JPH0542619A - Laminated body and manufacturing method thereof - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a laminate having a brushed surface layer having excellent scratch resistance, tear resistance, dimensional stability and the like of the surface portion, and having excellent feel and appearance, and such a brushed material. To provide a method for obtaining a raised product at the same time as molding, without using a complicated processing method such as flocking of the treated laminate. [Structure] 40-90 parts by weight of a base material layer, an ethylene-based ionomer resin or an ethylene / unsaturated carboxylic acid copolymer, and a partially cross-linked olefin-based thermoplastic elastomer 60-
A napped laminate comprising 10 parts by weight of a surface layer of a polymer composition and a mold having needle-shaped holes under which the surface layer is softened and pressed. The manufacturing method and the napped laminate thus obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate having a raised surface layer having excellent physical properties and excellent touch and aesthetics, and a method for producing the same.

[0002]

2. Description of the Related Art Various laminated materials are used as materials for automobile interior materials such as ceiling materials, door linings, instrument panels, and carrying cases for musical instruments and home appliances, and their surface layers are excellent. It is required to have a fabric tone in order to obtain a good feel. Conventionally, such surface layer material, for example, polyvinyl chloride,
Partially cross-linked olefin elastomers, polypropylene, etc. are used.As a method of raising hair, after molding these with a mold, flocking with a primer after applying a primer or machine raising, or conversely, flocking to the material beforehand There was also a method of molding a fluffed material with a mold. However, when such a multi-step processing method is adopted, there are drawbacks such as an increase in cost or collapse of the raised hair which has been carefully formed, and improvement thereof has been demanded.

[0003]

For this reason, the present inventors have studied a method of processing the surface into a fabric at the same time as molding. As a result, they have found a molding method capable of obtaining a raised product which is beautiful and has an excellent feeling when a material obtained by combining specific materials is used. It has been found that such a raised product is also excellent in scratch resistance, tear resistance, dimensional stability and the like of the surface portion. Therefore, an object of the present invention is to provide a laminate having a raised surface layer having excellent scratch resistance, tear resistance, dimensional stability, feel and appearance, and a method for producing the same.

[0004]

The present invention provides a laminate comprising a substrate layer and a surface layer, wherein the surface layer comprises 40 to 90 parts by weight of an ethylene ionomer resin or an ethylene / unsaturated carboxylic acid copolymer. The present invention relates to a laminate comprising a polymer composition of 60 to 10 parts by weight of a partially crosslinked olefin-based thermoplastic elastomer, and having its surface napped.

The present invention also relates to a polymer composition comprising a base material layer, 40 to 90 parts by weight of an ethylene-based ionomer resin or an ethylene / unsaturated carboxylic acid copolymer and 60 to 10 parts by weight of a partially crosslinked olefinic thermoplastic elastomer. The present invention relates to a method for producing a napped laminate, which comprises forming a laminate comprising a surface layer into a mold having needle-like holes under the condition that the surface layer is softened and pressed.

The resin (A) used as the first component of the surface layer of the present invention is ethylene / α, β-unsaturated carboxylic acid copolymer (I) or a base resin of this copolymer,
All or part of the carboxyl group, usually 5 to 90%
The ethylene-based ionomer resin (II) is obtained by neutralizing the above with a metal ion, and the ethylene-based ionomer resin is particularly preferable.

Considering the heat resistance of the surface layer, the proportion of ethylene units in the copolymer (I) is usually about 75-99.5 mol%, preferably 88-98 mol%.
The proportion of the α, β-unsaturated carboxylic acid unit is usually 0.5 to 15 mol%, preferably 1 to 6 mol%.
Is.

When the copolymer (I) is neutralized to form the ethylene ionomer resin (II), among the carboxylic acid groups in the copolymer, the carboxylic acid groups neutralized by metal ions are The ratio (neutralization degree) is usually 5 to 90%, but in order to obtain a composition having particularly excellent scratch resistance, the neutralization degree is 15 to 90%, particularly 40 to 90%.
% Is preferably used.

As the α, β-unsaturated carboxylic acid constituting the above-mentioned copolymer, acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, maleic anhydride and the like, α, β-having 3 to 8 carbon atoms. Unsaturated carboxylic acids are used,
Among these, acrylic acid and methacrylic acid are particularly preferable.

