JPH1016137A - Rubber and thermoplastic elastomer laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber and thermoplastic elastomer laminate of superior flexing and cracking resistance to heat resistance deterioration properties and dynamic fatigue and also provide a pneumatic tire and a hose of the above-said laminate structure. SOLUTION: A layer composed of a rubber composition is laminated with a layer composed of a polyamide thermoplastic resin composition, an elastomer composition and a thermoplastic elastomer composition containing one or more compounds selected out of (i) halogenated copper, hindered phenol, hindered amine and aromatic amine or containing a thermoplastic elastomer composition containing (ii) a crystalline curing agent or a crystallization inhibitor.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber / thermoplastic elastomer laminate excellent in heat deterioration resistance and durability such as vibration fatigue, and a pneumatic tire and hose having the rubber / thermoplastic elastomer laminate structure. About.
More specifically, the present invention has a good balance between gas permeation resistance and flexibility possessed by itself, good heat deterioration resistance during molding of a laminate, and long-term vibration after molding. The present invention relates to the provision of a rubber / thermoplastic elastomer laminate which is excellent in flexural durability and can be used for tires, hoses and the like.

[0002]

2. Description of the Related Art A polyamide resin / rubber laminate obtained by subjecting a rubber composition to a surface treatment and coating a solution-based polyamide resin with a thickness of 500 μ or less has excellent solvent resistance and gas resistance. Japanese Patent Application Laid-Open No. Sho 59-1 shows that the rubber composition exhibits permeability, anti-migration properties of components in a rubber compound, abrasion resistance and the like.
It is disclosed by Japanese Patent Publication No. 2366 and already known.
Since such a laminate has the above-mentioned characteristics, it is suitably used for an inner liner layer of a tire, an inner tube of a hose, and the like. However, the above-mentioned polyamide resin has a problem that adhesion to rubber is substantially poor, and also has a drawback that cracks occur when repeatedly subjected to severe dynamic fatigue after lamination with rubber.

Accordingly, the present invention relates to a laminate of a thermoplastic elastomer composition and a rubber in which a polyamide-based thermoplastic resin is used as a continuous phase (matrix) and an elastomer is used as a dispersed phase (domain) instead of the polyamide-based resin. Have improved the adhesiveness and provided a material with a particularly excellent balance between gas permeability resistance and flexibility. Inadequate in terms of flex crack resistance under mechanical fatigue.

Further, in order to improve the heat resistance of the polyamide resin, copper halide, hindered phenol, hindered amine and aromatic amine are added to the polyamide resin (“Polyamide Resin Handbook”, Nikkan Kogyo Shimbun) It is known that the crystal of the polyamide resin is refined with a crystal nucleating agent. However, when a composition containing these compounds and a rubber composition are laminated on a thermoplastic elastomer composition having a polyamide resin as a continuous phase and an elastomer as a dispersed phase, extrusion molding, vulcanization, etc. of the laminate are performed. There is no known document showing the fact that both the heat deterioration resistance during molding and the heat deterioration resistance during use and the bending crack resistance are improved.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to maintain characteristics of a thermoplastic elastomer composition comprising a polyamide thermoplastic resin as a continuous phase and an elastomer as a dispersed phase, which have excellent gas permeability and flexibility. And a rubber excellent in heat cracking resistance against thermal fatigue deterioration and dynamic fatigue when used to form a laminate with the rubber composition while further increasing the heat deterioration resistance during vulcanization. -To provide a thermoplastic elastomer laminate. Another object of the present invention is to provide a pneumatic tire and a hose having a rubber / thermoplastic elastomer laminated structure excellent in the above-mentioned various properties.

[0006]

According to the present invention, according to the present invention, a polyamide-based thermoplastic resin composition is added to an elastomer composition and (i) a compound selected from copper halide, hindered phenol, hindered amine and aromatic amine. Provided is a rubber / thermoplastic elastomer laminate obtained by laminating a layer comprising a thermoplastic elastomer composition (A) containing at least one or more species and a layer comprising a rubber composition (B).

According to the present invention, there is further provided a rubber-thermoplastic elastomer laminate containing (ii) a crystal nucleating agent or a crystallization inhibitor in the thermoplastic elastomer composition (A).

According to the present invention, a layer comprising the thermoplastic elastomer composition (A) or a layer containing (ii) a crystal nucleating agent or a crystallization inhibitor in the thermoplastic elastomer composition (A) and a rubber composition Using a rubber / thermoplastic elastomer laminated structure consisting of a layer composed of the product (B), it has excellent gas permeation resistance, excellent flexibility, no thermal denaturation during molding, and heat resistance deterioration that can withstand severe use conditions Pneumatic tires and hoses are provided that have flexibility and flex crack resistance to dynamic fatigue during use.

