JPH01168446A - Laminate - Google Patents

Abstract

PURPOSE:To obtain a laminate having excellent heat resistance and dimensional stability by laminating a layer made of grafted polyolefin elastomer, and a layer made of polyamide, polyurethane or polyester. CONSTITUTION:Since a thermoplastic elastomer for forming a layer A is of a grafted polyolefin series elastomer and made of partly crosslinked olefin copolymer rubber, olefin plastic, preferably peroxide decomposition type olefin plastic, it has excellent fluidity, heat resistance, thermal aging resistance and rubber elasticity. The polyamide, polyurethane and polyester for forming a layer B all have excellent oil resistance and damage resistance, thereby holding predetermined oil resistance and damage resistance on one face of a laminate. Thus, the adhesive properties between the layers A and B are remarkably excellent, and excellent heat resistance and dimensional stability can be obtained.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a laminate comprising a layer made of a graft-modified polyolefin elastomer and a layer made of polyamide, polyurethane, or polyester. More specifically, the mixture of peroxide crosslinked olefin copolymer rubber and olefin plastic is selected from the group consisting of unsaturated carboxylic acid or its rust conductor, unsaturated epoxy monomer, and unsaturated hydroxy monomer. A layer consisting of a graft-modified polyolefin elastomer partially crosslinked by dynamic heat treatment in the presence of an organic peroxide together with at least one selected monomer, and a layer consisting of polyamide, polyurethane or polyester. It relates to a laminate formed by laminating layers.

(Prior Art and its Problems) Polyvinyl chloride sheets whose surfaces are embossed and have leather patterns embossed thereon have been used as interior materials for automobile floors, walls, ceilings, and the like.

However, since the polyvinyl chloride sheet itself contains a plasticizer, there are problems such as the surface becoming sticky, the sheet becoming hard due to evaporation of the plasticizer, and the inside of the car becoming foggy.

Furthermore, instead of using a single sheet of polyvinyl chloride, a laminate in which the polyvinyl chloride sheet is sequentially lined with a foam layer and, if necessary, a resin aggregate layer, has also been used.

This laminate is manufactured through the following steps.

(1) Flexible polyvinyl chloride is calender-molded to produce a sheet.

(2) A mixture of polyol and polyisocyanate is applied to the surface of this sheet and treated with urethane to make it matte.

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

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

(4) The back side of the sheet with the embossed surface is treated with flame to melt it, and is pressed with a separately supplied polyurethane foam sheet using 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) Molding the resin aggregate into a predetermined shape using a thermoforming method such as vacuum forming or pressure forming.

(7) After preheating the polyvinyl chloride-polyurethane foam-adhesive laminated sheet, it is placed on the resin aggregate molded product, and both are thermoformed to integrate.

Conventional laminates used as interior materials have a problem in that the manufacturing process is extremely complicated.

In addition, since such laminates use soft polyvinyl chloride sheets that themselves contain plasticizers, they have the same problems as mentioned above, such as stickiness on the surface and fogging inside the car. .

Other materials include (1) a composite of vulcanized rubber whose main component is ethylene-propylene-diene copolymer rubber with excellent weather resistance and heat resistance, adhesive, and nylon fiber; (2) the same vulcanized rubber Composite material of adhesive with excellent wear resistance (3) Soft polyvinyl chloride for profile extrusion molding is used. (1)
, (2) is based on a vulcanized product of ethylene-propylene-diene copolymer rubber, which has excellent weather resistance and heat resistance, so it has excellent weather resistance, heat resistance, and dimensional stability. However, the manufacturing process is extremely complicated, consisting of a kneading process of ethylene-propylene-diene copolymer rubber and a filler, an extrusion molding process, a surface puffing process, an adhesive coating process, a drying process, and a fiber flocking process. On the other hand, since (3) is manufactured by extrusion molding soft polyvinyl chloride into a profile, the manufacturing process is simplified. However, heat resistance and dimensional stability are poor, (1), (
Practical performance is inferior to 2).