The copolymer may be a terpolymer containing ethylene, an α, β-unsaturated carboxylic acid, and an ester of an α, β-unsaturated carboxylic acid as a third component. Examples of the α, β-unsaturated carboxylic acid ester as the third component include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, butyl methacrylate, dimethyl fumarate and the like having 4 carbon atoms. .Alpha.,. Beta.-unsaturated carboxylic acid esters of .about.8 are preferably used, and acrylic acid and methacrylic acid esters are particularly preferable. The proportion of the α, β-unsaturated carboxylic acid ester unit in the copolymer is usually 0 to 10 mol%, preferably 0 to 6 mol%.

The metal ion for neutralizing the carboxylic acid group of the ethylene copolymer is a metal ion having a valence of 1 to 3, particularly I and I in the periodic table of elements.
A metal ion having a valence of 1 to 3 of group I, III, IVA and VIII, and specifically, Na ⁺ , K ⁺ , Li
⁺ , Cs ⁺ , Ag ⁺ , Hg ⁺ , Cu ⁺ , Be ⁺⁺ , M
g ⁺⁺ , Ca ⁺⁺ , Sr ⁺⁺ , Ba ⁺⁺ , Cu ⁺⁺ , Cd ⁺⁺ , Hg
⁺⁺ , Sn ⁺⁺ , Pb ⁺⁺ , Fe ⁺⁺ , Co ⁺⁺ , Ni ⁺⁺ , Z
^Examples include n ⁺⁺ , Al ⁺⁺⁺ , Sc ⁺⁺⁺ , Fe ⁺⁺⁺ , Y ^{+++ and the} like. These metal ions may be a mixed component of two or more kinds, and may be a mixed component with an ammonium ion. Of these metal ions, Zn ⁺⁺ and Na ⁺ are particularly preferable.

AS of the ethylene ionomer resin or ethylene / unsaturated carboxylic acid copolymer used in the present invention
The melt flow rate (190 ° C.) measured according to TM D 1238 is usually 0.1 to 1000 dg / min,
The range is preferably 0.1 to 30 dg / min, particularly preferably 0.1 to 10 dg / min.

The resin (A) used in these surface layers may be 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.

The partially crosslinked olefinic thermoplastic elastomer (B) used as another component of the surface layer of the present invention contains a partially crosslinked ethylene / α-olefinic copolymer rubber and a polyolefin resin as essential components. It is preferably a partially cross-linked rubber composition containing a polyolefin and an ethylene / α-olefin copolymer rubber as an essential component, or a mixture of this partially cross-linked 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 1 in total of both components.
When the amount is 00 parts by weight, the former is 5 to 80 parts by weight, especially 20 to 70 parts by weight, and the latter is 20 to 95 parts by weight, especially 3
It is preferably from 0 to 80 parts by weight. Further, when the rubber composition is partially crosslinked, a peroxide non-crosslinking type hydrocarbon rubber or a mineral oil softener may be allowed to coexist. These components are contained in the thermoplastic elastomer (B) in an amount of 50% by weight.
The following can be used so that the content is preferably in the range of 5 to 40% by weight.

More specifically, (a) ethylene / α-olefin copolymer rubber 20
˜95 parts by weight (b) Polyolefin resin 5 to 80 parts by weight (where (a) + (b) is selected to be 100 parts by weight) and (c) Peroxide non-crosslinking type hydrocarbon rubber-like substance (D) Partially crosslinked rubber composition obtained by dynamically heat treating a mixture consisting of 0 to 100 parts by weight, preferably 5 to 80 parts by weight of at least one component selected from mineral oil softeners in the presence of a crosslinking agent. A mixture of 100 to 30 parts by weight of the product (i) and 0 to 70 parts by weight of the polyolefin resin (ii) (however, the total amount of (b) and (ii) in the final mixture is 5 per 100 parts by weight of the final mixture. ~ 80 parts by weight).

The ethylene / α-olefin copolymer rubber (a) which is a raw material of the thermoplastic elastomer (B) is, for example, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene ternary or multi-polymer rubber, Ethylene-propylene-1-butene copolymer rubber, ethylene-
1-butene copolymer rubber, ethylene-1-butene-non-conjugated diene multi-component copolymer rubber, and the like, which has ethylene and an α-olefin having 3 to 14 carbon atoms as a main component and has a crystallinity of 20% or less, preferably 10%. The following are low crystalline or amorphous elastomers or mixtures thereof. Among them, preferred are ethylene-propylene copolymer rubber and ethylene-
It is a propylene-non-conjugated diene terpolymer rubber.

