JP2574336B2 - Laminate - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a laminate obtained by laminating a layer composed of a graft-modified polyolefin-based elastomer and a layer composed of polyamide, polyurethane or polyester. More specifically, a mixture of a peroxide cross-linked olefin copolymer rubber and an olefin plastic is selected from the group consisting of unsaturated carboxylic acids or derivatives thereof, unsaturated epoxy monomers and unsaturated hydroxy monomers. A layer comprising a graft-modified polyolefin-based elastomer partially crosslinked by dynamically heat-treating in the presence of an organic peroxide together with at least one monomer obtained, and a layer comprising a polyamide, polyurethane or polyester The present invention relates to a laminate obtained by the above method.

(Prior Art and its Problems) As interior materials such as floors, walls, ceilings and the like of automobiles, polyvinyl chloride sheets having a leather pattern embossed on the surface and grained 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, such a laminate also uses a soft polyvinyl chloride sheet containing a plasticizer itself, and thus has problems such as surface stickiness and fogging in the vehicle, as described above. .

Other materials include (1) a vulcanized rubber mainly composed of ethylene-propylene-diene copolymer rubber having excellent weather resistance and heat resistance, a composite material of an adhesive and nylon fiber, and (2) a vulcanized rubber of the same type. (3) Soft polyvinyl chloride for profile extrusion molding is used.
(1) and (2) are excellent in weather resistance, heat resistance, and dimensional stability because they are based on a vulcanized product of ethylene-propylene-diene copolymer rubber excellent in weather resistance and heat resistance. However, the manufacturing process is a kneading process of ethylene-propylene-diene copolymer rubber and filler, an extrusion molding process, a surface buffing process,
It is very complicated, consisting of an adhesive application step, a drying step, and a fiber flocking step. On the other hand, in the case of (3), since the soft polyvinyl chloride is manufactured by extrusion molding, the manufacturing process is simplified. However, heat resistance and dimensional stability are poor, and (1),
Practical performance is inferior to (2).

(Means for solving the problems) (a) Ethylene / propylene non-conjugated diene rubber 95 to 10
(B) 5 to 90 parts by weight of olefin-based plastic (the total amount of components (a) and (b) is 100 parts by weight) (c) unsaturated carboxylic acid or its derivative, unsaturated epoxy monomer And at least one monomer selected from the group consisting of unsaturated hydroxy monomers and 100 parts by weight of the total of components (a) and (b).
The blend containing 0.01 to 10 parts by weight is dynamically heat treated in the presence of 0.1 to 1% by weight of organic peroxide based on the total amount of components (a), (b) and (c) A laminate comprising a layer made of a crosslinked graft-modified polyolefin-based elastomer (A) and a layer made of polyamide, polyurethane, or polyester (B).

According to the present invention, the blend further includes:
For 100 parts by weight of the total amount of the components (a) and (b),
Further, there is provided a laminate according to the aspect, further comprising: (d) 0 to 100 parts by weight of a peroxide non-crosslinked rubbery substance, and / or (e) 0 to 200 parts by weight of a mineral oil-based softener.

(Function) In the laminate of the present invention, the thermoplastic elastomer constituting the layer (A) is a graft-modified polyolefin-based elastomer, and a partially crosslinked ethylene / propylene non-conjugated diene rubber is converted to an olefin-based plastic, preferably, for example, Like polypropylene, it is made of an olefin-based plastic (peroxide-decomposition type olefin-based plastic) that is mixed with a peroxide and kneaded under heating to thermally decompose to reduce the molecular weight and increase the fluidity of the resin. It has heat resistance, heat resistance, heat aging resistance, and rubber elasticity.

Further, the polyamide, polyurethane, and polyester, which are resins constituting the layer (B), all have excellent oil resistance and scratch resistance, so that one side of the laminate has a predetermined oil resistance. And the scratch resistance is maintained.

Further, when the layer (B) is composed of a polyurethane foam, the laminate is further provided with flexibility and lightness.

The laminate of the present invention sufficiently exerts the advantages of a graft-modified polyolefin-based elastomer and a polyamide, polyurethane or polyester because the elastomer is easily bonded physically and chemically to an unsaturated carboxylic acid or unsaturated carboxylic acid. This is because they are uniformly knitted by epoxy monomers or unsaturated hydroxy monomers.

