JP2577464B2 - Laminated molded article and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a laminated molded article and a method for producing the same, and more particularly, to a laminated article having excellent heat resistance, cold resistance, oil resistance, solvent resistance, abrasion resistance and scratch resistance. And a method for producing the same.

Technical background of the invention and its problems Conventionally, the surface of a three-dimensional molded product is protected with a skin layer of a synthetic resin, or as a decorative or printed molded body, a core layer made of a synthetic resin is made of another synthetic resin. 2. Description of the Related Art A laminated molded article in which a skin layer is laminated is known.

This laminated molded article is obtained by vacuum-forming a synthetic resin sheet on the inner wall surface of the cavity of the injection mold by vacuum molding, pre-molding, and then injection-molding a synthetic resin in a fluidized plasticized state in the cavity. , Mainly automotive interior and exterior parts,
Widely used for applications such as building materials.

Such a molded article has an advantage in that if a material to which characters and patterns are added in advance as the skin layer is used, it is not necessary to further apply a painting after molding the three-dimensional molded article.

However, conventionally, as a synthetic resin sheet or film used as a skin layer, polyvinyl chloride or the like is used. However, the conventional skin layer material has poor suction at the time of vacuum forming, and the three-dimensional shape of the formed body is complicated. It is difficult to form, and there are problems such as cracks at corners and wrinkles at some parts. In addition, there is a problem that crimping by transfer of a crimp pattern on the inner wall surface of the cavity of the mold is not always good. Furthermore, in the skin layer of polyvinyl chloride, etc., there is a problem that heat resistance, cold resistance, oil resistance, solvent resistance, abrasion resistance and scratch resistance are poor, and the plasticizer bleeds out.
There was a problem that the touch was bad as an automobile interior part.

Object of the Invention The present invention is intended to solve the above problems, and is a soft laminated molding excellent in heat resistance, cold resistance, oil resistance, solvent resistance, abrasion resistance and scratch resistance. It is intended to provide a body and a method for its manufacture.

Another object of the present invention is to provide a laminated molded article having excellent characteristics described above and having a soft and sharp grain pattern, and a method for producing the same.

SUMMARY OF THE INVENTION The first laminated molded article according to the present invention comprises: (a) a core layer made of a synthetic resin; and (b) an intermediate layer (I) made of a polyolefin foam or a polyurethane foam provided on the core layer. And (c) selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid derivatives, unsaturated epoxy monomers and unsaturated hydroxy monomers provided on the intermediate layer (I). (D) an intermediate layer (II) made of a modified polyolefin-based elastomer graft-modified with at least one graft monomer, and (d) a polyamide provided on the intermediate layer (II).
A skin layer made of at least one polymer selected from the group consisting of polyurethane and polyester.

The first method for producing a laminated molded article according to the present invention comprises the intermediate layer (I) composed of the polyolefin foam or the polyurethane foam, the intermediate layer (II) composed of the modified polyolefin-based elastomer, and the polymer. After preheating a three-layer sheet composed of a skin layer and
A step of obtaining a preformed product having a concave portion by suction-contacting the three-layer sheet to the inner wall surface of the cavity of the vacuum forming die; and bringing the preformed product into close contact with the inner wall surface of the cavity of the vacuum forming die. A step of obtaining a molded product having a concave portion by clamping the mold in a state or in close contact with the cavity inner wall surface of the molding die separate from the vacuum molding die; Injection molding a synthetic resin in a fluidized plasticized state into a concave portion of the molded article to be molded to obtain a laminated molded article according to claim 1.

Further, the method for producing a second laminated molded article according to the present invention includes:
A three-layer sheet composed of the intermediate layer (I) made of the polyolefin foam or the polyurethane foam, the intermediate layer (II) made of the modified polyolefin-based elastomer, and the skin layer made of the polymer was preheated. Then, the three-layer sheet is suction-contacted to the inner wall surface of the cavity of the vacuum forming die to obtain a preformed product having a concave portion, and the preformed product adhered to the inner wall surface of the cavity of the vacuum forming die. The synthetic resin in the flow plasticized state is poured into the concave portion of the mold or the concave portion of the pre-formed product which is brought into close contact with the inner wall surface of the cavity of the molding die separate from the vacuum molding die to perform stamping molding. And a step of obtaining the laminated molded article according to claim 1 through the steps.

Further, the third method for producing a laminated molded article according to the present invention is characterized in that the modified polyolefin elastomer comprises a core layer made of the synthetic resin, an intermediate layer (I) made of the polyolefin foam or the polyurethane foam, and the modified polyolefin elastomer. After preheating a four-layer sheet composed of the intermediate layer (II) and the skin layer made of the polymer,
It is characterized in that the layered sheet is vacuum-formed to obtain a laminated molded article according to claim 1.

Next, the second laminated molded article according to the present invention comprises (a) a core layer made of a synthetic resin, and (b) an unsaturated carboxylic acid, an unsaturated carboxylic acid derivative provided on the core layer, An intermediate layer (II) comprising a modified polyolefin-based elastomer graft-modified with at least one graft monomer selected from the group consisting of an unsaturated epoxy monomer and an unsaturated hydroxy monomer; (II) a skin layer made of at least one polymer selected from the group consisting of polyamide, polyurethane and polyester, provided on the top.

The fourth method for producing a laminated molded article according to the present invention is directed to the intermediate layer (II) comprising the modified polyolefin-based elastomer.
After preheating the two-layer sheet composed of the polymer and the skin layer made of the polymer, the two-layer sheet is suction-adhered to the inner wall surface of the cavity of the vacuum forming die to obtain a preformed product having a concave portion. A step in which the preformed article is brought into close contact with the inner wall surface of the cavity of the vacuum forming die or in a state in which it is brought into close contact with the inner wall surface of the cavity of the molding die separate from the vacuum forming die. A step of obtaining a molded article having a concave portion by tightening, and a step of injecting and molding a synthetic resin in a flow plasticized state into the concave portion of the molded article which is in close contact with the inner wall surface of the mold. A laminated molded article according to claim 5 is obtained.

Further, the fifth method of manufacturing a laminated molded product according to the present invention includes:
After preheating a two-layer sheet composed of the intermediate layer (II) composed of the modified polyolefin-based elastomer and a skin layer composed of the polymer, the two-layer sheet is placed on the inner wall surface of the cavity of the vacuum molding die. A step of obtaining a preformed product having a concave portion by suction contact, and forming the preformed product in the concave portion of the preformed product that is in close contact with the inner wall surface of the cavity of the vacuum forming die, or separately from the vacuum forming die. A step of pouring a synthetic resin in a fluidized plasticized state into a concave portion of the pre-formed product closely contacted with the inner wall surface of the mold for stamping and forming the laminated molded product according to claim 5. It is characterized by:

Further, the sixth method for producing a laminated molded article according to the present invention comprises a core layer composed of the synthetic resin, an intermediate layer (II) composed of the modified polyolefin-based elastomer, and a skin layer composed of the polymer. After preheating the resulting three-layer sheet, the three-layer sheet is vacuum-formed to obtain a laminated molded article according to claim 5.

In addition, the term “sheet” in this specification is used including a film.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a laminated molded product according to the present invention and a method for producing the same will be specifically described with reference to the drawings.

FIGS. 1 (a) to 1 (d) are process diagrams in the first and fourth methods for manufacturing a laminated molded article according to the present invention, and FIGS.
FIG. 3 is a schematic view of one apparatus used in the second and fifth methods for manufacturing a laminated molded article according to the present invention, and FIG. 3 is a plan view showing a sampling point of a test piece.

First, the first laminated molded article according to the present invention will be described.

The first laminated molded article according to the present invention comprises a core layer composed of a synthetic resin, an intermediate layer (I) composed of a polyolefin foam or a polyurethane foam, an intermediate layer (II) composed of a modified polyolefin-based elastomer, and a polymer. And an epidermis layer.

Core Layer In the present invention, the core layer is made of a synthetic resin, and in the present invention, a synthetic resin such as a thermoplastic resin and a thermoplastic elastomer is preferably used.

Specific examples of the thermoplastic resin include low-density polyethylene, high-density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, and ethylene and propylene, regardless of whether they are crystalline or amorphous. Polyolefins such as random or block copolymers of α-olefins such as styrene, 1-butene and 4-methyl-1-pentene; ethylene-acrylic acid copolymers; ethylene-vinyl acetate copolymers; ethylene-vinyl alcohol copolymers Polymers, ethylene-vinyl compound copolymers such as ethylene-vinyl chloride copolymer, polystyrene, acrylonitrile
Styrene copolymers, ABS, styrene resins such as methyl methacrylate / styrene copolymer, α-methylstyrene / styrene copolymer, polyvinyl chloride, polyvinylidene chloride, vinyl chloride / vinylidene chloride copolymer, acrylic acid Examples of the ester include polyvinyl compounds such as polymethyl acrylate and polymethyl methacrylate; polyamides such as nylon 6, nylon 6-6, nylon 6-10, nylon 11, and nylon 12; and thermoplastic polyesters such as polyethylene terephthalate and polybutylene terephthalate. , Polycarbonate, polyphenylene oxide or the like, or a mixture thereof, or a silicone-based or urethane-based resin.

Specific examples of the thermoplastic elastomer include modified polyolefin-based elastomers, polyolefin-based elastomers, styrene-based elastomers, ester-based elastomers, urethane-based elastomers, and vinyl chloride-based elastomers that constitute the intermediate layer (II) described below. Is mentioned.

In the present invention, from the above synthetic resins,
The synthetic resin to be used is appropriately selected in consideration of molding conditions, applications, properties, prices, and the like. However, a polyolefin-based resin, particularly, polypropylene is preferably used in view of the impact resistance, weather resistance, and the like of the obtained laminated molded article.

Further, in the present invention, if necessary, foam the synthetic resin with a foaming agent, or to the synthetic resin,
Additives such as wood flour, fiber flakes, and inorganic fillers can be included in a range that does not impair the required physical properties or for the purpose of further improving the physical properties.

Intermediate layer (I) The intermediate layer (I) in the present invention comprises a polyolefin foam or a polyurethane foam.

Specific examples of the polyolefin foam include a polyethylene foam, a polypropylene foam, and a foam of a blend of polyethylene and polypropylene.

When the above-mentioned polyurethane foam is used as the intermediate layer (I), the polyurethane foam is a soft foam having a substantially continuous cell structure from the viewpoints of flexibility, heat resistance, sound absorption and the like. A polyurethane foam having a magnification in the range of about 10 to 100 times is preferably used.

