JPH07241946A - Laminate - Google Patents

Abstract

PURPOSE:To obtain an easy-to-recycle, flexible and tough laminate by bonding a thermoplastic elastomer layer and a foamed body layer of a specific resin composition comprised of an ethylene copolymer and a polyhydric alcohol. CONSTITUTION:A laminate is made by bonding a thermoplastic elastomer layer and a specific foam layer together. The specific foam layer is a copolymer containing ethylene and at least radical polymerizing acid anhydrides as a component monomer, and is comprised of a resin composition consisting of an ethylene copolymer accounting for 1 to 20wt.% of the radical polymerizing acid anhydride group, polyhydric alcohol compound having 3 or more hydroxyl groups, and a reaction accelerator. In the composition, the mole ratio per unit of the hydoxyl group of the polydyric alcohol compound is set at 0.01 to 10 and the content of a reaction accelerator is set at 0.001 to 20 pts.wt. versus 100 pts.wt. for the ethylene copolymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a laminate. More specifically, it relates to a laminate suitably used as an interior material for automobiles, vehicles, ships and the like.

[0002]

2. Description of the Related Art As an interior material for floors, walls, ceilings, etc. of automobiles, vehicles, ships, etc., and as a skin material for chairs, sofas, etc., the surface is generally embossed, and the surface of the material has a textured leather pattern. A laminate having a vinyl chloride layer, which is lined with a polyurethane or polyolefin-based crosslinked foam layer and optionally with a substrate material, has been conventionally used. In recent years, interest in environmental issues has increased, and substitution of materials that do not generate toxic gases during combustion processing and materials that can be easily reused is progressing. Under such a trend, studies have been earnestly conducted to replace the conventionally used vinyl chloride-based skin material with a thermoplastic elastomer which is a non-chlorine-based material, and some have already been put to practical use. However, various foaming materials used as backing materials for giving the skin material cushioning properties are almost crosslinked. Even if the skin material uses a thermoplastic elastomer because the gel derived from this crosslinked foam material is mixed, it causes a significant problem in molding processability at the time of its reuse, and it is also great in the field of use of the recycled material. There were restrictions.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art and to provide a laminate which is easy to reuse and has good appearance, flexibility and toughness.

[0004]

[Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have conducted extensive studies and as a result, (A) a thermoplastic elastomer layer, (B) a specific ethylene-based copolymer, and a polyhydric alcohol. It was found that a laminate obtained by laminating foam layers of a resin composition containing a reaction accelerator can be reused by heating and melting again in a state of containing not only the thermoplastic elastomer layer but also the foam layer. The present invention has been completed based on such findings.

That is, an object of the present invention is at least (A) a thermoplastic elastomer layer, and (B) (a) a copolymer containing ethylene and at least a radical-polymerizable acid anhydride as constituent monomers. The ethylene-based copolymer in which the unit derived from the radical-polymerizable acid anhydride group is 0.1 to 20% by weight, and the unit derived from the other radical-polymerizable comonomer may be 40% by weight or less, The unit (b) contains a polyhydric alcohol compound having two or more hydroxyl groups in the molecule and (c) a reaction accelerator, and the unit derived from the radical-polymerizable acid anhydride in the component (a) is the component (b). ), The molar ratio of the units of the hydroxyl groups in the polyhydric alcohol compound is 0.01 to 10 and the reaction accelerator which is the component (c) is 100 parts by weight of the ethylene copolymer which is the component (a). Foam layer comprising a crosslinked resin composition is in the range of 0.001 to 20 parts by weight per part,
It can be solved by a laminated body formed by laminating.

The foam constituting the laminate according to the present invention is characterized by being flexible, having high strength, excellent heat resistance and being recyclable. This is because at a relatively low temperature, the acid anhydride group contained in the ethylene-based copolymer reacts with the hydroxyl group contained in the polyhydric alcohol compound to form a crosslinked structure, but at a relatively high temperature, It is presumed that the reaction of dissociation proceeds reversibly. The contents of the present invention will be described in detail below.

First, examples of the thermoplastic elastomer used for forming the thermoplastic elastomer layer of the laminate of the present invention include olefinic thermoplastic elastomers that are generally used. The following can be illustrated as such an olefinic thermoplastic elastomer. (1) Various polyolefin resins represented by a homopolymer of ethylene or propylene or a copolymer with a small amount of another comonomer, and ethylene and α- having 3 to 14 carbon atoms.
Thermoplastic comprising a binary copolymer rubber with an olefin, or a mixture of partially crosslinked ethylene / α-olefin copolymer rubbers, which is a terpolymer rubber obtained by further copolymerizing various polyene compounds Resin composition. (2) A thermoplastic resin composition obtained by dynamically heat treating a composition of a polyolefin resin and an ethylene / α-olefin copolymer rubber. (3) A thermoplastic resin composition obtained by dynamically blending a polyolefin resin and a product obtained by dynamically heat treating a composition of a polyolefin resin and an ethylene / α-olefin copolymer rubber. (4) Various peroxide cross-linkable polyolefin resins represented by homopolymers of ethylene or propylene, or copolymers of these with a small amount of a comonomer, and ethylene.
A thermoplastic resin composition obtained by dynamically heat treating a composition with an α-olefin copolymer rubber can be mentioned. Other thermoplastic elastomers may also include styrene-based thermoplastic elastomers. As the styrene-based thermoplastic elastomer, for example, a block copolymer composed of a polymer block of a monovinyl aromatic hydrocarbon such as styrene and an elastomeric polymer block of a conjugated diene such as butadiene or isoprene, or a hydrogenated derivative thereof is used as a base. The thermoplastic resin composition made into a polymer can be mentioned. These base polymers can be usually produced by a conventional method such as living polymerization using a lithium-based catalyst. Above all, a block copolymer comprising a styrene polymer block and a polymer block of butadiene and / or isoprene or a hydrogenated derivative thereof is generally used. Further, a polyolefin resin can be added to the above base polymer for use. Examples of such polyolefin resins include homopolymers or copolymers of α-olefins such as polypropylene, polyethylene and poly-4-methylpentene-1;
Alternatively, for example, with ethylene-based copolymers such as ethylene-vinyl acetate copolymer and ethylene-acrylic acid ester copolymer, for example, polystyrene, high-impact polystyrene, α-methylstyrene containing styrene as a main component, para-methylstyrene, etc. Examples thereof include styrene resins such as copolymers.

