JP6477194B2 - Polyamide elastomer and laminate - Google Patents

Description

  The present invention relates to a polyamide elastomer and a laminate.

  Laminates of polyamide elastomer and rubber are used for automobile parts, shoe parts, sports parts, belt parts and the like. For example, Patent Document 1 discloses an outsole having a structure in which rubber and polyamide elastomer are melt-bonded. Patent Document 2 discloses a polyamide elastomer / rubber composite obtained by bringing a polyamide elastomer into contact with a vulcanized rubber member under heating.

JP 2004-161964 A JP 2004-352789 A JP 2004-352790 A JP 2004-352794 A

  However, none of these polyamide elastomers has high heat resistance and chemical resistance and has high adhesive strength to rubber, and either one is insufficient.

  An object of the present invention is to provide a polyamide elastomer having excellent heat resistance and chemical resistance and high adhesive strength to rubber.

The inventors have
A polyamide elastomer (X) comprising a polyamide unit (A) and a polyetherdiamine unit (B), wherein the polyamide unit (A) is represented by a unit represented by the general formula (1) and a general formula (2) Including units,
It has been found that the polyamide elastomer for laminates in which the polyetherdiamine unit (B) contains a unit represented by the general formula (3) solves the above-mentioned problems.

(Here, R1 represents a hydrocarbon molecular chain having 1 to 20 carbon atoms or an alkylene group having 1 to 20 carbon atoms.)

(Here, x and z are 1-20, and y is 4-50.)

  The polyamide elastomer of the present invention is excellent in heat resistance and chemical resistance and has high adhesive strength to rubber.

The polyamide elastomer of the present invention comprises a polyamide unit (A) and a polyether diamine unit (B),
The polyamide unit (A) includes a unit represented by the general formula (1) and a unit represented by the general formula (2),
The polyether diamine unit (B) includes a unit represented by the general formula (3).
[Polyamide unit (A)]
The polyamide unit (A) includes a unit represented by the general formula (1) and a unit represented by the general formula (2).

  The proportion of the polyamide unit (A) in the total amount of the polyamide elastomer (X) is not limited to the crystallinity of the polyamide component affecting the mechanical properties such as strength and elastic modulus, and the elastomer such as rubber elasticity and flexibility. From the viewpoint of manifesting the function and performance, the content is preferably 10 to 95% by weight, more preferably 20 to 95% by weight, still more preferably 25 to 85% by weight, and particularly preferably 30 to 80% by weight.

Examples of the compound providing the unit represented by the general formula (1) include oxalic acid or a salt thereof, oxalic acid monoester or a salt thereof, or oxalic acid diester. (These compounds may hereinafter be referred to as oxalic acid compounds.)
The oxalic acid compound can be used as a raw material for the polyamide elastomer (X), and oxalic acid diester is preferably used from the viewpoint of suppressing side reactions in the polycondensation reaction.

  As the oxalic acid diester, an oxalic acid diester having an alkoxy group having 1 to 6 carbon atoms, an oxalic acid diester having a cycloalkoxy group having 2 to 6 carbon atoms, and / or an oxalic acid diaryl ester are preferable.

  Examples of the oxalic acid diester having an alkoxy group having 1 to 6 carbon atoms include dimethyl oxalate, diethyl oxalate, di (n or iso) propyl oxalate, di (n, iso, sec or tert) butyl oxalate, and dihexyl oxalate. It is done.

  Examples of the oxalic acid diester having a cycloalkoxy group having 2 to 6 carbon atoms include dicyclohexyl oxalate.

  Examples of the succinic acid diaryl ester include diphenyl succinate.

  Among these, dibutyl oxalate and / or diphenyl oxalate are preferable, and dibutyl oxalate is more preferable.

  The proportion of the unit represented by the general formula (1) in the total amount of the polyamide unit (A) is preferably 18 to 50% by weight, more preferably 20 to 45% by weight, and still more preferably from the viewpoint of heat resistance. 22 to 40% by weight.

