JP2920837B2 - Laminate - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a laminate excellent in scratch resistance, bleed resistance, dimensional stability upon heating, tear resistance, dimensional stability and various moldability.

[Conventional technology]

As an interior material for automobiles, for example, a ceiling material, a door lining, an instrument panel, or a skin material used for a use such as a carrying case of a musical instrument or a home appliance, it has a natural leather feel in order to give a high-class feeling. Things are sought. Conventionally, polyvinyl chloride has been used exclusively as such a material, but problems such as inability to reduce the thickness, increase in weight due to high specific gravity, and difficulty in incineration and recycling of waste materials have been pointed out. Are being replaced by partially crosslinked olefin-based thermoplastic elastomers. More specifically, a two-layer laminate composed of a partially cross-linked olefin-based thermoplastic elastomer skin layer and a thermoplastic resin foam layer or a hard plate layer, or a laminate formed by sequentially forming these three layers is used for the above-mentioned purpose. It has been used for
However, when such a partially crosslinked olefin-based thermoplastic elastomer is used as a skin layer, the surface is apt to be scratched, the scratch resistance is problematic, and a light stabilizer, a flame retardant, etc., added for the purpose of modifying the resin. The problem of so-called surface whitening, in which the additive bleeds over time on the surface, has been newly pointed out. In addition, since partially crosslinked olefin elastomers are inferior in melt drawability and melt tension, when considering various molding methods, for example, in extrusion molding, thin film moldability in which a sheet cannot be thinned, and in vacuum molding, Therefore, there is a problem that deep drawing cannot be performed.

In order to solve these problems, a top coat treatment of coating the surface with a vinyl chloride-based paint such as polyurethane is performed, but the effect of improving the scratch resistance is not sufficient. It remains as an unsolved problem that the agent emerges and does not contribute to the improvement of thin film formability and deep drawability at all.

As an alternative to such a top coat treatment, a polymer resin composition skin layer and a thermoplastic resin foam layer comprising a mixture of a partially crosslinked olefin-based thermoplastic elastomer and an ethylene-based ionomer as disclosed in JP-A-1-226325 are proposed. Have been.

By using such a structure, the above-mentioned scratch resistance, bleeding of the additive, thin-film formability, and deep-drawing formability were satisfactorily improved, but a multilayer structure with a thermoplastic resin foam layer or the like was obtained. In the above, it is a new problem that the heating dimensional change rate is large and the tear strength is weak,
These improvements have been strongly desired.

[Problems to be solved by the invention]

As a result of studying from the above viewpoints, the present inventors have found a desired skin layer, and have completed the present invention. Accordingly, an object of the present invention is to provide a novel laminate excellent in scratch resistance, bleed resistance, tear strength, dimensional stability under heating, and various moldability.

[Summary of the Invention]

According to the present invention, on the base material layer, via an intermediate layer made of a partially crosslinked olefin elastomer, a weight consisting of 40 to 90 parts by weight of an ethylene ionomer resin and 10 to 60 parts by weight of a partially crosslinked olefinic thermoplastic elastomer. A laminate formed by forming a skin layer of the united composition is provided.

The ethylene ionomer resin (A) used in the skin layer of the present invention is an ethylene / α, β-unsaturated carboxylic acid copolymer (I) or an ethylene / α, β-unsaturated carboxylic acid / α,
The carboxyl groups of the β-unsaturated carboxylic acid ester copolymer (II) and the like are all or a part, usually 5 to 90%, neutralized with metal ions. Considering the heat resistance of the skin layer, the proportion of ethylene units in the copolymers (I) and (II) is usually about 75 to 99, 5 mol%, preferably 88 to 98 mol%. The proportion occupied by the β-unsaturated carboxylic acid unit is usually 0.5 to 15 mol%, preferably 1 to 6 mol%. The proportion occupied by α, β-unsaturated carboxylic acid ester units is usually 0 to 10 mol%, preferably 0 to 6 mol%.

The proportion of carboxylic acid groups (neutralization degree) neutralized by metal ions among the carboxylic acid groups in the copolymer (I) or (II) is usually from 5 to 90%, but is particularly preferable when it is resistant. In order to obtain a composition having excellent scratching properties, the degree of neutralization is 15
It is preferable to use those having a concentration of from 90% to 90%, especially from 40% to 90%.

