For example, 20 parts by mass with respect to 100 parts by mass of the rubber component. The amount is preferably 60 parts by mass or more and more preferably 25 parts by mass or more and 50 parts by mass or less.
本発明に係るゴム組成物にカーボンブラックを配合する場合において、カーボンブラックの配合量は、特に限定されず、目的に応じて適宜調節できるが、前記ゴム成分１００質量部に対して、例えば、１０質量部以上６０質量部以下であることが好ましく、２０質量部以上５０質量部以下であることがより好ましい。また、カーボンブラックとシリカとを併用する場合、カーボンブラックとシリカとの合計配合量は、前記ゴム成分１００質量部に対して、５０質量部以上１２０質量部以下であることが好ましく、６０質量部以上９０質量部以下であることがより好ましい。
When carbon black is compounded in the rubber composition according to the present invention, the compounding amount of carbon black is not particularly limited and may be appropriately adjusted according to the purpose. The amount is preferably not less than 60 parts by mass and more preferably not less than 20 parts by mass and not more than 50 parts by mass. When carbon black and silica are used in combination, the total blending amount of carbon black and silica is preferably 50 parts by mass or more and 120 parts by mass or less, and 60 parts by mass with respect to 100 parts by mass of the rubber component. More preferably, it is 90 parts by mass or less.
本発明に係るゴム組成物において、カーボンブラックとシリカとを併用する場合、カーボンブラックとシリカの総配合量（１００質量％）に対するシリカの比率は２０～７８質量％が好ましく、３０～７２質量％がより好ましく、３４～６７質量％であると更に好ましい。シリカ比率を上記の範囲内
When carbon black and silica are used in combination in the rubber composition according to the present invention, the ratio of silica to the total amount of carbon black and silica (100% by mass) is preferably 20 to 78% by mass, and 30 to 72% by mass. Is more preferable, and further preferably 34 to 67% by mass. Silica ratio within the above range
＜その他の成分＞
本発明におけるゴム組成物は、上述した、ゴム成分、ポリエステルポリオール樹脂、及び必要により配合される充填剤の他にも、その他の成分を、発明の効果を損なわない程度に含んでもよい。当該その他の成分として、例えば、他の熱可塑性樹脂（芳香族環を有するポリエステルポリオール樹脂以外）、軟化剤、加硫剤、加硫促進剤、シランカップリング剤、老化防止剤、加硫促進助剤、オゾン劣化防止剤、及び界面活性剤等の、ゴム工業で通常使用されている添加剤からなる群から選択される少なくとも１種を適宜含んでもよい。 <Other ingredients>
The rubber composition in the present invention may contain other components in addition to the above-mentioned rubber component, polyester polyol resin, and filler to be blended as necessary, to the extent that the effects of the invention are not impaired. As the other components, for example, other thermoplastic resin (other than polyester polyol resin having an aromatic ring), softening agent, vulcanizing agent, vulcanization accelerator, silane coupling agent, antioxidant, vulcanization accelerating aid At least one selected from the group consisting of additives usually used in the rubber industry, such as an agent, an antiozonant, and a surfactant, may be appropriately contained.
本発明におけるゴム組成物は、上述した、ゴム成分、ポリエステルポリオール樹脂、及び必要により配合される充填剤の他にも、その他の成分を、発明の効果を損なわない程度に含んでもよい。当該その他の成分として、例えば、他の熱可塑性樹脂（芳香族環を有するポリエステルポリオール樹脂以外）、軟化剤、加硫剤、加硫促進剤、シランカップリング剤、老化防止剤、加硫促進助剤、オゾン劣化防止剤、及び界面活性剤等の、ゴム工業で通常使用されている添加剤からなる群から選択される少なくとも１種を適宜含んでもよい。 <Other ingredients>
The rubber composition in the present invention may contain other components in addition to the above-mentioned rubber component, polyester polyol resin, and filler to be blended as necessary, to the extent that the effects of the invention are not impaired. As the other components, for example, other thermoplastic resin (other than polyester polyol resin having an aromatic ring), softening agent, vulcanizing agent, vulcanization accelerator, silane coupling agent, antioxidant, vulcanization accelerating aid At least one selected from the group consisting of additives usually used in the rubber industry, such as an agent, an antiozonant, and a surfactant, may be appropriately contained.
（他の熱可塑性樹脂）
本発明に係るゴム組成物は、上記芳香族環を有するポリエステルポリオール樹脂の少なくともいずれか１種に加えて、他の熱可塑性樹脂をさらに含んでもよい。前記他の熱可塑性樹脂の種類については、特に限定はされず、例えば、Ｃ５系樹脂、Ｃ９系樹脂、Ｃ５～Ｃ９系樹脂、ジシクロペンタジエン系樹脂、ロジン系樹脂、アルキルフェノール系樹脂、又はテルペンフェノール系樹脂等が挙げられる。これらは水添されていてもよく、水添されていなくてもよい。他の熱可塑性樹脂をさらに含むと、ゴム成分又は芳香族環を有するポリエステルポリオール樹脂等との相溶性が向上するため、ゴム組成物を加工し易くなる。 (Other thermoplastic resins)
The rubber composition according to the present invention may further contain another thermoplastic resin in addition to at least one kind of the polyester polyol resin having an aromatic ring. The type of the other thermoplastic resin is not particularly limited, and examples thereof include C 5 resin, C 9 resin, C 5 to C 9 resin, dicyclopentadiene resin, rosin resin, alkylphenol resin. Or a terpene phenolic resin or the like. These may or may not be hydrogenated. When the thermoplastic resin further contains another thermoplastic resin, the compatibility with the rubber component or the polyester polyol resin having an aromatic ring is improved, so that the rubber composition is easily processed.
