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WO2016163477A1 - Composition de caoutchouc pour bande de roulement et pneumatique obtenu à l'aide de celle-ci - Google Patents

Composition de caoutchouc pour bande de roulement et pneumatique obtenu à l'aide de celle-ci Download PDF

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Publication number
WO2016163477A1
WO2016163477A1 PCT/JP2016/061437 JP2016061437W WO2016163477A1 WO 2016163477 A1 WO2016163477 A1 WO 2016163477A1 JP 2016061437 W JP2016061437 W JP 2016061437W WO 2016163477 A1 WO2016163477 A1 WO 2016163477A1
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Prior art keywords
rubber
group
mass
silica
diene
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Ceased
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PCT/JP2016/061437
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English (en)
Japanese (ja)
Inventor
加藤　学
亮太 高橋
隆裕 岡松
美昭 桐野
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Yokohama Rubber Co Ltd
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Yokohama Rubber Co Ltd
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Publication of WO2016163477A1 publication Critical patent/WO2016163477A1/fr
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/22—Incorporating nitrogen atoms into the molecule
    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • 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
    • 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

Definitions

  • the present invention relates to a rubber composition for a tire tread and a pneumatic tire using the same.
  • silica or carbon black is blended as a reinforcing filler.
  • silica has less heat generation, higher fuel economy, and less change in hardness due to temperature than carbon black.
  • tread rubber has been increasing in recent years.
  • the performance is affected by the reactivity and dispersibility of the silica, and how to disperse the silica during rubber mixing is important.
  • styrene butadiene rubber tends to have different rubber properties depending on the polymerization method.
  • Styrene butadiene rubber is mainly polymerized by emulsion polymerization method and solution polymerization method, and styrene butadiene rubber polymerized by emulsion polymerization method has a longer molecular chain than that polymerized by solution polymerization method, and the polymer chain Is characterized by relatively few vinyl groups, that is, low reactivity with a coupling agent (for example, silica coupling agent) added to improve the dispersibility of silica.
  • a coupling agent for example, silica coupling agent
  • silica when a large amount of silica is added to a rubber composition containing a styrene butadiene rubber and natural rubber polymerized by an emulsion polymerization method, the dispersibility improvement effect of silica on the rubber component, which is the original purpose of adding a coupling agent, is improved. Difficult to function, silica is agglomerated in the rubber, and the properties such as set resistance, fuel efficiency, grip performance etc. that are normally expected to be added by adding silica are rather impaired. It was. However, the styrene butadiene rubber polymerized by the emulsion polymerization method has the advantages of excellent processability and low cost. Accordingly, a rubber composition containing the styrene butadiene rubber polymerized by this emulsion polymerization method and natural rubber has a large amount of silica. Development of a method for dispersing the materials has been desired.
  • the present invention improves the silica dispersibility of a rubber composition containing a styrene butadiene rubber polymerized by an emulsion polymerization method and natural rubber, and is excellent in set resistance, fuel efficiency and grip performance when made into a tire. It is an object to provide a rubber composition for a tread and a pneumatic tire using the rubber composition.
  • a rubber composition containing a diene rubber, silica, and a silane coupling agent includes a natural rubber and an emulsion polymerization as the diene rubber.
  • a relatively large amount of silica can be blended by blending a predetermined amount of a modified polymer having a modification rate of 0.02 to 4.0 mol% obtained by modifying a styrene butadiene rubber with a carboxy group-containing nitrone compound.
  • the dispersibility of the silica is good, and when it is made into a tire, it is excellent in set resistance, fuel efficiency and grip performance, and the present invention has been achieved. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • the diene rubber includes a natural rubber and a modified polymer obtained by modifying an emulsion-polymerized styrene butadiene rubber with a carboxy group-containing nitrone compound, and a modification rate of 0.02 to 4.0 mol%.
  • the content of the modified polymer in the diene rubber is 10 to 90% by mass
  • the content of the natural rubber in the diene rubber is 10 to 90% by mass
  • a rubber composition for a tire tread wherein the content of the silica is 60 to 140 parts by mass with respect to 100 parts by mass of the diene rubber.
