WO2010047315A1 - Composition de caoutchouc et stratifié de polyamide - Google Patents

Composition de caoutchouc et stratifié de polyamide Download PDF

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WO2010047315A1
WO2010047315A1 PCT/JP2009/068030 JP2009068030W WO2010047315A1 WO 2010047315 A1 WO2010047315 A1 WO 2010047315A1 JP 2009068030 W JP2009068030 W JP 2009068030W WO 2010047315 A1 WO2010047315 A1 WO 2010047315A1
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rubber
compound
mass
range
acid
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PCT/JP2009/068030
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Japanese (ja)
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洋司 奥下
修一 前田
佳史 赤川
竜弥 榎本
利雄 森山
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宇部興産株式会社
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Priority to JP2010534806A priority Critical patent/JP5472116B2/ja
Publication of WO2010047315A1 publication Critical patent/WO2010047315A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40—Polyamides containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • C08K5/435—Sulfonamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur

Definitions

  • the present invention relates to a rubber composition capable of providing a polyamide laminate having a high adhesive force, comprising a polyether polyamide elastomer and a crosslinked rubber, and the polyamide laminate.
  • Laminates of polyamide elastomer and rubber are useful as automotive parts, shoe parts, sports parts, belt parts and the like.
  • a rubber is disposed on the grounding portion side of the base portion, and a polyamide elastomer is disposed on the bonding surface side.
  • Patent Document 2 discloses a resin / rubber composite in which a resin member obtained by bringing a polyamide elastomer into contact with a vulcanized rubber member under heating and a vulcanized rubber member are directly bonded.
  • Patent Document 3 discloses a method for producing a composite material in which a composition comprising an elastomer having a block based on polyamide 6, an elastomer having a carboxylic acid group or a dicarboxylic anhydride group, and a crosslinking system is vulcanized in a mold. Is described. However, in these techniques, the adhesive strength (adhesive strength) between the polyamide elastomer and the rubber is not satisfactory.
  • An object of the present invention is to solve the above problems and provide a polyamide laminate having high interlayer adhesion between a polyamide elastomer and a crosslinked rubber, and a rubber composition used as a material for the crosslinked rubber.
  • the inventors of the present invention provide a polyamide laminate in which a crosslinked rubber obtained from a rubber composition containing silica and a plasticizer having a specific structure in a specific ratio and a polyether polyamide elastomer having a specific structure are stacked.
  • the inventors have found that the above problems can be achieved. That is, the present invention provides the following [1] and [2].
  • (C) A rubber composition comprising 0.5 to 10 parts by mass and a crosslinking agent (D) 0.1 to 3 parts by mass.
  • R 1 and R 2 represents an alkyl group having 1 to 10 carbon atoms, the remaining represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 3 represents an alkyl group having 1 to 4 carbon atoms.
  • N is an integer of 0 to 5, and when n is 2 or more, a plurality of R 3 may be the same or different.
  • R 6 represents a linking group containing a hydrocarbon chain.
  • the present invention it is possible to provide a polyamide laminate having high interlayer adhesion between a polyamide elastomer and a crosslinked rubber, and a rubber composition used as a material for the crosslinked rubber.
  • the rubber composition of the present invention is used as a material for the crosslinked rubber in a laminate of a polyether polyamide elastomer and a crosslinked rubber (hereinafter referred to as “polyamide laminate”), and contains the following rubber component (A), silica (B), a plasticizer (C), and a crosslinking agent (D) are contained in the ratio shown below, respectively.
  • the rubber composition of the present invention contains natural rubber and / or diene synthetic rubber as the rubber component (A).
  • the diene synthetic rubber is not particularly limited, and any known rubber can be used.
  • polymers of diene monomers such as butadiene rubber (BR), isoprene rubber, butyl rubber and chloroprene rubber; acrylonitrile-diene copolymer rubbers such as acrylonitrile butadiene rubber (NBR), nitrile chloroprene rubber and nitrile isoprene rubber; styrene Examples thereof include styrene-diene copolymer rubbers such as butadiene rubber (SBR), styrene chloroprene rubber, and styrene isoprene rubber, and ethylene propylene diene rubber (EPDM).
  • SBR butadiene rubber
  • EPDM ethylene propylene diene rubber
  • butadiene rubber, acrylonitrile butadiene rubber, styrene are used from the viewpoint of interlayer adhesive strength (hereinafter simply referred to as “adhesive strength”) in a laminate of a polyether polyamide elastomer and a crosslinked rubber obtained from a rubber composition.
  • Adhesive strength interlayer adhesive strength
  • butadiene rubber and isoprene rubber are preferred, butadiene rubber, acrylonitrile butadiene rubber and styrene butadiene rubber are more preferred, and butadiene rubber is even more preferred.
  • the rubber component (A) among natural rubber and the diene synthetic rubber, one kind may be used alone, or two or more kinds may be used in combination.
  • Polybutadiene rubber or a combined system of polybutadiene rubber and natural rubber is preferred.
  • the use ratio of the polybutadiene rubber and the natural rubber is preferably 80:20 to 20:80, more preferably 70:30 to 30:70 in terms of mass ratio.
  • the butadiene rubber preferably contains 90% or more of cis-1,4 bonds from the viewpoint of adhesive strength.
  • Silica (B) in the rubber composition of the present invention is used to increase the adhesive strength.
  • the silica include wet silica (hydrous silicic acid) and dry silica (anhydrous silicic acid), but wet silica is preferable from the viewpoint of adhesive strength.
  • the wet silica preferably has a nitrogen adsorption specific surface area (N 2 SA) of 140 to 280 m 2 / g, more preferably 170 to 250 m 2 / g, according to the BET method.
