WO2019031227A1 - Pneumatique - Google Patents

Pneumatique Download PDF

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Publication number
WO2019031227A1
WO2019031227A1 PCT/JP2018/027673 JP2018027673W WO2019031227A1 WO 2019031227 A1 WO2019031227 A1 WO 2019031227A1 JP 2018027673 W JP2018027673 W JP 2018027673W WO 2019031227 A1 WO2019031227 A1 WO 2019031227A1
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WIPO (PCT)
Prior art keywords
mass
rosin
meth
parts
styrene
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PCT/JP2018/027673
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English (en)
Japanese (ja)
Inventor
達也 宮崎
勝也 松芳
洋樹 阿部
霖 周
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ハリマ化成株式会社
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Publication of WO2019031227A1 publication Critical patent/WO2019031227A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin

Definitions

  • the present invention relates to a pneumatic tire.
  • Rosin-based resins are used as a method for improving wet grip performance and cut tip performance. Both solid and liquid rosin resins are used, and the double bond in the rosin resin is susceptible to thermal oxidation degradation, so that those which have been esterified or modified such as maleic acid modification may also be used. It is used.
  • the rosin-based resin has a suitable acid value, that is, a carboxyl group, and has a cyclic structure, so that it is characterized by having a good affinity with carbon black, sulfur and the like.
  • rosin-based resins can improve wet grip performance and elongation at break to improve cut tip performance, they have a disadvantage that fuel consumption performance is significantly deteriorated, and therefore relatively low fuel consumption performance is not required. It has only been used in treads for truck and bus tires and industrial tires.
  • An object of the present invention is to solve the above-mentioned problems and to provide a pneumatic tire capable of achieving both good wet grip performance, elongation at break and low fuel consumption performance.
  • the present invention was prepared using a rubber composition containing a rosin and a styrene- (meth) acrylic copolymer having a weight average molecular weight of 3,000 or more and having an acid value of 2 to 30 mg KOH / g and sulfur.
  • the present invention relates to a pneumatic tire having a tread.
  • the content of the styrene- (meth) acrylic copolymer in a total content of 100% by mass of the rosin and the styrene- (meth) acrylic copolymer is 2 to 20% by mass preferable.
  • the softening point of the mixture is 30 to 100.degree.
  • content of the styrene butadiene rubber in 100 mass% of rubber components in the said rubber composition is 10 mass% or more.
  • a rubber composition containing sulfur and a mixture containing rosins and a styrene- (meth) acrylic copolymer having a weight average molecular weight of 3,000 or more and having an acid value of 2 to 30 mg KOH / g is used. Since it is a pneumatic tire having a manufactured tread, it is possible to achieve both good wet grip performance, elongation at break and low fuel consumption performance.
  • the pneumatic tire of the present invention comprises a rubber composition containing rosins and a styrene- (meth) acrylic copolymer having a weight average molecular weight of 3,000 or more and having an acid value of 2 to 30 mg KOH / g, and sulfur. It has a tread made using.
  • the rubber composition containing a conventional rosin resin has a Tan ⁇ peak in the Tan ⁇ viscoelasticity curve showing affinity with rubber as compared with a rubber composition containing a terpene resin. I found it low. From this, it is considered that the conventional rosin-based resin has poor micro-entanglement with rubber such as SBR, BR, NR, etc., that is, the compatibility is poor, and the fuel consumption performance is deteriorated.
  • a mixture containing the rosins of the present invention and a predetermined styrene- (meth) acrylic copolymer and having a predetermined acid value has a structural unit derived from a styrenic monomer, and thus interacts with rubber such as SBR. Since micro-entanglement of resin and polymer is promoted, low fuel consumption performance can be improved, and since aromatic groups and COOH groups can promote adhesion grip and sulfur dispersion, good wet grip performance, elongation at break and low fuel consumption It is presumed that the performance can be compatible.
  • Rubber composition As a rubber component which can be used for the above rubber composition, isoprene rubber, styrene butadiene rubber (SBR), butadiene rubber (BR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), styrene-isoprene And diene rubbers such as butadiene copolymer rubber (SIBR). These may be used alone or in combination of two or more.
  • SBR, BR and isoprene rubbers are preferable, SBR is more preferable and abrasion resistance is more preferable since it interacts with the above mixture and tends to obtain the effect of the present invention significantly (synergistically). From the viewpoint that performance or tensile performance tends to be obtained, the combined use of SBR and BR or isoprene rubber is more preferable.
  • the SBR is not particularly limited, and for example, emulsion-polymerized styrene butadiene rubber (E-SBR), solution-polymerized styrene butadiene rubber (S-SBR) and the like can be used. These may be used alone or in combination of two or more.
  • E-SBR emulsion-polymerized styrene butadiene rubber
  • S-SBR solution-polymerized styrene butadiene rubber
  • the amount of styrene in SBR is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more.
  • the amount of styrene is preferably 50% by mass or less, more preferably 47% by mass or less, and still more preferably 45% by mass or less. Within the above range, the effects of the present invention tend to be obtained well.
  • the styrene content of SBR is calculated by H 1 -NMR measurement.
  • Mw of SBR is preferably at least 100,000, more preferably at least 200,000. Further, the Mw is preferably at most 1,600,000, more preferably at most 1,500,000, further preferably at most 1,400,000. Within the above range, the effects of the present invention tend to be obtained well.
  • Mw of SBR is determined by gel permeation chromatography (GPC) (GPC-8000 series manufactured by Tosoh Corp., detector: differential refractometer, column: TSKGEL SUPERMALTPORE HZ- manufactured by Tosoh Corp.) Based on the measurement value by M), it can obtain
  • GPC gel permeation chromatography
  • non-modified SBR or modified SBR may be used. These may be used alone or in combination of two or more.
  • the modified SBR may be any SBR having a functional group capable of interacting with a filler such as silica, for example, an end modified with at least one end of SBR modified with a compound having the above functional group (modifier).
  • SBR terminal-modified SBR having the above functional group at the end
  • main chain modified SBR having the above functional group in the main chain
  • main chain terminal modified SBR having the above functional group at the main chain and at the end
  • main chain terminal modified SBR having the above functional group, at least one end of which is modified with the above modifier, or a polyfunctional compound having two or more epoxy groups in the molecule (coupling), a hydroxyl group And terminal-modified SBR in which an epoxy group is introduced.
  • Examples of the functional group include amino group, amide group, silyl group, alkoxysilyl group, isocyanate group, imino group, imidazole group, urea group, ether group, carbonyl group, oxycarbonyl group, mercapto group, sulfide group, disulfide Group, sulfonyl group, sulfinyl group, thiocarbonyl group, ammonium group, imide group, hydrazo group, azo group, azo group, diazo group, carboxyl group, nitrile group, pyridyl group, alkoxy group, hydroxyl group, oxy group, epoxy group etc. .