  The compound that provides the unit represented by the general formula (2) contained in the polyamide unit (A) may be any compound that can form an amide bond with an oxalic acid compound, and may be an aliphatic diamine, alicyclic diamine, aromatic. Examples include diamines.

  Aliphatic diamines include ethylene diamine, propylene diamine, 1,4-butane diamine, 1,5-pentane diamine, 2-methyl-1,5-pentane diamine, 1,6-hexane diamine, 1,9-nonane diamine, 2 -Methyl-1,8-octanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14- Tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-no Njiamin, and the like.

  Examples of the alicyclic diamine include cyclohexane diamine, methyl cyclohexane diamine, and isophorone diamine.

  As aromatic diamines, p-phenylenediamine, m-phenylenediamine, p-xylenediamine, m-xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether Etc.

  One or two or more of these diamines can be used.

  Among these diamines, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexanediamine, 1,9-nonanediamine, 2 which can be polymerized below the decomposition temperature of the polyamide elastomer of the present invention, 2 One or more diamines selected from the group consisting of -methyl-1,8-octanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine and 1,12-dodecanediamine are preferred. More preferably one or more diamines selected from the group consisting of 2-methyl-1,5-pentanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,12-dodecanediamine, 1,12-dodecanediamine is more preferred.

  The proportion of the unit represented by the general formula (2) in the total amount of the polyamide unit (A) is preferably 50 to 90% by weight, more preferably 55 to 85% by weight, and still more preferably from the viewpoint of heat resistance. 60 to 80% by weight.

  The polyamide unit (A) may contain units other than the unit represented by the general formula (1) and the unit represented by the general formula (2) as long as the effects of the present invention are not impaired. Examples of the compound providing such a unit include linear aliphatic dicarboxylic acid, dimer acid, alicyclic dicarboxylic acid, and aromatic dicarboxylic acid.

  Examples of linear aliphatic dicarboxylic acids include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3- Examples include diethyl succinic acid, azelaic acid, sebacic acid, dodecanedioic acid, and suberic acid.

  Dimer acid refers to a dimerized aliphatic dicarboxylic acid obtained by dimerizing an unsaturated fatty acid obtained by fractional distillation of triglycerides.

  Hydrogenated dimer acid refers to a hydrogenated product of dimer acid.

  As the dimer acid and hydrogenated dimer acid, “Prepol 1004”, “Prepol 1006”, “Prepol 1009”, “Prepol 1013” and the like can be used.

  Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentane dicarboxylic acid and 1,4-cyclohexane dicarboxylic acid.

Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3 -Phenylenedioxydiacetic acid, dibenzoic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc. Can be mentioned. One or more of these compounds can be added and added during the polycondensation reaction. Furthermore, in addition to the above compounds, polycarboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be represented by the general formula (1) contained in the polyamide unit (A) within the range in which melt molding is possible. It can also be used as a compound (raw material) that provides a unit other than the unit represented by formula (2) and the unit represented by formula (2).
[Polyetherdiamine unit (B)]
The polyether diamine unit (B) includes a unit represented by the general formula (3).

  As a compound providing the unit represented by the general formula (3), polypropylene glycol is obtained by adding propylene oxide to both ends of poly (oxytetramethylene) glycol and the like, and then ammonia or the like is added to the end of the polypropylene glycol. Polyether diamine etc. manufactured by making it react can be used.

  In the unit represented by the general formula (3), x and z are 1 to 20, preferably 1 to 18, more preferably 1 to 16, still more preferably 1 to 14, particularly preferably 1 to 12, y is 4 to 50, preferably 5 to 45, more preferably 6 to 40, still more preferably 7 to 35, and particularly preferably 8 to 30.

  In the unit represented by the general formula (3), when x and z are smaller than the above range, it is not preferable because the transparency of the obtained elastomer is particularly poor, and when y is smaller than the above range. The rubber elasticity is low, which is not preferable. Moreover, when x and z are larger than the above range and when y is larger than the above range, the compatibility with the polyamide component is lowered and it is difficult to obtain a tough elastomer.