  • Suitable wet silica includes, for example, AQ, VN3, LP, NA manufactured by Tosoh Silica Co., Ltd., Ultrazil VN3 manufactured by Degussa (N 2 SA: 210 m 2 / g), and the like.
  • the compounding amount of silica (B) is selected in the range of 35 to 80 parts by mass with respect to 100 parts by mass of the rubber component (A). If the content is less than 35 parts by mass, sufficient adhesive strength cannot be obtained. On the other hand, if the content exceeds 80 parts by mass, the adhesive strength decreases. From the above viewpoint, the amount of silica is preferably in the range of 40 to 70 parts by mass. Carbon black can be used in combination with the silica.
  • R 1 and R 2 represents an alkyl group having 1 to 10 carbon atoms, the remaining represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 3 represents an alkyl group having 1 to 4 carbon atoms.
  • N is an integer of 0 to 5, and when n is 2 or more, a plurality of R 3 may be the same or different.
  • the alkyl group having 1 to 10 carbon atoms in R 1 and R 2 of the above formula (1) may be linear, branched or cyclic.
  • One of R 1 and R 2 is an alkyl group having 1 to 10 carbon atoms, and the other is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, Examples include various hexyl groups, various octyl groups, various decyl groups, cyclopentyl groups, cyclohexyl groups, and cyclohexylmethyl groups.
  • Examples of the alkyl group having 1 to 4 carbon atoms represented by R 3 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. It is done.
  • n is an integer of 0 to 5, and when n is 2 or more, a plurality of R 3 may be the same or different.
  • R 1 is an alkyl group having 1 to 10 carbon atoms
  • R 2 is a hydrogen atom
  • R 3 is a methyl group
  • n is 0 or 1 Amide derivatives are preferred.
  • arylsulfonic acid amide derivatives include benzenesulfonic acid alkylamides and toluenesulfonic acid alkylamides.
  • benzenesulfonic acid alkylamides include benzenesulfonic acid propylamide, benzenesulfonic acid butyramide, and benzenesulfonic acid 2-ethylhexylamide.
  • Toluenesulfonic acid alkylamides include N-ethyl-o-toluenesulfonic acid butyramide, N-ethyl-p-toluenesulfonic acid butyramide, N-ethyl-o-toluenesulfonic acid 2-ethylhexylamide, N-ethyl-p. -Toluenesulfonic acid 2-ethylhexylamide and the like.
  • R 4 represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms represented by R 4 may be linear, branched or cyclic.
  • Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl groups, and various pentyl groups.
  • Examples include hexyl group, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, various icosyl groups, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group and the like.
  • hydroxybenzoic acid alkyl ester derivative represented by the above formula (2) examples include methyl o- or p-hydroxybenzoate, butyl o- or p-hydroxybenzoate, o- or hexyl p-hydroxybenzoate.
  • N-octyl o- or p-hydroxybenzoate 2-ethylhexyl o- or p-hydroxybenzoate, decyl o- or p-hydroxybenzoate, dodecyl o- or p-hydroxybenzoate, o- or p- Examples include tetradecyl hydroxybenzoate, hexadecyl o- or p-hydroxybenzoate, octadecyl o- or p-hydroxybenzoate, and the like.
  • the plasticizer (C) may be used alone or in combination of two or more.
  • the plasticizer (C) preferably has a solubility parameter (SP value) represented by the following formula that is close to the SP value of the polyether polyamide elastomer described later.
  • the solubility parameter is represented by the square root of CED (cohesive energy density) ((MJ / m 3 ) 1/2 ] indicating intermolecular bonding force.
  • the SP value can be calculated from the Fedors equation described in pages 147 to 154 of “Polymer Engineering and Science” (Vol. 14, No. 2, 1974).
  • the SP value is preferably It is desirable to select those in the range of 19 to 25, more preferably in the range of 19 to 24.5, and still more preferably in the range of 19 to 24.
  • the compounding amount of the plasticizer (C) is 0.5 to 10 parts by mass, preferably 1 to 8 parts by mass, more preferably 1.5 to 7 parts by mass with respect to 100 parts by mass of the rubber component (A). More preferably, it is 1 to 6 parts by mass. If the blending amount of this plasticizer is less than 0.5 parts by mass, the effect of improving the adhesive strength is insufficient. On the other hand, if it exceeds 10 parts by mass, the adhesive strength decreases. In addition, if SP value is in the said range, you may use together plasticizers, softeners, etc. other than the said plasticizer as needed.
  • Crosslinking agent (D) As the crosslinking agent (D) in the rubber composition of the present invention, conventionally known compounds such as sulfur and organic peroxides can be used, and among these, organic peroxides are preferred.
  • organic peroxides that can be used as a crosslinking agent for natural rubber and diene-based synthetic rubber include t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, Dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, 1,3 -Bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,
  • t- butyl perbenzoate and the like.
  • dicumyl peroxide and 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane are preferable from the viewpoint of crosslinkability and adhesive strength.
  • These organic peroxides may be used alone or in combination of two or more.
  • the compounding amount of the crosslinking agent (D) is selected in the range of 0.1 to 3 parts by mass, preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the rubber component (A). If the blending amount of the crosslinking agent is less than 0.1 parts by mass, the crosslinking does not proceed sufficiently and the adhesive strength is insufficient, and if it exceeds 3 parts by mass, the crosslinked rubber becomes too hard.
  • silane coupling agent (E) In the rubber composition of this invention, in order to improve the dispersibility of the silica in a rubber composition and to improve adhesive strength, a silane coupling agent (E) can be contained if desired.