The thermoplastic elastomer composition used for the rubber-thermoplastic elastomer laminate according to the present invention is a composition comprising a polyamide-based thermoplastic resin composition and an elastomer composition, wherein the polyamide-based thermoplastic resin composition Is a continuous phase (matrix), and at least a part of the elastomer composition is uniformly mixed as a dispersed phase (domain) in the continuous phase. The thickness may be determined as appropriate according to the balance of thickness, gas permeability resistance, flexibility, etc., but the preferred range is 10/90 to 90/10, more preferably 15/90, by weight of the polyamide-based thermoplastic resin / elastomer composition. / 85 to 90/10.

The polyamide-based thermoplastic resin has an air permeability coefficient of 25 × 10 ⁻¹² cc · cm / cm ² · sec.
・ CmHg or less, preferably 0.1 × 10 ⁻¹² to 10 × 10
^-12 cc · cm / cm ² · sec · cmHg, freon gas (HFC
The gas permeability coefficient of 134a) is 5.0 mg · mm / 24h · cm
² or less, preferably 2.0 mg · mm / 24 h · cm ² or less, and a Young's modulus of more than 500 MPa, preferably 500 to 30
Any polyamide resin of 00 MPa can be used,
As such a polyamide resin, for example, nylon 6
(N6), nylon 66 (N66), nylon 46 (N
46), nylon 11 (N11), nylon 12 (N1
2), nylon 610 (N610), nylon 612
(N612), nylon 6/66 copolymer (N6 / N6
6), nylon 6/66/610 copolymer (N6 / 66
/ 610), nylon MXD6, nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer and the like.

The elastomer may include any elastomer component having an air permeability coefficient of greater than 25 × 10 ⁻¹² cc · cm / cm ² · sec · cmHg and a Young's modulus of 500 MPa or less, or an arbitrary blend thereof, or a blend thereof. Add necessary amounts of compounding agents such as reinforcing agents, fillers, cross-linking agents, softeners, anti-aging agents, and processing aids that are generally compounded with elastomers to improve the dispersibility and heat resistance of the elastomer. The elastomer composition described above can be used.

Examples of the elastomer include diene rubbers and hydrogenated products thereof (for example, NR, IR,
Epoxy natural rubber, SBR, BR (high cis BR and low cis BR), NBR, hydrogenated NBR, hydrogenated SBR), olefin rubber (for example, ethylene propylene rubber (E
PDM, EPM), maleic acid-modified ethylene propylene rubber (M-EPM), butyl rubber (IIR), copolymer of isobutylene and aromatic vinyl or diene monomer, acrylic rubber (ACM), ionomer), halogen-containing rubber (for example, Brominated product of Br-IIR, Cl-IIR, isobutylene paramethylstyrene copolymer (Br-IP
MS), chloroprene rubber (CR), hydrin rubber (C
HC, CHR), chlorosulfonated polyethylene (CS
M), chlorinated polyethylene (CM), maleic acid-modified chlorinated polyethylene (M-CM)), silicone rubber (eg, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber), sulfur-containing rubber (eg, polysulfide) Rubber), fluorine rubber (for example, vinylidene fluoride rubber, fluorine-containing vinyl ether rubber, tetrafluoroethylene-propylene rubber, fluorine-containing silicon rubber, fluorine-containing phosphazene rubber), thermoplastic elastomer (for example, styrene-based elastomer) Olefin-based elastomers, polyester-based elastomers, urethane-based elastomers, polyamide-based elastomers).

According to the present invention, the thermoplastic elastomer composition comprising the above-mentioned polyamide-based thermoplastic resin composition and the elastomer composition is used in an amount of (i) halogenated with respect to 100 parts by weight of the polyamide-based thermoplastic resin composition. 0.001 to 1.0 part by weight, preferably 0.005 to 0.5 part by weight, of one or more compounds selected from copper, hindered phenol, hindered amine and aromatic amine, or (i) ), And (ii) a nucleating agent or a crystallization inhibitor in a total amount of (i) and (ii) of 0.001 to 1.0 part by weight, preferably 0.01 to 0.1 part by weight.
Add 5 parts by weight. If the amount is too small, the rubber / thermoplastic elastomer laminate cannot exhibit the desired heat deterioration resistance and flex crack resistance. Conversely, if the amount is too large, a certain effect or more cannot be achieved. .