That is, in the laminate of the present invention, 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, Since the laminated interface between the layer (A) and the layer (B) is firmly bonded, the above-mentioned advantages are achieved.

As described above, according to the present invention, a laminate excellent in oil resistance, mechanical strength, and heat aging resistance is provided by the action of each of the above components.

(Description of Preferred Embodiments) Thermoplastic Elastomer Layer (A) In the laminate of the present invention, the thermoplastic elastomer used for the layer (A) is a graft-modified polyolefin-based elastomer, and (a) ethylene-propylene non-conjugated diene rubber 95 to Ten
Parts by weight, preferably 95 to 60 parts by weight, (b) 5 to 90 parts by weight, preferably 5 to 40 parts by weight of the olefin-based plastic, (the total amount of the components (a) and (b) is 100 parts by weight) (c ) At least one monomer selected from the group consisting of unsaturated carboxylic acids or derivatives thereof, unsaturated epoxy monomers, and unsaturated hydroxy monomers, the sum of the components (a) and (b) A blend containing 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight, is added in an amount of 0.1 to 1% by weight based on the total amount of the components (a), (b) and (c). Is obtained by dynamically performing a heat treatment in the presence of an organic peroxide of the formula (1) to partially crosslink.

The blends to be subjected to the heat treatment include the above (a)
To the total amount of components (a) and (b) in addition to component (c)
(D) 0 to 100 parts by weight, preferably 5 to 100 parts by weight, particularly preferably 5 to 50 parts by weight, and / or (e) mineral oil-based softener per 100 parts by weight It is desirable to further add 0 to 200 parts by weight, preferably 3 to 100 parts by weight, particularly preferably 3 to 80 parts by weight, from the viewpoint of improving the moldability of the obtained thermoplastic elastomer.

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

By blending the components (b), (d) and (e) in the above range, a composition having excellent rubber properties such as rubber elasticity and excellent fluidity and moldability can be obtained.

By blending the component (c) in the above range, the moldability and the heat adhesion to a resin or a metal are improved.

(A) Ethylene-propylene non-conjugated diene rubber The ethylene-propylene non-conjugated diene rubber, which is a peroxide-crosslinked copolymer rubber used in the present invention, is an amorphous elastic copolymer, mixed with an organic peroxide,
Crosslinking by kneading under heating reduces fluidity,
Or it stops flowing.

The non-conjugated diene is dicyclopentadiene, 1,
4-hexadiene, dicyclooctadiene, methylene norbornene, ethylidene norbornene, and the like.

The ethylene / propylene non-conjugated diene rubber preferably used in the present invention includes a molar ratio of ethylene units to propylene units (ethylene / propylene).
Propylene) is 50/50 to 90/10, especially 55/45
To 85/15 are preferably used, particularly ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber and ethylene / propylene-5-ethylidene-
A 2-norbornene-dicyclopentadiene quaternary copolymer is preferable in that a thermoplastic elastomer having excellent heat resistance, 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, an elastomer composition having excellent tensile properties and fluidity can be obtained.

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

(B) 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, homo- or copolymer resins of isotactic and syndiotactic monoolefins, representatives of which are commercially available.

Suitable starting olefin materials 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-decomposable olefin-based plastics and polyethylene.

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 refers to an olefin plastic in which the fluidity of the resin increases.For example, isotactic polypropylene or propylene and other small amount of α-olefin Copolymer, for example, propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-
1-hexene copolymer, propylene-4-methyl-1-
Penten copolymers and the like can be mentioned. Melt index (ASTM)
-D-1238-65T, 230 ° C) is preferably from 0.1 to 50, particularly preferably from 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.

(C) Unsaturated carboxylic acid or its derivative, unsaturated epoxy monomer or unsaturated hydroxy monomer In the present invention, the unsaturated carboxylic acid or its derivative used as one of the components (c) is specifically Include α, β unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, and bicyclo [2,2,1] hept-
Unsaturated carboxylic acids such as 2-ene-5,6-dicarboxylic acid,
Anhydrides of α, β unsaturated carboxylic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, hycyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid Anhydrides of unsaturated carboxylic acids such as acid anhydrides, methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid,
Dimethyl tetrahydrophthalic anhydride, bicyclo [2,2,
1] Esters of unsaturated carboxylic acids such as hept-2-ene-5,6-dimethyl carboxylate.
Among these, maleic acid, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid or anhydrides thereof are preferred.

