WO2018123192A1 - Composition de résine thermoplastique, doublure intérieure, et pneu - Google Patents

Composition de résine thermoplastique, doublure intérieure, et pneu Download PDF

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Publication number
WO2018123192A1
WO2018123192A1 PCT/JP2017/036370 JP2017036370W WO2018123192A1 WO 2018123192 A1 WO2018123192 A1 WO 2018123192A1 JP 2017036370 W JP2017036370 W JP 2017036370W WO 2018123192 A1 WO2018123192 A1 WO 2018123192A1
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Prior art keywords
copolymer
thermoplastic resin
ethylene
resin composition
vinyl alcohol
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PCT/JP2017/036370
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English (en)
Japanese (ja)
Inventor
峻 佐藤
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横浜ゴム株式会社
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Priority to JP2018558829A priority Critical patent/JPWO2018123192A1/ja
Publication of WO2018123192A1 publication Critical patent/WO2018123192A1/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
    • B60C5/00—Inflatable pneumatic tyres or inner tubes
    • B60C5/12—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim
    • B60C5/14—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim with impervious liner or coating on the inner wall of the tyre
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • 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
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a thermoplastic resin composition, an inner liner for a pneumatic tire comprising the thermoplastic resin composition, and a pneumatic tire including the inner liner. More specifically, the present invention relates to a thermoplastic resin composition comprising a matrix phase containing an ethylene-vinyl alcohol copolymer and polyamide and a dispersed phase containing a halogenated isomonoolefin-paraalkylstyrene copolymer, and its thermoplasticity. The present invention relates to an inner liner for a pneumatic tire made of a resin composition and a pneumatic tire including the inner liner.
  • Thermoplastic in which a rubber composition containing a halogenated isoolefin paraalkylstyrene copolymer is dispersed in a thermoplastic resin composition containing polyamide and ethylene vinyl alcohol copolymer or polyvinyl alcohol, and the rubber composition is crosslinked.
  • An elastomer composition is known (Japanese Patent Laid-Open No. 2012-46614).
  • thermoplastic resin composition comprising a matrix phase containing an ethylene-vinyl alcohol copolymer and polyamide and a dispersed phase containing a halogenated isomonoolefin-paraalkylstyrene copolymer is used as an inner liner of a pneumatic tire. Gas barrier properties slightly decrease due to fatigue.
  • the present invention relates to a thermoplastic resin composition comprising a matrix phase containing an ethylene-vinyl alcohol copolymer and polyamide and a dispersed phase containing a halogenated isomonoolefin-paraalkylstyrene copolymer as a material for an inner liner for tires. It is an object of the present invention to provide a thermoplastic resin composition that is capable of producing an inner liner that is excellent in durability and less deteriorated in gas barrier properties due to fatigue when used as an adhesive.
  • thermoplastic resin composition comprising a matrix phase containing an ethylene-vinyl alcohol copolymer and polyamide and a dispersed phase containing a halogenated isomonoolefin-paraalkylstyrene copolymer having a molecular weight of 270 or less. It has been found that by blending a certain phthalate ester, it is possible to efficiently suppress a decrease in gas barrier properties due to fatigue, and both durability and gas barrier properties can be achieved, thereby completing the present invention.
  • the present invention relates to a thermoplastic resin composition
  • a thermoplastic resin composition comprising a matrix phase containing an ethylene-vinyl alcohol copolymer and a polyamide and a dispersed phase containing a halogenated isomonoolefin-paraalkylstyrene copolymer, wherein the composition comprises A phthalic acid ester having a molecular weight of 270 or less based on 0.5 to 20 parts by weight based on 100 parts by weight of an ethylene-vinyl alcohol copolymer is characterized in that
  • thermoplastic resin composition comprising a matrix phase containing an ethylene-vinyl alcohol copolymer and polyamide and a dispersed phase containing a halogenated isomonoolefin-paraalkylstyrene copolymer, wherein the composition is ethylene -A thermoplastic resin composition comprising 0.5 to 20 parts by weight of a phthalic acid ester having a molecular weight of 270 or less based on 100 parts by weight of a vinyl alcohol copolymer.
  • phthalate ester is dimethyl phthalate or diethyl phthalate.
  • the weight ratio of the ethylene-vinyl alcohol copolymer and the polyamide contained in the matrix phase is 95/5 to 40/60, [1] or [2]
  • the thermoplastic resin composition as described.
