WO2015155965A1 - ゴム組成物及び空気入りタイヤ - Google Patents
ゴム組成物及び空気入りタイヤ Download PDFInfo
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- WO2015155965A1 WO2015155965A1 PCT/JP2015/001893 JP2015001893W WO2015155965A1 WO 2015155965 A1 WO2015155965 A1 WO 2015155965A1 JP 2015001893 W JP2015001893 W JP 2015001893W WO 2015155965 A1 WO2015155965 A1 WO 2015155965A1
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- acrylate polymer
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- 0 CC*OC(C1(CC(C)(C)C)*(C)CI*1)=O Chemical compound CC*OC(C1(CC(C)(C)C)*(C)CI*1)=O 0.000 description 1
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
Definitions
- the present invention relates to a rubber composition and a pneumatic tire using the same.
- Patent Document 2 proposes blending a high softening point resin made of C9 resin containing indene.
- the grip performance is excellent, the rolling resistance performance is deteriorated, and a good balance between the wet grip performance and the rolling resistance performance cannot be obtained. Further, since the rubber composition becomes hard at low temperatures, the grip performance deteriorates, and there remains a problem in low temperature performance.
- Patent Document 3 proposes blending a (meth) acrylate polymer having a glass transition point as high as 70 ° C. or higher and a relatively high molecular weight in order to improve dry performance, wet performance, and low fuel consumption. ing. In this case, the balance between wet grip performance and rolling resistance performance is improved by blending a (meth) acrylate polymer having a high glass transition point.
- the grip performance deteriorates due to the rubber composition becoming hard at a low temperature, and the low temperature performance decreases.
- Patent Document 4 a (meth) acrylate polymer having a reactive silyl group at the terminal and having a weight average molecular weight of 500 to 100,000 is blended with diene rubber together with silica and a silane coupling agent.
- the (meth) acrylate polymer reacts with silica by having a reactive silyl group at the terminal, thereby improving the dispersibility of the silica and contributing to improving the rolling resistance performance. is there. It is not disclosed that wet grip performance can be improved while suppressing deterioration of low temperature performance and rolling resistance performance by blending a (meth) acrylate polymer having a high molecular weight and a low glass transition point.
- An object of the present invention is to provide a rubber composition capable of improving wet grip performance while suppressing deterioration of low temperature performance and rolling resistance performance.
- the rubber composition according to the embodiment has a (meth) acrylate-based weight having a weight average molecular weight of 5,000 to 1,000,000 and a glass transition point of ⁇ 70 to 0 ° C. with respect to 100 parts by mass of a rubber component made of a diene rubber. It contains 1 to 100 parts by mass of the coalescence.
- the pneumatic tire according to the embodiment uses the rubber composition.
- wet grip performance can be improved while suppressing deterioration of low temperature performance and rolling resistance performance by blending the specific (meth) acrylate polymer with the diene rubber.
- a (meth) acrylate polymer having a weight average molecular weight of 5,000 to 1,000,000 and a glass transition point of ⁇ 70 to 0 ° C. is blended with a rubber component composed of a diene rubber. It is made.
- a (meth) acrylate polymer with a high molecular weight and a low glass transition point in this way into a diene rubber By blending a (meth) acrylate polymer with a high molecular weight and a low glass transition point in this way into a diene rubber, the viscoelasticity of the rubber composition is changed, and the deterioration of rolling resistance performance is suppressed. The wet grip performance can be demonstrated.
- an increase in the elastic modulus at a low temperature can be suppressed and deterioration of the low temperature performance can be suppressed.
- diene rubber as the rubber component examples include natural rubber (NR), synthetic isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), nitrile rubber (NBR), and chloroprene rubber (CR).
- NR natural rubber
- IR synthetic isoprene rubber
- BR butadiene rubber
- SBR styrene butadiene rubber
- NBR nitrile rubber
- chloroprene rubber CR
- Butyl rubber (IIR) styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, and the like. These may be used alone or in combination of two or more. Can be used. Among these, at least one selected from the group consisting of NR, BR and SBR is preferable.
- the (meth) acrylate polymer is a polymer containing one or more (meth) acrylate units, that is, a homopolymer obtained by polymerizing a monomer containing one or more (meth) acrylates. Or it is a copolymer.
- (meth) acrylate means one or both of acrylate and methacrylate.
- (Meth) acrylic acid means one or both of acrylic acid and methacrylic acid.
- the (meth) acrylate polymer those having a weight average molecular weight (Mw) of 5000 (g / mol) or more are used.
- Mw weight average molecular weight
- the upper limit of a weight average molecular weight is not specifically limited, Usually, it is 1 million (g / mol) or less.
- the weight average molecular weight of the (meth) acrylate polymer is preferably 10,000 to 500,000, more preferably 30,000 to 500,000, still more preferably 50,000 to 500,000, and particularly preferably 12 10,000 to 400,000.
- the (meth) acrylate polymer one having a low Tg having a glass transition point (Tg) of ⁇ 70 to 0 ° C. is used.
- Tg glass transition point
- the glass transition point of the (meth) acrylate polymer is preferably ⁇ 70 to ⁇ 20 ° C., more preferably ⁇ 60 to ⁇ 30 ° C.
- an alkyl (meth) acrylate polymer (homopolymer or copolymer) having a repeating unit (namely, alkyl (meth) acrylate unit) represented by the following general formula (1): It is preferable that
- R 1 is a hydrogen atom or a methyl group, and R 1 present in the same molecule may be the same or different.
- R 2 is an alkyl group having 4 to 18 carbon atoms, and R 2 present in the same molecule may be the same or different.
- the alkyl group for R 2 may be linear or branched.
- R 2 is preferably an alkyl group having 6 to 16 carbon atoms, and more preferably an alkyl group having 8 to 12 carbon atoms.