Examples of the α, β-unsaturated carboxylic acid constituting the copolymer include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, maleic anhydride and the like.
8, an α, β-unsaturated carboxylic acid is used.
-Esters of unsaturated carboxylic acids include α, β- having 4 to 8 carbon atoms such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, butyl methacrylate and dimethyl fumarate.
Unsaturated carboxylic esters are preferably used. Among these, particularly preferred α, β-unsaturated carboxylic acids are acrylic acid and methacrylic acid, and preferred esters are esters of acrylic acid and methacrylic acid.

Further, as the metal ion for neutralizing the carboxylic acid group of the ethylene copolymer, a metal ion having a valence of 1 to 3, especially a group I, II, III, IV A and VIII in the periodic table of elements. It is a metal ion having a valence of 1 to 3, and specifically, Na ⁺ , K ⁺ , Li ⁺ , Cs ⁺ , Ag ⁺ , Hg ⁺ , Cu ⁺ ,
Be ⁺⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Sr ⁺⁺ , Ba ⁺⁺ , Cu ⁺⁺ , Cd ⁺⁺ , Hg ⁺⁺ , Sn
⁺⁺ , Pb ⁺⁺ , Fe ⁺⁺ , Co ⁺⁺ , Ni ⁺⁺ , Zn ⁺⁺ , Al ⁺⁺ , Sc ⁺⁺ , Fe
⁺⁺⁺ , Y ^{+++, and the} like. These metal ions are 2
More than one kind of mixed component may be used, or a mixed component with ammonium ion may be used. Among these metal ions, Zn ⁺⁺ and Na ⁺ are particularly preferable.

ASTM of the ethylene ionomer resin used in the present invention
Melt flow rate measured according to D 1238 (190 ° C)
Is usually in the range of 0.1 to 1000 dg / min, preferably 0.1 to 30 dg / min, particularly preferably 0.1 to 10 dg / min.

As the ethylene-based ionomer resin, a resin modified with a diamine, a polyamide oligomer, an epoxy group-containing olefin polymer, or the like for the purpose of improving heat resistance and appearance may be used.

The partially crosslinked olefin-based thermoplastic elastomer (B) used as a component of the skin layer of the present invention or as an intermediate layer contains a partially crosslinked ethylene / α-olefin copolymer rubber and a polyolefin resin as essential components. Preferably, a rubber composition containing a polyolefin and an ethylene / α-olefin copolymer rubber as essential components is partially crosslinked, or a mixture of the partially crosslinked product and a polyolefin resin. The mutual ratio of the polyolefin resin component and the ethylene / α-olefin copolymer rubber component contained in the thermoplastic elastomer (B) is 5 to 80 parts by weight when the total of both components is 100 parts by weight. 20 to 70 parts by weight, the latter 20 to 95 parts by weight, especially
It is preferably 30 to 80 parts by weight. When the rubber composition is partially crosslinked, a peroxide non-crosslinkable hydrocarbon-based rubber or a mineral oil-based softening agent may be allowed to coexist. These components can be used so as to be contained in the thermoplastic elastomer (B) in an amount of 50% by weight or less, preferably 5 to 40% by weight.

More specifically, (a) 20 to 95 parts by weight of ethylene / α-olefin copolymer rubber (b) 5 to 80 parts by weight of polyolefin resin (where (a) + (b) is 100 parts by weight) And (c) at least one component selected from the group consisting of a peroxide-non-crosslinked hydrocarbon-based rubbery substance and (d) a mineral oil-based softening agent. Of a partially crosslinked rubber composition (I) obtained by dynamically heat-treating the mixture in the presence of a crosslinking agent and 100 to 30 parts by weight of a polyolefin resin (II) (provided that the final mixture (B) and (II) so that the total amount is 5 to 80 parts by weight per 100 mixtures of the final mixture.

In the present invention, the ethylene / α-olefin-based copolymer rubber (a) which is a raw material of the thermoplastic elastomer includes, for example, ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene tertiary or multipolymer rubber, ethylene- Propylene-1-butene copolymer rubber, ethylene-
Ethylene such as 1-butene copolymer rubber, ethylene-1-butene-nonconjugated diene multi-component copolymer rubber and C3-C3
A crystallinity of 20% or less mainly containing α-olefin of 14,
It is preferably 10% or less of a low crystalline or amorphous elastomer or a mixture thereof. Among them, ethylene-propylene copolymer rubber and ethylene-propylene-nonconjugated diene terpolymer rubber are preferable.