  As a commercial product of a compound that provides the unit represented by the general formula (3), XTJ-533 manufactured by HUNTSMAN (USA) (in formula (1), x is approximately 12, y is approximately 11, and z is approximately 11), XTJ -536 (in formula (1), x is about 8.5, y is about 17, and z is about 7.5), XTJ-542 (in formula (1), x is about 3, y is about 9, z Is approximately 2), and XTJ-559 (in formula (3), x is approximately 3, y is approximately 14, z is approximately 2), and the like can be used.

  Further, examples of the compound that provides the unit represented by the general formula (3) include XYX type triblock polyether diamine. For example, XYX-1 (in the formula (1), x is approximately 3, y is approximately 14, z is approximately 2), XYX-2 (in formula (1), x is approximately 5, y is approximately 14, z is approximately 2), and XYX-3 (in formula (1), x is approximately 3, y is It is also possible to use about 19, z is about 2), or the like.

  The proportion of the polyetherdiamine unit (B) in the total amount of the polyamide elastomer (X) is preferably 2 from the viewpoint of expressing the properties as an elastomer such as bending fatigue and the excellent mechanical strength characteristic of the polyamide. It is -87 weight%, Most preferably, it is 7-78 weight%.

The proportion of the unit represented by the general formula (1) contained in the total amount of the polyetherdiamine unit (B) is preferably 50 to 100% by weight, more preferably 60 to 100% by weight from the viewpoint of developing the properties as an elastomer. %, More preferably 70 to 100% by weight.
[Polyamide elastomer (X)]
A polyamide elastomer (X) comprising a polyamide unit (A) and a polyetherdiamine unit (B), wherein the polyamide unit (A) is represented by a unit represented by the general formula (1) and a general formula (2) Including units,
The polyether diamine unit (B) includes a unit represented by the general formula (3).

  From the viewpoint of making the polyamide elastomer (X) sufficiently high in molecular weight, it is preferable that the number of acid terminal groups and the number of amino terminal groups of the compound (raw material) to be used are the same as the whole compound. That is, the total number of moles of amino end groups of the compound providing the polyamide unit (A) and the compound providing the polyetherdiamine unit (B) is the number of moles of acid end groups of the compound providing the polyamide unit (A) It is preferable to be the same.

  Polyamide elastomer (X) has a relative viscosity (ηr) measured at 25 ° C. of 1.0 g / dl trifluoroacetic acid solution, preferably from 1.0 to 4. 0, more preferably 1.2 to 3.0.

  From the viewpoint of heat resistance, the polyamide elastomer (X) preferably has a melting point (Tm) of 180 ° C. or higher, more preferably 200 ° C. or higher.

  The polyamide elastomer (X) has an elastic modulus of preferably 900 MPa or less, more preferably 800 MPa or less, from the viewpoint of the development of elastomer properties.

  The polyamide elastomer (X) has an elongation recovery rate of preferably 45% or more, more preferably 55% or more, measured from a 20% elongation condition, from the viewpoint of the development of elastomer properties.

  As a method for producing the polyamide elastomer (X), it can be produced by using any known method, but from the viewpoint of high molecular weight and productivity, the general formulas (1), (2), It can be obtained by subjecting the compound providing the unit represented by (3) to a polycondensation reaction batchwise or continuously.