  • these functional groups may have a substituent.
  • an amino group preferably an amino group having a hydrogen atom of 1 to 6 carbon atoms substituted by an alkyl group having 1 to 6 carbon atoms
  • an alkoxy group preferably an alkoxysilyl group because the effects of the present invention are more suitably obtained.
  • An alkoxy group having 1 to 6 carbon atoms) and an alkoxysilyl group are preferable.
  • SBR for example, SBR manufactured and sold by Sumitomo Chemical Co., Ltd., JSR Co., Ltd., Asahi Kasei Co., Ltd., Nippon Zeon Co., Ltd., etc. can be used.
  • the content of SBR in 100% by mass of the rubber component is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and particularly preferably 70% by mass or more.
  • the content is 10% by mass or more, the effect of the present invention tends to be favorably obtained by the interaction with the mixture.
  • the upper limit of the content is not particularly limited, and may be, for example, 100% by mass in the case of a racing tire.
  • the BR is not particularly limited, and, for example, BR having a high cis content, BR containing syndiotactic polybutadiene crystals, and the like can be used. These may be used alone or in combination of two or more.
  • BR may be non-modified BR or modified BR. These may be used alone or in combination of two or more. As modified BR, modified BR into which the same functional group as the above-mentioned modified SBR is introduced is mentioned.
  • BR for example, products such as Ube Industries, Ltd., JSR Ltd., Asahi Kasei Corporation, Nippon Zeon Ltd., etc. can be used.
  • the content of BR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more.
  • the content is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, particularly preferably 40% by mass from the viewpoint of achieving both wet grip performance and wear resistance performance. It is below. Within the above range, the effects of the present invention tend to be obtained better.
  • isoprene rubber examples include natural rubber (NR), isoprene rubber (IR), modified NR, modified NR, modified IR and the like.
  • NR natural rubber
  • IR isoprene rubber
  • modified NR for example, those common in the tire industry, such as SIR20, RSS # 3 and TSR20, can be used.
  • the IR is not particularly limited, and, for example, IR 2200 or the like common in the tire industry can be used.
  • modified NR deproteinized natural rubber (DPNR), high purity natural rubber (UPNR), etc.
  • modified NR epoxidized natural rubber (ENR), hydrogenated natural rubber (HNR), grafted natural rubber, etc.
  • modified IR examples include epoxidized isoprene rubber, hydrogenated isoprene rubber, grafted isoprene rubber and the like. These may be used alone or in combination of two or more.
  • the content of isoprene-based rubber in 100% by mass of the rubber component varies in appropriate value depending on the expected level of processing performance, tensile performance, and grip performance.
  • the content is, for example, 0% by mass for racing tires, 100% by mass for truck and bus tires (for rough roads), and 5 to 70% by mass for general purpose passenger car tires Good.
  • the rubber composition contains a mixture containing rosins and a styrene- (meth) acrylic copolymer having a weight average molecular weight of 3,000 or more, and having an acid value of 2 to 30 mg KOH / g.
  • Rosins are obtained as solid hydrocarbons and the like secreted from trees (eg, pine and the like) such as conifers, and contain resin acids having reactive double bonds.
  • the resin acid is a compound having a carboxyl group derived from a tree, and specific examples of the resin acid having a reactive double bond include abietic acid, parastringic acid, neoabietic acid, levopimaric acid and the like.
  • Such rosins are classified according to the presence or absence of modification, and specifically, as rosins, non-modified rosin (unmodified rosin) and rosin modified body (rosin derivative) can be mentioned.
  • non-modified rosin examples include tall rosin (also known as tall oil rosin), gum rosin, wood rosin, asymmetric rosin, polymerized rosin, hydrogenated rosin, and other chemically modified rosins. These unmodified rosins can be used alone or in combination of two or more. As the unmodified rosin, preferably, tall rosin is mentioned.
  • the rosin-modified product is a modified product of the above-mentioned unmodified rosin, such as rosin esters, unsaturated carboxylic acid modified rosins, unsaturated carboxylic acid modified rosin esters, amide compounds of rosin, amine salts of rosin, etc. Can be mentioned.
  • the rosin esters can be obtained, for example, by reacting the above-described unmodified rosin with a polyhydric alcohol by a known esterification method.
  • polyhydric alcohols include dihydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylene glycol, tetramethylene glycol, 1,3-butanediol and 1,6-hexanediol, for example, glycerin, Trihydric alcohols such as methylol propane, trimethylol ethane, triethylol ethane, for example, tetrahydric alcohols such as pentaerythritol, dipentaerythritol etc., such as triethanolamine, tripropanolamine, triisopropanolamine, N-isobutyldiethanolamine, N And amino alcohols such as normal butyl diethanolamine.
  • polyhydric alcohols can be used alone or in combination of two or more.
  • the blending ratio of non-modified rosin and polyhydric alcohol is such that the molar ratio of hydroxyl group of polyhydric alcohol to carboxyl group of non-modified rosin (OH / COOH) is, for example, 0.2 to 1.2.
  • the reaction temperature is, for example, 150 to 300 ° C.
  • the reaction time is, for example, 2 to 30 hours.
  • known catalysts can be blended at an appropriate ratio, as necessary.
  • the unsaturated carboxylic acid-modified rosins can be obtained, for example, by reacting the above-mentioned non-modified rosins with ⁇ , ⁇ -unsaturated carboxylic acids by a known method.
  • ⁇ , ⁇ -unsaturated carboxylic acids include ⁇ , ⁇ -unsaturated carboxylic acids and acid anhydrides thereof, and specific examples thereof include fumaric acid, maleic acid, and maleic anhydride, Itaconic acid, citraconic acid, citraconic anhydride, acrylic acid, methacrylic acid and the like.
  • These ⁇ , ⁇ -unsaturated carboxylic acids can be used alone or in combination of two or more.
  • the blending ratio of the non-modified rosin and the ⁇ , ⁇ -unsaturated carboxylic acid is, for example, 1 mole or less of the ⁇ , ⁇ -unsaturated carboxylic acid with respect to 1 mole of the non-modified rosin.
  • the reaction temperature is, for example, 150 to 300 ° C.
  • the reaction time is, for example, 1 to 24 hours.
  • known catalysts can be blended at an appropriate ratio, as necessary.
  • the unsaturated carboxylic acid-modified rosin esters can be obtained, for example, by sequentially or simultaneously reacting the above-described non-modified rosin with the above-described polyhydric alcohols and the above-described ⁇ , ⁇ -unsaturated carboxylic acids. it can.