The copper halide in the additive (i) includes, for example, cuprous iodide, cupric iodide, cuprous chloride, cupric chloride, cuprous bromide, and copper bromide. Cupric, cuprous and cupric fluorides, and mixtures of these copper halide compounds with potassium halides and the like, and hindered phenols such as n-octadecyl-3-
(4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,3 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxyphenyl)
Benzylbenzene, 1,3,5-tris (4-hydroxy-3,5-di-t-butylbenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) -trione, ethylene glycol- Bis- [3,3-bis (3′-t-
Butyl-4'-hydroxyphenyl) butyrate], tetrakis [methylene-3 (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] methane, 3,
9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,
1-dimethylethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-
Hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxycinnamamide), N, N'-bis [3- (3
5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2'-oxamido-bis-ethyl-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2 '-Methylene-bis (4-methyl-6-t-butylphenol) terephthalate, 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, , 2'-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 2,2-bis [4-
{2- (3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)} ethoxyphenyl] propane and the like.

Examples of the hindered amine include dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate polycondensate and poly [{6- (1,1 , 3,3) -Tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl {2,2,6,6-tetramethyl-4-piperidyl) imino {hexamethylene} (2 2,6,6) -Tetramethyl-4-piperidyl) imino}], 2- [3,
5-di-t-butyl-4-hydroxybenzyl) -2-
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butylmalonate, N, N'-bis (3-aminopropyl) ethylenediamino-2,4-bis [N-butyl-N -(1,2,2,6,6-pentamethyl-4-
Piperidyl) amino] -6-chloro-1,3,5-triazine condensate and the like;
β-naphthylamine, phenyl-α-naphthylamine,
1,2-dihydro-2,2,4-trimethylquinoline,
β-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, N-N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-
Phenylenediamine, diallyl-p-phenylenediamine, N-phenyl-N '-(1,3 dimethylbutyl)-
p-phenylenediamine and the like.

In the additive (ii), the crystal nucleating agent includes inorganic fine particles (eg, talc, silica, graphite), metal oxides (eg, magnesium oxide,
Aluminum oxide), oligomer (for example, caprolactam dimer), high melting point nylon (for example, nylon 6, nylon 66, nylon 6.66 having a melting point of 200 ° C. or higher)
Nylon 6T, Nylon 22, Nylon 46), carboxylic acid (eg, adipic acid, benzoic acid), carboxylic acid amide (eg, succinamide, malonamide, phthalamide), metal carboxylate (eg, sodium adipate, sodium benzoate) And higher alcohol waxes (eg, cetyl alcohol, stearyl alcohol, olein alcohol) and the like. As the crystallization inhibitor, lithium chloride, lithium bromide, lithium fluoride and the like are effectively used.

In the thermoplastic elastomer composition used in the present invention, when the compatibility between the specific polyamide-based thermoplastic resin and the elastomer component is different from each other, it is preferable to further compatibilize the two with a suitable compatibilizer. Is preferred. Furthermore, by mixing the compatibilizing agent, the interfacial tension between the polyamide-based thermoplastic resin and the elastomer component is reduced, and as a result, the particle size of the elastomer forming the dispersed phase becomes fine. It will be more effectively expressed. Such a compatibilizer is generally a copolymer having a structure of both or one of a polyamide-based thermoplastic resin and an elastomer component, or an epoxy group, a carbonyl group capable of reacting with a polyamide-based thermoplastic resin or an elastomer component. , A copolymer having a halogen group, an amino group, an oxazoline group, a hydroxyl group and the like. These may be selected according to the type of the polyamide-based thermoplastic resin and the elastomer component to be mixed, and those usually used include styrene / ethylene / butylene block copolymer (SEBS) and its maleic acid-modified product, EPDM, Examples include EPDM / styrene or EPDM / acrylonitrile graft copolymers and their maleic acid-modified products, styrene / maleic acid copolymers, and reactive phenoxines. The amount of such a compatibilizer is not particularly limited, but is preferably 0.5 to 10 parts by weight based on 100 parts by weight of the polymer component (total of the polyamide-based thermoplastic resin and the elastomer component).