(Means for solving the problems) According to the present invention, (a) Peroxide crosslinked olefin copolymer rubber 1
00 to 10 parts by weight, (b) Olefin plastic 0 to 90 parts by weight, (total amount of components (a) and (b) is 100 parts by weight) (c) Unsaturated carboxylic acid or its derivative, unsaturated A blend containing 0.01 to 10 parts by weight of at least one monomer selected from the group consisting of epoxy monomers and unsaturated hydroxy monomers is dynamically heat-treated in the presence of an organic peroxide. a layer consisting of a partially crosslinked graft-modified polyolefin elastomer (^);
A laminate characterized in that layers made of polyamide, polyurethane, or polyester (B) are laminated.

According to the invention, the blend further comprises (a)
In addition to 100 parts by weight of the total amount of component (b) and component (b), (d) peroxide non-crosslinked rubbery material 'xO to 100 parts by weight.
and/or (e) 0 to 200 parts by weight of a mineral oil softener.

(Function) In the laminate of the present invention, the thermoplastic elastomer constituting the layer (A) is a graft-modified polyolefin elastomer containing partially crosslinked olefin copolymer rubber and an olefin plastic, preferably peroxide. Because it is made of decomposable olefin plastic,
It has excellent fluidity, heat resistance, heat aging resistance, and rubber elasticity.

In addition, the resins constituting layer (B), polyamide, polyurethane, and polyester, all have excellent oil resistance and scratch resistance, so that one side of the laminate has a specified oil resistance. and scratch resistance is maintained.

Furthermore, when the layer (B) is composed of polyurethane foam, the laminate is further imparted with flexibility and lightness.

The laminate of the present invention fully exhibits the advantages of the graft-modified polyolefin elastomer and polyamide, polyurethane, or polyester because the elastomer has unsaturated carboxylic acids and unsaturated acids that easily bond physically and chemically to polyurethane. This is because they are uniformly modified with epoxy monomers or unsaturated hydroxy monomers.

That is, in the laminate of the present invention, compared to when an unmodified thermoplastic elastomer is used or when a third component having a segment compatible with polyamide, polyurethane or polyester is added to the elastomer, The above-mentioned advantages are achieved because the lamination interface between layer (A) and layer (B) is strongly bonded.

Thus, according to the present invention, due to the action of each of the above components,
A laminate with excellent oil resistance, mechanical strength, and heat aging resistance is provided.

(Description of preferred embodiments) Plastic elastomer (^) In the laminate of the present invention, the thermoplastic elastomer used in the layer (A) is a graft-modified polyolefin elastomer, and (a) peroxide crosslinked olefin copolymer rubber. 1
00 to 10 parts by weight, preferably 95 to 10 parts by weight,
Particularly preferably 95 to 60 parts by weight, (b) Olefinic plastic 0 to 90 parts by weight, preferably 5 to 90 parts by weight, particularly preferably 5 to 40 parts by weight.
parts by weight, (total amount of components (a) and (b) is 100 parts by weight) (c) unsaturated carboxylic acid or its derivative, unsaturated epoxy monomer or unsaturated hydroxy monomer 0.01 A blend containing from 1 to 10 parts by weight, preferably from 0.1 to 5 parts by weight, is dynamically heat treated in the presence of an organic peroxide to achieve partial crosslinking.

In addition, in addition to the above-mentioned components (a) to (c), the blend to be heat-treated must contain a total of 1 % of components (a) and (b).
00! per part of (d) peroxide non-crosslinked rubbery material 0 to 100 parts by weight, preferably 5 to 100 parts by weight, particularly preferably 5 to 50 parts by weight, and/or (e
) From the viewpoint that further blending of 0 to 200 parts by weight, preferably 3 to 100 parts by weight, particularly preferably 3 to 80 parts by weight of a mineral oil-based softener particularly improves the moldability of the resulting thermoplastic elastomer. desirable.

By blending component (a) within the above range, a composition with excellent rubber properties such as rubber elasticity and moldability can be obtained.

By blending components (b), (d), and (e) within the above ranges, a composition with excellent rubber properties such as rubber elasticity, as well as excellent fluidity and moldability can be obtained.

By blending component (c) within the above range, moldability and thermal adhesion to resins and metals will be excellent.