As the olefinic thermoplastic elastomer or styrene thermoplastic elastomer, one containing a softening agent for rubber is used, if necessary. The softening agent for rubber weakens the intermolecular force of the rubber during the normal roll processing of the rubber to facilitate the processing, and at the same time, carbon black,
A petroleum fraction used for the purpose of increasing the flexibility and rubber elasticity by promoting the dispersion of white carbon or by decreasing the hardness of vulcanized rubber. Mineral oil-based softening agents or synthetic resin-based softening agents are used. Used. As the mineral oil-based softening agent, naphthene-based oil, paraffin-based oil, aromatic oil, etc., and as the synthetic resin-based softening agent, the number average molecular weight is 2500.
The following polybutene, polyisobutylene having a viscosity average molecular weight of 70,000 or less, etc. may be mentioned. Such a rubber softening agent can be used in the range of 0 to 60% by weight. If it is used in excess of this range, the strength of the thermoplastic elastomer is lowered, or the softening agent for rubber oozes out to cause problems such as impairing the appearance, which is not preferable.

It is possible to use other additives, compounding agents and fillers in the thermoplastic elastomer according to the present invention as long as the characteristics of the composition are not impaired. Specific examples of these are glass and carbon black. Inorganic fillers such as zinc oxide, clay, talc, ground calcium carbonate, kaolin, diatomaceous earth, silica, alumina, asbestos and graphite, as well as organic fillers, antioxidants (heat-resistant stabilizers), UV absorbers ( Examples thereof include light stabilizers), antistatic agents, flame retardants, lubricants (slip agents, antiblocking agents), reinforcing agents, coloring agents (dyes, pigments), and fragrances.

In the present invention, the ethylene-based copolymer which is the component (a) of the foam layer is a copolymer obtained by copolymerizing at least ethylene and a radical-polymerizable acid anhydride. The present ethylene-based copolymer may be copolymerized with another radically polymerizable comonomer (hereinafter referred to as a third monomer), if necessary.

Here, as the radically polymerizable acid anhydride,
There are various ones, specifically, for example, maleic anhydride, itaconic anhydride, endic acid anhydride, citraconic anhydride, 1-butene-3,4-dicarboxylic acid anhydride,
Examples thereof include alkenyl succinic anhydride having a double bond at the terminal having at most 18 carbon atoms and alkadienyl succinic anhydride having a double bond at the terminal having at most 18 carbon atoms. These radical-polymerizable acid anhydrides may be used alone or in combination of two or more. Of these, maleic anhydride and itaconic anhydride are preferably used.

In the present invention, the ethylene-based copolymer as the component (a) has a unit derived from the radical-polymerizable acid anhydride in the range of 0.1 to 20% by weight, preferably 0.5 to 10% by weight. is there. If the amount of the unit derived from the radical-polymerizable acid anhydride is less than 0.1% by weight, the heat resistance and mechanical strength of the resulting foam will be reduced, which is not preferable. On the other hand, if it exceeds 20% by weight, the properties such as flexibility and moisture absorption resistance are impaired, and at the same time, the cost increases, which is not preferable.

The third monomer which can be used in combination with the radical-polymerizable acid anhydride is an ethylenically unsaturated ester compound, an ethylenically unsaturated amide compound, an ethylenically unsaturated carboxylic acid compound, an ethylenically unsaturated ether compound. , And ethylenically unsaturated hydrocarbon compounds.

Specifically, the ethylenically unsaturated ester compounds include vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. Hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate, dimethyl fumarate, fumarate Diethyl acid, dipropyl fumarate, dibutyl fumarate,
Examples thereof include methyl maleate, ethyl maleate, propyl maleate, butyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, and the like.

As the ethylenically unsaturated amide compound,
(Meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N
-Octyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, etc. can be illustrated.

Examples of the ethylenically unsaturated carboxylic acid compound include (meth) acrylic acid, maleic acid and fumaric acid. Ethylenically unsaturated ether compounds include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether,
Examples thereof include octadecyl vinyl ether and phenyl vinyl ether. Ethylenically unsaturated hydrocarbon compounds and other compounds include styrene and α-
Methylstyrene, norbornene, butadiene, acrylonitrile, methacrylonitrile, acrolein, crotonaldehyde, trimethoxyvinylsilane, triethoxyvinylsilane, vinyl chloride, vinylidene chloride and the like can be mentioned. If necessary, two or more kinds of these third monomers may be used together.