- Examples of the (meth) acrylate constituting the (meth) acrylate polymer include, for example, n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, N-nonyl acrylate, n-decyl acrylate, n-undecyl acrylate, n-dodecyl acrylate, n-tridecyl acrylate, n-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, methacrylic acid n-alkyl (meth) acrylates such as n-heptyl, n-octyl methacrylate, n-nonyl methacrylate, n-decyl methacrylate, n-undecyl methacrylate, and
- the (meth) acrylate polymer may be a polymer of a monomer containing at least one selected from the group consisting of isodecyl methacrylate and n-dodecyl methacrylate, and more preferably a methacrylic polymer.
- a polymer of a monomer containing acid isodecyl may be used.
- isoalkyl refers to an alkyl group having a methyl side chain at the second carbon atom from the end of the alkyl chain.
- isodecyl refers to a C10 alkyl group having a methyl side chain at the second carbon atom from the chain end, and includes not only an 8-methylnonyl group but also 2,4,6-trimethyl in formula (7) below. This concept includes a heptyl group.
- the (meth) acrylate polymer is a homopolymer or copolymer having a repeating unit represented by the above general formula (1), wherein R 2 is represented by the following general formula (2). But you can. That is, the alkyl (meth) acrylate polymer according to the embodiment has a repeating unit represented by the following general formula (2A).
- Z is an alkylene group having 1 to 15 carbon atoms, and Z in the same molecule may be the same or different.
- Z may be linear or branched.
- R 1 is a hydrogen atom or a methyl group (preferably a methyl group), and R 1 in the same molecule may be the same or different.
- Examples of the (meth) acrylate composing such a (meth) acrylate polymer include the above-mentioned isoalkyl (meth) acrylate.
- (meth) acrylate (more preferably methacrylate) having such an isoalkyl group a further effect is obtained in that a decrease in hardness at room temperature can be suppressed.
- Z in the formulas (2) and (2A) is preferably an alkylene group having 5 to 15 carbon atoms, more preferably an alkylene group having 7 to 11 carbon atoms. This is advantageous for improving the balance between wet grip performance and rolling resistance performance while suppressing the rise.
- the (meth) acrylate polymer is represented by the general formula (1), wherein R 2 is represented by the general formula (2), and the general formula (1).
- R 2 in the formula may have a repeating unit represented by the following general formula (3). That is, the alkyl (meth) acrylate polymer according to the embodiment has a repeating unit represented by the general formula (2A) and a repeating unit represented by the following general formula (3A).
- the addition form of these repeating units may be random addition or block addition, and is preferably random addition.
- Q is an alkylene group having 2 to 16 carbon atoms, and Q in the same molecule may be the same or different.
- Q may be linear or branched.
- R 1 is a hydrogen atom or a methyl group (preferably a methyl group), and R 1 in the same molecule may be the same or different.
- the (meth) acrylate polymer is such a copolymer, it has the effect of improving the balance between wet grip performance and rolling resistance performance while suppressing a decrease in normal temperature hardness and an increase in low temperature elastic modulus. Can be increased.
- (meth) acrylate constituting the repeating unit represented by the formula (3A) include, for example, those of the above-listed (meth) acrylates excluding isoalkyl (meth) acrylate.
- Q in the formulas (3) and (3A) is preferably an alkylene group having 2 to 10 carbon atoms, and more preferably a branched alkylene group having 4 to 8 carbon atoms.
- R 2 represented by the general formula (3) R 2 may be represented by the following general formula (3B).
- Q 1 is an alkylene group having 1 to 6 carbon atoms (more preferably 1 to 3), and may be linear or branched (preferably linear).
- Q 2 is a methyl group or an ethyl group.
- the ratio (copolymerization ratio) between the repeating unit represented by the formula (2A) and the repeating unit represented by the formula (3A) is not particularly limited.
- the ratio of the repeating unit of the formula (2A) is 30 mol% or more and less than 100 mol%
- the formula (3A) The ratio of the repeating unit may be more than 0 mol% and 70 mol% or less, the ratio of the repeating unit of the formula (2A) is 40 to 90 mol%, and the ratio of the repeating unit of the formula (3A) is 10 to 60 mol%. Good.
- the monomer which comprises the (meth) acrylate type polymer which concerns on this embodiment consists of (meth) acrylate fundamentally, ie, the said (meth) acrylate is a main component, but in the range which does not impair an effect.
- Other vinyl compounds may be used in combination.
- (meth) acrylate unit preferably the alkyl (meth) acrylate unit of the said Formula (1)
- the content is preferably 90 mol% or more.
- the (meth) acrylate polymer has a content of the repeating unit of the above formula (2A) with respect to all repeating units of 30 mol% or more (more preferably 40 mol% or more), and the formula ( 90 mol% in total of the content of the repeating unit of 2A) and the content of other (meth) acrylate units (preferably the repeating unit of formula (1) excluding the repeating unit of formula (2A)) That's all.
- the (meth) acrylate polymer used in this embodiment is not used as a silica dispersant, it does not have a reactive group that binds to silica, and therefore has no reactive silyl group at the terminal. It is a (meth) acrylate polymer.
- Examples of such a (meth) acrylate polymer include the following embodiments [x], [y] and [z], and these may be used alone or in combination of two kinds. You may use together.
- the (meth) acrylate polymer [x] has a terminal structure represented by the following general formula (4). That is, the (meth) acrylate polymer [x] has a structure in which the group represented by the formula (4) is directly bonded to the terminal of the vinyl polymer chain formed by polymerizing the monomer made of the (meth) acrylate. .
- the terminal structure represented by Formula (4) may be present at both ends of the (meth) acrylate polymer, or may be present at one end.
- R 3 and R 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, but they are not both hydrogen atoms.
- R 3 and R 4 are preferably each independently a methyl group or an ethyl group, more preferably a methyl group.
- R 5 is a saturated or unsaturated alkyl group having 2 to 20 carbon atoms.
- the saturated or unsaturated alkyl group may be linear or branched. Accordingly, R 5 is more specifically a straight-chain saturated or unsaturated alkyl group having 2 to 20 carbon atoms, or a branched saturated or unsaturated alkyl group having 3 to 20 carbon atoms.