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

The Mooney viscosity [ML _{1 + 4} [100 ° C.]] of these binary or multicomponent copolymers is usually 10 to 180, preferably 40 to 140, and their iodine value (unsaturation) is preferably. It is 16 or less.

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

The polyolefin resin (b) to be mixed with the ethylene / α-olefin copolymer rubber during the dynamic heat treatment includes 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 mol% or less of other polymerizable monomers. Polymers such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid methyl acid copolymer, ethylene- Examples thereof include methyl methacrylate copolymers and the like, which are resinous polymer substances. In the present invention, among them, Melflot (ASTM-D-1238-65T) has a density of 0.
1 to 50 g / 10 min, especially 5 to 20 g / 10 min, and a crystallinity of 4 determined by X-ray diffraction measurement method.
0% or more of polyolefin resin is preferably used.

Particularly preferred as the polyolefin resin (b) is a melt flow rate of 0.1 to 5.
0, a peroxide-decomposable polyolefin resin having a degree of crystallinity of 40% or more (a polyolefin resin that is mixed with peroxide and thermally decomposed to reduce the molecular weight to increase the fluidity of the resin), specifically Is isotactic polypropylene, or a copolymer of propylene and other α-olefin of 15 mol% or less, for example, propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, An example is a propylene-4-methyl-1-pentene copolymer.

As the polyolefin resin (b), the above-mentioned peroxide decomposition type polyolefin resin and peroxide crosslinking type polyolefin resin (mixed with peroxide,
A mixture with a polyolefin resin which is cross-linked by kneading under heating to reduce the fluidity of the resin), for example, a mixture of low and medium density polyethylene is also preferably used.

Next, in preparing the thermoplastic elastomer,
The (c) peroxide non-crosslinking hydrocarbon-based rubber-like substance that is blended as necessary includes, for example, polyisobutylene,
Butyl rubber, propylene 70 mol% or more of propylene-
Hydrocarbon rubber-like substance that does not deteriorate in fluidity by mixing with peroxide such as ethylene copolymer rubber, propylene-1-butene copolymer rubber, atactic polypropylene, etc. Say. Of these, polyisobutylene and propylene-1-butene copolymer rubber are most preferred.

Further, (d) a mineral oil-based softening agent generally weakens the intermolecular action force of the rubber during roll processing of the rubber, facilitates the processing, and helps disperse carbon black, white carbon, or the like, or A high boiling point petroleum fraction used for the purpose of lowering the hardness of vulcanized rubber to increase flexibility and elasticity, and is classified into paraffin type, naphthene type, aromatic type and the like.

These peroxide non-crosslinked hydrocarbon type rubbery substances (c) and / or mineral oil type softening agents (d)
Is not necessarily blended in the preparation of the thermoplastic elastomer, but the flow characteristics of the polymer composition of the present invention,
In order to further improve the molding processability, up to 100 parts by weight of (c) and / or (d) is added to 100 parts by weight of the total amount of the ethylene-α-olefin copolymer rubber (a) and the polyolefin resin (b). , Preferably 5 to 1
It is preferable to add 00 parts by weight.

Further, the polyolefin resin (ii) optionally mixed after the dynamic heat treatment of the copolymer rubber (a) and the polyolefin resin (b) is the polyolefin resin (b) added during the dynamic heat treatment. Resins similar to those listed above can be used. The melt flow rate of these polyolefin resins (ii) (ASTM-D-1
238-65T, 190 [deg.] C., but 230 [deg.] C. for the propylene-based polymer) is preferably 5 to 100, particularly preferably 10 to 50. When the polyolefin resin is added both during and after the dynamic heat treatment, even if the polyolefin resin (b) and the polyolefin resin (ii) are of the same type,
Different types may be used.

To prepare a thermoplastic elastomer, an ethylene / α-olefin copolymer rubber of 95 to 20 is used.
Parts by weight and 5 to 80 parts by weight of the polyolefin resin (b),
If necessary, about 0.05 to 100 parts by weight of a blend (hereinafter referred to as an object to be treated) of a blend obtained by further mixing 0 to 100 parts by weight of a peroxide non-crosslinked rubber (c) and / or a mineral oil-based softening agent (d). 2% by weight, preferably 0.1 to 0.5% by weight, of a cross-linking agent may be blended and dynamically heat-treated to partially cross-link. Dynamically heat-treating here means kneading in a molten state.