Specifically, it can be obtained by (i) a two-stage polymerization method, (ii) a one-stage polymerization method, or (iii) a prepolymer method comprising a pre-polycondensation step and a post-polycondensation step.
(I-1) Two-stage polymerization method: pre-polycondensation step First, the inside of the reactor is purged with nitrogen, and then a compound that provides units represented by the general formulas (1), (2), and (3) is mixed. When mixing, a solvent in which the above three components are both soluble may be used. Solvents in which the three components are both soluble include aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as trichlorobenzene, phenol solvents such as phenol and cresol, 2,2,2-tri A halogenated alcohol solvent such as fluoroethanol can be exemplified, and a preferable solvent is toluene. The temperature in the reactor charged in this way is increased under normal pressure while stirring and / or nitrogen bubbling. The reaction temperature is preferably controlled so that the final temperature reaches 80 to 150 ° C., preferably 100 to 140 ° C. The reaction time at the final temperature reached is 3-6 hours.
(I-2) Two-stage polymerization method: post-polycondensation step In order to further increase the molecular weight, the polymer produced in the pre-polycondensation step is gradually heated in the reactor under normal pressure. In the temperature rising process, the temperature finally reaches the final polycondensation step, that is, preferably 80 to 150 ° C., and finally reaches a temperature range of preferably 220 ° C. or more and 280 ° C. or less, more preferably 230 ° C. or more and 270 ° C. or less It is preferable to carry out the reaction preferably for 1 to 8 hours, more preferably 2 to 6 hours including the temperature rising time. Furthermore, in the post-polymerization step, polymerization can be performed under reduced pressure as necessary. The preferable final pressure in the case of carrying out the vacuum polymerization is less than 0.1 MPaG to 13.3 PaG.
(Ii) One-stage polymerization method First, a compound that provides the units represented by the general formulas (2) and (3) is placed in a reaction vessel and purged with nitrogen, and then the temperature is raised to the primary reaction temperature under normal pressure or pressurized conditions. The primary reaction temperature is preferably 100 ° C. to 200 ° C., more preferably 120 ° C. to 180 ° C., from the viewpoint of preventing thermal decomposition of the compound that provides the unit represented by the general formula (1). Thereafter, at the primary reaction temperature, a compound that provides a unit represented by the general formula (1) is injected into the reaction vessel under normal pressure or pressurized conditions, and a polycondensation reaction is started.

After starting the polycondensation reaction, the temperature is raised to the secondary reaction temperature while maintaining normal pressure or pressurized conditions. The secondary reaction temperature is preferably 160 ° C. or higher and 270 ° C. or lower, more preferably 180 ° C. or higher and 260 ° C. or lower, from the viewpoint of uniformly melting and kneading the product. The pressure in the reaction vessel until reaching the secondary reaction temperature is adjusted to 0.1 to 1 MPaG. After reaching the secondary reaction temperature, the pressure is released and the temperature is raised to the tertiary reaction temperature. The tertiary reaction temperature is preferably 200 ° C. or higher and 280 ° C. or lower, more preferably 220 ° C. or higher and 270 ° C. or lower, from the viewpoint of preventing thermal decomposition of the compound providing the unit represented by the general formula (3). After reaching the tertiary reaction temperature, the polycondensation reaction is continued for 0.5 to 30 hours under a normal pressure nitrogen stream or reduced pressure as necessary. A preferable final pressure in the case of carrying out the vacuum polymerization is 0.1 MPaG to 13.3 PaG.
(Iii) Prepolymer method The compound which provides the unit represented by General formula (1), (2) by the procedure of said (i-1) two-stage polymerization method: a pre-polycondensation process or (ii) one-stage polymerization method. React to obtain a prepolymer. Next, a compound providing a unit represented by the general formula (3) and a prepolymer produced by the procedure of the above (i-1) two-stage polymerization method: post-polycondensation step or (ii-1) one-stage polymerization method React.

  In the production of the polyamide elastomer (X), there is no particular limitation on the method of charging the raw material (compound), but from the viewpoint of not reducing the crystallinity of the polyamide component and the function and performance as an elastomer, from the raw material charging ratio The calculated polyamide unit (A) is preferably 10 to 95% by weight, more preferably 30 to 80% by weight, based on the total amount of the polyamide elastomer, and the polyether diamine unit (B) calculated from the raw material charge ratio is The total amount of polyamide elastomer is preferably 2 to 87% by weight, more preferably 7 to 78% by weight. Further, the total number of moles of amino terminal groups in the total amount of the compound that provides the polyamide unit (A) and the polyetherdiamine unit (B) is the same as the total number of moles of the acid end groups of the compound that provides the polyamide unit (A). It is desirable to do.

