JP3504382B2 - Multi-layer laminate - Google Patents

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is suitable for use as an interior material for automobiles, vehicles, ships and the like, has excellent heat resistance and softness, can be relatively easily foam-molded, and is easily laminated. Multi-layer laminate.

[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 above-mentioned multilayer laminate has been used conventionally. In recent years, interest in environmental problems has increased, and substitution of materials that do not generate toxic gases during combustion processing and materials that can be easily reused is progressing. In such a flow, many proposals have been made to replace the conventionally used vinyl chloride-based material with a non-chlorine-based material such as a polyolefin-based material (for example, JP-A-55-71738, JP-A-55-71738). JP-A-55-71739, JP-A-58-12
9006, Japanese Patent Application Laid-Open No. 62-81443, Japanese Patent Application Laid-Open No. 1-292065).

On the other hand, a foaming material is used as a backing material for imparting cushioning properties to the above-mentioned skin material, but the foaming material is limited to almost two types of urethane foam or crosslinked foam polypropylene in terms of performance. It is the actual situation. Moreover, in the present day when the demand for recycling is increasing from the viewpoint of global resource protection, the latter cross-linked expanded polypropylene is the only foam material that meets these requirements, and aggressive development and improvement are proceeding. (For example, JP-A-56-34732)
JP-A-62-34930, etc.).

[0004]

However, the above-mentioned cross-linked foamed polypropylene is required to have an extremely high level of technique such as resin cross-linking method and foaming conditions as well as selection of resin composition and foaming agent, and electron beam irradiation apparatus, There was a problem that special equipment such as a continuous heating foaming furnace was required. Further, since it is inferior in adhesiveness to other materials, it is necessary to use an adhesive, and there is a problem that heat welding such as a hot pressing method or a far infrared heating method cannot be performed. The present invention has been made in view of such circumstances, and it is an object of the present invention to provide a multilayer laminate which has excellent heat resistance and flexibility, can be foam-molded relatively easily, and can be easily laminated. .

[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.
To 96 skin layers (I) consisting of a thermoplastic elastomer, (a1) ethylene, an unsaturated carboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid anhydride and an unsaturated dicarboxylic acid half ester. 1 to 99% by weight and (a) an ethylene-based copolymer which is obtained by copolymerizing at least one kind of monomer and has a content of units derived from ethylene of 30 to 99.5% by weight.
2) Obtained by copolymerizing ethylene with at least one monomer selected from the group consisting of an epoxy group-containing unsaturated compound, an amino group-containing unsaturated compound and a hydroxyl group-containing unsaturated compound, and derived from ethylene The content of the unit
Ethylene copolymer of 99.5% by weight Organic blowing agent capable of decomposing at 100 to 250 ° C with respect to 100 parts by weight of the component (A) in the ethylene resin composition (A) consisting of 99 to 1% by weight. (B) A multilayer laminate comprising at least three layers of a foam layer (II) obtained by foaming a resin composition containing 0.1 to 50 parts by weight and a base material layer (III) made of a wood-based phenol resin material. It provides the body. Hereinafter, the present invention will be described in detail.

The skin layer (I) 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. Shore A hardness is 55
If less than, the resin becomes too soft and sticky,
Scratch resistance decreases. On the other hand, if it exceeds 96, the resin becomes too hard and the touch is impaired, which is not preferable.

The Shore A hardness is ASTM D224.
It is a value measured according to 0. As the thermoplastic elastomer used in the present invention, 1 using the slit die method
The ratio of the melt viscosity eta ₂ in the melt viscosity eta ₁ and a shear rate of 10 ² sec ^-1 at a shear rate of 10 ¹ sec ^-1 when measured at _{70 ℃ (η 1 / η 2} ) is 3.5-8, especially It is preferably from 4.5 to 7. The slit die method is a width of 20 mm and a height of 1.5 at a temperature of 170 ° C.
This is a method of measuring melt viscosity using a slit die having a length of 60 mm and a length of 60 mm. For this method, see CD Han,
Rheology in Polymer Processing, Academic, NewYor
k, (1976) or JL White, Principles of Polyme
r Engineering Rheology, John Wiley, New York, (199
There is detailed description in 0). Specifically, the viscosity can be measured using a commercially available viscometer having a slit die (Toyo Seiki Seisakusho Labo Plastomill D20-20 type).

