JP2595302B2 - Laminate - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a laminate comprising a thermoplastic elastomer layer and a polyurethane layer, and more specifically, to tensile strength, heat resistance, flexibility, and light weight. TECHNICAL FIELD The present invention relates to a laminate which has excellent surface tackiness and is particularly useful as an interior material for vehicles such as automobiles.

(Prior art and its problems) As interior materials such as floors, walls, and ceilings of automobiles, polyvinyl chloride sheets having a leather pattern embossed on the surface and having a grain pattern thereon have been conventionally used. .

However, since the polyvinyl chloride sheet contains a plasticizer in the polyvinyl chloride itself, there are problems such as that the surface is sticky, the sheet becomes hard due to evaporation of the plasticizer, and the inside of the vehicle becomes cloudy.

Also, instead of using a single sheet of polyvinyl chloride,
A laminate in which a foam layer and, if necessary, a resin aggregate layer are successively backed on this has been conventionally used.

This laminate is manufactured through the following steps.

(1) A sheet is prepared by calendering soft polyvinyl chloride.

(2) A matte treatment is performed by applying a mixture of a polyol and a polyisocyanate to the sheet surface and subjecting the mixture to urethane treatment.

This matting treatment is to prevent the sheet surface from becoming glossy at the time of thermoforming in the step (7) described later.

(3) Embossing to form a grained leather pattern on the surface.

(4) The back surface of the sheet whose front surface is embossed is flame-treated to be melted, and is pressed against a separately supplied polyurethane foam sheet by a roll.

(5) An adhesive layer is further provided on the polyurethane foam sheet side of the laminated sheet of the polyvinyl chloride sheet and the polyurethane foam sheet.

(6) A resin aggregate having a predetermined shape is formed by a thermoforming method such as vacuum forming or pressure forming.

(7) After preliminarily heating the polyvinyl chloride-polyurethane foam-adhesive laminate sheet, it is placed on a resin aggregate molded article, and both are thermoformed and integrated.

As described above, the conventional laminated body used as an interior material has a problem that the manufacturing process is extremely complicated.

In addition, since such a laminate itself uses a soft polyvinyl chloride sheet containing a plasticizer, it has problems such as surface stickiness and fogging of the vehicle, as described above.

Therefore, an object of the present invention is to effectively eliminate defects such as surface tackiness and fogging in a vehicle, and to provide a heat-resistant tensile strength.
An object of the present invention is to provide a laminate excellent in flexibility and lightness and extremely useful as a vehicle interior material for automobiles and the like.

(Means for Solving the Problems) The present invention has been made to achieve the above object, and is characterized in that a specific material is selected as a material for forming a layer.

That is, according to the present invention, a laminate comprising a thermoplastic elastomer layer (A) and a polyurethane layer (B), wherein the thermoplastic elastomer layer (A) comprises: (i) a peroxide-crosslinked olefin copolymer 10 to 90 parts by weight of rubber, (ii) 90 to 10 parts by weight of olefin-based plastic, (the total amount of components (i) and (ii) is 100 parts by weight), and (iii) unsaturated polycarboxylic acid or its anhydride. Object 0.01 to 1
(Iv) a thermoplastic elastomer composition obtained by dynamically heat-treating a blend consisting of 0 parts by weight in the presence of an organic peroxide, by adding (iv) at least two functional groups selected from an amino group, an amide group and a hydroxyl group. Compounds contained in individual molecules 0.01 to
A laminate, wherein 10 parts by weight are blended and heat-treated.

(Function) The layer (A) in the laminate of the present invention is made of a thermoplastic elastomer, which contains an unsaturated polycarboxylic acid or an anhydride thereof in the presence of an organic peroxide. Dynamically heat treated,
Since the compound (iv) is prepared by blending and heat-treating, it has excellent fluidity, heat resistance, heat aging resistance, and rubber elasticity, and the interface with the layer (B) is firmly adhered. It has the feature of

Further, the polyurethane constituting the layer (B) has an oil resistance and a scratch resistant layer, whereby predetermined oil resistance and scratch resistance are maintained on one surface of the laminate.