When the third monomer is used in combination, the content of the third monomer in the ethylene copolymer as the component (a) used in the present invention is 40% by weight or less, preferably 30% by weight or less. When the content of the third monomer exceeds 40% by weight, the moldability is significantly reduced, which is not preferable.

MFR of ethylene copolymer used in the present invention (according to condition 4 of Table 1 of JIS K-7210)
Is preferably in the range of 0.1 to 1000 g / 10 minutes, more preferably 0.1 to 100 g / 10 minutes, and particularly preferably 0.1 to 30 g / 10 minutes. MFR is 0.1g
If it is less than / 10 minutes or exceeds 1000 g / 10 minutes, a resin composition meeting the object of the present invention cannot be obtained.
Such an ethylene-based copolymer can be produced by a generally known method, that is, a polymerization process such as bulk, solution, suspension or emulsion. Manufacturing equipment and technology are available.

2 in the molecule, which is the component (b) of the foam layer.
Specific examples of the polyhydric alcohol compound having at least one hydroxyl group include glycols such as ethylene glycol, diethylene glycol and triethylene glycol; 1,4 butanediol, 1,6 hexanediol and 1,8 octanediol. , 1,10-decanediol, trimethylolethane, trimethylolpropane,
Alcohol compounds such as pentaerythritol; saccharides such as arbitol, sorbitol, sorbitan, xylose, alaminose, glucose, galactose, sorbose, fructose, palatinose, maltotriose, and malezitose; saponification products of ethylene-vinyl acetate copolymer, polyvinyl Examples thereof include alcohols, polyolefin oligomers having a plurality of hydroxyl groups, and polymers having a plurality of hydroxyl groups in the molecule such as ethylene-hydroxyethyl (meth) acrylate copolymer. The polyhydric alcohol compound is represented by the general formula (1) or (2) (R) _a C (CH ₂ OH) _b (1) (wherein R is hydrogen and the number of carbon atoms is 1). To 12 chain or cyclic alkyl groups or aralkyl groups, a represents an integer of 0 to 2, b represents an integer of 2 to 4, and a + b = 4.
Is selected to satisfy. )

[Chemical 2] (In the formula, n is an integer of 0 to 10.) A polyoxyalkylene compound having a structure in which ethylene oxide or propylene oxide is added to a polyhydric alcohol compound and a general formula (3) R′-COOH ... (3) (In the formula, R'represents a chain or cyclic alkyl group having 2 to 25 carbon atoms or an aralkyl group.), And an organic carboxylic acid compound represented by the above general formula ( It is also possible to use a polyglycerin ester having two or more hydroxyl groups in the molecule, which is obtained by dehydration condensation with the polyglycerin represented by 2).

Specific examples of these polyoxyalkylene compounds include 1,3-dihydroxypropane, 2,2-dimethyl-1,3-dihydroxypropane, trimethylolethane and 1,1,1-trimethylol. Propane, 1,1,
1-trimethylolhexane, 1,1,1-trimethyloldodecane, 2-cyclohexyl-2-methylol-1,3-dihydroxypropane, 2- (p-methylphenyl) -2-methylol-
1,3-dihydroxypropane, pentaerythritol,
Examples thereof include those obtained by adding ethylene oxide or propylene oxide to glycerin, diglycerin, hexaglycerin, octaglycerin, decaglycerin and the like.

Specific examples of the above-mentioned polyglycerin ester include glycerin monostearate, glycerin monooleate, glycerin monolaurate, glycerin monocaprylate, glycerin monohexanoate and glycerin monophenethyl. Ester, glycerin monopropionate, diglycerin monostearate, diglycerin distearate, diglycerin monooleate, diglycerin monohexanoate, diglycerin dioctanoate, tetraglycerin monostearate, tetraglycerin tristearate Rate, tetraglycerin tetrastearate, tetraglycerin trihexanoate, tetraglycerin monophenethyl ester, hexaglycerin monostearate,
Hexaglycerin distearate, hexaglycerin pentastearate, hexaglycerin trioleate,
Hexaglycerin monolaurate, hexaglycerin pentalaurate, decaglycerin monostearate, decaglycerin octastearate, decaglycerin pentaoleate, decaglycerin dilaurate, pentadecaglycerin distearate, pentadecaglycerin decaoleate, octadeca Examples thereof include glycerin tetrastearate.

Further, as the polyhydric alcohol compound, sorbitan or a sorbitan alkyl ester of a sorbitan derivative having two or more hydroxyl groups in the molecule and an organic carboxylic acid compound represented by the general formula (3) is used. You can also

Specific examples of the sorbitan alkyl ester include sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, sorbitan monocaprylate, sorbitan monohexanoate, sorbitan monophenethyl ester and sorbitan monopropio. And sorbitan tristearate, sorbitan tetrastearate and the like.

The polyhydric alcohol compound having two or more hydroxyl groups in the molecule of the component (b) is preferably one having a melting point of 300 ° C. or lower among the above polyhydric alcohol compounds. Alkylene compounds and polyglycerin esters are preferably used. And
These polyhydric alcohol compounds may be used alone or in combination of two or more.

The amount of the polyhydric alcohol compound as the component (b) used is such that the unit derived from the radical-polymerizable acid anhydride contained in the ethylene copolymer as the component (a) is added to the polyhydric alcohol compound. The molar ratio of hydroxyl groups contained is 0.01 to
The range is 10. In this case, the range of 0.05 to 5 is more preferable. When this molar ratio is less than 0.01, it becomes insufficient to introduce the crosslinked structure into the composition in an effective amount, and when the molar ratio exceeds 10, the crosslinking reaction structure is effectively introduced. In addition to being pointless, it is not preferable because it is costly.

In the present invention, the reaction accelerator which is the component (c) of the foam layer is derived from the radical-polymerizable acid anhydride contained in the ethylene-based binary copolymer or the ethylene-based multi-component copolymer. It is a compound that activates the carbonyl group contained in the unit and promotes the reaction between the hydroxyl group and the acid anhydride.

There are various kinds of reaction accelerators, and one example thereof is a metal salt of an organic carboxylic acid. As the metal salt of an organic carboxylic acid, a metal salt of a fatty acid having 1 to 30 carbon atoms, for example, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, Behenic acid, benzoic acid, terephthalic acid, etc. and IA of the periodic table
Group IIA, IIA, IIB, IIIB metals (eg Li, N
a, K, Mg, Ca, Zn, Al, etc.). Specifically, lithium acetate, sodium acetate, magnesium acetate, aluminum acetate, potassium butyrate, calcium butyrate, zinc butyrate, sodium octanoate, calcium octanoate, potassium decanoate, magnesium decanoate, zinc decanoate, lithium laurate, Sodium laurate, calcium laurate, aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, magnesium palmitate, sodium stearate, potassium stearate, calcium stearate, zinc stearate, Examples thereof include sodium oleate, sodium behenate, sodium benzoate, potassium terephthalate and the like. Preferably,
Lithium laurate, sodium laurate, calcium laurate, aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, magnesium palmitate, sodium stearate, potassium stearate, calcium stearate,
Zinc stearate, sodium oleate, etc. are used.

Another example of the metal salt of an organic carboxylic acid is a resin having a metal salt structure of a carboxylic acid. Examples of such resins include metals of Group IA, Group IIA, Group IIB, and Group IIIB of ethylene and radically polymerizable unsaturated carboxylic acid (for example, Li, Na, K, Mg, Ca, Zn, Al, etc.).
Examples thereof include those having a structure in which a salt is copolymerized, or those having a structure in which ethylene and a metal salt of the radical-polymerizable carboxylic acid and another radical-polymerizable unsaturated carboxylic acid and / or a derivative thereof are multi-polymerized. To be

Further, a metal salt of a radical-polymerizable unsaturated carboxylic acid (free unsaturated carboxylic acid may be polymerized and neutralized later on a polyolefin resin such as polyethylene, polypropylene or ethylene-propylene copolymer. .) Is graft-polymerized, or a resin having a structure in which a metal salt of a radical-polymerizable carboxylic acid and another radical-polymerizable unsaturated carboxylic acid and / or a derivative thereof are simultaneously graft-polymerized to a polyolefin resin. Can be mentioned. The radically polymerizable unsaturated carboxylic acid and its derivative used here include (meth) acrylic acid, maleic acid,
Fumaric acid, monomethyl maleate, monomethyl fumarate, monoethyl maleate, monoethyl fumarate, monobutyl maleate, monobutyl fumarate, methyl (meth) acrylate, dimethyl maleate, dimethyl fumarate, diethyl maleate, diethyl fumarate, Mention may be made of dibutyl maleate, dibutyl fumarate and the like.

Another example of the reaction accelerator is a tertiary amine compound. Specific examples of the tertiary amine compound used here include trimethylamine, triethylamine, triisopropylamine, trihexylamine, trioctylamine, trioctadecylamine,
Dimethylethylamine, methyldioctylamine, dimethyloctylamine, diethylcyclohexylamine,
N, N-diethyl-4-methylcyclohexylamine and the like can be mentioned.

Another example of the reaction accelerator is a quaternary ammonium salt. Specific examples of the quaternary ammonium salt used here include tetramethylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetramethylammonium bromide, tetraethylammonium bromide, tetraethylammonium iodide and the like.

Further, as another example of the reaction accelerator, IA
Examples thereof include hydroxides of group IIIB, group IIIB, and group IIIB metals.
Specific examples include calcium hydroxide, magnesium hydroxide, aluminum hydroxide and the like. Also I
Examples thereof include halides of Group A and Group IIB metals. Specific examples thereof include calcium chloride, calcium bromide, magnesium chloride and the like.

Further, oxo acid and IA group, IIA group, IIB
Salts of group IIIB metals can be mentioned as other examples of the reaction accelerator according to the present invention. As a concrete example,
Examples thereof include sodium nitrate, calcium nitrate, zinc nitrate, magnesium nitrate, aluminum nitrate, sodium phosphate and the like.

Furthermore, LiBF ₄ , NaBF ₄ , KBF ₄ , NaPF ₆ ,
KPF ₆ , NaPCl ₆ , KPCl ₆ , NaFeCl ₄ , NaSnCl ₄ , NaSbF ₆ ,
Alkali metal salts of Lewis acids such as KSbF ₆ , NaAsF ₆ and KAsCl ₆ can also be mentioned as other examples of the reaction accelerator.

Among the above-exemplified reaction accelerators, metal salts of organic carboxylic acids are preferably used. Further, the above-exemplified reaction accelerators may be used in combination of two or more kinds at the same time, if necessary.

The amount of these reaction accelerators used is 0.
001 to 20 parts by weight, more preferably 0.01 to 20 parts by weight.
It is in the range of 15 parts by weight. If this amount is less than 0.001 part by weight, the reaction becomes too slow and it becomes difficult to effectively introduce the crosslinked structure into the resin composition. Further, if this amount is more than 20 parts by weight, it is meaningless in terms of improving the reaction rate and is not economically preferable.

Further, the crosslinkable resin composition according to the present invention may contain various additives within a range that does not impair the characteristics of the composition.
Compounding agents, fillers and the like can be used. Specific examples of these are antioxidants (heat stabilizers), ultraviolet absorbers (light stabilizers), antistatic agents, antifogging agents, flame retardants, lubricants (slip agents, antiblocking agents), glass fillers, etc. Inorganic fillers, organic fillers, reinforcing agents, colorants (dyes, pigments), and fragrances.

As a method for obtaining a foam from the above-mentioned crosslinkable resin composition, it is possible to produce by a generally used gas foaming method. Specifically, the crosslinkable resin composition can be melt-kneaded with a volatile foaming agent under pressure and extrusion-molded at atmospheric pressure to obtain a foam. The volatile foaming agent used in the present invention is a volatile foaming agent having a normal pressure boiling point not higher than the melting point of the crosslinkable resin composition of the present invention,
For example, propane, butane, pentane, isobutane, neopentane, isopentane, hexane, butadiene, and other aliphatic hydrocarbons, as well as methyl chloride, methylene chloride, dichlorofluoromethane, chlorotrifluoromethane, dichlorodifluoromethane, chlorodifluoromethane, difluoro Methane, trichlorofluoromethane, dichlorotetrafluoroethane, monochloropentafluoroethane, 1,1,1,2-tetrafluoroethane,
1-chloro-1,1-difluoroethane, 1,2-dichloro-2,2,2
-One or more volatile blowing agents selected from halogenated hydrocarbons such as trifluoroethane and 1,1-dichloro-1-fluoroethane.

Also, in foaming, a small amount of talc, which is known as a "nucleating agent" as a foam cell regulator, fine calcium silicate, aluminum stearate, calcium carbonate, barium sulfate, a trace amount of a decomposable organic foaming agent or inorganic. A foaming agent (such as a mixture of polycarboxylic acid and sodium bicarbonate) can be used. Furthermore, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, N-methylstearic acid, N-ethylstearic acid amide, N-N'-dimethylstearic acid amide, dilauric acid amide, distearic acid amide, di-stearic acid amide, Higher fatty acid amides such as palmitic acid amide, dodecylamine,
Tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, docosylamine, N-methyloctadecylamine, N-ethyloctadecylamine,
A foaming shrinkage inhibitor represented by saturated higher alkyl amines such as hexadecyl propylene amine and octadecyl propylene amine can be used.

The crosslinkable resin composition for forming a foam contains the component (a), the component (b) and the component (c) as main components, and further various polyolefin resins are blended depending on the use and purpose. can do. Examples of such polyolefin resins include homopolymers such as polyethylene, polypropylene, polyisoprene, polybutene, poly-3-methylbutene-1, poly-4-methylpentene-1, polybutadiene and polystyrene.
Further, copolymers of the respective comonomers constituting these homopolymers, for example, ethylene-propylene copolymers; butene-1, 4-methylpentene-1, hexene-1, octene-1, etc. Chain low density polyethylene; copolymers such as propylene-ethylene block copolymers may also be mentioned. Furthermore, a mixture of the above resins, a graft copolymer, a block copolymer; ethylene-
A vinyl acetate copolymer etc. can also be mentioned. The blending amount of the above-mentioned polyolefin resin is the component (a) and the component (b).
And 10 of a composition or molded product containing the component (c) as a main component
The amount is preferably 200 parts by weight or less with respect to 0 parts by weight. If the blending amount of the polyolefin resin exceeds 200 parts by weight, the heat resistance and mechanical strength originally possessed by the foam of the present invention may not be exhibited.

As a method for producing the crosslinkable resin composition which forms this foam, various commonly known resin mixing methods can be used. As a specific example, a Henschel mixer or a tumbler may be used for dry blending, and a kneader such as a pressure kneader, a roll, a Banbury mixer, a static mixer, or a screw extruder may be used. It may be melt-kneaded. At this time, a uniform mixture can be obtained by previously dry-blending and melt-kneading the resulting mixture.

It is also possible to melt mix the components during molding of the foam of the resin composition. That is, it is also possible to mix (dry blend) the respective components in the form of pellets, powder, etc., and melt-mix using the stage of producing the foam. The crosslinkable resin composition forming a foam,
Since a cross-linked structure is not formed during melting and kneading performed at a relatively high temperature, it is possible to extrude with a volatile foaming agent by an extruder. Then, after this is formed into a foam, in the cooling and solidifying process, a crosslinked structure is formed, a cohesive force is increased, and heat resistance and opportunity strength are improved.
Furthermore, even if a crosslinked structure is once formed, it can be recycled because the structure is dissociated by melting to restore the moldability. Then, a cross-linked structure is formed again in the cooling process after newly molding, and a high-strength molded product is produced.

The lamination of the thermoplastic elastomer layer and the foam layer of the present invention can be carried out by various commonly used methods. For example, a method of laminating by co-extruding a thermoplastic elastomer layer at the time of molding a foam, a method of laminating a foam layer at a thermoplastic elastomer sheet previously molded at the time of molding of a foam, a thermoplastic A method of laminating a thermoplastic elastomer to a foam sheet preformed at the time of molding an elastomer, a thermoplastic elastomer layer and a foam layer are commonly known as a curable adhesive, a solvent-based adhesive, a hot melt adhesive, etc. A method of laminating with an adhesive is used.

The thickness of the thermoplastic elastomer layer and the foam layer according to the present invention differs depending on the use of the laminate molded product, and when used as an interior material for automobiles, vehicles, ships, etc., it is generally heat-resistant. The plastic elastomer layer has a thickness of about 0.1 to 2 mm, and the foam layer has a thickness of about 1 to 30 mm. Even in the case of the same automobile, the thickness of the skin layer is relatively thin in the ceiling material. A relatively thick cover, various pillars, and sheets are used. The laminate thus obtained is characterized by being flexible, having high strength, excellent heat resistance, and recyclable. Furthermore, by coextruding or laminating the thermoplastic layer and the foam layer, sufficient adhesiveness is exhibited without the need for an adhesive, so that the process can be simplified and the cost can be reduced.

The laminate according to the present invention can be used by further laminating it with a substrate material. Specific examples of the substrate material include resin wood, plastic cardboard, resin felt, glass-filled phenolic resin plate, corrugated board, polypropylene honeycomb, polystyrene foam, glass fiber reinforced polypropylene plate, or a material obtained by laminating a non-woven fabric to these. .

[0046]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited thereto. The foam is used to measure the heat resistance of the obtained laminate.
It was cut out into 30 mm × 30 mm × 1 mm and put in a silicone oil bath at 120 ° C for about 10 minutes to measure the heat shrinkage shrinkage ratio of the sides of the laminate. The heat shrinkage rate was calculated by the following formula. Heat shrinkage rate (%) = (1- (length of one side after test) / (length of one side before test)) x 100 Also, the molded laminate was pulverized and 220 ℃ with a 40mmφ extruder.
Melt kneading with, extruding from a T-die with a width of 400 mm and a gap of 0.3 mm, forming a sheet, observing the appearance of the sheet,
A sheet having a good surface condition was evaluated as ◯, and one having a large unevenness and being unusable for use was evaluated as x, and the surface condition of the sheet by recycling was determined.

Reference Example 1 Ethylene / propylene / ethylidene norbornene terpolymer [Ethylene / propylene molar ratio 70/30, iodine value 14, Mooney viscosity (M
L _{1 + 4} , 121 ° C.) 59] 49% by weight, polypropylene [MFR (JIS K7210, Table 1, condition 14) 15
g / 10 minutes] 20% by weight, naphthenic process oil 3
0% by weight and 1% by weight of a mixture of 1,3-bis (t-butylperoxyisopropyl) benzene / trimethylolpropane triacrylate in a weight ratio of 4/6 were mixed in a Henschel mixer, after which this mixture was added to 120% by weight. ~
Add to a Banbury mixer preheated to 140 ° C and
The mixture was kneaded at 80 to 190 ° C. for 10 minutes to carry out a crosslinking reaction. This was designated as thermoplastic elastomer (1).

Reference Example 2 Ethylene / propylene / ethylidene norbornene terpolymer [Ethylene / propylene molar ratio 70/30, iodine value 14, Mooney viscosity (M
L _{1 + 4} , 121 ° C.) 59] 69% by weight, polypropylene [MFR (JIS K7210, Table 1, condition 14) 15
g / 10 min] 30% by weight and 1,3-bis (t-butylperoxyisopropyl) benzene / trimethylolpropane triacrylate in a weight ratio of 4/6 1
% By weight was mixed in a Henschel mixer, and then this mixture was put into a Banbury mixer preheated to 120 to 140 ° C. and kneaded at 180 to 190 ° C. for 10 minutes to carry out a crosslinking reaction. This was designated as a thermoplastic elastomer (2).

Reference Example 3 Ethylene / Propylene Binary Copolymer [Ethylene / Propylene Molar Ratio 70/30, M
FR (JIS K7210, Table 1, Condition 14) 0.02
g / 10 minutes, Mw / Mn = 5.3, in decalin 135 ° C.
Has an intrinsic viscosity of 5.4 dl / g] 43% by weight, polypropylene [MFR (JIS K7210, Table 1, condition 14)
0.5 g / 10 min, crystal melting point 160 ° C.] 19% by weight, paraffinic process oil 36% by weight and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane /
2% by weight of a mixture of triallyl isocyanurate in a weight ratio of 5/5 was mixed in a Henschel mixer, and then this mixture was put into a Banbury mixer preheated to 120 to 140 ° C. and kept at 180 to 190 ° C. for 10 minutes. The mixture was kneaded and cross-linked. This was designated as a thermoplastic elastomer (3).

Reference Example 4 A styrene-based thermoplastic elastomer (Lavalon S352C manufactured by Mitsubishi Yuka, SEBS block polymer JIS-K6301 A hardness 50) was used as the thermoplastic elastomer (4).

Reference Example 5 A styrene-based thermoplastic elastomer (Lavalon ME6301C manufactured by Mitsubishi Yuka, SEBS block polymer JIS-K6301 A hardness 60) was used as the thermoplastic elastomer (5).

Reference Example 6 Using a high-pressure polyethylene production facility having a tank reactor, MFR (JISK721
0 Condition of Table 1 4) 10 g / 10 min, the unit derived from maleic anhydride is 3.0% by weight, and the unit derived from methyl acrylate is 19% by weight Copolymerization of ethylene with maleic anhydride and methyl acrylate A coalesce was manufactured. The composition of the copolymer was determined by infrared absorption spectrum. As a metal salt of 93.5 parts by weight of the copolymer, 1.5 parts by weight of an ethylene oxide (5.0 mol) adduct of pentaerythritol (hydroxyl group / anhydride group = 0.55) and an organic carboxylic acid, MFR (JIS K7210 Table 1, condition 4) 3.0 g / 10 minutes, density 0.94 g / cm ^3.
5 parts by weight of a partially neutralized product of ethylene-methacrylic acid copolymer (a) (methacrylic acid content 18% by weight, copolymer obtained by neutralizing about 10% of the methacrylic acid <sodium salt>). Mixed. Upon mixing, the three components were blended with a Henschel mixer, and then melt-kneaded at 220 ° C. and pelletized using a 30 mmφ different-direction biaxial extruder. This was designated as a crosslinkable resin composition (6).

Reference Examples 7 to 14 Using the ethylene copolymer, polyhydric alcohol and reaction accelerator shown in Table 1, a crosslinkable resin composition (7 to 14) was produced in the same manner as in Reference Example 6. did. The symbols in Table 1 are explained below. MA = methyl acrylate BA = butyl acrylate PE-50E Pentaerythritol ethylene oxide (5.0 mol%) adduct HEA Ethylene and 2-hydroxyethyl acrylate (8% by weight) copolymer TM-30P Propylene oxide of trimethylolpropane ( 3.0
Mol%) Adduct DG-CM Caprylic monoester of decaglycerin PG-CT Caprylic monoester of pentaglycerin PE-45P Propylene oxide (4.5 mol%) adduct of pentaerythritol DG-80E Ethylene oxide of decaglycerin ( 8.0 mol%) adduct metal salt (a) Na of ethylene-methacrylic acid (18 wt%) copolymer
Salt (10% molar neutralization of methacrylic acid), MFR (JIS-
K7210, Table 1, Condition 4) 3.0 g / 10 min Metal salt (b) = sodium stearate

Reference Example 15 A cross-linkable resin composition (6) of Reference Example 6 was produced in the same manner as in Reference Example 6 except that the polyhydric alcohol was omitted. This was made into resin composition (15).

Example 1 100 parts by weight of the crosslinkable resin composition (6) of Reference Example 6 and talc (average particle size of about 2.0 μm)
m) 1.0 part by weight was kneaded at 220 ° C. in a tandem extruder consisting of a 50 mmφ extruder and a 65 mmφ extruder, and chlorodifluoromethane and 1-chloro-1,1-difluoroethane as volatile foaming agents were added in the middle of the extruder. Of 40:60
13 parts by weight of the mixture (based on weight) is press-fitted and the lip width is
A T-die having a gap of 00 mm and 0.4 mm was extruded into the atmosphere at a die temperature of 170 ° C. to produce a foam sheet. Next, the thermoplastic elastomer (1) of Reference Example 1 and an ethylene-based adhesive resin (Showa Denko Product "Adtex E"
Extruder 2 equipped with a 35 mmφ screw
Using a sheet forming machine having a table and a lip width of 300 mm and a two-layer T-type die, a thickness of 300 μm (thickness configuration: 250/5
The two-layer sheet of 0) was extruded, and the foamed sheet was laminated on the adhesive layer side (the adhesive resin side was in contact with the foamed body) to obtain a laminate. The heat resistance shrinkage rate of the obtained laminate was as good as 2%, and the appearance of the recycled sheet was also good.

Example 2 The thermoplastic elastomer (2) of Reference Example 2 was prepared by using a sheet molding machine having two extruders equipped with 35 mmφ screws and a lip width 300 mm two-layer T-type die, and having a thickness of 250 μm. A single layer sheet was formed. 5 parts by weight of 100 parts by weight of the crosslinkable resin composition (7) of Reference Example 7 and 1.0 part by weight of talc (average particle size of about 2.0 μm).
A tandem extruder consisting of a 0 mmφ extruder and a 65 mmφ extruder was kneaded at 220 ° C., and chlorodifluoromethane and 1-chloro-1,1 were used as volatile foaming agents from the middle of the extruder.
13 parts by weight of a mixture of 40:60 (weight basis) of difluoroethane, pressed in, lip width 600 mm, 0.4 mm
A foamed sheet was manufactured by extruding from a T-type die having a gap of 2 to a die temperature of 170 ° C. into the atmosphere. Next, the above-mentioned single layer sheet and the foamed sheet were coated with a commercially available adhesive and bonded together. The heat resistance shrinkage rate of the obtained laminate was as good as 1%, and the appearance of the recycled sheet was also good.

(Examples 3 to 8) Using the thermoplastic elastomer and the foam composition shown in Table 2, a laminate was produced in the same manner as in Example 1.

Example 9 100 parts by weight of the crosslinkable resin composition (14) of Reference Example 14 and talc (average particle size of about 2.
0 μm) 1.0 part by weight with a 50 mmφ extruder and 65 mmφ
It is 22 in one of the tandem extruder consisting of extruder
The mixture was kneaded at 0 ° C., and 13 parts by weight of a 40:60 (weight basis) mixture of chlorodifluoromethane and 1-chloro-1,1-difluoroethane as a volatile foaming agent was press-fitted from the middle of the extruder, and a lip width of 600 mm, A T-die having a 0.4 mm gap is extruded into the atmosphere at a die temperature of 170 ° C. to produce a foamed sheet, and the other extruder is used to knead the thermoplastic elastomer (1) of Reference Example 1 at 190 ° C. Then, it was extruded simultaneously with the foamed sheet to obtain a laminate. The heat-shrinkage rate of this laminate was as good as 3%, and the appearance of the recycled sheet was also good.

Comparative Example 1 The same as Example 1 except that the resin composition (15) of Reference Example 15 containing no polyhydric alcohol compound of the crosslinkable resin composition (6) of Reference Example 6 was used. Went to. Since the viscosity was too low, the cells of the foam were coarse, and the heat resistance was low, and a laminate which could be used was not obtained.

Comparative Example 2 An example except that a commercially available polyethylene foam (expansion ratio 15 times) produced by electron beam crosslinking was used in place of the crosslinkable resin composition (6) of Reference Example 6. The same procedure as 1 was performed.

Comparative Example 3 An example except that a commercially available polypropylene foam (expansion ratio 15 times) produced by electron beam crosslinking was used in place of the crosslinkable resin composition (6) of Reference Example 6. The same procedure as 1 was performed.

Comparative Example 4 The procedure of Example 1 was repeated, except that a commercially available crosslinked polyurethane foam (foaming ratio: 15 times) was used instead of the crosslinkable resin composition (6) of Reference Example 6.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

Since the foam constituting the laminate of the present invention is flexible, has high strength, is excellent in heat resistance, and can be recycled, it is possible to laminate a thermoplastic elastomer having a recyclability as a skin layer. A laminate that is easy to reuse and has a good appearance, flexibility and toughness can be obtained. INDUSTRIAL APPLICABILITY The laminate of the present invention can be widely used for applications such as interior materials for automobiles, vehicles and ships.

Claims (7)

[Claims] 1. A copolymer containing at least (A) a thermoplastic elastomer layer and (B) (a) ethylene and at least a radical-polymerizable acid anhydride as a constituent monomer, and the radical-polymerizability in the copolymer. An ethylene-based copolymer in which the unit derived from an acid anhydride group is 0.1 to 20% by weight and may contain the unit derived from another radically polymerizable comonomer in an amount of 40% by weight or less, (b) intramolecular To 2
A polyhydric alcohol compound which is a component (b) with respect to a unit derived from a radical-polymerizable acid anhydride in the component (a), which contains a polyhydric alcohol compound having one or more hydroxyl groups and (c) a reaction accelerator. The molar ratio of the units of the hydroxyl groups in the product is 0.
Crosslinkable resin in the range of 01 to 10 and 0.001 to 20 parts by weight of the reaction accelerator as the component (c) relative to 100 parts by weight of the ethylene copolymer as the component (a). A laminated body formed by laminating a foam layer made of the composition. 2. The polyhydric alcohol compound of component (b) is
The following general formula (1) or (2) (R) _a C (CH ₂ OH) _b ………… (1) (In the formula, R is hydrogen, a chain or cyclic alkyl having 1 to 12 carbon atoms. The group or an aralkyl group is represented, a is an integer of 0 to 2, b is an integer of 2 to 4, and a + b = 4.
Is selected to satisfy. ) [Chemical 1] (In the formula, n is an integer of 0 to 10.) A polyoxyalkylene compound having a structure in which ethylene oxide or propylene oxide is added to a polyhydric alcohol compound and a general formula (3) R′-COOH ... (3) (In the formula, R'represents a chain or cyclic alkyl group having 2 to 25 carbon atoms or an aralkyl group.), And an organic carboxylic acid compound represented by the above general formula ( 1 of polyglycerin esters having two or more hydroxyl groups in the molecule, which are obtained by dehydration condensation with polyglycerin represented by 2).
The laminate according to claim 1, which comprises at least one kind. 3. The method according to claim 1, wherein the reaction accelerator which is the component (c) of the crosslinkable resin composition forming the foam layer is a metal salt of a polymer containing a carboxyl group or a metal salt of an organic carboxylic acid. The laminate described. 4. A thermoplastic elastomer comprising 100 to 40% by weight of a blend of (a) a partially cross-linked ethylene-α-olefin copolymer rubber and a polyolefin resin, and (b) 0 to 60% by weight of a softening agent for rubber. Claim 1 consisting of
The laminated body according to any one of 3 above. 5. The laminate according to claim 1, wherein the thermoplastic elastomer is a styrene-based thermoplastic elastomer. 6. The laminate according to claim 1, wherein the foam layer made of the crosslinkable resin composition is a foam layer having a crosslinked structure in the cooling process during the melt molding. 7. The laminate according to claim 1, wherein the foam layer is a foam layer obtained by melt-kneading a volatile foaming agent under pressure and extruding the mixture under atmospheric pressure.