JPH02217237A - laminate - Google Patents

Abstract

PURPOSE:To obtain a lightweight laminated material having no problem of surface stickiness due to the exudation of a plasticizer and excellent in heat resistance by laminating a thermoplastic elastomer layer composed of a blend of a polyolefinic resin, a partial cross-linked substance of ethylene/alpha-olefin copolymer rubber and ethylene/alpha-olefin copolymer rubber having a carboxyl group or an anhydride group thereof to a polyurethane foam layer CONSTITUTION:A thermoplastic elastomer consisting of a polyolefinic resin and a partial cross-linked substance of ethylene/alpha-olefin copolymer rubber is prepared and ethylene/alpha-olefin copolymer rubber containing a carboxyl group or an anhydride group thereof is blended with said elastomer to prepare an adhesive thermoplastic elastomer. Either one of foams composed of soft, semihard or hard resins classified from the aspect of hardness and polyester or polyester type resins classified from the aspect of a polyol component is used to be laminated to the adhesive thermoplastic elastomer composed of said blend.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a laminate. More specifically, the present invention relates to a laminate that is effectively used as an interior material for automobiles.

[Conventional technology]

Interior materials for automobile floors, walls, ceilings, etc. consist of a polyvinyl chloride layer with a leather pattern embossed on the surface and embossed therein, which is then combined with a foam layer and, if necessary, resin aggregate. Laminates lined with sequential layers are conventionally used.

Such laminates are manufactured through the following steps: (1) Calender molding of soft polyvinyl chloride to produce a sheet (2) Adding polyol and polyisocyanate to the surface of this sheet. The purpose of this matte treatment is to apply a mixture and apply urethane treatment to prevent the sheet surface from becoming glossy during thermoforming in step (7) (3) Embossing Processing to form a grained leather pattern on the surface (4) The back side of the sheet with the embossed surface is flame-treated and melted, and is crimped with a separately supplied polyurethane foam sheet using a roll (5 ) An adhesive layer is further provided on the polyurethane foam sheet side of the laminated sheet of a polyvinyl chloride sheet and a polyurethane foam sheet. (6) A resin aggregate of a predetermined shape is formed by a thermoforming method such as vacuum forming or pressure forming. Molding (7) After preheating the polyvinyl chloride-polyurethane foam-adhesive laminated sheet, it is placed on the resin aggregate molded product and the two are thermoformed to integrate. However, in place of such a polyvinyl chloride layer, polyolefin resins, partially crosslinked products of ethylene/α-olefin copolymer rubber, and ethylene/α-olefin copolymer rubber containing a carboxyl group or its anhydride group can be used. It has been found that the use of a thermoplastic elastomer layer made of a blend is significantly superior in several respects in terms of manufacturing and properties. That is.

(a) Such a laminate consists of a polyolefin resin, a partially crosslinked ethylene/α-olefin copolymer rubber, and an ethylene/α-olefin copolymer rubber containing a carboxyl group or its anhydride group.
About 150 to 250 olefin copolymer rubber blend
The extruded thermoplastic elastomer in a molten state is extruded from an extruder at ℃ using the T-die method, and is passed between a pair of rolls in a laminated state with a polyurethane foam sheet, at which time the thermoplastic elastomer sheet The polyurethane foam sheet is produced so as to be brought into contact with the embossing roll side whose temperature is 60 to 70°C, and the polyurethane foam sheet is brought into contact with the unheated normal roll side.

As a result, the steps corresponding to steps (1) to (4) described above when using soft polyvinyl chloride are performed in just one step, thereby providing a laminate with an embossed surface. That is, since this laminate does not become glossy when integrally molded by heating with an aggregate molded product, which is performed later, there is no need to particularly provide a matting step such as the step (2). In connection with this, in the case of polyvinyl chloride, it is necessary to form it into a sheet shape in advance as in step (1) above in order to apply the matte treatment, but the present invention In this case, the thermoplastic elastomer can be extruded into a sheet and simultaneously (sequentially) fused to the polyurethane foam sheet, which is explained in step (4) above.
) also eliminates the need for processes such as flame treatment of polyvinyl chloride sheets for adhesion with polyurethane foam sheets, as seen in .

Furthermore, the embossing of the thermoplastic elastomer sheet can be carried out simultaneously with the lamination with the polyurethane foam sheet, and there is no need to provide a separate embossing step such as step (3).

(b) Regarding the properties of the laminate, this laminate has excellent lightness, flexibility, and surface scratch resistance, and has a sticky surface that does not occur when soft polyvinyl chloride containing a plasticizer is used. In addition, thermoplastic elastomers and polyurethane foams both have excellent heat resistance, so the laminate as a whole also has excellent heat resistance, making it an effective material for interior materials in automobiles, where the interior gets hot, especially in the summer. can be used.

[Means to solve the problem]

The present invention relates to a laminate that is effectively used for such purposes, and the laminate comprises a polyolefin resin, a partially crosslinked ethylene/α-olefin copolymer rubber, and ethylene having a carboxyl group or its anhydride group. - A thermoplastic elastomer layer made of a blend of α-olefin copolymer rubber and a polyurethane foam layer are flM-formed.