  • a silane coupling agent a sulfur-containing silane coupling agent or an amino group-containing silane coupling agent can be used.
  • the sulfur-containing silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-triethoxy).
  • Ethoxysilylethyl) tetrasulfide bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercapto Ethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthio Carbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl te
  • bis (3-triethoxysilylpropyl) tetrasulfide manufactured by Degussa Japan Co., Ltd., trade name “Si69”, average number of S 3.8] and bis (3-triethoxysilylpropyl) polysulfide mixture [Degussa Japan Co., Ltd., trade name “Si75”, average number of S 2.4] is preferable.
  • amino group-containing silane coupling agents include N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, and ⁇ -aminopropyl.
  • Triethoxysilane N-phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltris (2-methoxyethoxy) silane, N-methyl- ⁇ -aminopropyltrimethoxysilane, N -Vinylbenzyl- ⁇ -aminopropyltriethoxysilane and the like.
  • These silane coupling agents may be used singly or in combination of two or more.
  • the blending amount of the silane coupling agent (E) is preferably 1 to 10% by mass with respect to the silica (B). If this compounding amount is 1% by mass or more, the compounding effect of the silane coupling agent is exhibited. On the other hand, if it is 10 mass% or less, gelatinization of a rubber component can be suppressed. From the above viewpoint, the amount of the silane coupling agent (E) is more preferably 3 to 7% by mass.
  • the accelerator may further contain an anti-aging agent, polyethylene glycol, zinc white, stearic acid and the like.
  • the vulcanization accelerator include thiazoles such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide and N-cyclohexyl-2-benzothiazylsulfenamide, and guanidines such as diphenylguanidine.
  • the anti-aging agent examples include N-isopropyl-N′-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, 6-ethoxy-2, Examples include 2,4-trimethyl-1,2-dihydroquinoline, high-temperature condensate of diphenylamine and acetone.
  • the rubber composition of the present invention includes the rubber component (A), silica (B), plasticizer (C), cross-linking agent (D), and silane coupling agent (E) used as necessary and other various chemicals. Can be prepared by kneading using a kneading machine such as a Banbury mixer, roll, or internal mixer.
  • the rubber composition of the present invention thus obtained can be used as a material for the crosslinked rubber in a laminate of a polyether polyamide elastomer and a crosslinked rubber to give a polyamide laminate having high interlayer adhesion. it can.
  • the crosslinked rubber can be formed into a desired shape such as a sheet by a known method such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding, or the like, from a rubber composition as a raw material. Furthermore, you may perform a crosslinking process in a post process as needed.
  • the polyamide laminate of the present invention has a structure in which a polyether polyamide elastomer obtained by polymerizing the following various raw materials and a crosslinked rubber obtained from the above-described rubber composition of the present invention are laminated.
  • a polyether polyamide elastomer obtained by polymerizing the following various raw materials and a crosslinked rubber obtained from the above-described rubber composition of the present invention are laminated.
  • the polyether polyamide elastomer used in the polyamide laminate of the present invention comprises a polyamide-forming monomer [namely, aminocarboxylic acid compound (X1) and / or lactam compound (X2)], XYX type triblock polyetherdiamine compound (Y). (Y is polyoxybutylene) and those obtained by polymerizing dicarboxylic acid (Z) are preferred.
  • the polyether polyamide elastomer there is a ratio such that the terminal carboxylic acid or carboxy group contained in the polyamide-forming monomer, XYX type triblock polyether diamine, and dicarboxylic acid and the terminal amino group are approximately equimolar. preferable.
  • the XYX-type triblock polyether diamine and dicarboxylic acid are the amino group of the polyether diamine and the carboxy group of the dicarboxylic acid.
  • the ratio is preferably such that the groups are approximately equimolar.
  • aminocarboxylic acid compound (X1) and lactam compound (X2) aminocarboxylic acid compound (X1) and lactam compound (X2)
  • the aminocarboxylic acid compound (X1) used for the polyether polyamide elastomer is a compound represented by the following formula (3).
  • R 5 represents a linking group containing a hydrocarbon chain, and is preferably an aliphatic, alicyclic or aromatic hydrocarbon group having 2 to 20 carbon atoms or an alkylene group having 2 to 20 carbon atoms, More preferably, the hydrocarbon group having 3 to 18 carbon atoms or the alkylene group having 3 to 18 carbon atoms, more preferably the hydrocarbon group having 4 to 15 carbon atoms or the alkylene group having 4 to 15 carbon atoms, The hydrocarbon group having 10 to 15 carbon atoms or the alkylene group having 10 to 15 carbon atoms is particularly preferable.
  • the lactam compound (X2) used for the polyether polyamide elastomer is a compound represented by the following formula (4).
  • R 6 represents a linking group containing a hydrocarbon chain, and is preferably an aliphatic, alicyclic or aromatic hydrocarbon group having 3 to 20 carbon atoms or an alkylene group having 3 to 20 carbon atoms, More preferably, the hydrocarbon group having 3 to 18 carbon atoms or the alkylene group having 3 to 18 carbon atoms, more preferably the hydrocarbon group having 4 to 15 carbon atoms or the alkylene group having 4 to 15 carbon atoms, The hydrocarbon group having 10 to 15 carbon atoms or the alkylene group having 10 to 15 carbon atoms is particularly preferable.
  • aminocarboxylic acid compound (X1) and the lactam compound (X2) at least one aliphatic or alicyclic group selected from ⁇ -aminocarboxylic acid, lactam, or a compound synthesized from diamine and dicarboxylic acid and salts thereof And / or polyamide-forming monomers containing aromatics are used.
