JP3504370B2 - Multi-layer laminate - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to, for example, automobiles, vehicles,
The present invention relates to a multilayer laminate that is preferably used as an interior material for ships and the like.

[0002]

2. Description of the Related Art Conventionally, floors, walls of automobiles, vehicles, ships, etc.
Polyvinyl chloride is generally used as the uppermost layer for interior materials such as ceilings and as skin materials for doors, chairs, sofas, etc., and this is lined with a polyurethane or polypropylene-based crosslinked foam layer and, if necessary, a substrate material. The laminated body is used. In recent years, interest in environmental problems has increased, and substitution of materials that do not generate toxic gas during combustion processing and materials that can be easily reused is progressing. Under such a circumstance, studies have been eagerly conducted to replace the conventionally used vinyl chloride-based material with a polyolefin-based material which is a non-chlorine-based material, for example, a polyolefin-based resin and a partially cross-linked α-olefin. Blends of system copolymer rubbers (JP-A-55-71739, JP-A-58-12900)
No. 6, JP-A 1-292065, etc.) and a blend of a polyolefin resin and a non-crosslinked α-olefin copolymer rubber (JP-A-54-22453, JP-A-54-48846, JP-A-62-81443) and the like have been developed.

On the other hand, as a foaming material used as a backing material for giving a cushioning property to a skin material, it is assumed that it substantially satisfies various required performances.
Almost foamed urethane or cross-linked foamed polypropylene 2
The reality is that the types are limited. In particular, at the present time when the demand for reusability is increasing, cross-linked expanded polypropylene is the only polyolefin-based foam material, and is disclosed in, for example, JP-A-56-34732 and JP-A-62-62.
The foam and the like disclosed in Japanese Patent No. 34930 are being actively developed and improved.

[0004]

However, in the crosslinked foamed polypropylene material, not only the resin composition and the foaming agent are selected, but also extremely advanced techniques such as the resin crosslinking method and the foaming conditions are required, and the electron beam irradiation apparatus, There was a problem that special equipment such as a continuous heating and foaming furnace was also required. In addition, urethane foam and cross-linked foamed polypropylene that are currently used in the foam layer are inferior in adhesiveness to other materials, so it is necessary to use an adhesive, and heat welding such as thermoforming press or far infrared heating method is not required. There was a problem that I could not. The present invention has been made in view of such a situation, heat resistance, good flexibility, capable of relatively easy foam molding, using a polyolefin-based foam excellent in adhesiveness A multi-layer laminate is provided.

[0005]

Means for Solving the Problems The inventors of the present invention have made various studies to solve the above problems, and have invented a multilayer laminate having the following constitution. That is, the present invention has a Shore A hardness of 55.
~ 96 skin layer (A) consisting of a thermoplastic elastomer, and (b1) ethylene-based copolymer obtained by copolymerizing ethylene and at least a radical-polymerizable acid anhydride (b2) organic thermal decomposition with respect to 100 parts by weight. Mold blowing agent 0.1
A foam layer (B) obtained by foaming a mixture of 40 parts by weight, and a base material layer (C) of a wood-based phenol resin
And a multi-layered laminate comprising at least three layers.

The present invention will be described in detail below. The skin layer (A) constituting the multilayer laminate of the present invention is a thermoplastic elastomer having a Shore A hardness of 55 to 96. The Shore A hardness is preferably 60 to 95, and particularly preferably 65 to 90. If the Shore A hardness is less than 55, the resin becomes too soft and becomes sticky or scratch resistance is deteriorated, while if it exceeds 96, the resin becomes too hard and the touch is impaired, which is not preferable. In addition, Shore A
The hardness is a value measured according to ASTM D2240. The thermoplastic elastomer used in the present invention is 1
Melt viscosity η ₁ and shear rate 10 ² s by the slit die method at a shear rate of 10 ¹ sec ^-1 when measured at 70 ° C.
It is preferable that the ratio (η ₁ / η ₂ ) of melt viscosity η ₂ by the slit die method at ec ⁻¹ is 3.5 to 8, and particularly 4.5 to 7. The slit die method is used at a temperature of 1
Width 20 mm, height 1.5 mm, length 60 at 70 ° C
It is a method of measuring the melt viscosity using a mm slit die. For this method, see CD Han, Rheology in P
olymer Processing, Academic, NewYork, (1976) or JL White, Principles of Polymer Engineering
See Rheology, John Wiley, New York, (1990) for more information. Specifically, a viscometer having a commercially available slit die (Toyo Seiki Seisakusho Labo Plastomill D20-20
Type) can be used for measurement.

Specific examples of the thermoplastic elastomer preferably used in the skin layer (A) of the present invention include a polypropylene block and a copolymer block of propylene and ethylene and / or α-olefin having 4 to 12 carbon atoms. A propylene-α-olefin copolymer (hereinafter referred to as "PP
"Copolymer"). Examples of the α-olefin used here include 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-dimethyl-1-pentene, vinylcyclopentane, vinyl. Cyclohexane etc. are mentioned. These α-olefins may be used alone or in combination of two or more. Such a PP copolymer is
It becomes possible to obtain stronger adhesive strength in the case of directly adhering to the foam layer described later.

Further, in the above PP copolymer, the proportion of the copolymer block consisting of a copolymer of propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms in the whole PP copolymer is: Generally, 35 to 75% by weight is preferable, 38 to 70% by weight is more preferable, and 40 to 65% by weight is particularly preferable.