Intermediate layer (II) The modified polyolefin-based elastomer constituting the intermediate layer (II) used in the present invention includes, specifically, (a) a peroxide-crosslinked olefin copolymer rubber 10
0 to 10 parts by weight, preferably 95 to 10 parts by weight, particularly preferably 95 to 60 parts by weight, and (b) 0 to 90 parts by weight, preferably 5 to 90 parts by weight, particularly preferably 5 to 40 parts by weight of an olefin-based plastic. (C) an unsaturated carboxylic acid, a derivative of an unsaturated carboxylic acid, and (c) a part by weight (the total amount of the components (a) and (b) is 100 parts by weight);
A blend containing 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, of at least one graft monomer selected from the group consisting of unsaturated epoxy monomers and unsaturated hydroxy monomers. Thermoplastic elastomers obtained by dynamically performing heat treatment in the presence and partially cross-linking them.

In addition, in addition to the above components (a) to (c), components (a) and (b)
(D) 0 to 100 parts by weight, preferably 5 to 100 parts by weight of a peroxide non-crosslinked type rubbery substance per 100 parts by weight of
Particularly preferably, 5 to 50 parts by weight, and / or (e)
From the viewpoint that the addition of 0 to 200 parts by weight, preferably 3 to 100 parts by weight, particularly preferably 3 to 80 parts by weight of the mineral oil-based softener improves the moldability of the obtained thermoplastic elastomer. desirable.

By blending the component (a) in 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) within the above range, a composition excellent in moldability and thermal adhesion to resins and metals can be obtained.

(A) Peroxide-crosslinked olefin copolymer rubber The peroxide-crosslinked olefin copolymer rubber used in the present invention includes, for example, ethylene-propylene copolymer rubber, ethylene-propylene non-conjugated diene rubber, and ethylene-butadiene copolymer rubber. Amorphous elastic copolymers containing olefins as the main component, such as coalesced rubber, are mixed with organic peroxides, kneaded under heating, and then crosslinked to reduce the fluidity or lose the flow of rubber. Say. The non-conjugated diene refers to dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene norbornene, ethylidene norbornene, and the like.

In the present invention, among these copolymer rubbers, ethylene-propylene copolymer rubber and ethylene-propylene non-conjugated diene rubber are preferably used, and usually, the molar ratio of ethylene unit to propylene unit (ethylene / propylene) is 50. / 50-90 / 10 ethylene-propylene copolymer rubber, ethylene-propylene non-conjugated diene rubber is used, especially the above-mentioned molar ratio is 55 / 45-85 / 15 ethylene-
Propylene copolymer rubber and ethylene-propylene non-conjugated diene rubber are preferably used. Among them, ethylene-
Propylene non-conjugated diene copolymer rubber, especially ethylene-
Propylene-5-ethylidene-2-norbornene copolymer rubber and ethylene-propylene-5-ethylidene-
2-norbornene-dicyclopentadiene quaternary copolymer is preferred in that a thermoplastic elastomer composition having excellent heat resistance, tensile properties and rebound resilience can be obtained.

The Mooney viscosity of the copolymer rubber [ML _{1 + 4} (100
° C)], 10 to 250, particularly preferably 40 to 150. By using the above copolymer rubber having a Mooney viscosity within this range, a thermoplastic elastomer composition having excellent tensile properties and fluidity can be obtained.

Further, the iodine value (unsaturation degree) of the above copolymer rubber is
It is preferably 25 or less. By using the above copolymer rubber having an iodine value in this range, a thermoplastic elastomer composition having an excellent balance between fluidity and rubber-like properties can be obtained.

(B) Olefin-based Plastic The olefin-based plastic used in the present invention comprises a crystalline high-molecular-weight solid product obtained by polymerizing one or more monoolefins by either a high-pressure method or a low-pressure method. . Such olefin-based plastics include, for example, homo- or copolymer resins composed of isotactic and syndiotactic monoolefins, and representative ones thereof are commercially available.

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, Examples thereof include 1-decene and a mixed olefin of two or more of these. Regarding the polymerization mode, any of a random type and 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?
An olefin-based plastic which is mixed with a peroxide and kneaded under heating to thermally decompose to reduce the molecular weight and increase the fluidity of the resin. Examples of such an olefin-based plastic include isotactic polypropylene and propylene. And a small amount of other α-olefin, such as propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1
-Hexene copolymer, propylene-4-methyl-1-pentene copolymer, and the like. The melt index (ASTM-D-1238-65T, 230 ° C.) of the olefin plastic used in the above mixing is preferably in the range of 0.1 to 50, particularly preferably 5 to 20. In the present invention, the olefin-based plastic contributes to improving the fluidity and heat resistance of the composition.

(C) Unsaturated carboxylic acid or derivative thereof, unsaturated epoxy monomer, unsaturated hydroxy monomer The unsaturated carboxylic acid or derivative thereof used as one of the components (c) in the present invention is specifically described below. Are α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and tetrahydrophthalic acid, bicyclo [2,2,1] hept-2-ene-5, Unsaturated carboxylic acids such as 6-dicarboxylic acid, anhydrides of α, β-unsaturated carboxylic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and bicyclo [2,2,1] hepto Anhydrides of unsaturated carboxylic acids such as -2-ene-5,6-dicarboxylic anhydride, methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, fumaric acid Diethyl, dimethyl itaconate, diethyl citrate,
Dimethyl tetrahydrophthalic anhydride, bicyclo [2,2,
1] Esters of unsaturated carboxylic acids such as dimethyl-2-hept-2-ene-5,6-dicarboxylate. Among them, maleic acid, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid or anhydrides thereof are preferably used.

In the present invention, examples of the unsaturated epoxy monomer which is another component of the component (c) include, specifically, unsaturated monocarboxylic acids such as glycidyl acrylate, glycidyl methacrylate, and glycidyl p-styrylcarboxylate. Glycidyl ester: 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 ester or polyglycidyl ester of unsaturated polycarboxylic acid such as methyl-2,3-dicarboxylic acid: allyl 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,
unsaturated glycidyl ethers such as glycidyl ether of o-vinylphenol, glycidyl ether of m-vinylphenol, and glycidyl ether of p-vinylphenol: 2- (o-vinylphenyl) ethylene oxide;
(P-vinylphenyl) ethylene oxide, 2- (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-gussidylstyrene, 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, aryl-2,3-epoxycyclopentyl ether and the like are preferably used.

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

These components (c) act as a graft modifier during a dynamic heat treatment described later, and bond the laminate interface between the skin layer made of polyamide, polyurethane or polyester and the intermediate layer (II) made of modified polyolefin elastomer. Has the function of strengthening power.

(D) Peroxide non-crosslinked rubbery substance The component (d) component peroxide noncrosslinked rubbery substance is, for example, polyisobutylene, butyl rubber (IIR),
A hydrocarbon-based rubbery substance which does not crosslink even when mixed with a peroxide and kneaded under heating and does not decrease in fluidity, such as propylene-ethylene copolymer rubber of 70 mol% or more, atactic polypropylene, etc. Say. Among them,
Polyisobutylene and butyl rubber (IIR) are most preferred for performance and handling.

The peroxide non-crosslinked rubbery substance improves the flowability of the thermoplastic elastomer composition, and a peroxide noncrosslinked rubbery substance having a Mooney viscosity of 60 or less is particularly preferred.

(E) Mineral oil-based softening agent The mineral oil-based softening agent of the above component (e) generally mixes rubber as a filler, while weakening the intermolecular force of the rubber and facilitating the processing. A high-boiling petroleum fraction used to help disperse carbon black and white carbons, or reduce the hardness of vulcanized rubber to increase its flexibility and elasticity. It is a paraffinic, naphthenic, aromatic They are distinguished by tribes.

Production of Modified Polyolefin-Based Elastomer In the laminated molded article of the present invention, the modified polyolefin-based elastomer constituting the intermediate layer (II) includes the components (a) to (c) described above and, if necessary, (d)
And / or by blending the components of (e) according to the quantitative ratios described above, dynamically heat treating in the presence of an organic peroxide, and partially crosslinking.

Also, a fibrous filler, a polyolefin plastic, or a filler may be used as long as the fluidity (moldability) and rubber properties of the modified polyolefin-based thermoplastic elastomer and the adhesiveness to a skin layer made of polyamide, polyurethane or polyester are not impaired. Agents, for example, glass fiber, potassium titanate fiber, high density polyethylene, medium density polyethylene, 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 Alternatively colorants example, it can be compounded carbon black, titanium oxide, zinc white, 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, anti-aging agents, weather-resistant stabilizers, antistatic agents, metal soaps, waxes, etc. Lubricants and the like can be blended in amounts that are used in olefin-based plastics or olefin-based copolymer rubbers.

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.

Specific examples of the organic peroxide used for producing the modified polyolefin-based elastomer in the present invention include dicumyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di- (tert-butyl). Peroxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (t
ert-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,
Examples include tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide, and the like.

Among them, 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 are preferred, with 1,3-bis (tert-butylperoxyisopropyl) benzene being most preferred.

The amount of the organic peroxide is determined according to the above (a),
0.05 to 3% by weight based on the total amount of the components (b) and (c),
Preferably it is chosen to be in the range of 0.1-1% by weight. When the amount is within the above range, the resulting modified polyolefin-based elastomer has sufficient rubber-like properties such as heat resistance, tensile properties, elastic recovery and rebound resilience and strength, and has excellent moldability.

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

As the kneading apparatus, a conventionally known kneading apparatus such as an open-type mixing roll, a non-open-type Banbury mixer, an extruder, a kneader, or a continuous mixer is specifically used. Among them, it is preferable to use a non-open type device,
The kneading is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide. Kneading is carried out at a temperature at which the half-life of the organic peroxide used is less than 1 minute, usually at 150 to 280 ° C.
The reaction may be performed at 170 to 240 ° C. for 1 to 20 minutes, preferably 1 to 10 minutes. The applied shearing force is usually 10 to 10 ⁴ sec ⁻¹ , preferably 10 ² to 10 ³ sec ⁻¹ at a shear rate.

In the present invention, sulfur, p-quinonedioxime, p, p '
-Dibenzoylquinone dioxime, N-methyl-N, 4-
Peroxy crosslinking aids such as dinitrosoaniline, nitrobenzene, diphenylguanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, eletine glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene Polyfunctional methacrylate monomers such as glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate or vinyl stearate 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 the olefin-based plastic mainly containing the object to be treated, and has an organic peroxide solubilizing action, Since it functions as a peroxide dispersing agent, it is most preferable because a cross-linking effect by heat treatment is uniform and a composition having good balance between fluidity and physical properties can be obtained. In the present invention, the compounding amount of such a cross-linking aid or polyfunctional vinyl monomer is 0.1 to 2% by weight based on the whole object to be treated.
In particular, the content is preferably in the range of 0.3 to 1% by weight. By blending in this range, a composition having excellent fluidity and not causing a change in physical properties due to heat history at the time of processing and molding the composition can be obtained.