Specific examples of the thermoplastic elastomer preferably used in the skin layer (I) of the present invention include a polypropylene block and a copolymer block of propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms. A propylene-α-olefin copolymer (hereinafter referred to as "PP
Abbreviated as "copolymer"). As the α-olefin used here, 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.

As the PP copolymer used in the present invention, those having the following characteristics (a) and (b) are particularly preferable. That is, (a) the para-xylene insoluble matter at a temperature of 25 ° C. is in the range of 25 to 65% by weight, and (b) the para-xylene soluble matter at a temperature of 25 ° C.
(I) The content (FP) of the units derived from the average propylene in the two-site model is 35 to 80% by weight, and (ii) the copolymer (P) produced at the active site where propylene is preferentially polymerized in the two-site model. content of units derived from propylene (P _P) is 65 to 95 wt% of _H) and (iii) P _H
The ratio (P _f1 ) in the para-xylene soluble component 1.00 is in the range of 0.60 to 0.90.

The (a) para-xylene insoluble matter is an insoluble matter when the PP copolymer is dissolved in para-xylene at a temperature of 130 ° C. in an amount of about 1% by weight and then cooled to 25 ° C. The para-xylene insoluble content in the polymer is preferably 25 to 65% by weight, and particularly preferably 30 to 60% by weight.

Further, the (b) para-xylene soluble component is a component dissolved by the above-mentioned operation, and it is preferable that the properties obtained 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 in which propylene and ethylene are copolymerized using a catalyst, the propylene content (P _H ) of the copolymer (P _H ) generated at the active site where propylene is preferentially polymerized
_P ) and the propylene content (P ′ _P ) of the copolymer produced at the active sites where ethylene is preferentially polymerized, and the ratio of P _{H to} the entire copolymer (P _f1 ) is used as a parameter. Then, the probability equation shown in Table 1 is obtained.

[0014]

[Table 1]

[0015] 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%, especially 7
0 to 90% by weight is preferred. Further, (iii) P _f1 is preferably 0.50 to 0.90, and particularly 0.55 to
0.85 is preferable.

Polymerization of the PP copolymer according to the present invention is carried out in the presence of an inert hydrocarbon such as hexane, heptane, kerosene or a liquefied α-olefin solvent such as propylene, a slurry method, a vapor phase weight without solvent. According to legal method, the temperature condition is room temperature to 130 ° C, preferably 50 to 90 ° C,
The pressure is ^{2 to} 50 kg / cm2. As the reactor in the polymerization step, those usually used in the technical field can be appropriately used, and for example, a stirred tank type reactor, a fluidized bed type reactor, a circulation type reactor can be used as a continuous type, an anti-batch type or a batch type. Either method is acceptable. Specifically, it can be obtained using a known multistage polymerization method. That is, it is a method of polymerizing propylene and / or propylene-α-olefin copolymer in the first-stage reactor and then copolymerizing propylene and α-olefin in the second-stage reaction. Kaihei 3
-97747, JP-A-3-205439,
JP-A-4-153203, JP-A-5-93024
Japanese Patent Application Laid-Open No. 4-261423.

The PP copolymer used in the present invention generally has a melt flow rate (measured according to JIS K7210, Table 1, Condition 14; hereinafter referred to as "MFR") of 0.0.
5 to 50 g / 10 minutes, preferably 0.1 to 10 g / 10
Min, more preferably 0.5 to 5 g / 10 min.

Further, as another thermoplastic elastomer used in the skin layer (I) of the present invention, for example, a mixture of polyolefin and a partially cross-linked 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 cross-linked 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.

Polyolefin resin and ethylene / α-o
The partially crosslinked product of the reffin copolymer rubber is 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. Polio
As the reffin resin, the ease of forming the sheet, the sheet
Polyethylene is used in terms of scratch resistance and the like. Special
Low density polyethylene and polypropylene on 10/90
It is preferable to use by mixing at a weight ratio of 70 to 30.
Yes. In addition, ethylene / α-olefins that are partially crosslinked
As a copolymer rubber, ethylene is mainly used from the viewpoint of strength.
And the α-olefin are in a molar ratio of 50/50 to 90/10.
Ratio, preferably in a molar ratio of 70/30 to 85/15,
Mooney viscosity ML_{1+ Four} (121 ℃) is about 20 or more,
It is preferably about 40-80. Ethylene / α-o
Partial cross-linking of reffin-based copolymer rubber is generally a raw material resin.
0.1 to 2 parts by weight of peroxide per 100 parts by weight
It is carried out by heat treatment dynamically.