  • Examples of the diamine synthesized from diamine and dicarboxylic acid and salts thereof include at least one diamine compound selected from aliphatic diamine, alicyclic diamine and aromatic diamine, or derivatives thereof.
  • Examples of the dicarboxylic acid include at least one dicarboxylic acid compound selected from aliphatic dicarboxylic acid, alicyclic dicarboxylic acid and aromatic dicarboxylic acid, or derivatives thereof.
  • a polyether polyamide elastomer having a low specific gravity, large tensile elongation, excellent impact resistance, and good melt moldability can be obtained. it can.
  • the molar ratio of diamine to dicarboxylic acid is preferably in the range of 0.9 to 1.1, more preferably in the range of 0.93 to 1.07, and in the range of 0.95 to 1.05. Is more preferable, and the range of 0.97 to 1.03 is particularly preferable. If this molar ratio is within the above range, high molecular weight can be easily achieved.
  • diamine examples include ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2, Examples thereof include diamine compounds such as aliphatic diamines having 2 to 20 carbon atoms such as 2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, and 3-methylpentamethylenediamine.
  • dicarboxylic acid examples include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and aliphatic dicarboxylic acid having 2 to 20 carbon atoms such as dodecanedioic acid. Can be mentioned.
  • lactams include aliphatic lactams having 5 to 20 carbon atoms such as ⁇ -caprolactam, ⁇ -enantolactam, ⁇ -undecalactam, ⁇ -dodecalactam, and 2-pyrrolidone.
  • ⁇ -aminocarboxylic acid examples include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like. ⁇ 20 aliphatic ⁇ -aminocarboxylic acids and the like.
  • XYX type triblock polyether diamine (Y) XYX type triblock polyether diamine (Y) used for polyether polyamide elastomer is a compound represented by the following formula (5), and propylene oxide is added to both ends of poly (oxytetramethylene) glycol and the like.
  • Polyether diamine produced by reacting ammonia or the like with the end of the polypropylene glycol can be used after being converted into polypropylene glycol.
  • XYX-type triblock polyether diamine examples include XTJ-533 manufactured by HUNTSMAN (USA) (wherein x is about 12, y is about 11, and z is about 11), XTJ-536 ( In equation (5), x is approximately 8.5, y is approximately 17, z is approximately 7.5), and XTJ-542 (in equation (5), x is approximately 3, y is approximately 9, z is approximately 2) etc. can be used.
  • XYX type triblock polyether diamine (Y)
  • XYX-1 in formula (5), x is about 3, y is about 14, z is about 2
  • XYX-2 in formula (5), x is approximately 5, y is approximately 14, z is approximately 4
  • XYX-3 in formula (5), x is approximately 3, y is approximately 19, z is approximately 2), and the like can also be used.
  • x and z are 1 to 20, preferably 1 to 18, more preferably 1 to 16, more preferably 1 to 14, particularly preferably 1 to 12
  • y is 4 to 50, preferably 5 to 45, more preferably 6 to 40, more preferably 7 to 35, and particularly preferably 8 to 30.
  • the combination of x, y, and z includes x in the range of 2 to 6, y in the range of 6 to 12, z in the range of 1 to 5, or x in the range of 2 to 10, and y in the range of 13 to Preferred examples include a range of 28 and a combination of z in the range of 1 to 9.
  • the dicarboxylic acid compound (Z) used for the polyether polyamide elastomer is a compound represented by the following formula (6).
  • R 7 represents a linking group containing a hydrocarbon chain, and is preferably an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 20 carbon atoms or an alkylene group having 1 to 20 carbon atoms. And more preferably the hydrocarbon group having 1 to 15 carbon atoms or the alkylene group having 1 to 15 carbon atoms, more preferably the hydrocarbon group having 2 to 12 carbon atoms or the alkylene group having 2 to 12 carbon atoms. Particularly preferably, it represents the above hydrocarbon group having 4 to 10 carbon atoms or an alkylene group having 4 to 10 carbon atoms.
  • M represents 0 or 1.
  • dicarboxylic acid compound (Z) at least one dicarboxylic acid selected from aliphatic, alicyclic and aromatic dicarboxylic acids or derivatives thereof can be used.
  • dicarboxylic acid examples include linear aliphatic dicarboxylic acids having 2 to 25 carbon atoms such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, Or aliphatic dicarboxylic acids such as dimerized aliphatic dicarboxylic acids having 14 to 48 carbon atoms (dimer acid) obtained by dimerization of unsaturated fatty acids obtained by fractionation of triglycerides and hydrogenated products thereof (hydrogenated dimer acid) And alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid.
  • dimer acid and hydrogenated dimer acid trade names “Pripol 1004”, “Plipol 1006”, “Plipol 1009”, “Plipol
  • the ratio of the polyamide-forming monomer to the total components of the polyether polyamide elastomer is preferably 10 to 95% by mass, more preferably 15 to 90% by mass, more preferably 15 to 85% by mass, and particularly preferably 15 to 80% by mass. %, Most preferably 15 to 70 mass. If the ratio of the polyamide-forming monomer to all the components of the polyether polyamide elastomer is 10% by mass or more, the crystallinity of the polyamide component can be improved, and mechanical properties such as strength and elastic modulus can be improved. it can. If it is 95 mass% or less, the function and performance as elastomers, such as rubber elasticity and a softness
  • the ratio of the total amount of the (Y) compound and the (Z) compound with respect to all the components of the polyether polyamide elastomer is preferably 5 to 90% by mass, more preferably 10 to 85% by mass, more preferably 15 to 85%. % By weight, particularly preferably 20 to 85% by weight, most preferably 30 to 85% by weight.