The kneading is preferably carried out in a non-open type apparatus, preferably in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The temperature is usually 150-280 ° C,
Preferably 170 to 240 ° C., kneading time is usually 1 to 20
Minutes, preferably 1-10 minutes.

Examples of the cross-linking agent used for partial cross-linking include organic peroxides, sulfur, phenolic vulcanizing agents, oximes, polyamines and the like. Among these, physical properties of the thermoplastic elastomer obtained are considered. Therefore, organic peroxides and phenolic vulcanizing agents are the preferred crosslinking agents. Examples of the phenol-based vulcanizing agent include alkylphenol formaldehyde resin, triazine-formaldehyde resin, and melamine-formaldehyde resin. As the organic peroxide, 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-butylperoxypalerate, dibenzoylperoxide, tert-butylperoxybenzoate, and the like can be mentioned, but among them, bisperoxide-based compounds are preferred because of their low odor and high scorch stability. Is preferred, 1,3-bis (ter
t-Butylperoxyisopropyl) benzene is most suitable.

In the partial cross-linking heat treatment, crosslinking aids such as p-quinone dioxime and p, p'-dibenzoylquinone dioxime, and polyfunctional vinyls such as divinylbenzene (DVB), diethylene glycol methacrylate and polyethylene diglycol methacrylate. Since more uniform and saturated crosslinking reaction can be realized by blending the monomers, it is preferable to blend these crosslinking aids and polyfunctional vinyl monomers. Especially divinylbenzene (D
VB) is most preferable because the crosslinking effect by heat treatment is uniform and a thermoplastic elastomer having a good balance of fluidity and physical properties can be obtained.

As the partially crosslinked olefinic thermoplastic elastomer (B), those having a Shore hardness (JISA) of 95 or less, particularly 50 to 95 are preferable.

The polymer composition for forming the surface layer of the present invention is an ethylene ionomer resin, ethylene / unsaturated carboxylic acid copolymer, or ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid ester copolymer. It contains a copolymer (A) and a partially crosslinked olefinic plastic elastomer (B) as essential components. The mixing ratio of (A) and (B) is 40 to 90 parts by weight of (A), preferably 50 to 50 parts by weight.
It is 10 to 60 parts by weight, preferably 15 to 5 parts by weight, relative to 85 parts by weight. With such a blending ratio, it is possible to obtain the one having desired performance.

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

The surface layer also contains various fillers such as carbon black, crew, talc, calcium carbonate,
Ground calcium carbonate, kaolin, diatomaceous earth, silica,
Alumina, asbestos, graphite, whiskers, metal powder, glass spheres, glass fibers, carbon fibers, etc. and colorants such as titanium oxide, zinc white, red iron oxide, ultramarine blue, dark blue, azo pigments, lake pigments, phthalocyanine pigments, etc. Additives such as known antioxidants, plasticizers, heat resistance stabilizers, weather resistance stabilizers, antistatic agents, metal soaps, lubricants such as waxes, and flame retardants can be added. These fillers, colorants, and additives may be added at the stage of preparing the olefinic thermoplastic elastomer as described above, or may be added at the stage of preparing the polymer composition.

Melt flow rate as a polymer composition (value at 190 ° C., load 2160 g, abbreviated as MFR)
0.1 to 50 g / 10 min, especially 0.1 to 1
It is preferably 0 g / 10 minutes.

In order to prepare the above-mentioned polymer composition, a resin (A) such as an ethylene-based ionomer, a thermoplastic olefin-based elastomer (B), and optionally other components are dried simultaneously or sequentially. It is performed by blending or melt blending. Dry blend
Mix using various blenders such as Henschel mixer, tumbler mixer, ribbon blender, and melt blend by using various mixers such as single-screw extruder, twin-screw extruder, Banbury mixer, rolls, various kneaders, etc. The mixing order is not particularly limited.

The base material layer used in the present invention is a foam layer,
A hard plate layer, or a single layer or multiple layers such as a combination layer thereof. 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 the base material layer.

As the thermoplastic resin which can be used as the foam layer, those exemplified above as the polyolefin resin (b), for example, polypropylene and poly-1.
-Such as polyolefins such as butene and poly-4-methyl-1-pentene, ethylene / vinyl acetate copolymers, ethylene / ethyl acrylate copolymers, ethylene / methyl methacrylate copolymers, ethylene ionomer resins Other than the olefin / polar vinyl monomer copolymer, polystyrene, polyvinyl chloride, polyester, polyamide and the like can be exemplified. Among these, it is desirable to use the polyolefin resin from the viewpoint of secondary moldability, recyclability, etc., or in consideration of the interlayer adhesiveness with the intermediate layer when the intermediate layer is provided between the surface layer and the intermediate layer. The foaming ratio of the foamed product varies depending on the purpose of use, but is usually 5 to 70 times, preferably 10 to 50 times.
About twice is good.