本発明に係るゴム組成物は、上記芳香族環を有するポリエステルポリオール樹脂の少なくともいずれか１種に加えて、他の熱可塑性樹脂をさらに含んでもよい。前記他の熱可塑性樹脂の種類については、特に限定はされず、例えば、Ｃ５系樹脂、Ｃ９系樹脂、Ｃ５～Ｃ９系樹脂、ジシクロペンタジエン系樹脂、ロジン系樹脂、アルキルフェノール系樹脂、又はテルペンフェノール系樹脂等が挙げられる。これらは水添されていてもよく、水添されていなくてもよい。他の熱可塑性樹脂をさらに含むと、ゴム成分又は芳香族環を有するポリエステルポリオール樹脂等との相溶性が向上するため、ゴム組成物を加工し易くなる。 (Other thermoplastic resins)
The rubber composition according to the present invention may further contain another thermoplastic resin in addition to at least one kind of the polyester polyol resin having an aromatic ring. The type of the other thermoplastic resin is not particularly limited, and examples thereof include C 5 resin, C 9 resin, C 5 to C 9 resin, dicyclopentadiene resin, rosin resin, alkylphenol resin. Or a terpene phenolic resin or the like. These may or may not be hydrogenated. When the thermoplastic resin further contains another thermoplastic resin, the compatibility with the rubber component or the polyester polyol resin having an aromatic ring is improved, so that the rubber composition is easily processed.
また、本発明に係るゴム組成物に他の熱可塑性樹脂を含む場合、当該他の熱可塑性樹脂の配合量は、特に限定はされないが、前記ゴム成分１００質量部に対して５質量部以上５０質量部以下であることが好ましい。前記他の熱可塑性樹脂の配合量が５質量部以上５０質量部以下であると、ゴム組成物をタイヤに用いた場合の制動性能がより向上する。
When the rubber composition according to the present invention contains another thermoplastic resin, the compounding amount of the other thermoplastic resin is not particularly limited, but is 5 parts by mass or more and 50 parts by mass or more with respect to 100 parts by mass of the rubber component. It is preferably less than or equal to parts by mass. When the blending amount of the other thermoplastic resin is 5 parts by mass or more and 50 parts by mass or less, braking performance when the rubber composition is used in a tire is further improved.
（軟化剤）
本発明に係るゴム組成物は、軟化剤をさらに含んでもよい。ゴム組成物に軟化剤を含むことにより、柔軟性をさらに付与できるため、氷上性能をより向上させることができる。 (Softener)
The rubber composition according to the present invention may further contain a softening agent. By including the softening agent in the rubber composition, flexibility can be further imparted, and thus the performance on ice can be further improved.
本発明に係るゴム組成物は、軟化剤をさらに含んでもよい。ゴム組成物に軟化剤を含むことにより、柔軟性をさらに付与できるため、氷上性能をより向上させることができる。 (Softener)
The rubber composition according to the present invention may further contain a softening agent. By including the softening agent in the rubber composition, flexibility can be further imparted, and thus the performance on ice can be further improved.
ここで、前記軟化剤としては、脂肪族エステル、リン酸エステル、鉱物由来のミネラルオイル、石油由来のアロマチックオイル、パラフィンオイル、ナフテンオイル、天然物由来のパームオイル、ヒマワリ油、ひまし油、綿実油、大豆油等が挙げられる。軟化剤は、１種を単独で用いてもよく、２種以上組み合わせて用いてもよい。
Here, as the softening agent, aliphatic ester, phosphate ester, mineral oil derived from minerals, aromatic oil derived from petroleum, paraffin oil, naphthene oil, palm oil derived from natural products, sunflower oil, castor oil, cottonseed oil, Soybean oil and the like can be mentioned. The softening agents may be used alone or in combination of two or more.
本発明に係るゴム組成物が軟化剤を含む場合において、本発明のゴム組成物の軟化剤の含有量は、ゴム成分１００質量部に対して、２０質量部以下であることが好ましく、１５質量部以下であることがより好ましい。軟化剤の配合量が、上記範囲を満たすと、氷上性能と摩耗性能とが両立し易くなる。
When the rubber composition according to the present invention contains a softening agent, the content of the softening agent in the rubber composition of the present invention is preferably 20 parts by mass or less, and 15 parts by mass with respect to 100 parts by mass of the rubber component. It is more preferably not more than part. When the blending amount of the softening agent satisfies the above range, the performance on ice and the wear performance are easily compatible with each other.
（加硫剤）
本発明に係るゴム組成物は、加硫剤をさらに含んでもよい。加硫剤としては、特に限定されず、目的に応じて適宜選択することができ、例えば、硫黄又はビスマレイミド化合物等が挙げられる。加硫剤は、１種を単独で用いてもよく、２種以上組み合わせて用いてもよい。 (Vulcanizing agent)
The rubber composition according to the present invention may further contain a vulcanizing agent. The vulcanizing agent is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include sulfur and bismaleimide compounds. The vulcanizing agents may be used alone or in combination of two or more.
本発明に係るゴム組成物は、加硫剤をさらに含んでもよい。加硫剤としては、特に限定されず、目的に応じて適宜選択することができ、例えば、硫黄又はビスマレイミド化合物等が挙げられる。加硫剤は、１種を単独で用いてもよく、２種以上組み合わせて用いてもよい。 (Vulcanizing agent)
The rubber composition according to the present invention may further contain a vulcanizing agent. The vulcanizing agent is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include sulfur and bismaleimide compounds. The vulcanizing agents may be used alone or in combination of two or more.