  • the hardness (Shore D) of the polyether polyamide elastomer is preferably in the range of 15 to 70, more preferably in the range of 18 to 70, still more preferably in the range of 20 to 70, and particularly preferably in the range of 25 to 70. is there.
  • the hardness (Shore D) can be measured according to ASTM D2240.
  • the flexural modulus of the polyether polyamide elastomer is preferably 20 to 450 MPa, more preferably 20 to 400 MPa, still more preferably 20 to 350 MPa, and particularly preferably 20 to 300 MPa.
  • the elastic modulus is within the above range, an elastomer having particularly excellent toughness and rubber elasticity can be obtained.
  • the flexural modulus can be measured according to ASTM D790.
  • the flexural strength of the polyether polyamide elastomer is preferably 0.8 to 15 MPa, more preferably 1 to 13 MPa, still more preferably 1.1 to 10 MPa, and particularly preferably 1.2 to 9 MPa.
  • the bending strength of the polyether polyamide elastomer is within the above range, an elastomer having an excellent balance between toughness such as bending strength and rubber elasticity can be obtained.
  • the bending strength can be measured according to ASTM D790.
  • the tensile yield strength of the polyether polyamide elastomer is preferably in the range of 3 to 25 MPa, more preferably in the range of 3 to 22 MPa, still more preferably in the range of 3 to 20 MPa, and particularly preferably in the range of 3 to 18 MPa.
  • the tensile yield point strength is in the above range, an elastomer having particularly excellent toughness and rubber elasticity can be obtained.
  • the tensile yield point strength can be measured according to ASTM D638.
  • the tensile elongation at break of the polyether polyamide elastomer is preferably 300% or more, more preferably 600% or more. If it is less than this range, the performance as an elastomer such as toughness and rubber elasticity becomes difficult to be exhibited, which may not be preferable.
  • the tensile elongation at break can be measured according to ASTM D638.
  • the polyether polyamide elastomer does not break in the measurement of impact strength with an Izod notch at 23 ° C. (abbreviated as NB) because it is particularly excellent in impact resistance.
  • the impact strength with an Izod notch can be measured according to ASTM D256.
  • the deflection temperature under load of the polyether polyamide elastomer is preferably 50 ° C. or higher. Within the above range, the material is less likely to be deformed during use, which is preferable. In the present invention, the deflection temperature under load can be measured according to ASTM D648.
  • the relative viscosity ( ⁇ r) of the polyether polyamide elastomer is preferably in the range of 1.2 to 3.5 (0.5 mass / volume% metacresol solution, 25 ° C.).
  • Method for producing polyether polyamide elastomer As an example of a method for producing a polyether polyamide elastomer, three components of a polyamide-forming monomer, an XYX type triblock polyether diamine and a dicarboxylic acid are melt-polymerized under pressure and / or normal pressure, and further if necessary. A method comprising a step of melt polymerization under reduced pressure can be used, and further, three components of polyamide-forming monomer, XYX type triblock polyetherdiamine and dicarboxylic acid are simultaneously melt polymerized under pressure and / or normal pressure, If necessary, a method comprising a step of melt polymerization under reduced pressure can be used. It is also possible to use a method in which a polyamide-forming monomer and a dicarboxylic acid are first polymerized and then an XYX type triblock polyether diamine is polymerized.
  • the polyamide forming monomer, the XYX type triblock polyether diamine and the dicarboxylic acid are preferably charged with respect to all components. Is in the range of 10 to 95% by mass, more preferably in the range of 15 to 90% by mass, and the XYX type triblock polyether diamine is preferably in the range of 3 to 88% by mass, more preferably in the range of 8 to 79% by mass.
  • the XYX type triblock polyether diamine and the dicarboxylic acid are preferably charged so that the amino group of the XYX type triblock polyether diamine and the carboxy group of the dicarboxylic acid are approximately equimolar.
  • the polymerization temperature is preferably 150 to 300 ° C, more preferably 160 to 280 ° C, and further preferably 180 to 250 ° C. If the polymerization temperature is 150 ° C. or higher, the polymerization reaction proceeds favorably, and if it is 300 ° C. or lower, thermal decomposition is suppressed and a polymer having good physical properties can be obtained.
  • the polyether polyamide elastomer can be produced by a method comprising steps of normal pressure melt polymerization or normal pressure melt polymerization followed by low pressure melt polymerization when ⁇ -aminocarboxylic acid is used as the polyamide-forming monomer.
  • Polymerization time is usually 0.5 to 30 hours. If the polymerization time is 0.5 hours or more, the molecular weight can be increased, and if it is 30 hours or less, coloring due to thermal decomposition and the like can be suppressed, and a polyether polyamide elastomer having desired physical properties can be obtained. .
  • the production of the polyether polyamide elastomer can be carried out batchwise or continuously, and a batch reactor, a single- or multi-tank continuous reactor, a tubular continuous reactor, etc. can be used alone or in combination. Can be used.
  • monoamines and diamines such as laurylamine, stearylamine, hexamethylenediamine, and metaxylylenediamine, acetic acid, Monocarboxylic acids such as benzoic acid, stearic acid, adipic acid, sebacic acid and dodecanedioic acid, or dicarboxylic acids can be added.
  • the addition amount of the above-mentioned monoamine, diamine, monocarboxylic acid, dicarboxylic acid and the like is preferably in a range in which the properties of the obtained polyether polyamide elastomer are not inhibited, and the relative viscosity of the finally obtained elastomer is 1.2. It is preferable to add appropriately so as to be in the range of ⁇ 3.5 (0.5 mass / volume% metacresol solution, 25 ° C.).