A rubber-like polymer may be mixed with the thermoplastic elastomer used in the skin layer (I) exemplified above, if necessary. Examples of the rubber-like polymer include natural rubber, butadiene rubber, isoprene rubber, chloroprene rubber, styrene-butadiene rubber, isobutene-isoprene rubber, acrylonitrile-butadiene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated. Diene copolymer rubber, propylene-butene rubber, butyl rubber, silicone rubber, chlorosilicon rubber, nitrile rubber, epichlorohydrin rubber, styrene / isoprene-styrene block copolymer, styrene-ethylene / isoprene-styrene block copolymer,
Examples thereof include styrene / butadiene-styrene block copolymers. Alternatively, a mixture of rubber softening agents can be 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 least, a petroleum fraction used for the purpose of increasing flexibility and rubber elasticity,
It is classified into paraffinic, naphthenic, aromatic and the like. Paraffinic process oil is preferably used.

Further, a phthalate ester type plasticizer or silicone oil may be added to the thermoplastic elastomer of 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 rubber-like polymer, rubber softening agent, phthalate ester plasticizer or silicone oil is 60% by weight or less, preferably 30% by weight or less, more preferably 20% by weight, based on the PP copolymer. % Or less.

The thermoplastic elastomer used in the skin layer (I) 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 (a1) used in the foamed layer (II) of the present invention comprises ethylene, an unsaturated carboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid anhydride and an unsaturated dicarboxylic acid half ester. Obtained by copolymerizing at least one monomer selected from the group consisting of (collectively referred to as "second component (1)" above), and having a content of ethylene-derived units of 30 to 99. The copolymer is 0.5% by weight. As a typical example of the second component (1),
(Meth) acrylic acid, α-ethylacrylic acid, etc., having at most 25 unsaturated monocarboxylic acids, or maleic acid, itaconic acid, tetrahydrophthalic acid, citraconic acid, etc., having 4 to 50 carbon atoms Unsaturated dicarboxylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, endic acid anhydride, dodecenyl succinic anhydride, 1-butene-3,4-dicarboxylic acid anhydride, carbon number of at most 1
Examples thereof include unsaturated dicarboxylic acid anhydrides having 4 to 50 carbon atoms, such as alkadienyl succinic anhydride having a double bond at the terminal. These may be used alone or in combination of two or more kinds.

The ethylene-based copolymer (a used in the present invention
As 1), in addition to ethylene and the second component (1), other monomers copolymerizable with ethylene are added and copolymerized, and the acid anhydride group in these copolymers is hydrolyzed. Those obtained by decomposing and / or denaturing with alcohol can be used. Examples of other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, Unsaturated carboxylic acid alkyl esters such as lauryl (meth) acrylate, benzyl (meth) acrylate, dimethyl fumarate, dimethyl maleate, vinyl esters such as vinyl acetate, propionate vinyl ester, (meth) acrylamide, N- Methyl (meth) acrylamide, N, N
An unsaturated amide compound such as dimethylmethacrylamide,
Unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid and fumaric acid, ethylenically unsaturated ether compounds such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and butyl vinyl ether, styrene, α-
Ethylenically unsaturated hydrocarbon compounds such as methylstyrene, norbornene and butadiene, ethylenically unsaturated compounds containing tertiary amino group such as (meth) acrylic acid dimethylaminoethyl ester, other (meth) acrylonitrile, acrolein, crotonaldehyde, triton Methoxyvinylsilane, (meth) acrylic acid trimethoxysilylpropyl ester, vinyl chloride, vinylidene chloride, N-vinylacetamide, N-vinylformamide and the like can be mentioned. These may be used alone or in combination of two or more kinds.

The content of units derived from ethylene in the ethylene-based copolymer (a1) is 30 to 99.5% by weight,
30 to 99.0% by weight is preferable, and 35 to 99.0 is particularly preferable.
Weight percent is preferred. If the content of the unit derived from ethylene is less than 30% by weight, the production becomes difficult and it is not economical. On the other hand, if it exceeds 99.5% by weight, the heat resistance decreases, which is not preferable. The copolymerization ratio of the second component (1) used in the copolymer is generally 30% by weight or less as the total amount thereof.

