JP5376112B2 - Multilayer structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multilayered structure excellent in adhesive strength between a polyether polyamide elastomer and a crosslinked diene-based rubber compound. <P>SOLUTION: In the multilayered structure, the polyether polyamide elastomer obtained by polymerizing an aminocarboxylic acid compound (A1) and/or a lactam compound (A2), a tri-block polyether diamine compound (B), and a dicarboxylic acid compound (C) and the crosslinked diene-based rubber compound containing 35-100 pts.wt. of silica in relation to a rubber component are stacked. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a multilayer structure of a polyether polyamide elastomer and a crosslinked diene rubber.

Laminates of polyamide elastomer and crosslinked diene rubber are useful as automotive parts, shoe parts, sports parts, belt parts and the like.
For example, in Patent Document 1, in an outsole composed of a grounding portion, a design portion, and a base portion, a rubber is disposed on the grounding portion side of the base portion, and a polyamide elastomer is disposed on the bonding surface side. An outsole having a structure in which an elastomer is melted and integrated and joined is disclosed. Patent Document 2 discloses a resin / rubber composite in which a resin member obtained by bringing a polyamide-based elastomer into contact with a vulcanized rubber member under heating and a vulcanized rubber member are directly bonded. However, it is difficult to say that these polyamide elastomers have sufficiently high adhesion strength to acid-unmodified rubber.

JP 2003-289902 A JP 2005-36147 A

  An object of the present invention is to solve the above-mentioned problems and to provide a multilayer structure excellent in adhesive strength between a polyether polyamide elastomer and a crosslinked diene rubber.

That is, the present invention provides an aminocarboxylic acid compound (A1) represented by the following formula (1) and / or a lactam compound (A2) represented by the following formula (2), and a triblock polyether represented by the following formula (3). A polyether polyamide elastomer obtained by polymerizing the diamine compound (B) and the dicarboxylic acid compound (C) represented by the following formula (4) and 35 to 100 parts by weight of silica with respect to the rubber component were crosslinked. A multilayer structure in which a diene rubber is laminated is provided.
^{_{H 2 N-R 1 -COOH (}} 1)
[However, R ¹ represents a linking group containing a hydrocarbon chain. ]

[However, R ² represents a linking group containing a hydrocarbon chain. ]

[However, x is in the range of 1 to 20, y is in the range of 4 to 50, and z is in the range of 1 to 20. ]
_{^{HOOC- (R 3) m -COOH (}} 4)
[However, R ³ represents a linking group containing a hydrocarbon chain, and m is 0 or 1. ]

  ADVANTAGE OF THE INVENTION According to this invention, the polyamide laminated body excellent in the adhesive strength of polyether polyamide elastomer and diene rubber can be provided.

[Polyether polyamide elastomer]
The polyether polyamide elastomer used in the present invention comprises a polyamide-forming monomer [that is, an aminocarboxylic acid compound (A1) and / or a lactam compound (A2)], an XYX type triblock polyetherdiamine compound (B) (Y is a poly It is a polyether polyamide elastomer obtained by polymerizing oxybutylene) and dicarboxylic acid (C).

  In 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.

  In particular, when one end of the polyamide-forming monomer is an amino group and the other end is a carboxylic acid or a carboxy group, 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 (A1) and lactam compound (A2)]
Next, the aminocarboxylic acid compound (A1) and the lactam compound (A2) will be described.
The aminocarboxylic acid compound (A1) used in the present invention is a compound represented by the following formula (1).
^{_{H 2 N-R 1 -COOH (}} 1)

Here, 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, 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, Particularly preferably, it represents the hydrocarbon group having 10 to 15 carbon atoms or the alkylene group having 10 to 15 carbon atoms.

The lactam compound (A2) used in the present invention is a compound represented by the following formula (2). Here, 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, 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, Particularly preferably, it represents the above hydrocarbon group having 10 to 15 carbon atoms or an alkylene group having 10 to 15 carbon atoms.

  As the aminocarboxylic acid compound (A1) and the lactam compound (A2), at least one aliphatic or alicyclic group selected from ω-aminocarboxylic acid, lactam, or one 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. In particular, by using a combination of an aliphatic diamine compound and an aliphatic dicarboxylic acid compound, 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 (diamine / 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.

  Specific examples of the diamine 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.

  Specific examples of the dicarboxylic acid 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. A dicarboxylic acid compound can be mentioned.

  Specific examples of the lactam include aliphatic lactams having 5 to 20 carbon atoms such as ε-caprolactam, ω-enantolactam, ω-undecalactam, ω-dodecalactam, and 2-pyrrolidone.

  Specific examples of the ω-aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like. ˜20 aliphatic ω-aminocarboxylic acids and the like.

[XYX type triblock polyether diamine (B)]
The XYX type triblock polyether diamine (B) used in the present invention is a compound represented by the following formula (3), and polypropylene is added by adding propylene oxide to both ends of poly (oxytetramethylene) glycol and the like. After making into glycol, polyether diamine etc. which are manufactured by making ammonia etc. react with the terminal of this polypropylene glycol can be used.

  Specific examples of the XYX type triblock polyether diamine (B) include XTJ-533 manufactured by HUNTSMAN (USA) (in the general formula (3), x is approximately 12, y is approximately 11, and z is approximately 11), XTJ-536 (In general formula (3), x is about 8.5, y is about 17, and z is about 7.5), and XTJ-542 (in general formula (3), x is about 3, y is about 9, For example, z is approximately 2).

  Further, as XYX type triblock polyether diamine (B), XYX-1 (general formula (3), x is about 3, y is about 14, z is about 2), XYX-2 (general formula (3) X is approximately 5, y is approximately 14, z is approximately 4), and XYX-3 (in general formula (3), x is approximately 3, y is approximately 19, z is approximately 2), etc. it can.

  In the XYX type triblock polyether diamine (B), x and z are 1 to 20, preferably 1 to 18, more preferably 1 to 16, more preferably 1 to 14, and 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. Further, as a combination of x, y and z, 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, and y is in the range of 13 to Preferred examples include a range of 28 and a combination of z in the range of 1-9.

  In the XYX type triblock polyether diamine (B), when x and z are each smaller than the above range, the resulting elastomer is inferior in transparency, which is not preferable. When y is smaller than the above range, rubber elasticity Is not preferable because of a low. 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.

[Dicarboxylic acid compound (C)]
The dicarboxylic acid compound (C) used in the present invention is a compound represented by the following formula (4).
_{^{HOOC- (R 3) m -COOH (}} 4)
Here, 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. 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.

  As the dicarboxylic acid compound (C), at least one dicarboxylic acid selected from aliphatic, alicyclic and aromatic dicarboxylic acids or derivatives thereof can be used.

  Specific examples of the dicarboxylic acid 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, 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 terephthalic acid and isophthalic acid. As the dimer acid and hydrogenated dimer acid, trade names “Pripol 1004”, “Plipol 1006”, “Plipol 1009”, “Plipol 1013” and the like manufactured by Unikema Corporation can be used.

  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. Can do. If it is 95 mass% or less, the function and performance as elastomers, such as rubber elasticity and a softness | flexibility, can be expressed.

  Moreover, the ratio of the total amount of the (B) compound and the (C) 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, and more preferably 15 to 85%. % By mass, particularly preferably 20 to 85% by mass, 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, more preferably in the range of 20 to 70, and particularly preferably in the range of 25 to 70. is there. In the present invention, 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, more preferably 20 to 350 MPa, and particularly preferably 20 to 300 MPa. When the elastic modulus is within the above range, an elastomer having particularly excellent toughness and rubber elasticity can be obtained. In the present invention, the flexural modulus 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, more preferably in the range of 3 to 20 MPa, and particularly preferably in the range of 3 to 18 MPa. When the tensile yield point strength is in the above range, an elastomer having particularly excellent toughness and rubber elasticity can be obtained. In the present invention, the tensile yield point strength can be measured according to ASTM D-638.

  The tensile elongation at break of the polyether polyamide elastomer is preferably 300% or more, particularly preferably 600% or more. If the amount is less than this range, performance as an elastomer such as toughness and rubber elasticity becomes difficult to be exhibited, which may not be preferable. In the present invention, the tensile elongation at break can be measured according to ASTM D-638.

  The flexural strength of the polyether polyamide elastomer is preferably 0.8 to 15 MPa, more preferably 1 to 13 MPa, more preferably 1.1 to 10 MPa, and particularly preferably 1.2 to 9 MPa. When 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. In the present invention, the bending strength can be measured according to ASTM D-790.

  It is preferable that 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. In the present invention, the impact strength with Izod notch can be measured in accordance with ASTM D-256.

  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 D-648.

  The relative viscosity (ηr) of the polyether polyamide elastomer is preferably in the range of 1.2 to 2.0 (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.

  In the production of the polyether polyamide elastomer, there is no particular limitation on the raw material charging method, but 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, particularly 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, particularly preferably in the range of 8 to 79% by mass. Among the raw materials, 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 particularly 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 ω-aminocarboxylic acid is used as the polyamide-forming monomer.

  On the other hand, when using a lactam or a diamine synthesized from a dicarboxylic acid and / or a salt thereof as a polyamide-forming monomer, an appropriate amount of water is allowed to coexist and melt polymerization under a pressure of 0.1 to 5 MPa is performed. And a subsequent method comprising normal pressure melt polymerization and / or reduced pressure melt polymerization.

  The 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 relative viscosity of the polyether polyamide elastomer is 2 or less. When the relative viscosity of the polyether polyamide elastomer exceeds 2, the adhesive strength with the crosslinked diene rubber is lowered.

  The crystallization temperature of the polyether polyamide elastomer is 138 ° C. or lower. When the crystallization temperature of the polyether polyamide elastomer exceeds 138 ° C., the adhesive strength with the crosslinked diene rubber decreases.

The interfacial tension at 200 ° C. between the polyether polyamide elastomer and the uncrosslinked diene rubber is 2 × 10 ⁻³ N / m or less. When the interfacial tension at 200 ° C. between the polyether polyamide elastomer and the uncrosslinked diene rubber is larger than 2 × 10 ⁻³ N / m, the adhesive strength between the polyether polyamide elastomer and the crosslinked diene rubber is lowered.

  The polyether polyamide elastomer and the uncrosslinked diene rubber were crosslinked inside the blend sample prepared by melt kneading 70 parts of the polyether polyamide elastomer and 30 parts of the uncrosslinked diene rubber at 200 ° C. The diene rubber dispersed phase particles not having a number average radius is 250 nm or less. On the other hand, when the number average radius of the uncrosslinked diene rubber dispersed phase particles exceeds 250 nm, the adhesive strength between the polyether polyamide elastomer and the crosslinked diene rubber decreases.

  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.

When producing a polyether polyamide elastomer, 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.
These amounts are preferably added as appropriate so that the relative viscosity of the finally obtained elastomer is in the range of 1.2 to 2.0 (0.5 mass / volume% metacresol solution, 25 ° C.). .

  The addition amount of the above-mentioned monoamine and diamine, monocarboxylic acid and dicarboxylic acid is preferably set within a range that does not hinder the properties of the obtained polyether polyamide elastomer.

  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 materials.

  Polyether polyamide elastomer is heat resistant agent, ultraviolet absorber, light stabilizer, antioxidant, antistatic agent, lubricant, slip agent, crystal nucleating agent, tackifier, and sealability improvement as long as its properties are not hindered. An 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 bending fatigue resistance, excellent resilience, low specific gravity, and low temperature flexibility. Excellent low temperature impact resistance, excellent stretch recovery, excellent sound deadening properties, rubber properties and transparency.

The polyether polyamide elastomer may be mixed with other resins. Specific examples of the other resins include polyamide resins excluding the polyether polyamide elastomer used in the present invention (for example, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66). Polymer), polyvinyl chloride, thermoplastic polyurethane, ABS resin, polyester resin (polybutylene terephthalate, polyethylene terephthalate, etc.), polynitrile resin, diene rubber, olefin rubber, and the like. By blending with these thermoplastic resins, the moldability, impact resistance, elasticity and flexibility of these resins can be improved.
The polyether polyamide elastomer has gas barrier properties, but the gas barrier properties can be further improved by mixing with other resins.

The polyether polyamide elastomer in the present invention is commercially available as “UBESTA XPA 9040X1, 9040F1, 9048X1, 9048F1, 9055X1, 9055F1, 9063X1, 9063F1, 9068X1, 9068F1, 9040X2, 9048X2, 9040F2, 9048F2, 9068TF1, 9063TF1, 9055TF1, 9048TF1 "(manufactured by Ube Industries, Ltd.) and the like can be used.
Polyether polyamide elastomer can obtain a sheet-like molded article by a known molding method such as injection molding, extrusion molding, blow molding or vacuum molding.

[Diene rubber sheet]
The diene rubber used in the present invention is not particularly limited, and any known rubber can be used. For example, polymers of diene monomers such as natural rubber, butadiene rubber (BR), isoprene rubber, butyl rubber and chloroprene rubber; acrylonitrile-diene copolymer such as acrylonitrile butadiene rubber (NBR), nitrile chloroprene rubber and nitrile isoprene rubber Rubber; styrene-diene copolymer rubber such as styrene butadiene rubber (SBR), styrene chloroprene rubber, styrene isoprene rubber, and ethylene propylene diene rubber (EPDM). Of these, butadiene rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, natural rubber, and isoprene rubber are preferable. These can be used alone or in combination of two or more.

Examples of the rubber reinforcing agent blended in the rubber composition according to the present invention include silica, various carbon blacks, white carbon, activated calcium carbonate, and ultrafine magnesium silicate. Of these, silica or a combination of silica and other reinforcing agents is preferable.

The silica particles must have a silica purity of 97% or higher. Silica having a purity of less than 97% does not have a sufficient rubber reinforcing effect, so that a rubber composition blended with such silica does not have sufficient wear resistance. The average particle diameter of the silica particles is 0.1 to 50 μ, preferably 1 to 50 μ, particularly preferably 5 to 50 μ. Such silica particles can be obtained, for example, by a method of pulverizing completely melted quartz glass so as to have an appropriate particle size. Further, pulverized natural quartz having a silica purity of 97% or more is also preferably used. Furthermore, particles obtained by hydrolyzing an organosilicon compound such as silane are also preferably used.
The compounding amount of silica is preferably 35 to 100 parts by weight, more preferably 35 to 90 parts by weight, more preferably 40 to 80 parts by weight, and particularly preferably 40 to 70 parts by weight with respect to the rubber component. If it is smaller than this range, the effect of improving the adhesive strength is insufficient, and if it exceeds this range, the rubber becomes too hard, which is not preferable.

A silane coupling agent may be used to mix rubber and silica well.
As the coupling agent, alkylphenol formaldehyde resin initial condensate, acid anhydride, silane coupling agent, titanate coupling agent and the like are preferable.

Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a chromium coupling agent, and a boron coupling agent. Preferably, it is a silane coupling agent.

The silane coupling agent in the present invention refers to a chemically decomposable organic functional group having affinity or reactivity with an organic resin to a hydrolyzable silyl group having affinity or reactivity with an inorganic material. It is a silane compound having a bonded structure. Examples of the hydrolyzable group bonded to silicon include an alkoxy group, a halogen, and an acetoxy group. Usually, an alkoxy group, particularly a methoxy group and an ethoxy group are preferably used. The number of hydrolyzable groups attached to one silicon atom is selected between 1 and 3. Examples of the organic functional group include an amino group, an epoxy group, a vinyl group, a carboxyl group, a mercapto group, a halogen group, a methacryloxy group, and an isocyanate group, and preferably an amino group or an epoxy group.

Specific examples of the silane coupling agent in the present invention include α-aminoethyltriethoxysilane, α-aminopropyltriethoxysilane, α-aminobutyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyl Methyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N -Benzyl-γ-aminopropy Amino group-containing silanes such as rutrimethoxysilane and N-vinylbenzyl-γ-aminopropyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycosoxypropyl Epoxy group-containing silanes such as triethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4 epoxyepoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Vinyl group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldimethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- ( N-Carboki Carboxyl group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyl Mercapto group-containing silanes such as diethoxysilane; Halogen-containing silanes such as γ-chloropropyltrimethoxysilane; γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxy (Meth) acrylic group-containing silanes such as silane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane; γ-isocyanatopropyltrimethoxysila , .Gamma. isocyanatopropyltriethoxysilane, .gamma. isocyanate propyl methyl diethoxy silane, isocyanate group-containing silanes such as .gamma. isocyanate propyl methyl dimethoxysilane and the like.

In this invention, the quantity of a silane coupling agent is 0.01-0.5 weight part with respect to the whole composition, Preferably it is 0.01-0.3 weight part. If it is less than 0.01 part by weight, the adhesion is insufficient, and if it exceeds 0.3 part by weight, the fluidity and surface properties of nylon itself are impaired.

  As the crosslinking agent, known crosslinking agents such as sulfur, organic peroxides, resin vulcanizing agents, and metal oxides such as magnesium oxide are used. Of these, organic peroxides are preferable. The amount of the crosslinking agent is preferably 0.1 to 5.0 parts by weight, more preferably 0.5 to 4.0 parts by weight, and still more preferably 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the rubber component. Part by weight, particularly preferably 0.5 to 2.5 parts by weight is preferred. This is why this range is preferred.

Examples of the organic peroxide include percarboxylic acid, organic hydroperoxide, and dioxirane compound.

Specific examples of percarboxylic acid include percarboxylic acid of lower fatty acids such as performic acid, peracetic acid, perpropionic acid, perbutanoic acid, 2-methylperpropionic acid, perpentanoic acid, 4-methylperbenzoic acid, 4 -T-butyl perbenzoic acid, 4-cyanoperbenzoic acid, 4-methoxyperbenzoic acid, 4-nitroperbenzoic acid, 3-chloroperbenzoic acid, 3-nitroperbenzoic acid, 2-methylperbenzoic acid, Examples thereof include perbenzoic acid derivatives such as 2-methoxyperbenzoic acid, 2,4-dichloroperbenzoic acid and 2-chloro-4-nitroperbenzoic acid, and peroxyphthalic acid derivatives such as magnesium monoperoxyphthalate.

Organic hydroperoxides include t-butyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cyclohexyl hydroperoxide, 4 -Aromatic hydroperoxides such as methylcyclohexyldimethylmethane hydroperoxide, cumene hydroperoxide, p-isopropylphenyl hydroperoxide.

Examples of the dioxirane compound include 3,3-dimethyldioxirane, methylpropyldioxirane, methylphenyldioxirane, diphenyldioxirane and the like.

Diene rubbers are commonly used additives such as vulcanization accelerators, fillers, plasticizers, softeners, vulcanization activators, co-vulcanizers, pigments, antioxidants, tackifiers, processing aids, and lubricants. , Coloring agents, foaming agents, dispersing agents, flame retardants, antistatic agents and the like can be added.
The production method of the diene rubber sheet is not particularly limited, and the diene rubber and the above additives are mixed and kneaded by using a rubber kneading apparatus such as a conventionally known roll or Banbury mixer, and the resulting mixture is obtained. A sheet-like molded product can be obtained by a known molding method such as injection molding, extrusion molding, blow molding, or vacuum molding.

[Multilayer structure]
The multilayer structure of the present invention is a laminate in which the polyether polyamide elastomer and the crosslinked diene rubber are laminated.
The multilayer structure of the present invention has one or more layers composed of a polyether polyamide elastomer and a crosslinked diene rubber layer. The thickness of each layer is not particularly limited, and can be adjusted according to the type of polymer constituting each layer, the total number of layers in the laminate, the application, and the like.
Moreover, although 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 | limited in particular, Any may be sufficient. Judging from the mechanism of the laminate manufacturing apparatus, it is preferably 7 layers or less, more preferably 2 to 5 layers.

  In addition, the multilayer structure of the present invention can be made of 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 Etc. can also be laminated.

  Furthermore, an adhesive layer may be provided for the purpose of improving the adhesion between the layers. As the adhesive layer, an olefin polymer containing a carboxy group and a salt thereof, an acid anhydride group, and an epoxy group is preferably used. Examples of the olefin polymer include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, polybutene, ethylene-propylene-diene copolymer, polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene- Examples include isoprene copolymers. In addition, a carboxylic acid ester may be copolymerized in an olefin polymer, such as an olefin- (meth) acrylic acid ester copolymer, a (meth) acrylic acid ester-acrylonitrile copolymer, and the like. Can be mentioned.

The carboxy group and its salt, the acid anhydride group and the epoxy group may be either a copolymer introduced into the main chain in the polyolefin molecule or a graft polymer introduced into the side chain.
Carboxy groups and salts thereof, acid anhydride groups, and epoxy groups include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1 , 2-dicarboxylic acid, endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid and metal salts of these carboxylic acids (Na, Zn, K, Ca, Mg), maleic anhydride , Itaconic anhydride, citraconic anhydride, fumaric anhydride, endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, itacone Examples thereof include glycidyl acid, glycidyl citraconic acid, and the like.

The multilayer structure of the present invention includes (1) a method of simultaneously molding each layer, (2) a method of molding and bonding each layer, (3) a method of laminating while further forming a layer on the layer (tandem method), etc. Or a combination thereof.
The polyether polyamide elastomer and the crosslinked diene rubber can be laminated by hot press molding or injection molding, and may be pressurized as necessary, or may be pressure molded in a reduced pressure atmosphere.
The molding temperature is preferably in the range of 120 to 250 ° C, more preferably in the range of 130 to 230 ° C, and particularly preferably in the range of 130 to 220 ° C.

Examples of the laminated structure of the polyether polyamide elastomer layer (X layer) and the crosslinked diene rubber layer (Y layer) in the multilayer structure 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 layer, Y layer / X layer / adhesive layer / base layer, X layer / Y layer / adhesive layer / base layer, base 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.
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.
As the 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 of the multilayer structure of the present invention and the crosslinked diene rubber is preferably 5 N / mm or more, more preferably 8 N / mm or more.

  Since the multilayer structure of the present invention has excellent heat-welding property to the diene rubber crosslinked with the polyamide elastomer, the multilayer structure has a strong adhesive strength between the polyamide elastomer and the diene rubber, and the tire member (inner liner) Carcass, sidewalls, base treads, chafers, rims, beads, etc.), various vibration absorbing members, door lock members, radiator mounts and other automotive parts, sports shoes, working shoes, shoe soles and other shoe parts, It can be advantageously used for various industrial members such as vibration rubber.

For example, when applied to an inner liner of a tire, a polyamide elastomer can be used as an adhesive layer between the carcass and the inner liner. Alternatively, in order to increase gas barrier properties, it is also possible to use a polyamide elastomer mixed with other resins, such as halogenated butyl rubber or EVOH, which are known materials, as an inner liner. May be laminated directly.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated, this invention is not limited to these Examples. The characteristic values of the polyether polyamide elastomer were measured as follows.

(1) Relative viscosity (ηr) (0.5 mass / volume% metacresol solution, 25 ° C.)
Using reagent-grade m-cresol as a solvent, it was measured at 25 ° C. using an Ostwald viscometer at a concentration of 5 g / dm ³ .

(2) Terminal carboxy group concentration ([COOH])
40 ml of benzyl alcohol was added to about 1 g of the polymer, heated and dissolved in a nitrogen gas atmosphere, phenolphthalein was added as an indicator to the obtained sample solution, and titrated with an N / 20 potassium hydroxide-ethanol solution.

(3) Terminal amino group concentration ([NH ₂ ])
About 1 g of the polymer was dissolved in 40 ml of a phenol / methanol mixed solvent (volume ratio: 9/1), thymol blue was added as an indicator to the obtained sample solution, and titrated with N / 20 hydrochloric acid.

(4) Melting point (Tm) and crystallization temperature (Tc)
Tm and Tc were measured under a nitrogen atmosphere using a differential scanning calorimeter DSC-50 manufactured by Shimadzu Corporation. The temperature was raised from room temperature to 230 ° C. at a rate of 10 ° C./min (referred to as a temperature rise first run), held at 230 ° C. for 10 minutes, and then lowered to −100 ° C. at a rate of 10 ° C./min (temperature fall first run). Then, the temperature was raised to 230 ° C. at a rate of 10 ° C./min (referred to as a temperature raised second run). From the obtained DSC chart, the exothermic peak temperature of the temperature decrease first run was Tc, and the endothermic peak temperature of the temperature increase second run was Tm.

(5) Composition The composition of the polyether polyamide elastomer was determined from a proton NMR spectrum measured at room temperature using JNM-EX400WB type FT-NMR manufactured by JEOL Ltd. at a concentration of 4% by mass using heavy trifluoroacetic acid as a solvent. The composition of each component was determined.

(6) Hardness Shore D was measured according to ASTM D2240. It measured using the sheet | seat of thickness 6mm shape | molded by injection molding. The measurement was performed at a temperature of 23 ° C.

(7) Mechanical properties: Measurements (i) to (iv) shown below were performed by molding the following test pieces by injection molding.
(I) Tensile test (tensile yield point strength and tensile elongation at break): A Type I test piece described in ASTM D638 was measured according to ASTM D638.
(Ii) Bending test (flexural modulus and bending strength): Measured according to ASTM D790 using a test piece having a test piece size of 6.35 mm × 12.7 mm × 127 mm.
(Iii) Impact strength (with Izod notch): Measured at 23 ° C. in accordance with ASTM D256 using a test piece with dimensions of 12.7 mm × 12.7 mm × 63.5 mm.
(Iv) Deflection temperature under load: It was measured at a load of 0.45 MPa in accordance with ASTM D648 using a test piece having a test piece size of 6.35 mm × 12.7 mm × 127 mm.

<Production Example 1: Production of PAE1>
In a 70 liter pressure vessel equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure regulator and polymer outlet, 12.231 kg of 12-aminododecanoic acid manufactured by Ube Industries, Ltd., adipic acid 1 0.089 kg, XYX type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN, amine value: 1.94 meq / g) 7.680 kg, 6 g of sodium hypophosphite monohydrate and heat-resistant agent Minox 917) 60 g was charged. After sufficiently replacing the inside of the container with nitrogen, the temperature inside the container was raised from room temperature to 230 ° C. over 3.5 hours while the pressure inside the container was adjusted to 0.05 MPa while supplying nitrogen gas at 186 liters / hour. Polymerization was carried out at 230 ° C. for 4 hours while adjusting the internal pressure to 0.05 MPa to obtain a polymer. After completion of the polymerization, 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 pellet was a colorless and translucent tough polymer rich in rubber elasticity, and ηr = 1.98.

<Production Example 2: Production of PAE2>
In a 70 liter pressure vessel equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure regulator and polymer outlet, 12.248 kg of 12-aminododecanoic acid manufactured by Ube Industries, Ltd., adipic acid 1 .092 kg, XYX type triblock polyether diamine (XTJ-542, manufactured by HUNTSMAN, amine value: 1.94 meq / g) 5.256 kg, isophorone diamine (trade name: VESTAMIN IPD) 0.404 kg, hypochlorous 6 g of sodium phosphate monohydrate and 60 g of heat-resistant agent (Tominox 917 manufactured by Yoshitomi Pharmaceutical) were charged. After sufficiently replacing the inside of the container with nitrogen, the temperature inside the container was raised from room temperature to 230 ° C. over 3.5 hours while the pressure inside the container was adjusted to 0.05 MPa while supplying nitrogen gas at 186 liters / hour. Polymerization was carried out at 230 ° C. for 4 hours while adjusting the internal pressure to 0.05 MPa to obtain a polymer. After completion of the polymerization, 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 pellet was a colorless and translucent tough polymer rich in rubber elasticity, and ηr = 1.99.

<Production Example 3: Production of PAE3>
12-aminododecanoic acid (manufactured by Ube Industries, Ltd.) 12.897 kg and adipine in a 70 liter pressure vessel equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure regulator and polymer outlet 0.906 kg of acid (special grade reagent) was charged. After sufficiently replacing the container with nitrogen, the container was gradually heated while supplying nitrogen gas at a flow rate of 300 liters / hour. Stirring was performed at a speed of 20 rpm. The temperature was raised from room temperature to 240 ° C. over 3 hours, and polymerization was carried out at 230 ° C. for 4 hours to synthesize nylon 12 oligomers.
To this oligomer, 6.197 kg of polytetramethylene glycol (manufactured by BASF, PolyTHF1000), 0.020 kg of tetrabutylzirconate and 0.050 kg of an antioxidant (trade name: Tominox 917, manufactured by Yoshitomi Pharmaceutical) were charged. After sufficiently replacing the inside of the container with nitrogen, heating was performed gradually while supplying nitrogen gas at a flow rate of 300 liters / hour. Stirring was performed at a speed of 20 rpm. The temperature was raised from room temperature to 210 ° C. over 3 hours, heated at 210 ° C. for 3 hours, then gradually reduced in pressure to 50 Pa over 1 hour, polymerized for 2 hours, and then increased over 30 minutes. The temperature and pressure were reduced, and polymerization was completed at 230 ° C. and about 30 Pa for 3 hours. Next, stirring was stopped, nitrogen gas was supplied into the polymerization layer, and the pressure was returned to normal pressure. Next, a colorless and transparent polymer in a molten state was drawn out from the polymer outlet, cooled with water, and pelletized to obtain about 13 kg of pellets.
The obtained polymer was polyether ester amide, and the pellets were white tough and flexible polymer rich in rubber elasticity, and ηr = 2.01.

Examples 1-5 and Comparative Examples 1-4
(1) Preparation of polyether polyamide elastomer (PAE) sheet About 25 g of the pellets of PAE1 to 3 obtained in the above production example were set in a spacer (150 mm × 150 mm, thickness 1.5 mm). Next, the above spacer, metal plate and Teflon (registered trademark, the same applies hereinafter) sheet are set to have a layer structure of metal plate / Teflon sheet / spacer / Teflon sheet / metal plate, and this is set 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 10 kg / cm ² , taken out, cooled and molded for 2 minutes.

(2) Production of diene rubber sheet Among rubber compounding ingredients shown in Table 1, 1.7 liter of Banbury mixer for testing is used for rubber, PAE and compounding agent excluding crosslinking agent (including sulfur) and vulcanization accelerator. The mixture was kneaded at a start temperature of 90 ° C. for 5 minutes to obtain a primary kneaded product. At this time, the maximum kneading temperature was 170 ° C to 180 ° C.
Next, the primary kneaded product was kneaded with a crosslinking agent (containing sulfur) and a vulcanization accelerator on a 10-inch roll at 60 ° C. to obtain a secondary kneaded product. Next, the obtained secondary mixture was cured in a press machine under conditions of 160 ° C., 10 MPa, 15 minutes (30 minutes in the case of sulfur), and a rubber sheet of 150 mm × 150 mm × 2 mm was prepared.
(3) Production of Laminate Sheet The PAE sheet and diene rubber sheet produced in (1) and (2) above are used in the combinations shown in Table 2, and are laminated in three layers so as to be PAE / diene rubber / PAE. The spacer was set to a spacer of 150 mm × 150 mm and a thickness of 5 mm.
Next, the spacer, the metal plate layer, and the Teflon sheet were set so that the layer configuration was metal plate / Teflon sheet / spacer / Teflon sheet / metal plate, and this was set on a press molding machine. Next, the temperature was set to 160 ° C., preheating was performed at the above temperature for 5 minutes without applying pressure, and then press-pressing at 10 kg / cm ² for 5 minutes at the same temperature, followed by taking out and cooling for 2 minutes to form. The sample was cut out with a width of 25 mm and used for a T peel test as a test sample.

(4) Peel strength Peel strength was measured at a tensile rate of 50 mm / min using Tensilon 2500 manufactured by Orientec Corporation. The results are shown in Table 2.

  From Table 2, the multilayer structures of Examples 1 to 5 have higher adhesive strength between PAE and crosslinked diene rubber than Comparative Examples 1 to 4, and heat welded to PAE crosslinked diene rubber. It can be seen that the properties are excellent.

Claims (6)

An aminocarboxylic acid compound (A1) represented by the following formula (1) and / or a lactam compound (A2) represented by the following formula (2), a triblock polyetherdiamine compound (B) represented by the following formula (3), And a polyether polyamide elastomer obtained by polymerizing the dicarboxylic acid compound (C) represented by the following formula (4):
The rubber component is laminated with a crosslinked diene rubber containing 35 to 100 parts by weight of silica ,
A multilayer structure having a peel strength of 5 N / mm or more .
H2N-R1-COOH (1)
[However, R1 represents a linking group containing a hydrocarbon chain. ]

[However, R2 represents a linking group containing a hydrocarbon chain. ]

[However, x is in the range of 1 to 20, y is in the range of 4 to 50, and z is in the range of 1 to 20. ]
HOOC- (R3) m-COOH (4)
[However, R3 represents a linking group containing a hydrocarbon chain, and m is 0 or 1. ]   2. The multilayer laminate according to claim 1, wherein the diene rubber contains 0.1 to 5.0 parts by weight of a crosslinking agent relative to the rubber component. ^3. The multilayer structure according to claim 1, wherein the polyether polyamide elastomer m-cresol as a solvent has a relative viscosity of 2 or less measured at 25 ° C. using an Ostwald viscometer at a concentration of 5 g / dm ^3. body.   The diene rubber is at least one selected from the group consisting of butadiene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, natural rubber, isoprene rubber, and butyl rubber. The multilayer structure described.   The multilayer structure according to any one of claims 1 to 4, wherein the diene rubber contains a coupling agent.   The multilayer structure according to any one of claims 1 to 5, wherein the diene rubber is crosslinked and then laminated with a polyether polyamide elastomer.