Here, the non-conjugated diene is dicyclopentadiene,
Examples thereof include 1,4-hexadiene, cyclooctadiene, methylene norbornene, 5-ethylidene-2-norbornene, and the like. Among them, a copolymer containing dicyclopentadiene and 5-ethylidene-2-norbornene as a third component is preferable.

Mooney viscosity of these binary or multi-component copolymers (ML
_{1 + 4} (100 ° C.)] is usually 10 to 180, preferably 40 to 140, and its iodine value (unsaturation degree) is preferably 16 or less.

The amount of each structural unit contained in these elastomers is such that in the 1-olefin portion, ethylene units / α-olefin units are 50/50 to 90/10, preferably 60/40 to 84/16.
(Molar ratio) of 1-olefin (ethylene +
(α-olefin) unit / non-conjugated diene unit (in the case of a ternary or multi-component copolymer) is usually 98/2 to 90/10, preferably 97/3 to 94/6 (molar ratio).

In the present invention, the polyolefin resin (b) to be mixed with the ethylene / α-olefin copolymer rubber at the time of dynamic heat treatment includes ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene. 1-
An olefin homopolymer, a copolymer of two or more thereof, or a copolymer of an α-olefin and 15 mol% or less of another polymerizable monomer, for example, an ethylene-vinyl acetate copolymer, an ethylene-acryl Acid copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylate copolymers, ethylene-methyl methacrylate copolymers, etc. Substances. In the present invention, 0.1 to 50 g / 10 of the melt float (ASTM-D-1238-65T) is used.
Polyolefin resin having a crystallinity of at least 40% by weight, especially 5 to 20 g / 10 minutes, and a crystallinity determined by X-ray diffraction measurement is preferably used.

In the present invention, a particularly preferred polyolefin resin (b) is a peroxide-decomposable polyolefin resin having a melt flow rate of 0.1 to 50 and a crystallinity of 40% or more (mixed with peroxide, heated and kneaded to be thermally decomposed. Polyolefin resin whose molecular weight decreases and the fluidity of the resin increases), specifically, isotactic polypropylene or a copolymer of propylene with 15% by mole or less of other α-olefin such as a propylene-ethylene copolymer , Propylene-1-butene copolymer, propylene-1-hexene copolymer and propylene-4-methyl-1-pentene copolymer.

Further, in the present invention, the peroxide decomposable polyolefin resin and a peroxide cross-linked polyolefin resin (a polyolefin resin which is mixed with peroxide and kneaded under heating to be cross-linked to lower the fluidity of the resin),
For example, a mixture with low and medium density polyethylene having a density of 0.910 to 0.940 g / cm ² is also preferably used as the polyolefin resin (b).

Next, in the preparation of the thermoplastic elastomer, (c) the peroxide non-crosslinked hydrocarbon-based rubber-like substance blended as necessary includes, for example, polyisobutylene, butyl rubber, propylene-ethylene copolymer having a propylene content of 70 mol% or more. A hydrocarbon-based rubbery substance which does not crosslink even when mixed with a peroxide such as a coalesced rubber, a propylene-1-butene copolymer rubber, an atactic polypropylene and the like and is kneaded under heating and does not decrease in fluidity. Of these, polyisobutylene and propylene-1-butene copolymer rubber are most preferred.

(D) Mineral oil-based softeners are usually used to roll rubber to reduce the intermolecular force of the rubber, to facilitate the processing and to assist the dispersion of carbon black, white carbon, etc., or vulcanized rubber. Is a high-boiling petroleum fraction used for the purpose of increasing the flexibility and elasticity by reducing the hardness, and is classified into paraffinic, naphthenic, aromatic and the like.

In the present invention, the peroxide non-crosslinked hydrocarbon-based rubber-like substance (c) and / or the mineral oil-based softening agent (d) need not necessarily be blended in preparing the thermoplastic elastomer. In order to further improve the flow characteristics of the coalesced composition, and thus the moldability, (c) and / or (C) based on 100 parts by weight of the total of the ethylene-α-olefin copolymer rubber (a) and the polyolefin resin (b). d) up to 100 parts by weight, preferably 5 to 1
It is preferable to add 00 parts by weight.