Further, the ethylene-based copolymer (a2) used in the foam layer (II) is selected from the group consisting of ethylene, an epoxy group-containing unsaturated compound, an amino group-containing unsaturated compound and a hydroxyl group-containing unsaturated compound. Obtained by copolymerizing at least one kind of monomer (collectively referred to as "second component (2)" above), and the content of units derived from ethylene is 30 to 99.5% by weight. It is an ethylene-based copolymer. Examples of the epoxy group-containing unsaturated compound of the second component (2) include compounds represented by the following general formulas (I) to (III).

[0028]

[Chemical 1]

[Chemical 2]

[Chemical 3] (In the formula, R ₁ has 2 carbon atoms having an ethylenically unsaturated bond.
To 18 hydrocarbon groups, R ₂ is a linear or branched alkylene group having 1 to 12 carbon atoms, and X is —O— or —N.
The H-, Y is -CH ₂ -O- or

[Chemical 4] [However, R ₃ represents hydrogen or a methyl group]

Typical examples of these are glycidyl (meth) acrylate, glycidyl (meth) acrylamide, glycidyl alkyl (meth) acrylate, glycidyl itaconic acid esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-
p-glycidyl ether, (4-glycidyloxy-
3,5-dimethylphenyl) methyl (meth) acrylamide and the like can be mentioned.

As the amino group-containing unsaturated compound, radically polymerizable unsaturated amine having 3 to 25 carbon atoms, (alkyl) aminoalkyl (meth) acrylate having 3 to 25 carbon atoms, and 3 to 25 carbon atoms ( Alkyl) aminoalkyl (meth) acrylamide and the like are used, for example, vinylbenzylamine, (aminocarbonyl) methyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, (meth) acrylamide,
Examples thereof include N- (2-morpholinoethyl) (meth) acrylamide and N- (3-propylaminopropyl) (meth) acrylamide.

Further, as the hydroxyl group-containing unsaturated compound, a hydroxyl group-containing radically polymerizable unsaturated compound having 3 to 25 carbon atoms and a hydroxyalkyl (meth) having 3 to 25 carbon atoms.
Acrylate, hydroxyalkyl (meth) acrylamide having 3 to 25 carbon atoms and the like are used, and for example, 2-hydroxyethyl vinyl ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxycyclohexyl (meth) acrylate, 4-hydroxybutyl (meth). )
Acrylate, 2-hydroxypropyl (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylate and the like can be mentioned.

The ethylene-based copolymer (a used in the present invention
As for 2), a multi-component copolymer obtained by copolymerizing ethylene and the second component (2) with another monomer copolymerizable with ethylene may be used. The other monomer can be selected from the group of compounds exemplified as the other monomer used in the ethylene copolymer (a1). Further, other examples of the ethylene-based copolymer (a2) include, for example, a saponified product of an ethylene-vinyl acetate copolymer (the same as using vinyl alcohol as the second component (2)), ethylene- Examples thereof include saponified products of vinyl formamide copolymer (the same as using vinyl amine as the second component (2)).

The content of units derived from ethylene in the ethylene-based copolymer (a2) is 30 to 99.5% by weight,
30 to 99.0% by weight is preferable, and 35 to 99.0 is particularly preferable.
Weight percent is preferred. If the content of the unit derived from ethylene is less than 30% by weight, the production becomes difficult and it is not economical. On the other hand, if it exceeds 99.5% by weight, the heat resistance decreases, which is not preferable. The copolymerization ratio of the second component (2) used in the copolymer is generally 30% by weight or less as the total amount thereof. The ethylene-based copolymer (a
1) and the ethylene-based copolymer (a2) MFR (JI
SK7210, Table 1, measured under condition 4) is generally 0.
01-1000g / 10 minutes, 0.05-500g
/ 10 minutes is preferable, and 0.1 to 500 g / 10 minutes is particularly preferable.

Among these ethylene-based copolymers, when produced by a copolymerization method, it is usually 500 to 2500.
Ethylene and the second component (1) or the second component (2) in the presence of a radical polymerization initiator (for example, an organic peroxide) at a temperature of 120 to 260 ° C. under a high pressure of kg / cm ² , or these and others. It can be produced by copolymerizing the above monomers, and their methods are well known. In addition, the ethylene-based copolymer (a
The method of production by hydrolysis and / or modification with alcohol among 1) is also well known.