  • first, non-modified rosin and polyvalent alcohol are reacted, and then ⁇ , ⁇ -unsaturated carboxylic acids are reacted, or first, non-modified rosin and ⁇ , ⁇ -
  • the unsaturated carboxylic acids are reacted, and then the polyhydric alcohol is reacted.
  • the reaction conditions in the esterification reaction of non-modified rosin with polyhydric alcohol and the modification reaction of non-modified rosin with ⁇ , ⁇ -unsaturated carboxylic acids can be the same as described above.
  • the amide compound of rosin can be obtained, for example, by reacting the above-mentioned non-modified rosin with an amidifying agent.
  • an amidifying agent include primary and / or secondary polyamine compounds, polyoxazoline compounds, and polyisocyanate compounds.
  • a primary and / or secondary polyamine compound is a compound having two or more primary and / or secondary amino groups in one molecule, which is obtained by condensation reaction with a carboxyl group contained in non-modified rosin Rosin can be amidated.
  • polyamine compounds specifically, for example, ethylenediamine, N-ethylaminoethylamine, 1,2-propanediamine, 1,3-propanediamine, N-methyl-1,3-propanediamine, bis (3 -Aminopropyl) ether, 1,2-bis (3-aminopropoxy) ethane, 1,3-bis (3-aminopropoxy) -2,2-dimethylpropane, 1,4-diaminobutane, laurylaminopropyl Linear diamines such as amines, for example 2-aminomethylpiperidine, 4-aminomethylpiperidine, 1,3-di (4-piperidyl) -propane, cyclic diamines such as homopiperazine,
  • the polyoxazoline compound is a compound having two or more polyoxazoline rings in one molecule, and the rosin can be amidated by an addition reaction with a carboxyl group contained in non-modified rosin.
  • examples of such polyoxazoline compounds include 2,2 ′-(1,3-phenylene) -bis (2-oxazoline). These polyoxazoline compounds can be used alone or in combination of two or more.
  • the polyisocyanate compound is a compound having two or more isocyanate groups in one molecule and can amidate a rosin by addition condensation decarboxylation reaction with a carboxyl group contained in non-modified rosin.
  • polyisocyanate compounds for example, aromatic diisocyanates (for example, tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof), phenylene diisocyanate (m-, p-phenylene diisocyanate or Mixtures), 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof), 4,4'-toluidine diisocyanate etc.)
  • Aromatic aliphatic diisocyanates eg, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyan
  • amidating agents can be used individually or in combination of 2 or more types.
  • the mixing ratio of non-modified rosin and amidifying agent is the molar ratio (OH of the active group (primary and / or secondary amino group, polyoxazoline ring, isocyanate group) of amidifying agent to the carboxyl group of non-modified rosin / Active group) is, for example, 0.2 to 1.2.
  • the reaction temperature is, for example, 120 to 300 ° C.
  • the reaction time is, for example, 2 to 30 hours.
  • known catalysts can be blended at an appropriate ratio, as necessary.
  • the amine salt of rosin can be obtained by neutralizing the carboxyl group contained in unmodified rosin with a tertiary amine compound.
  • tertiary amine compounds include triC1-4 alkylamines such as trimethylamine and triethylamine, heterocyclic amines such as morpholine, and the like. These tertiary amine compounds can be used alone or in combination of two or more.
  • rosin modified product for example, rosin modified phenols, for example, rosin alcohols obtained by reducing the carboxyl group of rosins (non-modified rosin, unsaturated carboxylic acid modified rosins, etc.) may be mentioned. These rosin modifications can be used alone or in combination of two or more.
  • rosin modification body Preferably, rosin ester is mentioned.
  • rosins can be used alone or in combination of two or more.
  • modified products of tall rosin are mentioned, and more preferably, rosin esters of tall rosin are mentioned.
  • rosins Preferably, content of a carboxyl group is not excessively high, but having an appropriate acid value is mentioned.
  • the acid value of the rosins usually exceeds 0 mg KOH / g, for example, 100 mg KOH / g or less, preferably 30 mg KOH / g or less, more preferably 10 mg KOH / g or less.
  • an acid value is measured based on the Example mentioned later (following same.).
  • the carboxyl group of rosins can be reduced by well-known esterification processing, and an acid value can also be adjusted to the said range.
  • the styrene- (meth) acrylic copolymer is a polymer of a monomer component containing a styrenic monomer and a (meth) acrylic monomer.
  • (meth) acrylic is defined as acrylic and / or methacryl.
  • styrenic monomers examples include styrene and derivatives thereof. Specifically, aromatic vinyl monomers such as styrene (vinylbenzene), p-methylstyrene, o-methylstyrene, ⁇ -methylstyrene, ethylvinylbenzene and the like It can be mentioned. These styrenic monomers can be used alone or in combination of two or more. As a styrene-type monomer, Preferably, styrene is mentioned.
  • the (meth) acrylic monomer is a copolymerizable monomer having a (meth) acrylic group and, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylic Isopropyl acid, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate ( (Meth) acrylate isopentyl, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, (meth) acrylate Isoborn
  • the (meth) acrylic monomer can be used alone or in combination of two or more. In addition, when two or more types of (meth) acrylic-type monomers are used together, the combined use ratio of them is suitably set according to the objective and a use.
  • the (meth) acrylic monomer preferably contains isobornyl (meth) acrylate, more preferably methyl (meth) acrylate, ethyl (meth) acrylate and isobornyl (meth) acrylate.
  • the monomer component may contain, besides styrenic monomers and (meth) acrylic monomers, copolymerizable monomers copolymerizable therewith.
  • copolymerizable monomers include unsaturated carboxylic acids such as (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, cinnamic acid, etc., for example, fumaric anhydride, maleic anhydride, itaconic anhydride Unsaturated dicarboxylic acid anhydrides such as monomethyl itaconate, monobutyl itaconate, 2-acryloyloxyethyl phthalic acid, etc., eg 2-methacryloyloxyethyl trimellitic acid, 2-methacryloyloxy Unsaturated tricarboxylic acid monoesters such as ethyl pyromellitic acid For example, sulfonyls such as styrene sulfonic
  • diene monomers such as chloroprene.
  • the copolymerizable monomers can be used alone or in combination of two or more. When a copolymerizable monomer is used, preferably, it does not contain a diene monomer as the copolymerizable monomer.
  • the monomer component preferably does not contain a copolymerizable monomer, and is composed of a styrenic monomer and a (meth) acrylic monomer.
  • the content of the styrenic monomer and the (meth) acrylic monomer is, for example, 50% by mass or more, preferably more than 50% by mass, preferably 60% by mass, based on the total amount of the monomer components. It is at least 70% by mass, for example, at most 95% by mass, preferably at most 90% by mass, more preferably at most 80% by mass.
