JPS60201940A - Laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to product jΔ fields. More specifically, the present invention relates to a laminate consisting of a thermoplastic elastomer layer and a polyurethane foam layer.

Soft or semi-hard vinyl chloride resin with an embossed surface and textured leather pattern for various uses such as automobile interior materials, building materials, furniture, home appliance housings, bags, sporting goods, and office supplies. Laminates are conventionally used in which a skin layer is successively lined with a foam layer and optionally a resin aggregate layer.

After that, ``instead of soft or semi-hard vinyl chloride resin, which is sticky due to the exudation of the agent, we used a thermoplastic elastomer that has excellent heat resistance, flexibility, lightness, and processability for the skin. The Q-type bond layer as a layer was proposed by one of the applicants (Japanese Patent Application Laid-Open No. 57-20344).
No. 59-1561 and No. 59-279
No. 35), and it has come into actual use.

By the way, when a thermoplastic elastomer is used as the skin layer material and the foam layer is a polyethylene or polypropylene foam, preferably a crosslinked foam, it is possible to bond by a heat fusion method such as roll compression ( (Japanese Unexamined Patent Publication No. 57-20344 mentioned above), when polyurethane foam is used as the skin layer material, which is superior to polyolefin resin foam in terms of sound insulation, ability to absorb molding distortion during molding, cost, etc., polyurethane foam The body has poor adhesion to thermoplastic elastomers and cannot be easily bonded by heat fusion or the like, and even if it were possible to do so, it would not be able to provide sufficient adhesion for practical use.

Therefore, as a thermoplastic elastomer, a method using a partially crosslinked product of polyolefin AkH'dJ, 5 containing a carboxyl group or its acid anhydride group and an ethylene-α-olefin base rubber (the method described above) Special 1
jiJ 1982 1561) or e) polyolefin resins, ethylene-α-olefin eutectic rubbers and carboxyl groups or their acid anhydrides 'III M'
A method using a blend of ethylene-α-olefin conjugate rubber having r: (Japanese Unexamined Patent Publication No. 59-27935 mentioned above) has been proposed.

Although each of these proposed methods satisfactorily serves the intended adhesion purpose, the product JΔ is typically The thermoplastic elastomer sheet is brought into contact with an embossing roll at a roll temperature of about 60 to 70°C, and the polyurethane foam sheet is brought into contact with the unheated normal roll side. It is done with proper care.

Considering the heat resistance of the Boliu I-Tan foam used in this lamination, the bonding conditions are milder and the bonding is easier, and it has been evaluated as a preferable bonding method from the viewpoints of workability, safety and hygiene, etc. It would be highly desirable if high adhesive strength levels could be achieved, such as by hot melt adhesive methods. The present invention provides a method for solving such problems.

Therefore, the present invention relates to a laminate, which contains vinyl ester-containing f as an intermediate adhesive of a laminate consisting of one layer of thermoplastic elastomer and polyurethane foam
fi about 25 to 65 mff1% ethylene-vinyl ester copolymer, ethylenically unsaturated carboxyl] ethylene-ethylenically unsaturated carboxyl yeast ester copolymer having a raccoon ester content of about 24 to 45 mff; At least one type of graft modified product of α, β-ethylenically unsaturated carboxylic acid or its acid anhydride is used as a copolymer.

Examples of the ethylene-hinyl ester copolymer used as a type of intermediate adhesive include ethylene and, for example, vinyl vinyl, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprylate, vinyl stearate, vinyl acrylate, vinyl crotonate, Vinyl esters such as vinyl oleate and vinyl acetate, preferably copolymerized with vinyl acetate, are used, and if necessary, other monomers may be further copolymerized.