The PP copolymer preferably used in the present invention preferably has the following characteristics (a) and (b). That is, (a) the content of insolubles in para-xylene at a temperature of 25 ° C. is in the range of 25 to 65% by weight, and (b) the content of insolubles in para-xylene at a temperature of 25 ° C. is (i) the average of the two-site model. The content (FP) of units derived from propylene is 35 to 80% by weight,
(Ii) 2 copolymer produced in the active sites of polymerization preferentially propylene in site model (P _H) content of units derived from propylene (P _P) is 65 to 95 wt% and (iii) P _H The ratio (P _f1 ) in the para-xylene solubles is in the range of 0.60 to 0.90. (A)
Para-xylene insoluble matter refers to PP copolymer at a temperature of 130 ° C.
It is an insoluble matter when it is dissolved in para-xylene at about 1% by weight and then cooled to 25 ° C. The para-xylene insoluble matter in the PP copolymer of the present invention is preferably 25 to 65% by weight, particularly 30 to 60%. Weight percent is preferred.

Further, the (b) para-xylene soluble component is a component dissolved by the above operation, and it is preferable that the properties determined by the two-site model are within the above range. As a method for determining P _P and P _H , first, the components soluble in para-xylene at a temperature of 25 ° C. of the PP copolymer are 1, 2,
-Dissolve in a mixed solvent of trichlorobenzene / deuterated benzene by heating at a temperature of 120 ° C so that the polymer concentration becomes 10% by weight. This solution is placed in a ¹⁰ mmφ glass sample tube and the ¹³ C-NMR spectrum is measured to obtain the value.

The two-site model is a model assuming a polymerization reaction mechanism, and is a model of HN CHENG, Jounal of Applied Pol.
ymer Sience, Vol.35, 1639-1650 (1988). That is, in the model of copolymerizing propylene and ethylene using a catalyst, polymerized preferentially ethylene and propylene content (P _P) of the copolymer generated at the active sites of polymerization preferentially propylene (P _H) Assuming that the propylene content (P ' _P ) of the copolymer formed at the active sites is two, and the ratio of P _{H to} the entire copolymer (P _f1 ) is a parameter, the probability equation shown in Table 1 is obtained. To be

[0012]

[Table 1]

[0013] and the relative intensity ratio of each peak of the resulting ¹³ C-NMR spectrum, 3 P _P, P _'P and P _f1 such that the intensity ratio obtained from the probability equation shown in Table 1 matches
It is obtained by optimizing the individual parameters.
The attribution of each peak in the ¹³ C-NMR spectrum is CJ.
Carman, et al, Macromolecules, Vol.10, 536-544 (19
77).

The (i) average propylene content (FP) of the para-xylene-soluble component in the PP copolymer of the present invention is determined by the following equation (1) using the above three parameters. FP is preferably 35 to 80 wt% as determined by _{FP = P P × P f1 +} P 'P × (1-P f1) (1) the formula (1), is particularly preferred 40 to 70 wt%. Also,
(Ii) P _P is preferably 65 to 95 wt%, in particular 70
90% by weight is preferred. Further, (iii) P _f1 is 0.
50 to 0.90 is preferable, and 0.55 to 0.85 is particularly preferable.

Polymerization of the PP copolymer is carried out by a slurry method carried out in the presence of an inert hydrocarbon such as hexane, heptane, kerosene or the like or a liquefied α-olefin solvent such as propylene, a gas phase polymerization method in the absence of a solvent, and the like. The temperature conditions are room temperature to 130 ° C, preferably 50 to 90 ° C, pressure 2 to 50K.
It is performed under the condition of g / cm ² . As the reactor in the polymerization step, those usually used in the technical field can be appropriately used,
For example, any of a continuous method, a reverse batch method and a batch method may be used by using a stirred tank reactor, a fluidized bed reactor and a circulation reactor. Specifically, it can be obtained using a known multistage polymerization method. That is, after polymerizing propylene and / or propylene-α-olefin copolymer in the first-stage reactor,
This is a method of copolymerizing propylene and α-olefin in the second-stage reaction, and is, for example, JP-A-3-97747, JP-A-3-205439, and JP-A-4-153.
No. 203, No. 5-93024, No. 4
It is described in, for example, Japanese Patent Publication No.-261423. The PP copolymer used in the present invention is based on JIS K7210,
Table 1, condition 14 temperature 230 ° C., load 2.16 Kg
Has a melt flow rate (hereinafter referred to as "MFR") of usually 0.05 to 50 g / 10 minutes, preferably 0.1 to 50 g / 10 minutes.
10 g / 10 minutes, more preferably 0.5 to 5 g / 10
Minutes.

Further, as the other thermoplastic elastomer used in the skin layer (A) of the present invention, for example, a mixture of polyolefin and a partially crosslinked product of ethylene / α-olefin copolymer rubber can be mentioned. Specifically, the following can be exemplified. 1) Various polyolefin resins represented by a homopolymer of ethylene or propylene or a copolymer with a small amount of another comonomer, and a binary copolymer rubber of ethylene and an α-olefin having 3 to 14 carbon atoms, or A thermoplastic resin composition comprising a mixture of partially crosslinked ethylene / α-olefin copolymer rubber, which is a terpolymer rubber obtained by further copolymerizing various polyene compounds. 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 an ethylene / α-olefin copolymer rubber with a product obtained by heat-treating the composition. 4) Various peroxide non-crosslinking polyolefin resins represented by ethylene or propylene homopolymers or copolymers of these with a small amount of comonomer and ethylene.
Examples thereof include a thermoplastic composition obtained by dynamically heat treating a composition with an α-olefin-based copolymer rubber.