  • the (meth) acrylic monomer is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and for example, 50% by mass or less, preferably less than 50% by mass More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less. If the content of the styrene-based monomer and the (meth) acrylic-based monomer is in the above range, the grip performance and the mechanical strength can be improved.
  • the styrene- (meth) acrylic copolymer can be obtained by polymerizing the above-mentioned monomer components by a known method. Specifically, for example, a monomer component, a polymerization initiator and a solvent are charged into a predetermined reaction vessel and reacted. In this method, the reaction can also proceed while dropping a part or all of the polymerization initiator into the reaction vessel.
  • the polymerization initiator examples include radical polymerization initiators, and preferably, radical polymerization initiators other than azo compounds, specifically, peroxide compounds, sulfides, sulfins, sulfinic acids, etc. And more preferably peroxide compounds.
  • the peroxide compound may be used in combination with a reducing agent as a redox polymerization initiator.
  • a peroxide type compound an organic peroxide, an inorganic peroxide, etc. are mentioned, for example, Preferably, an inorganic peroxide is mentioned.
  • organic peroxide examples include benzoyl peroxide, lauroyl peroxide, acetyl peroxide, capryel peroxide, 2,4-dichlorobenzoyl peroxide, isobutyl peroxide, acetylcyclohexylsulfonyl peroxide, and t-butylperoxide.
  • inorganic peroxides include persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate, hydrogen peroxide, bromate salts such as potassium permanganate, sodium bromate and potassium bromate, perboronic acid Sodium perborate, such as potassium perborate, ammonium perborate, sodium percarbonate, potassium percarbonate, ammonium percarbonate, percarbonate, sodium perphosphate, potassium perphosphate, ammonium perphosphate, etc. And the like, preferably persulfates, more preferably potassium persulfate and ammonium persulfate, and still more preferably ammonium persulfate. These polymerization initiators can be used alone or in combination of two or more.
  • the proportion of the polymerization initiator is, for example, 1 part by mass or more, preferably 2 parts by mass or more, and for example, 10 parts by mass or less, preferably 7 parts by mass or less, based on 100 parts by mass of the total monomer components. It is.
  • the solvent examples include water; ketone solvents such as acetone and methyl ethyl ketone; monohydric alcohol solvents such as methanol, ethanol, propanol, isopropanol and butanol; ethylene glycol monoethyl ether, propylene glycol monomethyl ether Glycol ether solvents such as, for example, ester ether solvents such as propylene glycol monomethyl ether acetate, hydrocarbon solvents such as cyclohexane, methylcyclohexane, toluene, xylene and the like, preferably hydrocarbon solvents, More preferably, toluene is mentioned. These solvents can be used alone or in combination of two or more.
  • the blending ratio of the solvent is not particularly limited, and is appropriately set according to the purpose and application.
  • a crosslinking agent, a chain transfer agent, etc. can be suitably blended with the above-mentioned monomer component, polymerization initiator and solvent.
  • a crosslinking agent for example, a bifunctional crosslinking agent (for example, methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, divinyl benzene, allyl (meth) acrylamide, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) Acrylate, triethylene glycol di (meth) acrylate, allyl (meth) acrylate etc., multifunctional crosslinking agent (eg 1,3,5-triacryloylhexahydro-S-triazine, triallylisocyanurate, triacrylic acid Pentaerythritol, trimethylolpropane acrylate, diacryloylimide, etc., N-substituted acrylamide monomers (eg, N, N'-dimethyl acrylamide, diacetone acrylamide, isopropyl acrylic) And the like, preferably a bifunctional crosslinking agent and an N-substitute
  • chain transfer agent for example, isopropyl alcohol, for example, mercaptos (eg, mercaptoethanol, thiourea, thioglycolic acid, mercaptopropionic acid, thiosalicylic acid, thiolactic acid, aminoethanethiol, thioglycerol, thiomalic acid, etc.),
  • mercaptos eg, mercaptoethanol, thiourea, thioglycolic acid, mercaptopropionic acid, thiosalicylic acid, thiolactic acid, aminoethanethiol, thioglycerol, thiomalic acid, etc.
  • allyls eg, allyl alcohol, sodium allyl sulfonate, sodium methallyl sulfonate etc.
  • These chain transfer agents can be used alone or in combination of two or more. The blending ratio of these chain transfer agents is appropriately set according to the purpose and application.
  • the polymerization conditions vary depending on the types of the monomer component, the polymerization initiator, the solvent and the like, but the polymerization temperature is, for example, 85 ° C. or more, preferably 100 ° C. or more.
  • the polymerization time is, for example, 5 hours or more, preferably 7 hours or more. And, by such polymerization reaction, a styrene- (meth) acrylic copolymer can be obtained.
  • the weight average molecular weight (standard polystyrene conversion molecular weight by GPC measurement) of the resulting styrene- (meth) acrylic copolymer is 3,000 or more, preferably 4,000 or more, more preferably 5,000 or more, still more preferably 7,000 or more. . Good wet grip performance is obtained as it is 3000 or more.
  • the weight average molecular weight is, for example, 35000 or less, preferably 20000 or less, more preferably 13000 or less, and still more preferably 10000 or less. If it is 35000 or less, the resin dispersion tends to be better, and the effects of the present invention tend to be obtained better.
  • the weight average molecular weight of the styrene- (meth) acrylic copolymer is measured according to the examples described later (the same applies hereinafter).
  • the above mixture can be obtained by mixing rosins and a styrene- (meth) acrylic copolymer by a known method.
  • the mixing method is not particularly limited, it is preferable to mix the rosins and the styrene- (meth) acrylic copolymer in a dissolved state, for example, rosins and the styrene- (meth) acrylic copolymer in toluene, etc. And the like, and a method of melting rosins and a styrene- (meth) acrylic copolymer at a high temperature and then mixing them.
  • the content of the rosins in the total content 100% by mass of the rosins and the styrene- (meth) acrylic copolymer is, for example, 80% by mass or more, preferably 83% by mass or more, more preferably 88% by mass or more, further preferably 93% by mass or more, for example, 98% by mass or less, preferably 97% by mass or less, more preferably 96% by mass or less.
  • the content of styrene- (meth) acrylic copolymer in the total content 100% by mass of the rosins and styrene- (meth) acrylic copolymer is preferably 2% by mass or more, more preferably , 3 mass% or more, more preferably 4 mass% or more, particularly preferably 6 mass% or more, for example, preferably 20 mass% or less, more preferably 17 mass% or less, further preferably 12 It is preferably at most 7% by mass, particularly preferably at most 7% by mass. If it is the said range, the grip performance and mechanical strength can be improved.