In particular, when the layer (B) is made of a polyurethane foam, flexibility and light weight are imparted to the laminate.

The laminate of the present invention functions as a laminate having both advantages of the thermoplastic elastomer and the polyurethane, because the thermoplastic elastomer contains the above functional group, thereby firmly bonding to the polyurethane. It seems to be due to

(Description of Preferred Embodiment) Thermoplastic Elastomer Layer (A) The thermoplastic elastomer layer (A) in the laminate of the present invention comprises: (i) 10 to 90 parts by weight of a peroxide-crosslinked olefin copolymer rubber; 90 to 10 parts by weight of plastic, (the total amount of component (i) and component (ii) is 100 parts by weight) and (iii) unsaturated polycarboxylic acid or its anhydride 0.01 to 1
(Iv) a thermoplastic elastomer composition obtained by dynamically heat-treating a blend consisting of 0 parts by weight in the presence of an organic peroxide, by adding (iv) at least two functional groups selected from an amino group, an amide group and a hydroxyl group. Compounds contained in individual molecules 0.01 to
Composed of 10 parts by weight and heat treated.

The mixing ratio of the copolymer rubber component of the component (i) and the olefin plastic of the component (ii) is usually (i) /
(Ii) = 10/90 to 90/10, preferably 20/80 to 80/20
It is. By setting the content in this range, a thermoplastic elastomer having excellent moldability, rubbery properties and fluidity can be obtained.

By using a compound containing at least two functional groups selected from an unsaturated divalent carboxylic acid or an anhydride thereof as the component (iii) and an amino group, an amide group and a hydroxyl group as the component (iv), the polyurethane layer Adhesion with (B) is provided.

Further, the thermoplastic elastomer forming the (A) layer includes:
One or more compounding agents selected from the group consisting of (v) a peroxide non-crosslinked rubbery substance, (vi) a mineral oil-based softener, and (vii) a fibrous filler, in addition to the components (i) to (iv). Can be blended. Component (v) has a maximum of 100 parts by weight, based on 100 parts by weight of the total of components (i) and (ii),
Up to 200 parts by weight of component (vi) and up to 100 parts by weight of component (vii) can be blended.

The compounding agents of the components (v) to (vi) serve to improve the moldability of the thermoplastic elastomer, and the component (vi)
The compounding agent of i) helps to improve rigidity.

(I) Peroxide-crosslinked olefin copolymer rubber The peroxide-crosslinked olefin copolymer rubber used in the present invention is, for example, ethylene-propylene-
Like non-conjugated diene rubber and ethylene-butadiene copolymer rubber, it is an amorphous elastic copolymer containing olefin as a main component, which is mixed with an organic peroxide and kneaded under heating to be crosslinked to reduce fluidity. Or the rubber that no longer flows. The non-conjugated diene refers to dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylenenorbornene, ethylidene norbornene and the like.

In the present invention, among these copolymer rubbers, ethylene-propylene copolymer rubber, ethylene-propylene-
Non-conjugated diene rubber, wherein the molar ratio of ethylene units to propylene units (ethylene / propylene) is 50/50 to 90 /
Those which are 10 and especially those which are 55/45 to 85/15 are preferably used.Especially, ethylene-propylene-non-conjugated diene copolymer rubber, particularly ethylene-propylene-ethylidene norbornene copolymer rubber is heat-resistant. This is preferable in that a thermoplastic elastomer having excellent properties, tensile properties and resilience can be obtained.

Mooney viscosity of this copolymer rubber ML _{1 + 4} (100 ℃)
Is preferably from 10 to 250, particularly preferably from 40 to 150. When the Mooney viscosity is in this range, the thermoplastic elastomer has excellent tensile properties and fluidity.

Further, the iodine value (unsaturation degree) of the copolymer rubber is preferably 25 or less. When the iodine value is within this range, a thermoplastic elastomer having a good balance between fluidity and rubber properties can be obtained.

(Ii) Olefin-based Plastic The olefin-based plastic in the present invention comprises a crystalline high molecular weight solid product obtained from polymerization of one or more monoolefins by either a high-pressure method or a low-pressure method. Examples of such resins include, for example, isotactic and syndiotactic monoolefin polymer resins, representative of which are commercially available.

Examples of suitable raw olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-
Hexene, 1-octene, 1-decene and a mixture of two or more of these can be mentioned. Regarding the polymerization mode, a random type or a block type can be adopted as long as a resinous material can be obtained.

Among them, preferred olefin-based plastics are peroxide decomposition type.

What is peroxide decomposable olefin plastic?
It is mixed with peroxide and kneaded under heating to be thermally decomposed to reduce the molecular weight and increase the fluidity of the resin.This refers to an olefin plastic in which the fluidity of the resin increases. Propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1
-Hexene copolymer, propylene-4-methyl-1-pentene copolymer and the like. Melt index (ASTM-
D-1238-65T, 230 ° C) 0.1 to 50, especially 5 to
A range of 20 is preferred. In the present invention, the olefin plastic has a role of improving the fluidity of the composition and improving the heat resistance.

(Iii) Unsaturated polycarboxylic acid or anhydride The unsaturated polycarboxylic acid or anhydride used as component (iii) in the present invention includes, specifically, maleic acid, itaconic acid, citraconic acid, tetrahydroacid Α, β unsaturated divalent carboxylic acids such as phthalic acid, bicyclo [2,2,
1] Unsaturated divalent carboxylic acids such as hept-2-ene-5,6-dicarboxylic acid and their anhydrides can be exemplified. Among them, maleic anhydride and bicyclo [2,
2,1] Hept-2-ene-5,6-dicarboxylic acid anhydrides are preferred, which act as graft modifiers.

(Iv) A compound containing at least two functional groups selected from an amino group, an amide group and a hydroxyl group in a molecule.

The following compounds can be exemplified as the component (iv).

(A) amino alcohol 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 2-amino-1-butanol, 2-amino-2-methyl -1-propanol, 2-amino-1-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, N-aminoethylethanolamine and the like.

(B) polyamines ethylenediamine, propylenediamine, trimethyldiamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetriamine, tetomaethylenepentamine, phenylenediamine, tolylenediamine, N-methylphenylenediamine, Aminodiphenylamine, diaminodiphenylamine, methylhydrazine, ethylhydrazine and the like.

(C) dicarboxylic amides oxamide, aronamide, succinamide, adipamide, maleamide, d-tartaramide, etc. (d) polyol ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, Among these, amino alcohols and polyamines are preferred, such as glycerin and pentaerythritol, and N-aminoethylethanolamine and triethylenetetramine are particularly preferred.

By heat-treating a blend of the thermoplastic elastomer and the component (iv), the adhesion of the obtained thermoplastic elastomer to polyurethane is remarkably improved.

(V) Peroxide non-crosslinked rubbery substance The peroxide non-crosslinked rubbery substance of the component (v) is
Hydrocarbons which do not crosslink even if mixed with peroxide and kneaded under heating, such as polyisobutylene, butyl rubber, propylene-ethylene copolymer rubber of 70 mol% or more, atactic polypropylene, etc., and which do not decrease in fluidity. Refers to rubbery substances of the system. Of these, polyisobutylene is most preferred for performance and handling.

Such a component improves the flowability of the elastomer composition, and particularly preferably has a Mooney viscosity of 60 or less.

(Vi) Mineral oil-based softener (vi) The mineral oil-based softener, which is a component, usually reduces the intermolecular force of rubber when rolling rubber, thereby facilitating the processing, and carbon black blended as a filler. A high-boiling petroleum fraction used for the purpose of increasing the flexibility and elasticity by helping the dispersion of white carbon, etc. or reducing the hardness of the flowing rubber; paraffinic, naphthenic, aromatic Etc.

(Vii) Fibrous filler The fibrous filler in the present invention has a diameter of 0.1 μm.
Those having a length of about m to 15 μm and a length of about 5 μm to 10 mm are preferred. Specific examples include glass fibers (chopped strands, rovings, milled glass fibers, glass flakes, etc.), wollastonite, cut fibers, rock fibers, microfibers. Fibers, processed mineral fibers, carbon fibers, gypsum fibers, aromatic polyamide fibers, potassium titanate fibers and the like can be mentioned. Among these, milled glass fibers, glass flakes, and potassium titanate fibers are preferred. Further, the fibrous filler is more preferably treated with various coupling agents such as silane-based, chromium-based, and titanium-based in order to further improve the wetting of the matrix with the thermoplastic elastomer.

The fibrous filler may be incorporated at the time of graft bonding or at a later stage.

In the present invention, a polyolefin-based plastic can be blended with the thermoplastic elastomer composition after the partial cross-linking. In this case, the polyolefin-based plastic (A): thermoplastic elastomer composition is used on a weight basis. (B) is from 0: 100 to 75:25, that is,
300 parts by weight for 100 parts by weight of the thermoplastic elastomer,
In particular, it is preferable to blend the olefin-based plastic at a ratio of up to 200 parts by weight.

Examples of the polyolefin-based plastic blended with the thermoplastic elastomer composition include, for example, high-, medium- to low-density polyethylenes known per se, isotactic polypropylene and copolymers of propylene with other small amounts of α-olefins, such as propylene- Examples thereof include an ethylene copolymer, a propylene-1-butene copolymer, a propylene-1-hexene copolymer, and a propylene-4-methyl-1-pentene copolymer. Melt index of olefin plastic mixed (ASTM-D-12
(38-65T, 230 ° C) is preferably in the range of 0.1 to 50, especially 5 to 20. In the present invention, the olefin-based plastic has a role of improving the fluidity of the composition and improving the heat resistance.

Production of Graft-Modified Polyolefin-Based Elastomer In the laminate of the present invention, the thermoplastic elastomer constituting the layer (A) includes the components (i) to (iii) described above, and if necessary, (v) to (vii) Can be produced by blending one or more of the components according to the quantitative ratios described above, dynamically heat-treating in the presence of the organic peroxide, and subsequently blending and heat-treating component (iv).

In addition, as long as the fluidity (moldability) of the produced thermoplastic elastomer, rubber properties and adhesion to the polyurethane layer are not impaired, a filler such as calcium carbonate is used.
Calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite,
Glass fibers, glass spheres, shirasu balloons, carbon fibers, etc. or coloring agents, such as carbon black, titanium oxide, zinc white, red iron, ultramarine blue, navy blue, azo pigments, nitroso pigments, lake pigments, phthalocyanine pigments, etc. it can.

In the present invention, known heat-resistant stabilizers such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based or amine-based stabilizers, antioxidants, weather-resistant stabilizers, antistatic agents, lubricants such as metal soaps and waxes. And the like can be blended to the extent that they are used in olefin-based plastics or olefin-based copolymer rubber.

In the present invention, a blend of the above-mentioned components is dynamically heat-treated in the presence of an organic peroxide to produce a modified polyolefin-based elastomer.

Dynamic heat treatment refers to kneading in a molten state.

Examples of the organic peroxide used for producing the modified polyolefin-based elastomer in the present invention include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butyl
-Butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert- Butyl peroxybenzoate, te
rt-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide,
Lauroyl peroxide, tert-butyl cumyl peroxide and the like can be mentioned.

Of these, odor and scorch stability are 2,5.
-Dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene , 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and n-butyl-4,4-bis (tert-butylperoxy)
Valerate is preferred, and 1,3-bis (tert-butylperoxyisopropyl) benzene is most preferred.

The amount of the organic peroxide is 0.01 to 3% by weight, preferably 0.03% by weight, based on the total amount of the components (i), (ii) and (iii).
It is preferable to select so as to be in the range of 1 to 1% by weight.
Rubber properties such as heat resistance, tensile properties, elastic recovery and rebound resilience of the elastomer obtained by such selection,
The result is excellent strength and moldability.

As the kneading device, conventionally known devices such as an open-type mixing roll, a non-open-type Banbury mixer, an extruder, a kneader, and a continuous mixer can be used. Of these, it is preferable to use a non-open type device, and it is preferable to knead the mixture in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The kneading is carried out at a temperature at which the half-reduction of the organic peroxide used is less than 1 minute, usually 150 to 280 ° C., preferably
1 to 20 minutes at 170 to 240 ° C, preferably 3 to
Do it for 10 minutes.

In the present invention, sulfur, p-quinonedioxime, p, p '
-Dibenzoylquinone dioxime, N-methyl-N, 4
A peroxy crosslinking aid such as dinitrosoaniline, nitrobenzene, diphenylguanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, Polyfunctional methacrylate monomers such as polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate or vinyl stearate can be blended. By blending such a compound, a uniform and mild crosslinking reaction can be expected. In particular, in the present invention, when divinylbenzene is used, it is easy to handle, has good compatibility with the olefin rubber and / or olefin plastic as the main component of the object to be treated, and has an organic peroxide solubilizing action. Since it acts as a peroxide dispersing agent, it is most preferable because a cross-linking effect by heat treatment is uniform, and a composition having a good balance between fluidity and physical properties can be obtained. In the present invention, the compounding amount of such a crosslinking assistant or polyfunctional vinyl monomer is preferably in the range of 0.1 to 2% by weight, particularly preferably 0.3 to 1% by weight, based on the whole object to be treated.

In order to accelerate the decomposition of organic peroxides, tertiary amines such as triethylamine, tributylamine, 2,4,6-tris (dimethylamine) phenol, aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium A decomposition accelerator such as naphthenate such as lead, mercury and the like can also be used.

Polyurethane Layer (B) In the present invention, as the polyurethane constituting the layer (B) laminated on the thermoplastic elastomer layer (A), any known polyurethane can be used. For example, any of polyester-based and polyether-based materials classified from the viewpoint of the raw material polyol component, and soft, semi-hard or hard materials classified from the viewpoint of hardness can be used.

In particular, when the laminate of the present invention is used as an interior material of a vehicle such as an automobile, the layer (B) is preferably formed in the form of a polyurethane sheet. In this case, it is desirable to use a thermoplastic polyurethane in terms of ease of lamination.

Further, a polyurethane foam may be used as the layer (B). When using a foam, from the viewpoint of flexibility, heat resistance, sound absorption and the like, it is a soft foam having a substantially continuous cell structure, and has an expansion ratio of about 10 to
Those in the range of about 100 times can be used.

Structure of Laminate The laminate of the present invention is obtained by laminating the above-mentioned thermoplastic elastomer layer (A) and polyurethane layer (B).

The lamination method varies depending on the shape, size, required physical properties, and the like of the final product, but for example, it can be manufactured as follows.

When polyurethane is used as the polyurethane layer (B): (1) Using a calender roll molding machine or a compression molding machine at a temperature at which at least one of the previously molded (A) and (B) layers is melted. Heat fusion.

(2) Extrusion of (B), which has been formed into a sheet in advance,
It is heat-sealed to the calendered (A).

(3) (A) and (B) are simultaneously extruded by a multilayer extruder and heat-sealed.

When a polyurethane foam is used as the polyurethane layer (B): A sheet is formed by extruding or calendering the graft-modified polyolefin-based elastomer, and the sheet is laminated with a polyurethane foam sheet using a pressure roll.

The thickness of the thermoplastic elastomer layer (A) and the thickness of the polyurethane layer (B) are generally in the range of 0.1 to 50 mm, and the thickness of the polyurethane layer (B) is in the range of 5 μm to 10 mm, although the laminate of the present invention thus produced varies depending on its use and the like.

(Effect of the Invention) The laminate of the present invention is lighter in weight than soft polyvinyl chloride or the like, has no stickiness on the surface due to detection of a plasticizer or the like, and is excellent in heat resistance and dimensional stability. Therefore,
In addition to automotive interior materials and sealing materials, it can be effectively used as furniture, building materials, housing for home appliances, bags, sporting goods, office supplies, and the like.

(Examples) Hereinafter, the present invention will be described specifically with reference to Examples. The gel content of the thermoplastic elastomer was measured according to the following method.

Measurement of gel content A 100 mg sample of the thermoplastic elastomer was weighed and
A piece cut into 0.5 mm × 0.5 mm × 0.5 mm pieces was immersed in 30 ml of cyclohexane at 23 ° C. for 48 hours in a closed container.Then, the sample was taken out on a filter paper and weighed at room temperature for at least 72 hours. Dry until dry.

From the weight of the dried residue, all cyclohexane-insoluble components other than the polymer component (fibrous filler, filler,
Pigment) and the weight of the olefin-based plastic component in the sample before immersion in cyclohexane,
It is referred to as “corrected final weight (Y)”.

On the other hand, the weight of the peroxide-crosslinked olefin copolymer rubber in the sample, [that is, from the weight of the sample, a cycloxane-soluble component other than the peroxide-crosslinked olefin copolymer rubber (for example, mineral oil or plasticizer) and an olefin-based plastic The weight of the component and the cyclohexane-insoluble component (the fibrous filler, filler, pigment, etc.) other than the polymer component is reduced] is referred to as “corrected initial weight (X)”.

 Here, the gel content is determined by the following equation.

Example 1 Ethylene / propylene / ethylidene norbornene copolymer rubber 75 parts by weight Ethylene content 70 mol% Iodine value 12 Mooney viscosity ML _{1 + 4} (100 ° C) (hereinafter abbreviated as EDPM) 120 Polypropylene MFR (ASTM D 1238-65T, 230 ℃) 13g / 10m
In (hereinafter abbreviated as PP), 25 parts by weight were kneaded with a Banbury mixer at 180 ° C. for 5 minutes in a nitrogen atmosphere, and then passed through a roll to produce square pellets with a sheet cutter.

Next, the above-mentioned square pellet, maleic anhydride (hereinafter abbreviated as MAH) 0.5 part by weight divinylbenzene (hereinafter abbreviated as DVB) 0.5 part by weight 1,3-bis (t-butylperoxyisopropyl) benzene (hereinafter abbreviated as peroxide) 0.3 Parts by weight were stirred and mixed with a Henschel mixer.

Next, this mixture was extruded at a temperature of 220 ° C. under a nitrogen atmosphere using a single screw extruder having an L / D of 30 and a screw diameter of 50 mm.

Further, the square pellet and N-aminoethylethanolamine (hereinafter abbreviated as AEA)
Using a single screw extruder, 1.0 part by weight was extruded under a nitrogen atmosphere at a temperature of 220 ° C. to produce a thermoplastic elastomer.

The gel content of this elastomer was measured by the method described above, and the results are shown in Table 1.

Next, this elastomer was compression-molded at a temperature of 190 ° C. to form a sheet, and the following physical properties were measured.

Strength: T _g kgf / cm ^{2 According to} JIS K 6301, the tensile strength at break was measured at a tensile speed of 200 mm / min.

Flexibility: Torsional rigidity kgf / cm ² Conforms to ASTM D 1043 Moldability: MFR g / 10 min Conforms to ASTM D 1238 230 ° C 2.16 kg Next, a T-die extrusion molding of a thermoplastic elastomer with a diameter of 90 mm manufactured by Toshiba Machine Co., Ltd. Using a machine, the screw is full light, L / D = 22, the extrusion temperature is 220 ° C, the T-die is a coat hanger die, and is extruded into a sheet at a pulling speed of 2.5 m / min. Thermoplastic elastomer,
Laminated with a polyurethane sheet (Nippon Polyurethane: thermoplastic polyurethane P26SRNAT, 0.5mm thick), pass between a pair of rolls, with the thermoplastic elastomer on the roll side at a roll temperature of 60 ° C and the polyurethane roll at room temperature So that the thermoplastic elastomer layer (A) has a thickness of 1.0 mm and the polyurethane layer (B) has a thickness of 0.5 mm
Was produced. Next, the interlayer adhesion strength of the obtained laminate was measured by the following method. The results are shown in Table 1.

Test piece: width 25 mm, length 100 mm Test method: 180 degree peeling Peeling speed: 25 mm / min Adhesive strength: The value was obtained by dividing the peeling load by the width of the test piece.

 In addition, when the base material was broken, it was described as material breakage.

Comparative example 1 It carried out similarly to Example 1 except not adding maleic anhydride and N-aminoethylethanolamine.

Example 2 Example 1 except that 1.0 part by weight of triethylenetetramine was used instead of N-aminoethylethanolamine.
The same was done.

Example 3 It carried out like Example 1 except the compounding quantity of peroxide being 0.4 weight part, the compounding quantity of maleic anhydride being 1.0 weight part, and the compounding quantity of N-aminoethylethanolamine being 2.0 weight part.

Example 4 In addition to raw material polymers EPDM and PP, butyl rubber (IIR-0.65 manufactured by Esso, degree of unsaturation 0.8 mol%, hereinafter abbreviated as IIR) was added.
The procedure was performed in the same manner as in Example 1 except that 0 parts by weight and 30 parts by weight of paraffin oil were mixed.

Example 5 Example 4 was repeated except that 1.0 part by weight of triethylenetetramine was used instead of N-aminoethylethanolamine.
The same was done.

Example 6 The same procedure as in Example 4 was carried out except that the amount of peroxide was changed to 0.4 parts by weight, the amount of maleic anhydride was changed to 1.0 parts by weight, and the amount of N-aminoethylethanolamine was changed to 2. parts by weight.

Example 7 Instead of a polyurethane sheet, the foaming ratio was 40 times, and the thickness was 4 mm.
Example 4 was carried out in the same manner as in Example 4, except that the polyurethane foam of Example 4 was used.

Comparative Example 2 The same procedure was performed as in Example 1 except that maleic anhydride and N-aminoethylethanolamine were not added.

Example 8 The same procedure as in Example 1 was carried out except that the addition amounts of divinylbenzene and peroxide were changed.

Example 9 The same operation as in Example 4 was carried out except that the amounts of divinylbenzene and peroxide were changed.

Claims (1)

(57) [Claims] 1. A laminate comprising a thermoplastic elastomer layer (A) and a polyurethane layer (B), wherein the thermoplastic elastomer layer (A) comprises: (i) a peroxide-crosslinked olefin copolymer rubber 10 to 90 parts by weight, (ii) 90 to 10 parts by weight of an olefin-based plastic, (the total amount of components (i) and (ii) is 100 parts by weight), and (iii) 0.01 to 0.01 parts of an unsaturated polycarboxylic acid or an anhydride thereof. 1
(Iv) at least two functional groups selected from an amino group, an amide group and a hydroxyl group are added to a thermoplastic elastomer composition obtained by dynamically heat-treating a blend consisting of 0 parts by weight in the presence of an organic peroxide. Compounds contained in individual molecules 0.01 to
A laminate characterized in that 10 parts by weight are blended and heat-treated.