加硫剤の配合量としては、特に限定されず、目的に応じて適宜調節することができ、例えば、ゴム成分１００質量部に対して、０．１質量部以上２．０質量部以下が好ましく、１．０質量部以上２．０質量部以下がより好ましく、１．２質量部以上１．８質量部以下が特に好ましい。
The compounding amount of the vulcanizing agent is not particularly limited and can be appropriately adjusted according to the purpose. For example, 0.1 part by mass or more and 2.0 parts by mass or less is preferable with respect to 100 parts by mass of the rubber component. , 1.0 parts by mass or more and 2.0 parts by mass or less are more preferable, and 1.2 parts by mass or more and 1.8 parts by mass or less are particularly preferable.
（加硫促進剤）
本発明に係るゴム組成物は、加硫促進剤をさらに含んでもよい。前記加硫促進剤としては、特に限定されず、目的に応じて適宜選択することができ、例えば、グアニジン類、スルフェンアミド類、チアゾール類、チオウレア及びジエチルチオウレアの中から選ばれる少なくとも１種であることが好ましい。加硫促進剤は、１種を単独で用いてもよく、２種以上組み合わせて用いてもよい。 (Vulcanization accelerator)
The rubber composition according to the present invention may further contain a vulcanization accelerator. The vulcanization accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one selected from guanidines, sulfenamides, thiazoles, thiourea and diethylthiourea. Preferably. The vulcanization accelerators may be used alone or in combination of two or more.
本発明に係るゴム組成物は、加硫促進剤をさらに含んでもよい。前記加硫促進剤としては、特に限定されず、目的に応じて適宜選択することができ、例えば、グアニジン類、スルフェンアミド類、チアゾール類、チオウレア及びジエチルチオウレアの中から選ばれる少なくとも１種であることが好ましい。加硫促進剤は、１種を単独で用いてもよく、２種以上組み合わせて用いてもよい。 (Vulcanization accelerator)
The rubber composition according to the present invention may further contain a vulcanization accelerator. The vulcanization accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one selected from guanidines, sulfenamides, thiazoles, thiourea and diethylthiourea. Preferably. The vulcanization accelerators may be used alone or in combination of two or more.
加硫促進剤の配合量としては、特に限定されず、目的に応じて適宜調節することができ、例えば、ゴム成分１００質量部に対して０．１質量部以上２０質量部以下である。０．１質量部以上であると、加硫の効果が得られやすく、２０質量部以下であると、加硫の過度の進行を抑制できる。
The compounding amount of the vulcanization accelerator is not particularly limited and can be appropriately adjusted according to the purpose, and is, for example, 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the rubber component. When the amount is 0.1 parts by mass or more, the effect of vulcanization is easily obtained, and when the amount is 20 parts by mass or less, excessive progress of vulcanization can be suppressed.
（シランカップリング剤）
本発明に係るゴム組成物は、充填剤としてシリカを含む場合には、シランカップリング剤をさらに含むことが好ましい。シランカップリング剤を用いることによって、シリカの分散性の向上、ゴム加工時の作業性の向上、又は耐摩耗性の向上といった効果が得られる。シランカップリング剤は１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 (Silane coupling agent)
When the rubber composition according to the present invention contains silica as a filler, it preferably further contains a silane coupling agent. By using the silane coupling agent, the effects of improving the dispersibility of silica, the workability during rubber processing, or the abrasion resistance can be obtained. The silane coupling agent may be used alone or in combination of two or more.
本発明に係るゴム組成物は、充填剤としてシリカを含む場合には、シランカップリング剤をさらに含むことが好ましい。シランカップリング剤を用いることによって、シリカの分散性の向上、ゴム加工時の作業性の向上、又は耐摩耗性の向上といった効果が得られる。シランカップリング剤は１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 (Silane coupling agent)
When the rubber composition according to the present invention contains silica as a filler, it preferably further contains a silane coupling agent. By using the silane coupling agent, the effects of improving the dispersibility of silica, the workability during rubber processing, or the abrasion resistance can be obtained. The silane coupling agent may be used alone or in combination of two or more.
前記シランカップリング剤は、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（エボニック・デグッサ社製の商品名「Ｓｉ６９」等）、ビス（３－トリエトキシシリルプロピル）トリスルフィド、ビス（３－トリエトキシシリルプロピル）ジスルフィド、ビス（２－トリエトキシシリルエチル）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－トリメトキシシリルエチル）テトラスルフィド、３－メルカプトプロピルトリメトキシシラン、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、２－メルカプトエチルトリエトキシシラン、３－トリメトキシシリルプロピル－Ｎ，Ｎ－ジメチルチオカルバモイルテトラスルフィド、３－トリエトキシシリルプロピル－Ｎ，Ｎ－ジメチルチオカルバモイルテトラスルフィド、２－トリエトキシシリルエチル－Ｎ，Ｎ－ジメチルチオカルバモイルテトラスルフィド、３－トリメトキシシリルプロピルベンゾチアゾリルテトラスルフィド、３－トリエトキシシリルプロピルベンゾリルテトラスルフィド、３－トリエトキシシリルプロピルメタクリレートモノスルフィド、３－トリメトキシシリルプロピルメタクリレートモノスルフィド、ビス（３－ジエトキシメチルシリルプロピル）テトラスルフィド、３－メルカプトプロピルジメトキシメチルシラン、ジメトキシメチルシリルプロピル－Ｎ，Ｎ－ジメチルチオカルバモイルテトラスルフィド、ジメトキシメチルシリルプロピルベンゾチアゾリルテトラスルフィド、３－オクタノイルチオプロピルトリエトキシシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、又は３－［エトキシビス（３，６，９，１２，１５－ペンタオキサオクタコサン－１－イルオキシ）シリル］－１－プロパンチオール（エボニック・デグッサ社製の商品名「Ｓｉ３６３」等）等が挙げられる。なお、これらのシランカップリング剤は、１種を単独で用いてもよく、２種以上組み合わせて用いてもよい。
Examples of the silane coupling agent include bis(3-triethoxysilylpropyl) tetrasulfide (trade name “Si69” manufactured by Evonik Degussa), bis(3-triethoxysilylpropyl) trisulfide, bis(3 -Triethoxysilylpropyl) disulfide, bis(2-triethoxysilylethyl) tetrasulfide, bis(3-trimethoxysilylpropyl) tetrasulfide, bis(2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxy Silane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl- N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzoyl tetrasulfide , 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N -Dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropyl benzothiazolyl tetrasulfide, 3-octanoylthiopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl Trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or 3-[ethoxybis(3,6,9,12,15-penta Examples thereof include oxaoctacosan-1-yloxy)silyl]-1-propanethiol (trade name “Si363” manufactured by Evonik Degussa). In addition, these silane coupling agents may be used individually by 1 type, and may be used in combination of 2 or more type.