Further, the foaming agent (B) used in the foaming layer (II) of the present invention has a decomposition temperature higher than the melting temperature of the ethylene copolymers (a1) and (a2), There is no particular limitation as long as it decomposes in a temperature range of 100 to 250 ° C., but a decomposition temperature of 110 ° C. or higher is desirable, and 130 ° C. or higher is particularly preferable. Preferable examples of the foaming agent include compounds such as dinitrosopentamethylenetetramine, azobisisobutyronitrile, azodicarbonamide, paratoluenesulfonylhydrazide, 4,4′-oxybisbenzenesulfonylhydrazide, hydrazine and the like. A mixture of

These foaming agents can further enhance the foaming effect by being used in combination with a foaming auxiliary agent. The 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 (zinc white). ), Lead sulfate, 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 proportion of the ethylene copolymer (a1) in the ethylene resin composition (A) used for the foamed layer of the present invention is 1 to 99% by weight, preferably 5 to 95% by weight, and particularly 10 to 90% by weight. % Is preferred. (A1)
Is less than 1% by weight or more than 99% by weight, the heat resistance is lowered, which is not preferable. Moreover, the compounding quantity of a foaming agent is 0.1-50 weight part with respect to 100 weight part of ethylene-type resin compositions (A), 1.0-40 weight part is preferable and especially 2.0-30. Weight parts are preferred.
If the composition ratio of the foaming agent is less than 0.1 part by weight, the expansion ratio will be insufficient. On the other hand, if it exceeds 50 parts by weight, the cushioning property is deteriorated, which is not preferable.

In the foamable composition thus obtained, a crosslinked structure can be introduced relatively easily without using a special device such as an electron beam irradiation device, and the foaming method also requires a special heating and foaming furnace. No such device is required. In addition, the foamable resin composition according to the present invention has a feature that it exhibits good adhesiveness to other materials. The most distinctive feature is that when the foamable resin composition is heated and foamed, other materials such as the above-mentioned thermoplastic elastomer, as well as various substrate materials described later and a thermal bonding method such as a thermoforming press are used. It can be laminated by using it, and its adhesive strength is also good.

Further, the base material layer (III) in the present invention is
It is a plate made of wood-based phenol resin. The wood-based phenol resin plate is obtained by impregnating a wood-based material such as pulp fiber, pulp chips, and sawdust with a phenol resin and heating and compression molding. This resin plate can be used as a single layer, or a multilayer structure using 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 as an intermediate layer. It can also be used. The base material has many advantages such as light weight, strength, and relatively low cost.

In the multilayer laminate of the present invention, the thickness of the skin layer (I) is preferably 0.1 to 2 mm, more preferably 0.2 to 1.5 mm, and particularly preferably 0.3 to 1 mm. . The thickness of the foam layer (II) is preferably 1 to 10 mm, more preferably 1 to 8 mm, and particularly preferably 2 to 8 mm.
The expansion ratio is preferably 1.5 to 50 times, more preferably 2 to 40 times, and particularly preferably 2 to 30 times.
The thickness of the base material layer (III) is preferably 0.5 to 25 mm, more preferably 1 to 20 mm, and particularly preferably 2 to 15 mm.

[0040]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. . The method for measuring each physical property and the method for evaluating the multilayer laminate will be described below. (1) Melt viscosity It was measured using a Labo Plastomill D20-20 type manufactured by Toyo Seiki Seisakusho, which has a slit die having a width of 20 mm, a height of 1.5 mm and a length of 60 mm. (2) Para-xylene-insoluble matter The polymer was once dissolved in para-xylene at a temperature of 130 ° C to a concentration of about 1% by weight, then cooled to a temperature of 25 ° C, and the precipitated matter was used as the para-xylene-insoluble matter. (3) ¹³ C-NMR spectrum Para-xylene solubles were measured under the following conditions. Measuring equipment: JNM-GS manufactured by JEOL Ltd.
X400 measurement mode: Proton decoupling method pulse width: 8.0 μsec Pulse repetition time: 5.0 sec Integration number: 20000 times Solvent: 1,2,4-trichlorobenzene /
Mixed solvent of deuterated benzene (75/25% by volume) Internal standard: Hexamethyldisiloxane sample concentration: 300 mg / 3.0 ml Solvent measurement temperature: 120 ° C