In the present invention, examples of the unsaturated epoxy monomer which is another component of the component (c) include 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, endo-cis-bicyclo [2,2,1] Hept-5-ene-2-
Monoglycidyl esters or polyglycidyl esters of unsaturated polycarboxylic acids such as methyl-2,3-dicarboxylic acid; allylic glycidyl ether, 2-methylallyl glycidyl ether, glycidyl ether of o-allylphenol, m-allyl Glycidyl ether of phenol, glycidyl ether of p-allylphenol, glycidyl ether of isopropenylphenol, glycidyl ether of o-vinylphenol, m-
Unsaturated glycidyl ethers such as glycidyl ether of vinylphenol and glycidyl ether of p-vinylphenol; 2- (o-vinylphenyl) ethylene oxide, 2- (p-vinylphenyl) ethylene oxide,
-(O-vinylphenyl) propylene oxide, 2-
(P-vinylphenyl) propylene oxide, 2- (o
-(Allylphenyl) ethylene oxide, 2- (p-allylphenyl) ethylene oxide, 2- (o-allylphenyl) 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,
Preferred are 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, aryl-2,3-epoxycyclopentyl ether and the like.

Further, the unsaturated hydroxy monomer which is another one of the component (c) of the present invention is a monomer having at least one ethylenically unsaturated bond and at least one hydroxyl group, for example, hydroxyethyl acrylate, hydroxypropyl Acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, etc., and particularly, hydroxyethyl (meth)
Acrylate and hydroxypropyl (meth) acrylate are preferred.

These components (c) act as a graft modifier during a dynamic heat treatment to be described later, and function to strengthen the adhesive force at the lamination interface between the layer made of polyamide, polyurethane or polyester and the graft-modified polyolefin-based elastomer layer. Have.

(D) Peroxide non-crosslinked rubber-like substance The peroxide non-crosslinked rubber-like substance of the component (d) is, for example, polyisobutylene, butyl rubber (IIR), propylene-ethylene copolymer rubber having 70% by mole or more of propylene, attack It refers to a hydrocarbon-based rubber-like substance such as tic polypropylene which does not crosslink even when mixed with a peroxide and kneaded under heating and does not decrease in fluidity. Of these, polyisobutylene and butyl rubber (IIR) are 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.

(E) Mineral oil-based softener The mineral oil-based softener as the component (e) 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 elasticity and flexibility by reducing the hardness of vulcanized rubber or to help disperse white carbon, etc., paraffinic, naphthenic,
They are classified into aromatic and the like.

Production of Graft-Modified Polyolefin-Based Elastomer In the laminate of the present invention, the elastomer constituting the layer (A) includes the components (a) to (c) described above and, if necessary, (d) and / or (e). It is produced by blending the components according to the quantitative ratios described above, dynamically heat treating in the presence of an organic peroxide, and partially crosslinking.

In addition, within a range that does not impair the fluidity (moldability) of the thermoplastic elastomer to be produced, rubber-like properties, and adhesion to the polyamide, polyurethane or polyester layer, fibrous fillers, polyolefin plastics, or fillers, for example, Glass fiber, potassium titanate fiber, high-, medium-, 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 fiber, glass sphere, shirasu balloon, carbon fiber, etc. or coloring agent, for example, carbon black, titanium oxide, zinc It can be formulated red iron oxide, ultramarine, Prussian blue, azo pigments, nitroso pigments, lake pigments, phthalocyanine pigments.

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 modified polyolefin-based elastomer is produced by dynamically heat-treating a blend of the above-described components in the presence of an organic peroxide to partially crosslink.

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-tolumethylcyclohexane, 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-butylcumyl 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 selected so as to be in the range of 0.1 to 1% by weight based on the total amount of the components (a), (b) and (c). By adjusting the blending amount to the above range,
The rubber properties and strength such as heat resistance, tensile properties, elastic recovery and rebound resilience of the obtained elastomer are sufficient and the moldability is excellent.