  • the halogenated isomonoolefin-paraalkylstyrene copolymer is 10 to 150 parts by weight based on 100 parts by weight of the total amount of the ethylene-vinyl alcohol copolymer and the polyamide, according to [1] to [3]
  • the thermoplastic resin composition according to any one of the above.
  • thermoplastic resin composition according to any one of [1] to [4], wherein the dispersed phase further contains an elastomer having an acid anhydride group.
  • thermoplastic resin composition according to any one of [1] to [5], wherein the halogenated isomonoolefin-paraalkylstyrene copolymer is dynamically crosslinked with a crosslinking agent.
  • An inner liner for a pneumatic tire comprising the thermoplastic resin composition according to any one of [1] to [6].
  • a pneumatic tire including the inner liner according to [7].
  • thermoplastic resin composition of the present invention can produce an inner liner that is excellent in low-temperature durability and has little deterioration in gas barrier properties due to fatigue.
  • the present invention relates to a thermoplastic resin composition
  • a thermoplastic resin composition comprising a matrix phase containing an ethylene-vinyl alcohol copolymer and a polyamide and a dispersed phase containing a halogenated isomonoolefin-paraalkylstyrene copolymer, wherein the composition comprises A phthalic acid ester having a molecular weight of 270 or less based on 0.5 to 20 parts by weight based on 100 parts by weight of an ethylene-vinyl alcohol copolymer is characterized in that
  • thermoplastic resin composition comprising a matrix phase containing an ethylene-vinyl alcohol copolymer and polyamide and a dispersed phase containing a halogenated isomonoolefin-paraalkylstyrene copolymer
  • the phthalic acid ester used in the present invention has a molecular weight of 270 or less, preferably 100 to 260, more preferably 130 to 250. If the molecular weight is too high, there is a possibility that deterioration of gas barrier properties due to fatigue cannot be suppressed.
  • Specific examples of the phthalate ester plasticizer having a molecular weight of 270 or less include dimethyl phthalate (molecular weight: 194.2), ethyl methyl phthalate (molecular weight: 208.2), diethyl phthalate (molecular weight: 222.2). ), Dipropyl phthalate (molecular weight: 250.3).
  • dimethyl phthalate and diethyl phthalate are preferable from the viewpoint of suppressing a decrease in gas barrier properties due to fatigue.
  • the phthalic acid ester to be used may be one kind or a mixture of two or more kinds.
  • the phthalic acid ester whose molecular weight exceeds 270 may be contained in the range which does not inhibit the effect of this invention.
  • the blending amount of the phthalic acid ester having a molecular weight of 270 or less is 0.5 to 20 parts by weight, preferably 0.8 to 15 parts by weight, based on 100 parts by weight of the ethylene-vinyl alcohol copolymer.
  • the amount is preferably 1 to 10 parts by weight. If the blending amount of the phthalic acid ester having a molecular weight of 270 or less is too small, the effect of suppressing the deterioration of gas barrier properties due to fatigue may not be sufficient, and conversely if too large, the gas barrier properties before fatigue may be deteriorated. .
  • the thermoplastic resin composition of the present invention comprises a matrix phase and a dispersed phase.
  • the thermoplastic resin composition of the present invention has a so-called sea-island structure.
  • the matrix phase includes an ethylene-vinyl alcohol copolymer and a polyamide.
  • the dispersed phase comprises a halogenated isomonoolefin-paraalkylstyrene copolymer.
  • the dispersed phase preferably further comprises an elastomer having acid anhydride groups. Phthalates are mainly contained in the matrix phase.
  • the ethylene-vinyl alcohol copolymer (hereinafter also referred to as “EVOH”) used in the present invention is composed of an ethylene unit (—CH 2 CH 2 —) and a vinyl alcohol unit (—CH 2 —CH (OH) —).
  • EVOH ethylene-vinyl alcohol copolymer
  • the copolymer may contain other structural units as long as the effects of the present invention are not impaired.
  • the ethylene-vinyl alcohol copolymer used in the present invention has an ethylene unit content, that is, an ethylene composition ratio of preferably 32 to 48 mol%, more preferably 38 to 48 mol%.
  • the ethylene-vinyl alcohol copolymer is a saponified product of an ethylene-vinyl acetate copolymer, and the saponification degree is preferably 90% or more, more preferably 98% or more. If the saponification degree of the ethylene-vinyl alcohol copolymer is too small, the gas barrier property is lowered and the thermal stability is also lowered.