  • liquid softener in addition to the essential rosins and styrene- (meth) acrylic copolymers, solid resins other than rosins and styrene- (meth) acrylic copolymers (other solid resins),
  • the liquid softener may be further mixed. Among them, it is preferable to further mix the liquid softener. As a result, the softening point of the above mixture is lowered, and the dispersibility of the resin is further improved, so there is a tendency that better grip performance is obtained.
  • a liquid softener is a softener that is liquid at room temperature (23 ° C.), and for example, liquid coumarone indene resin, oil, liquid rosin ester, low temperature plasticizer (TOP, BXA-N etc.), etc. It can be mentioned. Among them, liquid coumarone-indene resin and oil are preferable, and liquid coumarone-indene resin is more preferable from the viewpoint of reducing the softening point of the mixture and improving the dispersibility of the resin and improving the grip performance of the tire.
  • the liquid coumarone-indene resin is a resin containing coumarone and indene as a monomer component constituting a skeleton (main chain) of the resin.
  • monomer components contained in the skeleton besides coumarone and indene include styrene, ⁇ -methylstyrene, methyl indene and vinyl toluene.
  • the softening point of the liquid coumarone-indene resin is, for example, -20 ° C or more, preferably -10 ° C or more, more preferably -5 ° C or more, and for example, 20 ° C or less, preferably 15 ° C or less .
  • the oils include, for example, process oils, vegetable oils and fats, or mixtures thereof.
  • process oil for example, paraffin-based process oil, aroma-based process oil, naphthene-based process oil and the like can be used.
  • vegetable oil, castor oil, cotton seed oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, peanut oil, pine oil, pine tar, tall oil, corn oil, corn oil, vegetable oil, sesame oil, Olive oil, sunflower oil, palm kernel oil, soy sauce, jojoba oil, macadamia nut oil, soy sauce and the like can be mentioned. These may be used alone or in combination of two or more.
  • the above mixture contains other components (other components).
  • other components for example, dispersants, vulcanization accelerating assistants, reinforcing agents, antiaging agents, antidegradants, anti-cracking agents, silane coupling agents, vulcanization retarders, vulcanization activators, etc. are known. And additives. These other components may be used alone or in combination of two or more.
  • the content of the other components in 100% by mass of the mixture is not particularly limited as long as the excellent effects of the present invention are not impaired, but for example, 20% by mass or less, preferably 10% by mass or less Preferably, it is 5% by mass or less, and usually 0% by mass or more.
  • the content of the solid resin and the liquid softener in 100% by mass of the mixture is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass from the viewpoint of achieving the effects of the present invention well. % Or more, and usually 100% by mass or less.
  • the content of the rosin in 100% by mass of the solid resin and the liquid softener is, for example, 70% by mass or more, preferably 75% by mass or more, more preferably 80% by mass or more. It is 98 mass% or less, preferably 97 mass% or less, more preferably 96 mass% or less.
  • the content of the styrene- (meth) acrylic copolymer in 100% by mass of the solid resin and the liquid softener is, for example, 2% by mass or more, preferably 3% by mass or more, more preferably 4% % Or more, for example, 20% by mass or less, preferably 17% by mass or less, more preferably 12% by mass or less, and still more preferably 7% by mass or less.
  • the total content of rosins and styrene- (meth) acrylic copolymer in 100% by mass of solid resin and liquid softener is, for example, 70% by mass or more, preferably 75% by mass or more, more preferably Is 80% by mass or more, more preferably 85% by mass or more, and the upper limit is not particularly limited, and it may be 100% by mass in the case of a compounding system having good resin dispersibility, for example, many softeners However, Preferably, it is 95 mass% or less.
  • the total content of solid resin and other solid resin and liquid softener in 100% by mass of liquid softener preferably, content of liquid softener, more preferably content of liquid coumarone indene resin
  • Is for example, 0% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and for example, 25% by mass or less, preferably 15% by mass or less.
  • the amount of the liquid softener is too large, there is a tendency that the rosins, which are the main components for improving the core grip performance and the tensile performance, become insufficient. If it is the said range, the improvement of grip property and a tensile characteristic can be aimed at.
  • the acid value of the mixture is 2 mg KOH / g or more, preferably 5 mg KOH / g or more, more preferably 7 mg KOH / g or more, and still more preferably 9 mg KOH / g or more.
  • the amount is 2 mg KOH / g or more, the cohesion of the resin is not insufficient, and a good elongation at break and wet grip performance can be obtained.
  • the acid value is 30 mg KOH / g or less, preferably 25 mg KOH / g or less, more preferably 20 mg KOH / g or less, still more preferably 15 mg KOH / g or less, particularly preferably 12 mg KOH / g or less. .
  • Cohesive force is not too large as it is 30 mgKOH / g or less, dispersion
  • the improvement of grip property and mechanical strength can be aimed at.
  • the acid value of the mixture is preferably derived only from the acid value of the rosins. Moreover, when an acid value is excessively high etc., the carboxyl group of the said mixture can be reduced by well-known esterification processing, and an acid value can also be adjusted in the said range.
  • the softening point of the above mixture is, for example, 30 ° C. or more, preferably 35 ° C. or more, more preferably 40 ° C. or more, still more preferably 60 ° C. or more, particularly preferably 65 ° C. or more.
  • the softening point is, for example, 130 ° C. or less, preferably 120 ° C. or less, more preferably 100 ° C. or less, still more preferably 90 ° C. or less, particularly preferably 80 ° C. or less.
  • the softening point is a temperature at which the softening point defined in JIS K 6220-1: 2001 is measured by a ring and ball softening point measuring apparatus and a ball is lowered.
  • the content of the above mixture is 0.1 parts by mass or more, preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, based on 100 parts by mass of the rubber component Preferably, it is 10 parts by mass or more, and most preferably 15 parts by mass or more.
  • the effect of this invention is acquired as it is 0.1 mass part or more.
  • the content is, for example, 50 parts by mass or less, preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. When the amount is 50 parts by mass or less, good fuel economy tends to be maintained.
  • the said rubber composition may contain resin separately from the said mixture.
  • the resin is not particularly limited as long as it is generally used in the tire industry, and coumarone indene resin, ⁇ -methylstyrene resin, terpene resin, p-t-butylphenol acetylene resin, acrylic resin, etc. may be mentioned. Be These may be used alone or in combination of two or more.
  • the rubber composition contains sulfur.
  • Sulfur includes powdery sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, soluble sulfur and the like generally used in the rubber industry. These may be used alone or in combination of two or more.
  • sulfur for example, products such as Tsurumi Chemical Industry Co., Ltd., Karuizawa Sulfur Co., Ltd., Shikoku Kasei Kogyo Co., Ltd., Flexis Japan Co., Ltd., Nippon Hyoryu Kogyo Co., Ltd., Hosoi Kagaku Kogyo Co., Ltd. can be used.