The material of the rubber layer in the rubber-thermoplastic elastomer laminate according to the present invention is not particularly limited, and may be any rubber material conventionally used as a rubber material for tires or hoses. Such rubbers include, for example, NR, IR, BR, SBR, NB
R and other diene rubbers, butyl rubbers, halogenated butyl rubbers, halides of isobutylene-P-methylstyrene copolymer, ethylene-propylene copolymer rubber (EP
M), ethylene-propylene-diene terpolymer rubber (EPDM), chlorine rubber such as CR, CHR, CHC, CM, CSM, styrene elastomer, etc., reinforcing agent such as carbon black, softener such as process oil And a rubber composition to which a compounding agent such as a plasticizer, a vulcanizing agent, a vulcanizing aid, an antioxidant, and a processing aid are added.

In the method for producing the thermoplastic elastomer composition (A) of the present invention, the polyamide thermoplastic resin and the aforementioned elastomer component (unvulcanized product in the case of rubber) are melted in advance by a twin-screw kneading extruder or the like. During or before kneading, one of the compounds (i) selected from the group consisting of copper halide, hindered phenol, hindered amine and aromatic amine
Add seed or more. If necessary, the nucleating agent or crystallization inhibitor (ii) is added simultaneously or sequentially with (i). Then, the elastomer component and only the component (i) or the components (i) and (ii) are dispersed in the polyamide resin forming the continuous phase (matrix). When vulcanizing the elastomer component, a vulcanizing agent and, if necessary, a vulcanizing aid may be added under kneading to dynamically vulcanize the elastomer component. Various compounding agents (excluding vulcanizing agents and vulcanizing auxiliaries) to the polyamide-based thermoplastic resin or the elastomer component may be added during the above kneading, but they should be mixed before kneading. Is preferred. The kneader used for kneading the polyamide-based thermoplastic resin component and the elastomer component and the additive component (i) or the components (i) and (ii) is not particularly limited, and a screw extruder, a kneader, Banbury mixer, 2
A shaft kneading extruder and the like can be mentioned. Among them, a twin-screw kneading extruder is used for kneading a polyamide-based thermoplastic resin component, an elastomer composition component, and an additive component (i), or components (i) and (ii), and dynamic vulcanization of an elastomer component. Is preferred. Furthermore, you may knead sequentially using two or more types of kneaders. As a condition for the melt-kneading, the temperature may be at least the temperature at which the polyamide-based thermoplastic resin component melts. The shear rate during kneading is 1000 to 750.
It is preferably 0 sec ^-1 . The total kneading time is preferably 30 seconds to 10 minutes, and when a vulcanizing agent is added, the vulcanization time after the addition is preferably 15 seconds to 5 minutes.

The thermoplastic elastomer composition according to the present invention may further comprise a filler (calcium carbonate, titanium oxide, alumina, clay, etc.) and a reinforcing agent such as carbon black, white carbon, etc., which are generally added to the polymer compound. A softener, a plasticizer, a processing aid, a pigment, a dye, an antioxidant, and the like can be arbitrarily compounded as long as the requirements for the air (gas) transmittance and the Young's modulus are not impaired. Further, the elastomer component can dynamically vulcanize the elastomer component at the time of mixing with the thermoplastic resin. The vulcanizing agent, vulcanization aid, vulcanization conditions (temperature, time) and the like for dynamically vulcanizing the elastomer component may be appropriately determined depending on the composition of the elastomer component to be added, and are particularly limited. Not something.

As the vulcanizing agent, a general rubber vulcanizing agent (crosslinking agent) can be used. Specifically, ionic vulcanizing agents include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenamide (CBS), N
-Oxydiethylene benzothiazyl-2-sulfenamide, Nt-butyl-2-benzothiazolesulfenamide, 2- (thymolporinyldithio) benzothiazole, and the like. About 4 phr [parts by weight per 100 parts by weight of the rubber component (polymer)] can be used. Examples of the organic peroxide vulcanizing agent include benzoyl peroxide, t-butyl hydroperoxide, 2,4-bichlorobenzoyl peroxide, and 2,5-dimethyl-2,5-di (t-butyl). Peroxy) hexane, 2,5-dimethylhexane-2,
Examples thereof include 5-di (peroxyl benzoate), and for example, about 1 to 20 phr can be used. Further, examples of the phenol resin-based vulcanizing agent include brominated alkylphenol resins and mixed cross-linking systems containing a halogen donor such as tin chloride and chloroprene and an alkylphenol resin. Can be. In addition, zinc white (about 5 phr), magnesium oxide (about 4 phr), litharge (10 to 20 phr)
phr), p-quinonedioxime, p-dibenzoylquinonedioxime, tetrachloro-p-benzoquinone,
Poly-p-dinitrosobenzene (about 2 to 10 phr),
Methylene dianiline (about 0.2 to 10 phr) can be exemplified.