The vinyl ester is copolymerized so that it is contained in the copolymer in an amount of about 25-65%, preferably about 30-50%. A copolymer with a vinyl ester content lower than this will not be able to achieve the desired adhesive strength, while a copolymer with a vinyl ester content higher than this will reduce heat resistance. Similarly, ethylene-ethylene used as an intermediate adhesive ethylene and acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, hymic acid,
Crotonic acid, α-chloroacrylic acid, maleic anhydride,
An alkyl ester of ethylenically unsaturated carboxylic acid having about 12 carbon atoms or less, such as itaconic anhydride and hymic anhydride, preferably a copolymer with ethyl acrylate is used, and other monomers may be added as necessary. Furthermore, it may be copolymerized. The ethylenically unsaturated carboxylic acid ester is present in an amount of about 24-45% in the copolymer, preferably about 30-45%.
It is copolymerized so that it is contained in a proportion of 45%. If a copolymerization ratio lower than this is used, the target adhesion cannot be obtained, while if a copolymerization ratio higher than this is used, heat resistance will decrease.

These ethylene-based conjugates can be used as is or α,
It is used after being graft-modified with β-ethylenically unsaturated carboxylic acid or its acid anhydride, and these generally have a melt 70
- Those with a rate of about 0.1 to 1000g710min are preferably used. Examples of α,β-ethylenically unsaturated carboxylic acids or their acid anhydrides include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, hymic acid, crotonic acid, α-chloroacrylic acid, and anhydride. Maleic acid, itaconic anhydride, himic anhydride, etc., preferably maleic anhydride, acrylic acid, methacrylic acid, etc. are used. These ethylenically unsaturated carboxylic acids or their acid anhydrides are generally graft copolymerized in such a proportion that the amount of the graft modified product is about 5.0 ffi% or less. Even if the grafting ratio is higher than this, the adhesion strength will not be increased any further. Kraft modification is carried out according to a conventional method by a solution method using a solvent or a melt method using an extruder, roll, etc. in the presence of a radical generator such as organic peroxide@.

The above intermediate adhesives may include ethylene-acrylic acid co-composite, ethylene-methacrylic acid co-composite, ethylene-α-
Olefin copolymerized various thermoplastic resins, adhesives,
Heat stabilizers, thickeners, lubricants, fillers, colorants, etc. can also be added.

The thermoplastic elastomer layer and the polyurethane foam layer, which are bonded together via such an intermediate adhesive, are both conventional or used in the same way.

Examples of thermoplastic elastomers that form the skin layer of the laminate and are made of a blend of a polyolefin-based resin and a partially crosslinked product of an ethylene/α-olefin copolymer comb include the following: .

(1) Typical examples include homopolymers of ethylene or propylene, or co-combinations with other polymerizable monomers.
Various polyolefin resins and ethylene and carbon number 3
~14 binary copolymerized rubber reeds with α-olefin Qyu This is a ternary copolymer rubber made by copolymerizing various polyene compounds with ethylene/α-A reflex copolymer rubber. A thermoplastic composition consisting of a partially crosslinked blend (for example, see Japanese Patent Publication No. 53-21021 and Japanese Patent Application Laid-open No. 71738/1983) (b) Poly-substituted fin thread resin and ethylene α- A thermoplastic composition obtained by dynamically heat-treating a blend with an olefin copolymer rubber (for example, Japanese Patent Publication No. 53-34210
No. 53-149240 and JP-A-53-149240
-149241 publication) ■) A blend of polyolefin resin and ethylene/α-olefin copolymer rubber is dynamically heat-treated at °C, and then a polyolefin resin is further blended. thermoplastic compositions (e.g., JP-A-53-145857 and JP-A-53-145857)
16554) αV) Peroxide crosslinked polyolefin resins represented by ethylene homopolymers or copolymers with small amounts of other polymerizable monomers, propylene homopolymers or small amounts of other polymerizable monomers A thermoplastic composition obtained by dynamically heat-treating a blend of a peroxide non-crosslinked polyolefin resin represented by a copolymer with a dust-blending monomer and an ethylene/α-olefin yarn copolymer rubber. (See, for example, Japanese Patent Application Laid-open No. H1'j 55-71739.) In these various thermoplastic elastomers, partially crosslinked products of polyolefin resin and ethylene/α-olefin co-enriched rubber are 80/20 ~20780, preferably 7
They are used by blending them at a ratio of 0/30 to 30/70. As the polyolefin resin, polyethylene, especially low density polyethylene and polypropylene are used in a ratio of 10/90 to 70/30 from the viewpoint of ease of molding during sheet molding, scratch resistance of the sheet, etc. It is preferable to use them by mixing them. 'Mata, partially cross-linked Sarubegi ethylene/α-olefin yarn as a composite rubber of 11 people,
7'Mooney Adhesive temperature 1iL, +4 (121℃) is about 20 or more,
Is it used for about 40 to 80 times?
,l't L,I. And these ethylene α-
The partial crosslinking of olefinic rubber is generally about 0 for thermoplastic elastomer 100 i; i N FdS.
．． A dynamic heat treatment is carried out using organic peroxides of 1 to 2 types.

+ L-(:, These thermoplastic elastomers may contain polyisobutylene, butyl rubber, etc. ('
The peroxide non-crosslinked hydrocarbon exemplified by B can be further blended with a thread-rubber-like substance and/or a mineral oil-based softener T.

A polyurethane foam sheet laminated on one layer of a thermoplastic elastomer made of such blend strength 1 using an intermediate adhesive, and a polyurethane foam sheet classified in terms of Cj''L1 hardness, such as soft, hard reed or hard, or a polyol component. Any foams of polyester or polyether yarns classified in terms of The laminate has flexibility, heat resistance, and absorbency.
He is 71'r in terms of sex etc. Further, the foaming ratio used is about 1 to 301 廓.

When polyolefin thread resin aggregate is further laminated,
In the polyolefin resin used to form the aggregate τ, wood flour, fiber 7.11: fragments,
Inorganic fillers and the like can be mixed. These polyolefin resin aggregates are generally used, for example, in resin boards,
It is molded into a predetermined shape in plastic cardboard, resin felt, etc. in one pass.

Heat 11 of a laminate that is integrally molded with such an aggregate molded product
■The thickness of the plastic-injected elastomer layer and the foam layer varies depending on the use of the laminated molded product. For example, when used as an automobile internal equipment, the thickness is generally about 0.1 to 25 mm.
11 The latter is about 1 to 301 yuan, and even in such applications, ceiling materials are relatively thin due to the thickness of the skin layer, and comparisons with dash boards, foil house covers, various pillars, sheets, etc. Used with a strong focus.

Lamination of the thermoplastic elastomer layer and the polyurethane foam layer using an intermediate adhesive can be carried out, for example, as follows.

(1) The process is performed by molding in advance by the inflation method, T-die method, etc./(- by sandwiching the intermediate adhesive film between two base materials and bonding them under heat, or by at least one of the methods). A layer of intermediate adhesive 1'4L,
(2) A method of laminating the thermoplastic elastomer and the intermediate adhesive through a molten film of an intermediate adhesive such as sandwich lamination method or the T-die method. For applications such as lifting where it is difficult to co-extrude with an adhesive, an embossed sheet of thermoplastic elastomer with a grained, smeared or slit surface pattern is pre-formed and placed on the tip of the extruder. (3) Hot-melt method is to press the intermediate adhesive in the form of a film extruded from a die into a roll with a thermoplastic elastomer embossed sheet and a polyurethane foam from both sides. Intermediate adhesive V, if necessary, add wax for viscosity adjustment, adhesive for upward adhesion, and other hot melt 'rtf!Adhesive formulations can be applied with a hot melt gun or other means. The laminate bonded using an intermediate adhesive in this way is a method in which the other base materials are bonded together by pressure bonding while paying the profit margin of 4r. It has outstanding interlayer adhesion between the intermediate adhesive layer and the polyurethane foam layer, and has excellent interlayer adhesion between the polyurethane foam IFj and the polyurethane foam layer. It is not possible to separate the two.

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

Example 1 Ethylene-vinyl acetate co-1 combination (Mitsui Polychemical product EV45X: vinyl acetate content ml 45%, melt flow rate) 95 g/10 minutes) was heated using an extruder (screw diameter 20 order, I, /D -20) to about 2. OKgA
The T-shaped tube was fed at a feeding rate of 100 hrs and was attached to the tip of the extruder.
At a polymer temperature of about 170°C from the die, the thickness is about 50 μm.
It was extruded as a film. When the extruded molten film is led to a pressure roll, a thermoplastic elastomer sheet (about 0.2 mm thick and embossed on the surface) is applied from both sides to serve as an intermediate adhesive layer. C1, G) and polyurethane foam sheet (Curabo product: polyether type, foaming ratio 40 times, thickness 2,5111
! 1) were respectively inserted, the two base materials were pressed together via the film-like intermediate adhesive, and sand lamination was performed by winding up at a winding speed of about 5 ti/min.

Note) Thermoplastic elastomer used: (Component A) ethylene/propylene/ethylidene norbornene ternary copolymer rubber; ethylene unit/furopylene unit (molar ratio): 70/30, iodine value 15, Mooney viscosity (
ML, +4.121°C) 61 (B component) Isotactic polypropylene resin; Melt index 1a9/
10 minutes (230°C) (O component) 7-tene process oil (D component) i,3-bis(tert-butylperoxyisoglobil)benzene 20%, divinylbenzene 30m layer% and paraffin mineral oil 50% A mixture consisting of 70 parts by weight of the above (component A), 30 parts by weight (component B), (
Component 0) 10*iit parts and 1 part (Component D) were mixed in a Henschel mixer, and then the mixture was
The mixture was transferred to a closed Banbury mixer preheated to 140°C, and kneaded and crosslinked at 180-190°C for 10 minutes.

70 parts by weight of the partially crosslinked ethylene/propylene yarn co-polymerized rubber thus obtained and low density polyethylene (
Blend with 30 parts by weight of Mitsui Polychemical product Mirason 11) The adhesive strength of the obtained laminate was measured as follows.

An aluminum plate was adhered to the side of the polyurethane foam layer of Shin Fl (25×120 mash) using a commercially available double-sided adhesive tape 1 and fixed. Next, using a solvent, the intermediate adhesive layer and each base material are separated by about 5Qj1m, and the mold temperature is increased to 6cm.
After being left to dry for more than an hour, the thermoplastic nylastomer layer and the polyurethane foam-aluminum board-supported layer were each held in an autograph (Autograph P-100 manufactured by Shimadzu Corporation) and heated to a temperature of 23°C. Under these conditions, the sample was pulled at a tensile rate of 200 fill/min, and the 180' peel strength was measured.

The measurement result was 1.2/25 mol of the base material of the polyurethane foam layer.

In addition, there is no delamination, no damage due to fusion of the polyurethane foam layer itself (reduction in layer thickness), and no discoloration, which often occur when bonding conditions such as temperature, pressure, and time are not gentle. A thin thermoplastic elastomer sheet with a thickness of about 0.2 toughness? Even when used, a good texture was obtained without any doubt that the irregularities of the polyurethane foam layer affected the surface condition of the thermoplastic elastomer layer, and the laminate was judged to be an extremely preferable laminate for practical use.

Furthermore, in order to investigate changes in the interlayer adhesion of this laminate over time, we tested it in an atmosphere of 50°C for 1 month (temporal change test); Test) When the adhesive strength was measured in the same manner after being left for each time, the base material of the polyurethane foam layer was destroyed, and no decrease in adhesive strength was observed at all.

In addition, the thermal shock test was repeated three times for the next cycle, and the adhesive strength of the laminate after undergoing such thermal history was measured, and it was found that the base material of the polyurethane foam layer was also destroyed. No decrease in adhesive strength was observed.

80℃ atmosphere - 15.5 hours Room temperature atmosphere - 0.5 hours - 25℃ atmosphere - 7.5 hours Room temperature atmosphere - 0.5 hours 50℃ atmosphere - 15.5 hours (90% relative humidity) Room temperature atmosphere - 0. 5 hours - 25° C. atmosphere - 7.5 hours Room temperature atmosphere - 0.5 hours Example 2 In Example 1, other ethylene-vinyl acetate co-Bc joint rod (Mitsui Boliumical product 1rV 40 X: Hinyl acetate content m: 40 Arashi mouse%, melt flow rate 659
710) was used as the intermediate adhesive, and the same laminate as A1 was tested and evaluated.

As a result, the base material of the polyurethane foam was destroyed as in Example 1, and the adhesive strength was 1.1 to 9/2.
51+IjilAtsukQ Also, we conducted a similar adhesive strength change test over time, heat resistance test, and thermal shock test.All of them showed that the base material of the polyurethane foam layer was damaged, and the decrease in adhesive strength was It was not recognized at all.

Example 3 Ethylene-vinyl acetate copolymer 1 used in Example 1
00 parts (*wrinkle, same hereinafter), 1 part of maleic anhydride, and 0.2 parts of an 80% mineral spirit solution of tert-butyl peroxybenzoate were tri-blended in advance and homogenized, and the mixture was then homogenized using an extruder (Suf IJ). Knee diameter 30 mm, L
/D-32) at a feed rate of about 5 h/hour, and graft modification was carried out while maintaining the total temperature of the middle part of the extruder at 200°C. The obtained maleic anhydride graft modified product had a graft ratio (by titration method) of O, lk amount% (maleic anhydride reaction baseline 70%), and a melt flow rate (J engineering 5).
5190℃ by K-6760, 2160 g) approx. 65
It has a value of .

In place of the ethylene-vinyl acetate co-vehicle combination used in Example 1, the maleic anhydride graft modified product was used as an intermediate adhesive, and the resulting laminate was subjected to similar tests and evaluations.

As a result, the base material of the polyurethane foam layer was destroyed as in Example 1, and the adhesive strength was 1.3 kg/
It was 25 ccm. Of course, the appearance and feel of the laminate were good, and no decrease in adhesive strength was observed after being left in an atmosphere at 50° C. for one month.

Example 4 In Example 3, another ethylene-vinyl acetate copolymer (Mitsui Polychemical product KV-150i containing 1 ft of hinyl acetate 33% by weight, melt 70-rate 319/10
The grafting ratio was 0.8.
A maleic anhydride-grafted modified product was obtained with a melt flow rate of approximately 15 g/10 min.

In place of the ethylene-vinyl acetate co-extrusion mixture used in Example 1, the above maleic anhydride graft modified product was used as an intermediate adhesive, and the resulting laminate was subjected to similar tests and evaluations.

The result was that the base material of the polyurethane foam layer was destroyed as in Example 1, and the adhesive strength was 1.0 Kg/
25 #Im.

In addition, in order to mold aggregate for automobile ceiling materials, we used a male and female hot press to mold plastic cardboard (iomm pitch, thickness 3+o+) from polypropylene filled with 30% talc into 95. °C, 2~
Press molding was carried out for 40 seconds under heating and pressurizing conditions.

A film of the maleic anhydride graft modified product (thickness 5
0μ), the foam side of the laminate is placed on the aggregate molded product, and pressed again to integrate the two into a matured shape,
Manufactured ceiling materials. When the adhesive strength of the resulting ceiling material was similarly measured, it was found that the base material of the polyurethane foam layer was destroyed.

Comparative Examples 1 to 2 In Example Work or 3, another ethylene-vinyl acetate copolymer (Mitsui Polychemical a EV-450i vinyl acetate-containing lid 19% by weight, melt flow L, -) 159
/10 minutes) or its maleic anhydride grafted modified product (grafting rate 0.3% by mass, melt flow rate approximately 10
9/10 minutes) was used as the intermediate adhesive, and the temperature of the extruded polymer at the exit of the T-die during base material lamination was set to 200° C. to form a laminate, and the obtained laminate was subjected to similar tests and evaluations.

The results showed that in all cases, peeling was observed at the interface of the first layer of thermoplastic elastomer, and the adhesive strength was 0. IKp/25ml
It showed only a low value of 11.

Comparative Example 3 In Examples 3 to 4, a maleic anhydride graft-modified polyolefin containing mO, 05 Honya% was used as the maleic anhydride-grafted modified product, and T-die exit extrusion at the time of base material lamination was used. A laminate was formed at a polymer temperature of 230°C.

When the obtained laminate was subjected to the same tests and evaluations as in Example 1, it was found that the interfaces on both base material sides easily peeled off, resulting in poor adhesion.

In forming this laminate, the polymer temperature was adjusted to 300°C.
℃, and when bonding with the base material, i.e., when high pressure is applied between the chill roll and the nip roll to form a laminate, the polyurethane foam layer will break the base material.Good adhesion. However, because the bonding conditions are too severe, a portion of the polyurethane foam layer melts and breaks, reducing the thickness of the foam layer, making it impossible to obtain a satisfactory laminate. . Furthermore, if a maleic anhydride graft-modified polyolefin is used as an intermediate adhesive, the adhesive layer formed from it will be a relatively hard film, so even if a laminate with no problems in adhesiveness is obtained, it will be stiff and stiff. Since the laminate exhibits a rough feel and has an unsatisfactory texture, it is not possible to form a desirable laminate.

Example 5 Tertiary butyl peroctoate was blended in advance with the ethylene-vinyl acetate copolymer used in Example 1, and this was blended in an extruder (screw diameter 30mm, L/D -32, extruder middle temperature Similar tests and evaluations were carried out on the laminate obtained in the same manner as in Example 1, using as an intermediate adhesive a material that was supplied to a temperature of 200°C and crosslinked to reduce the melt flow rate to approximately 109/lo min. I did this.

The result was the substrate failure of the polyurethane foam layer as in Example 1, and the adhesive strength was 0.7 Kv'.
25 JllK.

Examples 6 to 7 In Example 1 or 2, the T-die exit extrusion temperature during base material lamination was changed to 160° C., and the obtained laminate was subjected to similar tests and evaluations.

The results showed that the base material of the polyurethane foam layer was destroyed as in Example 1, and the adhesive strength was Q, 6.
Kg/25m.

Example 8 Ethylene-vinyl acetate copolymer (vinyl acetate-containing foot 28
%, melt flow rate approximately 259,710 minutes) and 20 parts of a rosin ester adhesive (Arayo Chemical Products Alcon P115) were melt-mixed using an extruder, pelletized, and pelletized using an extruder (screw diameter 20rrm
, L/D-20) at a feed rate of 2.0 increments, and extruded from a T-die attached to the tip of the former at a temperature of about 170°C, with a width line of 15° and a thickness of about 50 μm. An intermediate adhesive film was preformed.

On the other hand, the thermoplastic elastomer mixed pellets used in Example 1 in the same proportion were processed using an extruder (screw diameter 4Q ta
x , , L/D -28) and extruded from a T-die attached to the tip at a polymer temperature of about 225°C to produce a thermal i + workable elastomer with a width line of 20 crm and a thickness of about 0.2 tone. When forming a sheet and leading the sheet in a molten state to a chill roll, at the same time, the intermediate adhesive film and the polyurethane foam sheet used in Example 1 are rolled together in this order, and the presser U-roll (3) is rolled. ), the two substrates were pressed together via the intermediate adhesive layer, and wound up at a winding speed of about 4 m7 to form a laminate.

When the obtained laminate was subjected to the same tests and evaluations as in Example 1, results were obtained that the polyurethane foam layer had a base material failure and an adhesive strength of 1.0 h/25 ++an.

Example 9 In Example 1, instead of the ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer (Mitsui Polychemical product A-709i ethyl acrylate content 35
% richness, melt flow rate 28 g/10 min), and the T-die exit extruded polymer temperature at the time of base material lamination to 220 g/10 min.
The laminate kl was formed at a temperature of .degree.

When the obtained laminate was subjected to all the tests and evaluations similar to those in Example 1, results were obtained that the base material failure of the polyurethane foam layer and the adhesive strength were 0.81'W/25 fl.

Comparative Example 4 In Example 9, another ethylene-ethyl acrylate copolymer (E-polychemical product A-702; ethyl acrylate containing company i9 points t%, melt flow rate 5 g/1
0 minutes) was used as an intermediate adhesive to form a laminate 'fr:.

When the obtained laminate was subjected to the same tests and evaluations as in Example 1, peeling was observed on the polyurethane foam layer side, and the adhesive strength FiO was only a low value of 2 Kf/25 ms.

Comparative Examples 5 to 6 In Example 1, instead of the ethylene-vinyl acetate co-polymer, ethylene-methacrylic acid co-polymer (Mitsui Polychemical Products 221 Rel AOR0910 or 1525) was used.
i Methacrylic acid content 9% or tri: 15%, melt flow rate 109/10 min or 25 g
/10 minutes), and the temperature of the extruded polymer when laminating the base material. A laminate was formed at Lk of 230°C.

When the obtained 81-layer body was subjected to the same tests and evaluations as in Example 1, the interfaces on both base material sides easily peeled off, resulting in poor adhesion.

Comparative Example 7 In Example 8, Comparative Example 5 was used as the intermediate adhesive film.
A laminate was formed by using a film of ethylene-methacrylic copolymer AOR0910).

When the obtained laminate was subjected to the same tests and evaluations as in Example 1, it was found that the interface on both base material sides easily peeled off, resulting in poor adhesion.

Example 10 In Example 3, graft modification was carried out using the ethylene-acrylic ethyl copolymer used in Example 9 instead of the ethylene-vinyl acetate copolymer, and the grafting rate was 0.5. A maleic anhydride graft modified product of
When a laminate was formed using this and the same tests and evaluations as in Example 1 were performed on the obtained laminate, it was found that the base material failure of the polyurethane foam layer and the adhesive strength were 0.9 Kt/25%. The following results were obtained.

Representative Patent Attorney Yoshi 1) Toshio Procedural Amendment March 18, 1985 Commissioner of the Patent Office Gakudono Shiga 1 Display of the case 1982 Patent Application No. 57945 2 Name of the invention laminate 3 Person making the amendment Case and Relationship between Patent applicant name Mitsui DuPont Polychemical Co., Ltd. Address 1-2-7-5 Shibadaimon, Minato-ku, Tokyo Target of amendment In line 5 of page 17, after “blend”, “is used as a thermoplastic elastomer”. ” is added.

Claims (1)

[Scope of Claims] 1. An ethylene-vinyl ester copolymer with a vinyl ester content of approximately 25 to 65*%, an ethylene non-containing adhesive as an intermediate adhesive for a laminate consisting of a thermoplastic elastomer layer and a polyurethane foam layer. Ethylene-ethylenically unsaturated carboxylic acid ester co-polymerization containing about 24 to 45% saturated carbon modified ester and α,β-ethylenically unsaturated carboxylic acid or its acid anhydride of these ethylenic co-polymerizations A laminate using at least one type of graft modified product. 2. Claim 1: A single layer of ill plastic elastomer is formed from a blend of a partially crosslinked product of ethylene-α-olefin concentric base rubber and a polyolefin resin.
Laminated body as described in section. 3. As an intermediate adhesive for a laminate formed by successively laminating a thermoplastic elastomer layer, a polyurethane foam layer, and a polyolefin resin commercial N, vinyl-C-sulfur-containing a
1 Contains about 25-65% ethylene-vinyl ester co-composite, ethylenically unsaturated carboxylic ester containing about 2
At least one type of 4-45% ethylene-ethylenically unsaturated carboxylic acid ester copolymer and a graft modified product of these ethylene copolymer with α,β-ethylenically unsaturated carboxylic acid or its acid anhydride. A laminate made using wo.