前記シランカップリング剤の配合量については、シランカップリング剤の種類などにより異なるが、シリカの配合量に対して、１質量％以上２５質量％以下の範囲であることが好ましく、２質量％以上２０質量％以下の範囲であることがより好ましく、３質量％以上１８質量％以下の範囲であることが特に好ましい。シランカップリング剤の配合量を１質量％以上とすることにより、ゴム組成物の発熱性の低減の効果を得やすく、カップリング剤としての効果を充分に発揮できる。また、前記配合量を２５質量％以下とすることにより、ゴム成分のゲル化を抑制できる。
The blending amount of the silane coupling agent varies depending on the type of the silane coupling agent and the like, but is preferably in the range of 1% by mass or more and 25% by mass or less with respect to the blending amount of silica, and 2% by mass or more. The range is more preferably 20% by mass or less, and particularly preferably 3% by mass or more and 18% by mass or less. By setting the amount of the silane coupling agent to be 1% by mass or more, the effect of reducing the heat buildup of the rubber composition can be easily obtained, and the effect as the coupling agent can be sufficiently exhibited. Further, by setting the blending amount to 25% by mass or less, gelation of the rubber component can be suppressed.
（老化防止剤）
本発明に係るゴム組成物は、老化防止剤をさらに含んでもよい。前記老化防止剤としては、公知のものを用いることができ、特に制限されない。例えば、フェノール系老化防止剤、イミダゾール系老化防止剤、アミン系老化防止剤等を挙げることができる。これら老化防止剤は、１種又は２種以上を併用できる。 (Anti-aging agent)
The rubber composition according to the present invention may further include an antioxidant. As the antiaging agent, known ones can be used and are not particularly limited. For example, a phenol anti-aging agent, an imidazole anti-aging agent, an amine anti-aging agent, etc. can be mentioned. These antioxidants can be used alone or in combination of two or more.
本発明に係るゴム組成物は、老化防止剤をさらに含んでもよい。前記老化防止剤としては、公知のものを用いることができ、特に制限されない。例えば、フェノール系老化防止剤、イミダゾール系老化防止剤、アミン系老化防止剤等を挙げることができる。これら老化防止剤は、１種又は２種以上を併用できる。 (Anti-aging agent)
The rubber composition according to the present invention may further include an antioxidant. As the antiaging agent, known ones can be used and are not particularly limited. For example, a phenol anti-aging agent, an imidazole anti-aging agent, an amine anti-aging agent, etc. can be mentioned. These antioxidants can be used alone or in combination of two or more.
（加硫促進助剤）
本発明に係るゴム組成物は、加硫促進助剤をさらに含んでもよい。前記加硫促進助剤については、例えば、亜鉛華（ＺｎＯ）、又は脂肪酸等が挙げられる。脂肪酸としては、飽和若しくは不飽和、直鎖状若しくは分岐状のいずれの脂肪酸であってもよく、脂肪酸の炭素原子数も特に制限されないが、例えば炭素原子数１～３０個が好ましく、１５～３０個の脂肪酸がより好ましく、より具体的にはシクロヘキサン酸（シクロヘキサンカルボン酸）、側鎖を有するアルキルシクロペンタン等のナフテン酸；ヘキサン酸、オクタン酸、デカン酸（ネオデカン酸等の分岐状カルボン酸を含む）、ドデカン酸、テトラデカン酸、ヘキサデカン酸、オクタデカン酸（ステアリン酸）等の飽和脂肪酸；メタクリル酸、オレイン酸、リノール酸、リノレン酸等の不飽和脂肪酸；ロジン、トール油酸、アビエチン酸等の樹脂酸などが挙げられる。これらは１種単独で用いてもよく、２種以上を併用してもよい。本発明においては、亜鉛華又はステアリン酸を好適に用いることができる。 (Vulcanization acceleration aid)
The rubber composition according to the present invention may further contain a vulcanization acceleration aid. Examples of the vulcanization acceleration aid include zinc white (ZnO), fatty acids, and the like. The fatty acid may be saturated or unsaturated, linear or branched fatty acid, and the number of carbon atoms of the fatty acid is not particularly limited, but for example, the number of carbon atoms is preferably 1 to 30, and preferably 15 to 30. Individual fatty acids are more preferable, and more specifically, cyclohexanoic acid (cyclohexanecarboxylic acid), naphthenic acid such as alkylcyclopentane having a side chain; hexanoic acid, octanoic acid, decanoic acid (branched carboxylic acid such as neodecanoic acid Saturated fatty acids such as dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid (stearic acid); unsaturated fatty acids such as methacrylic acid, oleic acid, linoleic acid, linolenic acid; rosin, tall oil acid, abietic acid, etc. Examples thereof include resin acids. These may be used alone or in combination of two or more. In the present invention, zinc white or stearic acid can be preferably used.