(4) Heat-resistant average grain change rate The multi-layered laminate having the surface textured was heated in a gear oven at 100 ° C. for 24 hours, and the average grain depth before and after this heating test was measured by a surface roughness meter and the change. Expressed as a rate (%). (5) Heat-resistant dimensional change multilayer laminated sheet (size 10 cm × 10 cm) 12
After heating in a gear oven at 0 ° C. for 1 hour, the thickness and area were measured and expressed as the volume change rate (%). (6) Tactile sensation and cushioning Tactile sensation were evaluated by comparison with a vinyl chloride skin for automobile interiors, and those having almost the same warmth, smoothness, and softness without stickiness were considered good. The cushioning property was evaluated by comparison with a laminate for automobile interior (skin: 0.5 mm thick vinyl chloride, foam layer: 2 mm thick cross-linked polypropylene foam), and those having almost the same cushioning feeling were evaluated as good. . (7) Using a tensile tester, the adhesive strength test piece (25 mm width) was used as a skin layer-
The T-type peel strength between the foam layer and between the foam layer and the base material layer (pulling speed: 200 mm / min) was measured. In this test, the material in which the foam layer or the base material layer was destroyed was designated as "material fracture".

Further, as a thermoplastic elastomer, a mixture of a partially cross-linked ethylene / α-olefin copolymer rubber and a polyolefin shown in Reference Examples 1 to 4 and Table 2,
And the propylene-alpha-olefin copolymer shown in Table 2 was used. Further, the following two types of substrates were used. Substrate A: Pulp fiber impregnated with phenolic resin 15
Resin plate substrate B having a thickness of 3 mm, which was hot pressed at 0 ° C. for 1 minute and compression-cured: a honeycomb structure using corrugated paper as an intermediate layer, both outer layers impregnating pulp fiber with phenol resin, and 150 ° C. Thickness of 1 minute by hot pressing and compression hardening
mm-thick resin plate having a total thickness of 15 mm

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.

[0047]

[Table 2]

As the ethylene-based copolymer (a1), the copolymers (ECA1 to 7) shown in Table 3 were used. Further, the ethylene-based copolymer (a2) shown in Table 4 (EC
B1-5) was used. Further, the ECA, ECB and the foaming agent were kneaded at a resin temperature of 110 ° C. using a 37 mmφ-same-direction twin-screw extruder, and the foamable resin composition (PO
F1-16) were prepared.

[0049]

[Table 3]

[0050]

[Table 4]

[0051]

[Table 5]

Foaming agent A: azodicarbonamide / ZnO
= 50/50 (weight ratio) mixture blowing agent B: azodicarbonamide / p, p'-oxobis (benzenesulfonylhydrazide) = 50/50 (weight ratio) mixture blowing agent C: azodicarbonamide / dinitrosopenta Mixture of tetramine / urea = 50/25/25 (weight ratio) Blowing agent D: sodium hydrogen carbonate / citric acid = 90/10
(Weight ratio) mixture

Example 1 A thermoplastic elastomer (1) was molded into a sheet having a size of 150 mm × 150 mm at a resin temperature of 210 ° C. using a 25 mmφ-T die extruder and cut into a size of 150 mm × 150 mm. Next, the POF1 shown in Table 5 was formed into a sheet having a thickness of 1 mm at a resin temperature of 110 ° C. using the T die extruder, cut into a size of 150 mm × 150 mm. In a press machine in which the upper and lower molds are adjusted to 180 ° C., an aluminum press plate, a base material A cut to a size of 200 × 200 mm, a POF1 sheet, and a thermoplastic elastomer.
(1) Sheets were sequentially placed, and a press plate made of aluminum having a grain, which was coated with a release agent with a 3 mm spacer interposed, was placed on the base material A, and hot pressing was performed only by the weight of the upper die.
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 foaming ratio was calculated to be 4.3 times. Further, when the heat resistance of the obtained multilayer laminate was evaluated, the average grain change rate was 5% and the volume change was less than 3%. The touch and cushioning properties were also good. Furthermore, when the interlayer adhesive strength of the multilayer laminate was measured, the skin layer-
It was confirmed that the material of the foam layer was destroyed between the foam layers and the material of the base layer was destroyed between the foam layer and the base material layer to have good adhesiveness. The above results are shown in Table 6.