The polyolefin resin and the ethylene / α-olefin copolymer rubber partially crosslinked product are 80/20.
To 20/80 weight ratio, preferably 70/30 to 30 /
It is used by mixing so as to have a weight ratio of 70. As the polyolefin-based resin, polyethylene is used from the viewpoints of ease of forming the sheet, scratch resistance of the sheet, and the like. Especially low density polyethylene and polypropylene 10/90
It is preferable to use them by mixing them in a weight ratio of 70/30. Further, as the ethylene / α-olefin copolymer rubber which is partially crosslinked, mainly from the viewpoint of strength, the molar ratio of ethylene and α-olefin is 50/50 to 90/10, preferably 70/30 to 85 /. A molar ratio of 15 and a Mooney viscosity ML 1 _{+ 4} (121 ° C.) of about 20 or more, more preferably about 40 to 80 are preferable. Partial crosslinking of the ethylene / α-olefin copolymer rubber is generally carried out by dynamically heat-treating it with 0.1 to 2 parts by weight of peroxide with respect to 100 parts by weight of the raw material resin.

If desired, the thermoplastic elastomer used in the skin layer (A) exemplified above may be a peroxide non-crosslinking hydrocarbon rubber-like substance represented by polyisobutylene, butyl rubber or the like and / or a softening agent for rubber. A mixture of is used. A rubber softening agent usually weakens the intermolecular force of rubber during roll processing, facilitates processing, promotes dispersion of carbon black, white carbon, etc., or reduces the hardness of vulcanized rubber. At the very least, it is a petroleum fraction used for the purpose of increasing flexibility and rubber elasticity, and is classified into paraffin type, naphthene type, aromatic type and the like. Paraffinic process oil is preferably used.

Further, a phthalate ester plasticizer or silicone oil may be added to the thermoplastic elastomer used in the present invention. Examples of the phthalate ester-based plasticizer used here include those commonly used as plasticizers for vinyl chloride resins. Specific examples of the phthalate plasticizer include dimethyl phthalate,
Diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di2-ethylhexyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, dinolyl phthalate, diisodecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, Examples thereof include butylbenzyl phthalate, butyllauryl phthalate, and methyloleyl phthalate. Among these, it is recommended to use dimethyl phthalate, diethyl phthalate, and diisobutyl phthalate. The silicone oil used here is an oil containing a Si group, and examples thereof include those used as hydraulic oils, mold release agents, defoaming agents, paint additives, and cosmetics additives. Specific examples of the silicone oil include dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, alkyl-modified silicone, amino-modified silicone, epoxy-modified silicone, carboxyl-modified silicone, mercapto-modified silicone, chloroalkyl-modified silicone, and alkyl high-grade silicone. Examples thereof include alcohol-modified silicone, alcohol-modified silicone, polyether-modified silicone and fluorine-modified silicone. Among these, it is recommended to use dimethylpolysiloxane, methylhydrogenpolysiloxane, and methylphenylpolysiloxane.

The above-mentioned softening agent for rubber, phthalate ester-based plasticizer or silicone oil is in the range of not more than 60% by weight, preferably 30%, based on the PP copolymer.
It can be added in a range of not more than 20% by weight, more preferably not more than 20% by weight.

The thermoplastic elastomer used in the skin layer (A) of the present invention may contain other additives, compounding agents and fillers as long as the characteristics of the material are not impaired. Specific examples of these are glass, carbon black, zinc oxide, clay, talc, ground calcium carbonate,
In addition to inorganic fillers such as kaolin, diatomaceous earth, silica, alumina, asbestos and graphite, organic fillers, antioxidants (heat stabilizers), ultraviolet absorbers (light stabilizers),
Examples thereof include antistatic agents, flame retardants, lubricants (slip agents, antiblocking agents), reinforcing agents, coloring agents (dyes and pigments), foaming agents, and fragrances.

The ethylene copolymer (b1) used in the foam layer (B) of the present invention is a copolymer containing ethylene and at least a radical-polymerizable acid anhydride as a constituent monomer. The radically polymerizable acid anhydride used here is
A compound having one or more radically polymerizable unsaturated bond and one or more acid anhydride group in the molecule and capable of introducing an acid anhydride group into the molecule by polymerization. The acid anhydride group is preferably cyclic. Examples of such a compound include maleic anhydride, itaconic anhydride, citraconic anhydride, endic acid anhydride, dodecenyl succinic anhydride, 1-butene-3,4-dicarboxylic acid anhydride, and at most 1 carbon atom.
Examples thereof include alkadienyl succinic anhydride having a double bond at the terminal of 8. These may be used alone or in combination of two or more kinds. Among these, maleic anhydride and itaconic anhydride are preferably used.