[0022] If necessary, a vulcanization accelerator may be added. Examples of the vulcanization accelerator include general vulcanization accelerators such as aldehyde / ammonia, guanidine, thiazole, sulfenamide, thiuram, dithioate, and thiourea, for example, About 2 phr can be used. Specifically, hexamethylenetetramine or the like is used as the aldehyde / ammonia vulcanization accelerator, diphenylguanidine is used as the guanidine vulcanization accelerator, and dibenzothiazyl disulfide is used as the thiazole vulcanization accelerator. DM), 2-mercaptobenzothiazole and its Zn salt, cyclohexylamine salt, etc., as sulfenamide-based vulcanization accelerators, cyclohexylbenzothiazylsulfenamide (CBS), N-oxydiethylenebenzothiazyl-2- Examples of thiuram-based vulcanization accelerators such as sulfenamide, Nt-butyl-2-benzothiazolesulfenamide, 2- (thymopolynyldithio) benzothiazole and the like include tetramethylthiuram disulfide (TMTD), tetraethyl Thiuram disulfide, tetrame Le monosulfide (TMTM), dipentamethylenethiuram tetrasulfide and the like, as the dithio acid salt-based vulcanization accelerator,
Zn-dimethyldithiocarbamate, Zn-diethyldithiocarbamate, Zn-di-n-butyldithiocarbamate, Zn-ethylphenyldithiocarbamate, T
e-diethyldithiocarbamate, Cu-dimethyldithiocarbamate, Fe-dimethyldithiocarbamate,
Examples of thiourea-based vulcanization accelerators such as pipecoline pipecolyl dithiocarbamate include ethylene thiourea and diethyl thiourea. As a vulcanization accelerating auxiliary, a general rubber auxiliary may be used in combination, for example, zinc white (about 5 phr), stearic acid, oleic acid and Zn salt thereof (about 2 to 4 phr). Etc. can be used.

The thermoplastic elastomer composition (A) prepared by the above method is then formed into a film by extrusion or calendering. The method of forming a film may be a method of forming a normal thermoplastic resin or thermoplastic elastomer into a film.

The thin film thus obtained has a structure in which at least a part of the elastomer component is dispersed as a discontinuous phase (domain) in a continuous phase (matrix) of a polyamide-based thermoplastic resin component. (I) or components (i) and (ii) are in a state of being uniformly dispersed in the continuous phase and the discontinuous phase. By taking the dispersion structure in such a state, it is possible to impart a balance between flexibility and gas permeation resistance to the film, and since the elastomer component is dispersed and crosslinked, the heat distortion resistance is improved, and the solvent resistance is improved.・ In addition to the improvement of water resistance, the addition of the additive component (i), the nucleating agent, and the crystallization inhibitor (ii) improves the heat deterioration resistance and provides good chemical stability. It is possible to obtain effects such as improvement, and because the polyamide-based thermoplastic resin covers the dispersed phase of the elastomer component as a continuous phase, processing of the polyamide-based thermoplastic resin becomes possible, so that a normal resin molding machine, That is, it can be formed into a film by extrusion molding or calendar molding.

An example of a method for manufacturing a pneumatic tire having an air permeation preventing layer comprising a thin film of the thermoplastic elastomer composition (A) according to the present invention will be described below.
The thermoplastic elastomer composition (A) previously kneaded as described above is extruded into a thin film having a predetermined width and thickness, and the thin film is attached to a cylinder on a tire molding drum. The members used for normal tire production, such as a carcass layer, a belt layer, and a tread layer made of unvulcanized rubber, are sequentially laminated thereon, and the drum is pulled out to obtain a green tire. Next, by heating and vulcanizing this green tire according to a conventional method,
A lightweight pneumatic tire having desired heat deterioration resistance and flex crack resistance can be manufactured. In addition, also when providing an air permeation prevention layer on the outer peripheral surface of a carcass layer, it can be performed according to this. The material of the rubber layer to which the air permeation preventing layer according to the present invention is adhered is not particularly limited, and any rubber material conventionally used as a rubber material for tires (for example, NR, IR, BR, SBR, etc.) A rubber composition comprising a diene rubber, a halogenated butyl rubber, an ethylene-propylene copolymer rubber, a styrene elastomer or the like, and a compounding agent such as carbon black, process oil, or a vulcanizing agent.