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, partial crosslinking is performed,
A modified polyolefin-based elastomer graft-modified with the component (c) is obtained.

In the present invention, the graft-modified polyolefin-based elastomer is partially crosslinked when 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 the sample was taken out on a filter paper and kept at room temperature for 72 hours or more at constant weight. 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-based copolymer rubber in the sample, ie, from the weight of the sample, cyclohexane-soluble components (eg, mineral oil and plasticizer) other than the peroxide-crosslinked olefin-based copolymer rubber and the olefin-based plastic The weight of cyclohexane-insoluble components (fibrous fillers, fillers, pigments, etc.) other than the component and the five polymer components] is defined as “corrected initial weight (X)”.

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

The above-mentioned modified polyolefin-based elastomer is excellent in flexibility, heat resistance and cold resistance, and also excellent in adhesion to polyamide, polyurethane or polyester.

Skin Layer The polymer constituting the skin layer used in the present invention is at least one polymer selected from the group consisting of polyamide, polyurethane and polyester.

The polyamide used in the present invention includes hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis ( Aminomethyl)
Aliphatics such as 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
Polyamides obtained from lactams such as -caprolactam and ω-laurolactam, copolymerized polyamides composed of these components, and mixtures of these polyamides. Specific examples include nylon 6, nylon 66, and nylon.
610, nylon 9, nylon 11, nylon 12, nylon 6
/ 66, nylon 66/610, nylon 6/11 and the like.

As the polyurethane used in the present invention, any known polyurethane can be used. For example, any polyurethane such as polyester-based polyurethane and polyether-based polyurethane classified from the viewpoint of the raw material polyol component, and soft, semi-rigid or rigid polyurethane classified from the viewpoint of hardness can be used.

In particular, when the laminated molded article of the present invention is used as an interior material of a vehicle such as an automobile, it is preferable to form the skin layer in the form of a polyurethane sheet. In this case, it is desirable to use a thermoplastic polyurethane in terms of ease of lamination.

Specific examples of the polyester used in the present invention include thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene isophthalate.

The above polyamide, polyurethane, polyester,
Because of their excellent heat resistance, oil resistance, solvent resistance, abrasion resistance, and scratch resistance, these polymers are most suitable as a surface outer layer material of a molded article.

Core layer / intermediate layer (I) / intermediate layer (II) as described above
The first laminated molded article according to the present invention having a four-layer structure of / skin layer is obtained according to the first, second or third manufacturing method according to the present invention as described below.

First, a method for manufacturing the first laminated molded product according to the present invention will be described.

As a first step in the first production method according to the present invention, an intermediate layer (I) composed of the polyolefin foam or polyurethane foam, an intermediate layer (II) composed of the modified polyolefin-based elastomer, and the polymer are formed. After preheating the three-layer sheet composed of the skin layer, the three-layer sheet is suction-adhered to the inner wall surface of the cavity of the vacuum forming die to obtain a preform having a concave portion.

The method for producing the three-layer sheet varies depending on the shape, size, required physical properties, and the like of the final product. Examples of the method for producing the three-layer sheet include a sheet made of the polyolefin foam or the polyurethane foam, There is a production method in which a sheet made of a modified polyolefin-based elastomer and a sheet made of the polymer are heat-sealed using a molding machine such as a calender roll molding machine or a compression molding machine to obtain the three-layer sheet.

In the present invention, if necessary, an embossing process may be performed on the surface of the skin layer made of the polymer using an embossing roll, or letters and patterns may be printed on the surface of the skin layer in the printing step. Good.

In the present invention, the thickness of each layer of the three-layer sheet varies depending on the use of the laminated molded article, but generally the intermediate layer (I)
Is 0.5 to 10 mm, the thickness of the intermediate layer (II) is 0.1 to 50 mm,
It is preferable that the thickness of the skin layer is in the range of 5 to 500 µm.

In the first method for producing a laminated molded product according to the present invention, for example, an apparatus as shown in FIG. 1 is used. As shown in FIGS. 1 (a) to 1 (d), this apparatus is provided with at least one pair of male and female vacuum injection molds (1, 2). The female mold 1 is provided with an air suction path 7 connected to a vacuum pump 6 for reducing the pressure inside the cavity 3. Also, on the inner wall surface of the cavity of the female mold 1,
Embossed or embossed patterns are engraved as necessary.

With the pair of male and female molds (1, 2) open, the three-layer sheet 4 is extended so as to cover the cavity opening of the female mold 1 (FIG. 1 (a)). The preliminary heating is performed by bringing the heater section 5 of the preheating device close to the layer sheet 4.
The preheating temperature is usually from 150 to 200 ° C. As means for preheating, not only the approach of the heater section 5 but also various means such as blowing of warm air and contact of a heating roll can be used.

Thereafter, the inside of the cavity 1 of the female mold 1 is made negative pressure by suction by the vacuum pump 6, and the three-layer sheet 4 is brought into close contact with the inner wall surface of the cavity by suction to obtain a preform (FIG. 1 (b)).

At this time, the three-layer sheet 4 adheres extremely well according to the cavity shape of the mold (1, 2), and does not cause any cracks or wrinkles. Further, since the texture penetrates deeply into the unevenness forming the grain pattern, the grain pattern can be transferred very well.

Next, as a second step in the first manufacturing method according to the present invention, the preformed product obtained in the first step is in close contact with the inner wall surface of the cavity of the vacuum forming die or the vacuum forming The mold is clamped in a state in which the mold is in close contact with the inner wall surface of the cavity of the molding die separate from the die to obtain a molded product having a concave portion.

The mold clamping is performed using a pair of male and female dies (1, 2) as shown in FIG. 1 (c).

Finally, as a third step in the first manufacturing method according to the present invention, molding is performed by injecting a synthetic resin in a flow plasticized state into a concave portion of a molded product that is in close contact with the cavity inner wall surface of the mold. I do.

The synthetic resin in the above-mentioned fluidized plasticized state refers to, for example, a molten resin obtained by heating, kneading and dispersing with a screw type extruder, or a resin made into a fluidized plasticized state with a solvent.

The injection molding is performed by injection-filling a synthetic resin in a fluidized plasticized state from a nozzle 8 of an injection molding machine into a concave portion of a molded product and performing mold clamping. The mold is cooled or heated. After the resin has solidified, the first laminated molded article according to the present invention is taken out as a product.

The trimming for taking out the product can be performed in the molds (1, 2) at the same time as the mold clamping, so that trimming in a subsequent step is unnecessary.

Next, a method for manufacturing the second laminated molded product according to the present invention will be described.

As a first step in the second production method according to the present invention, an intermediate layer (I) made of the polyolefin foam or polyurethane foam, an intermediate layer (II) made of the modified polyolefin-based elastomer, and the polymer are used. After preheating the three-layer sheet composed of the skin layer, the three-layer sheet is suction-adhered to the inner wall surface of the cavity of the vacuum forming die to obtain a preform having a concave portion.

The three-layer sheet is the same as the three-layer sheet described in the first method for producing a laminated molded article according to the present invention.

In the second manufacturing method according to the present invention, for example, a manufacturing apparatus as shown in FIG. 2 is used.

As shown in FIG. 2, this apparatus includes a pair of molding dies (1, 2) with the female mold 1 facing down and the male mold 2 facing up, and the molds (1, 2) are opened. The three-layer sheet 4
Is supplied between the molds (1, 2) while being pre-heated by the heater section 5 of the pre-heating device, is stretched so as to cover the cavity opening of the female mold 1, and then is suctioned by the vacuum pump 6. The three-layer sheet 4 is brought into close contact with the inner wall surface of the cavity of the mold (1, 2) by suction to obtain a preform having a concave portion. Also in this case, as in the case of the above-described first manufacturing method according to the present invention, the suction adhesion of the three-layer sheet 4 to the mold cavity 3 and the transferability of the grain pattern are good.

Next, as a second step in the second manufacturing method according to the present invention, in the concave portion of the preformed product that is in close contact with the cavity inner wall surface of the vacuum forming die, or A synthetic resin in a flow plasticized state is poured into a concave portion of a preform, which is brought into close contact with the cavity inner wall surface of a separate molding die, and stamping molding is performed.

The synthetic resin in the fluidized plasticized state is extruded from the extruder 10 and poured from the injection nozzle 11 into the recess of the preform. Further, in the present invention, the injection nozzle 11 movable in the X-Y direction over the entire concave portion of the preform is moved in accordance with the locus of a predetermined program, and the synthetic resin in the fluidized plasticized state is converted into the preform. It is preferable to perform the injection over the entire recess.

Note that the synthetic resin in the fluidized plasticized state refers to, for example, a molten resin obtained by heating, kneading, and dispersing with a screw type extruder, or a resin that is made into a fluidized plasticized state with a solvent.

The stamping molding is performed by clamping using the mold 2. By performing this mold clamping, the synthetic resin in the fluidized plasticized state becomes a mold (1, 2).
Because the cavity 3 flows and fills with the pressing force, the molded body is solidified by subsequent cooling or the like, and then the first laminated molded body according to the present invention is taken out as a product.

Also in this case, the trimming can be performed in the mold (1, 2) at the same time as the mold clamping, so that trimming in a later step is unnecessary.

Next, a method of manufacturing the third laminated molded product according to the present invention will be described.

In the third method for producing a laminated molded product according to the present invention, the core layer made of the synthetic resin, the intermediate layer (I) made of the polyolefin foam or the polyurethane foam,
Intermediate layer (I) comprising the modified olefin-based elastomer
After preheating a four-layer sheet composed of I) and the skin layer made of the polymer, the four-layer sheet is vacuum-formed.

The method for producing the four-layer sheet, like the method for producing the three-layer sheet, differs depending on the shape, size, required physical properties, and the like of the final product. For example, the sheet made of the synthetic resin, the polyolefin foam, or A method of obtaining a four-layer sheet by heat-sealing a sheet made of a polyurethane foam, a sheet made of the modified polyolefin-based elastomer, and a sheet made of the polymer using a molding machine such as a calender roll molding machine or a compression molding machine. There is.

Also in the third manufacturing method according to the present invention, embossing may be performed on the surface of the skin layer made of the polymer, and characters, pictures, and patterns may be printed on the surface of the skin layer in the printing step. In addition, the formation of the grain pattern can also be performed using a vacuum-forming mold having a grain pattern.