As the ethylene-based copolymer used in the present invention, in addition to ethylene and a radical-polymerizable acid anhydride, other radical-polymerizable compounds copolymerizable with ethylene can be used.
It is also possible to use a copolymerized multi-component copolymer as a monomer. Examples of the third monomer include methyl (meth) acrylate, ethyl (meth) acrylate, and (meth)
Unsaturation of propyl acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, dimethyl fumarate, dimethyl maleate, etc. Vinyl esters such as carboxylic acid alkyl ester, vinyl acetate ester, and propionate vinyl ester,
Unsaturated amide compounds such as (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethylmethacrylamide, unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, methyl vinyl ether, ethyl vinyl ether Ethylenically unsaturated ether compounds such as propyl vinyl ether and butyl vinyl ether,
Ethylenically unsaturated hydrocarbon compounds such as styrene, α-methylstyrene, norbornene and butadiene, tertiary amino group-containing ethylenically unsaturated compounds such as dimethylaminoethyl ester of (meth) acrylic acid, and (meth) acrylonitrile, acrolein, Crotonaldehyde, trimethoxyvinylsilane, (meth) acrylic acid trimethoxysilylpropyl ester, vinyl chloride, vinylidene chloride,
Examples thereof include N-vinylacetamide and N-vinylformamide. These comonomers may be used alone or in combination of two or more.

The proportion of the units derived from the radical-polymerizable acid anhydride in the ethylene copolymer is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, and particularly preferably. Is 1.0 to 5% by weight. Also,
The proportion of the units derived from the third monomer contained in the ethylene copolymer is at most 30% by weight, preferably 25% by weight or less. As a method for producing the above ethylene-based copolymer, it is possible to use various methods such as radical solution polymerization, but generally, using a normal high-pressure process low-density polyethylene production equipment and its technology. Manufactured.

The organic thermal decomposition type foaming agent (b2) used by adding to the ethylene copolymer is 110 to 250 ° C.
And decomposes in the range to generate a gas, and has a decomposition temperature higher than the crystal melting point of the ethylene copolymer. Particularly, those having a decomposition temperature of 120 ° C. or higher are preferable, and those having a decomposition temperature of 130 ° C. or higher are particularly preferably used. Specific examples of such an organic thermal decomposition type foaming agent include dinitrosopentamethylenetetramine,
Azobisisobutyronitrile, azodicarbonamide,
Examples thereof include compounds such as paratoluenesulfonyl hydrazide, 4,4′-oxybisbenzenesulfonyl hydrazide and hydrazine, or a mixture thereof.

These organic heat-decomposable foaming agents can further enhance the foaming effect by being used in combination with a foaming auxiliary. This foaming aid cannot be unconditionally specified because it depends on the type of the foaming agent used. For example, when azodicarbonamide is used as the foaming agent, the foaming aid may be zinc oxide or sulfuric acid. Lead, urea, zinc stearate, etc. are used. When the foaming agent is dinitrosopentamethylenetetramine, salicylic acid, phthalic acid, boric acid, urea resin or the like is used as the foaming aid. The amount of the foaming agent used is 0.1 to 40 parts by weight, preferably 0.5 to 30 parts by weight, and more preferably 1 to 100 parts by weight of the ethylene copolymer.
~ 15 parts by weight.

The foam obtained by adding the exemplified organic pyrolysis type foaming agent to the ethylene copolymer and heat-foaming it forms a crosslinked structure at the time of foam molding. Although the mechanism of forming the crosslinked structure is not clear, it is speculated that it is caused by the reaction of the decomposition product or decomposition intermediate of the organic thermal decomposition type foaming agent with the acid anhydride group contained in the ethylene copolymer. ing. By thus introducing the crosslinked structure into the foam layer, the laminate of the present invention can maintain high heat resistance.

In order to introduce the crosslinked structure more efficiently, the ethylene-based copolymer (b1) and the organic thermal decomposition type foaming agent (b2) are further added with a functional group capable of reacting with an acid anhydride group in the molecule. The reactive compound (b3) having two or more of can be added and used. Examples of the functional group contained in the reactive compound include a hydroxyl group, an amino group, an epoxy group and an isocyanate group. Of these, a hydroxyl group, an amino group and an epoxy group are preferred. Of these, a hydroxyl group is preferable. The types of functional groups in the reactive compound may be the same or different.

Examples of polyhydric alcohol compounds having two or more hydroxyl groups in the molecule and derivatives thereof include glycols such as ethylene glycol, diethylene glycol and triethylene glycol; 1,4 butanediol,
1,6 hexanediol, 1,8 octanediol,
Alcohol compounds such as 1,10-decanediol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol; arbitol,
Sugars such as sorbitol, sorbitan, xylose, alaminose, glucose, galactose, sorbose, fructose, palatinose, maltotriose, and malezitose; saponification products of ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyolefin oligomers having a plurality of hydroxyl groups, ethylene -Hydroxyethyl (meth)
Acrylate [(meth) acrylate means methacrylate and acrylate. The same shall apply hereinafter], such as a copolymer having a plurality of hydroxyl groups in the molecule.

The polyhydric alcohol compound may be represented by the general formula (2) or (3) (R) _a C (CH ₂ OH) _b (2) (wherein R is hydrogen and the number of carbon atoms is 1 to 12). Represents a chain or cyclic alkyl group or aralkyl group, a represents an integer of 0 to 2, b represents an integer of 2 to 4, and a + b = 4.
Is selected to satisfy. _{) HO-CH 2 CH (OH} ) CH 2 -O- [CH 2 CH (OH) CH 2 -O] n -H (3) ( wherein, n is represented by an integer of 0.) Polyoxyalkylene compound having a structure in which ethylene oxide or propylene oxide is added to polyhydric alcohol compound and general formula (4) R'-COOH (4) (In the formula, R'is a chain having 2 to 25 carbon atoms. Or a cyclic alkyl group or an aralkyl group), which is obtained by dehydration condensation of an organic carboxylic acid compound represented by the formula) and the polyglycerol represented by the general formula (3). A polyglycerol ester having a hydroxyl group can also be used.