Further, in the present invention, the polyolefin resin (II) mixed as required after the dynamic heat treatment is the same resin as the polyolefin resin (b) added during the dynamic heat treatment, that is, ethylene, propylene, 1-butene, Homopolymers of 1-olefins such as 1-hexene and 4-methyl-1-pentene, copolymers of two or more thereof, or copolymers of α-olefins with 15% by mole or less of other polymerizable monomers. Polymers, for example, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene- Examples thereof include a methyl methacrylate copolymer and a resinous polymer substance. The melt flow rate of these polyolefin resins (II) (ASTM-D-1238-65T, 190 ° C,
5 to 100 for propylene-based polymer at 230 ° C), especially 10 to 50
It is preferred that When the polyolefin resin is added both during the dynamic heat treatment and after the heat treatment, the polyolefin resin (b) and the polyolefin resin (II) may be the same or different.

To prepare the thermoplastic elastomer in the present invention, the ethylene / α-olefin copolymer rubber of 95 to
20 parts by weight and 5 to 80 parts by weight of the polyolefin resin (b),
If necessary, about 0.05 to 2 parts by weight based on 100 parts by weight of a blend (hereinafter referred to as an object to be treated) obtained by mixing 0 to 100 parts by weight of a non-crosslinked rubber of perchioside (c) and / or a mineral oil-based softener (d). %, Preferably 0.1 to 0.5 parts by weight of a crosslinking agent, and dynamically heat-treated to perform partial crosslinking.

Here, dynamically heat-treating means kneading in a molten state.

The kneading is preferably performed in a non-release type apparatus, and is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The temperature is usually 150-280 ° C, preferably 170-2
The kneading time at 40 ° C. is usually 1 to 20 minutes, preferably 1 to 10 minutes.

Examples of the crosslinking agent used for partial crosslinking in the present invention include organic peroxides, sulfur, phenolic vulcanizing agents, oximes, and polyamines. Among them, physical properties of the obtained thermoplastic elastomer are mentioned. Thus, organic peroxides and phenolic vulcanizing agents are preferred crosslinking agents.

The phenolic vulcanizing agent used in the present invention includes alkylphenol formaldehyde resin, triazine-
Formaldehyde resin and melamine-formaldehyde resin can be mentioned.

Further, as the organic peroxide used in the present invention,
Dicumyl oxide, di-tert-butyl peroxide, 2,
5-dimethyl-2,5-bis (tert-butylperoxy) hexane, 2,3-dimethyl-2,5-bis (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butyloxyisopropyl) Benzene 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-
Butyl-4,4-bis (tert-butylperoxypallate, dibenzoyl peroxide, tert-butylperoxybenzoate and the like can be mentioned. Among them, bisperoxide is preferred because of its low odor and high scorch stability. Preferred are compounds based on 1,3-bis (tert-butylperoxyisopropyl) benzene.

In addition, p-quinone dioxime,
A more uniform and saturated cross-linking reaction by compounding a cross-linking aid such as p, p'-dibenzoylquinone dioxime and a polyfunctional vinyl monomer such as divinylbenzene (DVB), diethylene glycol methacrylate, and polyethylene diglycol methacrylate. Can be realized,
It is preferable to mix these crosslinking aids and polyfunctional vinyl monomers. In particular, divinylbenzene (DVB) is most preferable because the crosslinking effect by heat treatment is uniform and a thermoplastic elastomer having a good balance between fluidity and physical properties can be obtained.

The partially crosslinked olefinic thermoplastic elastomer (B) of the present invention preferably has a Shore hardness (JISA) of 95 or less, particularly preferably 50 to 95.

The polymer composition for forming the skin layer of the present invention contains an ethylene ionomer resin (A) and a partially crosslinked olefin plastic elastomer (B) as essential components.
The mixing ratio of (A) and (B) is (A) 40 to 90 parts by weight, preferably 50 to 85 parts by weight, and (B) 10 to 60 parts by weight, preferably 15 to 5 parts by weight. A desired performance can be obtained by using such a mixing ratio.

To the polymer layer, 15% by weight or less, preferably 12% by weight or less of ethylene-α-olefin copolymer rubber (C) can be added for the purpose of further reducing the surface gloss. As the copolymer rubber (C), the same rubber as the above-mentioned ethylene / α-olefin-based polymer rubber (a) that can be used for preparing the thermoplastic elastomer (B) can be used. Of course, the rubber (C) and the rubber (a) may be the same or different.

Such a skin layer also includes various fillers such as carbon black, clay, talc, calcium carbonate, heavy calcium carbonate, kaolin, diatomaceous earth, silica, alumina,
Asbestos, graphite, whiskers, metal powder, glass spheres, glass fiber, carbon fiber, etc. and coloring agents, for example,
Titanium oxide, zinc oxide, red iron oxide, ultramarine, navy blue, azo pigments, lake pigments, phthalocyanine pigments, and other additives, such as known antioxidants, plasticizers, heat stabilizers, weather stabilizers, and antistatic agents And a lubricating material such as metal soap and wax, and a flame retardant material.

These fillers, coloring agents, and additives may be added at the stage of preparing the olefin-based thermoplastic elastomer as described above, or may be added at the stage of preparing the polymer composition.

The polymer composition has a melt flow rate (at a temperature of 190 ° C. and a load of 2160 g or less, abbreviated as MFR) of 0.1 to 50 g / 10 min.
In particular, those having a concentration of 0.1 to 10 g / 10 minutes are preferable.

In order to prepare the polymer composition, the ethylene-based ionomer resin (A), the olefin-based thermoplastic elastomer (B), and other optional components are dry-blended or melt-blended simultaneously or sequentially. This is done by: Dry blending is performed using various blenders such as a Henschel mixer, a Dybler mixer, and a ribbon blender. And then melt-mixing, and the mixing order is not particularly limited.

The surface of the skin layer can be grained for decorative purposes or for further reducing the gloss.

In the present invention, a layer made of the above-mentioned partially crosslinked olefin-based elastomer is used as the intermediate layer. The partially crosslinked olefin-based elastomer used here may, of course, be the same as or different from the partially crosslinked olefin-based elastomer used as a component of the skin layer.

Although different depending on the purpose of use, the total thickness of the skin layer and the intermediate layer is usually about 0.1 to 5 mm, preferably about 0.2 to 3 mm.
The thickness ratio between the skin layer and the intermediate layer is 10% for the skin layer / intermediate layer.
~ 60/90 ~ 40, preferably 20 ~ 50/80 ~ 50. If the thickness of the skin layer is excessively small, the scratch resistance, dimensional stability and bleed resistance tend to decrease, and if the thickness of the intermediate layer is excessively small, the tear strength tends to decrease.

The substrate layer used in the present invention is a foam layer, a hard plate layer,
Alternatively, it is a single layer or a multiple layer such as a combination layer of these. In order to obtain a laminate having good cushioning properties, it is desirable to provide a foam layer or a foam-hard plate combination layer as a substrate layer.

Examples of the thermoplastic resin which can be used as a foam layer include those exemplified above as the polyolefin resin (b), for example, polypropylene, poly-1-butene,
Polyolefins such as poly-4-methyl-1-pentene and olefins such as ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ethylene / methyl methacrylate copolymer, and ethylene ionomer resin. In addition to the polar vinyl monomer copolymer, polystyrene, polyvinyl chloride, polyester, polyamide and the like can be exemplified. Among these, it is desirable to use a polyolefin resin from the viewpoints of interlayer adhesion to the intermediate layer, secondary moldability, recyclability, and the like.

The expansion ratio of the foam varies depending on the purpose of use, but it is usually 5 to 70 times, preferably about 10 to 50 times.

In the laminate of the present invention, a hard plate layer can be provided adjacent to the foam layer for the purpose of improving the rigidity of the laminate, protecting the surface of the foam, maintaining the shape, and improving the strength. The layer used for this purpose is a layer that is harder than the skin layer, and is made of a thermoplastic resin or a thermosetting resin, or a wooden plywood,
A wood board such as a particle board and a fiber board such as a fiber board and a felt board impregnated with phenolic resin are suitable. Examples of such thermoplastic resins include polyolefins such as polyethylene, polypropylene, poly-1-butene, and poly-4-methyl-1-pentene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene.・ Methyl methacrylate copolymer, olefin such as ethylene ionomer ・ Polyolefin resin such as polar vinyl monomer copolymer, styrene resin such as polystyrene, high impact polystyrene, AS resin, ABS resin, polyvinyl chloride, polyester , Polyamide and the like. Among them, when importance is attached to interlayer adhesiveness, processability, cyclability, and the like, it is preferable to use the same type of resin as the thermoplastic resin foam layer, and it is preferable to use, for example, a polyolefin resin.

When a thermoplastic resin layer is used as the third hard plate layer, various fillers and additives may be blended in the resin for the purpose of rigidity, heat deformation resistance, and an effect of increasing the amount. Examples of such fillers include wood powder, corrugated cardboard pieces, and the like, in addition to the fillers exemplified above as those that can be blended with the thermoplastic elastomer.

