WO2011027703A1 - Élastomère polyéther-polyamide et stratifié de polyamide - Google Patents

Élastomère polyéther-polyamide et stratifié de polyamide Download PDF

Info

Publication number
WO2011027703A1
WO2011027703A1 PCT/JP2010/064436 JP2010064436W WO2011027703A1 WO 2011027703 A1 WO2011027703 A1 WO 2011027703A1 JP 2010064436 W JP2010064436 W JP 2010064436W WO 2011027703 A1 WO2011027703 A1 WO 2011027703A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyether
polyamide elastomer
mass
compound
polyamide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2010/064436
Other languages
English (en)
Japanese (ja)
Inventor
利雄 森山
孝治 中村
佳史 赤川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ube Corp
Original Assignee
Ube Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ube Industries Ltd filed Critical Ube Industries Ltd
Priority to JP2011529879A priority Critical patent/JPWO2011027703A1/ja
Publication of WO2011027703A1 publication Critical patent/WO2011027703A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • 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

Definitions

  • the present invention relates to a polyether polyamide elastomer and a polyamide laminate comprising a polyether polyamide elastomer and a crosslinked rubber and capable of giving a polyamide laminate having high adhesive strength.
  • 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.
  • the present invention solves the above problems and provides a polyether polyamide elastomer that can provide a polyamide laminate having a high adhesive strength, and a polyamide laminate having a high adhesive strength, comprising a polyether polyamide elastomer and a crosslinked rubber. Objective.
  • the present inventors have found that the above-described problem can be achieved by laminating a polyether polyamide elastomer having a specific structure and a crosslinked rubber. That is, the present invention provides the following [1] and [2].
  • Polyamide elastomer Polyamide elastomer.
  • a polyamide laminate comprising 0.01 to 7 parts by mass of a silane coupling agent with respect to 100 parts by mass of the polyether polyamide elastomer.
  • H 2 N—R 1 —COOH (1) [However, R 1 represents a linking group containing a hydrocarbon chain. ]
  • R 2 represents a linking group containing a hydrocarbon chain.
  • a polyether polyamide elastomer that can be provided with a polyamide laminate having a high adhesive strength, and a polyamide laminate having a high adhesive strength, each comprising a polyether polyamide elastomer and a crosslinked rubber.
  • the polyether polyamide elastomer of the present invention is a polyether polyamide elastomer used in a laminate with a crosslinked rubber, and contains 0.01 to 7 parts by mass of a silane coupling agent with respect to 100 parts by mass of the polyether polyamide elastomer. It is characterized by.
  • the polyether polyamide elastomer of the present invention comprises an aminocarboxylic acid compound (X1) represented by the following formula (1) and / or a lactam compound (X2) represented by the following formula (2), and a triamide represented by the following formula (3).
  • the block polyether diamine compound (Y) and the dicarboxylic acid compound (Z) represented by the following formula (4) are preferably obtained by polymerization.
  • R 1 represents a linking group containing a hydrocarbon chain.
  • R 2 represents a linking group containing a hydrocarbon chain.
  • the polyamide-forming monomer [ie, aminocarboxylic acid compound (X1) and / or lactam compound (X2)], triblock polyetherdiamine compound (Y), and dicarboxylic acid compound (Z)
  • a ratio such that the terminal carboxylic acid or carboxy group contained and the terminal amino group are approximately equimolar is preferred.
  • the triblock polyether diamine compound (Y) and the dicarboxylic acid compound (Z) are amino acids of the polyether diamine.
  • the ratio is preferably such that the group and the carboxy group of the dicarboxylic acid are approximately equimolar.
  • aminocarboxylic acid compound (X1) and lactam compound (X2) The aminocarboxylic acid compound (X1) used for the production of the polyether polyamide elastomer is a compound represented by the following formula (1).
  • R 1 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.
  • R 1 is more preferably the hydrocarbon group having 3 to 18 carbon atoms or the alkylene group having 3 to 18 carbon atoms, and more preferably the hydrocarbon group having 4 to 15 carbon atoms or the alkylene group having 4 to 15 carbon atoms. And particularly preferably the hydrocarbon group having 10 to 15 carbon atoms or the alkylene group having 10 to 15 carbon atoms.
  • the lactam compound (X2) used for the production of the polyether polyamide elastomer is a compound represented by the following formula (2).
  • R 2 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.
  • R 2 is more preferably the hydrocarbon group having 3 to 18 carbon atoms or the alkylene group having 3 to 18 carbon atoms, and further 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 preferably the hydrocarbon group having 10 to 15 carbon atoms or the alkylene group having 10 to 15 carbon atoms.
  • 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.
  • diamines synthesized from diamines and dicarboxylic acids and salts thereof include at least one diamine compound selected from aliphatic diamines, alicyclic diamines and aromatic diamines, or derivatives thereof.