(a) Heto 9 5 fruits 5 fruits 1 2 balls 11 clear △ The peroxide crosslinked olefin copolymer rubber used in the present invention is, for example, ethylene-brobylene copolymer rubber. , ethylene-propylene nonconjugated diene rubber,
Ethylene-butadiene copolymer rubber is an amorphous elastic copolymer mainly composed of olefin, and when mixed with an organic peroxide and kneaded under heat, it crosslinks and reduces fluidity or becomes fluid. Refers to rubber that wears off.

In addition, non-conjugated diene is dicyclopentadiene, 1.4
- refers to hexadiene, dicyclooctadiene, methylene norbornene, ethylidene norbornene, etc.

In the present invention, among these copolymer rubbers, ethylene-propylene copolymer rubber and ethylene-propylene non-conjugated diene rubber are preferably used, and the molar ratio of ethylene units to propylene units (ethylene/propylene) is 50.
Those having a ratio of 150 to 90/10, especially those having a ratio of 55/45 to 85/15 are preferably used, and among them, ethylene-propylene non-conjugated diene copolymer rubber, especially ethylene-propylene-5-ethylidene-2- Norbornene copolymer combs and ethylene-propylene-5-ethylidene-2-norbornene-dicyclopentadiene quaternary copolymers are preferred in that thermoplastic elastomers with excellent heat resistance, tensile properties, and impact resilience can be obtained.

In addition, the Mooney viscosity of this copolymer rubber is ML++4 (10
(0°C) is preferably 10 to 250, particularly 40 to 150. Mooney viscosity within this range provides an elastomer composition with excellent tensile properties and fluidity.

Further, the iodine value (degree of unsaturation) of the copolymer rubber is preferably 25 or less, and within this range, a thermoplastic elastomer with well-balanced fluidity and rubber properties can be obtained.

(b) Olefinic Plastics The olefinic plastics of the present invention consist of crystalline, high molecular weight solid products obtained from the polymerization of one or more monoolefins by either high-pressure or low-pressure processes. Examples of such resins include isotactic and syndiotactic monoolefin homo- or copolymer resins, representative of which are commercially available.

Suitable raw material olefins include, for example, ethylene, phlopylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, Examples include 5-methyl-1-hexene, 1-octene, 1-decene, and mixtures of two or more of these. The polymerization mode may be either random type or block type, as long as a resin-like product can be obtained.

Among these, preferred olefin plastics are peroxide decomposition type olefin plastics and polyethylene.

Peroxide-decomposable olefin plastics are olefin plastics that are mixed with peroxide and kneaded under heat to thermally decompose, reduce the molecular weight, and increase the fluidity of the resin, such as isotactic polypropylene and propylene. copolymers with small amounts of other α-olefins, such as propylene-ethylene copolymers,
Propylene-1-butene copolymer, propylene-1-
Examples include hexene copolymer and propylene-4-methyl-1-pentene copolymer. Melt index of olefin plastics to be mixed (ASTM
-D-1238-65T, 230°C) is preferably in the range of 0.1 to 50, particularly 5 to 20.

In the present invention, the olefin plastic has the role of improving the fluidity and heat resistance of the composition.

Examples of unsaturated carboxylic acids or derivatives thereof used as one of the components (c) in the present invention include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and tetrahydrophthalic acid. α like
, β-unsaturated carboxylic acid, unsaturated carboxylic acid such as bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride Anhydrides of alpha, beta unsaturated carboxylic acids such as acids, bicyclo[2,2,13hept-2
-Anhydrides of unsaturated carboxylic acids such as nin-5,6-dicarboxylic anhydride, methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconate, tetrahydro anhydride Dimethyl phthalate, bicyclo [
Examples include esters of unsaturated carboxylic acids such as dimethyl 2,2,1]hept-2-ene-5,6 dicarboxylate. Among these, maleic acid, bicyclo[2
, 2,1]hept-2-ene-5,6-dicarboxylic acid or anhydrides thereof are preferred.