本発明に係るゴム組成物は、加硫促進助剤をさらに含んでもよい。前記加硫促進助剤については、例えば、亜鉛華（ＺｎＯ）、又は脂肪酸等が挙げられる。脂肪酸としては、飽和若しくは不飽和、直鎖状若しくは分岐状のいずれの脂肪酸であってもよく、脂肪酸の炭素原子数も特に制限されないが、例えば炭素原子数１～３０個が好ましく、１５～３０個の脂肪酸がより好ましく、より具体的にはシクロヘキサン酸（シクロヘキサンカルボン酸）、側鎖を有するアルキルシクロペンタン等のナフテン酸；ヘキサン酸、オクタン酸、デカン酸（ネオデカン酸等の分岐状カルボン酸を含む）、ドデカン酸、テトラデカン酸、ヘキサデカン酸、オクタデカン酸（ステアリン酸）等の飽和脂肪酸；メタクリル酸、オレイン酸、リノール酸、リノレン酸等の不飽和脂肪酸；ロジン、トール油酸、アビエチン酸等の樹脂酸などが挙げられる。これらは１種単独で用いてもよく、２種以上を併用してもよい。本発明においては、亜鉛華又はステアリン酸を好適に用いることができる。 (Vulcanization acceleration aid)
The rubber composition according to the present invention may further contain a vulcanization acceleration aid. Examples of the vulcanization acceleration aid include zinc white (ZnO), fatty acids, and the like. The fatty acid may be saturated or unsaturated, linear or branched fatty acid, and the number of carbon atoms of the fatty acid is not particularly limited, but for example, the number of carbon atoms is preferably 1 to 30, and preferably 15 to 30. Individual fatty acids are more preferable, and more specifically, cyclohexanoic acid (cyclohexanecarboxylic acid), naphthenic acid such as alkylcyclopentane having a side chain; hexanoic acid, octanoic acid, decanoic acid (branched carboxylic acid such as neodecanoic acid Saturated fatty acids such as dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid (stearic acid); unsaturated fatty acids such as methacrylic acid, oleic acid, linoleic acid, linolenic acid; rosin, tall oil acid, abietic acid, etc. Examples thereof include resin acids. These may be used alone or in combination of two or more. In the present invention, zinc white or stearic acid can be preferably used.
なお、本発明に係るゴム組成物を製造する方法については、特に限定はされず、ゴム組成物を構成する各成分（ゴム成分、充填剤及びその他の成分）を、配合し、混練すること等によって得ることができる。
The method for producing the rubber composition according to the present invention is not particularly limited, and each component (rubber component, filler and other components) constituting the rubber composition is blended and kneaded. Can be obtained by
ここで、本発明に係るゴム組成物を用いるタイヤの部位としては、タイヤ内部を形成するゴム部材であれば制限されることなく適用できる。例えば、前記ゴム部材としては、ベルトコーティングゴム、カーカスコーティングゴム、トレッド（トレッドベースゴム等）、ショルダー部、サイドウォール部、ビード部におけるスティフナーゴム、ベルト層間のゴム、トレッド部とベルトとの間のクッションゴム若しくはベルトとカーカスとの間のゴム、再生タイヤ用のクッションゴム、又はタイヤの補修用ゴム等が挙げられる。
Here, as the part of the tire using the rubber composition according to the present invention, any rubber member forming the inside of the tire can be applied without limitation. For example, as the rubber member, a belt coating rubber, a carcass coating rubber, a tread (tread base rubber, etc.), a shoulder portion, a sidewall portion, a stiffener rubber in a bead portion, a rubber between belt layers, a tread portion and a belt Examples thereof include cushion rubber, rubber between the belt and the carcass, cushion rubber for recycled tires, and rubber for repairing tires.
「タイヤ用トレッド」
本発明に係るタイヤ用トレッドは、上述したゴム組成物を用いたことを特徴とする。路面と直接接触する部位であるタイヤ用トレッドに、本発明のゴム組成物が用いられているため、高い氷上性能が維持できる。 "Treads for tires"
The tire tread according to the present invention is characterized by using the above-mentioned rubber composition. Since the rubber composition of the present invention is used for the tire tread that is a portion that comes into direct contact with the road surface, high performance on ice can be maintained.
本発明に係るタイヤ用トレッドは、上述したゴム組成物を用いたことを特徴とする。路面と直接接触する部位であるタイヤ用トレッドに、本発明のゴム組成物が用いられているため、高い氷上性能が維持できる。 "Treads for tires"
The tire tread according to the present invention is characterized by using the above-mentioned rubber composition. Since the rubber composition of the present invention is used for the tire tread that is a portion that comes into direct contact with the road surface, high performance on ice can be maintained.
「タイヤ」
本発明に係るタイヤは、上述したゴム組成物を用いたことを特徴とする。本発明のタイヤは、前記ゴム組成物が用いられているため、高い氷上性能が維持できる。 "tire"
The tire according to the present invention is characterized by using the rubber composition described above. Since the tire of the present invention uses the rubber composition, high tire performance on ice can be maintained.
本発明に係るタイヤは、上述したゴム組成物を用いたことを特徴とする。本発明のタイヤは、前記ゴム組成物が用いられているため、高い氷上性能が維持できる。 "tire"
The tire according to the present invention is characterized by using the rubber composition described above. Since the tire of the present invention uses the rubber composition, high tire performance on ice can be maintained.