  • phosphoric acid In the production of the polyether polyamide elastomer, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc. are used as a catalyst as necessary, and phosphorous acid, hypophosphorous acid, and Inorganic phosphorus compounds such as these alkali metal salts and alkaline earth metal salts can be added.
  • the addition amount is usually 50 to 3000 ppm with respect to the charged raw material.
  • the polyether polyamide elastomer thus obtained has a heat resistance agent, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a lubricant, a slip agent, a crystal nucleating agent, and an adhesive as long as its properties are not hindered.
  • a property-imparting agent, a sealing property improving agent, an antifogging agent, a release agent, a plasticizer, a pigment, a dye, a fragrance, a flame retardant, a reinforcing material, and the like can be added.
  • Polyether polyamide elastomer has low water absorption, excellent melt moldability, excellent moldability, excellent toughness, excellent hydrolysis resistance, excellent bending fatigue resistance, excellent anti-elasticity, and low specific gravity Excellent in low temperature and flexibility, excellent in low temperature impact resistance, excellent in stretch recovery, excellent in sound deadening properties, excellent in rubbery properties and transparency.
  • the polyether polyamide elastomer in the present invention is a commercially available product such as “UBESTA XPA 9040X1, 9040F1, 9048X1, 9048F1, 9055X1, 9055F1, 9063X1, 9063F1, 9068X1, 9068F1, 9040X2, and 9048X2.
  • 9040F2, 9048F2 "(manufactured by Ube Industries, Ltd.) and the like can be used.
  • the polyamide laminate of the present invention is a laminate in which the polyether polyamide elastomer and a crosslinked rubber obtained from the rubber composition are laminated.
  • the polyamide laminate of the present invention has one or more layers composed of a polyether polyamide elastomer and a crosslinked rubber layer.
  • the thickness in particular of each layer is not restrict
  • the number of layers of a laminated body is two or more layers, the whole number of layers in a laminated body is not restrict
  • polyamide laminate of the present invention can be prepared from any base material such as thermoplastic resin, paper, metal-based material, unstretched, uniaxially or biaxially stretched plastic film or sheet, woven fabric, non-woven fabric, metallic cotton, woody material. Etc. can also be laminated.
  • base material such as thermoplastic resin, paper, metal-based material, unstretched, uniaxially or biaxially stretched plastic film or sheet, woven fabric, non-woven fabric, metallic cotton, woody material. Etc. can also be laminated.
  • the polyamide laminate of the present invention is (1) a method for simultaneously molding each layer, (2) a method for molding and laminating each layer, (3) a method for laminating while further forming a layer on the layer (tandem method), (4) A method in which a rubber is inserted into a mold and a polyether polyamide elastomer is injection molded and laminated. (5) A polyether polyamide elastomer molded by an arbitrary method is inserted into a mold in a rubber crosslinking step. Then, it can be obtained by a method of laminating and the like, or a method of combining these.
  • the molding temperature is preferably 160 to 300 ° C., more preferably 190 to 270 ° C.
  • the polyether polyamide elastomer when the polyether polyamide elastomer is injection molded.
  • the polyether polyamide elastomer When the polyether polyamide elastomer is inserted to crosslink the rubber, it is desirable to perform the crosslinking at a temperature exceeding the melting point of the polyether polyamide elastomer, and is generally performed at 160 to 170 ° C. for about 5 to 15 minutes. If the temperature is low or the time is short, the rubber may not be cross-linked or the heat welding strength may not be sufficient, and if the temperature is high or the time is too long, the rubber may deteriorate. This is not preferable.
  • Examples of the laminated structure of the polyether polyamide elastomer layer (X layer) and the crosslinked rubber layer (Y layer) in the polyamide laminate of the present invention include X layer / Y layer, X layer / Y layer / X layer, Y layer.
  • X layer / Y layer X layer / Y layer, X layer / Y layer / base material layer, base material layer / X layer / Y layer, X layer / Y layer / X layer / base material layer, Y layer / X layer / Y layer / group Material layer, Y layer / X layer / adhesive layer / base material layer, X layer / Y layer / adhesive layer / base material layer, base material layer / adhesive layer / X layer / Y layer / X layer / adhesive layer / base material Layer, base material layer / adhesive layer / Y layer / X layer / Y layer / adhesive layer / base material layer, and the like.
  • the base layer is obtained from inorganic fibers made from natural / synthetic fibers, glass / ceramics, etc .; films, sheets, membranes and molded articles obtained from other polymer materials, excluding the polymers of the X layer and Y layer Woven fabric, knitted fabric, braided fabric, non-woven fabric, etc .; glass, metal, ceramics, coating film, paper, etc .; leather etc. can be used.
  • adhesive layer known adhesive components, adhesive sheets and films, and the like can be used, and those that do not impair the characteristics of the present invention are preferably used.
  • the peel strength between the X layer and the Y layer of the polyamide laminate of the present invention is preferably 5 N / mm or more, more preferably 8 N / mm or more, and even more preferably 10 N / mm or more.
  • the peel strength can be measured by the method described in the examples.
  • the polyamide laminate of the present invention uses a rubber composition having a high adhesive force to the polyether polyamide elastomer as a material for the crosslinked rubber, it has a strong adhesive strength between the polyether polyamide elastomer and the crosslinked rubber. It is advantageous for tire parts, various vibration absorbing members, door lock members, radiator mounts and other automotive parts, sports shoes, work shoes, shoe parts such as shoe soles, and various industrial parts such as anti-vibration rubber. Can be used.