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 polyglycerin ester as described above 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, the polyhydric alcohol compound is obtained by dehydration condensation of sorbitan or a sorbitan derivative having two or more hydroxyl groups in the molecule and an organic carboxylic acid compound represented by the general formula (4). It is also possible to use sorbitan alkyl esters. As the sorbitan alkyl ester, specifically, for example, sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, sorbitan monocaprylate, sorbitan monohexanoate, sorbitan monophenethyl ester, sorbitan monopropionate, Examples thereof include sorbitan tristearate and sorbitan tetrastearate. Among these, preferred are those having a valence (number of hydroxyl groups in one molecule) of 3 to 7.

Examples of compounds having a plurality of amino groups in the molecule include ethylenediamine, diaminopropane, diaminobutane, 1,2-dimethyl-1,3-propanamine,
Hexamethylenediamine, 2-methyl-1,5-pentadiamine, diaminoheptane, diaminooctane, 2,
5-dimethyl-2,5-hexanediamine, diaminononane, diaminodecane, diaminododecane, diethylenetriamine, N- (aminoethyl) -1,3-methyldipropanediamine, 3,3'-diamino-N-methyldipropylamine , 3,3'-iminobispropylamine, triethylenetetramine, tris (2-aminoethyl) amine, tetraethylenepentamine, 1,4-diaminocyclohexane, polyethyleneimine, 4,4'-
Examples thereof include diaminodiphenylmethane and 1,4-diaminocyclohexane.

Alternatively, a compound having both an amino group and a hydroxyl group can be used. For example, ethanolamine 2-hydroxyethylhydrazine, 3-amino-1-propanol, DL-2-amino-1-propanol, DL-1
-Amino-2-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 2-amino-1-
Pentanol, DL-2-amino-1-pentanol,
6-amino-1-hexanol, 2- (2-aminoethoxy) ethanol and the like are used.

Examples of the compound having a plurality of epoxy groups in the molecule include sorbitol polyglycidyl ether,
Polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, hydroquinone diglycidyl ether, diglycidyl bisphenol A and hydrogenated products thereof, phthalic acid diglycidyl ester, trimethylolpropane triglycidyl ether, butanediol diglycidyl ether, epoxidized soybean oil , Epoxidized linseed oil, cyclohexanedimethanol diglycidyl ether, hexanetriol glycidyl ether,
Alicyclic epoxy resin, heterocyclic epoxy resin, brominated epoxy resin, bisphenol A-epichlorohydrin resin, polyfunctional epoxy resin, aliphatic epoxy resin, brominated novolac type epoxy resin, brominated bisphenol A type Examples thereof include epoxy resin, biphenyl type epoxy resin, polyglycidyl amine type epoxy resin, ester type epoxy resin, orthocresol novolac type epoxy resin, phenol novolac type epoxy resin and the like.

Examples of the compound having a plurality of isocyanate groups in the molecule include ethylene diisocyanate, diisocyanate butane, diisocyanate hexane, diisocyanate dodecane, diisocyanate-2-methylpentane and m-phenylenediene. Isocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-
Naphthylene diisocyanate, 4 ', 4', 4 "-triphenylmethane triisocyanate, 4,4 'diphenylmethane triisocyanate, 3,3'-dimethyl-
4,4'-diphenylene diisocyanate, m-xylylene-diisocyanate, p-xylylene-diisocyanate, isophorone diisocyanate and the like can be mentioned.
The melting point of the compound of these reactive compounds (b3) is 300
It is preferably below ℃. In addition, these compounds are
You can use more than one type at the same time.

The amount of the reactive compound (b3) used in the present invention is the amount in the reactive compound (b3) based on the unit derived from the radical-polymerizable acid anhydride contained in the ethylene copolymer (b1). It is desirable that the molar ratio of the functional groups is 0.01 to 10. It is more preferably 0.1 to 7, and even more preferably 0.2 to 5. Foamed layer (B) described above
The resin composition used in, for example, as a crosslinking reaction accelerator, sodium acetate, sodium stearate, a metal salt of an organic carboxylic acid such as calcium laurate, a polymer having a metal salt structure of a carboxylic acid such as an ionomer, A tertiary amine or a quaternary ammonium salt can be added and used.

As described above, the ethylene-based copolymer (b
1) and an organic thermal decomposition type foaming agent (b2), or a foaming composition comprising an ethylene copolymer (b1), an organic thermal decomposition type foaming agent (b2) and a reactive compound (b3) It is possible to introduce a crosslinked structure relatively easily without using a special device such as an electron beam irradiation device, and the foaming method does not particularly require a device such as a heating foaming furnace. Absent. Further, the foamable resin composition used in the present invention exhibits good adhesiveness to other materials. The most distinctive feature is that when the foamable resin composition is heated and foamed, it is simultaneously laminated with another material, for example, the above-mentioned thermoplastic elastomer and the base material described later using a thermal bonding method such as a thermoforming press. Is possible,
The adhesive strength is also good.