  • dicarboxylic acid include at least one dicarboxylic acid compound selected from aliphatic dicarboxylic acids, alicyclic dicarboxylic acids and aromatic dicarboxylic acids, or derivatives thereof.
  • 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 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.
  • lactam examples include aliphatic lactams having 5 to 20 carbon atoms such as ⁇ -caprolactam, ⁇ -enantolactam, ⁇ -undecalactam, ⁇ -dodecalactam, 2-pyrrolidone, and the like.
  • ⁇ -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.
  • Triblock polyether diamine compound (Y) The triblock polyether diamine compound (Y) used for the production of the polyether polyamide elastomer is a compound represented by the following formula (3).
  • the triblock polyether diamine compound (Y) is obtained by adding propylene oxide to both ends of poly (oxytetramethylene) glycol or the like to form polypropylene glycol, and then reacting ammonia or the like with the end of the polypropylene glycol.
  • XYX type triblock polyether diamine compound etc. which are manufactured can be used.
  • XYX-type triblock polyether diamine compound (Y) examples include XTJ-533 (in the formula (5), x is about 12, y is about 11, and z is about 11) manufactured by HUNTSMAN USA, XTJ- 536 (in formula (5), x is about 8.5, y is about 17, z is about 7.5), and XTJ-542 (in formula (5), x is about 3, y is about 9, z Is about 2).
  • XYX type triblock polyether diamine compound (Y) XYX-1 (in the formula (5), x is about 3, y is about 14, z is about 2)
  • XYX-2 in the formula (5) , X is about 5, y is about 14, z is about 4
  • XYX-3 in formula (5), x is about 3, y is about 19, z is about 2), and the like can also be used.
  • x and z are preferably 1 to 20, more preferably 1 to 18, more preferably 1 to 16, still more preferably 1 to 14, and particularly preferably 1.
  • y is preferably 4 to 50, more preferably 5 to 45, more preferably 6 to 40, still more preferably 7 to 35, and particularly preferably 8 to 30.
  • x is in the range of 2 to 6
  • y is in the range of 6 to 12
  • z is in the range of 1 to 5, or x is in the range of 2 to 10
  • y is 13
  • Preferred examples include combinations in the range of ⁇ 28 and z in the range of 1-9.
  • the resulting elastomer may be inferior in transparency, which is not preferable, and when y is smaller than the above range. Is not preferable because rubber elasticity may be lowered. Further, when x and z are larger than the above range, or when y is larger than the above range, the compatibility with the polyamide component becomes low and it is difficult to obtain a tough elastomer, which is not preferable.
  • the dicarboxylic acid compound (Z) used for the production of the polyether polyamide elastomer is a compound represented by the following formula (4).
  • R 3 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. .
  • R 3 is more preferably the hydrocarbon group having 1 to 15 carbon atoms or the alkylene group having 1 to 15 carbon atoms, and more preferably the hydrocarbon group having 2 to 12 carbon atoms or the alkylene group having 2 to 12 carbon atoms. And particularly preferably the hydrocarbon group having 4 to 10 carbon atoms or the alkylene group having 4 to 10 carbon atoms.
  • M represents 0 or 1.
  • the dicarboxylic acid compound (Z) at least one dicarboxylic acid selected from aliphatic, alicyclic and aromatic dicarboxylic acids or derivatives thereof can be used.
  • the dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, etc., linear aliphatic dicarboxylic acid having 2 to 25 carbon atoms, Alternatively, aliphatic dicarboxylic acids such as dimerized aliphatic dicarboxylic acids having 14 to 48 carbon atoms (dimer acid) obtained by dimerizing unsaturated fatty acids obtained by fractional distillation 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
  • the ratio of the polyamide-forming monomer [aminocarboxylic acid compound (X1) and / or lactam compound (X2)] 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, it is 15 to 85% by mass, particularly preferably 15 to 80% by mass, and most preferably 15 to 70% by 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.
  • the function and performance as elastomers such as rubber elasticity and a softness
  • the ratio of the total amount of the triblock polyether diamine compound (Y) and the dicarboxylic acid compound (Z) 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, it is 15 to 85% by mass, particularly preferably 20 to 85% by mass, and most preferably 30 to 85% by mass.
  • 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 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 in accordance with 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 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, it may be unpreferable because performance as an elastomer such as toughness and rubber elasticity is hardly exhibited.
  • the tensile elongation at break can be measured according to ASTM D638.
  • the polyether polyamide elastomer is not broken (abbreviated as NB) in the measurement of impact strength with an Izod notch at 23 ° C., because it is particularly excellent in impact resistance.
  • the impact strength with an Izod notch can be measured based on 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.
  • 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.).