  • Production Example 1 (Production of polyether polyamide elastomer (PAE)) UBE Industries, Ltd. 12-aminododecanoic acid (ADA) 11.231 kg, ABA in a 70 liter reaction vessel equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure regulator and polymer outlet Type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN, amine value: 1.94 meq / g) 7.680 kg, adipic acid (AA) 1.089 kg, sodium hypophosphite monohydrate 6 g and heat-resistant agent (Tomitox 917 manufactured by Yoshitomi Pharmaceutical) 60 g was charged.
  • PAE polyether polyamide elastomer
  • the temperature inside the container was raised to 230 ° C. over 3.5 hours while adjusting the pressure in the container to 0.05 MPa while supplying nitrogen gas at a flow rate of 186 liters / hour.
  • Polymerization was carried out at 230 ° C. for 4 hours while adjusting the pressure at 0.05 MPa to obtain a polymer.
  • stirring was stopped, and the colorless and transparent polymer in a molten state was drawn out from the polymer outlet in a string shape, cooled with water, and pelletized to obtain about 15 kg of pellets.
  • Examples 1 to 6 and Comparative Examples 1 to 3 (1) Production of Polyether Polyamide Elastomer (PAE) Sheet About 25 g of the PAE pellets obtained in Production Example 1 were set in a spacer (150 mm ⁇ 150 mm, thickness 1.5 mm). Next, set the spacer, metal plate, and Teflon (registered trademark, hereinafter the same) sheet so as to have a layer structure of metal plate / Teflon sheet / spacer / Teflon sheet / metal plate, and set it in a press molding machine. The sample was preheated at 190 ° C. for 1 minute without pressure, then pressed and pressed at 190 ° C. for 1 minute at 1 MPa, taken out, cooled and molded for 2 minutes.
  • PAE Polyether Polyamide Elastomer
  • Example 1 instead of the PAE obtained in Production Example 1, nylon 12 (PA12) [product name “3030U” manufactured by Ube Industries, Ltd.] was used, and the nylon 12 sheet was heated at 210 ° C. A laminate sheet was produced in the same manner as in Example 1 except that it was produced, and the T peel strength was measured. The results are shown in Table 1.
  • BR Butadiene rubber, manufactured by Ube Industries, Ltd., trade name “UBEPOL-BR130B” (cis 1,4-bond content 96%)
  • Natural rubber Standard Malaysian natural rubber
  • NBR Acrylonitrile butadiene rubber, manufactured by JSR Corporation, trade name “N230SV”
  • Silica wet silica, manufactured by Tosoh Silica Co., Ltd., trade name “Nipsil AQ”
  • Carbon black Asahi Carbon Co., Ltd., trade name “Asahi # 70”
  • HDPE 2-ethylhexyl p-hydroxybenzoate (SP value 19.5 (MJ / m 3 ) 1/2 ), manufactured by Kao Corporation, trade name “EXCEPARL HD-PB”
  • BBSA Benzenesulfonic acid butyramide (SP value 23.5 (MJ / m 3 ) 1/2 ), manufactured by Daihachi Chemical Industry Co., Ltd., trade name “Val-BS” (8) Processing
  • the polyamide laminate sheets of Examples 1 to 6 have a much higher T peel strength than Comparative Examples 1 to 4. Further, it can be seen from Comparative Example 2 that even if carbon black is used instead of silica, the effect of improving the T peel strength is not observed.
  • the rubber composition of the present invention is used as a material for the rubber in a laminate of a polyether polyamide elastomer and a crosslinked rubber, and can give the polyamide laminate having a high interlayer adhesion.
  • the polyamide laminate of the present invention has strong adhesive strength between the polyether polyamide elastomer and the crosslinked rubber. Therefore, the tire member, various vibration absorbing members, door lock members, radiator mounts and other automobile parts, sports shoes, work Shoes, shoe parts such as shoe soles, various industrial parts such as anti-vibration rubber, and parts that are deformed due to insufficient strength with rubber alone, such as non-slip rubber, rubber tubes, sporting goods, electricity It can be suitably used for applications such as product grips.

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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)
  • Laminated Bodies (AREA)
  • Polyamides (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L’invention concerne une composition de caoutchouc, utilisée comme matériau pour un caoutchouc réticulé pour un stratifié d’un élastomère polyéther-polyamide et du caoutchouc. La composition de caoutchouc comprend 35-80 parties en masse de silice (B), 0,5-10 parties en masse d’un plastifiant ayant une certaine structure (C), et 0,1-3 parties en masse d’un agent de réticulation (D) par rapport à 100 parties en masse d’un caoutchouc naturel et/ou d’un caoutchouc synthétique de la série diénique (A). Le stratifié de polyamide est formé par stratification d’un élastomère polyéther-polyamide, obtenu par polymérisation d’un certain matériau, et d’un caoutchouc réticulé obtenu à partir de la composition de caoutchouc. L’invention concerne également le stratifié de polyamide, ayant une force adhésive intercouche élevée entre l’élastomère de polyamide et le caoutchouc réticulé, et le matériau pour le caoutchouc réticulé.