The content of the component (c) in the thermoplastic elastomer composition is measured by an infrared absorbance analysis method or a chemical analysis method.

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-life of the organic peroxide to be used is less than 1 minute, usually at 150 to 280 ° C., preferably at 17 ° C.
1 to 20 minutes at 0 to 240 ° C., preferably 1 to 10 minutes
Mixing may be performed for a minute. The applied shearing force is usually 10 to 10 ⁴ sec ⁻¹ , preferably 10 ² to 10 ³ sec ^{−1 in} terms of shear rate.

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
Multifunctional methacrylate monomer such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, polyfunctionality such as vinyl butyrate or vinyl stearate Vinyl monomers can be blended. 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 the olefin-based rubber and olefin-based plastic which are the main components of the object to be treated, and has a solubilizing effect on organic peroxides. Since the composition acts as a dispersing aid, it is most preferable because a composition having a uniform cross-linking effect by heat treatment and a good balance of 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 0.3 to 1% by weight, based on the whole object to be treated. As a result, it is possible to obtain a composition which has excellent fluidity and does not cause a change in physical properties due to heat history at the time of processing and molding the composition.

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

As described above, by the dynamic heat treatment in the presence of the organic peroxide, a partial cross-linking is performed, and a polyolefin-based elastomer graft-modified with the component (c) is obtained.

In the present invention, the phrase that the graft-modified polyolefin-based elastomer is partially crosslinked means that the gel content measured by the following method is 20% or more, preferably 20 to 99.5.
%, Particularly preferably in the range of 45 to 98%.

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, and then the sample was taken out on a filter paper and kept at room temperature for 72 hours or more. Dry until dry.

From the weight of the dried residue, all cyclohexane-insoluble components other than the polymer component (fibrous filler, filler,
Pigment, etc.) 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 ethylene / propylene non-conjugated diene rubber in the sample, [that is, from the weight of the sample, a cyclohexane-soluble component (eg, steel oil or plasticizer) other than the ethylene / propylene non-conjugated diene rubber, an olefin-based plastic component, and a polymer component Other than the weight of the cyclohexane-insoluble components (fibrous fillers, fillers, pigments, etc.) other than the above] are referred to as “corrected initial weight (X)”.

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

Production of Laminate The laminate of the present invention is produced by laminating a layer composed of the graft-modified polyolefin-based elastomer (A) produced as described above and a layer composed of the following polyamide, polyurethane or polyester (B). can do.

Polyamide layer (B) As the polyamide in the present invention, hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4 Aliphatics such as bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), m- or p-xylylenediamine;
Obtained by polycondensation of alicyclic, aromatic and other diamines with adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid and other aliphatic, alicyclic and aromatic dicarboxylic acids. polyamide,
polyamide obtained by condensation of aminocarboxylic acids such as ε-aminocaproic acid and 11-aminoundecanoic acid, ε
And polyamides obtained from lactams such as -caprolactam and ω-laurolactam, copolymerized polyamides comprising these components, and mixtures of these polyamides. Specifically, nylon 6, nylon 66, nylon 61
0, nylon 9, nylon 11, nylon 12, nylon 6/6
6, nylon 66/610, 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 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 an expansion ratio of about 10 to 10
Those having a range of about 0 times can be used.

Polyester layer (B) As the polyester in the present invention, a thermoplastic polyester such as polyethylene terephthalate, polybutylene terephthalate, or polyethylene isophthalate is used.

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

(1) The (A) layer and the (B) layer formed in advance are heat-sealed at a temperature higher than at least one of the layers is melted using a calender roll forming machine, a compression molding machine or the like.

(2) The previously molded (B) is heat-sealed to the extruded and calendered (A).

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

When a polyurethane foam is used as (B), a sheet is formed by extruding or calendering a graft-modified polyolefin-based elastomer, and the sheet is laminated with a polyurethane foam sheet using a pressure roll. Thereby, a laminate having excellent interlayer adhesion can be obtained.

Although the laminate of the present invention thus produced varies depending on its use and the like, the thickness of the thermoplastic elastomer layer (A) is generally 0.1 to 50 mm, and the thickness of the polyamide, polyurethane or polyester layer (B) is 5 μm to 10 μm.
Is preferably within the range.

(Effect of the Invention) The laminate of the present invention has remarkably excellent interlayer adhesion between the thermoplastic elastomer layer (A) and the polyamide, polyurethane or polyester layer (B), and is lighter than flexible polyvinyl chloride or the like. There is no stickiness on the surface due to exudation of plasticity and the like, and it is also excellent in heat resistance and dimensional stability. Therefore, in addition to automotive interior materials and sealing materials, furniture,
It can be used effectively as building materials, housing for home appliances, bags, sporting goods, office supplies and the like.

In the present invention, the content ratio of the component (a) to the component (b) in the thermoplastic elastomer composition can be measured by the D.S.C. method and / or the infrared absorption spectrometry. The contents of the 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) Example 1 Ethylene content 70 mol%, iodine value 12, Mooney fiscal year ML
_{1 + 4} (100 ° C) 120 ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (hereinafter referred to as EPDM (1)
80 parts by weight, MFR (ASTM D1238-65T, 230 ° C) 1
3, polypropylene with a density of 0.91 g / cm ³ (hereinafter abbreviated as PP) 20
The mixture was kneaded at 180 ° C. for 5 minutes in a nitrogen atmosphere using a Banbury mixer in a nitrogen atmosphere, and then passed through a roll to form a sheet, which was formed into a square pellet by a sheet cutter. Next, this square pellet, 0.3 parts by weight of 1,3-bis (tert-butylperoxyisopropyl) benzene (hereinafter abbreviated as peroxide (a)), 0.5 part by weight of divinylbenzene (hereinafter abbreviated as DVB),
0.5 parts by weight of maleic anhydride (hereinafter abbreviated as MAH) was stirred and mixed with a Henschel mixer. The mixture is then L / D = 3
0, in a nitrogen atmosphere with a single screw extruder with a screw diameter of 50 mm, 220
Extruded at ℃ to produce a graft-modified polyolefin-based elastomer (A). Then, the gel content of the copolymer rubber in the modified polyolefin-based elastomer (A) was measured by the method described above, and the measured values are shown in Table 1.

Next, this modified polyolefin-based elastomer (A)
The sheet was compression molded at 190 ° 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 _B kgf / cm ² According to JISK6301, the tensile strength at break was measured at a tensile speed of 220 mm / min.

Flexibility: Torsional rigidity kgf / cm ² Conforms to ASTM D1043 Moldability: MER g / 10 min Conforms to ASTM D1238 230 ° C 2.16 kg Next, a modified polyolefin-based elastomer (A) is extruded from a T-die with a diameter of 90 mm manufactured by Toshiba Machine Co., Ltd. Using a machine, the screw is full flight, 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 take-up speed of 2.5 m / min. The modified polyolefin-based elastomer is converted to a polyamide sheet (Nylon 6 manufactured by Toray Industries, Inc., trade name: Alamine CM1021 0.5mm
Thickness) is passed through a pair of rolls in a laminated state, in which case the modified polyolefin-based elastomer is brought into contact with the roll side at a roll temperature of 60 ° C, and the polyamide is brought into contact with the roll side at room temperature. A laminate having a thickness of 1.0 mm and a polyamide layer 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: value obtained by dividing the peeling load by the width of the test piece (kg / cm) The substrate was broken In the case, it was described as material destruction.

Comparative example 1 It carried out similarly to Example 1 except having set the compounding quantity of maleic anhydride to 0.

Example 2 Example 2 was repeated except that the amount of peroxide (a) was changed to 0.6 parts by weight and the amount of maleic anhydride was changed to 2.0 parts by weight.

Example 3 In producing the modified polyolefin-based elastomer (A), butyl rubber (manufactured by Esso) was added in addition to EPDM (1) and PP.
Example 1 except that IIR-065, a degree of unsaturation of 0.8 mol% (hereinafter abbreviated as IIR) and a paraffinic oil were blended as shown in Table 1.
The same was done.

Example 4 The same procedure as in Example 3 was carried out except that 0.5 parts by weight of maleic anhydride was changed to 0.5 parts by weight of glycidyl methacrylate.

Example 5 The same procedure as in Example 3 was carried out except that EPDM, PP, IIR, oil and maleic anhydride were as shown in Table 1.

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

Example 8 Except that EPDM (1) was 75 parts by weight and PP was 25 parts by weight,
A graft-modified polyolefin-based elastomer (A) was produced in the same manner as in Example 1.

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

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

Next, a modified polyolefin-based elastomer was prepared using a 90 mm diameter T-die extruder manufactured by Toshiba Machine Co., Ltd.
Extruded under the same conditions as above, and the extruded sheet-like modified polyolefin-based elastomer in a molten state is converted into a polyurethane sheet (Nippon Polyurethane; thermoplastic polyurethane P2
6SRNAT, 0.5mm thick) and passed between a pair of rolls, in which case the modified polyolefin elastomer is brought into contact with the roll side at a roll temperature of 60 ° C, and the polyurethane is brought into contact with the roll side at room temperature. 1.0mm thick elastomer layer (A), polyurethane layer (B)
A laminate having a thickness of 0.5 mm was produced. Next, the interlayer adhesion strength of the obtained laminate was measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative example 2 It carried out similarly to Example 8 except having made the compounding quantity of maleic anhydride 0.

Example 9 The same operation as in Example 8 was carried out except that the amount of peroxide was changed to 0.6 part by weight and the amount of maleic anhydride was changed to 2.0 part by weight.

Example 10 A modified polyolefin-based elastomer was produced by the method described in Example 3, and a laminate was produced in the same manner as in Example 8.

Example 11 The same operation as in Example 10 was carried out except that 0.5 part by weight of glycidyl methacrylate was used instead of 0.5 part by weight of maleic anhydride.

Example 12 The same procedure was performed as in Example 10, except that 0.5 parts by weight of maleic anhydride was changed to 0.5 parts by weight of hydroxypropyl methacrylate.

Example 13 Instead of a polyurethane sheet, the expansion ratio was 40 times, and the thickness was 4 m.
Example 12 was carried out except that a polyurethane foam of m was used.

Example 14 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 15 Example 15 was carried out in the same manner as in Example 8 except that the amount of peroxide was changed to 0.9 parts by weight and the amount of maleic anhydride was changed to 3.5 parts by weight.

Example 16 It carried out like Example 3 except having changed maleic anhydride into hydroxypropyl methacrylate.

 The results are shown in Table 1.

Example 17 Example 3 was repeated except that the amount of peroxide (a) was changed to 1 part by weight, maleic anhydride was changed to 3 parts by weight of glycidyl methacrylate, and the polyamide sheet was changed to a polyester sheet (Lumirror thickness 0.3 mm, manufactured by Toray Industries, Inc.). The same was done. The results are shown in Table 1.

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Claims (3)

(57) [Claims] (1) 95 to 10 parts by weight of an ethylene / propylene non-conjugated diene rubber, (b) 5 to 90 parts by weight of an olefin-based plastic, (the total amount of the components (a) and (b) is 100 parts by weight) (C) at least one monomer selected from the group consisting of unsaturated carboxylic acids or derivatives thereof, unsaturated epoxy monomers and unsaturated hydroxy monomers, (a) and (b)
The blend containing 0.01 to 10 parts by weight, based on 100 parts by weight of the total amount of the components, contains 0.1 to 1% by weight of the organic peroxide based on the total amount of the components (a), (b) and (c). A layer comprising a graft-modified polyolefin-based elastomer (A) which is dynamically heat-treated underneath and partially cross-linked, and a layer comprising a polyamide, a polyurethane or a polyester (B). Laminate. 2. The blend according to claim 2, further comprising: (d) 0 to 100 parts by weight of a peroxide non-crosslinked rubbery substance, based on 100 parts by weight of the total of the components (a) and (b); The laminate according to claim 1, further comprising: e) 0 to 200 parts by weight of a mineral oil-based softener. 3. The (a) ethylene / propylene non-conjugated diene rubber is 95 to 60 parts by weight, and the (b) olefin-based plastic is 5 to 40 parts by weight (total amount of the components (a) and (b)). 3. The laminate according to claim 1, wherein the weight of the laminate is 100 parts by weight.