Next, the base material layer (C) used in the present invention is a plate material made of a wood-based phenol resin. The wood-based phenolic resin plate can be obtained by impregnating a wood-based material such as pulp fiber, pulp chips, and sawdust with a phenolic resin and performing heat compression molding. This resin plate can be used as a single layer, or as a multilayer structure in which a honeycomb structure made of a material such as synthetic resin film, cardboard paper or metal foil, or a foam structure using a resin material is sandwiched between intermediate layers. Can also be used. This base material has many advantages such as light weight, strength, and relatively low cost, and has been widely used for base materials such as vehicle ceilings, doors, panels, and building materials. . Further, since the base material has a rough surface, it exhibits good adhesiveness not only when it is adhered using an adhesive, but also when it is thermally adhered using a thermoplastic resin. Therefore,
Even in the case of laminating and adhering with the foamable resin mixture used in the foam layer (B) of the present invention, there is an advantage that it is possible to perform thermal adhesion with the present base material at the same time when the foamable resin mixture is heated and foam-molded. is there.

In the multi-layer laminate of the present invention, the thickness of the skin layer (A) is preferably 0.1 to 2 mm, more preferably 0.
2 to 1.5 mm, particularly preferably 0.3 to 1 mm. The thickness of the foam layer (B) is preferably 1 to 10 mm, more preferably 1 to 8 mm, particularly preferably 2 to
It is 8 mm. The expansion ratio is preferably 1.5 to 50 times, more preferably 2 to 40 times, particularly preferably 2 times.
~ 30 times. Furthermore, the thickness of the base material layer (C) is 0.5.
-25 mm is preferable, and more preferably 1-20 m.
m, particularly preferably 2 to 15 mm.

[0042]

EXAMPLES The present invention will be specifically described below with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited to these. . The method for measuring each physical property and the method for evaluating the multilayer laminate will be described below. (1) Measurement of melt viscosity ratio (η ₁ / η ₂ ) with a slit die Toyo Seiki Seisakusho Labo Plastomill D20-20 type having a slit die of width 20 mm, height 1.5 mm, length 60 mm Used at a temperature of 170 ° C and a shear rate of 10 ¹
The melt viscosity was measured eta ₂ in the melt viscosity eta ₁ and shear rate of 10 ² in. (2) Paraxylene insoluble content and soluble content measurement Polymer was once dissolved in paraxylene to a concentration of about 1% by weight at a temperature of 130 ° C, then cooled to a temperature of 25 ° C, and the precipitate was insoluble in paraxylene. The content that did not precipitate was defined as the para-xylene-soluble content, and the weight ratio was determined. The para-xylene solubles were used for the next measurement of the ¹³ C-NMR spectrum.

(3) Measurement of ¹³ C-NMR spectrum Measuring instrument: JNM-GSX manufactured by JEOL Ltd.
400 Measurement mode: Proton decoupling method Pulse width: 8.0 μs Pulse repetition time: 5.0 s Integration number: 20000 times Solvent: 1,2,4-trichlorobenzene / deuterated benzene mixed solvent (75/25 volume %) Internal standard: Hexamethyldisiloxane Sample concentration: 300 mg / 3.0 ml Solvent measurement temperature: 120 ° C. (4) Evaluation of heat-resistant wrinkle flowability As for the wrinkle flowability, the multi-layered laminate obtained by subjecting the surface skin to the texture treatment is used.
After heating in a gear oven at 0 ° C. for 24 hours, the average grain depth before and after this heating test was measured with a surface roughness meter, and the rate of change was evaluated. It was judged that the smaller the rate of change, the higher the resistance to wrinkle flow, and conversely, the greater the rate of change, especially those having a rate of change of more than 20%, the poorer the wrinkle flowability. (5) Heat-resistant thickness change A multilayer laminate sheet having a constant thickness of 10 cm × 10 cm was heated in a gear oven at 120 ° C. for 1 hour, and then the thickness of the multilayer laminate sheet was measured to measure the rate of change. . (6) Tactile sensation and cushioning The tactile sensation of the multilayer laminate is evaluated by comparison with the currently used vinyl chloride skin for automobile interiors, and it is desired to have almost the same warmth, smoothness and softness without stickiness. It was good. The cushioning property was evaluated by comparison with the currently used automobile interior laminate (skin: 0.5 mm thick vinyl chloride, foam layer: 2 mm thick cross-linked polypropylene foam), and it has almost the same cushion feeling. Things were good. (7) Adhesive strength The multilayer laminate was cut into a test piece having a width of 25 mm, and a T-type peeling strength (pulling speed 20
0 mm / min) was measured. In this test, the material in which the foam layer was broken was designated as "material broken".

As the thermoplastic elastomer, a mixture of a partially crosslinked ethylene / α-olefin copolymer rubber shown in Reference Examples 1 to 4 and Table 2 and a polyolefin, and a propylene-α-olefin copolymer shown in Table 2 are used. A polymer (PP copolymer) was used.

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
Mix 0% by weight and 1% by weight of a mixture of 1,3-bis (tertiary butylperoxyisopropyl) benzene / trimethylolpropane triacrylate / paraffinic mineral oil in a weight ratio of 2/3/5 with a Henschel mixer. Then
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 thermoplastic elastomer (1). Shore A hardness is 71, melt viscosity ratio (η ₁
/ Η ₂ ) was 4.9.

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% by weight of a mixture of 1,3-bis (tertiary butylperoxyisopropyl) benzene / trimethylolpropane triacrylate / paraffinic mineral oil in a weight ratio of 2/3/5. , Henschel mixer, then add the mixture to a Banbury mixer preheated to 120-140 ° C., 180-19
The mixture was kneaded at 0 ° C. for 10 minutes to carry out a crosslinking reaction. This was designated as a thermoplastic elastomer (2). The Shore A hardness was 82, and the melt viscosity ratio was 5.4.