- R 5 is an alkyl group or alkenyl group having 2 to 18 carbon atoms, such as ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, s-butyl group, pentyl group.
- the (meth) acrylate polymer [x] can be obtained, for example, by polymerizing the above (meth) acrylate using a radical polymerization initiator represented by the following general formula (5).
- R 3 , R 4 and R 5 are the same as in formula (4).
- X is a halogen atom, for example, a chlorine atom, a bromine atom or an iodine atom, and preferably a bromine atom.
- the radical polymerization initiator is an initiator having an ⁇ -haloester group and having a living radical polymerization initiating ability by atom transfer radical polymerization (ATRP). A radical is generated in the presence of a transition metal complex to cause a polymerization reaction. Progresses.
- a metal complex having a group 7 element, 8 group, 9 group, 10 group, or 11 element as a central metal in the periodic table is preferable, and more preferably zero-valent copper, monovalent Copper, divalent ruthenium, divalent iron, or divalent nickel complex.
- a monovalent copper complex is preferable, and a copper (I) complex having an amine / imine polydentate ligand, for example, a copper halide (for example, copper chloride, copper bromide) / amine complex is preferably used. .
- the structure of the (meth) acrylate [x] thus obtained has a group represented by the formula (4) at one end of the vinyl polymer chain containing the repeating unit represented by the formula (1). And having a halogen atom at the other end, and represented by the following general formula (6) as one embodiment.
- R 1 , R 2 , R 3 , R 4 , R 5 and X are the same as those in the formula (1), the formula (4) and the formula (5), and n is the formula (1).
- the number of repeating units is an integer of 1 or more.
- the halogen terminal of the (meth) acrylate polymer [x] may be blended in the rubber composition as it is, or a halogen terminal substituted with another structure may be used.
- the (meth) acrylate polymer [y] is synthesized by radical polymerization using an initiator composed of an azo compound.
- the azo compound as the radical polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 1,1′-azobis (cyclohexanecarbonitrile) (ABCN), 2,2′-azobis ( 2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethyl) Valeronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis [ N- (2-propenyl) -2-methylpropionamide] and the like.
- AIBN 2,2′-azobisisobutyronitrile
- ABCN 1,1′-
- a (meth) acrylate polymer having a residue derived from the azo compound at one end is obtained.
- the other terminal has a residue derived from an azo compound when the termination reaction is recombination, and when the termination reaction is disproportionation, the terminal (meth) acrylate unit is saturated with a saturated bond.
- the one with the bond is obtained.
- a (meth) acrylate polymer having a (CH 3 ) 2 (NC) C-group at one end can be obtained.
- the (meth) acrylate polymer [z] is a star polymer synthesized using a polyfunctional initiator. That is, in the (meth) acrylate polymer [z], the arm portion composed of the vinyl polymer chain containing the (meth) acrylate unit was extended from the core portion derived from the polyfunctional initiator by the atom transfer radical polymerization method. It is a multi-branched polymer with a structure.
- polyfunctional initiator examples include compounds having a plurality of (preferably three or more) functional groups having a living radical polymerization initiating ability, such as hexafunctional dipentaerythritol hexakis (2-bromoisobutyrate), Examples include tetrafunctional pentaerythritol tetrakis (2-bromoisobutyrate), trifunctional 1,1,1-tris (2-bromoisobutyloxymethylene) ethane, and the like.
- the blending amount of the (meth) acrylate polymer can be 1 to 100 parts by mass, more preferably 100 parts by mass of the rubber component made of diene rubber.
- the amount is 2 to 50 parts by mass, and more preferably 3 to 30 parts by mass.
- the rubber composition according to the present embodiment includes a reinforcing filler, a silane coupling agent, oil, zinc white, stearic acid, anti-aging agent, wax, and vulcanizing agent.
- a reinforcing filler such as silane coupling agent, oil, zinc white, stearic acid, anti-aging agent, wax, and vulcanizing agent.
- Various additives generally used in rubber compositions, such as vulcanization accelerators, can be blended.
- silica such as wet silica (hydrous silicic acid) or carbon black is preferably used. More preferably, silica is used to improve the balance between rolling resistance performance and wet grip performance, and silica alone or a combination of silica and carbon black is preferred.
- the compounding amount of the reinforcing filler is not particularly limited, and may be, for example, 20 to 150 parts by mass, more preferably 30 to 100 parts by mass with respect to 100 parts by mass of the rubber component.
- the blending amount of silica is not particularly limited, and may be, for example, 20 to 150 parts by mass, more preferably 30 to 100 parts by mass with respect to 100 parts by mass of the rubber component.
- the blending amount of the silane coupling agent is preferably 2 to 20% by mass, more preferably 4 to 15% by mass. %.
- the blending amount of the vulcanizing agent is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component.
- the vulcanization accelerator include various vulcanization accelerators such as sulfenamide-based, thiuram-based, thiazole-based, and guanidine-based compounds. be able to.
- the blending amount of the vulcanization accelerator is not particularly limited, but is preferably 0.1 to 7 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component. .
- the rubber composition according to the present embodiment can be prepared by kneading according to a conventional method using a commonly used Banbury mixer, kneader, roll, or other mixer. That is, for example, in the first mixing stage, other additives excluding the vulcanizing agent and the vulcanization accelerator are added and mixed together with the (meth) acrylate polymer to the diene rubber, and then the resulting mixture is obtained.
- a rubber composition can be prepared by adding and mixing a vulcanizing agent and a vulcanization accelerator in the final mixing stage.
- the rubber composition thus obtained can be used for various rubber members such as tires, vibration-proof rubbers, and conveyor belts.
- it is used for tires, and can be applied to various parts such as passenger cars, large tires for trucks and buses, tires such as tread parts and sidewall parts of pneumatic tires of sizes. That is, the rubber composition is molded into a predetermined shape by, for example, extrusion processing according to a conventional method, and combined with other components, and then vulcanized at, for example, 140 to 180 ° C. to produce a pneumatic tire. can do.
- polymer 1 a (meth) acrylate polymer (hereinafter referred to as polymer 1) according to Synthesis Example 1 was obtained.
- the number average molecular weight (Mn) was 54000
- the weight average molecular weight (Mw) was 67000
- Mw / Mn) was 1.24
- Tg glass transition point
- Polymer 3 has a structure in which an arm portion of six polyisodecyl methacrylate (ie, poly-2,4,6-trimethylheptyl methacrylate) chains extends from a core portion derived from a hexafunctional polyfunctional initiator. It was a star polymer, Mn was 270000, Mw was 351000, Mw / Mn was 1.30, and Tg was ⁇ 40 ° C.
- polyisodecyl methacrylate ie, poly-2,4,6-trimethylheptyl methacrylate
- Synthesis Example 4 Synthesis of (meth) acrylate polymer
- Vinyl monomer / initiator (molar ratio) 200
- n-dodecyl methacrylate was used instead of isodecyl methacrylate used in the synthesis of Polymer 1
- Synthesis Example 4 A (meth) acrylate polymer (hereinafter referred to as polymer 4) was obtained.
- Polymer 4 had an Mn of 61000, an Mw of 87000, an Mw / Mn of 1.45, and a Tg of ⁇ 65 ° C.
- Synthesis Example 5 Synthesis of (meth) acrylate polymer
- Vinyl monomer / initiator (molar ratio) 200
- n-butyl acrylate was used instead of isodecyl methacrylate used in the synthesis of Polymer 1
- Synthesis Example 5 A (meth) acrylate polymer (hereinafter referred to as polymer 5) was obtained.
- Polymer 5 had an Mn of 31000, Mw of 39000, Mw / Mn of 1.26, and Tg of ⁇ 54 ° C.
- Synthesis Example 6 Synthesis of (meth) acrylate polymer
- Synthesis was performed in the same manner as in Synthesis Example 1 except that the molar ratio of isodecyl methacrylate (vinyl monomer) and ethyl 2-bromoisobutyrate (initiator) used in the synthesis of polymer 1 was changed to 50 (vinyl monomer / initiator).
- a (meth) acrylate polymer according to Example 6 (hereinafter referred to as polymer 6) was obtained.
- Polymer 6 had a number average molecular weight (Mn) of 12000, a weight average molecular weight (Mw) of 15000, a molecular weight distribution (Mw / Mn) of 1.25, and a glass transition point (Tg) of ⁇ 42 ° C.
- Synthesis Example 8 Synthesis of (meth) acrylate polymer
- polymerization initiating group (molar ratio) in vinyl monomer / initiator 200
- polymer 8 a (meth) acrylate polymer according to Synthesis Example 8 (hereinafter referred to as polymer 8) was obtained.
- Polymer 8 has a structure in which an arm portion of three polyisodecyl methacrylate (ie, poly-2,4,6-trimethylheptyl methacrylate) chains extends from a core portion derived from a trifunctional polyfunctional initiator. It was a star polymer, Mn was 135000, Mw was 170000, Mw / Mn was 1.26, and Tg was -39 ° C.
- polyisodecyl methacrylate ie, poly-2,4,6-trimethylheptyl methacrylate
- Synthesis Example 9 Synthesis of (Meth) acrylate Polymer (Comparative Example)]
- Vinyl monomer / initiator (molar ratio) 200
- t-butyl methacrylate was used instead of isodecyl methacrylate used in the synthesis of Polymer 1
- Synthesis Example 9 A (meth) acrylate polymer (hereinafter referred to as polymer 9) was obtained.
- Polymer 9 had Mn of 34000, Mw of 42000, Mw / Mn of 1.24, and Tg of 120 ° C.
- Synthesis Example 10 Synthesis of (meth) acrylate polymer (comparative example)] Synthesis was performed in the same manner as in Synthesis Example 1 except that the molar ratio (vinyl monomer / initiator) of isodecyl methacrylate (vinyl monomer) and ethyl 2-bromoisobutyrate (initiator) used in the synthesis of polymer 1 was set to 10.
- a (meth) acrylate polymer (hereinafter referred to as polymer 10) according to Example 10 was obtained.
- Polymer 10 had Mn of 2700, Mw of 3400, Mw / Mn of 1.26, and Tg of ⁇ 50 ° C.
- Synthesis Example 13 Synthesis of (meth) acrylate polymer
- a (meth) acrylate polymer according to Synthesis Example 13 (hereinafter referred to as polymer 13) was obtained.
- Polymer 13 had Mn of 100,000, Mw of 260000, Mw / Mn of 2.60, and Tg of ⁇ 41 ° C.
- the (meth) acrylate copolymer (hereinafter referred to as polymer 16) according to Synthesis Example 16 was obtained by reprecipitation purification of the resulting solution in methanol.
- Polymer 16 had an Mn of 110000, an Mw of 260000, an Mw / Mn of 2.36, and a Tg of ⁇ 35 ° C.
- the (meth) acrylate copolymer (hereinafter referred to as polymer 17) according to Synthesis Example 17 was obtained by reprecipitation purification of the resulting solution in methanol.
- Polymer 17 had Mn of 100,000, Mw of 250,000, Mw / Mn of 2.50, and Tg of ⁇ 30 ° C.
- VSL5025 ⁇ BR: “Ubepol BR150B” manufactured by Ube Industries, Ltd.
- Silica “Nip Seal AQ” manufactured by Tosoh Silica Co., Ltd.
- Silane coupling agent bis (3-triethoxysilylpropyl) tetrasulfide, “Si69” manufactured by Evonik Degussa ⁇
- Zinc flower “Zinc flower 1” manufactured by Mitsui Mining & Smelting Co., Ltd.
- Anti-aging agent “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
- Stearic acid “Lunac S-20” manufactured by Kao Corporation ⁇ Sulfur: Hosoi Chemical Co., Ltd.
- tan ⁇ Using a rheometer E4000 manufactured by UBM, the loss factor tan ⁇ was measured under the conditions of a frequency of 10 Hz, a static strain of 10%, a dynamic strain of 2%, and a temperature of 0 ° C. The index was displayed. The larger the index, the larger the tan ⁇ , and the better the wet grip performance.
- Results are as shown in Tables 1 and 2.
- the rolling resistance performance is substantially deteriorated when Examples 1 to 16 are blended with the above-mentioned specific (meth) acrylate polymers 1 to 8 and 12 to 19 with respect to Comparative Example 1 as a control.
- the wet grip performance was significantly improved.
- the elastic modulus at low temperature did not increase greatly and was excellent in low temperature performance.
- Comparative Example 2 using a (meth) acrylate polymer having a high glass transition point and Comparative Example 5 containing an aromatic aliphatic copolymer petroleum resin improved wet grip performance, but low temperature performance. Was unsatisfactory in terms of the balance between the two.
- Comparative Examples 3 and 4 in which a (meth) acrylate polymer having a small molecular weight was blended, the effect of improving wet grip performance was not obtained. Further, in Comparative Examples 3, 4 and 5, a decrease in hardness at normal temperature was observed, and there was concern about a decrease in steering stability.
- Examples 1 to 16 Examples 4 and 5 using linear (meth) alkyl acrylate tend to decrease the hardness at room temperature, and in particular, the tendency is greater in the acrylate type than in the methacrylate type. It was. On the other hand, in Examples 1 to 3 and 6 to 16 using (meth) acrylate having an isoalkyl group, the decrease in hardness at room temperature was suppressed. Among those having an isoalkyl group, other examples that are methacrylate-based are superior to Example 9 that is acrylate-based because of the effect of suppressing the decrease in hardness at room temperature. From these facts, it was found that the (meth) acrylate polymer is preferably an isoalkyl (meth) acrylate polymer, and more preferably an isoalkyl methacrylate polymer.
- a copolymer of isoalkyl (meth) acrylate and another (meth) acrylate is particularly excellent in the balance of wet grip performance / rolling resistance performance / low temperature performance / normal temperature hardness. It was.
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Abstract
Description
ゲルパーミエーションクロマトグラフィ(GPC)での測定により、ポリスチレン換算にて求めた。詳細には、測定試料は0.2mgをTHF1mLに溶解させたものを用いた。(株)島津製作所製「LC-20DA」を使用し、試料をフィルター透過後、温度40℃、流量0.7mL/分でカラム(Polymer Laboratories社製「PL Gel3μm Guard×2」)を通し、Spectra System社製「RI Detector」で検出した。
JIS K7121に準拠して示差走査熱量測定(DSC)法により、昇温速度:20℃/分にて(測定温度範囲:-150℃~50℃)測定した。
30gのメタクリル酸イソデシル(即ち、メタクリル酸2,4,6-トリメチルヘプチル)と、0.129gの2-ブロモイソ酪酸エチルと、0.115gのN,N,N',N'',N''-ペンタメチルジエチレントリアミンを混合し(ビニルモノマー/開始剤(モル比)=200)、1時間窒素バブリングした。その後、反応溶液に0.190gの臭化銅(I)を添加し、70℃で5時間保持した。得られた溶液のメタノールへの再沈精製により、合成例1に係る(メタ)アクリレート系重合体(以下、ポリマー1という。)を得た。ポリマー1は、下記式(7)で表されるものであって、ポリイソデシルメタクリレート鎖の片末端に式(4)の構造(R3=R4=メチル基、R5=エチル基)を有するものであり、数平均分子量(Mn)が54000、重量平均分子量(Mw)が67000、分子量分布(Mw/Mn)が1.24、ガラス転移点(Tg)が-41℃であった。
30gのメタクリル酸イソデシル(即ち、メタクリル酸2,4,6-トリメチルヘプチル)と、100mLのトルエンと、0.218gのアゾビスイソブチロニトリルとを混合し(ビニルモノマー/開始剤(モル比)=100)、1時間窒素バブリングした後、反応溶液を60℃で8時間保持した。得られた溶液のメタノールへの再沈精製により、合成例2に係る(メタ)アクリレート系重合体(以下、ポリマー2という。)を得た。ポリマー2は、Mnが100000、Mwが260000、Mw/Mnが2.60、Tgが-40℃であった。
ポリマー1の合成に用いた2-ブロモイソ酪酸エチルの代わりに、ペンタエリスリトールヘキサキス(2-ブロモイソブチレート)を用いること以外は合成例1と同様の手法により(ビニルモノマー/開始剤中の重合開始基(モル比)=200)、合成例3に係る(メタ)アクリレート系重合体(以下、ポリマー3という。)を得た。ポリマー3は、6官能の多官能開始剤に由来するコア部から、6本のポリイソデシルメタクリレート(即ち、ポリ-2,4,6-トリメチルヘプチルメタクリレート)鎖のアーム部が伸張した構造を持つ星型ポリマーであり、Mnが270000、Mwが351000、Mw/Mnが1.30、Tgが-40℃であった。
ポリマー1の合成に用いたメタクリル酸イソデシルの代わりに、メタクリル酸n-ドデシルを用いること以外は合成例1と同様の手法により(ビニルモノマー/開始剤(モル比)=200)、合成例4に係る(メタ)アクリレート系重合体(以下、ポリマー4という。)を得た。ポリマー4は、Mnが61000、Mwが87000、Mw/Mnが1.45、Tgが-65℃であった。
ポリマー1の合成に用いたメタクリル酸イソデシルの代わりに、アクリル酸n-ブチルを用いること以外は合成例1と同様の手法により(ビニルモノマー/開始剤(モル比)=200)、合成例5に係る(メタ)アクリレート系重合体(以下、ポリマー5という。)を得た。ポリマー5は、Mnが31000、Mwが39000、Mw/Mnが1.26、Tgが-54℃であった。
ポリマー1の合成に用いたメタクリル酸イソデシル(ビニルモノマー)と2-ブロモイソ酪酸エチル(開始剤)のモル比(ビニルモノマー/開始剤)を50とした以外は合成例1と同様の手法により、合成例6に係る(メタ)アクリレート系重合体(以下、ポリマー6という。)を得た。ポリマー6は、数平均分子量(Mn)が12000、重量平均分子量(Mw)が15000、分子量分布(Mw/Mn)が1.25、ガラス転移点(Tg)が-42℃であった。
ポリマー2の合成に用いたアゾビスイソブチロニトリルの代わりに、アゾビス(4-メトキシ-2,4-ジメチルバレロニトリルを用い(ビニルモノマー/開始剤(モル比)=100)、また窒素バブリング後の反応溶液の温度を30℃とした以外は合成例2と同様の手法により、合成例7に係る(メタ)アクリレート系重合体(以下、ポリマー7という。)を得た。ポリマー7は、Mnが95000、Mwが250000、Mw/Mnが2.63、Tgが-41℃であった。
ポリマー3の合成に用いたペンタエリスリトールヘキサキス(2-ブロモイソブチレート)の代わりに、1,1,1-トリス(2-ブロモイソブチルオキシメチレン)エタンを用いること以外は合成例3と同様の手法により(ビニルモノマー/開始剤中の重合開始基(モル比)=200)、合成例8に係る(メタ)アクリレート系重合体(以下、ポリマー8という。)を得た。ポリマー8は、3官能の多官能開始剤に由来するコア部から、3本のポリイソデシルメタクリレート(即ち、ポリ-2,4,6-トリメチルヘプチルメタクリレート)鎖のアーム部が伸張した構造を持つ星型ポリマーであり、Mnが135000、Mwが170000、Mw/Mnが1.26、Tgが-39℃であった。
ポリマー1の合成に用いたメタクリル酸イソデシルの代わりに、メタクリル酸t-ブチルを用いること以外は合成例1と同様の手法により(ビニルモノマー/開始剤(モル比)=200)、合成例9に係る(メタ)アクリレート系重合体(以下、ポリマー9という。)を得た。ポリマー9は、Mnが34000、Mwが42000、Mw/Mnが1.24、Tgが120℃であった。
ポリマー1の合成に用いたメタクリル酸イソデシル(ビニルモノマー)と2-ブロモイソ酪酸エチル(開始剤)のモル比(ビニルモノマー/開始剤)を10とした以外は合成例1と同様の手法により、合成例10に係る(メタ)アクリレート系重合体(以下、ポリマー10という。)を得た。ポリマー10は、Mnが2700、Mwが3400、Mw/Mnが1.26、Tgが-50℃であった。
30gのメタクリル酸イソデシル(即ち、メタクリル酸2,4,6-トリメチルヘプチル)と、100mLのトルエンと、3.13gのα-メチルスチレンダイマーと、0.218gのアゾビスイソブチロニトリルとを混合し、1時間窒素バブリングし、その後、反応溶液を60℃で8時間保持した。得られた溶液のメタノールへの再沈精製により、合成例11に係る(メタ)アクリレート系重合体(以下、ポリマー11という。)を得た。ポリマー11は、Mnが2500、Mwが3800、Mw/Mnが1.52、Tgが-50℃であった。
ポリマー2の合成に用いたメタクリル酸2,4,6-トリメチルヘプチルの代わりに、アクリル酸イソデシル(即ち、アクリル酸8-メチルノニル)を用いること以外は合成例2と同様の手法により(ビニルモノマー/開始剤(モル比)=100)、合成例12に係る(メタ)アクリレート系重合体(以下、ポリマー12という。)を得た。ポリマー12は、Mnが90000、Mwが230000、Mw/Mnが2.56、Tgが-60℃であった。
ポリマー2の合成に用いたメタクリル酸2,4,6-トリメチルヘプチルの代わりに、メタクリル酸8-メチルノニルを用いること以外は合成例2と同様の手法により(ビニルモノマー/開始剤(モル比)=100)、合成例13に係る(メタ)アクリレート系重合体(以下、ポリマー13という。)を得た。ポリマー13は、Mnが100000、Mwが260000、Mw/Mnが2.60、Tgが-41℃であった。
ポリマー2の合成に用いたメタクリル酸2,4,6-トリメチルヘプチルの代わりに、メタクリル酸10-メチルウンデシルを用いること以外は合成例2と同様の手法により(ビニルモノマー/開始剤(モル比)=100)、合成例14に係る(メタ)アクリレート系重合体(以下、ポリマー14という。)を得た。ポリマー14は、Mnが98000、Mwが240000、Mw/Mnが2.45、Tgが-43℃であった。
ポリマー2の合成に用いたメタクリル酸2,4,6-トリメチルヘプチルの代わりに、メタクリル酸12-メチルトリデシルを用いること以外は合成例2と同様の手法により(ビニルモノマー/開始剤(モル比)=100)、合成例15に係る(メタ)アクリレート系重合体(以下、ポリマー15という。)を得た。ポリマー15は、Mnが99000、Mwが250000、Mw/Mnが2.53、Tgが-46℃であった。
[合成例16:(メタ)アクリレート系重合体の合成]
25gのメタクリル酸2,4,6-トリメチルヘプチルと、5.48gのメタクリル酸n-オクチルと、100mLのトルエンと、0.227gのアゾビスイソブチロニトリルとを混合し(ここで、メタクリル酸2,4,6-トリメチルヘプチル:メタクリル酸n-オクチル(モル比)=80:20、ビニルモノマー/開始剤(モル比)=100である。)、1時間窒素バブリングし、その後、反応溶液を60℃で8時間保持した。得られた溶液のメタノールへの再沈精製により、合成例16に係る(メタ)アクリレート系共重合体(以下、ポリマー16という。)を得た。ポリマー16は、Mnが110000、Mwが260000、Mw/Mnが2.36、Tgが-35℃であった。
25gのメタクリル酸2,4,6-トリメチルヘプチルと、5.48gのメタクリル酸2-エチルヘキシルと、100mLのトルエンと、0.227gのアゾビスイソブチロニトリルとを混合し(ここで、メタクリル酸2,4,6-トリメチルヘプチル:メタクリル酸2-エチルヘキシル(モル比)=80:20、ビニルモノマー/開始剤(モル比)=100である。)、1時間窒素バブリングし、その後、反応溶液を60℃で8時間保持した。得られた溶液のメタノールへの再沈精製により、合成例17に係る(メタ)アクリレート系共重合体(以下、ポリマー17という。)を得た。ポリマー17は、Mnが100000、Mwが250000、Mw/Mnが2.50、Tgが-30℃であった。
ポリマー17の合成に用いたメタクリル酸2,4,6-トリメチルヘプチルとメタクリル酸2-エチルヘキシルのモル比を50:50とした以外は合成例17と同様の手法により、合成例18に係る(メタ)アクリレート系共重合体(以下、ポリマー18という。)を得た。ポリマー18は、Mnが100000、Mwが250000、Mw/Mnが2.50、Tgが-17℃であった。
ポリマー17の合成に用いたメタクリル酸2,4,6-トリメチルヘプチルとメタクリル酸2-エチルヘキシルのモル比を30:70とした以外は合成例17と同様の手法により、合成例19に係る(メタ)アクリレート系共重合体(以下、ポリマー19という。)を得た。ポリマー19は、Mnが100000、Mwが260000、Mw/Mnが2.60、Tgが-13℃であった。
ラボミキサー(ラボプラストミル)を使用し、下記表1および2に示す配合(質量部)に従って、まず、第一混合段階で、ジエン系ゴム成分に対し硫黄及び加硫促進剤を除く他の配合剤を添加し混練した(排出温度=160℃)。次いで、得られた混練物に、最終混合段階で、硫黄と加硫促進剤を添加し混練して(排出温度=90℃)、ゴム組成物を調製した。表1および2中の各成分の詳細は、以下の通りである。
・SBR:ランクセス(株)製「VSL5025」
・BR:宇部興産(株)製の「ウベポールBR150B」
・シリカ:東ソー・シリカ(株)製「ニップシールAQ」
・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・デグサ社製「Si69」
・亜鉛華:三井金属鉱業(株)製「亜鉛華1種」
・老化防止剤:大内新興化学工業(株)製「ノクラック6C」
・ステアリン酸:花王(株)製「ルナックS-20」
・硫黄:細井化学工業(株)製「ゴム用粉末硫黄150メッシュ」
・加硫促進剤:大内新興化学工業(株)製「ノクセラーCZ」
・2次加硫促進剤:大内新興化学工業(株)製「ノクセラーD」
・ポリマー1~19:上記合成例1~19で合成したもの
・樹脂1:東ソー(製)、芳香族脂肪族共重合体系石油樹脂「ペトロタック100」
得られた各ゴム組成物について、160℃×20分で加硫して所定形状の試験片を作製し、得られた試験片を用いて、動的粘弾性試験を行って0℃及び60℃でのtanδと、-10℃での貯蔵弾性率E’を測定するとともに、常温(23℃)での硬度を測定した。測定方法は次の通りである。
Claims (11)
- ジエン系ゴムからなるゴム成分100質量部に対し、重量平均分子量が5000~100万でありかつガラス転移点が-70~0℃である(メタ)アクリレート系重合体を1~100質量部含有するゴム組成物。
- 前記一般式(2)中のZが炭素数5~15のアルキレン基である、請求項3又は4記載のゴム組成物。
- 前記(メタ)アクリレート系重合体が、末端に反応性シリル基を持たない(メタ)アクリレート系重合体である、請求項1~5のいずれか1項に記載のゴム組成物。
- 前記(メタ)アクリレート系重合体が、アゾ化合物からなる開始剤を用いたラジカル重合により合成された(メタ)アクリレート系重合体である、請求項1~6のいずれか1項に記載のゴム組成物。
- 前記(メタ)アクリレート系重合体が、多官能開始剤を用いて合成された星型ポリマーである、請求項1~6のいずれか1項に記載のゴム組成物。
- 前記(メタ)アクリレート系重合体が、メタクリル酸イソデシルを含むモノマーの重合体である、請求項1~9のいずれか1項に記載のゴム組成物。
- 請求項1~10のいずれか1項に記載のゴム組成物を用いた空気入りタイヤ。
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Cited By (12)
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JP2017110069A (ja) * | 2015-12-15 | 2017-06-22 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
WO2017104135A1 (ja) * | 2015-12-15 | 2017-06-22 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JP2017521516A (ja) * | 2014-07-01 | 2017-08-03 | コンパニー ゼネラール デ エタブリッスマン ミシュラン | メタクリレート単位を含有するエラストマーを含むゴム組成物 |
JP2018039867A (ja) * | 2016-09-05 | 2018-03-15 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JP2018083890A (ja) * | 2016-11-22 | 2018-05-31 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JP2018095735A (ja) * | 2016-12-13 | 2018-06-21 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JP2018095732A (ja) * | 2016-12-13 | 2018-06-21 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JP2018095734A (ja) * | 2016-12-13 | 2018-06-21 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JP2018095733A (ja) * | 2016-12-13 | 2018-06-21 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JP2018131559A (ja) * | 2017-02-16 | 2018-08-23 | 横浜ゴム株式会社 | スタッドレスタイヤ用ゴム組成物 |
JP2019112559A (ja) * | 2017-12-25 | 2019-07-11 | Toyo Tire株式会社 | タイヤ用ゴム組成物、及びそれを用いた空気入りタイヤ |
JP2020041083A (ja) * | 2018-09-12 | 2020-03-19 | Toyo Tire株式会社 | ゴム組成物及び空気入りタイヤ |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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FR3024152B1 (fr) * | 2014-07-24 | 2016-07-15 | Michelin & Cie | Pneumatique muni d'une bande de roulement comprenant une composition de caoutchouc comprenant une resine thermoplastique de polymethacrylate de methyle |
EP3831873A1 (en) * | 2019-12-03 | 2021-06-09 | The Goodyear Tire & Rubber Company | Rubber composition and an article of manufacture comprising a rubber composition |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001348463A (ja) * | 2000-06-08 | 2001-12-18 | Sumitomo Rubber Ind Ltd | タイヤ用ゴム組成物 |
JP2009144175A (ja) * | 2009-03-30 | 2009-07-02 | Bridgestone Corp | (共)重合体、ゴム組成物及び空気入りタイヤ |
JP2011178991A (ja) * | 2010-02-04 | 2011-09-15 | Yokohama Rubber Co Ltd:The | タイヤパンクシール材 |
JP2012021149A (ja) * | 2010-06-15 | 2012-02-02 | Yokohama Rubber Co Ltd:The | ゴム組成物およびこれを用いる空気入りタイヤ |
JP2013133436A (ja) * | 2011-12-27 | 2013-07-08 | Yokohama Rubber Co Ltd:The | タイヤトレッド用ゴム組成物および空気入りタイヤ |
JP2014055205A (ja) * | 2012-09-11 | 2014-03-27 | Yokohama Rubber Co Ltd:The | スタッドレスタイヤ用ゴム組成物およびスタッドレスタイヤ |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5763548A (en) * | 1995-03-31 | 1998-06-09 | Carnegie-Mellon University | (Co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization |
US6300407B1 (en) * | 1998-03-06 | 2001-10-09 | Rohm And Haas Company | Polymeric (meth)acrylate plasticizers and processing aids for elastomers |
KR100673429B1 (ko) * | 2000-01-11 | 2007-01-24 | 시바 스페셜티 케미칼스 홀딩 인크. | Atrp 마크로모노머로부터의 콤 공중합체 |
US20090314407A1 (en) * | 2008-06-24 | 2009-12-24 | Gm Global Technology Operations, Inc. | Reducing tire rolling resistance through pre-heating |
-
2015
- 2015-04-02 CN CN201580030185.3A patent/CN106459509B/zh not_active Expired - Fee Related
- 2015-04-02 US US15/301,260 patent/US20170009066A1/en not_active Abandoned
- 2015-04-02 WO PCT/JP2015/001893 patent/WO2015155965A1/ja active Application Filing
- 2015-04-02 DE DE112015001730.5T patent/DE112015001730T5/de not_active Ceased
- 2015-04-02 JP JP2016512592A patent/JP6096381B2/ja active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001348463A (ja) * | 2000-06-08 | 2001-12-18 | Sumitomo Rubber Ind Ltd | タイヤ用ゴム組成物 |
JP2009144175A (ja) * | 2009-03-30 | 2009-07-02 | Bridgestone Corp | (共)重合体、ゴム組成物及び空気入りタイヤ |
JP2011178991A (ja) * | 2010-02-04 | 2011-09-15 | Yokohama Rubber Co Ltd:The | タイヤパンクシール材 |
JP2012021149A (ja) * | 2010-06-15 | 2012-02-02 | Yokohama Rubber Co Ltd:The | ゴム組成物およびこれを用いる空気入りタイヤ |
JP2013133436A (ja) * | 2011-12-27 | 2013-07-08 | Yokohama Rubber Co Ltd:The | タイヤトレッド用ゴム組成物および空気入りタイヤ |
JP2014055205A (ja) * | 2012-09-11 | 2014-03-27 | Yokohama Rubber Co Ltd:The | スタッドレスタイヤ用ゴム組成物およびスタッドレスタイヤ |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017521516A (ja) * | 2014-07-01 | 2017-08-03 | コンパニー ゼネラール デ エタブリッスマン ミシュラン | メタクリレート単位を含有するエラストマーを含むゴム組成物 |
JP2017110069A (ja) * | 2015-12-15 | 2017-06-22 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
WO2017104135A1 (ja) * | 2015-12-15 | 2017-06-22 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
US10723866B2 (en) | 2015-12-15 | 2020-07-28 | Toyo Tire Corporation | Rubber composition and pneumatic tire |
DE112016005729T5 (de) | 2015-12-15 | 2018-10-25 | Toyo Tire & Rubber Co., Ltd. | Kautschukzusammensetzung und pneumatischer Reifen |
JP2018039867A (ja) * | 2016-09-05 | 2018-03-15 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JP2018083890A (ja) * | 2016-11-22 | 2018-05-31 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JP2018095733A (ja) * | 2016-12-13 | 2018-06-21 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JP2018095734A (ja) * | 2016-12-13 | 2018-06-21 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JP2018095732A (ja) * | 2016-12-13 | 2018-06-21 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JP2018095735A (ja) * | 2016-12-13 | 2018-06-21 | 東洋ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JP2018131559A (ja) * | 2017-02-16 | 2018-08-23 | 横浜ゴム株式会社 | スタッドレスタイヤ用ゴム組成物 |
JP2019112559A (ja) * | 2017-12-25 | 2019-07-11 | Toyo Tire株式会社 | タイヤ用ゴム組成物、及びそれを用いた空気入りタイヤ |
JP7025201B2 (ja) | 2017-12-25 | 2022-02-24 | Toyo Tire株式会社 | タイヤ用ゴム組成物、及びそれを用いた空気入りタイヤ |
JP2020041083A (ja) * | 2018-09-12 | 2020-03-19 | Toyo Tire株式会社 | ゴム組成物及び空気入りタイヤ |
JP7129289B2 (ja) | 2018-09-12 | 2022-09-01 | Toyo Tire株式会社 | ゴム組成物及び空気入りタイヤ |
Also Published As
Publication number | Publication date |
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CN106459509A (zh) | 2017-02-22 |
JPWO2015155965A1 (ja) | 2017-04-13 |
DE112015001730T5 (de) | 2016-12-29 |
CN106459509B (zh) | 2018-09-14 |
US20170009066A1 (en) | 2017-01-12 |
JP6096381B2 (ja) | 2017-03-15 |
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