An example of a method for manufacturing a hose having a gas permeation preventing layer comprising a thin film of the thermoplastic elastomer composition (A) according to the present invention will be described. First, the thermoplastic kneaded and prepared as described above is first described. Using the pellets of the elastomer composition (A), the thermoplastic elastomer composition (A) is extruded by a resin extruder by a resin extruder by a crosshead extrusion method onto a mandrel to which a release agent has been previously applied to form an inner tube. Further, the other thermoplastic elastomer composition of the present invention or the general thermoplastic elastomer composition is extruded using an extruder for resin on the inner tube, or an unvulcanized rubber composition is extruded with an extruder for rubber to form an outer layer of the inner tube. It may be formed. Next, an adhesive is applied to the inner tube as needed, and applied by spraying or the like. Furthermore, a braiding machine is used to braid a reinforcing thread or a reinforcing steel wire on the inner tube. After an adhesive is applied on the reinforcing layer for adhesion to the outer tube as necessary, the rubber composition is similarly extruded by a crosshead rubber extruder to form an outer tube. When the mandrel is pulled out after the last vulcanization, the hose of the present invention is obtained. Although the mandrel is used in the above manufacturing method, the hose can be manufactured without using a mandrel by a normal method of manufacturing a rubber / resin composite hose. The hose of the present invention has at least an inner tube, a reinforcing layer, and an outer tube, and the inner tube is further composed of an inner layer and an outer layer as necessary. The inner tube may be further multi-layered or a stress crack preventing layer may be provided.

[0027]

EXAMPLES Hereinafter, the present invention will be further described with reference to examples, but it goes without saying that the scope of the present invention is not limited to these examples.

Examples 1 to 5 and Comparative Examples 1 and 2 (1) First, samples are prepared using the compounding ratios indicated by I to VII in Table 1 below. Each of the nylon resin pellets and the compatibilizer are charged from the first input port of the twin-screw kneading extruder. After melt-kneading, the rubber component pellets are input from the second input port, and the rubber component is finely dispersed in the nylon resin. After the dispersion, 0.5 parts by weight of zinc white, 2.0 parts by weight of stearic acid, and 1.0 part by weight of zinc stearate are charged as a crosslinking system with respect to 100 parts by weight of the elastomer from the third inlet, The rubber component was dynamically crosslinked to fix the dispersion of the rubber phase. Next, copper iodide, Irganox 1010, Tinuvin 144, a crystal nucleating agent A, a crystal nucleating agent B, a crystallization inhibitor C, and the like are charged from the fourth charging port. The obtained thermoplastic elastomer composition was extruded into a strand, cooled with water, and then pelletized with a resin pelletizer. next,
The pellets were formed into a film having a width of 400 mm and a thickness of 0.20 mm using a resin single screw extruder having a diameter of 40 mm and a T-die.

[0029]

[Table 1]

(2) On the other hand, kneading is carried out with a rubber Banbury kneader using the compounding ratio shown in Table 2 below. Each rubber polymer was put into a Banbury kneader, kneaded for 1 minute, and then each oil was added and kneaded for another 1 minute. Raise the ram, invert the kneaded material inside, lower the ram again, knead for another 2 minutes, add and knead the kneaded rubber composition with a rubber roll, add a vulcanizing system, each 2mm unvulcanized rubber sheet It was created.

[0031]

[Table 2]

(3) A urethane-based adhesive is applied to the rubber sheet (150 mm × 150 mm × 2 mm) prepared in the above (2), and the film prepared in the above (1) is bonded thereto, and the rubber composition and the heat A laminate of a plastic elastomer was obtained. This laminate was pressed with a small hand press at a press temperature of 18
It pressed at 0 degreeC, processing time for 10 minutes, and press pressure of 2.3 Mpa.

(4) A 360 mm width was cut out from the film prepared in the above (1), attached to a tire forming drum, and the splice was joined with a commonly used phenol resin adhesive. Next, a carcass on this film,
Tire members such as side, belt and tread were laminated and inflated to produce a green tire. This green tire was vulcanized at 185 ° C. for 15 minutes at a pressure of 2.3 MPa to finish a tire having a tire size of 165SR13.

(5) Using the film prepared in (1) above, the breaking strength and breaking elongation of the thermoplastic elastomer composition were measured. Next, a heat resistance evaluation test after vulcanization was performed using the laminate prepared in the above (3). Further, a durability running test of the tire was performed using the tire manufactured in the above (4).

The test measurement method and evaluation method used for these tests are as follows.