本発明に係るタイヤを製造する方法としては、慣用の方法を用いることができる。例えば、当該製造方法は、タイヤ成形用ドラム上に未加硫ゴムを含むカーカス層、ベルト、本発明に係るタイヤ用トレッド等のタイヤ製造に用いられる部材を順次貼り重ね、ドラムを抜き去ってグリーンタイヤとし、次いで、このグリーンタイヤを常法に従って加熱加硫することにより、所望のタイヤ（例えば、空気入りタイヤ）が製造されうる。
As a method for manufacturing the tire according to the present invention, a conventional method can be used. For example, the manufacturing method, a carcass layer containing an unvulcanized rubber on the drum for tire molding, a belt, members used for tire production such as a tread for a tire according to the present invention are sequentially laminated, and the drum is removed to remove green. A desired tire (for example, a pneumatic tire) can be manufactured by forming a tire and then subjecting this green tire to heat vulcanization according to a conventional method.
以下、実施例を挙げて本発明をさらに詳しく説明するが、これらの実施例は、本発明の例示を目的とするものであり、本発明を何ら限定するものではない。実施例で使用した材料の詳細は以下のとおりである。
Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are intended to illustrate the present invention and do not limit the present invention in any way. Details of the materials used in the examples are as follows.
（＊１）天然ゴム（ＮＲ）：ＲＳＳ＃３
（＊２）ブタジエンゴム（ＢＲ）：ＪＳＲ社製 商品名「ＢＲ０１」
（＊３）芳香族環を有するポリエステルポリオール：日本ゼオン社製 商品名「ゼオファイン１００Ｍ」（水酸基価：６０ｍｇＫＯＨ／ｇ、１分子あたりの水酸基数：５以上、重量平均分子量：４５，０００）
（＊４）ポリブチレンテレフタレート：東レ・デュポン社製 商品名「ハイトレル」
（＊５）カーボンブラック：Ｎ１３４、旭カーボン社製、窒素吸着比表面積（Ｎ２ＳＡ）＝１４６ｍ２／ｇ
（＊６）シリカ：東ソー・シリカ社製 商品名「ＮｉｐＳｉｌ（登録商標） ＡＱ」ＣＴＡＢ比表面積＝１５０ｍ２／ｇ、窒素吸着比表面積（Ｎ２ＳＡ）＝２００ｍ２／ｇ
（＊７）シランカップリング剤：ビス（３－トリエトキシシリルプロピル）テトラスルフィド、エボニックデグッサ社製 商品名「Ｓｉ６９」
（＊８）プロセスオイル：ナフテン系プロセスオイル 出光興産社製 商品名「ダイアナプロセスオイルＮＳ－２４」
（＊９）樹脂（他の熱可塑性樹脂）：Ｃ５系樹脂 東燃化学社製 商品名「Ｅｓｃｏｒｅｚ １１０２」
（＊１０）ステアリン酸
（＊１１）老化防止剤：Ｎ－イソプロピル－Ｎ’－フェニル－ｐ－フェニレンジアミン
（＊１２）加硫促進剤：ジ－２－ベンゾチアゾリルジスルフィド（ＭＢＴＳ） 大内新興化学工業社製 商品名「ノクセラーＤＭ」
（＊１３）加硫促進剤：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（ＣＢＳ） 三新化学工業社製 商品名「サンセラーＣＭ－Ｇ」
（＊１４）発泡剤（ＤＰＴ）：ジニトロソペンタメチレンテトラミン (*1) Natural rubber (NR): RSS#3
(*2) Butadiene rubber (BR): JSR's trade name "BR01"
(*3) Polyester polyol having an aromatic ring: product name "Zeofine 100M" manufactured by Nippon Zeon Co., Ltd. (hydroxyl value: 60 mg KOH/g, number of hydroxyl groups per molecule: 5 or more, weight average molecular weight: 45,000)
(*4) Polybutylene terephthalate: Product name “Hytrel” manufactured by Toray DuPont
(*5) Carbon black: N134, manufactured by Asahi Carbon Co., Ltd., nitrogen adsorption specific surface area (N 2 SA)=146 m 2 /g
(*6) Silica: Tosoh Silica Co., Ltd. trade name “NipSil (registered trademark) AQ” CTAB specific surface area=150 m 2 /g, nitrogen adsorption specific surface area (N 2 SA)=200 m 2 /g
(*7) Silane coupling agent: bis(3-triethoxysilylpropyl) tetrasulfide, product name "Si69" manufactured by Evonik Degussa
(*8) Process oil: Naphthene type process oil Product name “Diana Process Oil NS-24” manufactured by Idemitsu Kosan Co., Ltd.
(* 9) resin (another thermoplastic resin): C 5 resin Tonen Chemical Corporation, trade name "Escorez 1102"
(*10) Stearic acid (*11) Anti-aging agent: N-isopropyl-N'-phenyl-p-phenylenediamine (*12) Vulcanization accelerator: Di-2-benzothiazolyl disulfide (MBTS) Ouchi Product name "Noccer DM" manufactured by Shinko Chemical Industry Co., Ltd.
(*13) Vulcanization accelerator: N-cyclohexyl-2-benzothiazolyl sulfenamide (CBS) Sanshin Chemical Industry Co., Ltd. product name “Sunceller CM-G”
(*14) Foaming agent (DPT): dinitrosopentamethylenetetramine
（＊２）ブタジエンゴム（ＢＲ）：ＪＳＲ社製 商品名「ＢＲ０１」
（＊３）芳香族環を有するポリエステルポリオール：日本ゼオン社製 商品名「ゼオファイン１００Ｍ」（水酸基価：６０ｍｇＫＯＨ／ｇ、１分子あたりの水酸基数：５以上、重量平均分子量：４５，０００）
（＊４）ポリブチレンテレフタレート：東レ・デュポン社製 商品名「ハイトレル」
（＊５）カーボンブラック：Ｎ１３４、旭カーボン社製、窒素吸着比表面積（Ｎ２ＳＡ）＝１４６ｍ２／ｇ
（＊６）シリカ：東ソー・シリカ社製 商品名「ＮｉｐＳｉｌ（登録商標） ＡＱ」ＣＴＡＢ比表面積＝１５０ｍ２／ｇ、窒素吸着比表面積（Ｎ２ＳＡ）＝２００ｍ２／ｇ
（＊７）シランカップリング剤：ビス（３－トリエトキシシリルプロピル）テトラスルフィド、エボニックデグッサ社製 商品名「Ｓｉ６９」
（＊８）プロセスオイル：ナフテン系プロセスオイル 出光興産社製 商品名「ダイアナプロセスオイルＮＳ－２４」
（＊９）樹脂（他の熱可塑性樹脂）：Ｃ５系樹脂 東燃化学社製 商品名「Ｅｓｃｏｒｅｚ １１０２」
（＊１０）ステアリン酸
（＊１１）老化防止剤：Ｎ－イソプロピル－Ｎ’－フェニル－ｐ－フェニレンジアミン
（＊１２）加硫促進剤：ジ－２－ベンゾチアゾリルジスルフィド（ＭＢＴＳ） 大内新興化学工業社製 商品名「ノクセラーＤＭ」
（＊１３）加硫促進剤：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（ＣＢＳ） 三新化学工業社製 商品名「サンセラーＣＭ－Ｇ」
（＊１４）発泡剤（ＤＰＴ）：ジニトロソペンタメチレンテトラミン (*1) Natural rubber (NR): RSS#3
(*2) Butadiene rubber (BR): JSR's trade name "BR01"
(*3) Polyester polyol having an aromatic ring: product name "Zeofine 100M" manufactured by Nippon Zeon Co., Ltd. (hydroxyl value: 60 mg KOH/g, number of hydroxyl groups per molecule: 5 or more, weight average molecular weight: 45,000)
(*4) Polybutylene terephthalate: Product name “Hytrel” manufactured by Toray DuPont
(*5) Carbon black: N134, manufactured by Asahi Carbon Co., Ltd., nitrogen adsorption specific surface area (N 2 SA)=146 m 2 /g
(*6) Silica: Tosoh Silica Co., Ltd. trade name “NipSil (registered trademark) AQ” CTAB specific surface area=150 m 2 /g, nitrogen adsorption specific surface area (N 2 SA)=200 m 2 /g
(*7) Silane coupling agent: bis(3-triethoxysilylpropyl) tetrasulfide, product name "Si69" manufactured by Evonik Degussa
(*8) Process oil: Naphthene type process oil Product name “Diana Process Oil NS-24” manufactured by Idemitsu Kosan Co., Ltd.
(* 9) resin (another thermoplastic resin): C 5 resin Tonen Chemical Corporation, trade name "Escorez 1102"
(*10) Stearic acid (*11) Anti-aging agent: N-isopropyl-N'-phenyl-p-phenylenediamine (*12) Vulcanization accelerator: Di-2-benzothiazolyl disulfide (MBTS) Ouchi Product name "Noccer DM" manufactured by Shinko Chemical Industry Co., Ltd.
(*13) Vulcanization accelerator: N-cyclohexyl-2-benzothiazolyl sulfenamide (CBS) Sanshin Chemical Industry Co., Ltd. product name “Sunceller CM-G”
(*14) Foaming agent (DPT): dinitrosopentamethylenetetramine
＜実施例１～２及び比較例１～２＞
表１に示す配合処方に従い、通常のバンバリーミキサーを用いて、実施例１～２及び比較例１のゴム組成物を調製した。そして、得られた加硫ゴムに対して、下記の方法により氷上性能を評価した。また、上記と同様に、表１に示す配合処方に従い、通常のバンバリーミキサーを用いて、比較例２のゴム組成物を調製して、下記の方法により氷上性能を評価する。表１に組成及び評価データを示す。 <Examples 1-2 and Comparative Examples 1-2>
According to the formulation shown in Table 1, the rubber compositions of Examples 1 and 2 and Comparative Example 1 were prepared using a normal Banbury mixer. Then, the obtained vulcanized rubber was evaluated for the performance on ice by the following method. Further, in the same manner as above, a rubber composition of Comparative Example 2 was prepared by using an ordinary Banbury mixer according to the formulation shown in Table 1, and the on-ice performance was evaluated by the following method. Table 1 shows the composition and evaluation data.
表１に示す配合処方に従い、通常のバンバリーミキサーを用いて、実施例１～２及び比較例１のゴム組成物を調製した。そして、得られた加硫ゴムに対して、下記の方法により氷上性能を評価した。また、上記と同様に、表１に示す配合処方に従い、通常のバンバリーミキサーを用いて、比較例２のゴム組成物を調製して、下記の方法により氷上性能を評価する。表１に組成及び評価データを示す。 <Examples 1-2 and Comparative Examples 1-2>
According to the formulation shown in Table 1, the rubber compositions of Examples 1 and 2 and Comparative Example 1 were prepared using a normal Banbury mixer. Then, the obtained vulcanized rubber was evaluated for the performance on ice by the following method. Further, in the same manner as above, a rubber composition of Comparative Example 2 was prepared by using an ordinary Banbury mixer according to the formulation shown in Table 1, and the on-ice performance was evaluated by the following method. Table 1 shows the composition and evaluation data.
「氷上性能の評価方法」
一辺が２５ｍｍの正方形で、厚さ２ｍｍの加硫ゴム（上記試験試料）の評価面を水濡れさせた後、これを固定した氷上に押しつけて往復させるときに発生する摩擦力をロードセルで検出し、動摩擦係数μを算出した。以下の表１において、比較例１の動摩擦係数μを１００として、指数表示した。指数値が大きい程、動摩擦係数μが大きく、氷上性能が良好であることを示す。 "Ice performance evaluation method"
After wetting the evaluation surface of a vulcanized rubber (the above-mentioned test sample) having a square shape of 25 mm on a side and a thickness of 2 mm, the frictional force generated when the vulcanized rubber was pressed against fixed ice and reciprocated was detected by a load cell. The dynamic friction coefficient μ was calculated. In Table 1 below, the dynamic friction coefficient μ of Comparative Example 1 is set to 100 and is indexed. The larger the index value, the larger the dynamic friction coefficient μ and the better the performance on ice.
一辺が２５ｍｍの正方形で、厚さ２ｍｍの加硫ゴム（上記試験試料）の評価面を水濡れさせた後、これを固定した氷上に押しつけて往復させるときに発生する摩擦力をロードセルで検出し、動摩擦係数μを算出した。以下の表１において、比較例１の動摩擦係数μを１００として、指数表示した。指数値が大きい程、動摩擦係数μが大きく、氷上性能が良好であることを示す。 "Ice performance evaluation method"
After wetting the evaluation surface of a vulcanized rubber (the above-mentioned test sample) having a square shape of 25 mm on a side and a thickness of 2 mm, the frictional force generated when the vulcanized rubber was pressed against fixed ice and reciprocated was detected by a load cell. The dynamic friction coefficient μ was calculated. In Table 1 below, the dynamic friction coefficient μ of Comparative Example 1 is set to 100 and is indexed. The larger the index value, the larger the dynamic friction coefficient μ and the better the performance on ice.
実施例１～２及び比較例１の結果からも把握されるように、本発明のゴム組成物を用いた、タイヤ用トレッド及びタイヤは、優れた氷上性能を持続する。
As can be understood from the results of Examples 1 and 2 and Comparative Example 1, the tire tread and the tire using the rubber composition of the present invention maintain excellent on-ice performance.
As can be understood from the results of Examples 1 and 2 and Comparative Example 1, the tire tread and the tire using the rubber composition of the present invention maintain excellent on-ice performance.
Claims (5)
- ゴム成分と、
前記ゴム成分１００質量部に対して、０．１質量部以上２０質量部以下の芳香族環を有するポリエステルポリオール樹脂と、を含有することを特徴とする、ゴム組成物。 Rubber component,
A rubber composition comprising: 0.1 part by mass or more and 20 parts by mass or less of a polyester polyol resin having an aromatic ring with respect to 100 parts by mass of the rubber component. - 前記芳香族環を有するポリエステルポリオール樹脂の重量平均分子量（Ｍｗ）は、２００００以上１０００００以下である、請求項１に記載のゴム組成物。 The rubber composition according to claim 1, wherein the polyester polyol resin having an aromatic ring has a weight average molecular weight (Mw) of 20,000 or more and 100,000 or less.
- 充填剤をさらに含有し、かつ前記充填剤は、シリカ及びカーボンブラックからなる群から選択される少なくとも１種を含む、請求項１又は２に記載のゴム組成物。 The rubber composition according to claim 1 or 2, further comprising a filler, and the filler contains at least one selected from the group consisting of silica and carbon black.
- 請求項１～３のいずれか１項に記載のゴム組成物を用いた、タイヤ用トレッド。 A tire tread using the rubber composition according to any one of claims 1 to 3.
- 請求項４のタイヤ用トレッドを備えた、タイヤ。
A tire comprising the tire tread of claim 4.
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| JP2020559257A JPWO2020122073A1 (en) | 2018-12-11 | 2019-12-10 | Rubber composition, tire tread and tire |
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| JP2018-231994 | 2018-12-11 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001216844A (en) * | 2000-01-31 | 2001-08-10 | Furukawa Electric Co Ltd:The | Wire harness with water cutoff grommet |
| JP2016117783A (en) * | 2014-12-18 | 2016-06-30 | 東洋ゴム工業株式会社 | Rubber composition for seismically isolated structure and rubber for seismically isolated structure |
| JP2017137414A (en) * | 2016-02-03 | 2017-08-10 | 中日本高速技術マーケティング株式会社 | Coated rubber composition |
| JP2017196833A (en) * | 2016-04-28 | 2017-11-02 | 株式会社ブリヂストン | Laminate, tire and manufacturing method therefor |
| JP2019026794A (en) * | 2017-08-02 | 2019-02-21 | 株式会社ブリヂストン | Rubber composition for vibration-proof rubber and vehicular vibration-proof rubber |
-
2019
- 2019-12-10 WO PCT/JP2019/048336 patent/WO2020122073A1/en active Application Filing
- 2019-12-10 JP JP2020559257A patent/JPWO2020122073A1/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001216844A (en) * | 2000-01-31 | 2001-08-10 | Furukawa Electric Co Ltd:The | Wire harness with water cutoff grommet |
| JP2016117783A (en) * | 2014-12-18 | 2016-06-30 | 東洋ゴム工業株式会社 | Rubber composition for seismically isolated structure and rubber for seismically isolated structure |
| JP2017137414A (en) * | 2016-02-03 | 2017-08-10 | 中日本高速技術マーケティング株式会社 | Coated rubber composition |
| JP2017196833A (en) * | 2016-04-28 | 2017-11-02 | 株式会社ブリヂストン | Laminate, tire and manufacturing method therefor |
| JP2019026794A (en) * | 2017-08-02 | 2019-02-21 | 株式会社ブリヂストン | Rubber composition for vibration-proof rubber and vehicular vibration-proof rubber |
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