Examples of the thermosetting resin that can be used as the hard plate include a phenol resin, a melamine resin, a urea resin, an epoxy resin, an unsaturated polyester resin, and a urethane resin.

The third layer is not limited to a single-layer sheet (or film), but may be a multi-layer or a specially configured layer, for example, a corrugated cardboard.

When a high-rigid laminate is required, these hard plate layers can be directly bonded to the intermediate layer without using a thermoplastic resin foam layer.

In order to produce the laminate of the present invention, a coextrusion method, a melt extrusion lamination method, a multicolor injection molding method, and other known means may be appropriately employed.

The thickness of each layer varies depending on the purpose of use, but the total thickness of the skin layer and the intermediate layer is usually 0.1 to 5 mm, preferably 0.2
~ 3 mm, the thermoplastic resin foam layer is usually 0.5 ~ 30 mm, preferably 1 ~ 20 mm, the hard plate layer is 0.5 ~ 20 mm, preferably,
It is good to set it in the range of 1 to 10 mm.

〔The invention's effect〕

According to the present invention, a laminate excellent in scratch resistance, bleed resistance, antistatic property, dimensional stability, and various moldability can be provided. Such laminates can be used in automobile parts, such as ceiling materials, door lining materials, instrument panels, bicycle parts, sporting goods, building supplies, electrical product housings, carrying cases for electrical products and musical instruments, bags and the like. It can be widely used for various molded products such as daily necessities and decorations. These can be manufactured by applying various molding methods such as injection molding, hollow molding, compression molding, vacuum molding, and stamping molding.

〔Example〕

 Next, the present invention will be described with reference to examples.

The following abbreviations have the following meanings.

 Ionomer (1) (Ethylene content 90 wt%, methacrylic
Lulic acid content 10wt%, metal ion Zn neutralization 72%, MFR 1g / 10
Min., 190 ° C, load 2160g or less) Ionomer (2) (ethylene content 85wt%, methacrylate
Lulic acid content 15wt%, metal ion Zn neutralization degree 60%, MFR 1g / 10
Min) ionomer (3) (ethylene content 85wt%, methacrylic
Luric acid content 15wt%, metal ion Mg neutralization degree 50%, MFR 1g / 10
Min) ionomer (4) (ethylene content 91 wt%, methacrylic
Lulic acid content 9wt%, metal ion Mg neutralization degree 18%, MFR 5g / 10
Min) Partially crosslinked olefinic thermoplastic elastomer (5)
(Hereinafter abbreviated as TPE) (Milastomer 8030B, MRF0.5g / 10min 230 ℃, Load 10kg,
Shore hardness (A) 85, Mitsui Petrochemical Industries, Ltd.) Partially crosslinked olefin-based thermoplastic elastomer (6)
(Milastomer 6030B, MRF0.2g / 10min 230 ℃, Load 10kg,
Shore hardness (A) 60, Mitsui Petrochemical Industry Co., Ltd. Thermoplastic foam (7) 20 times expanded polyethylene (hereinafter abbreviated as PEF) 2 m / m sheet
G (Single-sided SBR-based heat-sensitive adhesive treatment) Thermoplastic foam (8) 30 times expanded polypropylene (hereinafter abbreviated as PPF) 2m / m
High density polyethylene (9) (HIZEX 5000S, MFR1g / 10min, density 0.954g / cc,
Mitsui Petrochemical Industry Co., Ltd.) Polypropylene (10) (Mitsui Petrochemical Industry Polypro F601, MFR7g / 10min, 230
° C, load 2160, density 0.910g / cc, Mitsui Petrochemical Industries
Co., Ltd.) Corrugated cardboard (11) Thickness 3 m / m Examples 1 to 10 A predetermined amount of ionomer and TPE was fed to a 40 m / m diameter single screw extruder.
Using a die temperature of 200 ° C and a screw rotation speed of 40 rpm
Melt and mix under the conditions to create the skin layer resin shown in Table 1.
did.

Next, a co-extruded sheet molding machine consisting of a 65m / mφ extruder (for the intermediate layer) and a 40m / mφ extruder (for the skin layer) equipped with a 700m / m width die for multi-manifold type co-extrusion, and 3 Using a sheet take-up machine equipped with a metal roll, as shown in Table 1, using a resin for the skin layer and a resin for the intermediate layer having a predetermined thickness configuration, as a co-extruded sheet at a die temperature of 200 ° C. In the extruder and chill roll, PEF (6) and P
PR (7) and the resin for the intermediate layer were bonded. The surface to which PEF (6) was bonded was not treated with the SBR heat-sensitive adhesive. These laminated sheets were evaluated for physical properties and the like shown in Table 1.

[Scratch resistance]

The side surface of a 100-yen coin was rubbed against the surface of the resin for the skin layer, and the susceptibility to scratching was visually determined. Those that were not damaged were rated as O, and those that were damaged were rated X.

[Bleed resistance]

The laminated body of 10 cm × 10 cm was left in an oven maintained at a constant temperature of 110 ° C. ± 3 ° C. for 400 hours, and then the outer skin layer surface was observed.も の indicates that no bleed was observed on the surface, and X indicates that bleed was observed.

(Tear strength)

The resulting laminate was subjected to a tear test specified in JISK-6301.

Dumbbell B type, tearing speed 200mm / min, vertical direction: strength to tear parallel to the flow direction of the laminate sheet Horizontal direction: direction perpendicular to the above direction [Heating dimensional stability] From any place of the laminate , 250 m / m × 250 m / m are sampled, and 200 mm mark lines are drawn in the vertical and horizontal directions of the laminated sheet. For this test, 100
After leaving it for 3 hours in an oven maintained at a constant temperature of 2 ° C. ± 2 ° C., take it out, and measure the heating dimensional change rate based on the marked line.

Comparative Example-1 In Example-1, except that the TPE (5) as the resin for the intermediate layer was used alone without using the resin for the skin layer (the 40 m / m φ extruder was stopped), The evaluation was performed in exactly the same manner as in 1.

Comparative Example-2 In Example 1, the resin for the intermediate layer was not used (65 m /
m Stop the φφ extruder. The evaluation was performed in exactly the same manner as in Example 1 except for ()).

Example-11 Using a 65 m / m φ single screw extruder equipped with a 700 m / m φF die and a sheet take-off machine equipped with three metal rolls, the F die temperature was 220 ° C. for high-density polyethylene (9). Under the conditions, a 1 mm-thick sheet-like extruded sheet was further bonded to the PEF (7) side of the bonded sheet prepared in Example 1. Next, a vacuum forming test was performed on the bonded sheet under the following conditions.

Tester FE-36 type manufactured by Harmis Corporation Depth 150 mm Mold area 500 mm × 500 mm Heating condition 170 ° C., 50 seconds Cooling time 60 seconds Under the above conditions, a vacuum formed sample having a good appearance was obtained.

Example-12 A vacuum molding test was conducted in the same manner as in Example-11, except that polypropylene (10) was used instead of high-density polyethylene (9), and a vacuum-molded sample having a good appearance was obtained. was gotten.

Example 13 A two-layer sheet comprising the resin for the skin layer and the resin for the intermediate layer shown in Example 1 was prepared. Using this sheet in place of PEF (7) in Example-11, a laminated sheet with high-density polyethylene (9) was prepared. A vacuum forming test was performed on this bonded sheet in the same manner as in Example 11 to obtain a vacuum formed sample having a good appearance.

Example -14 A vacuum molding test was performed in the same manner as in Example 13 except that polypropylene (10) was used instead of high-density polyethylene (9) to obtain a good appearance. A vacuum molded sample was obtained.

Example -15 Using the laminated sheet and the cardboard (11) obtained in Example 1, compression molding was performed under the following conditions.

Tester 50TON press manufactured by Toho Press Co., Ltd. Test method (a) Set upper die temperature to 100 ° C and lower die temperature to 130 ° C.

(B) At the set temperature, compress the cardboard (11) to a thickness of 75% for 20 seconds. (Press pressure 150 kg / cm ² ) (c) After heat-pressing the corrugated cardboard, quickly attach the laminated sheet and compress again for 20 seconds. (Press pressure 150kg /
cm ² ) In this case, the compression ratio is 50%.

Under the above conditions, a compression molded sample having a good appearance was obtained.

Claims (1)

(57) [Claims] 1. A polymer comprising 40 to 90 parts by weight of an ethylene ionomer resin and 10 to 60 parts by weight of a partially crosslinked olefinic thermoplastic elastomer on a base material layer via an intermediate layer made of a partially crosslinked olefinic elastomer. A laminate having a composition skin layer formed thereon.