PCT/JP2009/068030 2008-10-21 2009-10-19 Composition de caoutchouc et stratifié de polyamide WO2010047315A1 (fr)

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JP2009291962A (ja) * 2008-06-02 2009-12-17 Ube Ind Ltd 多層構造体
JP2013006387A (ja) * 2011-06-27 2013-01-10 Yokohama Rubber Co Ltd:The ポリアミド系樹脂フィルムとゴムの積層体およびタイヤ
WO2013129293A1 (fr) * 2012-02-29 2013-09-06 Nok株式会社 Corps composite de résine stratifiée de caoutchouc
WO2014027649A1 (fr) * 2012-08-14 2014-02-20 三菱瓦斯化学株式会社 Composition de résine de polyéther polyamide
WO2014027650A1 (fr) * 2012-08-14 2014-02-20 三菱瓦斯化学株式会社 Composition de polyéther polyamide
WO2014027651A1 (fr) * 2012-08-14 2014-02-20 三菱瓦斯化学株式会社 Composition de polyéther polyamide
JP2014037466A (ja) * 2012-08-14 2014-02-27 Mitsubishi Gas Chemical Co Inc ポリエーテルポリアミド樹脂組成物
JP2014037465A (ja) * 2012-08-14 2014-02-27 Mitsubishi Gas Chemical Co Inc ポリエーテルポリアミド組成物
JP2014037467A (ja) * 2012-08-14 2014-02-27 Mitsubishi Gas Chemical Co Inc ポリエーテルポリアミド樹脂組成物
JP2014037464A (ja) * 2012-08-14 2014-02-27 Mitsubishi Gas Chemical Co Inc ポリエーテルポリアミド組成物
JP2014037463A (ja) * 2012-08-14 2014-02-27 Mitsubishi Gas Chemical Co Inc ポリエーテルポリアミド組成物
JP2014037462A (ja) * 2012-08-14 2014-02-27 Mitsubishi Gas Chemical Co Inc ポリエーテルポリアミド組成物
JP2015145129A (ja) * 2015-03-30 2015-08-13 横浜ゴム株式会社 ポリアミド系樹脂フィルムとゴムの積層体およびタイヤ
WO2016052705A1 (fr) * 2014-10-01 2016-04-07 株式会社ブリヂストン Structure de pneu et pneu
WO2016067842A1 (fr) * 2014-10-27 2016-05-06 株式会社ブリヂストン Pneu
JPWO2019208798A1 (ja) * 2018-04-26 2021-05-13 株式会社ブリヂストン 樹脂ゴム複合体、タイヤ、及び樹脂ゴム複合体の製造方法
US20220033624A1 (en) * 2018-12-20 2022-02-03 Total Marketing Services Rubber composition comprising esters from renewable sources as plasticizers

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JP2009291962A (ja) * 2008-06-02 2009-12-17 Ube Ind Ltd 多層構造体
JP2013006387A (ja) * 2011-06-27 2013-01-10 Yokohama Rubber Co Ltd:The ポリアミド系樹脂フィルムとゴムの積層体およびタイヤ
WO2013129293A1 (fr) * 2012-02-29 2013-09-06 Nok株式会社 Corps composite de résine stratifiée de caoutchouc
US9586383B2 (en) 2012-02-29 2017-03-07 Nok Corporation Rubber laminated resin composite
CN104114364A (zh) * 2012-02-29 2014-10-22 Nok株式会社 橡胶层叠树脂复合体
JP2014037466A (ja) * 2012-08-14 2014-02-27 Mitsubishi Gas Chemical Co Inc ポリエーテルポリアミド樹脂組成物
US9512314B2 (en) 2012-08-14 2016-12-06 Mitsubishi Gas Chemical Company, Inc. Polyether polyamide composition
JP2014037465A (ja) * 2012-08-14 2014-02-27 Mitsubishi Gas Chemical Co Inc ポリエーテルポリアミド組成物
JP2014037467A (ja) * 2012-08-14 2014-02-27 Mitsubishi Gas Chemical Co Inc ポリエーテルポリアミド樹脂組成物
JP2014037464A (ja) * 2012-08-14 2014-02-27 Mitsubishi Gas Chemical Co Inc ポリエーテルポリアミド組成物
JP2014037463A (ja) * 2012-08-14 2014-02-27 Mitsubishi Gas Chemical Co Inc ポリエーテルポリアミド組成物
JP2014037462A (ja) * 2012-08-14 2014-02-27 Mitsubishi Gas Chemical Co Inc ポリエーテルポリアミド組成物
WO2014027650A1 (fr) * 2012-08-14 2014-02-20 三菱瓦斯化学株式会社 Composition de polyéther polyamide
WO2014027649A1 (fr) * 2012-08-14 2014-02-20 三菱瓦斯化学株式会社 Composition de résine de polyéther polyamide
WO2014027651A1 (fr) * 2012-08-14 2014-02-20 三菱瓦斯化学株式会社 Composition de polyéther polyamide
JP5989279B1 (ja) * 2014-10-01 2016-09-07 株式会社ブリヂストン タイヤ骨格体およびタイヤ
WO2016052705A1 (fr) * 2014-10-01 2016-04-07 株式会社ブリヂストン Structure de pneu et pneu
WO2016067842A1 (fr) * 2014-10-27 2016-05-06 株式会社ブリヂストン Pneu
JP2016084424A (ja) * 2014-10-27 2016-05-19 株式会社ブリヂストン タイヤ
US10301450B2 (en) 2014-10-27 2019-05-28 Bridgestone Corporation Tire
JP2015145129A (ja) * 2015-03-30 2015-08-13 横浜ゴム株式会社 ポリアミド系樹脂フィルムとゴムの積層体およびタイヤ
JPWO2019208798A1 (ja) * 2018-04-26 2021-05-13 株式会社ブリヂストン 樹脂ゴム複合体、タイヤ、及び樹脂ゴム複合体の製造方法
JP7312411B2 (ja) 2018-04-26 2023-07-21 株式会社ブリヂストン 樹脂ゴム複合体、タイヤ、及び樹脂ゴム複合体の製造方法
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US11945952B2 (en) * 2018-12-20 2024-04-02 Total Marketing Services Rubber composition comprising esters from renewable sources as plasticizers

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