  The production of the polyamide elastomer (X) can be carried out batchwise or continuously. A batch reactor, a single- or multi-tank continuous reactor, a tubular continuous reactor, etc. can be used alone or as appropriate. They can be used in combination.

  In the production of polyamide elastomer (X), monoamines such as laurylamine, stearylamine, hexamethylenediamine, and metaxylylenediamine, or diamine, acetic acid, Monocarboxylic acids such as benzoic acid, stearic acid, adipic acid, sebacic acid and dodecanedioic acid, or dicarboxylic acids can be added. The amount used is appropriately added so that the relative viscosity (ηr) of the finally obtained elastomer is in the range of 1.0 to 4.0 (1.0 g / dl trifluoroacetic acid solution, 25 ° C.). Is preferred.

  In the production of the polyamide elastomer (X), the addition amount of the monoamine and diamine, monocarboxylic acid, dicarboxylic acid and the like is preferably in a range where the properties of the obtained polyamide elastomer are not inhibited.

  In the production of the polyamide elastomer (X), phosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc. are used as a catalyst as required, and phosphorous acid, hypophosphorous acid, and the like for the effect of both the catalyst and the heat-resistant agent. Inorganic phosphorus compounds such as 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 amount.

Polyamide elastomer (X) is a plasticizer, impact modifier, heat-resistant agent, other thermoplastic resin, ultraviolet absorber, light stabilizer, antioxidant, antistatic agent, lubricant, slip as long as its properties are not hindered. Agents, crystal nucleating agents, tackifiers, sealability improvers, antifogging agents, mold release agents, pigments, dyes, fragrances and the like can be added.
[Laminate]
The laminate of the present invention is preferably a laminate comprising a layer containing the polyamide elastomer (X) of the present invention and a layer containing a diene rubber.

  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). Among 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.

  Diene rubbers include vulcanizing agents (radical generators, sulfur vulcanizing agents, sulfur-containing organic compounds, sulfates, etc.), vulcanization accelerators, fillers, plasticizers, softeners, vulcanizing agents as commonly used additives. Sulfur activators, co-vulcanizers, pigments, antioxidants, tackifiers, processing aids, lubricants, colorants, foaming agents, dispersants, 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.

  The laminate of the present invention has one or more layers containing a polyamide elastomer (X) and a layer containing a diene rubber sheet. 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 laminate of the present invention may be any substrate, for example, thermoplastic resin, paper, metal-based material, unstretched, uniaxially or biaxially stretched plastic film or sheet, woven fabric, non-woven fabric, metallic cotton, wood, etc. It is also possible to laminate.

  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 laminated body of the present invention includes (1) a method of simultaneously molding each layer, (2) a method of molding and bonding the layers, and (3) a method of stacking layers while further layering (tandem method). Or a combination thereof.

  The layer containing the polyamide elastomer (X) and the layer containing the 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. Good.

  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 layer containing the polyamide elastomer (X) (X layer) and the layer containing the diene rubber (Y layer) in the 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 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 / Examples thereof include an adhesive layer / base material layer, base material layer / adhesive layer / Y layer / X layer / Y layer / adhesive layer / base material layer, and the like.

  The base layer is obtained from inorganic fibers made from natural / synthetic fibers, glass / ceramics, etc .; films, sheets, membranes and molded articles obtained from other polymer materials, excluding the polymers of the X layer and Y layer Woven fabric, knitted fabric, braided fabric, non-woven fabric, etc .; glass, metal, ceramics, coating film, paper, etc .; leather etc. can be used.

  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 and the Y layer of the laminate of the present invention is preferably 5 N / mm or more, more preferably 8 N / mm or more.

  Since the polyamide elastomer (X) has an excellent heat-welding property to the diene rubber, the polyamide elastomer (X) has a strong adhesive strength between the diene rubber and the polyamide elastomer (X). Because of its high heat resistance and chemical resistance, the laminate of the present invention is a tire member, various vibration absorbing members, door lock members, automobile parts such as radiator mounts, sports shoes, work shoes, shoes such as shoe soles, etc. It can be advantageously used for various industrial members such as automobile parts and vibration-proof rubber.