Breaking strength, breakage of thermoplastic elastomer material
The elongation at break was in accordance with JIS K6251 “Vulcanized rubber tensile test method”. The test piece was prepared by subjecting the film or sheet sample prepared in each of the above examples (1) to J parallel to the extrusion direction during extrusion molding.
I punched with IS3 dumbbell. Breaking strength and breaking elongation are determined from the obtained stress-strain curve.

Breakage of vulcanized thermoplastic elastomer material after vulcanization
Retention of strength and elongation The laminate prepared in each of the above examples (3) was treated with toluene for 24 hours.
After soaking for a period of time, the thermoplastic elastomer film is peeled off. The peeled thermoplastic elastomer film is punched out with a No. 3 dumbbell, and a tensile test is performed with an autograph. The breaking strength and the retention of elongation are determined by the following equations.

Endurance running test of tire Using a 165SR13 steel radial tire (rim 13 × 4 1 / 2-J) produced in each of the above examples (4), a load equivalent to four passengers in a 1500 cc class passenger car at an air pressure of 200 kPa. (65 kg / person) and drive 20,000 km on an actual road. After running, the tire is detached from the rim, and the liner layer on the inner surface of the tire is visually observed. If the liner layer has wrinkles that can be visually observed with cracks, or if the liner layer has peeled or lifted, it is judged as rejected. The purpose of this test is to comprehensively evaluate the strength deterioration, adhesion deterioration, and the like of the liner layer using an actual vehicle.

The results obtained are shown in Table 3 below.

[Table 3]

Examples 6 to 10 and Comparative Examples 3 and 4 (1) The only difference is that the rubber composition layer in the rubber / thermoplastic elastomer laminate structure is composed of rubber composition B. The method for preparing the test piece of the elastomer composition is the same as that described in (1) to (3) in Examples 1 to 5 and Comparative Examples 1 and 2.

(2) A hose test piece was prepared as follows. Using a resin extruder having a crosshead structure, a 150 μm tube of the thermoplastic elastomer compositions I to VII of Table 1 as the inner layer of the inner tube was placed on a 9 mm outer diameter nylon 11 mandrel previously coated with a release agent. After extruding with an inner diameter of 2 mm, the butyl rubber composition B was extruded to a thickness of 2 mm using a rubber extruder. Next, using a braiding machine, the dipped polyester fiber (Toray Co., Ltd., Tetron 1500 / d) is braided,
A reinforcing layer was formed. Further, using a rubber extruder, the butyl rubber composition B was extruded and molded, then double-wrapped with a nylon wrapping tape, and vulcanized under pressure at 153 ° C. for 60 minutes in a vulcanizing can. Was removed and the mandrel was pulled out to obtain a low permeability hose.

(3) A heat resistance evaluation test after vulcanization was performed using a test piece of the thermoplastic elastomer composition prepared in the above (1). Further, using the hose prepared in the above (2), tests for flexibility, HFC134 gas permeability and impulse durability of the hose were performed.

The breaking strength and breaking elongation of the thermoplastic elastomer materials used in these tests, and the test methods for their retention were the same as those used in Examples 1 to 5 and Comparative Examples 1 and 2. Test methods and evaluation methods for other hoses are as follows.

A method of measuring hose flexibility is to measure a bending force by bending a hose along an arc having a predetermined radius. The bending radius is 10 times the outer diameter of the hose (10
The measurement is started from D), and the bending force is sequentially measured up to three times (n = 2). From the curve obtained by plotting the relationship between the bending force and the bending radius obtained as a result, a numerical value at a specified radius (4 times) is read. Generally, the flexibility of conventional rubber hose is
It is at a level of 2.0 kgf, and some hoses having a resin tube structure are at a level of 6 to 7 kgf. In the case of a hose having such a resin tube structure, when the hose is mounted on a device in a narrow space such as an engine room, the workability is obviously poor, and empirically, the bending force is 3.5 kg.
If it is less than f, workability will be good. Also, the vibration absorption has a correlation with the flexibility, but this relationship is non-linear, and when the bending force is about 3.5 kgf or more, the reaction force sharply increases and the vibration absorption becomes extremely poor. Therefore, the bending force of the hose is preferably 3.5 kgf or less, more preferably 2.0 kgf or less.