Further, in the present invention, the unsaturated epoxy monomer which is another component (c) includes, for example, glycidyl esters of unsaturated monocarboxylic acids such as glycidyl acrylate, glycidyl methacrylate, and glycidyl p-styrylcarboxylate; Maleic acid, itaconic acid, citraconic acid, butenetricarboxylic acid, endo-cis-bicyclo[2
,2,1]hept-5-ene-2,3-dicarboxylic acid,
Monoglycidyl ester or polyglycidyl ester of unsaturated polycarboxylic acids such as endo-cis-bicyclo[2,2,1]hept-5-ene-2-methyl-2,3-dicarboxylic acid; allyl glycidyl ether, 2 −
Methylallyl glycidyl ether, 0-allylphenol glycidyl ether, m-allylylphenol glycidyl ether, p-allylylphenol glycidyl ether, isopropenylphenol glycidyl ether, 0-vinylphenol glycidyl ether, m- Glycidyl ether of vinylphenol, p-
Unsaturated glycidyl ethers such as glycidyl ether of vinylphenol; 2-(o-vinylphenyl)ethylene oxide, 2-(p-vinylphenyl)ethylene oxide, 2-(o-vinylphenyl)propylene oxide, 2-(p-vinylphenyl) ) propylene oxide, 2-(o-arylphenyl)ethylene oxide, 2-(p-arylphenyl)ethylene oxide, 2
-(o-arylphenyl)propylene oxide, 2-
(p-allylphenyl)propylene oxide, p-glycidylstyrene, 3,4-epoxy-1-butene, 3
．． 4-epoxy-3-methyl-1-butene, 3.4-epoxy-1-pentene, 3.4-epoxy-3-methyl-1-pentene, 5.6-epoxy-1-hexene, vinylcyclohexene monoxide, Argyl-2,3-
Epoxycyclobentyl ether and the like are preferred.

Furthermore, the unsaturated hydroxy monomer, which is another component (c) of the present invention, refers to a monomer having one or more ethylenically unsaturated bonds and one or more hydroxyl groups, such as hydroxyethyl acrylate, hydroxypropyl Examples include acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, and hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate are particularly preferred.

These component (c) acts as a graft modifier during the dynamic heat treatment described below, and has the function of strengthening the adhesive force at the laminated interface between the layer made of polyamide, polyurethane, or polyester and the graft-modified polyolefin elastomer layer. have

(d) Peroxide crosslinked rubber-like material The peroxide non-crosslinked rubbery material of component (d) includes, for example, polyisobutylene, butyl rubber (IIR),
Hydrocarbon-based rubbery substances that do not crosslink or reduce fluidity even when mixed with peroxide and kneaded under heat, such as propylene-ethylene copolymer rubber containing 70 mol% or more of propylene, atactic polypropylene, etc. say. Among these, polyisobutylene and butyl rubber (IIR)
However, it is also preferable in terms of performance and handling.

Such components improve the fluidity of the elastomer composition, and those having a Mooney viscosity of 60 or less are particularly suitable.

(e) Mineral oil softener (component) usually weakens the acting force between rubber molecules to facilitate processing when rubber is rolled, and is also blended as a filler. A high boiling point petroleum fraction used to assist in the dispersion of carbon black, white carbon, etc. or to reduce the hardness of vulcanized rubber and increase its flexibility and elasticity. They are classified by family, etc.

Production of graftable polyolefin elastomer In the laminate of the present invention, the elastomer constituting the layer (A) contains each of the components (a) to (c) described above and, if necessary, the components (d) and/or (e). It is produced by blending each component according to the above-mentioned ratios and dynamically heat-treating it in the presence of an organic peroxide to cause partial crosslinking.

In addition, fibrous fillers, polyolefin plastics, or fillers, such as fibrous fillers, polyolefin plastics, or fillers, may be used within the range that does not impair the fluidity (moldability), rubber properties, and adhesion with polyamide, polyurethane, or polyester layers of the thermoplastic elastomer to be produced. Glass fiber, potassium titanate fiber, high-5
Medium-1 low density polyethylene, isotactic polypropylene, propylene-α olefin copolymer, calcium carbonate, 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 bulbs, shirasu balloons, carbon fibers, etc. or colorants such as carbon black,
Titanium oxide, zinc white, red rose, ultramarine, navy blue, azo pigment, nitroso pigment, lake pigment, phthalocyanine pigment, etc. can be blended.

The present invention also includes known heat stabilizers, anti-aging agents, weathering stabilizers such as phenolic, sulfide, phenylalkane, phosphite or amine stabilizers;
Antistatic agents, metal soaps, lubricants such as wax, etc. can be blended to the extent used in olefin-based plastics or olefin-based copolymer rubbers.

In the present invention, a modified polyolefin elastomer is produced by dynamically heat-treating a blend of the above-mentioned components in the presence of an organic peroxide to partially crosslink it.

Dynamic heat treatment means kneading in a molten state.

Examples of the organic peroxide used in producing the modified polyolefin 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-butylperoxy)-3,3,5-tolumethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2.4-dichlorobenzoyl peroxide, tart-butyl peroxybenzoate, t
Examples include ert-butylberbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tart-butyl cumyl peroxide.

Among these, it ranks 2.5 in terms of odor and scorch stability.
-dimethyl-2,5-di(tart-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane,
-butylperoxy)hexyne-3,1,3-bis(t
ert-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 blending amount of this organic peroxide is (a), (b)
and (c) in a range of 0.05 to 3% by weight, preferably 0.1 to 1% by weight, based on the total amount of component (c). By setting the blending amount within the above range, the resulting elastomer will have sufficient rubber properties such as heat resistance, tensile properties, elastic recovery and rebound properties, and strength, and will also have excellent moldability.

Further, the content of component (c) in the thermoplastic elastomer composition is measured by infrared absorbance analysis or chemical analysis.

As the kneading device, conventionally known devices such as an open type mixing roll, a closed type Banbury mixer 1 extruder, and a kneader 1 continuous mixer are used. Among these, it is preferable to use a closed type apparatus, and it is preferable to knead in an inert gas atmosphere such as nitrogen or carbon dioxide gas. For kneading, the half-life of the organic peroxide used is 1.
Kneading may be carried out for 1 to 20 minutes, preferably 1 to 10 minutes, at a temperature of less than 1 minute, usually 150 to 280 t, preferably 170 to 240°C. In addition, the shearing force applied is usually 10 to 10'5ec-' at a shearing rate,
Preferably it is 10' to 10'5ec-'.

In the present invention, in the partial crosslinking treatment with the organic peroxide, sulfur, p-quinonedioxime, p, p
'-dibenzoylquinone dioxime, N-methyl-N,
4-Dinitrosoaniline, nitrobenzene, diphenylguanidine, trimethylolpropane-N, N'-m-
Peroxy crosslinking co-agents such as phenylene dimaleimide or polyfunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, vinyl Multifunctional vinyl compounds such as butyrad or vinyl stearate may be included. With 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 olefin rubber and olefin plastic, which are the main components of the treated material, and has an organic peroxide solubilizing effect and acts as a peroxide dispersion aid, so it can be crosslinked by heat treatment. This is most preferred because it provides a homogeneous effect and provides a composition with well-balanced fluidity and physical properties. In the present invention, the blending amount of such a crosslinking aid or polyfunctional vinyl monomer is preferably in the range of 0.1 to 2% by weight, particularly 0.3 to 1% by weight, based on the entire object to be treated. By blending within this range, it is possible to obtain a composition that has excellent fluidity and does not cause changes in physical properties due to heat history during processing and molding of the composition.

In addition, in order to promote the decomposition of organic peroxides, tertiary amines such as triethylamine, tributylamine, 2,4゜6-tris(dimethylamino)phenol, aluminum, cobalt, vanadium, copper, calcium, zirconium, etc. Decomposition accelerators such as naphthenates of manganese, magnesium, lead, mercury, etc. can also be used.

Dynamic heat treatment in the presence of organic peroxides, as described above, results in partial crosslinking (c
) A graft-modified polyolefin elastomer is obtained.

In the present invention, partially crosslinked graft-modified polyolefin elastomer means that the gel content measured by the following method is 20% or more, preferably 20 to 9
9.5%, particularly preferably within the range of 45 to 98%.

Weighed out 100 mg of a sample of Kasadoko lΩKouko thermoplastic elastomer, cut it into 0.5 mm x 0.5 mm x 5 mm strips, and added it to 30+au cyclohexane in a sealed container at 23°C. After soaking in water for 48 hours, the sample is taken out onto a filter paper and dried at room temperature for at least 72 hours until it reaches a constant weight.

From the weight of this dry residue, all cyclohexane-insoluble components other than polymer components (1a fibrous filler, filler,
(pigments, etc.) and the weight of the olefin plastic component in the sample before immersion in cyclohexane,
Let it be “corrected final weight (Y)”.

On the other hand, the weight of the peroxide crosslinked olefin copolymer rubber in the sample, [i.e., from the weight of the sample, ■cyclohexane-soluble components other than the peroxide crosslinked olefin copolymer rubber (e.g., mineral oil and plasticizer) and ■olefin system plastic components, and ■ cyclohexane-insoluble components other than polymer components (IA fibrous filler filler,
(pigments, etc.)] is defined as the "corrected initial weight (X)".

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

The laminate of the present invention comprises a layer consisting of the graft-modified polyolefin elastomer (A) produced as described above, and the following polyamide, polyurethane or polyester C.
It can be manufactured by laminating a layer consisting of B).

(211 Satgosei Ken) The polyamide in the present invention includes hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-trimethylhexamethylene diamine, 1,3- or 1 , 4-bis(aminomethyl)cyclohexane, bis(p-aminocyclohexylmethane), aliphatic, alicyclic, aromatic diamines such as m- or p-xylylene diamine and adipic acid,
Polyamides obtained by polycondensation with aliphatic, alicyclic, and aromatic dicarboxylic acids such as superic acid, sebacic acid, cyclohexane dicarboxylic acid, terephthalic acid, and isophthalic acid, ε-aminocaproic acid, 11-aminoundecanoic acid, etc. Examples include polyamides obtained by condensation of aminocarboxylic acids, polyamides obtained from lactams such as ε-caprolactam and ω-laurolactam, copolyamides made of these components, and mixtures of these polyamides.

Specifically, nylon 6, nylon 66, nylon 610
, nylon 9, nylon 11, nylon 12, nylon 6/66, nylon 667610, nylon 6/11, and the like.

Polyurethane Layer (B) As the polyurethane in the present invention, any known polyurethane can be used. For example, any polyester-based material or polyether-based material classified based on raw material polyol components, and soft, semi-hard, or hard material classified based on hardness may be used.

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

Moreover, a polyurethane foam can also be used as the layer (B). When using foam, flexibility,
From the standpoint of heat resistance, sound absorption, etc., a soft foam having a nearly continuous cell structure and a foaming ratio of about 10 to 100 times can be used.

Polyester Layer (B) As the polyester in the present invention, thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene isophthalate are used.

Structure of Laminate The laminate of the present invention comprises the above-mentioned thermoplastic elastomer layer (
It is obtained by laminating A) and a polyamide, polyurethane or polyester layer <8).

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

(1) The preformed layers (A) and (B) are heat-sealed using a calender roll molding machine, a compression molding machine, etc. at a temperature higher than that at which at least one of the layers melts.

(2) Extrusion molding of (B) which has been formed into a sheet in advance,
Heat-seal to (A) which is being calendered.

(3) Extrude (8) and (B) simultaneously using a multilayer extruder and heat-seal them.

When a polyurethane foam is used as the layer (B), a graft-modified polyolefin elastomer is extruded or calendar-molded to form a sheet, and this and a polyurethane foam sheet are laminated using a pressure roll. By doing so, a laminate with excellent interlayer adhesion can be obtained.

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

(Effects of the invention) The laminate of the invention has a thermoplastic elastomer layer (A)
and polyamide, polyurethane or polyester layer (B)
It has excellent interlayer adhesion with other materials, is lighter than soft polyvinyl chloride, etc., has no sticky surface due to exudation of plasticity, and has excellent heat resistance and dimensional stability. Therefore, in addition to automobile interior materials and sealing materials, it can also be effectively used as furniture, building materials, housings for household appliances, bags, sporting goods, office supplies, and the like.

In the present invention, (a
The content ratio of component ) and component (b) can be measured by the D-5-C method and/or infrared absorbance analysis,
The contents of components d) and (e) can be measured by a solvent extraction method (Soxhlet extraction method (solvent: acetone)) and/or an infrared absorbance analysis method.

(Example) Ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber (hereinafter referred to as EPDM 1)) 80 parts by weight, MFR (AST
M D123B-65T, 230℃) 13, density 0.9
1g/cm3 polypropylene (hereinafter abbreviated as PP) 20
The weight part was heated in a Banbury mixer at 180°C in a nitrogen atmosphere.
After kneading for 5 minutes, the mixture was passed through a roll to form a sheet, which was then cut into square pellets using a sheet cutter. Next, this square pellet and 1,3-bis(tert-butylperoxyisopropyl)benzene (hereinafter abbreviated as peroxide (a))
0.3 parts by weight, divinylbenzene (hereinafter abbreviated as DVB)
0.5 parts by weight, maleic anhydride (hereinafter abbreviated as MAR) 0
．． 5 parts by weight were stirred and mixed using a Henschel mixer. Next, this 'mixture was heated to L/D-30 with a screw diameter of 50 mm.
The mixture was extruded using a single screw extruder at 220° C. in a nitrogen atmosphere to produce a graft-modified polyolefin elastomer (8). Then, the gel content of the copolymer rubber in the modified polyolefin elastomer (A) was measured by the method described above,
Table 1 shows the measured values.

Next, add 1 portion of this modified polyolefin elastomer (A).
Compression molding was performed at 90°C to prepare a sheet for measuring physical properties, and the following physical properties were measured. The results are shown in Table 1.

Strength: T a kgf/cm2 The tensile strength at the breaking point was measured at a tensile rate of 220 H/min in accordance with JIS K6301.

Flexibility: Torsional rigidity kgf/cm' ASTM D104
Formability: MERg/10 min ASTM [112
38, 230°C 2.1 Bkg Next, the modified polyolefin elastomer (A) was heated using a T-die extrusion molding machine with a diameter of 90 mm manufactured by Toshiba Machine Co., Ltd., with the screw in full flight, L/D = 22, and extrusion temperature 22.
0℃, T die is coat hanger die, take-up speed 2.5m
The extruded molten modified polyolefin elastomer was extruded into a sheet at a speed of 1/min, and the extruded molten sheet-shaped modified polyolefin elastomer was laminated with a polyamide sheet (manufactured by Toshiku Co., Ltd., nylon 6 (trade name: Amilan CM102, 10.5 mm thick)). The modified polyolefin elastomer was brought into contact with the roll side at a roll temperature of 60°C, and the polyamide was brought into contact with the roll side at room temperature.The thickness of the modified polyolefin elastomer layer was 1.0 mm, and the thickness of the polyamide layer was A laminate having a thickness of 0.5 mm was produced. Next, the interlayer adhesive strength of the obtained laminate was measured by the following method.

The results are shown in Table 1.

Test piece: width 25+a+a, length 100mm Test method: 1
80 degree peeling tensile speed: 25 mm/mIn Adhesive strength: Shown as the value obtained by dividing the peeling load by the width of the test piece (
kg/cm ) In addition, when the base material was destroyed, it was described as material damage.

■Indigo ±1 Example 1 except that the amount of maleic anhydride was 0
I did the same thing.

Five-Layered Example 1 The same procedure as in Example 1 was carried out except that the amount of yuperoxide (a) was 0.6 parts by weight and the amount of maleic anhydride was 2.0 parts by weight.

Five layers ■1 When producing the modified polyolefin elastomer (A), in addition to EPDM (1) and PP, butyl rubber (IIR-065 manufactured by Esso, degree of unsaturation 0.8 mol%, hereinafter abbreviated as IIR) is used. The same procedure as in Example 1 was carried out except that the mixture and paraffin oil were blended as shown in Table 1.

Toi Mei A The same procedure as in Example 3 was carried out except that 0.51 parts by weight of maleic anhydride was replaced by 0.5 parts by weight of glycidyl methacrylate.

1 EPDM% The same procedure as in Example 3 was carried out except that PP, IIR, oil, and maleic anhydride were changed as shown in Table 1.

The amounts of EPDM, PP, IIR, oil and maleic anhydride or glycidyl methacrylate were as shown in Table 1, and the amount of peroxide was 1.0 in Example 6.
The same procedure as in Example 3 was carried out except that the part by weight in Example 7 was 1.5 parts by weight. The results are also shown in Table 1.

A graft-modified polyolefin elastomer (A) was produced in the same manner as in Example 1, except that 7511 parts by weight of Togohanko EPDM (1) and 25 parts by weight of pp were used.

The gel content of this elastomer is shown in Table 2.

Next, a sheet was made from this elastomer in the same manner as in Example 1, and its physical properties were measured, and the results are shown in Table 2.

Next, a modified polyolefinic elastomer was molded using a T-die extrusion molding machine with a diameter of 90 mm manufactured by Toshiba Machinery Co., Ltd. in Example 1.
The sheet-shaped modified polyolefin elastomer in the extruded molten state was extruded under the same conditions as the polyurethane sheet (Japan Polyurethane: Thermoplastic Polyurethane P
26SRNAT, 0.5 mm thick) and passed between a pair of rolls, at which time the modified polyolefin elastomer was brought into contact with the roll side at a roll temperature of 60°C, and the polyurethane was brought into contact with the roll side at room temperature. Thickness of polyolefin elastomer layer (A): 1.0au
a, Interlayer adhesion strength was measured in the same manner as in Example 1 for the 0th-order laminate obtained by manufacturing a laminate with a polyurethane layer (B) having a thickness of 0.5 mm. The results are shown in Table 2.

±1 ±1 Example 8 except that the amount of maleic anhydride was 0
I did the same thing.

5 layers±1 The same procedure as in Example 8 was carried out except that the amount of peroxide was 0.6 parts by weight and the amount of maleic anhydride was 2.0 parts by weight.

Kizoku! A modified polyolefin elastomer was produced by the method described in Example 3, and a laminate was produced by the same method as in Example 8.

Example 1 except that 0.5 parts by weight of glycidyl methacrylate was added instead of 0.5 parts by weight of maleic anhydride.
It was carried out in the same manner as 0.

Example 10 was repeated except that 0.5 parts by weight of maleic anhydride was replaced by 0.5 parts by weight of hydroxypropyl methacrylate.

Instead of polyurethane sheet, foaming ratio is 40 times, thickness is 4
The same procedure as in Example 12 was carried out except that a polyurethane foam of mm was used.

Dog Group A 11 The same procedure as in Example 10 was carried out except that EPDM% PP% IIR, oil, and maleic anhydride were changed as shown in Table 2.

Example 1 The same procedure as in Example 8 was carried out except that the amount of peroxide blended was 0.9 parts by weight and the blended amount of maleic anhydride was 3.5 parts by weight.

The same procedure as in Example 3 was carried out except that hydroxypropyl methacrylate was used instead of maleic anhydride.

The results are shown in Table 1.

Aizoku ■Executed except that the amount of Euperoxide (a) was changed to 1 part by weight, the maleic anhydride was changed to 3 parts by weight of glycidyl methacrylate, and the polyamide sheet was changed to a polyester sheet (Toshishiku Co., Ltd. Lumirror thickness 0.3g++a) Similar to Example 3, the results are shown in Table 1.

Claims (3)

[Claims] (1) (a) 100 to 10 parts by weight of peroxide crosslinked olefin copolymer rubber, (b) 0 to 90 parts by weight of olefin plastic, (the total amount of components (a) and (b) is 100 parts by weight) ) (c) Contains 0.01 to 10 parts by weight of at least one monomer selected from the group consisting of unsaturated carboxylic acids or derivatives thereof, unsaturated epoxy monomers, and unsaturated hydroxy monomers. A layer consisting of a graft-modified polyolefin elastomer (A) in which the blend is dynamically heat-treated in the presence of an organic peroxide and partially crosslinked; and a layer consisting of polyamide, polyurethane, or polyester (B). A laminate characterized by being laminated with. (2) The blend further contains (d) 0 to 100 parts by weight of a peroxide non-crosslinked rubbery substance, based on 100 parts by weight of the total amount of components (a) and (b), and/or ( The laminate according to claim 1, characterized in that it contains e) 0 to 200 parts by weight of a mineral oil softener. (3) The (a) peroxide crosslinked olefin copolymer rubber is 95 to 60 parts by weight, and the (b) olefin plastic is 5 to 40 parts by weight (total of components (a) and (b)). 3. The laminate according to claim 1, wherein the amount is 100 parts by weight.