  • a polyamide-forming monomer, a triblock polyether diamine compound (Y), and a dicarboxylic acid compound (Z) are melt-polymerized under pressure and / or normal pressure, and further melt-polymerized under reduced pressure as necessary.
  • a method comprising steps can be used.
  • the three components of the polyamide-forming monomer, the triblock polyether diamine compound (Y) and the dicarboxylic acid compound (Z) are simultaneously melt polymerized under pressure and / or normal pressure, and if necessary, melt polymerization under reduced pressure.
  • a method comprising the steps of: A method of polymerizing the two components of the polyamide-forming monomer and the dicarboxylic acid compound (Z) first and then polymerizing the triblock polyether diamine compound (Y) can also be used.
  • the raw material charging method is not particularly limited, but the charging ratio of the polyamide-forming monomer, the triblock polyether diamine compound (Y) and the dicarboxylic acid compound (Z) is based on the total components.
  • the polyamide-forming monomer is preferably in the range of 10 to 95% by mass, more preferably 15 to 90% by mass, and the triblock polyether diamine compound (Y) is preferably 3 to 88% by mass, more preferably 8 to 79% by mass. Range.
  • the amino group of the triblock polyether diamine compound (Y) and the carboxy group of the dicarboxylic acid compound (Z) are approximately equimolar. It is preferable to charge as follows.
  • the polymerization temperature is preferably 150 to 300 ° C, more preferably 160 to 280 ° C, and still more preferably 180 to 250 ° C. When the polymerization temperature is 150 ° C. or higher, the polymerization reaction proceeds favorably, and when 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 a step of normal pressure melt polymerization or normal pressure melt polymerization followed by reduced pressure melt polymerization when ⁇ -aminocarboxylic acid is used as the polyamide-forming monomer.
  • a lactam or a diamine and a dicarboxylic acid synthesized as a polyamide-forming monomer and / or a salt thereof an appropriate amount of water is allowed to coexist and is usually melted under a pressure of 0.1 to 5 MPa.
  • It can be produced by a method comprising polymerization followed by normal pressure melt polymerization and / or reduced pressure melt polymerization.
  • the polymerization time is usually 0.5 to 30 hours.
  • 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 batch-type reaction kettles, single- or multi-tank continuous reaction devices, tubular continuous reaction devices, etc., alone or in combination as appropriate. Can be used.
  • monoamines and diamines such as laurylamine, stearylamine, hexamethylenediamine, metaxylylenediamine, acetic acid, for the purpose of adjusting the molecular weight and stabilizing the melt viscosity at the time of molding as necessary.
  • 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 and 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 to It is preferable to add suitably so that it may become the range of 3.5 (0.5 mass / volume% metacresol solution, 25 degreeC).
  • phosphoric acid In the production of the polyether polyamide elastomer, phosphoric acid, pyrophosphoric acid, polyphosphoric acid or the like can be added as a catalyst as necessary.
  • phosphorous acid, hypophosphorous acid, and inorganic phosphorus compounds such as alkali metal salts and alkaline earth metal salts thereof can be added to achieve the effects of both the catalyst and the heat-resistant agent.
  • the addition amount is usually 50 to 3000 ppm with respect to the charged raw material.
  • silane coupling agent In the polyether polyamide elastomer used in the present invention, a silane coupling agent is contained in an amount of 0.01 to 7 parts by mass with respect to 100 parts by mass of the polyether polyamide elastomer from the viewpoint of improving the adhesive strength.
  • 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
  • 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.
  • Said silane coupling agent can be used individually by 1 type or in combination of 2 or more types.
  • the addition amount of the silane coupling agent is 0.01 parts by mass or more with respect to 100 parts by mass of the polyether polyamide elastomer, sufficient welding strength is exhibited.
  • the addition amount is not necessarily large, and if it exceeds a certain amount, the thermal welding strength is not improved any more.
  • the blending amount of the silane coupling agent is 0.01 to 7 parts by mass, preferably 0.05 to 7 parts by mass, and preferably 0.08 to 6 parts per 100 parts by mass of the polyether polyamide elastomer. Part by mass is more preferable, 0.1 to 5 parts by mass is still more preferable, and 0.1 to 3 parts by mass is particularly preferable.
  • the method for adding the silane coupling agent is not particularly limited. When the polyether polyamide elastomer is polymerized, it may be placed in a polymerization tank at the end of the polymerization, or may be kneaded, dry blended into pellets or blended as a master batch.
  • the polyether polyamide elastomer obtained as described above has a heat resistance, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a lubricant, a slip agent, a crystal nucleating agent, as long as its properties are not impaired.