In the laminate of the present invention, a hard plate layer may 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 such a purpose is a layer harder than the surface layer, such as a thermoplastic resin or a thermosetting resin, or wood plywood, a wood board such as particle board, a fiber board or a phenol resin impregnated felt board. A fiber board or the like is suitable. As such a thermoplastic resin, various polyethylenes, polypropylenes, polyolefins such as poly-1-butene, poly-4-methyl-1-pentene, ethylene / vinyl acetate copolymers, ethylene / ethyl acrylate copolymers, ethylene・ Methyl methacrylate copolymer, olefin / polar vinyl monomer copolymer such as ethylene ionomer, polystyrene, high impact polystyrene, AS resin, styrene resin such as ABS resin, polyvinyl chloride, polyester, polyamide, etc. You can Among these, interlayer adhesion, processability,
When importance is attached to recyclability, it is preferable to use the same resin as the thermoplastic resin foam layer, for example, it is preferable to use a polyolefin resin. ..

When a thermoplastic resin layer is used as the third hard plate layer, rigidity, heat deformation resistance, and
You may mix | blend various fillers and additives for the purpose of a weight increase effect. Examples of such fillers may be wood powder, corrugated cardboard pieces, etc. in addition to the fillers exemplified above as those which can be blended with the thermoplastic elastomer.

Examples of the thermosetting resin usable as the hard plate include phenol resin, melamine resin, urea resin, epoxy resin, unsaturated polyester resin, urethane resin and the like. The third layer is not limited to a single-layer sheet (or film) shape, but may be a multi-layer or a layer having a special structure, for example, a corrugated board shape.

Further, particularly when a highly rigid laminate is required, it is possible not to use the thermoplastic resin foam layer but to directly bond these hard plate layers to the surface layer.

In the laminate of the present invention, when a layer including a foamed layer is used as the base material layer, when importance is attached to the dimensional stability upon heating and tear strength, a layer of a partially crosslinked olefin elastomer is provided together with the foamed layer. It is preferable that the base material layer is used and the layer of the partially crosslinked olefin elastomer is adjacent to the surface layer. That is, the dimensional stability under heating and the tear strength can be remarkably improved by forming a laminate in which an intermediate layer made of a partially crosslinked olefin elastomer is provided between the surface layer and the thermoplastic resin foam substrate layer. As the partially cross-linked olefin-based elastomer, the same as the above-mentioned (B) mentioned as the material constituting the surface layer can be used.

The surface layer of the laminate of the present invention is nap-treated. The raised portion may be present in the entire surface layer or partially, and has a diameter of 0.01 to 1 mm, particularly 0.05 to
0.5 mm, the length is 0.01 to 20 mm, especially 0.1.
It is preferably formed by gathering a large number of fine hairs having a length / diameter ratio of 5 or more and having a length of 05 to 2 mm.

In order to produce such a raised laminate, it is preferable to employ the following method. That is, a flat plate-shaped laminate raw material is produced by a coextrusion method, a melt extrusion method, and the like, and then a mold having needle-shaped holes is used. By molding by molding, pressure molding, plug assist molding, press molding, etc., the surface layer material is softened and pressure-welded to the molding die,
Since it enters the needle-shaped hole, a molded product having a raised hair is obtained. When the polymer composition, which is the surface layer material of the laminate of the present invention, is molded by the above-mentioned various molding methods, the resin flow at the time of molding is good, the drawing transfer property is excellent, and it is deep in the fine needle-shaped holes of the mold. Since it can be penetrated, a laminate having a large number of raised fibers can be obtained.

In the above-mentioned molding, the molding temperature is a temperature at which the raw material for the laminate is plastically deformed, and it is, for example, 70 to 250 ° C., particularly 110 to 190 ° C., though it varies depending on the composition of the surface layer and the kind of the base material layer. is there. Further, the shape and size of the needle-like hole correspond to the above-mentioned raised portion.