[Physical property measurement, molding, evaluation method]
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Measurement, molding, and evaluation were performed by the following methods.

(1) Relative viscosity (ηr)
The relative viscosity was measured at 25 ° C. with an Ostwald viscometer using a trifluoroacetic acid solution having a polyamide elastomer concentration of 1.0 g / dl.

(2) Melting point (Tm)
The melting point was measured under a nitrogen atmosphere using a PYRIS Diamond DSC manufactured by PerkinELmer.

  The obtained polyamide elastomer is heated from 30 ° C. to 280 ° C. at a rate of 10 ° C./min (referred to as a temperature rising first run), held at 280 ° C. for 3 minutes, and then up to 30 ° C. at a rate of 10 ° C./min. The temperature was lowered (referred to as a first temperature-decreasing run), and then the temperature was raised to 280 ° C. at a rate of 10 ° C./min (referred to as a temperature-rising second run). The endothermic peak temperature of the elevated temperature second run was defined as the melting point (Tm).

(3) Film formation Polyamide elastomer film formation was performed by the following method using Toho Machinery's vacuum press TMB-10.

  The obtained polyamide elastomer was heated and melted at 240 to 270 ° C. for 3 minutes in a reduced pressure atmosphere of 500 to 700 PaG, then pressed at 10 MPaG for 1 minute, and then the reduced pressure atmosphere was returned to normal pressure. And cooled for 3 minutes to obtain a film having a thickness of 0.25 mm and 1 mm.

(4) Elastic modulus From the film of 0.25 mm thickness obtained in the above (3), a JIS tensile No. 8 dumbbell was punched out to produce a dumbbell specimen. The dumbbell test piece was subjected to a tensile test using TENSILON RTA-500 manufactured by ORIENTEC. In a 23 ° C. environment, a tensile test was performed under the conditions of a distance between chucks of 30 mm and a tensile speed of 30 mm / min, and the elastic modulus was calculated from the slope of the stress-strain line between elongations of 0.5% and 2%.

(5) Extension recovery rate Dumbbell test pieces were prepared in the same manner as in (4) above, and the extension recovery rate was measured with a tester of TENSILON RTA-500 manufactured by ORIENTEC. Residual strain A when the stress becomes zero when the distance between chucks is 30 mm and the tensile speed is 100 mm / min, and the tension is returned to the original speed at the same speed when stretched by 3.2 mm in a 23 ° C. environment. (Mm) was determined. The elongation recovery rate was calculated by substituting the obtained residual strain A into the following formula (1).

(6) Durability test for each liquid The 1 mm thick film obtained in (3) above was cut into a square with a side of 40 mm, and the cut film was converted into each liquid at 23 ° C. (ion-exchanged water, methanol, 10% by weight). (Nitric acid, 10% by weight hydrochloric acid), the film was taken out every predetermined time, and the weight of the film was measured. When the rate of increase in the film weight lasts three times in the range of 0.2%, it is judged that the absorption of the liquid into the polyamide resin film has reached saturation, and when the film reaches the weight and saturation before immersion. The weight change rate (%) was calculated from the weight of the film.

(7) Laminate The rubber compounding components shown in Table 1 were kneaded at 90 ° C. for 4.5 minutes using a Banbury mixer in the ratio shown in Table 1.

  The kneaded product was adjusted to 1 mm in thickness with a press at 165 ° C., 10 MPa, and 8 minutes.

  The 1 mm film obtained in the above (3) is placed on the lower side, and the obtained diene rubber molded product is placed on the upper side, and the temperature of the upper mold is set to 200 with a vacuum press TMB-10 manufactured by Toho Machinery Co., Ltd. C., the temperature of the lower mold was set to 260.degree. C., and the laminate was pressed at 20 MPa for 1 minute.