  • a tackifier, a seal improver, 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, melt moldability, molding processability, toughness, hydrolysis resistance, flex fatigue resistance, rebound resilience, low specific gravity, low temperature flexibility, low temperature impact resistance, elongation recovery It excels in properties, silencing, rubber-like properties and transparency.
  • Ube Industries, Ltd. 9068F1, 9040X2, 9048X2, 9040F2, and 9048F2 can also be used.
  • the polyamide laminate of the present invention is a laminate of a polyether polyamide elastomer and a crosslinked rubber, and the polyether polyamide elastomer is an aminocarboxylic acid compound (X1) represented by the above formula (1) and / or the above formula ( It is obtained by polymerizing a lactam compound (X2) represented by 2), a triblock polyetherdiamine compound (Y) represented by the above formula (3), and a dicarboxylic acid compound (Z) represented by the above formula (4). It is characterized by containing 0.01 to 7 parts by mass of a silane coupling agent with respect to 100 parts by mass of the polyether polyamide elastomer.
  • the rubber composition used as the material of the crosslinked rubber preferably contains natural rubber and / or diene synthetic rubber as the rubber component.
  • 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.
  • natural rubber and the diene-based synthetic rubber can be used alone or in combination of two or more, but from the viewpoint of overall performance as a rubber component.
  • Polybutadiene rubber or a combination system of polybutadiene rubber and natural rubber is preferable.
  • 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.
  • crosslinking agent examples of the crosslinking agent that can be used in the production of the crosslinked rubber include conventionally known compounds such as organic peroxides and sulfur. Among these, organic peroxides are preferable.
  • examples of the organic peroxide 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-4,4-bis
  • dicumyl peroxide and 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane are preferable from the viewpoint of crosslinkability and adhesive strength.
  • Said organic peroxide can be used individually by 1 type or in combination of 2 or more types.
  • the amount of the crosslinking agent to be used is preferably 0.1 to 3 parts by mass, more preferably 0 with respect to 100 parts by mass of the rubber component (A), from the viewpoint of promoting crosslinking, improving adhesive strength, and flexibility of the crosslinked rubber. .5 to 2 parts by mass.
  • the rubber composition used as the material for the crosslinked rubber preferably contains silica, a plasticizer, a silane coupling agent and the like from the viewpoint of improving the adhesive strength.
  • Silica includes wet silica (hydrous silicic acid) and dry silica (anhydrous silicic acid), but wet silica is preferred from the viewpoint of adhesive strength.
  • 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, from the viewpoint of adhesive strength.
  • 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 is preferably in the range of 35 to 80 parts by mass with respect to 100 parts by mass of the rubber component. 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.
  • aryl sulfonic acid amide derivatives As the plasticizer, known aryl sulfonic acid amide derivatives, hydroxybenzoic acid alkyl ester derivatives, and the like can be used.
  • Specific examples of the arylsulfonic acid amide derivatives include benzenesulfonic acid alkylamides such as benzenesulfonic acid propylamide, benzenesulfonic acid butyramide and benzenesulfonic acid 2-ethylhexylamide, N-ethyl-o-toluenesulfonic acid butyramide, N And toluenesulfonic acid alkylamides such as -ethyl-p-toluenesulfonic acid butyramide, N-ethyl-o-toluenesulfonic acid 2-ethylhexylamide, N-ethyl-p-toluenesulfonic acid 2-
  • hydroxybenzoic acid alkyl ester derivatives include hydroxybenzoic acid alkyl esters having an alkyl group having 1 to 18 carbon atoms.
  • the blending amount of the plasticizer is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, and still more preferably 1.5 to 100 parts by weight with respect to 100 parts by weight of the rubber component from the viewpoint of improving the adhesive strength. 6 parts by mass.
  • silane coupling agent As the silane coupling agent, the above-mentioned sulfur-containing silane coupling agent and amino group-containing silane coupling agent can be used. The preferred examples are the same as described above.
  • the addition amount of the silane coupling agent is preferably 1 to 10% by mass and more preferably 3 to 7% by mass with respect to the silica from the viewpoint of the effect of addition and suppression of gelation of the rubber component. .
  • the accelerator can 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.
  • Examples of the anti-aging agent 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 is a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc., if necessary, in addition to the above-described rubber component and crosslinking agent, silica, plasticizer, silane coupling agent and other various chemicals.
  • the cross-linked rubber composition thus obtained can be used as a cross-linked rubber as a material for a laminate with a polyether polyamide elastomer, thereby giving a polyamide laminate having high interlayer adhesion.
  • the crosslinked rubber can be formed into a sheet shape from a rubber composition as a raw material by a known method such as injection molding, extrusion molding, blow molding, vacuum molding or compression molding. Furthermore, you may perform a crosslinking process in a post process as needed.
  • 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 constitution 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 / base layer, base layer / X layer / Y layer, X layer / Y layer / X layer / base layer, Y layer / X layer / Y layer / Base 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 / group Examples thereof include a material layer, a base material layer / adhesive layer / Y layer / X layer / Y layer / adhesive layer / base material layer.
  • the base material 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 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 10 N / mm or more, more preferably 15 N / mm or more, and further preferably 20 N / mm or more.
  • the peel strength can be measured by the method described in the examples. Since 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 automobile parts such as tire members, various vibration absorbing members, door lock members, radiator mounts, sports shoes, work shoes, shoe parts such as shoe soles, and various industrial members 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.
  • the obtained polymer was a white tough polymer rich in rubber elasticity, and the relative viscosity ( ⁇ r) was 1.98.
  • Examples 1 to 12 and Comparative Examples 1 to 4 (1) Preparation of polyether polyamide elastomer
  • the polyether polyamide elastomer pellets obtained in Production Example 1 were dry blended with the silane coupling agent (B) in the blending amounts shown in Table 1.
  • the upper and lower protruding portions on the right side in the figure were held with a chuck, and a T peel test was performed.
  • the T peel test was performed so that stress was applied to the welded surface surely by selectively peeling from the place where it was not first welded with the aluminum foil. 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%)
  • NR 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”
  • DCP Dicumyl peroxide, manufactured by NOF Corporation, trade name “Park Mill D”
  • 3M 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, manufactured by NOF Corporation, trade name “Perhexa 3M”
  • Sulfur powdered sulfur, manufactured by Tsurumi Chemical Co., Ltd.
  • Vulcanization accelerator Noxeller NS (manufactured by Ouchi Shinsei Chemical Co., Ltd.) (chemical name: N-tert-butyl-2-benzothiazyl sulfene) Amide)
  • Silane coupling agent C: Degussa Japan, trade name “Si69”
  • Anti-aging agent 6C N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “NOCRACK 6C”
  • the polyamide laminates of Examples 1 to 12 have a higher T peel strength than Comparative Examples 3 and 4.
  • the failure mode was a cohesive failure in which the rubber layer remained on the surface of the polyether polyamide elastomer, whereas in the comparative example, a partial cohesive failure was observed in the sample.
  • the other was interface peeling or base material destruction of the rubber layer.
  • Comparative Example 2 although the welding strength is obtained, the viscosity is too high and the moldability is very poor, and it is not suitable for actual use as an injection molding material.
  • the polyamide laminate of the present invention has a strong adhesive strength between the polyether polyamide elastomer and the crosslinked rubber, it is a tire member, various vibration absorbing members, door lock members, engine parts, radiator mounts and other automotive parts, sports shoes, Work shoes, shoe parts such as shoe soles, various industrial parts such as anti-vibration rubber, and parts that are subject to large deformation due to insufficient strength with rubber alone, such as non-slip rubber, rubber tubes, sports equipment, It can be suitably used for applications such as grips for electrical products.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne : un élastomère polyéther-polyamide qui permet d'obtenir un stratifié de polyamide qui comprend à la fois une couche d'élastomère polyéther-polyamide et une couche de caoutchouc réticulé et qui présente une résistance d'adhésion élevée ; et un stratifié de polyamide ayant une résistance d'adhésion élevée. L'invention concerne spécifiquement : [1] un élastomère polyéther-polyamide à stratifier avec un caoutchouc réticulé, qui contient 0,01 à 7 parties en masse d'un agent de couplage silane pour 100 parties en masse de l'élastomère polyéther-polyamide et [2] un stratifié de polyamide qui comprend une couche d'un élastomère polyéther-polyamide et une couche d'un caoutchouc réticulé, l'élastomère polyéther-polyamide étant un élastomère qui est préparé par polymérisation de (X1) un composé d'acide aminocarboxylique spécifique et/ou (X2) un composé de lactame, (Y) un composé de polyéther diamine triséquencé spécifique et (Z) un composé d'acide dicarboxylique spécifique, et 0,01 à 7 parties en masse d'un agent de couplage silane étant contenues pour 100 parties en masse de l'élastomère polyéther-polyamide.
PCT/JP2010/064436 2009-09-04 2010-08-26 Élastomère polyéther-polyamide et stratifié de polyamide Ceased WO2011027703A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2011529879A JPWO2011027703A1 (ja) 2009-09-04 2010-08-26 ポリエーテルポリアミドエラストマー及びポリアミド積層体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-205226 2009-09-04
JP2009205226 2009-09-04