The thickness of each layer of the laminate of the present invention varies depending on the purpose of use, but the base material layer is 0.5 to 20 mm, particularly 1 to 10 mm, and the surface layer is 0.05 to 30 including the raised part.
mm, and particularly preferably 0.1 to 1 mm.

[0049]

Examples Types of Resin Used (1) Ionomer and Ethylene Copolymer Various ionomers and ethylene / acrylic acid copolymer (E / MAA) shown in Table 1 were used.

[0050]

[Table 1]

(2) Partially crosslinked olefinic thermoplastic elastomer MFR (**) Shore hardness (A) TPE (1) Mirastomer 8030B (*) 0.5 dg / min 85 TPE (2) Mirastomer 6030B (*) 0.2 dg / min 60 (*) Mitsui Petrochemical Industry Co., Ltd., registered trademark (**) 230 ° C, load 10 kg

(3) Foamed polyethylene (PEF) 20 times foamed, 2 mm sheet (single-sided SBR type heat-sensitive adhesive treatment)

Molding method (1) Vacuum molding, vacuum / pneumatic molding, plug assist molding Sheet molding was carried out by each molding method using a COSMIC FK type test molding machine manufactured by Asano Laboratory Co., Ltd.

A base layer resin is prepared by stacking a base layer resin and a surface layer resin sheet with the surface layer resin sheet facing down, and optionally sandwiching an intermediate layer resin between them. A temperature sensor was attached to the back surface of the sheet, and the laminated sheet was preheated from both sides to a predetermined temperature with a heater, then placed on a mold having needle holes, and molded under the following conditions. The set temperature of the heater is +3 for the front surface layer compared to the back surface (base material layer) side
It was set to 0 ° C. (A) Vacuum degree (1) Vacuum forming: Vacuum degree 60 Torr (2) Vacuum / pneumatic forming: Vacuum degree 60 Torr, Pneumatic degree 5k
g / cm ² (3) Plug-assisted molding: Vacuum degree 60 Torr (b) Cooling for 10 seconds, mold clamping pressure 100 kg / cm ²
(Upper and lower) (c) Mold depth 60 mm, mold area 500 mm x 500 mm needle hole diameter 0.06 mm, length 0.6 mm

(2) Press molding A laminated sheet stock was prepared in the same manner as in the above vacuum forming method and the like, and a 50 ton press manufactured by Toho Press Co., Ltd. was used. To 180 ° C,
The temperature was controlled by a temperature sensor attached to the back surface of the base layer resin to heat it to a predetermined temperature, and then molding was performed under the following conditions. (A) Pressing pressure 150 kg / cm ² , pressing time 3 minutes (b) Needle hole diameter 0.06 mm, length 0.6 mm

Physical property measuring method (1) Scratch resistance The side surface of a 100-yen coin was rubbed on the surface of the resin for the surface layer, and the easiness of scratching was visually judged. Those that were not scratched were rated as ◯, and those that were scratched were rated as x.

(2) Tear strength The thus obtained laminate was subjected to a tear test specified in JIS K-6301. Dumbbell B type, tearing speed 200
mm / min, vertical direction: strength at which the laminate sheet is torn in parallel to the flow direction Horizontal direction: direction intersecting at right angles to the above direction

(3) Heating dimensional stability Three test pieces of 250 m / m × 250 m / m were sampled, and 200 m in each of the vertical direction and the horizontal direction of the laminate sheet.
Enter the mark of m. About this test, 100 ℃ ± 2
The sample is left in an oven kept at a constant temperature of ℃ for 3 hours and then taken out, and the rate of dimensional change by heating is measured based on the marked line.

(4) Transfer Rate of Needle Holes With respect to the needle hole length engraved in the mold in advance, the sheet raising length after sheet formation was measured, and the transfer rate was calculated by the following formula. Transfer rate = Brushed length / Needle hole length x 100

Example 1 The ionomer (1) and TPE (1) shown in Table 1 were blended in the proportions shown in Table 2, and a die temperature of 200 ° C. and a screw rotation speed were obtained using a 40 m / m diameter single screw extruder. The mixture was melt-mixed under the condition of 40 rpm to prepare a surface layer resin composition sheet.

Next, as a base material layer, 20 times expanded 2 mm expanded polyethylene (PE
F) Sheets were used, and these sheets were molded by the above-described vacuum molding method using a mold having needle-shaped holes to obtain a laminate. Further, with respect to the central portion of the sheet after molding, physical properties such as scratch resistance and needle hole transfer rate were evaluated. The results are shown in Table 2.
Shown in.