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, M _W / M _N = 3.5, 135 ° C in decalin
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 / triallyl isocyanurate in a weight ratio of 5 2% by weight of the mixture of / 5 was mixed with 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 (3). The Shore A hardness was 67, and the melt viscosity ratio was 4.6.

Reference Example 4 Ethylene / propylene / ethylidene norbornene terpolymer [Ethylene / propylene molar ratio 60/40, iodine value 18, Mooney viscosity (M
L _{1 + 4} , 121 ° C.) 63] was used as the thermoplastic elastomer (4). Shore A hardness is 50, melt viscosity ratio is 4.
It was 1.

[0049]

[Table 2]

As the ethylene-based copolymer, the copolymers (EPC1 to 7) shown in Table 3 were used. In addition, the EPC,
Mix the foaming agent, the reactive compound and the reaction accelerator, and
The foamable resin mixtures (POF1 to 25) shown in Table 1 were prepared.

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

[Table 4]

Foaming agent A: azodicarbonamide / ZnO
= 50/50 (weight ratio) mixture blowing agent B: azodicarbonamide / p, p'-oxybis (benzenesulfonylhydrazide) = 50/50 (weight ratio) mixture blowing agent C: azodicarbonamide / dinitrosopenta Mixing of tetramine / urea = 50/25/25 (weight ratio) Blowing agent D: sodium hydrogen carbonate / citric acid = 90/10
(Weight ratio) mixture DG-80E: decaglycerin ethylene oxide (8.0 mol) adduct PE-45P: pentaerythritol propylene oxide (4.5 mol) adduct TMP: trimethylolpropane E-HEA: ethylene- Hydroxyethyl methacrylate (8% by weight) copolymer [MFR (JIS-K7210
Table 1, condition 4) 30 g / 10 minutes] DG-ST: decaglycerin stearic acid triester HMD: 1,6-hexamethylenediamine DADM: 4,4'-diaminodiphenylmethane TMPTG: trimethylolpropane triglycidyl ether EP4080: Asahi Denka hydrogenated bisphenol A type epoxy resin HMDI: hexamethylene diisocyanate IPDI: isophorone diisocyanate metal salt (a): sodium salt of ethylene-methacrylic acid (18% by weight) copolymer [10 mol of carboxyl group % Neutralization, MFR (JIS-K7210 Table 1, condition 4) 3.
0 g / 10 min] Metal salt (b): Sodium stearate Further, the following two types of wood-based phenol resin plates were used as base materials. Substrate A: Pulp fiber impregnated with phenolic resin 150
Substrate B having a thickness of 3 mm, which was hot-pressed at 1 ° C for 1 minute and compression-hardened. Base material B: It has a honeycomb structure using corrugated paper as an intermediate layer, and both outer layers impregnate the pulp resin with a phenol resin and 1mm thick after hot pressing and compression hardening
Multilayer structure base material consisting of wood-based phenolic resin plate with a total thickness of 15 mm

Example 1 First, the thermoplastic elastomer (1) shown in Reference Example 1 was molded into a sheet having a thickness of 0.5 mm at a resin temperature of 210 ° C. using an extruder with a T die having a screw of 25 mmφ. Then, it was cut into a size of 150 mm × 150 mm. Then, the POF1 shown in Table 4 was heated at a resin temperature of 11 using a T-die extruder having a screw of 25 mmφ.
Molded into a sheet with a thickness of 1 mm at 0 ° C, 150 mm x 1
It was cut into a size of 50 mm. 180 upper and lower mold
The press machine adjusted to ℃, aluminum press flat plate, 200
Base material A, POF cut to a size of mm x 200 mm
1 sheet and thermoplastic elastomer (1) sheet in this order, and then a 3 mm spacer is sandwiched between the base material A and a crimped aluminum press plate coated with a release agent, and the upper die's own weight Heated and pressed only. After heating for 5 minutes, it was taken out from the press and immediately cooled with water to obtain a multilayer laminate.

The thickness of the foam layer of the obtained multilayer laminate is 3 m.
At m, the foam layer was cut off, the density was measured by the Archimedes method, and the expansion ratio was calculated to be 4.6. Further, when the heat resistance of the obtained multilayer laminate was evaluated, the average grain change rate was 6% and the thickness change was 4%. Also,
The touch and cushioning properties were also good. Furthermore, when the interlayer adhesive strength of the multilayer laminate was measured, it was confirmed that the foam layer had material destruction and had good adhesiveness. The above results are shown in Table 5.

Examples 2 to 30 Thermoplastic elastomers shown in Reference Examples 1 to 3 or Table 2
Using the expandable resin mixture and the base material shown in Table 4, a sheet was formed in the same manner as in Example 1. However, when the thermoplastic elastomer (9) is used, the sheet thickness is 1.0 m.
m. A skin layer and a foam layer were selected from the combinations shown in Table 5, and a multilayer laminate was obtained in the same manner as in Example 1. However, in Examples 6, 10, 14 and 23, the spacer thickness during pressing was set to 5 mm, and Examples 3, 4, and 1 were used.
In Nos. 7 to 21, the spacer thickness during pressing was 2 mm. Evaluation of the obtained multilayer laminate was performed in the same manner as in Example 1. The results are summarized in Table 5. In each case, a good multilayer laminate was obtained.