  • the content of sulfur is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, with respect to 100 parts by mass of the rubber component.
  • the content is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less.
  • the rubber composition preferably contains carbon black.
  • the carbon black is not particularly limited, and examples thereof include N134, N110, N220, N234, N219, N339, N330, N326, N351, N550, N762 and the like. These may be used alone or in combination of two or more.
  • the nitrogen adsorption specific surface area (N 2 SA) of carbon black is preferably 5 m 2 / g or more, more preferably 50 m 2 / g or more, and still more preferably 100 m 2 / g or more. If it is 5 m 2 / g or more, the reinforcing property is improved and there is a tendency that a sufficient breaking elongation can be obtained.
  • the N 2 SA is preferably 300 m 2 / g or less, more preferably 200 m 2 / g or less, and still more preferably 150 m 2 / g or less. If it is 300 m 2 / g or less, a good dispersion of carbon black can be easily obtained, and the effects of the present invention tend to be obtained well.
  • the nitrogen adsorption specific surface area of carbon black is determined according to JIS K 6217-2: 2001.
  • carbon black examples include products such as Asahi Carbon Co., Ltd., Cabot Japan Co., Ltd., Tokai Carbon Co., Ltd., Mitsubishi Chemical Co., Ltd., Lion Co., Ltd., Nippon Steel Carbon Co., Ltd., Columbia Carbon Co., Ltd., etc. Can be used.
  • the content of carbon black is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, with respect to 100 parts by mass of the rubber component.
  • the content is preferably 70 parts by mass or less, more preferably 65 parts by mass or less, still more preferably 30 parts by mass or less, and particularly preferably 10 parts by mass or less.
  • tires for commercial vehicles and tires for trucks and buses (for roadways) where wear resistance performance is highly required it is often 30 to 65 parts by mass.
  • the rubber composition preferably contains silica.
  • silica examples include dry method silica (anhydrous silicic acid), wet method silica (hydrous silicic acid) and the like, but wet method silica is preferable because it has many silanol groups. These may be used alone or in combination of two or more.
  • Nitrogen adsorption specific surface area (N 2 SA) of silica is preferably at least 70m 2 / g, more preferably at least 150m 2 / g. By setting it as 70 m 2 / g or more, the breaking elongation tends to be improved. Further, the N 2 SA is preferably from 300 meters 2 / g or less, more preferably 200m 2 / g. By making it 300 m 2 / g or less, processing performance tends to be improved.
  • the nitrogen adsorption specific surface area of silica is a value measured by the BET method according to ASTM D3037-81.
  • silica for example, products of Degussa, Rhodia, Tosoh Silica Corporation, Solvay Japan Ltd., Tokuyama Corporation etc. can be used.
  • the content of silica is preferably 7 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, most preferably 60 parts by mass with respect to 100 parts by mass of the rubber component. It is at least parts by mass, and most preferably at least 80 parts by mass. When the amount is 7 parts by mass or more, tensile performance and fuel economy tend to be improved.
  • the content is preferably 200 parts by mass or less, more preferably 140 parts by mass or less, still more preferably 135 parts by mass or less, and particularly preferably 130 parts by mass or less. If the amount is 200 parts by mass or less, the balance between processing performance, wet grip performance, and fuel economy performance tends to be improved.
  • the rubber composition contains silica
  • it preferably further contains a silane coupling agent.
  • the silane coupling agent is not particularly limited.
  • 3 mass parts or more are preferable with respect to 100 mass parts of silicas, and, as for content of a silane coupling agent, 5 mass parts or more are more preferable. If it is 3 parts by mass or more, the effect of the addition tends to be obtained. Moreover, 20 mass parts or less are preferable, and, as for the said content, 15 mass parts or less are more preferable. When the amount is 20 parts by mass or less, an effect commensurate with the compounding amount is obtained, and there is a tendency that good processability at the time of kneading can be obtained.
  • the rubber composition preferably contains a pluronic nonionic surfactant (polyxamer nonionic surfactant).
  • the pluronic type nonionic surfactant is also called polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene block polymer, polypropylene glycol ethylene oxide adduct, and generally, nonionic represented by the following formula (I) It is a surfactant.
  • the pluronic nonionic surfactant has a hydrophilic group composed of an ethylene oxide structure on both sides, and is composed of a propylene oxide structure so as to be sandwiched by this hydrophilic group It has a hydrophobic group.
  • a, b and c represent integers
  • the polymerization degree of the polypropylene oxide block of the pluronic nonionic surfactant (b in the above formula (I)) and the addition amount of polyethylene oxide (a + c in the above formula (I)) are not particularly limited, and the conditions of use, purpose, etc. It can be selected appropriately according to The higher the proportion of polypropylene oxide blocks, the higher the affinity to rubber and the slower the transition to the rubber surface tends to be. Among them, the degree of polymerization of the polypropylene oxide block (b in the above formula (I)) is preferably 100, because the bloom of the nonionic surfactant can be suitably controlled and the effects of the present invention can be more suitably obtained.
  • the addition amount of polyethylene oxide is preferably 100 or less, more preferably 3 to 65, still more preferably 5 to 55, particularly preferably 5 to 40, most preferably 10-40.
  • the bloom of the nonionic surfactant can be suitably controlled, and the effect of the present invention can be more suitably obtained.
  • Pluronic type nonionic surfactants Pluronic series manufactured by BASF Japan Ltd., New Pole PE series manufactured by Sanyo Chemical Industries, Ltd., Adeka Pluronic L or F series manufactured by Asahi Denka Kogyo Co., Ltd., first There may be mentioned Epan series manufactured by Kogyo Seiyaku Co., Ltd., Pronon series manufactured by NOF Corporation, or Unilobe. These may be used alone or in combination of two or more.
  • the content of the pluronic nonionic surfactant is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 1 part by mass or more with respect to 100 parts by mass of the rubber component. If the amount is 0.1 parts by mass or more, better wet grip performance tends to be obtained. Also, the content is preferably 5 parts by mass or less, more preferably 3 parts by mass or less. If the amount is 5 parts by mass or less, good fuel economy and elongation at break tend to be obtained.
  • the rubber composition preferably contains a wax.
  • the wax is not particularly limited, and petroleum waxes such as paraffin wax and microcrystalline wax; natural waxes such as plant waxes and animal waxes; and synthetic waxes such as polymers of ethylene and propylene. These may be used alone or in combination of two or more. Among them, petroleum waxes are preferable, and paraffin waxes are more preferable.
  • wax for example, products such as Ouchi Emerging Chemical Industry Co., Ltd., Nippon Seiwa Co., Ltd., Seiko Chemical Co., Ltd., etc. can be used.
  • the content of the wax is preferably 0.3 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, with respect to 100 parts by mass of the rubber component, from the viewpoint of the performance balance.
  • the rubber composition preferably contains a fatty acid.
  • fatty acid conventionally known fatty acids can be used.
  • stearic acid, oleic acid, palmitic acid and the like can be mentioned, and stearic acid is preferable from the viewpoint that the effects of the present invention tend to be obtained well.
  • a fatty acid products such as NOF Corporation, NOF, Kao Corporation, Fujifilm Wako Pure Chemical Industries, Ltd., Chiba Fatty Acid Corporation can be used.
  • the content of the fatty acid is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of the rubber component. Further, the content is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. Within the above numerical range, the effects of the present invention tend to be favorably obtained.
  • the rubber composition may contain an oil, or may not contain an oil when aiming at high grip performance and wear resistance.
  • the oils include those similar to the oils that can be used in the above mixtures. These may be used alone or in combination of two or more. Among them, a process oil is preferable, and an aromatic process oil is more preferable, because the effect of the present invention can be obtained well.
  • the content of oil is preferably 1 part by mass or more, more preferably 5 parts by mass or more, with respect to 100 parts by mass of the rubber component.
  • the content is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less.
  • the rubber composition preferably contains an antiaging agent.
  • anti-aging agents include naphthylamine anti-aging agents such as phenyl- ⁇ -naphthylamine; diphenylamine anti-aging agents such as octylated diphenylamine and 4,4'-bis ( ⁇ , ⁇ '-dimethylbenzyl) diphenylamine; N -Isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N, N'-di-2-naphthyl-p-phenylenediamine, etc.
  • P-phenylenediamine antidegradants P-phenylenediamine antidegradants; quinoline antidegradants such as polymers of 2,2,4-trimethyl-1,2-dihydroquinoline; 2,6-di-t-butyl-4-methylphenol
  • Monophenolic anti-aging agents such as styrenated phenols; tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydride] Kishifeniru) propionate] bis methane, tris, and the like polyphenolic antioxidants. These may be used alone or in combination of two or more. Among these, p-phenylenediamine based antioxidants and quinoline based antioxidants are preferred.
  • anti-aging agent for example, products of SEIKO CHEMICAL Co., Ltd., Sumitomo Chemical Co., Ltd., Ouchi Shinko Chemical Industry Co., Ltd., Flexis Co., Ltd., etc. can be used.
  • the content of the antiaging agent is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, with respect to 100 parts by mass of the rubber component. Further, the content is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. Within the above numerical range, the effects of the present invention tend to be favorably obtained.
  • the rubber composition preferably contains zinc oxide.
  • zinc oxide conventionally known ones can be used, and for example, products such as Mitsui Metal Mining Co., Ltd., Toho Zinc Co., Ltd., Huxsui Tech Co., Ltd., Shodo Chemical Industry Co., Ltd., Sakai Chemical Industry Co., Ltd., etc. Can be used.
  • the content of zinc oxide is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, with respect to 100 parts by mass of the rubber component. Further, the content is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. Within the above numerical range, the effects of the present invention tend to be obtained better.
  • the rubber composition preferably contains a vulcanization accelerator.
  • Thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, N-cyclohexyl-2-benzothiazylsulfenamide and the like as a vulcanization accelerator; tetramethylthiuram disulfide (TMTD Thiuram-based vulcanization accelerators such as tetrabenzylthiuram disulfide (TBzTD), tetrakis (2-ethylhexyl) thiuram disulfide (TOT-N), etc .; N-cyclohexyl-2-benzothiazolesulfenamide, Nt-butyl- 2-benzothiazolylsulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N, N'-diisopropyl-2-
  • guanidine based vulcanization accelerators such as diphenyl guanidine, diortotolyl guanidine, orthotolylbi guanidine and the like. These may be used alone or in combination of two or more. Among these, sulfenamide-based vulcanization accelerators and guanidine-based vulcanization accelerators are preferable because the effects of the present invention are more suitably obtained.
  • the content of the vulcanization accelerator is preferably 0.5 parts by mass or more, more preferably 0.7 parts by mass or more, still more preferably 1 part by mass or more, particularly preferably 3 parts by mass with respect to 100 parts by mass of the rubber component. Part or more. Further, the content is preferably 10 parts by mass or less, more preferably 7 parts by mass or less. Within the above numerical range, the effects of the present invention tend to be obtained better.
  • the rubber composition may contain, in addition to the above components, additives generally used in the tire industry, such as organic peroxide, calcium carbonate, talc, alumina, clay, aluminum hydroxide, sulfuric acid Examples thereof include fillers such as magnesium and rubber powder.
  • additives generally used in the tire industry such as organic peroxide, calcium carbonate, talc, alumina, clay, aluminum hydroxide, sulfuric acid
  • fillers such as magnesium and rubber powder.
  • the rubber composition can be produced, for example, by kneading the above-mentioned components using a rubber kneading apparatus such as an open roll or a Banbury mixer, and then vulcanizing.
  • a rubber kneading apparatus such as an open roll or a Banbury mixer
  • the rubber composition of the present invention is suitably used for a tread (cap tread) in contact with a road surface.
  • the pneumatic tire is manufactured by the usual method using the rubber composition. That is, the rubber composition containing the above components is extruded according to the tread shape in the unvulcanized stage, and is molded together with other tire members by a usual method on a tire molding machine. Form a vulcanized tire. The unvulcanized tire is heated and pressurized in a vulcanizer to obtain a tire.
  • the pneumatic tire can be suitably used as a tire for passenger cars, tires for large passenger cars, tires for large SUVs, tires for heavy load such as trucks and buses, tires for light trucks, and the like.
  • a toluene solution (50% by mass) of styrene- (meth) acrylic copolymer 1 was obtained.
  • the weight average molecular weight of the styrene- (meth) acrylic copolymer 1 was 31,455.
  • the acid value of the styrene- (meth) acrylic copolymer 1 was 0 mg KOH / g.
  • Production Example 2 A styrene- (meth) acrylic copolymer is prepared in the same manner as in Production Example 1 except that the reaction temperature is changed to 105 ° C. and the amount of the polymerization initiator dropped first is changed to 3 parts by mass with respect to Production Example 1. The toluene solution (50 mass%) of the polymer 2 was obtained. The weight average molecular weight of the styrene- (meth) acrylic copolymer 2 was 13901. The acid value of the styrene- (meth) acrylic copolymer 2 was 0 mg KOH / g.
  • Styrene- (meth) was prepared by the same method as in Preparation Example 1 except that the reaction temperature was changed to 108 ° C. and the amount of the polymerization initiator dropped first to 5.5 parts by mass with respect to Preparation Example 1.
  • the toluene solution (50 mass%) of the acryl copolymer 3 was obtained.
  • the weight average molecular weight of the styrene- (meth) acrylic copolymer 3 was 8607.
  • the acid value of the styrene- (meth) acrylic copolymer 3 was 0 mg KOH / g.
  • the system is gradually cooled to maintain the temperature at 180 ° C., and 50 parts by mass of a 50% by mass solution of styrene- (meth) acrylic copolymer 2 of Production Example 2 in the ester-modified product of tall rosin obtained That is, 10 parts by mass of the solid content of the styrene- (meth) acrylic copolymer 2) was dropped, and all the solvent was distilled off while mixing. As a result, a mixture 2 containing ester modified product of tall rosin (rosin esters) and a styrene- (meth) acrylic copolymer 2 was obtained.
  • the acid value was 19.1 mg KOH / g.
  • the system is gradually cooled to maintain the temperature at 180 ° C., and 50 parts by mass of a 50% by mass solution of styrene- (meth) acrylic copolymer 3 of Production Example 3 in the ester-modified product of tall rosin obtained That is, 5 parts by mass of the solid content of the styrene- (meth) acrylic copolymer 3) was dropped, and all the solvent was distilled off while mixing. As a result, a mixture 3 containing ester modified product of tall rosin (rosin esters) and a styrene- (meth) acrylic copolymer 3 was obtained.
  • the acid value was 22.6 mg KOH / g.
  • the system is gradually cooled to maintain the temperature at 180 ° C., and 50 parts by mass of a 50% by mass solution of styrene- (meth) acrylic copolymer 3 of Production Example 3 in the ester-modified product of tall rosin obtained That is, 5 parts by mass of the solid content of the styrene- (meth) acrylic copolymer 3) was dropped, and all the solvent was distilled off while mixing. As a result, a mixture 4 containing ester modified product of tall rosin (rosin esters) and a styrene- (meth) acrylic copolymer 3 was obtained.
  • the acid value was 9.8 mg KOH / g.
  • GPC-101 (made by Showa Denko)
  • Differential refractive index detector RI detector column built in part number
  • GPC-101 Part number KF-803, KF-802, KF-801 ⁇ 2 (made by Showa Denko)
  • Mobile phase tetrahydrofuran column flow rate: 1.0 mL / min
  • Sample concentration 5.0 g / L
  • Injection volume 100 ⁇ L
  • Measurement temperature 40 ° C
  • Molecular weight marker Standard polystyrene (SHODEX STANDARD, standard substance manufactured by Showa Denko KK)
  • NS 616 NS 616 manufactured by Nippon Zeon Co., Ltd. (non-oil-extended SBR, styrene content: 20% by mass, vinyl content: 66% by mass, Tg: -23 ° C, Mw: 240,000)
  • CB25 CB25 manufactured by LANXESS (rare-earth-based BR synthesized using an Nd-based catalyst, Tg: -110 ° C)
  • N220 Show black N220 (carbon black, N 2 SA: 114 m 2 / g) manufactured by Cabot Japan Ltd.
  • VN3 Degussa Ultrasil VN3 (silica, N 2 SA: 175 m 2 / g) Si75: Si75 (a silane coupling agent, bis (3-triethoxysilylpropyl) disulfide) manufactured by Degussa SE10: Haritaka SE10 (Halita Chemicals, Inc., hydrogenated rosin ester resin, softening point: 82 ° C., acid value: 6 mg KOH / g, Mw: 900) TF: Harrier Kasei Co., Ltd.
  • Harrier Star TF Rosin ester resin, softening point: 80 ° C., acid value: 8 mg KOH / g, Mw: 1000
  • xx 4401 Sylvatra xx 4401 ( ⁇ -methylstyrene resin (copolymer of ⁇ -methylstyrene and styrene) manufactured by Arizona Chemical Co., softening point: 85 ° C., acid value: 0 mg KOH / g, hydroxyl value: 0 mg KOH / g, Mw : 700, Tg: 43 ° C.)
  • PE-64 Newpol PE-64 (Pluronic-type nonionic surfactant (PEG / PPG-25 / 30 copolymer) manufactured by Sanyo Chemical Industries, Ltd.
  • Paraffin wax Ozo Ace 0355 manufactured by Nippon Seiwa Co., Ltd.
  • Stearic acid NOH made by NOF Co., Ltd.
  • AH-24 Idemitsu Kosan Co., Ltd.
  • Diana Process AH-24 (aroma based process oil) 6PPD Antigen 6C (anti-aging agent, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd.
  • Zinc flower Zinc oxide two-type powder sulfur manufactured by Mitsui Mining & Smelting Co., Ltd.
  • HK-200-5 (powdered sulfur containing 5% by mass oil) manufactured by Hosoi Chemical Industry Co., Ltd.
  • TBBS Noccellar NS (Vulcanization accelerator, N-tert-butyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Emerging Chemical Industry Co., Ltd.
  • DPG Noccellar D (Vulcanization accelerator, 1,3-diphenylguanidine) manufactured by Ouchi Shinko Chemical Co., Ltd.
  • Example and Comparative Example According to the formulation shown in Table 2, using a 1.7 L Banbury mixer manufactured by Kobe Steel, Ltd., chemicals other than sulfur and vulcanization accelerator are kneaded for 5 minutes under the conditions of a set temperature of 150 ° C., A kneaded material was obtained. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded using an open roll for 5 minutes at 80 ° C. to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition is molded into the shape of a tread, and is bonded together with other tire members to produce an unvulcanized tire, which is press vulcanized under conditions of 170 ° C. for 10 minutes to test tires ( Size: 195 / 65R15) was obtained. In addition, about vulcanized-rubber test-piece evaluation, it cut out and performed rubber from the tread part of the tire for a test.

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Abstract

La présente invention concerne un pneumatique qui est en mesure d'atteindre un bon équilibre entre une bonne performance d'adhérence sur sol mouillé, un bon allongement à la rupture et une bonne performance d'économie de consommation de carburant. La présente invention concerne un pneumatique qui présente une bande de roulement qui est produite à l'aide d'une composition de caoutchouc qui contient du soufre et un mélange qui contient une colophane et un copolymère styrène/(méth)acrylique présentant un poids moléculaire moyen en poids de 3000 ou plus, tout en présentant une valeur d'acide de 2 à 30 mg de KOH/g.
PCT/JP2018/027673 2017-08-08 2018-07-24 Pneumatique WO2019031227A1 (fr)

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CN115989152A (zh) * 2020-09-04 2023-04-18 住友橡胶工业株式会社 充气轮胎

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