  • the ethylene-vinyl alcohol copolymer is commercially available, for example, under the product name “EVAL” (registered trademark) from Kuraray Co., Ltd. and under the product name “SOANOL” (registered trademark) from Nippon Synthetic Chemical Industry Co., Ltd. It can be obtained.
  • EVAL registered trademark
  • SOANOL registered trademark
  • ethylene-vinyl alcohol copolymer having an ethylene composition ratio of 32 to 48 mol% and a saponification degree of 90% or more “EVAL” (registered trademark) H171B manufactured by Kuraray Co., Ltd.
  • the polyamide used in the present invention is not limited, but nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon 610, nylon 612, nylon 6/66, nylon 6/66/12, nylon MXD6, nylon 6T, nylon 9T, etc. are mentioned. Among these, nylon 6, nylon 6/66, and nylon 612 are preferable in terms of both durability and gas barrier properties.
  • the weight ratio of ethylene-vinyl alcohol copolymer to polyamide is preferably 95/5 to 40/60, more preferably 90/10 to 45/55, More preferably, it is 85/15 to 50/50.
  • proportion of the ethylene-vinyl alcohol copolymer is too low, the gas barrier property before fatigue is not sufficient, and when the proportion of the ethylene-vinyl alcohol copolymer is too high, the low-temperature durability is deteriorated.
  • the halogenated isomonoolefin-paraalkylstyrene copolymer used in the present invention can be produced by halogenating a copolymer of isomonoolefin and paraalkylstyrene, and the halogenated isomonoolefin and paraalkylstyrene.
  • the mixing ratio, polymerization rate, average molecular weight, polymerization form (block copolymer, random copolymer, etc.), viscosity, halogen atom, etc. are not particularly limited, depending on the physical properties required for the thermoplastic elastomer composition Can be arbitrarily selected.
  • Examples of the isomonoolefin constituting the halogenated isomonoolefin-paraalkylstyrene copolymer include isobutylene, isopentene, isohexene and the like, with isobutylene being preferred.
  • Examples of the paraalkyl styrene constituting the halogenated isomonoolefin-paraalkyl styrene copolymer include paramethyl styrene, paraethyl styrene, parapropyl styrene, parabutyl styrene and the like, and paramethyl styrene is preferable.
  • halogen constituting the halogenated isomonoolefin-paraalkylstyrene copolymer examples include fluorine, chlorine, bromine and iodine, with bromine being preferred.
  • a particularly preferred halogenated isomonoolefin-paraalkylstyrene copolymer is a brominated isobutylene-paramethylstyrene copolymer. Brominated isobutylene-paramethylstyrene copolymer has the formula (1)
  • Brominated isobutylene-paramethylstyrene copolymer is available from ExxonMobil Chemical Company under the trade name Exxpro TM.
  • the blending amount of the halogenated isomonoolefin-paraalkylstyrene copolymer is preferably 10 to 150 parts by weight, more preferably 20 parts based on 100 parts by weight of the total amount of the ethylene-vinyl alcohol copolymer and the polyamide. Is 140 parts by weight, more preferably 30-130 parts by weight. If the amount of the halogenated isomonoolefin-paraalkylstyrene copolymer is too small, the low-temperature durability is inferior. On the other hand, if the amount is too large, the fluidity at the time of melting decreases and the film-forming property deteriorates.
  • the halogenated isomonoolefin-paraalkylstyrene copolymer is preferably dynamically cross-linked by a cross-linking agent.
  • a cross-linking agent By dynamically crosslinking, the matrix phase and the dispersed phase of the thermoplastic resin composition can be fixed.
  • Dynamic crosslinking can be performed by melt-kneading a halogenated isomonoolefin-paraalkylstyrene copolymer together with a crosslinking agent.
  • crosslinking agent used for dynamic crosslinking examples include zinc white, stearic acid, zinc stearate, magnesium oxide, m-phenylene bismaleimide, alkylphenol resin and its halide, secondary amine and the like.
  • Secondary amines used as crosslinking agents include N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, polymerized 2,2,4-trimethyl-1,2-dihydroquinoline, etc. Is mentioned.
  • zinc white, stearic acid, zinc stearate, and N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine can be preferably used as a crosslinking agent for dynamic crosslinking.
  • the amount of the crosslinking agent is preferably 4 to 12 parts by weight, more preferably 6 to 9 parts by weight, based on 100 parts by weight of the halogenated isomonoolefin-paraalkylstyrene copolymer.
  • the amount of the crosslinking agent When the amount of the crosslinking agent is too small, dynamic crosslinking is insufficient, the fine dispersion of the halogenated isomonoolefin-paraalkylstyrene copolymer cannot be maintained, and durability is lowered. On the other hand, if the amount of the crosslinking agent is too large, it may cause scorching during kneading and processing, or cause foreign matter in the film.
  • the dispersed phase preferably further comprises an elastomer having acid anhydride groups.
  • an elastomer having an acid anhydride group By blending an elastomer having an acid anhydride group, durability at low temperatures and flexibility can be improved.
  • the elastomer having an acid anhydride group used in the present invention include a maleic anhydride-modified ethylene- ⁇ -olefin copolymer elastomer, a maleic anhydride-modified ethylene- (meth) acrylic acid copolymer elastomer, a maleic anhydride-modified ethylene- ( Examples include meth) acrylic acid ester copolymer elastomers.
  • (meth) acrylic acid means acrylic acid and methacrylic acid.
  • the maleic anhydride modified ethylene- ⁇ -olefin copolymer elastomer includes maleic anhydride modified ethylene-propylene copolymer elastomer, maleic anhydride modified ethylene-butene copolymer elastomer, maleic anhydride modified ethylene-hexene copolymer elastomer, maleic anhydride. Examples include acid-modified ethylene-octene copolymer elastomer.
  • maleic anhydride-modified ethylene- (meth) acrylic acid copolymer elastomers examples include maleic anhydride-modified ethylene-acrylic acid copolymer elastomers and maleic anhydride-modified ethylene-methacrylic acid copolymer elastomers.
  • maleic anhydride-modified ethylene- (meth) acrylic acid ester copolymer elastomer examples include maleic anhydride-modified ethylene-methyl acrylate copolymer elastomer, maleic anhydride-modified ethylene-ethyl acrylate copolymer elastomer, maleic anhydride-modified ethylene- Examples thereof include a methyl methacrylate copolymer elastomer and a maleic anhydride modified ethylene-ethyl methacrylate copolymer elastomer.
  • Particularly preferred elastomers having an acid anhydride group are maleic anhydride-modified ethylene-butene copolymer, maleic anhydride-modified ethylene-propylene copolymer, maleic anhydride-modified ethylene-octene copolymer, and the like.
  • Maleic anhydride-modified ethylene-butene copolymers are commercially available, and can be obtained from Mitsui Chemicals, Inc. under the trade names of TAFMER (registered trademark) MH7010, MH7020, and maleic anhydride-modified ethylene-propylene copolymers.
  • the polymer can be obtained from Mitsui Chemicals, Inc. under the trade names of TAFMER (registered trademark) MP0610 and MP0620, for example.
  • the amount of the elastomer having an acid anhydride group is preferably based on 100 parts by weight of the total amount of the ethylene-vinyl alcohol copolymer and the polyamide. Is 10 to 150 parts by weight, more preferably 20 to 140 parts by weight, and still more preferably 30 to 130 parts by weight. If the blending amount of the elastomer is too small, the effect of improving the low temperature durability and flexibility cannot be sufficiently obtained. If the blending amount of the elastomer is too large, the fluidity at the time of melting is lowered and the film-forming property is deteriorated.
  • the thermoplastic resin composition of the present invention comprises a resin other than an ethylene-vinyl alcohol copolymer and a polyamide, a halogenated isomonoolefin-paraalkylstyrene copolymer, an elastomer other than an elastomer having an acid anhydride group, and various additives. May be included as long as the effects of the present invention are not impaired. Additives include cross-linking agents, anti-aging agents, plasticizers, processing aids (metal soaps, etc.), cross-linking accelerators, cross-linking accelerators, reinforcing agents (fillers), scorch inhibitors, peptizers, organic modifiers. A quality agent, a softening agent, a tackifier, etc. can be mentioned.
  • the thermoplastic resin composition of the present invention includes, but is not limited to, an ethylene-vinyl alcohol copolymer, a polyamide, a halogenated isomonoolefin-paraalkylstyrene copolymer, a phthalate ester, and an acid. It can be produced by melt-kneading an elastomer having an anhydride group and other components at a temperature equal to or higher than the melting point of polyamide. When a crosslinking agent is added, the crosslinking agent may be mixed with the halogenated isomonoolefin-paraalkylstyrene copolymer in advance, or may be added before melt kneading, You may add in the middle.
  • the melt kneading temperature is a temperature equal to or higher than the melting point of the polyamide, but is preferably 20 ° C. higher than the melting point of the polyamide, for example, 180 to 300 ° C.
  • the time for melt kneading is usually 1 to 10 minutes, preferably 1 to 5 minutes.
  • thermoplastic resin composition of the present invention is preferably continuously kneaded with an ethylene-vinyl alcohol copolymer, polyamide, and halogenated isomonoolefin-paraalkylstyrene copolymer using a biaxial kneader, By kneading, a halogenated isomonoolefin-paraalkylstyrene copolymer is dispersed in a matrix phase composed of an ethylene-vinyl alcohol copolymer and a polyamide, and can be produced by dynamic crosslinking.
  • a rubber compound is prepared by mixing a halogenated isomonoolefin-paraalkylstyrene copolymer, a crosslinking agent, and other additives as necessary at 60 to 150 ° C.
  • Compound, polyamide, ethylene-vinyl alcohol copolymer and other resin or additive as required are charged into a twin-screw kneader with a set temperature of 220 to 250 ° C, and a halogenated isomonoolefin-paraalkylstyrene copolymer
  • the thermoplastic resin composition of the present invention can be obtained by dispersing the coalescence and dynamically crosslinking.
  • the present invention is also an inner liner for a pneumatic tire comprising the thermoplastic resin composition.
  • the thermoplastic resin composition of the present invention can be formed into a film using an extruder with a T-die or an inflation molding machine. Since the film comprising the thermoplastic resin composition of the present invention is excellent in gas barrier properties and durability, it can be suitably used as an inner liner of a pneumatic tire.
  • the present invention is also a pneumatic tire including the inner liner. More specifically, the pneumatic tire of the present invention is a pneumatic tire including a film of the thermoplastic resin composition as an inner liner.
  • a conventional method can be used.
  • the thermoplastic resin composition of the present invention is extruded into a film having a predetermined width and thickness, and this is adhered to a cylinder on a tire molding drum as an inner liner.
  • members used in normal tire production such as a carcass layer, a belt layer, a tread layer, and the like made of unvulcanized rubber are sequentially laminated and removed from the drum to obtain a green tire.
  • a desired pneumatic tire can be manufactured by heating and vulcanizing the green tire according to a conventional method.
  • EVOH ethylene-vinyl alcohol copolymers
  • Nylon 6 “UBE nylon” 1013B manufactured by Ube Industries, Ltd.
  • Nylon 6/66 “UBE nylon” 5023B manufactured by Ube Industries, Ltd.
  • halogenated isomonoolefin-paraalkylstyrene copolymer the following was used.
  • Brominated isobutylene-paramethylstyrene copolymer rubber (hereinafter referred to as “Br-IPMS”): Exxpro TM MDX89-4 manufactured by ExxonMobil Chemical Co.
  • Acid-modified polyolefin elastomer maleic anhydride-modified ethylene-butene copolymer “Tuffmer” (registered trademark) MH7010 manufactured by Mitsui Chemicals, Inc.
  • phthalic acid esters The following three types of phthalic acid esters were used. Dimethyl phthalate: manufactured by Daihachi Chemical Industry Co., Ltd., molecular weight 194.2 Diethyl phthalate: manufactured by Daihachi Chemical Industry Co., Ltd., molecular weight 222.2 Dibutyl phthalate: manufactured by Daihachi Chemical Industry Co., Ltd., molecular weight 278.3
  • Zinc oxide 3 types of zinc oxide manufactured by Shodo Chemical Co., Ltd.
  • thermoplastic resin composition An ethylene-vinyl alcohol copolymer, polyamide, brominated isobutylene-paramethylstyrene copolymer rubber, phthalate ester, acid-modified polyolefin elastomer, cross-linking agent, and anti-aging agent are blended as shown in Tables 1 and 2. It is put into a cylinder of a kneading extruder (manufactured by Nippon Steel Co., Ltd.), conveyed to a kneading zone set at a temperature of 230 ° C. and a residence time of about 3 to 8 minutes, and melt kneaded. Extruded into a strand from the attached die.
  • a kneading extruder manufactured by Nippon Steel Co., Ltd.
  • the obtained strand-shaped extrudate was pelletized with a resin pelletizer to obtain a pellet-shaped thermoplastic resin composition.
  • a resin pelletizer to obtain a pellet-shaped thermoplastic resin composition.
  • the change rate of the air permeability coefficient by fatigue and low-temperature durability were evaluated. The evaluation results are shown in Tables 1 and 2.
  • Extrusion temperature C1 / C2 / C3 / C4 / die 220/225/230/235 of the prepared pellet-shaped thermoplastic resin composition using a 40 mm ⁇ single screw extruder with 550 mm width T die (Pura Giken Co., Ltd.)
  • the film was formed into a film having an average thickness of 0.1 mm under extrusion conditions of / 235 ° C., a cooling roll temperature of 50 ° C., and a take-off speed of 4 m / min.
  • the film was cut into a predetermined size and bonded to an unvulcanized rubber composition sheet (average thickness 2 mm) blended as shown in Table 3, and then vulcanized and bonded at 180 ° C. for 10 minutes to give a thermoplastic resin composition.
  • a laminate of the product and the rubber composition was obtained.
  • the laminate was cut into a width of 5 cm and repeatedly deformed 1 million times with a constant strain tester (manufactured by Ueshima Seisakusho Co., Ltd.).
  • the air permeability coefficient of the laminate was measured at a temperature of 23 ° C. and a humidity of 0% RH, and the change rate of the air permeability coefficient due to fatigue was calculated by the following equation.
  • Change rate of air permeability coefficient due to fatigue Air permeability coefficient after deformation / Air permeability coefficient before deformation It was determined that the change rate of the air permeability coefficient due to fatigue was 2.0 or less as acceptable (with a suppression effect).
  • thermoplastic resin composition of the present invention can be suitably used for producing an inner liner for a pneumatic tire.

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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)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Tires In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine thermoplastique qui permet de fabriquer une doublure intérieure de pneu ayant une excellente durabilité à basses températures et qui est moins sensible à des propriétés de barrière aux gaz réduites sous l'effet de l'usure. La composition de résine thermoplastique comprend une phase matrice contenant un copolymère d'éthylène-alcool vinylique et un polyamide, et une phase dispersée contenant un copolymère d'isomonooléfine-paraalkylstyrène halogéné, où la composition est caractérisée en ce qu'elle contient de 0,5 à 20 parties en poids d'un ester de phtalate ayant un poids moléculaire de 270 ou moins pour 100 parties en poids du copolymère d'éthylène-alcool vinylique.
PCT/JP2017/036370 2016-12-28 2017-10-05 Composition de résine thermoplastique, doublure intérieure, et pneu WO2018123192A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002052904A (ja) * 2000-08-11 2002-02-19 Kuraray Co Ltd タイヤ内面用インナーライナー
JP2007291256A (ja) * 2006-04-26 2007-11-08 Sumitomo Rubber Ind Ltd 空気入りタイヤ
WO2012026167A1 (fr) * 2010-08-26 2012-03-01 横浜ゴム株式会社 Composition d'élastomère thermoplastique, et pneumatique l'utilisant
WO2012042975A1 (fr) * 2010-09-29 2012-04-05 横浜ゴム株式会社 Procédé pour la production de composition d'élastomère thermoplastique
JP2014031404A (ja) * 2012-08-01 2014-02-20 Bridgestone Corp ゴム組成物及びそれを用いた空気入りタイヤ
WO2017006827A1 (fr) * 2015-07-07 2017-01-12 横浜ゴム株式会社 Composition de résine thermoplastique, revêtement intérieur et pneu

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002052904A (ja) * 2000-08-11 2002-02-19 Kuraray Co Ltd タイヤ内面用インナーライナー
JP2007291256A (ja) * 2006-04-26 2007-11-08 Sumitomo Rubber Ind Ltd 空気入りタイヤ
WO2012026167A1 (fr) * 2010-08-26 2012-03-01 横浜ゴム株式会社 Composition d'élastomère thermoplastique, et pneumatique l'utilisant
WO2012042975A1 (fr) * 2010-09-29 2012-04-05 横浜ゴム株式会社 Procédé pour la production de composition d'élastomère thermoplastique
JP2014031404A (ja) * 2012-08-01 2014-02-20 Bridgestone Corp ゴム組成物及びそれを用いた空気入りタイヤ
WO2017006827A1 (fr) * 2015-07-07 2017-01-12 横浜ゴム株式会社 Composition de résine thermoplastique, revêtement intérieur et pneu

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