Comparative Examples 1 to 4 Multilayer laminates were prepared in the same manner as in Example 1 except that the type of thermoplastic elastomer was changed to that shown in Table 6.
evaluated. The results are summarized in Table 6. When the thermoplastic elastomer (4) or (12) is used, the thermoplastic elastomer is too soft and has insufficient heat resistance.
The texture was sticky and was poor. When the thermoplastic elastomer (10) or (11) was used, the thermoplastic elastomer was too hard and the feel was poor.

Comparative Example 5 A multilayer laminate was prepared in the same manner as in Example 17, except that POF23 shown in Table 4 was used as the expandable resin mixture.
evaluated. The results are summarized in Table 6. The heat resistance of the foam layer was insufficient and the foam layer melted.

Comparative Example 6 A multilayer laminate was prepared in the same manner as in Example 17, except that POF24 shown in Table 4 was used as the expandable resin mixture.
evaluated. The results are summarized in Table 6. The heat resistance of the foam layer was insufficient and the foam layer melted.

Comparative Example 7 A multilayer laminate was prepared in the same manner as in Example 17, except that POF25 shown in Table 4 was used as the expandable resin composition.
evaluated. The results are summarized in Table 6. Foaming was not sufficient, and the heat resistance of the foamed layer was insufficient, and the foamed layer melted.

Comparative Example 8 As a foam layer, a cross-linked expanded polypropylene sheet manufactured by Toray,
A multilayer laminate was prepared and evaluated by hot pressing in the same manner as in Example 1 except that a pef (foaming ratio: 25 times, thickness: 2 mm) was used. The results are summarized in Table 6. The interlayer adhesion strength between the skin layer and the foam layer was insufficient, resulting in interfacial peeling.

[0063]

[Table 5]

[0064]

[Table 5]

[0065]

[Table 6]

[0066]

EFFECT OF THE INVENTION The multilayer laminate of the present invention uses a polyolefin-based material which satisfies heat resistance and flexibility and can be foam-molded and laminated relatively easily. As it has excellent tactile sensation, it can be used for cars, vehicles,
It is useful as an interior material for ships and the like.

[Brief description of drawings]

FIG. 1 is an example of a nuclear magnetic resonance spectrum of isotope carbon of an ethylene-propylene copolymer.

FIG. 2 is a diagram showing names of carbons derived from a chain distribution in polyolefin.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akiyuki Fujii No. 2 Nakasu, Oita City, Oita Prefecture Showa Denko KK Oita Research Laboratory (56) Reference JP-A-6-316016 (JP, A) HEI 6-286039 (JP, A) JP-A-57-20344 (JP, A) JP-A-5-329983 (JP, A) Actual development Sho-64-3423 (JP, U) (58) Fields investigated (Int .Cl. ⁷ , DB name) B32B 1/00-35/00

Claims (8)

(57) [Claims] 1. A skin layer (A) made of a thermoplastic elastomer having a Shore A hardness of 55 to 96, and (b1) 100 parts by weight of an ethylene-based copolymer obtained by copolymerizing ethylene with at least a radical-polymerizable acid anhydride. On the other hand, (b2) an organic thermal decomposition type foaming agent: a foaming layer (B) obtained by foaming a mixture of 0.1 to 40 parts by weight, and a base material layer (C) made of a wood-based phenol resin. A multilayer laminate comprising at least 3 layers. 2. A skin layer (A) made of a thermoplastic elastomer having a Shore A hardness of 55 to 96, and (b1) above.
The component (b2) is 0.1 to 40 parts by weight with respect to 100 parts by weight of the component, and (b3) is a reactive compound having two or more functional groups capable of reacting with an acid anhydride group in the molecule, (b1)
Foamed layer obtained by foaming a composition in which the molar ratio of the functional group in the reactive compound as the component (b3) is 0.01 to 10 with respect to the unit derived from the radically polymerizable acid anhydride in the component. A multilayer laminate comprising at least three layers of (B) and a base material layer (C) made of a wood-based phenol resin. 3. The skin layer (A) has a shear rate of 10 ¹ sec ^-1.
A thermoplastic elastomer having a ratio (η ₁ / η ₂ ) of melt viscosity η ₁ measured by the slit die method and slit melt viscosity η ₂ measured by the slit die method at 3.5 to 8 at a shear rate of 10 ² sec ^-1 . The multilayer laminate according to claim 1 or claim 2. 4. The skin layer (A) is a propylene-α-olefin copolymer, and the propylene-α-olefin copolymer is 65 to 25% by weight of a polypropylene block and propylene, ethylene and / or carbon. Copolymer block with α-olefin of number 4 to 12 35 to 75% by weight
The multilayer laminate according to claim 3, which is a thermoplastic elastomer comprising 5. The functional group in the reactive compound (b3) is at least one selected from the group consisting of a hydroxyl group, an amino group, an epoxy group and an isocyanate group. The multilayer laminate according to item. 6. The unit in which the ethylene-based copolymer (a) of the foam layer (B) is derived from a radical-polymerizable acid anhydride is 0.1 to 0.1.
The multilayer laminate according to any one of claims 2 to 5, containing 20% by weight. 7. The skin layer (A) has a thickness of 0.1 to 2 mm, the foam layer (B) has a thickness of 1 to 10 mm, and the base material layer (C) has a thickness of 0. It is 5 to 25 mm.
The laminated body according to any one of 1 to 6. 8. The expansion ratio of the foam layer (B) is 1.5 to 50.
The multilayer laminate according to any one of claims 1 to 7, which is double.