  The obtained laminate was cut to a width of 10 mm and a length of 15 cm to obtain a test piece for an adhesive strength test.

(8) Adhesive strength test The test piece obtained in (7) above was subjected to a T-type peel test under the conditions of a tensile speed of 30 mm / min in a 23 ° C environment using a TENSILON RTA-500 tester manufactured by ORIENTEC. The maximum adhesive strength (N / mm) was measured.
[Production Example 1]
The inside of a 2 L separable flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, and raw material inlet was replaced with nitrogen gas, 1150 ml of dehydrated toluene, 156 g of 1,12-dodecanediamine (0.78 Mol), 91 g (0.087 mol) of XYX type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN) was charged. After this separable flask was placed in an oil bath and heated to 50 ° C., 175 g (0.87 mol) of dibutyl oxalate was charged. Next, the temperature of the oil bath was raised to 130 ° C., and the reaction was carried out for 5 hours under reflux. Note that all operations from preparation of raw materials to completion of the reaction were performed under a nitrogen stream of 50 ml / min.

10 g of the prepolymer obtained by the above operation and 0.02 g of sodium hypophosphite monohydrate were charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube. The operation of maintaining a reduced pressure of 13.3 PaG or less and then introducing nitrogen gas to normal pressure was repeated 5 times, and then transferred to a salt bath maintained at 250 ° C. under a nitrogen stream of 50 ml / min and reacted for 4 hours. Subsequently, nitrogen gas was introduced to normal pressure, then taken out from the salt bath and cooled to room temperature under a nitrogen stream of 50 ml / min to obtain a polyamide elastomer (hereinafter sometimes referred to as PAE1).
[Production Example 2]
5L equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure outlet, polymer outlet, and raw material inlet with a raw material feed pump directly connected by SUS316 piping of 1/8 inch diameter In a pressure vessel, 347 g (1.7 mol) of 1,12-dodecanediamine, 457 g (0.43 mol) of XYX type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN), sodium hypophosphite monohydrate 2.50 g of the product was charged and the inside of the pressure vessel was pressurized to 3.0 MPaG with nitrogen gas, and then the nitrogen gas was released to normal pressure to perform nitrogen substitution, and the system was heated under sealed pressure. After the primary reaction temperature (150 ° C.), 438 g (2.2 mol) of dibutyl oxalate was injected into the reaction vessel at a flow rate of 65 ml / min by a raw material feed pump. The internal pressure in the pressure vessel immediately after injection of the entire amount increased to 0.65 MPaG by 1-butanol generated by the polycondensation reaction, and the internal temperature increased to 155 ° C.

Distillation of butanol produced immediately after the injection was started, and the temperature was raised to the secondary reaction temperature (230 ° C.) while maintaining the internal pressure at 0.50 MPaG. Immediately after the internal temperature reached 230 ° C., 1-butanol produced by the polycondensation reaction was extracted from the pressure relief port. After releasing the pressure, the temperature was raised under a nitrogen stream of 260 ml / min, the temperature was raised to the tertiary reaction temperature (245 ° C.), and the temperature was maintained at 245 ° C. for 3 hours. Thereafter, the stirring was stopped, the inside of the system was pressurized to 3 MPaG with nitrogen and left to stand for 10 minutes. The extracted polyamide elastomer (hereinafter sometimes referred to as PAE2) was immediately cooled with water and recovered.
[Production Example 3]
Polymerization was conducted in the same manner as in Example 2 using 264 g (1.3 mol) of 1,12-dodecanediamine and 380 g (1.9 mol) of dibutyl oxalate, and the prepolymer was recovered.