The adhesive thermoplastic elastomers used in the present invention are represented by the known thermoplastic elastomers listed below, namely (i) homopolymers of ethylene or propylene or copolymers with small amounts of other polymerizable monomers. Various polyolefin resins and ethylene with 3 or more carbon atoms
A partially crosslinked blend of ethylene/α-olefin copolymer rubber, which is a binary copolymer rubber with 14 α-olefins or a ternary copolymer rubber obtained by further copolymerizing various polyene compounds with this rubber. thermoplastic elastomers (e.g.

Japanese Patent Publication No. 53-21021 and Japanese Patent Publication No. 55-71
(Refer to Publication No. 738) (...) A thermoplastic elastomer obtained by dynamically heat-treating a blend of a peroxide-decomposed polyolefin resin and an ethylene/α-olefin copolymer rubber in the presence of an organic peroxide (e.g. .

Japanese Patent Publication No. 53-34210, Japanese Patent Publication No. 53-1492
(See Publication No. 40 and Publication No. 53-149241) (
iii) A blend of a peroxide-decomposed polyolefin resin and an ethylene/α-olefin copolymer rubber is dynamically heat-treated in the presence of an organic peroxide, and a polyolefin resin is further blended with the resultant mixture. The obtained thermoplastic elastomer (for example, JP-A-53-14
5857 and 54-16554) (iv) Peroxide crosslinked polyolefin resins represented by ethylene homopolymers or copolymers with small amounts of other polymerizable monomers, propylene homopolymers It is obtained by dynamically heat-treating a blend of a peroxide non-crosslinked polyolefin resin and an ethylene/α-olefin copolymer rubber, which is represented by a copolymer or a copolymer with a small amount of other polymerizable monomer. thermoplastic elastomer (
For example, see JP-A-55-71739).

Specifically, after producing a thermoplastic elastomer made of a polyolefin resin and a partially crosslinked ethylene/α-olefin copolymer rubber according to a known method as described above,
An adhesive thermoplastic elastomer is prepared by blending this with an ethylene/α-olefin copolymer rubber containing a carboxyl group or its anhydride group.

Ethylene/α-olefin copolymer rubber containing carboxyl group or its anhydride group includes ethylene/α-olefin copolymer rubber containing carboxyl group or its anhydride group.
A copolymer of an olefin and a monomer compound containing a carboxyl group or its anhydride group is mainly used, and this type of copolymer can be produced by a known copolymerization method, ethylene/α-olefin copolymer rubber. It can be obtained by graft copolymerization method etc.

α-olefins copolymerized with ethylene etc.
Propylene, 1-butene, etc. are used, and monomer compounds containing a carboxyl group or its anhydride group include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, α of itaconic anhydride, himic acid, himic anhydride, etc.
, β-unsaturated carboxylic acids or their acid anhydrides are often used. Preferred is an ethylene/α-olefin copolymer rubber obtained by graft copolymerizing these α, β-unsaturated carboxylic acids or their acid anhydrides, and the resulting graft copolymer is slightly partially crosslinked. There are also some that are used in the same way. In addition, those obtained by oxidizing polyolefin and introducing carboxyl groups into the molecule are also used.

Further, these copolymer rubbers may contain a polyene component, and examples of the polyene component include dicyclopentadiene, ethylidene norbornene, and 1,4-hexadiene, and the copolymerization ratio thereof is as follows: Generally, it is preferable that the iodine value is 40 or less. Note that ethylene and α-olefin are generally used in a molar ratio of about 50,150 to 9,515.

These carboxyl group or anhydride group-containing ethylene/α-olefin copolymer rubbers generally have a Mooney viscosity of about 1 to 150 (at 100°C), preferably about 1
-100 is used, and its carboxyl group (-C00H) or anhydride group (however.

Anhydride groups are calculated assuming that there are two carboxyl groups)
The content can be selected broadly within the range of generally about 0.02 to 10% by weight, preferably about 0.05 to 5% by weight, and as mentioned above, these may be partially crosslinked. It is. Then, they are blended at a ratio such that the content of carboxyl groups in the blend is approximately 0.005 to 8% by weight, preferably approximately 0.1 to 4% by weight.

Furthermore, the ethylene/α-olefin copolymer rubber to be partially crosslinked contains ethylene and α-olefin in a molar ratio of approximately 50,150 to 90/10°, preferably approximately 70/30 to 85/15, mainly for strength reasons. In the case of this copolymer rubber, it is desirable to use a copolymer rubber having a Mooney viscosity ML, 4 (121'C) of about 20 or more, preferably about 40 to 80. The components may be copolymerized, and the amount thereof is preferably about 40 or less in terms of iodine value, and partial crosslinking of these ethylene/α-olefin copolymer rubbers is generally performed by adding 100 parts by weight of the thermoplastic elastomer. About 0.1~
This is done by dynamic heat treatment using 2 parts by weight of organic peroxide.

In these adhesive thermoplastic elastomers, the partially crosslinked ethylene/α-olefin copolymer rubber and the ethylene/α-olefin copolymer rubber containing a carboxyl group or its anhydride group have a ratio of about 80/20 to 20/80. Preferably in a weight ratio of about 70/30 to 30/70.

The polyolefin resin is blended in an amount of about 25 to 200 parts by weight per 100 parts by weight of the total amount.

In addition, the adhesive thermoplastic elastomer may contain peroxide non-crosslinked hydrocarbon rubber-like substances such as polyisobutylene, butyl rubber, etc., as necessary.
Alternatively, a mineral oil softener or the like may be further blended.

The polyurethane foam sheet to be laminated on the adhesive thermoplastic elastomer layer made of such a blend may be soft, semi-rigid, or rigid, classified in terms of hardness;
Alternatively, any polyester-based or polyether-based foam classified in terms of polyol components may be used. In particular, when a soft foam having a nearly completely open cell structure is used, the laminate obtained therefrom is excellent in flexibility, heat resistance, sound absorption, etc. Further, the foaming ratio used is approximately 10 to 100 times.

〔Effect of the invention〕

The laminate thus obtained has excellent interlayer adhesion between the thermoplastic elastomer layer and the polyurethane foam layer, and it is possible to separate the two layers without breaking the polyurethane foam layer. Can not.

The laminate according to the present invention is generally laminated with a thermoplastic elastomer layer having a thickness of about 0.1 to 20 mm, and a polyurethane foam layer having a thickness of about 0.5 to 20 mm,
It is lighter than conventional laminates of polyvinyl chloride and polyurethane foam, has no problem of sticky surfaces due to plasticizer leaching, and has excellent heat resistance. Therefore, in addition to interior materials for automobiles, it can be effectively used as surface materials for furniture, building materials, home appliance housings, bags, sporting goods, office supplies, and the like.

〔Example〕

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

Example 1 (Component A) Ethylene, propylene, 5-ethylidene-2
-Norbornene ternary copolymer rubber; ethylene unit l propylene unit (molar ratio'): 78/22, iodine value 15
, Mooney viscosity (ML□,,.

121℃) 61 (Component B) Isotactic polypropylene resin; Melt index 13g/10 minutes (230℃) (Component C) 1,3-bis(tert-butylperoxyisopropyl)
A mixture consisting of 20% by weight of benzene, 30% by weight of divinylbenzene and 50% by weight of paraffinic mineral oil The above (component A) 70 parts by weight, (component B) 30 parts by weight and (component C) 1 part by weight were mixed in a Henschel mixer. The mixture was then transferred to a closed Banbury mixer preheated to 120-140°C, and mixed and crosslinked at 180-190°C for 10 minutes.

The thus-produced thermoplastic elastomer flow heavy area was mixed with maleic anhydride-grafted ethylene/propylene copolymer rubber (ethylene/propylene molar ratio 80/20.
Mooney viscosity ML, (121°C) 60. j3A
/boxyl group content 0.5 weight2. A blend of 30 parts by weight (slightly partially crosslinked) was blended with Toshiba 9
Using a 0+a+*diameter T-die extrusion molding machine, screw is 7/L/7-phyto, L/D=22, extrusion temperature 220
'e, T-die or coat hanger die, take-up speed 2.5
■The adhesive thermoplastic elastomer in the extruded molten state is extruded into a sheet at a speed of 1/min.
The thermoplastic elastomer sheet is passed between a pair of rolls in a laminated state (with a thickness of 4 mm) at a roll temperature of 60°C.
The polyurethane foam sheet was brought into contact with the embossing roll at 0.degree. C., and the polyurethane foam sheet was brought into contact with the unheated normal roll to produce a laminate having a skin layer with a thickness of 0.3 mm.

Example 2 In Example 1, maleic anhydride grafted ethylene
Instead of the propylene copolymer rubber, use the same amount of maleic anhydride grafted ethylene/1-butene copolymer rubber (ethylene/l-butene molar ratio 90/10, Mooney viscosity 8.
(121°C) 40, carboxyl group content 0.5% by weight) was used.

Comparative Example In Example 1, the produced thermoplastic elastomer was extruded into a sheet without blending the maleic anhydride grafted polyethylene resin, and laminated with a polyurethane foam sheet.

A test piece with a width of 25 m+m and a length of 100 mm was cut out from the laminated sheets obtained in each of the above Examples and Comparative Examples and tested (test speed: 50 mm/min, measurement temperature: 25° C.).

The adhesive strength of each example was measured to be 200 g/25+a width (polyurethane foam fracture), but the adhesive strength of the comparative example was only 20 g/25 mo+width.

Claims (1)

[Claims] 1. Thermoplastic elastomer comprising a blend of a polyolefin resin, a partially crosslinked ethylene/α-olefin copolymer rubber, and an ethylene/α-olefin copolymer rubber having a carboxyl group or its anhydride group. A laminate consisting of a layer and a polyurethane foam layer. 2. Ethylene/α-olefin copolymer rubber obtained by graft copolymerizing α,β-unsaturated carboxylic acid or its acid anhydride is used as the ethylene/α-olefin copolymer rubber having a carboxyl group or its anhydride group. A laminate according to claim 1.