Publications (1)

Publication Number Publication Date
WO2011027703A1 true WO2011027703A1 (fr) 2011-03-10

Family

ID=43649241

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/064436 Ceased WO2011027703A1 (fr) 2009-09-04 2010-08-26 Élastomère polyéther-polyamide et stratifié de polyamide

Country Status (3)

Country Link
JP (1) JPWO2011027703A1 (fr)
TW (1) TW201121781A (fr)
WO (1) WO2011027703A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009291962A (ja) * 2008-06-02 2009-12-17 Ube Ind Ltd 多層構造体
EP2581237A4 (fr) * 2010-06-08 2014-08-20 Yokohama Rubber Co Ltd Pneumatique et stratifié
JP2015052037A (ja) * 2013-09-05 2015-03-19 住友精化株式会社 熱融着接着剤
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
JPWO2019208799A1 (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
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
JPWO2023080109A1 (fr) * 2021-11-05 2023-05-11
WO2024250632A1 (fr) * 2023-06-07 2024-12-12 中石油(上海)新材料研究院有限公司 Élastomère polyamide contenant un cycle triazine et son procédé de préparation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003289902A (ja) * 2002-03-29 2003-10-14 Mizuno Corp アウトソール及びそのアウトソールを用いた靴底
JP2004035729A (ja) * 2002-07-03 2004-02-05 Daicel Degussa Ltd 樹脂組成物及びそれを用いた複合体とその製造方法
JP2005036147A (ja) * 2003-07-17 2005-02-10 Daicel Degussa Ltd 複合体およびその製造方法
JP2009107183A (ja) * 2007-10-29 2009-05-21 Ube Ind Ltd ポリアミド積層体
WO2009093695A1 (fr) * 2008-01-23 2009-07-30 Ube Industries, Ltd. Composition de caoutchouc, composition de caoutchouc pour bande de roulement de base, composition de caoutchouc pour toile en caoutchouc, composition de caoutchouc pour flanc de pneu et pneu utilisant les compositions de caoutchouc

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003289902A (ja) * 2002-03-29 2003-10-14 Mizuno Corp アウトソール及びそのアウトソールを用いた靴底
JP2004035729A (ja) * 2002-07-03 2004-02-05 Daicel Degussa Ltd 樹脂組成物及びそれを用いた複合体とその製造方法
JP2005036147A (ja) * 2003-07-17 2005-02-10 Daicel Degussa Ltd 複合体およびその製造方法
JP2009107183A (ja) * 2007-10-29 2009-05-21 Ube Ind Ltd ポリアミド積層体
WO2009093695A1 (fr) * 2008-01-23 2009-07-30 Ube Industries, Ltd. Composition de caoutchouc, composition de caoutchouc pour bande de roulement de base, composition de caoutchouc pour toile en caoutchouc, composition de caoutchouc pour flanc de pneu et pneu utilisant les compositions de caoutchouc

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009291962A (ja) * 2008-06-02 2009-12-17 Ube Ind Ltd 多層構造体
EP2581237A4 (fr) * 2010-06-08 2014-08-20 Yokohama Rubber Co Ltd Pneumatique et stratifié
US9539859B2 (en) 2010-06-08 2017-01-10 The Yokohama Rubber Co., Ltd. Pneumatic tire and laminate
JP2015052037A (ja) * 2013-09-05 2015-03-19 住友精化株式会社 熱融着接着剤
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
US10301450B2 (en) 2014-10-27 2019-05-28 Bridgestone Corporation Tire
JP2016084424A (ja) * 2014-10-27 2016-05-19 株式会社ブリヂストン タイヤ
WO2016067842A1 (fr) * 2014-10-27 2016-05-06 株式会社ブリヂストン Pneu
JPWO2019208799A1 (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
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
JP7306638B2 (ja) 2018-04-26 2023-07-11 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
JPWO2023080109A1 (fr) * 2021-11-05 2023-05-11
WO2023080109A1 (fr) * 2021-11-05 2023-05-11 三洋化成工業株式会社 Polymère séquencé de semelle de chaussure, composition de résine de semelle de chaussure et semelle de chaussure
JP7750302B2 (ja) 2021-11-05 2025-10-07 三洋化成工業株式会社 シューズソール用ブロックポリマー、シューズソール用樹脂組成物及びシューズソール
WO2024250632A1 (fr) * 2023-06-07 2024-12-12 中石油(上海)新材料研究院有限公司 Élastomère polyamide contenant un cycle triazine et son procédé de préparation

Also Published As

Publication number Publication date
TW201121781A (en) 2011-07-01
JPWO2011027703A1 (ja) 2013-02-04

Similar Documents

Publication Publication Date Title
JP5472116B2 (ja) ゴム組成物及びポリアミド積層体
JPWO2011027703A1 (ja) ポリエーテルポリアミドエラストマー及びポリアミド積層体
JP5521314B2 (ja) 更生タイヤ用ゴム組成物および更生タイヤ
JP5544814B2 (ja) ゴム組成物及びその製造方法
JP5376112B2 (ja) 多層構造体
WO2009093695A1 (fr) Composition de caoutchouc, composition de caoutchouc pour bande de roulement de base, composition de caoutchouc pour toile en caoutchouc, composition de caoutchouc pour flanc de pneu et pneu utilisant les compositions de caoutchouc
EP1971642B1 (fr) Composition de résine polyamide renforcée de fibres de carbone
JP5589289B2 (ja) ゴム組成物
JP4978425B2 (ja) ポリアミド積層体
JP6110373B2 (ja) 熱安定化アクリレートエラストマー組成物およびその製造方法
KR100864605B1 (ko) 페인트 부착성이 강화된 열가소성 폴리아마이드 수지조성물
WO2008030600A2 (fr) Composition de résine de polyamide
JP2009255489A (ja) 多層構造体
CN103080188A (zh) 反应性聚酰胺树脂及聚酰胺树脂组合物
KR20160073965A (ko) 폴리아미드 수지 조성물, 제조 방법, 성형품
CN103732682B (zh) 用于制备热稳定聚酰胺填充的丙烯酸酯聚合物的方法
KR20100018451A (ko) 열가소성 엘라스토머 조성물 및 이를 사용하는 공기식 타이어
JP2010095604A (ja) ゴム組成物
JP6477194B2 (ja) ポリアミドエラストマーと積層体
JP5448054B2 (ja) タイヤトレッド用ゴムおよびそれを用いたタイヤ
JP3464759B2 (ja) ポリアミド樹脂、ポリアミド樹脂組成物および成形体
JP3460792B2 (ja) ポリアミド樹脂、ポリアミド樹脂組成物および成形体
JPS63221163A (ja) 樹脂組成物
JPS63221182A (ja) ホツトメルト接着剤
JPH01253439A (ja) ゴム積層体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10813652

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2011529879

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10813652

Country of ref document: EP

Kind code of ref document: A1