Measuring method of gas permeability of hose JRA200 (standard of Japan Refrigeration and Air Conditioning Industry Association)
Same as 1. A refrigerant (HFC134a) is supplied to a fitting assembly hose having a hose length of 0.45 m and a hose inner volume of 1 cm ^3.
0.6 ± 0.1 gram per unit. 9 at 100 ° C
It is left for 6 hours, the weight loss (gas permeation amount) between 24 hours and 96 hours is measured, and the numerical value is converted to gf / m / 72 hours. Conventionally, the gas leak rate of rubber hose is 20-25gf / m
/ 72 hours, and the refrigerant replacement cycle of the rubber hose is about 2 years. On the other hand, a replacement cycle of 10 years is required for maintenance-free operation. Therefore, for maintenance-free operation, regardless of the type of gas,
It is necessary that the gas leakage amount is 5 gf / m / 72 hours or less.

Hose Impulse Test An impact pressure test (impulse test) in accordance with JIS K6375 7.7 was conducted. The test oil is JIS K
Using two types of mineral oils defined in 2213 (turbine oil), a rectangular wave having a maximum pressure of 200 kgf / cm ² was repeatedly applied at an oil temperature of 93 ° C., and the number of days until breakage was measured. In addition, the test was terminated after 200,000 times when the impact pressure was applied up to 200,000 times and the material was not broken due to the deterioration crack of the inner layer material of the inner tube.

The results obtained are shown in Table 4 below.

[Table 4]

According to the results shown in Tables 3 and 4 above,
Thermoplastic elastomer composition using nylon 6/66 alone or nylon 6/66 and nylon 11 as the continuous phase thermoplastic resin and modified butyl (bromide of isobutylene-P-methylstyrene copolymer) as the elastomer component in the dispersed phase The compositions I to V in which a heat-resistant degrading agent (i) alone, a nucleating agent and a crystallization inhibitor are used in combination, and those using them on the inner surfaces of tires and hoses are NR / SBR rubber compositions and For tires using the same, good retention of physical properties after vulcanization and tire durability (to prevent the occurrence of cracks on the inner surface of the tire) can be obtained, and similarly good fringe hose based on IIR / chlorinated butyl can be obtained. It can be seen that the retention of physical properties after sulfurization, the flexibility of the hose, gas permeability, and impulse resistance can be obtained.

[0049]

As described above, according to the present invention,
Laminating the thermoplastic elastomer composition as a continuous phase using a polyamide thermoplastic resin as a continuous phase while maintaining the excellent balance between gas (air) permeability and flexibility of the thermoplastic elastomer composition itself using the elastomer composition as a dispersed phase. Since it is possible to obtain a thermoplastic elastomer composition having good heat deterioration resistance during body molding and excellent long-term flex crack resistance after molding, it can be used for a tire and hose laminate structure. Thereby, it is possible to provide a tire, a hose, and the like having gas (air) resistance and flexibility, and having excellent heat deterioration resistance and dynamic durability.

Claims (7)

[Claims] 1. A thermoplastic elastomer composition (A) comprising a polyamide thermoplastic resin composition and an elastomer composition and (i) at least one compound selected from copper halide, hindered phenol, hindered amine and aromatic amine. ) And a layer comprising the rubber composition (B). 2. The thermoplastic elastomer composition (A)
And (ii) a nucleating agent or a crystallization inhibitor.
2. The rubber / thermoplastic elastomer laminate according to item 1. 3. The elastomer composition according to claim 1, wherein the elastomer composition is at least one selected from the group consisting of a diene rubber and a hydrogenated product thereof, an olefin rubber, a halogen-containing rubber, a silicone rubber, a sulfur-containing rubber, a fluororubber, and a thermoplastic elastomer.
The rubber-thermoplastic elastomer laminate according to claim 1 or 2, which is a composition containing a seed. 4. The polyamide-based thermoplastic resin composition according to claim 1, wherein at least a part of the thermoplastic resin composition forms a continuous phase, and at least a part of the elastomer composition forms a dispersed phase.
4. The rubber / thermoplastic elastomer laminate according to any one of items 1 to 3. 5. The crystal nucleating agent of (ii) is selected from inorganic fine particles, metal oxides, oligomers, high-melting nylon, carboxylic acid, carboxylic amide, carboxylic metal salts, carboxylic esters, and higher alcohol waxes. One or more of the compounds described above, and the crystallization inhibitor of (ii) is:
At least one selected from metal salts such as lithium chloride;
The rubber-thermoplastic elastomer laminate according to claim 2. 6. A pneumatic tire having a rubber / thermoplastic elastomer laminated structure according to any one of claims 1 to 5. 7. A hose having a rubber / thermoplastic elastomer laminated structure according to any one of claims 1 to 5.