In the present invention, the thickness of each layer of the four-layer sheet varies depending on the use of the laminated molded article, but generally the thickness of the core layer is 0.1 to 50 mm, the thickness of the intermediate layer (I) is 0.5 to 10 mm, and the thickness of the intermediate layer (II) ) Is 0.1 ~ 50mm, skin layer thickness is 5 ~ 500μ
It is preferably within the range of m.

 The above preheating temperature is usually 150 to 250 ° C.

In the present invention, the four-layer sheet can be vacuum-formed using a concave mold for vacuum forming, or the four-layer sheet can be vacuum-formed using a convex mold for vacuum forming. it can.

The first laminated molded article according to the present invention is obtained by the vacuum molding. Trimming of the laminated molded body is usually performed after the above-mentioned vacuum molding.

Next, the second laminated molded article according to the present invention will be described.

The second laminated molded article according to the present invention includes a core layer made of a synthetic resin, an intermediate layer (II) made of a modified polyolefin-based elastomer, and a skin layer made of a polymer. The difference from the laminated molded article 1 is whether or not an intermediate layer (I) made of a polyolefin foam or a polyurethane foam is present. Therefore, the core layer in the second laminated molded article according to the present invention,
The intermediate layer (II) and the skin layer are the same as the core layer, the intermediate layer (II) and the skin layer in the first laminated molded article according to the present invention described above.

The second laminated molded article according to the present invention having the three-layer structure of the core layer / intermediate layer (II) / skin layer as described above is the fourth, fifth, or sixth aspect of the present invention as described below. Obtained according to the production method described above.

First, a fourth method for manufacturing a laminated molded product according to the present invention will be described.

The fourth method for producing a laminated molded article according to the present invention is the same as the method for producing a first laminated molded article according to the present invention described above,
The first laminate molding according to the present invention except that a two-layer sheet composed of an intermediate layer (II) made of the modified polyolefin-based elastomer and a skin layer made of the polymer is used instead of the three-layer sheet. It is the same as the body manufacturing method.

The method for producing the two-layer sheet varies depending on the shape, size, required physical properties, and the like of the final product. As the method for producing the two-layer sheet, specifically, a sheet comprising the modified polyolefin-based elastomer and A method of obtaining the two-layer sheet by heat-sealing a sheet made of the polymer using a molding machine such as a calendar roll molding machine and a compression molding machine, and forming the modified polyolefin-based elastomer into a sheet by extrusion molding or calendar molding. ,
Subsequently, this sheet and a sheet made of the polymer previously formed into a sheet are heat-fused to obtain the above-mentioned two-layer sheet, or the modified polyolefin-based elastomer and the polymer are simultaneously extruded by a multilayer extruder to obtain a hot melt. There is a method of obtaining the above two-layer sheet by attaching.

Next, a method of manufacturing the fifth laminated molded product according to the present invention will be described.

The fifth method for producing a laminated molded article according to the present invention is the same as the method for producing a second laminated molded article according to the present invention described above,
Second lamination molding according to the present invention, except that a two-layer sheet composed of an intermediate layer (II) made of the modified polyolefin-based elastomer and a skin layer made of the polymer is used instead of the three-layer sheet. It is the same as the body manufacturing method.

The two-layer sheet is the same as the two-layer sheet described in the fourth method for producing a laminate according to the present invention.

Next, a sixth laminated molded article according to the present invention will be described.

The method for producing a sixth laminated molded article according to the present invention is the same as the method for producing a third laminated molded article according to the present invention described above,
Except for using a three-layer sheet composed of a core layer composed of the synthetic resin, an intermediate layer (II) composed of the modified polyolefin-based elastomer, and a skin layer composed of the polymer instead of the four-layer sheet, This is the same as the third method of manufacturing a laminated molded article according to the present invention.

The three-layer sheet is the same as the three-layer sheet described in the first method for producing a laminated molded article according to the present invention.

Effects of the Invention The first laminated molded article according to the present invention comprises a core layer composed of a synthetic resin, an intermediate layer (I) composed of a polyolefin foam or a polyurethane foam, and an intermediate layer composed of a specific modified polyolefin-based elastomer ( II) and a skin layer made of a specific polymer, so that it has excellent heat resistance, cold resistance, oil resistance, solvent resistance, abrasion resistance, and scratch resistance, and has a soft feeling. is there. Further, when the first laminated molded article according to the present invention has a grain pattern, not only the above-described effects are obtained but also an effect is obtained in which a sharp grain pattern is formed.

According to the first, second, and third manufacturing methods of the laminated molded article according to the present invention, the first laminated molded article according to the present invention having the above-described various effects can be obtained. Further, the second laminated molded article according to the present invention includes a core layer made of a synthetic resin, an intermediate layer (II) made of a specific modified polyolefin-based elastomer, and a skin layer made of a specific polymer. Therefore, it is excellent in heat resistance, cold resistance, oil resistance, solvent resistance, abrasion resistance and scratch resistance, and has an effect of being rich in soft feeling. Further, when the second laminated molded article according to the present invention has a grain pattern, there is an effect that not only the above-described effects are obtained but also a sharp grain pattern is formed.

According to the fourth, fifth, and sixth manufacturing methods according to the present invention, the second laminated molded article according to the present invention having the various effects described above can be obtained.

Hereinafter, the present invention will be described with reference to examples, the present invention,
It is not limited to these examples.

First, the method for evaluating interlayer adhesion, grain depth, softness, abrasion resistance, scratch resistance, oil resistance, solvent resistance, heat resistance and cold resistance of the laminated molded articles obtained in the examples and comparative examples is described. Shown below.

[Evaluation method] (1) Interlaminar adhesiveness 1) Tensile peel test Peel the skin layer from the end of the test piece and peel in the direction of 180 ° reversal under the condition of a pull rate of 25 mm / min to peel, and the maximum peel load at that time Was divided by the width of the test piece, and this value was defined as the interlayer adhesive strength between the skin layer and the intermediate layer (II).

In the method for evaluating interlayer adhesion between the intermediate layer (II) and the intermediate layer (I) or the core layer, the intermediate layer (I
I) was peeled off, and a tensile peeling test was performed according to the above method to evaluate the peeling test.

Further, in the method for evaluating the interlayer adhesion between the intermediate layer (I) and the core layer, the intermediate layer (I) was peeled off, and a tensile peel test was performed in accordance with the above method to evaluate the evaluation.

The size of the test piece is 100 mm in length and 25 mm in width,
The test piece was collected from the portion shown in FIG. 3 of the laminated molded product.

2) Goban-peeling test With a sharp razor, 11 scratches of 1 mm in depth are made on the sheet surface at 2 mm intervals, and 11 similar scratches are made at right angles to the sheet surface.

As a result, 100 square cells cut into 2 mm square are formed.
Cellotape made by Nichiban Co., Ltd. was attached so as to cover all of the 100 cells, and the attached tape was vigorously peeled off, and the peeled state was observed.

The evaluation of the peeled state is the number / 100 remaining without peeling out of 100 pieces
Indicated by 100/100 indicates a state where no peeling occurred, and 0/100 indicates a state where the whole peeled.

The size of the test piece is 100 mm in length and 100 mm in width,
Test specimens were taken from the locations shown in FIG. 3 of the laminated molded product.

(2) Depth of Emboss The distance from the peak to the valley of the emboss transferred to the surface of the laminated molded article was measured.

(3) Soft feeling The surface of the laminated molded product was touched with a hand, and the feeling was displayed in five levels.

5 ... very soft 4 ... soft 3 ... normal 2 ... hard 1 ... very hard (4) Abrasion resistance The Taber abrasion test is performed under the condition of a CS-11 abrasion wheel and a load of 500 g, and 1000 rotations. The wear loss of the laminated molded article was measured.

(5) Scratch resistance Using a Taber type scratch tester, the blade edge of the cutter was brought into contact with the sample surface under a load of 100 g, and the sample was rotated once at 1 rpm, and then the surface was observed for scratches.

Rating: A Not at all.

B: Slightly recognized.

C Obviously recognized.

(6) Oil resistance 1 g of JIS No. 3 oil was dropped on the surface of the sheet, left at 70 ° C. for 168 hours, returned to room temperature, and when the surface was strongly wiped with a flannel cloth, was examined for any abnormality on the surface.

Rating: A No abnormality.

B: Traces such as cloudiness are recognized.

C Causes damage due to peeling and dissolution.

(7) Solvent resistance When the surface was strongly wiped with a flannel cloth containing industrial gasoline, it was examined whether there was any abnormality on the surface.

Rating A: No abnormality.

B: Traces such as cloudiness are recognized.

C: Damage due to peeling and dissolution occurs.

(8) Heat resistance A dumbbell No. 1 of JIS K 6301 tensile test piece was punched out from the longitudinal direction of the sheet, left at 120 ° C. for 500 hours, returned to room temperature, and subjected to a tensile test at a speed of 200 mm / min. Measure elongation (E Baged). On the other hand, the elongation at break (E Borig) of the sample before heat aging was measured in advance,
The retention of elongation at break was calculated.

AR (EB)% = E Baged / E Borig × 100 (9) Cold resistance A test piece of 20 mm width and 100 mm length is taken from the sheet, and both ends in the length direction are overlapped with the skin surface outside and the test piece is placed. After fixing the end opposite to the bent part,
After standing at ℃ for 20 minutes, a falling body of 5 kg was dropped from a height of 5 cm onto the bent portion, and then the skin was examined for cracks and cracks.

Examples of the first production method according to the present invention, etc. Example 1 [(i) Production of three-layer sheet composed of polypropylene foam layer, modified polyolefin-based elastomer layer and polyamide layer] Ethylene content 70 mol%, iodine value 12. Ethylene / propylene / 5- with Mooney viscosity [ML _{1 + 4} (100 ℃)] 120
Ethylidene-2-norbornene copolymer rubber (hereinafter referred to as EP
80 parts by weight of DM (1) and MFR (ASTM D 1238-65)
T, 230 ° C.) 13 g / 10 min, 20 parts by weight of polypropylene (hereinafter abbreviated as PP) having a density of 0.91 g / cm ³ were kneaded with a Banbury mixer in a nitrogen atmosphere at 180 ° C. for 5 minutes. The sheet was passed through a roll to form a sheet, which was formed into square pellets by a sheet cutter.

Next, 100 parts by weight of the square pellet and 1,3-bis (tert-
Butyl peroxyisopropyl) benzene (hereinafter abbreviated as peroxide (a)) 0.3 part by weight, divinylbenzene (hereinafter abbreviated as DVB) 0.5 part by weight, and maleic anhydride (hereinafter abbreviated as MAH) 0.5 part by weight were Henschel The mixture was mixed by stirring with a mixer. Next, this mixture was extruded at 220 ° C. in a nitrogen atmosphere with a single screw extruder having an L / D = 30 and a screw diameter of 50 mm to produce a graft-modified polyolefin diameter elastomer (hereinafter abbreviated as TPE-A).

Next, using a T-die extruder with a diameter of 90 mm manufactured by Toshiba Machine Co., Ltd.
= 22, extrusion temperature 220 ℃, T die is coat hanger die,
Extruded into a sheet at a take-off speed of 2.5 m / min. The extruded sheet-shaped TPE-A in a molten state was converted to a polyamide sheet (Nylon 6 manufactured by Toray Industries, Inc., trade name: Amiran CM1021,
50μm thick) and polypropylene foam (Toray product name PP
AN20030, foaming ratio 20; thickness 3 mm), laminated and passed between a pair of rolls, in which case, the polypropylene is in contact with the roll at a roll temperature of 60 ℃, and the polyamide sheet is in contact with the roll at room temperature The thickness of the modified polyolefin elastomer is 0.7 mm and the thickness of the polyamide is 5
A three-layer sheet having a thickness of 0 μm and a polypropylene foam thickness of 3 mm was produced.

[(Ii) Production of thermoplastic elastomer for core] Ethylene / propylene / ethylidene norbornene copolymer rubber having an ethylene content of 70 mol%, an iodine value of 15, and a Mooney viscosity of [ML _{1 + 4} (100 ° C.)] of 120 (hereinafter, referred to as “ 70 parts by weight of EPDM (abbreviated as (1)) and MFR (ASTM D 1238-65T, 230 ° C) 13
g / 10 minutes, density of 0.91 g / cm ³ polypropylene (hereinafter abbreviated as PP) 30 parts by weight and butyl rubber (Esso 11R-065, degree of unsaturation 0.8 mol%, hereinafter abbreviated as 11R) 10 parts by weight 30 parts by weight of paraffin-based process oil (hereinafter abbreviated as oil) in a nitrogen atmosphere at 190 ° C. using a Banbury mixer.
After kneading for 5 minutes, the kneaded material was passed through a roll to produce square pellets with a sheet cutter.

Next, 100 parts by weight of the square pellet and 1,3-bis (tert
0.3 parts by weight of -butylperoxyisopropyl) benzene (hereinafter abbreviated as peroxide (A)) and 0.5 parts by weight of divinylbenzene (hereinafter abbreviated as DVB) were stirred and mixed with a Henschel mixer. Next, the pellets were extruded with an extruder at 220 ° C. under a nitrogen atmosphere to obtain a thermoplastic elastomer [hereinafter, abbreviated as TPE (1)] of 3 g / 10 minutes of MFR.

[(Iii) Production of Laminated Molded Body] The above-described three-layer sheet is preheated, and the polyamide layer constituting the three-layer sheet is turned to the female mold side, and the female mold has a crimp pattern with a depth of 150 μm by vacuum molding. The female mold is closed after being drawn into close contact with the inner wall surface of the cavity where the is applied, and the thermoplastic resin for the core in a molten state is injected from the nozzle of the injection molding machine into the cavity from the male mold side. The elastomer [TPE (1)] was injected and solidified, and when the TPE (1) was integrated with the above-mentioned three-layer sheet, the mold was opened to obtain a laminated molded article composed of four layers.

 The vacuum forming conditions are as follows.

Heater temperature: 360 ° C. Preheating temperature: 45 seconds Vacuum pressure: 700 mmHg The conditions of the above injection molding are as follows.

Molding machine: Dynamelter (manufactured by Meiki Seisakusho) Molding temperature: 220 ° C Injection pressure: Primary pressure 1000 kg / cm ² Secondary pressure 700 kg / cm ² Injection speed: Maximum Molding cycle: 90 seconds / cycle Gate: Direct gate (land) Length 10mm, width 10mm,
(Thickness: 3 mm) The interlayer adhesion between the polyamide layer (skin layer) and the polypropylene foam layer [intermediate layer (I)], the TPE-A layer [intermediate layer ( II)] and the TPE (1) layer (core layer) with respect to the interlayer adhesion, emboss depth, softness, abrasion resistance, scratch resistance, oil resistance, solvent resistance, heat resistance and cold resistance described above. The method was evaluated.

 Table 1 shows the results of the evaluation.

Example 2 A laminate formed of four layers in the same manner as in Example 1 except that (i) the production of the three-layer sheet and (ii) the production of the thermoplastic elastomer for the core of Example 1 were carried out as follows. Was obtained and evaluated.

(I) Production of three-layer sheet In the production of (i) three-layer sheet of Example 1, EPDM was used.
The mixing ratio of (1) and PP is 60 parts by weight of EPDM (1), PP 40
Parts by weight, and butyl rubber (manufactured by Esso, IIR-06
5) A graft-modified polyolefin-based elastomer (hereinafter abbreviated as TPE-B) was produced in the same manner as in Example 1 except that 20 parts by weight and 40 parts by weight of paraffin-based process oil were added. -B, a polypropylene foam and a polyamide sheet (Nylon 12, manufactured by Daicel Huls, trade name: Diamide L2140, 50 μm thickness), the thickness of the modified polyolefin-based elastomer layer (TPE-B layer) was 0.7 in the same manner as in Example 1. mm, the thickness of the polypropylene foam layer was 3 mm, and the thickness of the polyamide layer was 50 μm.

(Ii) Production of thermoplastic elastomer for cores Ethylene propylene-ethylidene norbornene pellets with an ethylene content of 78 mol%, an iodine value of 10, a Mooney viscosity [ML _{1 + 4} (100 ° C)] of 160, and an oil extension of 40 parts by weight 60 parts by weight of a copolymer rubber (hereinafter abbreviated as EPDM (2)) (accordingly,
43 parts by weight of EPDM, 17 parts by weight of oil, 40 parts by weight of PP, and 2,5-dimethyl-2,5-di (t-butylperoxy)
Hexin-3 (hereinafter abbreviated as peroxide (B)) 0.5
Parts by weight with a Henschel mixer. Next, this mixture was extruded at 220 ° C. under a nitrogen atmosphere using a Warner twin-screw extruder (L / D = 43, meshing type, isotropic rotation, triple-type screw), and a thermoplastic elastomer [MFR 15 g / 10 min. , Abbreviated as TPE (2)].

 Table 1 shows the results of the evaluation.

Example 3 (i) Production of a three-layer sheet of Example 1 was carried out as follows, and instead of TPE (1), a melt index (ASTM D-1238-65T, 230 ° C.) 13 and a density of 0.91 g / A laminated molded body consisting of four layers was obtained and evaluated in the same manner as in Example 1 except that polypropylene having a cm ³ of a content [hereinafter abbreviated as PP (1)] was used.

(I) Production of three-layer sheet In the production of (i) three-layer sheet of Example 1, EPDM was used.
The mixing ratio of (1) and PP is 80 parts by weight of EPDM (1), PP 20
Parts by weight, and butyl rubber (manufactured by Esso, IIR-06
5) By adding 10 parts by weight and 30 parts by weight of paraffin-based process oil to produce unmodified polyolefin-based elastomer square pellets, graft-modified polyolefin-based elastomer (hereinafter, referred to as glycidyl methacrylate instead of maleic anhydride) TPE-C) and a modified polyolefin-based elastomer layer in the same manner as in Example 1 except that a polyester sheet (Lumirror manufactured by Toray Industries, Inc., 50 μm thick) was used instead of the polyamide sheet. A three-layer sheet was manufactured in which the thickness of the (TPE-C layer) was 0.7 mm, the thickness of the polypropylene foam layer was 3 mm, and the thickness of the polyester layer was 50 μm.

 Table 1 shows the results of the evaluation.

Example 4 The production of (i) a three-layer sheet of Example 1 was carried out as follows, and fine powder talc was replaced with 10 parts of TPE (1).
5% / 10% MFR containing 10% short fiber glass fiber
In the same manner as in Example 1 except that polypropylene (hereinafter, abbreviated as PP (2)) was used, a laminated molded article having four layers was obtained and evaluated.

(I) Production of three-layer sheet In the production of (i) three-layer sheet of Example 1, a graft-modified polyolefin-based elastomer (hereinafter abbreviated as TPE-D) is produced by using hydroxypropyl methacrylate instead of maleic anhydride. And a polyurethane sheet instead of a polyamide sheet (thermoplastic polyurethane P26SRNAT made by Nippon Polyurethane, 50 μm thick)
Except that the thickness of the modified polyolefin-based elastomer layer (TPE-D layer) was 0.7
mm, the thickness of the polypropylene foam layer was 3 mm, and the thickness of the thermoplastic polyurethane layer was 50 μm.

 Table 1 shows the results of the evaluation.

Example 5 In the production of (i) a three-layer sheet of Example 1, the graft-modified polyolefin-based elastomer (TPE) of Example 1 was used.
-A) 80 parts by weight of a constant density polyethylene (density 0.91
7 g / cm ³ , 20 parts by weight of a melt index 6.5 (190 ° C.), dry-blended and supplied to a T-die extruder. Thereafter, in the same manner as in Example 1, the modified polyolefin-based elastomer layer (TPE-E layer) ) Is 0.7 mm, the thickness of the polypropylene foam layer is 3 mm, and the thickness of the polyamide layer is 50 μm. A molded body was obtained and evaluated.

 Table 1 shows the results of the evaluation.

Comparative Example 1 The procedure of Example 1 was repeated, except that a soft vinyl chloride sheet (0.75 mm thick) containing 50 parts by weight of dioctyl phthalate was used instead of the three-layer sheet.
A laminated molded article having three layers was obtained and evaluated.

 Table 1 shows the results of the evaluation.

Comparative Example 2 A laminated molded article composed of three layers in the same manner as in Example 1 except that a single-layer sheet of TPE-A having no laminated polyamide sheet was used instead of the three-layer sheet. Was obtained and evaluated.

 Table 1 shows the results of the evaluation.

Comparative Example 3 In the production of the (i) three-layer sheet of Example 1, graft modification was not performed, and thereafter, the same as Example 1 was performed.
Unmodified polyolefin-based elastomer layer (TPE-F layer)
Is 0.7 mm, the thickness of the polypropylene foam layer is 3 mm, and the thickness of the polyamide layer is 50 μm.
A laminated molded article having four layers was obtained and evaluated in the same manner as in Example 1 except that a layer sheet was manufactured.

 Table 1 shows the results of the evaluation.

Example of the Second Manufacturing Method According to the Present Invention, etc. Example 11 A four-layer lamination was performed in the same manner as in Example 1 except that (iii) the production of the laminated molded body of Example 1 was performed as follows. A molded body was obtained and evaluated.

(Iii) Manufacture of laminated molded article The polyamide layer constituting the three-layer sheet was preheated by heating the three-layer sheet of Example 1 to the female mold side, and the female mold was embossed with a depth of 150 μm by vacuum molding. After drawing in close contact with the inner wall surface of the cavity where the pattern is applied, the thermoplastic elastomer for core [TPE (1)] in a molten state is placed on the three-layer sheet with good distribution, and the male mold is closed. TPE
When (1) was solidified and integrated with the above-mentioned three-layer sheet, the mold was opened to obtain a laminated molded body composed of four layers.

The vacuum forming conditions are the same as the vacuum forming conditions in the first embodiment.

The conditions for the stamping molding are as follows.

Molding machine: Ikegai ISM-300 Screw diameter: 50mmφ Resin temperature: 230 ° C Press pressure: 200kg / cm ² Molding cycle: 50 seconds / cycle Molded product: Length 500mm, width 500mm, thickness 3mm Table 2 shows the evaluation results. Shown in

Example 12 In Example 11, the three-layer sheet of Example 11 (Example 1) was used.
Example 2 in place of the three-layer sheet) and TPE (1)
A laminated molded article composed of four layers was obtained and evaluated in the same manner as in Example 11 except that the three-layer sheet of Example 2 and the TPE (2) of Example 2 were used.

 Table 2 shows the results of the evaluation.

Example 13 In Example 11, the three-layer sheet of Example 11 (Example 1) was used.
Example 3 in place of the three-layer sheet of Example 1) and TPE (1)
3-layer sheet and melt index (ASTM D 1238
-65T, 230 ° C) 3 and a density of 0.91 g / cm ³ , except that polypropylene (hereinafter abbreviated as PP (3)) was used. The evaluation was performed.

 Table 2 shows the results of the evaluation.

Example 14 In Example 11, the three-layer sheet of Example 11 (Example 1) was used.
Example 4) in place of the three-layer sheet) and TPE (1)
In the same manner as in Example 11, except that a three-layer sheet of MFR and polypropylene (hereinafter, abbreviated as PP (4)) containing 0.7% of MFR and 10% of MFR containing 15% of fine powder talc and 15% of short fiber glass fiber were used. And a laminated molded product having four layers was obtained and evaluated.

 Table 2 shows the results of the evaluation.

Example 15 In Example 11, the three-layer sheet of Example 11 (Example 1) was used.
Example 5 in place of the three-layer sheet of Example 1) and TPE (1)
A laminated molded article composed of four layers was obtained and evaluated in the same manner as in Example 11, except that the three-layer sheet of Example 4 and PP (4) of Example 4 were used.

 Table 2 shows the results of the evaluation.

Comparative Example 11 In Example 11, Comparative Example 1 was used instead of the three-layer sheet.
Other than using a soft vinyl chloride sheet (0.75mm thick)
In the same manner as in Example 11, a laminated molded body including three layers was obtained,
The evaluation was performed.

 Table 2 shows the results of the evaluation.

Comparative Example 12 A laminated molded article composed of three layers in the same manner as in Example 11, except that a single-layer sheet of TPE-A having no laminated polyamide sheet was used instead of the three-layer sheet in Example 11. Was obtained and evaluated.

 Table 2 shows the results of the evaluation.

Comparative Example 13 In Example 11, the three-layer sheet of Example 11 (Example 1) was used.
In Example 11 except that the three-layer sheet of Comparative Example 3 was used instead of the three-layer sheet of Example 11), and a laminated molded body composed of four layers was obtained and evaluated.

 Table 2 shows the results of the evaluation.

Example 21 of Third Manufacturing Method According to the Present Invention Example 21 [Production of Four-Layer Sheet] TPE-A and TPE (1) of Example 1 were extruded by T-die having a diameter of 90 mm manufactured by Toshiba Machine Co., Ltd. Extruded into a sheet at a screw speed of full flight, L / D = 22, extrusion temperature of 220 ° C., T-die coated hanger die, take-up speed of 2.5 m / min. / Polypropylene foam of Example 1 / TPE (1) and passed between a pair of rolls in a laminated state, and then TPE (1)
The sheet is in contact with a roll at a roll temperature of 60 ° C, and the polyamide sheet is in contact with a roll at room temperature. The thickness of the thermoplastic elastomer layer (TPE (1) layer) is 2 mm, and the thickness of the polypropylene foam layer is 3 mm. The modified polyolefin-based elastomer layer (TPE-A layer) has a thickness of 0.7
mm, and a four-layer sheet having a polyamide layer thickness of 50 μm was produced.

[Manufacture of laminated molded article] The above-described four-layer sheet is preheated, and the polyamide layer constituting the four-layer sheet is turned to the female mold side, and a crimp pattern with a depth of 150 µm of the female mold is formed by vacuum molding. After being drawn into close contact with the inner wall surface of the cavity, drawing was performed, and the mold was opened to obtain a laminated molded body composed of four layers.

 The vacuum forming conditions are as follows.

Heater temperature: 360 ° C Preheating time: 100 seconds Vacuum pressure: 700 mmHg Polyamide layer (skin layer) and TPE-A layer [intermediate layer (I)
I)], the interlayer adhesion between the polypropylene layer [intermediate layer (I)] and the TPE (1) layer (core layer),
Texture depth, soft feeling, abrasion resistance, scratch resistance, oil resistance,
The solvent resistance, heat resistance, and cold resistance were evaluated by the above evaluation method.

 Table 3 shows the results of the evaluation.

Example 22 In Example 21, TPE of Example 2 was used instead of TPE-A.
The polyamide sheet of Example 2 was used instead of the polyamide sheet of Example 21 (polyamide sheet of Example 1) using PE-B, and the TPE (2) of Example 2 was used instead of TPE (1). ) Was performed in the same manner as in Example 21 except that (4) was used, and a four-layer laminated molded product was obtained and evaluated.

 Table 3 shows the results of the evaluation.

Example 23 In Example 21, TPE of Example 3 was used instead of TPE-A.
Using PE-C and using the polyester sheet of Example 3 in place of the polyamide sheet of Example 21 (polyamide sheet of Example 1), and further using TPE (1),
A four-layer laminate was obtained and evaluated in the same manner as in Example 21 except that PP (1) of Example 3 was used.

 Table 3 shows the results of the evaluation.

Example 24 In Example 21, TPE of Example 4 was used instead of TPE-A.
Using PE-D and using the polyurethane sheet of Example 4 instead of the polyamide sheet of Example 21 (polyamide sheet of Example 1), and further using TPE (1),
A four-layer laminate was obtained and evaluated in the same manner as in Example 21, except that PP (2) of Example 4 was used.

 Table 3 shows the results of the evaluation.

Example 25 In Example 21, TPE of Example 5 was used instead of TPE-A.
A four-layer laminate was obtained and evaluated in the same manner as in Example 21 except that PE-E was used.

 Table 3 shows the results of the evaluation.

Comparative Example 21 In Example 21, the soft vinyl chloride sheet of Comparative Example 1 was used instead of the polyamide sheet.
A three-layer laminate was obtained and evaluated in the same manner as in Example 21 except that EA was not used.

 Table 3 shows the results of the evaluation.

Comparative Example 22 In the same manner as in Example 21, except that the TPE-A of Example 1 was used instead of the polyamide sheet and that TPE-A was not used as the intermediate layer (II) in Example 21, In this way, a three-layer laminated molded article was obtained and evaluated.

 Table 3 shows the results of the evaluation.

Comparative Example 23 In Example 21, TPE of Comparative Example 3 was used instead of TPE-A.
Except that PE-F was used, 4
A layered laminate was obtained and evaluated.

 Table 3 shows the results of the evaluation.

Example of the fourth production method according to the present invention, etc. Example 31 [(i) Production of two-layer sheet composed of modified polyolefin-based elastomer layer and polyamide layer] Ethylene content 70 mol%, iodine value 12, Mooney viscosity [ML _{1 + 4} (100 ℃)] 120 ethylene propylene 5-
Ethylidene-2-norbornene copolymer rubber (EPDM
(1)) 80 parts by weight and MFR (ASTM D 1238-65T, 230 ° C)
13 g / 10 minutes and 20 parts by weight of polypropylene (PP) having a density of 0.91 g / cm ³ were kneaded with a Banbury mixer in a nitrogen atmosphere at 180 ° C. for 5 minutes, and the kneaded material was passed through a roll to form a sheet. Into square pellets with a sheet cutter.

Next, 100 parts by weight of the square pellet and 1,3-bis (tert-
Butylperoxyisopropyl) benzene (peroxide (a)) 0.3 parts by weight and divinylbenzene (DVB) 0.5
Parts by weight and 0.5 parts by weight of maleic anhydride (MAH) were mixed by stirring with a Henschel mixer. The mixture was then added to L /
Extrusion was performed at 220 ° C. in a nitrogen atmosphere with a single screw extruder having a D = 30 and a screw diameter of 50 mm to produce a graft-modified polyolefin-based elastomer (TPE-A of Example 1).

Next, using a T-die extruder with a diameter of 90 mm manufactured by Toshiba Machine Co., Ltd.
= 22, extrusion temperature 220 ℃, T die is coat hanger die,
Extruded into a sheet at a take-off speed of 2.5 m / min, and the extruded sheet-like TPE-A in a molten state was converted to a polyamide sheet of Example 2 (Nylon 6 manufactured by Toray Industries, Inc .;
(CM1021, 50 μm thick) and passed between a pair of rolls. At that time, the TPE-A sheet was brought into contact with a roll at a roll temperature of 60 ° C, and the polyamide sheet was brought into contact with a roll at room temperature. Layer (TP
EA layer) has a thickness of 0.7 mm, and the polyamide layer has a thickness of 0.7 mm.
A two-layer sheet measuring 50 μm was produced.

[(Ii) Production of Thermoplastic Elastomer for Core] Ethylene propylene-ethylidene norbornene copolymer rubber (EPDM (EPDM) having an ethylene content of 70 mol%, an iodine value of 15, and a Mooney viscosity of [ML _{1 + 4} (100 ° C.)] of 120 1)) 70 parts by weight, MFR (ASTM D 1238-65T, 230 ° C) 13g / 10min, density
0.91 g / cm ³ of polypropylene (PP) 30 parts by weight and butyl rubber (Esso 11R-065, degree of unsaturation 0.8 mol%, below 1
1R) 10 parts by weight and 30 parts by weight of paraffin-based process oil (oil) are kneaded with a Banbury mixer in a nitrogen atmosphere at 190 ° C. for 5 minutes, and the kneaded material is passed through a roll, and then pelletized by a sheet cutter. Was manufactured.

Next, 100 parts by weight of the square pellet and 1,3-bis (tert
-Butylperoxyisopropyl) benzene (peroxide (A)) 0.3 part by weight and divinylbenzene (DVB) 0.
5 parts by weight were mixed by stirring with a Henschel mixer. Next, the pellets were extruded with an extruder at 220 ° C. under a nitrogen atmosphere to obtain a thermoplastic elastomer [MFR 3 g / 10 min.
TPE (1)] was obtained.

[(Iii) Production of Laminated Molded Body] The above-described two-layer sheet is preheated, the polyamide layer constituting the two-layer sheet is turned to the female mold side, and the female mold has a crimp pattern with a depth of 150 μm by vacuum forming. The female mold is closed after being drawn into close contact with the inner wall surface of the cavity where the is applied, and the thermoplastic resin for the core in a molten state is injected from the nozzle of the injection molding machine into the cavity from the male mold side. The elastomer [TPE (1)] was injected and solidified, and when the TPE (1) was integrated with the two-layer sheet, the mold was opened to obtain a three-layer laminated molded body.

 The vacuum forming conditions are as follows.

Heater temperature: 360 ° C. Preheating time: 45 seconds Vacuum pressure: 700 mmHg The conditions of the above injection molding are as follows.

Molding machine: Dynamelter (manufactured by Meiki Seisakusho) Molding temperature: 220 ° C Injection pressure: Primary pressure 1000 kg / cm ² Secondary pressure 700 kg / cm ² Injection speed: Maximum Molding cycle: 90 seconds / cycle Gate: Direct gate (land) Length 10mm, width 10mm,
(Thickness: 3 mm) The polyamide layer (skin layer) and TPE-A layer [intermediate layer (I
I)], TPE-A layer [intermediate layer (II)] and TP
The interlayer adhesion with the E (1) layer (core layer), texture depth, softness, abrasion resistance, scratch resistance, oil resistance, solvent resistance, heat resistance and cold resistance were evaluated by the above-described evaluation methods. .

 Table 4 shows the results of the evaluation.

Example 32 A laminate formed of three layers in the same manner as in Example 31 except that (i) production of the two-layer sheet and (ii) production of the thermoplastic elastomer for the core in Example 31 were carried out as follows. Was obtained and evaluated.

(I) Production of two-layer sheet In the production of (i) two-layer sheet of Example 31, EPDM was used.
The mixing ratio of (1) and PP is 60 parts by weight of EPDM (1), PP 40
Parts by weight, and butyl rubber (manufactured by Esso, IIR-06
5) Graft-modified polyolefin-based elastomer (TPE-B of Example 2) in the same manner as in Example 31 except that 20 parts by weight and 40 parts by weight of paraffin-based process oil were added.
Then, from this TPE-B and the polyamide sheet of Example 2 (Nylon 12, manufactured by Daicel Huls, trade name: Dyamide L2140, 50 μm thickness), a modified polyolefin-based elastomer layer ( TPE-B
Layer) is 0.7mm thick and the polyamide layer is 50μ thick
m was produced.

(Ii) Production of thermoplastic elastomer for cores Ethylene propylene-ethylidene norbornene pellets with an ethylene content of 78 mol%, an iodine value of 10, a Mooney viscosity [ML _{1 + 4} (100 ° C)] of 160, and an oil extension of 40 parts by weight 60 parts by weight of the copolymer rubber (EPDM (2)) (therefore, 43 parts by weight of EPDM and 17 parts by weight of oil), 40 parts by weight of PP, and 2,5-dimethyl-2,5-di (t- Butylperoxy) hexyne-
0.5 parts by weight of 3 (peroxide (B)) were mixed by stirring with a Henschel mixer. Next, this mixture was extruded at 220 ° C. under a nitrogen atmosphere using a Warner twin-screw extruder (L / D = 43, meshing type, isotropic rotation, triple-type screw), and M
FR 15g / 10min thermoplastic elastomer [TPE of Example 2
(2)] was obtained.

 Table 4 shows the results of the evaluation.

Example 33 The production of the (i) two-layer sheet of Example 31 was carried out as follows, and in place of TPE (1), a melt index (ASTM D-1238-65T, 230 ° C.) 13, a density of 0.91 g / A laminated molded article having three layers was obtained and evaluated in the same manner as in Example 31 except that polypropylene of cm ³ [PP (1) of Example 3] was used.

(I) Production of two-layer sheet In the production of (i) two-layer sheet of Example 31, EPDM was used.
The mixing ratio of (1) and PP is 80 parts by weight of EPDM (1), PP 20
Parts by weight, and butyl rubber (manufactured by Esso, IIR-06
5) 10 parts by weight and 30 parts by weight of paraffin-based process oil were added to produce square pellets of an unmodified polyolefin-based elastomer, and a graft-modified polyolefin-based elastomer was obtained by using glycidyl methacrylate instead of maleic anhydride (Example) No. 3 TPE-C), and the polyester sheet of Example 3 (Lumirror manufactured by Toray Industries, Inc., 50 μm thickness) instead of the polyamide sheet.
Was used in the same manner as in Example 31 except that the thickness of the modified polyolefin-based elastomer layer (TPE-C layer) was 0.7
mm and a two-layer sheet having a polyester layer thickness of 50 μm.

 Table 4 shows the results of the evaluation.

Example 34 The production of (i) the two-layer sheet of Example 31 was carried out as follows, and fine powdered talc was replaced with 10 parts of TPE (1).
5% / 10% MFR containing 10% short fiber glass fiber
Except that polypropylene [PP (2)]
In the same manner as in Example 31, a laminated molded body including three layers was obtained,
The evaluation was performed.

(I) Production of two-layer sheet In the production of (i) two-layer sheet of Example 31, a graft-modified polyolefin-based elastomer (TPE-D of Example 4) was produced using hydroxypropyl methacrylate instead of maleic anhydride. And the polyurethane sheet of Example 4 (Nippon Polyurethane thermoplastic polyurethane P26SRNAT,
A modified polyolefin-based elastomer layer (TPE-D
A two-layer sheet having a thickness of 0.7 mm and a thickness of the thermoplastic polyurethane layer of 50 μm was produced.

 Table 4 shows the results of the evaluation.

Example 35 Example (i) of producing a two-layer sheet in Example 31
31 graft-modified polyolefin elastomers (TPE
-A) 80 parts by weight of low-density polyethylene (density 0.91
7 g / cm ³ , melt index 6.5 (190 ° C.), 20 parts by weight, dry-blended and supplied to a T-die extruder, and thereafter, in the same manner as in Example 31, modified polyolefin-based elastomer layer (TPE-E layer) Was manufactured in the same manner as in Example 31 except that a two-layer sheet having a thickness of 0.7 mm and a polyamide layer having a thickness of 50 μm was produced, and evaluated.

 Table 4 shows the results of the evaluation.

Comparative Example 31 In the same manner as in Example 31, except that the soft vinyl chloride sheet (0.75 mm thick) of Comparative Example 1 containing 50 parts by weight of dioctyl phthalate was used instead of the two-layer sheet, A laminated molded article having two layers was obtained and evaluated.

 Table 4 shows the results of the evaluation.

Comparative Example 32 A laminated molded article consisting of two layers was produced in the same manner as in Example 31, except that a single-layer sheet of TPE-A having no laminated polyamide sheet was used instead of the two-layer sheet. Was obtained and evaluated.

 Table 4 shows the results of the evaluation.

Comparative Example 33 In the production of (i) the two-layer sheet of Example 31, the graft modification was not performed, and thereafter, the same as in Example 31,
Unmodified polyolefin-based elastomer layer (TPE-F layer)
Was manufactured in the same manner as in Example 31 except that a two-layer sheet having a thickness of 0.7 mm and a polyamide layer having a thickness of 50 μm was produced, and evaluated.

 Table 4 shows the results of the evaluation.

Example 41 of Fifth Manufacturing Method According to the Present Invention Example 41 A three-layer laminate in the same manner as in Example 31 except that (iii) the production of the laminated molded body of Example 31 was performed as follows. A molded body was obtained and evaluated.

(Iii) Manufacture of laminated molded article The polyamide layer constituting the two-layer sheet was preheated by heating the two-layer sheet of Example 31 to the female mold side, and the female mold was embossed with a depth of 150 μm by vacuum molding. After drawing in close contact with the inner wall surface of the cavity where the pattern is formed, the thermoplastic elastomer for core [TPE (1)] in a molten state is placed on the two-layer sheet with good distribution, and the male mold is closed. TPE
When (1) was solidified and integrated with the two-layer sheet, the mold was opened to obtain a three-layer laminated molded body.

The vacuum forming conditions are the same as the vacuum forming conditions in Example 31.

The conditions for the stamping molding are as follows.

Molding machine: Ikegai ISM-300 Screw diameter: 50mmφ Resin temperature: 230 ° C Press pressure: 200kg / cm ² Molding cycle: 50 seconds / cycle Molded product: Length 500mm, width 500mm, thickness 3mm Table 5 shows the evaluation results. Shown in

Example 42 In Example 41, the two-layer sheet of Example 41 (Example 31)
Example 32) in place of TPE (1) and TPE (1)
A laminated molded body consisting of three layers was obtained and evaluated in the same manner as in Example 41 except that the two-layer sheet of Example 2 and the TPE (2) of Example 32 were used.

 Table 5 shows the results of the evaluation.

Example 43 In Example 41, the two-layer sheet of Example 41 (Example 31)
Example 33) in place of TPE (1)
Sheet and melt index (ASTM D 1238)
-65T, 230 ° C) 3 and a laminated molded body consisting of three layers was obtained in the same manner as in Example 41 except that polypropylene having a density of 0.91 g / cm ³ [hereinafter abbreviated as PP (3)] was used. The evaluation was performed.

 Table 5 shows the results of the evaluation.

Example 44 In Example 41, the two-layer sheet of Example 41 (Example 31)
Example 34) in place of TPE (1)
In the same manner as in Example 41, except that a two-layer sheet of MFR and a polypropylene (hereinafter abbreviated as PP (4)) containing 0.7% of MFR and 10% of MFR containing 15% of fine powder talc and 15% of short fiber glass fiber were used. A laminated molded article having three layers was obtained and evaluated.

 Table 5 shows the results of the evaluation.

Example 45 In Example 41, the two-layer sheet of Example 41 (Example 31)
Example 35) in place of TPE (1) and TPE (1)
A laminated molded body consisting of three layers was obtained and evaluated in the same manner as in Example 41 except that the two-layer sheet of Example 44 and PP (4) of Example 44 were used.

 Table 5 shows the results of the evaluation.

Comparative Example 41 In Example 41, Comparative Example 31 was used instead of the two-layer sheet.
Other than using a soft vinyl chloride sheet (0.75mm thick)
In the same manner as in Example 41, a laminated molded body including two layers was obtained,
The evaluation was performed.

 Table 5 shows the results of the evaluation.

Comparative Example 42 A laminated molded article composed of two layers was produced in the same manner as in Example 41 except that a single-layer sheet of TPE-A having no laminated polyamide sheet was used instead of the two-layer sheet. Was obtained and evaluated.

 Table 5 shows the results of the evaluation.

Comparative Example 43 In Example 41, the two-layer sheet of Example 41 (Example 31)
, Except that the two-layer sheet of Comparative Example 33 was used in place of the two-layer sheet of Comparative Example 33, a laminated molded body having three layers was obtained and evaluated.

 Table 5 shows the results of the evaluation.

Example 51 Using a T-die extruder having a diameter of 90 mm manufactured by Toshiba Machine Co., Ltd., TPE-A and TPE (1) of Example 31 were used, the screw was full flight, L / D = 22, and the extrusion temperature was 220 ° C. The T-die is a coat hanger die, extruded into a sheet at a take-up speed of 2.5 m / min, and the polyamide sheet of Example 31 / TPE-A / TPE (1)
Pass it between a pair of rolls in a state of lamination,
At this time, the TPE (1) sheet is brought into contact with the roll at a roll temperature of 60 ° C., and the polyamide sheet is brought into contact with the roll at room temperature, so that the thermoplastic elastomer layer (TPE (1) layer)
Was 3 mm in thickness, the thickness of the modified polyolefin-based elastomer layer (TPE-A layer) was 0.7 mm, and the thickness of the polyamide layer was 50 μm.

[Manufacture of laminated molded article] The above three-layer sheet is pre-heated, and the polyamide layer constituting the three-layer sheet is turned to the female mold side, and a crimp pattern with a depth of 150 μm is applied to the female mold by vacuum molding. After being drawn into close contact with the inner wall surface of the cavity, drawing was performed, and the mold was opened to obtain a laminated molded body composed of four layers.

 The vacuum forming conditions are as follows.

Heater temperature: 360 ° C Preheating time: 100 seconds Vacuum pressure: 700 mmHg Polyamide layer (skin layer) and TPE-A layer [intermediate layer (I)
I)], the interlayer adhesion between the polypropylene layer [intermediate layer (I)] and the TPE (1) layer (core layer),
Texture depth, soft feeling, abrasion resistance, scratch resistance, oil resistance,
The solvent resistance, heat resistance, and cold resistance were evaluated by the above-described evaluation methods.

 Table 6 shows the results of the evaluation.

Example 52 In Example 51, TPE-A of Example 32 was used instead of TPE-A.
PE-B was used, and the polyamide sheet of Example 32 was used instead of the polyamide sheet of Example 51 (polyamide sheet of Example 31), and the TPE (2) of Example 32 was used instead of TPE (1). ) Was obtained in the same manner as in Example 51 except that (3) was used, and evaluation was performed.

 Table 6 shows the results of the evaluation.

Example 53 In Example 51, TPE of Example 33 was used instead of TPE-A.
Using PE-C, and using the polyester sheet of Example 33 instead of the polyamide sheet of Example 51 (polyamide sheet of Example 31), and further using TPE (1),
A three-layer laminate was obtained and evaluated in the same manner as in Example 51 except that PP (1) of Example 33 was used.

 Table 6 shows the results of the evaluation.

Example 54 In Example 51, TPE of Example 34 was used instead of TPE-A.
Using PE-D and replacing the polyamide sheet of Example 51 (polyamide sheet of Example 31) with the PP sheet of Example 34
A three-layer laminate was obtained and evaluated in the same manner as in Example 51 except that (2) was used.

 Table 6 shows the results of the evaluation.

Example 55 In Example 51, TPE of Example 35 was used instead of TPE-A.
A three-layer laminate was obtained and evaluated in the same manner as in Example 51 except that PE-E was used.

 Table 6 shows the results of the evaluation.

Comparative Example 51 In Example 51, the soft vinyl chloride sheet of Comparative Example 31 was used instead of the polyamide sheet, and TP
A two-layer laminate was obtained and evaluated in the same manner as in Example 51 except that EA was not used.

 Table 6 shows the results of the evaluation.

Comparative Example 52 In the same manner as in Example 51, except that the TPE-A of Example 31 was used instead of the polyamide sheet in Example 51, and that TPE-A was not used as the intermediate layer (II). Thus, a two-layer laminated molded body was obtained and evaluated.

 Table 6 shows the results of the evaluation.

Comparative Example 53 In Example 51, instead of TPE-A, the T of Comparative Example 33 was used.
Except that PE-F was used, 3
A layered laminate was obtained and evaluated.

 Table 6 shows the results of the evaluation.

[Brief description of the drawings]

FIGS. 1 (a) to 1 (d) show first and fourth embodiments according to the present invention.
FIG. 2 is a process diagram of a method of manufacturing a laminated molded article of the present invention, and FIG. 2 is a schematic view of one apparatus used in the second and fifth methods of producing a laminated molded article according to the present invention. It is a top view which shows the sampling point of a test piece. 1,2 molds, 3 cavities 4 three-layer sheets, 5 heaters 6 vacuum pumps, 7 air suction passages 8 nozzles, 10 extruders 11 injection nozzle

Continued on the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location B29C 51/10 9268-4F B29C 51/10 B32B 25/08 B32B 25/08 25/14 25/14 27/32 27/32 C 27/34 27/34 27/36 27/36 27/40 27/40 // B29L 9:00 31:58

Claims (8)

(57) [Claims] (1) a core layer made of a synthetic resin, (b) an intermediate layer (I) made of a polyolefin foam or a polyurethane foam provided on the core layer, and (c) this intermediate layer ( I) graft-modified with at least one graft monomer selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid derivatives, unsaturated epoxy monomers and unsaturated hydroxy monomers provided above; (D) an intermediate layer (II) made of a modified polyolefin elastomer, and (d) a polyamide provided on the intermediate layer (II).
A skin layer made of at least one polymer selected from the group consisting of polyurethane and polyester. 2. A three-layer structure comprising an intermediate layer (I) made of the polyolefin foam or polyurethane foam, an intermediate layer (II) made of the modified polyolefin-based elastomer, and a skin layer made of the polymer. After preheating the sheet, the three-layer sheet is suction-contacted to the inner wall surface of the cavity of the vacuum forming die to obtain a preformed product having a concave portion. A step of obtaining a molded product having a concave portion by clamping the mold in a state in which the mold is in close contact with the inner wall surface of the cavity or in a state in which the mold is in close contact with the inner wall surface of the molding die separate from the vacuum molding die; Injecting a synthetic resin in a flow plasticized state into a concave portion of a molded product that is in close contact with the inner wall surface of the cavity, and molding the laminated molded product according to claim 1. Method for manufacturing a laminated molded body according to claim. 3. A three-layer structure comprising an intermediate layer (I) composed of the polyolefin foam or polyurethane foam, an intermediate layer (II) composed of the modified polyolefin elastomer, and a skin layer composed of the polymer. After preheating the sheet, the three-layer sheet is suction-contacted to the inner wall surface of the cavity of the vacuum forming die to obtain a preformed product having a concave portion; The synthetic resin in the fluidized plasticized state is placed in the concave portion of the preformed product, or in the concave portion of the preformed product adhered to the cavity inner wall surface of the molding die separate from the vacuum molding die. A method for producing a laminated molded article, comprising: obtaining the laminated molded article according to claim 1 through a step of casting and stamping molding. 4. A core layer composed of the synthetic resin, an intermediate layer (I) composed of the polyolefin foam or polyurethane foam, an intermediate layer (II) composed of the modified polyolefin elastomer, and a skin composed of the polymer. After preheating the four-layer sheet composed of
A method for manufacturing a laminated molded product, comprising: forming the four-layer sheet under vacuum to obtain the laminated molded product according to claim 1. 5. A core layer composed of a synthetic resin, and (b) an unsaturated carboxylic acid, an unsaturated carboxylic acid derivative, an unsaturated epoxy monomer, and an unsaturated hydroxy acid provided on the core layer. An intermediate layer (II) comprising a modified polyolefin-based elastomer graft-modified with at least one graft monomer selected from the group consisting of monomers; and (c) a polyamide provided on the intermediate layer (II). ,
A skin layer made of at least one polymer selected from the group consisting of polyurethane and polyester. 6. A two-layer sheet comprising the intermediate layer (II) comprising the modified polyolefin-based elastomer and a skin layer comprising the polymer is preheated, and then the two-layer sheet is subjected to a vacuum forming mold. A step of obtaining a preformed product having a concave portion by suction and close contact with the inner wall surface of the cavity, and a state in which the preformed product is in close contact with the inner wall surface of the cavity of the vacuum forming die or the vacuum forming die. A step of obtaining a molded product having a concave portion by clamping the mold in a state of being in close contact with the cavity inner wall surface of the separate molding die, and flowing into the concave portion of the molded product closely contacting the cavity inner wall surface of the mold. A method for producing a laminated molded product, comprising: obtaining the laminated molded product according to claim 5 through a step of injecting and molding a synthetic resin in a plasticized state. 7. A two-layer sheet composed of an intermediate layer (II) made of the modified polyolefin-based elastomer and a skin layer made of the polymer is preheated, and then the two-layer sheet is subjected to a vacuum forming mold. A step of obtaining a preformed product having a concave portion by suction and close contact with the inner wall surface of the cavity, and a step of forming the preformed product in the concave portion of the preformed product closely contacting the inner wall surface of the cavity of the vacuum forming die or the vacuum forming die A step of pouring a synthetic resin in a flow plasticized state into a concave portion of a preform which is in close contact with an inner wall surface of a cavity of a separate molding die and performing stamping molding. A method for producing a laminated molded article, comprising obtaining a laminated molded article. 8. A core layer composed of the synthetic resin and an intermediate layer (II) composed of the modified polyolefin-based elastomer.
And preheating a three-layer sheet composed of the polymer and a skin layer made of the polymer, and then vacuum forming the three-layer sheet to obtain a laminated molded article according to claim 5. A method for producing a laminated molded article.