  • a modification rate represents the ratio (mol%) modified
  • the above carboxy group-containing nitrone compound is N-phenyl- ⁇ - (4-carboxyphenyl) nitrone, N-phenyl- ⁇ - (3-carboxyphenyl) nitrone, N-phenyl- ⁇ - (2-carboxyphenyl).
  • the amount of the carboxy group-containing nitrone compound used for modifying the emulsion-polymerized styrene-butadiene rubber is 0.1 to 10 parts by mass with respect to 100 parts by mass of the diene rubber.
  • a rubber composition for a tread and a pneumatic tire using the rubber composition can be provided.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the tire tread rubber composition of the present invention contains a diene rubber, silica, and a silane coupling agent.
  • the diene rubber is obtained by modifying a natural rubber and an emulsion-polymerized styrene butadiene rubber with a carboxy group-containing nitrone compound, and a modified polymer (hereinafter, referred to as 0.02 to 4.0 mol%)
  • the content of the carboxynitrone-modified polymer in the diene rubber is 10 to 90% by mass, and the content of the natural rubber in the diene rubber is 10 to 90% by mass.
  • the composition of the present invention dramatically increases the amount of silica compounded in the rubber composition by blending a predetermined amount of natural rubber and carboxynitrone-modified polymer as a diene rubber, and It is presumed that both excellent dispersibility can be achieved. Furthermore, when the content of the silica is 60 to 140 parts by mass with respect to 100 parts by mass of the diene rubber, it is considered that the set resistance, fuel efficiency and grip performance are excellent when the tire is formed. The reason is not clear, but it is presumed that it is as follows.
  • the composition of the present invention is obtained by modifying an emulsion-polymerized styrene-butadiene rubber with a carboxy group-containing nitrone compound, and contains a modified polymer (carboxynitrone-modified polymer) having a modification rate of 0.02 to 4.0 mol%.
  • the polymer / silica interface interaction is generally formed via a silane coupling agent, but the modified polymer interacts directly with silica via a carboxy group. That is, it is considered that the composition of the present invention can enhance the dispersibility while increasing the amount of silica by expressing both the interaction by the coupling agent and the interaction by the carboxy group. .
  • composition of the present invention as shown in Examples 1 and 2 to be described later, even if a large amount of 60 to 140 parts by mass of silica and 100 parts by mass of diene rubber is blended, The effect is reduced. Further, if silica is in the above numerical range, it will be excellent in set resistance, fuel efficiency and grip performance when made into a tire.
  • the diene rubber contained in the composition of the present invention includes natural rubber and a carboxynitrone-modified polymer.
  • the content of the natural rubber in the diene rubber is 10 to 90% by mass
  • the content of the carboxynitrone-modified polymer in the diene rubber is 10 to 90% by mass.
  • the diene rubber may contain a rubber component other than natural rubber and carboxynitrone-modified polymer.
  • the rubber component is not particularly limited, but isoprene rubber (IR), butadiene rubber (BR), aromatic vinyl-conjugated diene copolymer rubber (for example, solution-polymerized styrene butadiene rubber (SBR)), acrylonitrile-butadiene copolymer.
  • IR isoprene rubber
  • BR butadiene rubber
  • SBR aromatic vinyl-conjugated diene copolymer rubber
  • NBR butyl rubber
  • IIR halogenated butyl rubber
  • Br-IIR halogenated butyl rubber
  • Cl-IIR chloroprene rubber
  • CR chloroprene rubber
  • solution polymerization SBR is preferable.
  • Solution polymerized SBR generally has many vinyl groups and good reaction efficiency with a coupling agent, and is compatible with emulsion polymerized SBR, so that it is easy to obtain a synergistic effect in improving physical properties. From the viewpoint of further enhancing this effect, when the composition of the present invention contains solution-polymerized SBR, the content thereof is preferably 5 to 80% by mass, and more preferably 10 to 40% by mass.
  • the diene rubber contained in the composition of the present invention includes natural rubber.
  • the content of natural rubber in the diene rubber is 10 to 90% by mass.
  • the content is preferably 10 to 50% by mass, and more preferably 10 to 30% by mass. If the content of the natural rubber in the diene rubber is 10 to 90% by mass, the effect of the present invention can be sufficiently obtained.
  • the carboxynitrone-modified polymer in the present invention can be obtained by modifying an emulsion-polymerized styrene butadiene rubber with a nitrone compound containing a carboxy group.
  • the content of the carboxynitrone-modified polymer in the diene rubber is 10 to 90% by mass, preferably 20 to 70% by mass, and more preferably 30 to 60% by mass. Since the content of the carboxynitrone-modified polymer is within the above range, the dispersibility of the silica is improved even when a relatively large amount of silica is blended, and the set resistance, fuel efficiency and grip performance are excellent when the tire is formed. .
  • the carboxynitrone-modified polymer can be obtained by modifying emulsion-polymerized styrene butadiene rubber as described above.
  • Such an emulsion-polymerized styrene butadiene rubber can be produced using a styrene monomer and a butadiene monomer.
  • the styrene monomer used in the production of the styrene butadiene rubber is not particularly limited, and examples thereof include styrene, ⁇ -methyl styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 2-ethyl styrene, 3-ethylstyrene, 4-ethylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, dimethylaminomethylstyrene, and dimethylamino Examples include ethyl styrene.
  • styrene, ⁇ -methylstyrene, and 4-methylstyrene are preferable, and styrene is more preferable.
  • These styrene monomers can be used alone or in combination of two or more.
  • the butadiene monomer used in the production of the emulsion-polymerized styrene butadiene rubber is not particularly limited, and examples thereof include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), and 2,3-dimethyl. -1,3-butadiene, 2-chloro-1,3-butadiene and the like.
  • 1,3-butadiene or isoprene is preferably used, and 1,3-butadiene is more preferably used.
  • These butadiene monomers can be used alone or in combination of two or more.
  • the production method (polymerization method) of the emulsion-polymerized styrene-butadiene rubber is not particularly limited.
  • a styrene monomer and a butadiene monomer are dispersed in water using a surfactant such as disproportionated sodium rosinate as an emulsifier, A radical initiator, a catalyst, a chain transfer agent, and the like are added, and the polymerization can be obtained by a general cold polymerization method at a low polymerization temperature (for example, 5 ° C.).
  • the content of styrene units in the emulsion-polymerized styrene-butadiene rubber is 20 to 60% by mass or more, preferably 20 to 40% by mass. Grip property improves more because content of a styrene unit exists in the said range.
  • the content of styrene units (styrene content) in the emulsion-polymerized styrene-butadiene rubber represents the ratio (mass%) of styrene monomer units in the emulsion-polymerized styrene-butadiene rubber.
  • the weight average molecular weight (Mw) of the emulsion-polymerized styrene butadiene rubber is preferably 100,000 to 2,000,000 from the viewpoint of handleability.
  • the weight average molecular weight (Mw) is measured in terms of standard polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
  • the carboxynitrone-modified polymer in the present invention is modified using a nitrone compound containing a carboxy group (hereinafter also simply referred to as “carboxynitrone”).
  • carboxy nitrone is not particularly limited as long as it is a nitrone having at least one carboxy group (—COOH).
  • nitrone refers to a compound having a nitrone group represented by the following formula (1).
  • the carboxy nitrone is preferably a compound represented by the following general formula (2).
  • X and Y each independently represent an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an aromatic heterocyclic group which may have a substituent. However, at least one of X and Y has a carboxy group as a substituent.
  • Examples of the aliphatic hydrocarbon group represented by X or Y include an alkyl group, a cycloalkyl group, and an alkenyl group.
  • Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, Examples thereof include a tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, n-hexyl group, n-heptyl group, and n-octyl group.
  • alkyl groups having 1 to 6 carbon atoms are more preferred.
  • the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. Among them, a cycloalkyl group having 3 to 10 carbon atoms is preferable, and a cycloalkyl group having 3 to 6 carbon atoms is preferable. More preferred.
  • alkenyl group include a vinyl group, a 1-propenyl group, an allyl group, an isopropenyl group, a 1-butenyl group, and a 2-butenyl group. Among them, an alkenyl group having 2 to 18 carbon atoms is preferable. An alkenyl group having 2 to 6 carbon atoms is more preferable.
  • Examples of the aromatic hydrocarbon group represented by X or Y include an aryl group and an aralkyl group.
  • the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group. Among them, an aryl group having 6 to 14 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable. A phenyl group and a naphthyl group are more preferable.
  • Examples of the aralkyl group include a benzyl group, a phenethyl group, and a phenylpropyl group. Among them, an aralkyl group having 7 to 13 carbon atoms is preferable, an aralkyl group having 7 to 11 carbon atoms is more preferable, and a benzyl group is preferable. Further preferred.
  • Examples of the aromatic heterocyclic group represented by X or Y include, for example, pyrrolyl group, furyl group, thienyl group, pyrazolyl group, imidazolyl group (imidazole group), oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, pyridyl group. (Pyridine group), furan group, thiophene group, pyridazinyl group, pyrimidinyl group, pyrazinyl group and the like. Of these, a pyridyl group is preferable.
  • the group represented by X and Y has a substituent other than the carboxy group (hereinafter also referred to as “other substituent”) as long as at least one has a carboxy group as a substituent as described above. You may do it.
  • Other substituents that the group represented by X or Y may have are not particularly limited, and examples thereof include alkyl groups having 1 to 4 carbon atoms, hydroxy groups, amino groups, nitro groups, sulfonyl groups, alkoxy groups. Group, halogen atom and the like.
  • aromatic hydrocarbon group having such a substituent examples include an aryl group having a substituent such as a tolyl group and a xylyl group; and a substituent such as a methylbenzyl group, an ethylbenzyl group, and a methylphenethyl group.
  • the compound represented by the general formula (2) is preferably a compound represented by the following general formula (b).
  • m and n each independently represent an integer of 0 to 5, and the sum of m and n is 1 or more.
  • the integer represented by m is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, because the solubility in a solvent at the time of synthesizing carboxynitrone is improved and the synthesis is facilitated.
  • the integer represented by n is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, because the solubility in a solvent at the time of synthesizing carboxynitrone is improved and the synthesis is facilitated.
  • the total of m and n (m + n) is preferably 1 to 4, and more preferably 1 to 2.
  • Such carboxynitrones represented by the general formula (b) are not particularly limited, but N-phenyl- ⁇ - (4-carboxyphenyl) nitrones represented by the following formula (b1) and the following formula (b2): N-phenyl- ⁇ - (3-carboxyphenyl) nitrone represented, N-phenyl- ⁇ - (2-carboxyphenyl) nitrone represented by the following formula (b3), N represented by the following formula (b4) -(4-carboxyphenyl) - ⁇ -phenylnitrone, N- (3-carboxyphenyl) - ⁇ -phenylnitrone represented by the following formula (b5), and N- ( A compound selected from the group consisting of 2-carboxyphenyl) - ⁇ -phenylnitrone is preferred.
  • the method for synthesizing carboxynitrone is not particularly limited, and a conventionally known method can be used.
  • a compound having a hydroxyamino group (—NHOH) and a compound having an aldehyde group (—CHO) and a carboxy group have a molar ratio of hydroxyamino group to aldehyde group (—NHOH / —CHO) of 1.0.
  • the carboxynitrone-modified polymer in the present invention can be obtained by modifying an emulsion-polymerized styrene butadiene rubber with a nitrone compound containing a carboxy group.
  • the reaction mechanism during the production of the carboxynitrone-modified polymer is to react carboxynitrone with the double bond of the emulsion-polymerized styrene butadiene rubber.
  • a method for producing the carboxynitrone-modified polymer is not particularly limited, and examples thereof include a method in which the emulsion-polymerized styrene butadiene rubber and the carboxynitrone are mixed at 100 to 200 ° C. for 1 to 30 minutes.
  • the amount of the carboxynitrone used to synthesize the carboxynitrone-modified polymer by modifying the emulsion-polymerized styrene butadiene rubber (hereinafter also referred to as “CPN amount converted value”) is 100 parts by mass of the diene rubber.
  • the content is preferably 0.1 to 10 parts by mass, and more preferably 0.3 to 3 parts by mass.
  • 35 parts by mass of a carboxynitrone-modified polymer is contained in 100 parts by mass of a diene rubber, and the carboxynitrone-modified polymer reacts with 100 parts by mass of emulsion polymerization SBR and 1 part by mass of carboxynitrone.
  • the amount (addition amount) of carboxynitrone is not particularly limited, but is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the emulsion-polymerized styrene butadiene rubber. More preferably, it is 5 parts by mass.
  • the modification rate of the carboxynitrone-modified polymer is 0.02 to 4.0 mol%, and more preferably 0.10 to 2.0 mol%.
  • the lower limit value of the modification rate is preferably 0.20 mol% or more.
  • the modification rate represents the ratio (mol%) modified by carboxynitrone among all the double bonds derived from the butadiene (butadiene unit) of the emulsion-polymerized styrene butadiene rubber.
  • 3-butadiene represents a ratio (mol%) in which the structure of the above formula (4-1) or the above formula (4-2) is formed by modification with carboxynitrone.
  • the modification rate can be determined, for example, by performing NMR measurement of emulsion polymerization SBR before and after modification.
  • a carboxynitrone-modified polymer having a modification rate of 100 mol% also corresponds to a diene rubber.
  • the composition of the present invention contains silica.
  • the said silica is not specifically limited, The conventionally well-known arbitrary silica currently mix
  • Specific examples of silica include wet silica, dry silica, fumed silica, diatomaceous earth, and the like.
  • one type of silica may be used alone, or two or more types of silica may be used in combination.
  • the silica preferably has a CTAB adsorption specific surface area of 50 to 300 m 2 / g, more preferably 80 to 250 m 2 / g, from the viewpoint of suppressing silica aggregation.
  • CTAB adsorption specific surface area was determined by measuring the amount of n-hexadecyltrimethylammonium bromide adsorbed on the silica surface in accordance with JIS K6217-3: 2001 “Part 3: Determination of specific surface area—CTAB adsorption method”. Value.
  • the content of silica in the composition of the present invention is 60 to 140 parts by weight, preferably 70 to 130 parts by weight, and preferably 80 to 120 parts by weight with respect to 100 parts by weight of the diene rubber. Is more preferable.
  • silica in the above range the dispersibility is not deteriorated, and when set to a tire, the set resistance, fuel efficiency and grip performance are excellent.
  • the composition of the present invention contains a silane coupling agent.
  • the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, Bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxy Silane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl t
  • bis- (3-triethoxysilylpropyl) tetrasulfide and / or bis- (3-triethoxysilylpropyl) disulfide is preferably used from the viewpoint of reinforcing effect.
  • Si75 [bis- (3-triethoxysilylpropyl) disulfide; manufactured by Evonik Degussa] and the like can be mentioned.
  • the content of the silane coupling agent is preferably 2 to 16 parts by mass and more preferably 4 to 12 parts by mass with respect to 100 parts by mass of the silica. By containing the silane coupling agent in the above range, more sufficient set resistance can be ensured.
  • the composition of this invention can contain an additive further in the range which does not impair the effect and objective as needed.
  • the additive include fillers other than silica (for example, carbon black), zinc oxide (zinc white), stearic acid, thermoplastic resin, adhesive resin, peptizer, anti-aging agent, wax, and processing.
  • Various additives generally used for rubber compositions such as auxiliaries, aroma oils, liquid polymers, terpene resins, thermosetting resins, vulcanizing agents (for example, sulfur), and vulcanization accelerators can be used.
  • the composition of the present invention preferably contains carbon black.
  • the carbon black is not particularly limited, and examples thereof include various grades such as SAF-HS, SAF, ISAF-HS, ISAF, ISAF-LS, IISAF-HS, HAF-HS, HAF, HAF-LS, and FEF. These may be used, and these may be used alone or in combination of two or more.
  • the carbon black preferably has a nitrogen adsorption specific surface area (N 2 SA) of 10 to 300 m 2 / g, preferably 20 to 200 m 2 / g, from the viewpoint of processability when mixing the rubber composition. More preferably.
  • N 2 SA is a value obtained by measuring the amount of nitrogen adsorbed on the carbon black surface according to JIS K 6217-2: 2001 “Part 2: Determination of specific surface area—nitrogen adsorption method—single point method”. .
  • the content of the carbon black is not particularly limited, but is preferably 1 to 100 parts by mass, and preferably 3 to 60 parts by mass with respect to 100 parts by mass in total of the carboxynitrone-modified polymer and the diene rubber. It is more preferable.
  • the composition of the present invention may contain a terpene resin.
  • the composition of the present invention preferably contains an aromatic modified terpene resin obtained by polymerizing terpenes and an aromatic compound.
  • terpenes include ⁇ -pinene, ⁇ -pinene, dipentene, limonene, camphene and the like.
  • aromatic compound include styrene, ⁇ -methylstyrene, vinyl toluene, phenol, and indene.
  • the aromatic modified terpene resin a styrene modified terpene resin using a styrene compound as an aromatic compound is preferable.
  • the aromatic modified terpene resin is contained, the content is preferably 10 to 30 parts by mass, and more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the diene rubber.
  • the aromatic-modified terpene resin preferably has a softening point of 60 to 180 ° C, more preferably 100 to 130 ° C.
  • the softening point of the aromatic modified terpene resin is measured based on JIS K6220-1 (ring and ball method).
  • the composition of the present invention may contain a cyclic polysulfide as a vulcanizing agent.
  • a cyclic polysulfide it is preferable to use a cyclic polysulfide represented by the following general formula (s).
  • R represents a substituted or unsubstituted alkylene group having 4 to 8 carbon atoms, a substituted or unsubstituted oxyalkylene group having 4 to 8 carbon atoms (“—R 1 —O—”, R 1 Represents an alkylene group having 4 to 8 carbon atoms), or —R 2 —O—R 3 — (R 2 and R 3 each independently represents an alkylene group having 1 to 7 carbon atoms).
  • X represents an average of 3 to 5 numbers.
  • N represents an integer of 1 to 5.
  • the carbon number of R is preferably 4 to 8, and more preferably 4 to 7.
  • a substituent in R of the said Formula (s) a phenyl group, a benzyl group, a methyl group, an epoxy group, an isocyanate group, a vinyl group, a silyl group etc. are mentioned, for example.
  • S represents sulfur.
  • x is an average number of 3 to 5, and preferably an average number of 3.5 to 4.5.
  • n is an integer of 1 to 5, and preferably an integer of 1 to 4.
  • the cyclic polysulfide represented by the general formula (s) can be produced by an ordinary method, and examples thereof include a production method described in JP-A-2007-92086.
  • the production method of the composition of the present invention is not particularly limited, and specific examples thereof include, for example, kneading the above-described components using a known method and apparatus (for example, a Banbury mixer, a kneader, a roll, etc.). The method etc. are mentioned.
  • a known method and apparatus for example, a Banbury mixer, a kneader, a roll, etc.
  • the method etc. are mentioned.
  • the composition of the present invention contains sulfur or a vulcanization accelerator, components other than sulfur and the vulcanization accelerator are first mixed at a high temperature (preferably 60 to 120 ° C.) and cooled, and then sulfur or It is preferable to mix a vulcanization accelerator.
  • the composition of the present invention can be vulcanized or crosslinked under conventionally known vulcanization or crosslinking conditions.
  • composition of the present invention is used for tire treads, and is preferably used for tire treads of heavy duty tires.
  • the pneumatic tire of the present invention is a pneumatic tire manufactured using the composition of the present invention described above. Among these, a pneumatic tire manufactured using a tire tread is preferable.
  • FIG. 1 shows a schematic partial sectional view of a tire representing an example of an embodiment of the pneumatic tire of the present invention, but the pneumatic tire of the present invention is not limited to the embodiment shown in FIG.
  • a pneumatic tire in FIG. 1, includes a pair of left and right bead portions 1 and sidewall portions 2, and a tire tread portion 3 connected to both sidewall portions 2, and a carcass in which a steel cord is embedded between the pair of left and right bead portions 1.
  • the layer 4 is mounted, and the end portion of the carcass layer 4 is folded back from the tire inner side to the outer side around the bead core 5 and the bead filler 6.
  • a belt layer 7 is disposed over the circumference of the tire outside the carcass layer 4.
  • Belt cushions 8 are disposed at both ends of the belt layer 7.
  • An inner liner 9 is provided on the inner surface of the pneumatic tire to prevent the air filled inside the tire from leaking to the outside of the tire, and a tie rubber 10 for bonding the inner liner 9 is attached to the carcass layer 4. It is laminated between the inner liner 9.
  • the pneumatic tire of the present invention can be manufactured, for example, according to a conventionally known method. Moreover, as gas with which a tire is filled, inert gas, such as nitrogen, argon, helium other than the air which adjusted normal or oxygen partial pressure, can be used.
  • inert gas such as nitrogen, argon, helium other than the air which adjusted normal or oxygen partial pressure
  • Modified E-SBR Emulsion-polymerized styrene butadiene rubber (Nipol 1502 from Nippon Zeon Co., Ltd.) was placed in a Banbury mixer at 120 ° C. and masticated for 2 minutes, and then CPN (N-phenyl- ⁇ -4-carboxyphenylnitrone) was added to 100 parts by mass of rubber. On the other hand, 1 part by mass was added and mixed at 160 ° C. for 5 minutes with a denaturation temperature and time to prepare a modified E-SBR. The obtained modified E-SBR was subjected to NMR measurement to obtain a modification rate.
  • Cipol 1502 from Nippon Zeon Co., Ltd.
  • the modification rate of the carboxynitrone-modified polymer was 0.20 mol%.
  • the modification rate was determined as follows. That is, the peak area around 8.08 ppm (attributed to two protons adjacent to the carboxy group) of the polymer before and after modification was measured by 1 H-NMR measurement (CDCl 3 , 400 MHz, TMS) using CDCl 3 as a solvent. The denaturation rate was determined by measurement.
  • the 1 H-NMR measurement of the carboxynitrone-modified polymer was carried out using a sample dried under reduced pressure after repeated purification by dissolving the carboxynitrone-modified polymer in toluene and precipitating in methanol twice.
  • Modified S-SBR ⁇ Preparation of Carboxynitrone Modified Polymer (Modified S-SBR)>
  • a solution-polymerized styrene butadiene rubber (E581 manufactured by Asahi Kasei Co., Ltd.) is modified with CPN (N-phenyl- ⁇ -4-carboxyphenylnitrone) by the same preparation method as the modified E-SBR, thereby producing a modified S-SBR. did.
  • the obtained modified S-SBR was subjected to NMR measurement to determine the modification rate.
  • the modification rate of the carboxynitrone-modified polymer was 0.24 mol%.
  • a rubber composition for a tire tread was also simply referred to as a “rubber composition”.
  • the component shown by following Table 2 was mix
  • Examples 1 and 2 and Comparative Example 2 are represented by an index in which loss tangent of Comparative Example 1 is 100 (see Table 1), and Comparative Example 4 is represented by an index in which loss tangent of Comparative Example 3 is 100 ( (See Table 2).
  • ⁇ Pain effect> The obtained tire tread rubber composition (unvulcanized) was vulcanized at 160 ° C. for 20 minutes to prepare a tire tread rubber composition (vulcanized).
  • the prepared rubber composition for tire tread (vulcanized) was subjected to a strain shear modulus G ′ of 0.28% and a strain of 30.0% using a strain shear stress measuring machine (RPA2000, manufactured by ⁇ -Technology).
  • the shear modulus G ′ was measured, and the difference G′0.28 (MPa) ⁇ G′30.0 (MPa) was calculated as the Payne effect.
  • the results are shown in Tables 1 and 2. The result is an index of the reciprocal of the obtained numerical value.
  • Examples 1 and 2 and Comparative Example 2 are represented by an index with the Pain effect of Comparative Example 1 being 100 (see Table 1), and Comparative Example 4 is represented by an index having the Pain effect of Comparative Example 3 being 100 ( (See Table 2).
  • the CPN amount converted value represents the parts by mass of the nitrone compound used for the synthesis of the carboxynitrone-modified polymer with respect to 100 parts by mass of the diene rubber.
  • E-SBR emulsion polymerization styrene butadiene rubber, Nipol 1502 (manufactured by ZEON Corporation)
  • E-SBR Emulsion-polymerized styrene-butadiene rubber modified with carboxy group synthesized as described above (CPN-modified; 1 phr)
  • Modified S-SBR Solution-polymerized styrene butadiene rubber modified with a carboxy group synthesized as described above (CPN-modified; 1 phr)
  • Silane coupling agent Si69 (bis (3-triethoxysilylpropyl) tetrasulfide
  • Zinc flower Zinc flower No. 3 (manufactured by Shodo Chemical Co., Ltd.)
  • Sulfur Oil-treated sulfur (manufactured by Karuizawa Refinery)
  • Examples 1 and 2 have a lower Payne effect than Comparative Example 1 that does not contain a carboxynitrone-modified polymer, even though silica is blended in a large amount of 90 parts by mass. When used as a tire, it was excellent in fuel efficiency, grip performance and set resistance. Moreover, when Example 1 and Comparative Example 2 are compared, Comparative Example 2 does not contain a silane coupling agent, and thus has a high pain effect. When tires are used, any of fuel efficiency, grip performance, and set resistance is achieved. Was also confirmed to be inferior.
  • Comparative Example 4 in which a solution-polymerized styrene butadiene rubber polymerized by a solution polymerization method was modified and an emulsion-polymerized styrene butadiene rubber polymerized by an emulsion polymerization method were used.
  • Example 2 in which emulsion-polymerized styrene butadiene rubber was modified and used had a greater degree of improvement in the pane effect from each of the reference examples (Comparative Examples 1 and 3).
  • the fuel consumption performance, grip performance and set resistance were remarkably excellent.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention aborde le problème consistant à améliorer les propriétés de dispersion de la silice d'une composition de caoutchouc qui comprend un caoutchouc styrène/butadiène produit par polymérisation en émulsion et un caoutchouc naturel et à fournir : une composition de caoutchouc pour bandes de roulement qui permet d'obtenir des pneumatiques présentant d'excellentes propriétés de résistance à la déformation rémanente en compression, de performances de rendement du carburant, et de performances d'adhérence ; et un pneumatique obtenu à l'aide de la composition de caoutchouc. La composition de caoutchouc pour bandes de roulement selon la présente invention comprend des caoutchoucs à base de diène, de la silice et un agent de couplage silane, lesdits caoutchoucs à base de diène comprenant un caoutchouc naturel et un polymère modifié obtenu en modifiant un caoutchouc styrène/butadiène produit par polymérisation en émulsion avec un composé nitrone carboxylé, son degré de modification étant de 0,02 à 4,0 % en moles, la teneur en polymère modifié dans les caoutchoucs à base de diène étant de 10 à 90 % en masse et la teneur en caoutchouc naturel dans les caoutchoucs à base de diène étant de 10 à 90 % en masse, et la silice étant contenue en une proportion de 60 à 140 parties en masse pour 100 parties en masse des caoutchoucs à base de diène.
PCT/JP2016/061437 2015-04-07 2016-04-07 Composition de caoutchouc pour bande de roulement et pneumatique obtenu à l'aide de celle-ci Ceased WO2016163477A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007039499A (ja) * 2005-08-01 2007-02-15 Yokohama Rubber Co Ltd:The タイヤ用ゴム組成物
JP2008163283A (ja) * 2007-01-05 2008-07-17 Bridgestone Corp ゴム組成物及びそれを用いた空気入りタイヤ
JP2014101400A (ja) * 2012-11-16 2014-06-05 Yokohama Rubber Co Ltd:The 変性ポリマー
JP2015098591A (ja) * 2013-10-18 2015-05-28 横浜ゴム株式会社 ゴム組成物およびゴム製品

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007039499A (ja) * 2005-08-01 2007-02-15 Yokohama Rubber Co Ltd:The タイヤ用ゴム組成物
JP2008163283A (ja) * 2007-01-05 2008-07-17 Bridgestone Corp ゴム組成物及びそれを用いた空気入りタイヤ
JP2014101400A (ja) * 2012-11-16 2014-06-05 Yokohama Rubber Co Ltd:The 変性ポリマー
JP2015098591A (ja) * 2013-10-18 2015-05-28 横浜ゴム株式会社 ゴム組成物およびゴム製品

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