Subsequently, the total amount of the obtained prepolymer, 595 g (0.56 mol) of XYX type triblock polyether diamine (XTJ-542, manufactured by HUNTSMAN), and 2.42 g of sodium hypophosphite monohydrate were used in Examples In the same manner as in No. 2, a 5 L pressure vessel was charged and nitrogen substitution was performed. Next, the temperature in the tank was raised to 200 ° C. under a nitrogen stream, held at 200 ° C. for 1 hour, further heated to 245 ° C. and held at 245 ° C. for 3 hours. Thereafter, the obtained polyamide elastomer (hereinafter sometimes referred to as PAE3) was extracted from the lower part of the pressure vessel, and immediately cooled and recovered with water.
[Production Example 4]
Example 2 840 g (3.9 mol) of 12-aminododecanoic acid, 45 g (0.31 mol) of adipic acid, 321 g (0.30 mol) of XYX type triblock polyether diamine (XTJ-542 manufactured by HUNTSMAN) In the same manner as above, 5 L pressure vessel was charged and nitrogen substitution was performed. Next, the inside of a tank was heated up to 180 degreeC under nitrogen stream, and after hold | maintaining at 180 degreeC for 1 hour, it heated up further to 200 degreeC and hold | maintained at 200 degreeC for 3 hours. Thereafter, the obtained polyamide elastomer (hereinafter sometimes referred to as PAE4) was extracted from the lower part of the pressure vessel, and immediately cooled and recovered with water.
[Production Example 5]
Conducted was 1042 g (4.8 mol) of 12-aminododecanoic acid, 38 g (0.26 mol) of adipic acid, 257 g (0.26 mol) of polytetramethylene glycol having a number average molecular weight Mn = 989, and 4.10 g of tetrabutyl titanate. In the same manner as in Example 2, a 5 L pressure vessel was charged and nitrogen substitution was performed. Next, the temperature in the tank was raised to 200 ° C. under a nitrogen stream, held at 200 ° C. for 4 hours, further heated to 240 ° C., depressurized, and held at 240 ° C. and 10 Pa for 3 hours. Thereafter, the pressure was restored, and the obtained polyamide elastomer (hereinafter sometimes referred to as PAE5) was extracted from the lower part of the pressure vessel, and immediately cooled and recovered with water.

  Table 1 shows the measurement results of the relative viscosity, melting point, elastic modulus and elongation recovery rate of the polyamide elastomers obtained in Production Examples 1 to 5. Each unit of the structural units in Table 1 indicates a value calculated from the raw material charge ratio. In Table 2, HS is an abbreviation for hard segment and indicates a polyamide unit, and SS is an abbreviation for soft segment and indicates a polyetherdiamine unit (B). HS / SS in Table 2 refers to the weight ratio of the polyamide unit (A) and the polyetherdiamine unit (B).

  Table 3 shows the results of the durability test for each liquid of the polyamide elastomer obtained in Production Examples 1 to 5.

[Examples 1-12, Comparative Examples 1-8]
The laminated body of the combination shown in Table 4 was created, and the peel strength of the laminated body was measured. The results are shown in Table 4.

Claims (5)

A laminate comprising a layer containing a polyamide elastomer and a layer containing a diene rubber,
The polyamide elastomer is a polyamide elastomer (X) containing a polyamide unit (A) and a polyetherdiamine unit (B),
The polyamide unit (A) includes a unit represented by the general formula (1) and a unit represented by the general formula (2),
The said polyether diamine unit (B) contains the unit represented by General formula (3), The laminated body characterized by the above-mentioned.

(Here, R1 represents a hydrocarbon molecular chain having 1 to 20 carbon atoms or an alkylene group having 1 to 20 carbon atoms.)

(Here, x and z are 1-20, and y is 4-50.)
The laminate according to claim 1, wherein the polyamide elastomer has an elongation recovery rate of 55% or more and a melting point of 200 ° C or more . The laminate according to claim 1 or 2, wherein the unit represented by the general formula (2) includes a unit derived from an aliphatic diamine component having 5 to 18 carbon atoms.   The laminate according to any one of claims 1 to 3, wherein the polyamide elastomer (X) has a relative viscosity of 1.2 to 3.0 (1.0 g / dl trifluoroacetic acid solution, 25 ° C). The laminate according to any one of claims 1 to 4, wherein the diene rubber is at least one selected from the group consisting of butadiene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, natural rubber, and isoprene rubber.