[0062]

[Table 2]

Example 2 The resin for the surface layer was the same as in Example 1 except that the ionomer (1) and TPE (1) were melt-mixed at the same ratio, and the resin for the substrate layer was the same as in Example 1 SBR heat-sensitive adhesive. Although treated expanded polyethylene (PEF) was used, TPE (2) was used as the resin for the intermediate layer, and a 65 m / mφ extruder (for the intermediate layer) equipped with a multi-manifold type coextrusion 700 m / m width die was used. Using a coextrusion sheet forming machine consisting of a 40 m / mφ extruder (for surface layer) and a sheet take-off machine equipped with three metal rolls, at a die temperature of 200 ° C.,
Resin layer for surface layer / resin layer for intermediate layer = 0.3 / 0.7 is extruded as a coextrusion sheet having a thickness constitution, and in a cooling roll, the base layer resin and the intermediate layer resin are mixed with each other. SB of resin
The lamination was performed such that the surface not treated with the R heat-sensitive adhesive was the intermediate layer resin sheet. This was vacuum formed by the same method as in Example 1, and the physical properties of the sheet after forming were evaluated. The results are shown in Table 2.

Examples 3 to 8 Various ionomers and TPE shown in Table 1 were blended as the resin for the surface layer in the proportions shown in Table 2, and melt-mixed in the same manner as in Example 2 to prepare the resin for the surface layer. .. As the resin for the base layer and the resin for the intermediate layer, the SBR heat-sensitive adhesive-treated expanded polyethylene and TPE were bonded together as in Example 2, and this sheet and the various surface layer resins described above are molded as shown in Table 2. The sheet was molded by the method and the physical properties of the molded sheet were evaluated. The results are shown in Table 2.

Example 9 The ethylene / methacrylic acid copolymer (E / MAA) shown in Table 1 was used in place of the ionomer in Example 1, and Table 2 shows this and the TPE used in Example 1. The ingredients were blended in a ratio and melt-mixed in the same manner as in Example 1 to prepare a surface layer resin.

As the resin for the base layer (and the resin for the intermediate layer), the SBR heat-sensitive adhesive-treated expanded polyethylene (and TPE were used for bonding), and the above-mentioned surface layer resin was used. It was formed by the same vacuum forming method as in Example 1 and was formed by using a mold having needle-shaped holes to obtain a laminate. The physical properties of the molded sheet were evaluated.
The results are shown in Table 2.

Comparative Example 1 In Example 1, as the surface layer resin, TPE, which is one component of the surface layer resin of Example 1, was used alone and molded by vacuum molding in the same manner as in Example 1, The physical properties of the subsequent sheet were evaluated. The results are shown in Table 1.

[0068]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a napped laminate having excellent feel, appearance, scratch resistance, tear resistance, and dimensional stability. In particular, since the polymer composition constituting the surface layer is excellent in drawing transfer property, there is an advantage that it is possible to easily produce a laminate having different shapes and sizes of the raised portion.

Such a laminate is used for automobile parts such as ceiling materials, door lining materials, instrument panels and the like, bicycle parts, sports equipment, construction equipment, electric appliance housings, carrying cases for electric appliances and musical instruments, bags and the like. It can be widely used for various molded articles such as daily necessities and ornaments.

[Table 2]

[Table 2]

Claims (4)

[Claims] 1. A laminate comprising a substrate layer and a surface layer, wherein the surface layer comprises 40 to 90 parts by weight of an ethylene ionomer resin or an ethylene / unsaturated carboxylic acid copolymer, and 60 to 60 parts of a partially crosslinked olefinic thermoplastic elastomer. A laminate comprising 10 parts by weight of a polymer composition, the surface of which is raised. 2. The laminate according to claim 1, wherein the base material layer is a thermoplastic resin foam. 3. The laminate according to claim 2, wherein an intermediate layer made of a partially crosslinked olefin elastomer is provided between the surface layer and the thermoplastic resin foam substrate layer. 4. A base material layer and an ethylene-based ionomer resin or an ethylene / unsaturated carboxylic acid copolymer 40 to 90.
A laminate comprising a part by weight and a surface layer of the polymer composition of 60 to 10 parts by weight of a partially cross-linked olefinic thermoplastic elastomer is molded under a condition that the surface layer is softened and pressure-welded to a mold having needle-shaped holes. A method for producing a napped laminate, comprising: