JPH05138820A - Laminate and formed body thereof - Google Patents

Abstract

PURPOSE:To laminate respective constituent elements to each other by enough bonding strength and, at the same time, bestow heat resistance, fuel resistance and flexibility in combination by a constitution wherein the laminate concerned consists of thermoplastic elastic body containing acrylic elastomer and polyvinylidene fluoride resin and nylon resin. CONSTITUTION:The laminate concerned consists of thermoplastic elastic body containing acrylic elastomer and polyvinylidene fluoride resin and nylon resin. Plate-like or tubular formed body is made of the laminate. Or container is made of the laminate. On the other hand, another laminate may well consist of thermoplastic crosslinked elastic body containing acrylic elastomer, polyvinylidene chloride resin and crosslinker and nylon resin. Further, plate-like or tubular formed body may well be formed out of the another laminate. Thus, the respective constituent elements of the laminate are laminated to one another by enough bonding strength. At the same time, excellent heat resistance, fuel resistance, flexibility and vibration absorbing properties are bestowed to the laminate in combination.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate comprising a thermoplastic elastic body containing an acrylic elastomer and a polyvinylidene fluoride resin and a nylon resin, and a molded body thereof.

[0002]

2. Description of the Related Art Conventionally, nylon resins have been widely applied to the field of automobile parts and the like because they are excellent in fuel oil resistance such as heat resistance, gasoline resistance, alcohol resistance, etc. In contrast, although it has a high degree of durability due to its poor flexibility, it has not yet achieved sufficient practical use in the part where vibration absorption and flexibility are required.

On the other hand, it has been attempted to bond a nylon resin and a flexible elastomer, but since the nylon resin is difficult to fit in the elastomer, the adhesion between the two is poor, and the nylon resin and the elastomer are still laminated. The current situation is that the body has not been obtained.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made various studies in order to solve the problems of the above-mentioned nylon resin, and as a result, have found that a thermoplastic elastic body containing an acrylic elastomer and polyvinylidene fluoride resin or When the elastomer layer of the thermoplastic crosslinked elastic body and the nylon resin layer are laminated under specific conditions, the two adhere to each other with sufficient adhesive strength to obtain a laminate of the two, and the laminate has the nylon resin. In addition to having heat resistance and fuel oil resistance, it has the flexibility and vibration absorption properties of an elastomer layer having excellent flexibility, and it has been found that various molded products can be obtained from the laminated body. I arrived.

[0005]

That is, the present invention is a laminate comprising a thermoplastic elastomer containing an acrylic elastomer and a polyvinylidene fluoride resin and a nylon resin.

Further, the present invention is a laminate comprising a thermoplastic crosslinked elastic body containing an acrylic elastomer, a polyvinylidene fluoride resin and a crosslinking agent, and a nylon resin.

Further, the present invention provides a plate-like or tubular molded body made of a laminate of the thermoplastic elastic body or the thermoplastic crosslinked elastic body and a nylon resin, and a laminate of the thermoplastic elastic body and the nylon resin. It is a container consisting of.

The present invention will be described in detail below. The laminate of the present invention is a thermoplastic elastomer containing a specific acrylic elastomer and a polyvinylidene fluoride resin and a nylon resin, and by laminating them under specific heating conditions, both have sufficient adhesion strength. It is composed of a bonded laminated body.

The nylon resin used in the present invention is, for example, 6 nylon, 11 nylon, 12 nylon,
6,6 nylon, 46 nylon, 6,10 nylon,
Examples include 6,12 nylon and MXD6 nylon.

The acrylic elastomer used in the present invention, which constitutes the thermoplastic composite containing the acrylic elastomer and the polyvinylidene fluoride resin, is
A polymer containing an acrylic acid alkyl ester or an acrylic acid alkoxyalkyl ester as a main component and a copolymerizable ethylenically unsaturated compound as another component and a crosslinkable monomer is used.

Examples of alkyl acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylpentyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate, cyanomethyl acrylate, 1-cyanoethyl acrylate, 2-cyanoethyl acrylate, 1-cyanopropyl acrylate, 2-cyanopropyl acrylate , 3-cyanopropyl acrylate,
4-cyanobutyl acrylate, 6-cyanohexyl acrylate, 2-ethyl-6-cyanohexyl acrylate, 8-cyanooctyl acrylate and the like can be mentioned.

Examples of the acrylic acid alkoxyalkyl ester include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- (n-propoxy) ethyl acrylate, 2- (n-butoxy) ethyl acrylate and 3-methoxypropyl acrylate. , 3-ethoxypropyl acrylate, 2- (n-propoxy) propyl acrylate, 2- (n-butoxy) propyl acrylate and the like.

As the copolymerizable ethylenically unsaturated compound, various compounds can be used if necessary, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, 2-pentenoic acid and maleic acid. , Fumaric acid, itaconic acid, and other carboxyl group-containing compounds, 1,1-dihydroperfluoroethyl (meth) acrylate, 1,
1-dihydroperfluoropropyl (meth) acrylate, 1,1,5-trihydroperfluorohexyl (meth) acrylate, 1,1,2,2-tetrahydroperfluoropropyl (meth) acrylate, 1,1,7-
Fluorine-containing acrylic acid esters such as trihydroperfluoroheptyl (meth) acrylate, 1,1-dihydroperfluorooctyl (meth) acrylate and 1,1-dihydroperfluorodecyl (meth) acrylate,
Hydroxyl group-containing compounds such as 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and hydroxyethyl (meth) acrylate, tertiary amino such as diethylaminoethyl (meth) acrylate and dibutylaminoethyl (meth) acrylate Group-containing monomers, methyl methacrylate, methacrylates such as octyl methacrylate, alkyl vinyl ketones such as methyl vinyl ketone, vinyl ethyl ether, vinyl and allyl ethers such as allyl methyl ether, styrene, α-methylstyrene, chlorostyrene,
Vinyl aromatic compounds such as vinyltoluene, acrylonitrile, vinylnitrile such as methacrylonitrile,
Ethylene, propylene, vinyl chloride, vinylidene chloride,
Examples thereof include vinyl fluoride, vinylidene fluoride, vinyl acetate, vinyl propionate and alkyl fumarate.

Examples of the crosslinkable monomer include diene compounds and dihydrodicyclopentadienyl group-containing (meth)
Acrylic esters, epoxy group-containing ethylenically unsaturated compounds, active halogen-containing ethylenically unsaturated compounds, carboxyl group-containing ethylenically unsaturated compounds and active hydrogen group-containing ethylenically unsaturated compounds, specific examples thereof, Butadiene, isoprene, ethylidene norbornene, dicyclopentadiene, dihydrodicyclopentadiene (meth) acrylate, allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, 2-chloroethyl vinyl ether, 2-chloroethyl acrylate, 2-chloroethyl acrylate , 2-chloroethyl methacrylate, vinyl chloroacetate, acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic acid monomethyl ester, fumaric acid monomethyl ester Ether, N- methylol acrylamide, and allyl cyano acetate.

Acrylic elastomers used for the purpose of obtaining a high level of fuel oil resistance performance by mixing with polyvinylidene fluoride resin include 0 to 15% by weight of ethylene, 0 to 40% by weight of vinyl carboxylate, and 0 to 20% of acrylonitrile. It is obtained by polymerizing 60% by weight to 60% by weight of an alkoxyalkyl acrylate. A preferred acrylic elastomer is an alkoxyalkyl acrylate 80-
100% by weight, 0 to 20% by weight of acrylonitrile, 0 to 5% by weight of ethylene, and 0 to 5% by weight of fatty acid vinyl are polymerized. A more preferred acrylic elastomer is alkoxyalkyl acrylate 80-100.
% By weight and 0-20% by weight of acrylonitrile are polymerized, and particularly preferable acrylic elastomers are those by which 85-95% by weight of alkoxyalkyl acrylate and 5-15% by weight of acrylonitrile are polymerized.

Next, the polyvinylidene fluoride resin used in the present invention includes polyvinylidene fluoride and copolymers of vinylidene fluoride and other copolymerizable monomers. Examples of other copolymer monomers include hexafluoropropylene, pentafluoropropylene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene vinyl fluoride, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), and other olefins. And acrylic acid esters, and one or more of these are used for copolymerization.

The mixing amount of the polyvinylidene fluoride resin to the acrylic elastomer is the acrylic elastomer 1
10 parts by weight or more, preferably 20 parts by weight or more, more preferably 30 to 80 parts by weight with respect to 00 parts by weight is desirable, and if the amount is less than 10 parts by weight, the tensile strength of the mixture does not reach the practical strength. Further, a mixture containing 30 parts by weight or more of polyvinylidene fluoride resin gives good tensile strength. There is no upper limit for the content of polyvinylidene fluoride resin in the development of tensile strength, but as the mixing amount of polyvinylidene fluoride resin increases, the hardness of the molded product increases and the cost of the mixture also increases, so the elastomer The use as is gradually limited.

As the thermoplastic elastomer containing the acrylic elastomer and the polyvinylidene fluoride resin, a mixture obtained by mixing the acrylic elastomer and the polyvinylidene fluoride resin is used.

The method of mixing the acrylic elastomer and the polyvinylidene fluoride resin is usually a method of mixing rubber and thermoplastic resin, that is, an open roll used in the rubber industry or in preparing a blend of thermoplastic resins, A closed mixer such as a Banbury mixer or an extruder mixer such as a cokneader can be used.

The form of the polyvinylidene fluoride resin used in the present invention is not particularly limited, but, for example, powder, granules, granules, blocks, plates, or sheets may be used. it can.

When the polyvinylidene fluoride resin is a powder, the polyvinylidene fluoride resin powder is kneaded with the acrylic elastomer at a temperature lower than the melting point of the polyvinylidene fluoride resin, and the polyvinylidene fluoride is preliminarily added to the acrylic elastomer. It is also effective to mechanically disperse the resin powder as a solid and then heat the mixture to a temperature not lower than the melting point of the polyvinylidene fluoride resin to continue kneading to obtain a mixture. This method is excellent in that the polyvinylidene fluoride resin can be mechanically uniformly dispersed in the acrylic elastomer in advance.

Next, in the present invention, a cross-linking agent for cross-linking the acrylic elastomer may be contained, and the thermoplastic cross-linked elastic body of the present invention containing the cross-linking agent will be described. The thermoplastic crosslinked elastic body contains 100 parts by weight of an acrylic elastomer, 10 parts by weight or more of a polyvinylidene fluoride resin, and a crosslinking agent, and the crosslinking agent is substantially decomposed.

When a cross-linking agent of an acrylic elastomer is used for producing the thermoplastic cross-linked elastic body of the present invention, the cross-linking agent is a cross-linking agent corresponding to the cross-linkable monomer copolymerized with the acrylic elastomer. Is common. In the case of an acrylic elastomer in which the crosslinkable monomer is not copolymerized, an organic peroxide may be used, and a polyfunctional monomer and other additives may be used in combination therewith.

When the crosslinkable monomer is a diene compound or a dihydrodicyclopentadienyl group-containing (meth) acrylic acid ester, a vulcanizing agent used for organic peroxides and natural rubber is generally used as the crosslinking agent. Used. Also,
When the crosslinkable monomer is an epoxy group-containing ethylenic compound, in addition to a curing agent used for an epoxy resin, organic carboxylate ammonium, dithiocarbamate, quaternary ammonium salt, guanidine, sulfur compound, alkaline earth metal hydroxide The substance, lead oxide, and zinc oxide can be used. When the crosslinkable monomer is an active halogen-containing ethylenic compound, ammonium organic carboxylate,
Combinations of organic carboxylic acid alkali metal salts and sulfur compounds can be used. When the crosslinkable monomer is a carboxyl group-containing ethylenically unsaturated compound, an organic amine compound such as a guanidine compound can be used.

When an organic peroxide is used as the crosslinking agent,
As the organic peroxide, those generally used for crosslinking rubber can be used and are not particularly limited, and examples thereof include di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α, α-bis. (T-Butylperoxyisopropyl) benzene, 2,5-dimethyl 2,5-di (t-butylperoxy) hexane, 2,
5-Dimethyl-2,5-di (t-butylperoxy) hexyne-3,1,1-bis (t-butylperoxy)-
3,3,5-trimethylcyclohexane, n-butyl-
4,4-bis (t-butylperoxy) valerate,
2,2-bis (t-butylperoxy) butane, 2,2
-Bis (t-butylperoxy) octane and the like can be mentioned.

Although the amount of the crosslinking agent is not limited, it is usually used in an amount of about 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the acrylic elastomer. If it is less than 0.1 part by weight, the effect of addition is often small, and if it exceeds 10 parts by weight, the fluidity of the obtained composition may be impaired.

When a peroxide is used, it is more effective to use a polyfunctional monomer together, and the amount thereof is 0.5 part by weight or less relative to 100 parts by weight of the acrylic elastomer. Is. If it exceeds 0.5 parts by weight, the fluidity of the obtained composition may be impaired.

As the polyfunctional monomer, trimethylolpropane trimethacrylate is most effective, and triallyl isocyanurate, triallyl cyanurate, triallyl trimellitate, trimethylolpropane triacrylate, 1,6-hexane. Diol acrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, diallyl phthalate, 1,2
-Polybutadiene and the like are also applicable.

In addition, in the case of crosslinking with a peroxide, it may be effective to use a radical scavenger or a thiourea derivative together in order to balance the physical properties of the crosslinked product. It is desirable to use 3 parts by weight or less of the radical scavenger and 5 parts by weight or less of the thiourea derivative with respect to 100 parts by weight of the acrylic elastomer. If a large amount of radical scavenger is used, peroxide will be consumed, deviating from the purpose of balancing the physical properties of the crosslinked product. If a thiourea derivative is also used in a large amount, the reverse effect of deteriorating the physical properties of the crosslinked product occurs. It is desirable to use them alone or in combination within the above range.

As the radical scavenger, a compound generally used as a polymerization inhibitor or an antiaging agent, sulfur or a sulfur-containing compound is used, and representative examples thereof include phenothiazine and 2-6-di-t-butyl-p-cresol. And sulfur compounds such as vulcanization accelerators for rubber.

In addition to the above, various fillers, plasticizers, processing aids or stabilizers generally used in the rubber industry can be added to make the mixture suitable for use. If necessary, nitrile rubber, hydrogenated nitrile rubber, epichlorohydrin rubber, ethylene propylene rubber, butyl rubber, fluororubber and the like can be mixed.

When the amount of the filler used is 5 to 300 parts by weight based on 100 parts by weight of the acrylic elastomer, the mixed state and processability are improved, and more effective mixing becomes possible. If the amount is less than 5 parts by weight, the effect is often low.
If it exceeds the weight part, the workability may be deteriorated.

As the plasticizer, those which do not impair the object of the present invention and those which have an affinity for the composition, for example, α-
Examples thereof include olefin oligomers, polybutene, polyethers, polyesters and the like. Further, if desired, it can be mixed with other rubbers, for example, various other rubbers having excellent fuel oil resistance.

The thermoplastic crosslinked elastic body of the present invention shown above is a method for producing a thermoplastic elastic body containing no raw material containing the acrylic elastomer, the polyvinylidene fluoride resin and the crosslinking agent. It can be manufactured by a method similar to.

A layer is obtained by laminating the layer of the thermoplastic elastomer or the thermoplastic crosslinked elastic body containing the acrylic elastomer and the polyvinylidene fluoride resin and the layer of the nylon resin. Although the thickness of the layer of the thermoplastic elastic body or the thermoplastic crosslinked elastic body containing the vinylidene resin varies depending on the purpose of use,
Usually, the range of 1 to 20 mm, preferably 5 to 10 mm is desirable.

The thickness of the nylon resin layer varies depending on the purpose for which it is used, but is usually 0.5 to 5.0 mm,
The range of 2.0 to 3.0 mm is desirable.

Next, the method of laminating the layer of the thermoplastic resin or the thermoplastic crosslinked elastic body containing the acrylic elastomer and the polyvinylidene fluoride resin and the layer of the nylon resin is the kind of the nylon resin of the nylon resin layer to be used. For example, for 6-nylon and 12-nylon, it is desirable that the layers are laminated in the range of 15 ° C. lower than the melting point of the nylon resin of the nylon resin layer to 260 ° C. or less. If the temperature is lower than 15 ° C. below the melting point of the nylon resin, the adhesion strength of the laminate is not sufficient, and if it exceeds 260 ° C., the polyvinylidene fluoride resin begins to decompose and a toxic gas is generated, which is not desirable. Particularly, it is preferable that the temperature is not lower than 5 ° C. lower than the melting point of the nylon resin layer to obtain a laminate having sufficient adhesion strength.

In the case of 6,6 nylon, the temperature is lower than the melting point of the nylon resin of the nylon resin layer by 45 ° C. or more and 260 or more.
It is desirable to laminate in the range of ℃ or less.

In particular, in the present invention, the polyvinylidene fluoride resin is added before the thermoplastic elastomer containing the acrylic elastomer and the polyvinylidene fluoride resin or the laminate of the thermoplastic crosslinked elastic body and the nylon resin is obtained. When it is bathed at a temperature above the melting point, the adhesion with the nylon resin becomes good.

The thermoplastic crosslinked elastic material in the laminate is
Since the polyvinylidene fluoride resin is dispersed in the acrylic elastomer and the acrylic elastomer is cross-linked with a cross-linking agent, and the cross-linking agent has a substantially decomposed structure, adhesion with the nylon resin is improved. And the physical properties of compression set are good.

Next, the method for producing a plate-shaped or tubular molded body made of the laminate of the present invention is usually a method for molding a laminate of rubber or a thermoplastic resin, that is, press molding in a laminated state. And a method of manufacturing by extrusion molding with two extruders using a crosshead die.

The method for producing a container comprising the laminate of the present invention is usually a method for producing a thermoplastic resin container, such as blow molding or injection molding.

In the laminate of the present invention obtained as described above, the elastomer layer of the thermoplastic elastomer or the thermoplastic crosslinked elastic body containing the acrylic elastomer and the polyvinylidene fluoride resin and the nylon resin layer are sufficient. Laminated with a high adhesion strength, the laminate is an excellent material having the heat resistance and fuel oil resistance of nylon resin, as well as the flexibility and vibration absorption of an elastomer layer having excellent flexibility. Therefore, it can be molded into various plate-shaped or tubular molded bodies and containers and used in a wide range of applications.

That is, the laminate obtained in the present invention can be used as a suitable material for various containers such as automobile fuel oil pipes, hoses, tubes, diaphragms and belts.

[0045]

EXAMPLES The present invention will be specifically described below with reference to examples. Examples 1 to 31 and Comparative Examples 1 to 15 Using acrylic elastomers A and B and polyvinylidene fluoride resins, blend blends were obtained according to the blending formulations shown in Tables 1 to 5, and by the molding method shown below, A laminate of a thermoplastic elastomer layer of an acrylic elastomer and a polyvinylidene fluoride resin and a nylon resin layer was molded, and the adhesion strength of the molded product was measured. The results are shown in Tables 1-5.

The acrylic elastomers A and B, polyvinylidene fluoride resin, molding method and test method are shown below. From the results of the respective examples, in the case of 6 nylon (6PA) and 12 nylon (12PA), it is 1 from the melting point of the nylon resin layer.
It is recognized that when the temperature is lower by 5 ° C. or more, and when 6,6 nylon (66PA) is laminated at a temperature lower than the melting point of the nylon resin layer by 45 ° C. or more, the obtained laminate exhibits sufficient adhesion strength.

(1) Production of Acrylic Elastomer (1) -1 Production of Acrylic Elastomer A 2120 g of polyvinyl alcohol and 86 g of sodium acetate were dissolved in a 130-liter autoclave to prepare 45
Add an aqueous solution adjusted to Kg, add 8.6 Kg of vinyl acetate and 34.6 Kg of 2-methoxyethyl acrylate with stirring to emulsify, replace the inside of the autoclave with nitrogen gas, and then press in ethylene monomer from above. did. The ethylene pressure is 45 kg / cm ² at a polymerization temperature of 55 ° C.
Adjusted so that Separately add the polymerization initiator aqueous solution several times from the injection port, and stop the polymerization in about 10 hours.
Acrylic elastomer A was prepared by demonomerization, coagulation with a 3% borax aqueous solution, dehydration, and dehydration drying.
And

(1) -2 of the acrylic elastomer B
In a 130 liter autoclave, 43 kg of water, 4 kg of acrylonitrile, 3-methoxyethyl acrylate 3
6 kg, electrified Poval B-as polyvinyl alcohol
05 and B-17 700g each, sodium acetate 60g, ferric sulfate 2g, ethylenediaminetetraacetic acid 4g, cocatalyst 9
Add 0 g and stir to mix, keep the internal temperature of the autoclave at 45
℃ was made. The air above the autoclave was replaced with nitrogen.

A polymerization initiator aqueous solution was separately injected from an injection port to allow polymerization to proceed, and the injection was completed in 12 hours. An aqueous solution of Glauber's salt was added to the produced polymer emulsion to solidify the polymer, which was washed with water and dehydrated and dried to obtain an acrylic elastomer B.

(2) Polyvinylidene fluoride resin Polyvinylidene fluoride powder product KYN manufactured by Penwort Co., Ltd.
AR 741: melting point (165-170 ° C.) was used.

(3) Molding Method The acrylic elastomer was wound around a roll having a surface temperature of 40 ° C., the polyvinylidene fluoride resin was kneaded, and then the filler was kneaded. The blended mixture thus obtained and nylon resin are overlaid, and the mixture is pressed by a press molding machine at 160 ° C to 2 ° C.
It was pressed at 20 ° C. and 16 Kg / cm ² for 10 minutes.
Further, the molding was completed by cooling with water for 10 minutes in the pressurized state. The obtained laminate had a thickness of 8 mm, the thermoplastic elastomer layer containing the acrylic elastomer and the polyvinylidene fluoride resin had a thickness of 6 mm, and the nylon resin layer had a thickness of 2 mm.

(4) Method of measuring adhesion strength After leaving the obtained molded product for one day at room temperature, JIS
The adhesion strength was measured with K6301.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

[Table 4]

[0057]

[Table 5]

Examples 32 and 33 * (Molding method of Example 32) Acrylic elastomer A having the composition shown in Table 6 was wound around a roll having a surface temperature of 40 ° C., and a polyvinylidene fluoride resin was kneaded, and then filled. The agent was kneaded. Two extruders (extruder 1: L / D = 8, φ = 50 mm screw, extruder 2: extruder:
L / D = 8, φ = 50 mm screw), a crosshead die at a resin temperature of 170 ° C., a thermoplastic elastic layer containing an acrylic elastomer and a polyvinylidene fluoride resin on the inside, and a nylon resin on the outside at 240 ° C. A two-layer hose of layers was molded.

The obtained hose had a wall thickness of 4.0 mm, and the thermoplastic elastomer layer containing an acrylic elastomer and a polyvinylidene fluoride resin had a wall thickness of 2.5 mm.
The thickness of the nylon resin layer was 1.5 mm. Table 6 shows the adhesion strength of the obtained hose.