Examples 2 to 20 Using the thermoplastic elastomers shown in Reference Examples 1 to 3 or Table 2 and the expandable resin composition substrate shown in Table 5, sheets were molded in the same manner as in Example 1. did. However, when the thermoplastic elastomer (9) was used, the sheet thickness was 1.0 mm. Further, a skin layer, a foam layer and a substrate were selected from the combinations shown in Table 6, and a multilayer laminate was obtained in the same manner as in Example 1. However, in Examples 4 and 13, the spacer thickness at the time of pressing was 5 mm, and in Examples 7 to 11, the spacer thickness at the time of pressing was 2 mm. Evaluation of the obtained multilayer laminate was performed in the same manner as in Example 1. The results are shown in Table 6. In each case, a good multilayer laminate was obtained.

Comparative Examples 1 to 8 Using the skin layer, foam layer and base material layer shown in Table 7, a multilayer laminate was prepared in the same manner as in Example 1. The evaluation results are shown in Table 7. When the thermoplastic elastomer (4) or (12) was used, the thermoplastic elastomer was too soft and the heat resistance was insufficient, and the touch was sticky and poor. When the thermoplastic elastomer (10) or (11) was used, the thermoplastic elastomer was too hard and the feel was poor. Further, when POF 13 to 16 were used as the foamable resin composition, the heat resistance was insufficient and the foam layer melted.

Comparative Example 9 As a foam layer, a cross-linked foamed polypropylene sheet manufactured by Toray,
A pef (foaming ratio 25 times, thickness 2 mm) was used. The results are shown in Table 7. The interlayer adhesion strength between the skin layer and the foam layer was insufficient, resulting in interfacial peeling.

[0058]

[Table 6]

[0059]

[Table 7]

[0060]

INDUSTRIAL APPLICABILITY The multilayer laminate of the present invention is excellent in heat resistance and flexibility and can be foam-molded and laminated relatively easily, so that it can be used as an interior material for automobiles, vehicles, ships and the like. It is useful.

Continuation of the front page (56) Reference JP-A-6-316016 (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 (5)

(57) [Claims] 1. A skin layer (I) consisting of a thermoplastic elastomer having a Shore A hardness of 55 to 96, (a1) ethylene, an unsaturated carboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid anhydride and an unsaturated carboxylic acid. An ethylene-based copolymer obtained by copolymerizing at least one monomer selected from the group consisting of saturated dicarboxylic acid half esters and having a content of ethylene-derived units of 30 to 99.5% by weight. Copolymerization of 1 to 99% by weight and (a2) ethylene with at least one monomer selected from the group consisting of an epoxy group-containing unsaturated compound, an amino group-containing unsaturated compound and a hydroxyl group-containing unsaturated compound. The ethylene-based resin composition (A) consisting of 99-1% by weight of the ethylene-based copolymer obtained by the above, and the content of units derived from ethylene is 30-99.5% by weight, ( ) 10 to 100 parts by weight of component
Organic foaming agent (B) capable of decomposing at 0 to 250 ° C
A multilayer laminate comprising at least three layers of a foam layer (II) obtained by foaming a resin composition containing 0.1 to 50 parts by weight and a base material layer (III) made of a wood-based phenol resin material. 2. The thermoplastic elastomer of the skin layer (I) has a shear rate of 10 ¹ se measured by a slit die method.
The ratio of the melt viscosity eta ₂ in the melt viscosity eta ₁ and a shear rate of 10 ² sec ^-1 at _{^{c -1 (η 1 / η 2}} ) is 3.5-8
The multilayer laminate according to claim 1, which is 3. The thermoplastic elastomer of the skin layer (I) is a propylene-α-olefin copolymer, and the propylene-α-olefin copolymer is 65 to 25% by weight of a polypropylene block, propylene and ethylene. And / or a multi-layer laminate according to claim 1 or 2, which comprises 35 to 75% by weight of a block of a copolymer with an α-olefin having 4 to 12 carbon atoms. 4. The skin layer (I) has a thickness of 0.1 to 2 mm, the foam layer (II) has a thickness of 1 to 10 mm, and the base material layer (III) has a thickness of 0. It is 5 to 25 mm.
The multilayer laminate according to any one of 1 to 3. 5. The expansion ratio of the foam layer (II) is 1.5 to 50.
The multilayer laminate according to any one of claims 1 to 4, which is double.