* (Molding method of Example 33) Acrylic elastomer A having the composition shown in Table 6 was wound around a roll having a surface temperature of 40 ° C., and a polyvinylidene fluoride resin was kneaded, and then a filler was kneaded. Thing (MI =
5.9 g / 10 min, density 1.35) and nylon resin (MI = 19.0 g / 10 min, density 1.13) 2
Using a blow molding machine with a single extruder (extruder 1: L / D = 22, φ = 50 mm screw, extruder 2: L / D = 20, φ = 40 mm screw) The kneaded material containing the elastomer and the polyvinylidene fluoride resin was stored in a die with an accumulator, and the nylon resin was stored in another accumulator by the extruder 2.

At a resin temperature of 240 ° C., a thermoplastic elastic layer containing an acrylic elastomer and a polyvinylidene fluoride resin is formed on the inside, a nylon resin melted parison is formed on the outside, and blow molding is performed to obtain an average wall thickness of 1 liter. 1 mm
I made a square bobbin. The thermoplastic elastomer layer containing the acrylic elastomer and polyvinylidene fluoride resin has a thickness of 1.5 mm, and the nylon resin layer has a thickness of 0.5 m.
It was m. Table 6 shows the adhesion strength of the obtained container.

[0062]

[Table 6]

(Note) 1) Product name “Now Guard 445” manufactured by Uniroyal Co.,
4,4'-bis (2,2'-dimethylbenzyl) diphenylamine 2) Tokai Carbon Co., Ltd. product name "Cast 3"

Example 34 Acrylic elastomer A having the composition shown in Table 7 was wound around a roll having a surface temperature of 40 ° C., a polyvinylidene fluoride resin was kneaded, and then a filler was further kneaded. Two extruders (extruder 1: L / D = 8, φ = 50 mm screw, extruder 2: extruder:
L / D = 8, φ = 50 mm screw), a crosshead die at a resin temperature of 170 ° C., a thermoplastic elastic layer containing an acrylic elastomer and a polyvinylidene fluoride resin on the inside, and a nylon resin on the outside at 240 ° C. A two-layer hose of layers was molded.

The obtained hose had a wall thickness of 4.0 mm, and the thermoplastic elastomer layer containing an acrylic elastomer and a polyvinylidene fluoride resin had a wall thickness of 2.5 mm.
The thickness of the nylon resin layer was 1.5 mm. Table 7 shows the adhesion strength of the obtained hose.

[0066]

[Table 7]

(Note) 1) Product name “Now Guard 445” manufactured by Uniroyal Co.,
4,4'-bis (2,2'-dimethylbenzyl) diphenylamine 2) Tokai Carbon Co., Ltd. product name "Cast 3"

[0068]

As described above, the laminate of the present invention is
The elastomer layer of the thermoplastic elastomer or the thermoplastic crosslinked elastic body containing the acrylic elastomer and the polyvinylidene fluoride resin and the nylon resin layer are laminated with sufficient adhesion strength, and the laminate has the nylon resin. In addition to having heat resistance and fuel oil resistance, it has an excellent effect of having flexibility and vibration absorption which an elastomer layer having excellent flexibility has.

The laminate of the present invention can be molded into various plate-shaped or tubular molded bodies and containers and used in a wide range of applications.

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Claims (5)

[Claims] 1. A laminate comprising a thermoplastic elastic body containing an acrylic elastomer and a polyvinylidene fluoride resin and a nylon resin. 2. A plate-shaped or tubular molded body made of the laminated body according to claim 1. 3. A container comprising the laminate according to claim 1. 4. A laminate comprising a thermoplastic crosslinked elastic body containing an acrylic elastomer, a polyvinylidene fluoride resin and a crosslinking agent, and a nylon resin. 5. A plate-shaped or tubular molded body made of the laminated body according to claim 4.