JP3262653B2 - Laminated body capable of high frequency sealing and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminate and a method for producing the same. More specifically, the present invention relates to a laminate suitable as a polyolefin-based soft sheet capable of high-frequency sealing and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, vehicle interior materials, automobile interior materials, architectural interior materials, display panel materials, furniture materials, housing materials for household appliances, materials for bags, materials for sporting goods, materials for office supplies, etc. From the viewpoints of flexibility, scratch resistance, weather resistance, texture, and the like, materials using a soft or semi-hard polyvinyl chloride resin as a skin material are widely used. In particular, soft vinyl chloride is exclusively used for a skin material for a seat of an automobile, a skin material for an office chair, a flexible container, and the like from the viewpoint of being suitable for high-frequency sealing. However, recently, instead of polyvinyl chloride, due to environmental problems, oozing out of plasticizer,
The use of thermoplastic elastomers is expected as a material excellent in lightness, flexibility, surface scratch resistance and heat resistance. On the other hand, since the thermoplastic elastomer itself has poor adhesiveness, a method of expressing adhesiveness by using a polyolefin resin having a carboxyl group or an acid anhydride group as a component of the thermoplastic elastomer (Japanese Patent Laid-Open No. 59-56161) Publication) and ethylene having a carboxyl group or an acid anhydride group.
A method of expressing adhesiveness using an α-olefin copolymer rubber (JP-A-59-27935) has been proposed. Further, it is disclosed that a resin obtained by copolymerizing 24% by weight or more of an unsaturated ester with ethylene or a modified resin thereof is used as an adhesive resin (Japanese Patent Laid-Open No. Sho 60-2).
01940 and JP-A-3-190727). However, even if these methods are used, the adhesiveness cannot be said to be sufficient, and the processing method is limited, and it has been particularly difficult to perform high-frequency sealing. Therefore, at present, thermoplastic elastomers cannot be used in the fields of skin materials for automobile seats, skin materials for office chairs, flexible containers, and the like, which are manufactured by high-frequency sealing using soft vinyl chloride. there were.

[0003]

SUMMARY OF THE INVENTION The present invention provides a thermoplastic elastomer having high-frequency seal processability by using a resin having excellent high-frequency seal processability and excellent adhesion with a thermoplastic elastomer. It is an object of the present invention to provide a multilayer laminate that can be used in a field using high-frequency sealing such as a skin material for an automobile seat, a skin material for an office chair, and a flexible container, and a method for manufacturing the same.

[0004]

Means for Solving the Problems As a result of various studies for solving the above problems, the present inventor has found that by laminating a specific resin composition on a polyolefin-based thermoplastic elastomer, an automobile seat skin sheet material, an office Development of a high-frequency sealable multilayer laminate that can be suitably used for a wide range of applications conventionally used by high-frequency sealing processing of soft vinyl, such as skin materials for chairs and flexible containers, and a method for producing the same. did. That is, the intermediate layer is (1) partially crosslinked ethylene-α-olefin copolymer rubber.
Olefin-based thermoplastic elastomer comprising a blend of a polymer and a polyolefin-based resin, wherein the other two layers adjacent to the intermediate layer comprise (2) ethylene and a radical polymerizable acid anhydride and other radicals. A multi-component copolymer comprising a polymerizable comonomer, wherein (a) a unit derived from ethylene is 50 to 99% by weight; (b) a unit derived from a radically polymerizable acid anhydride is 0.1 to 5% by weight; A three-layer laminate comprising an ethylene-based copolymer in an amount of 10 to 50% by weight derived from a radical polymerizable comonomer, and a co-extrusion molding of the three-layer laminate.

Hereinafter, the present invention will be described specifically. The ethylene copolymer according to the present invention is a multicomponent copolymer composed of ethylene, a radical polymerizable acid anhydride, and another radical polymerizable comonomer. The radical polymerizable acid anhydride as referred to herein is a compound having one or more radically polymerizable unsaturated bonds and one or more acid anhydride groups in a molecule, and capable of introducing an acid anhydride group into a molecule by polymerization. Is shown. Specific examples of the compound include maleic anhydride, itaconic anhydride, endic acid anhydride, citraconic anhydride, 1-butene-3,4-dicarboxylic anhydride, and a compound having at most 1 carbon atom.
Examples thereof include an alkenyl succinic anhydride having a double bond at a terminal of 8 and an alkadienyl succinic anhydride having a double bond at a terminal of at most 18 carbon atoms. These may be used in combination of two or more. Of these, maleic anhydride and itaconic anhydride are particularly preferred.

As the radical polymerizable comonomer, many compounds can be used, and specific examples thereof include ethylenically unsaturated ester compounds, ethylenically unsaturated amide compounds, ethylenically unsaturated acid compounds, ethylenically unsaturated ether compounds, and ethylenically unsaturated ether compounds. And unsaturated hydrocarbon compounds. Specifically, as the ethylenically unsaturated ester compound, vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) ) Hexyl acrylate, octyl (meth) acrylate, (meth)
Lauryl acrylate, benzyl (meth) acrylate and the like can be exemplified. Examples of the ethylenically unsaturated amide compound include (meth) acrylamide, N-methyl (meth)
Acrylamide, N-ethyl (meth) acrylamide,
N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N, N-
Dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like can be exemplified. As the ethylenically unsaturated acid compound, (meth) acrylic acid can be exemplified. Examples of the ethylenically unsaturated ether compound include methyl vinyl ether, ethyl vinyl ether,
Examples thereof include propyl vinyl ether, butyl vinyl ether, octadecyl vinyl ether, and phenyl vinyl ether. Examples of the ethylenically unsaturated hydrocarbon compound and other compounds include styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, acrolein, trimethoxyvinylsilane, triethoxyvinylsilane, vinyl chloride, and vinylidene chloride. Of these, preferred compounds include vinyl acetate, (meth) acrylic esters, (meth) acrylic acid, and the like. If necessary, two or more of these comonomers may be used at the same time.

In producing the ethylene copolymer according to the present invention, basically, ordinary low-density polyethylene production equipment and techniques can be used. Generally, it is a bulk polymerization, and is performed under a pressure of 700 to 3000 atm.
It is produced by radical polymerization in a temperature range of 0 to 300 ° C.
Preferred polymerization pressure and polymerization temperature ranges are from 1,000 to 1,000.
2500 atm, average temperature in reactor is 150-270 ° C
It can be. If the pressure is 700 atm or less, the molecular weight of the polymer becomes low, and the moldability and the resin properties of the composition deteriorate.
Pressures above 3000 atmospheres are virtually meaningless and only increase manufacturing costs. When the average polymerization temperature is 100 ° C. or lower, the polymerization reaction is not stable, and the conversion into a copolymer is reduced, which is economically problematic. If the temperature exceeds 300 ° C., the molecular weight of the copolymer decreases, and at the same time, the risk of a runaway reaction occurs. It is desirable to use a vessel type reactor as an apparatus for production. In particular, radical polymerizable acid anhydrides have poor polymerization stability, and therefore require a high degree of uniformity in the reactor. If necessary, a plurality of reactors can be connected in series or in parallel to carry out multistage polymerization. Further, by dividing the inside of the reactor into a plurality of zones, more precise temperature control can be performed. The production of the ethylene-based copolymer used in the present invention can be carried out under at least one reaction condition under the above reaction conditions.
It is carried out in the presence of a free radical initiator. As the free radical initiator, generally known diacyl peroxides, peroxycarbonates, peroxyesters, ketone peroxides, peroxyketals, and other azo compounds are used. In polymerization, various chain transfer agents can be used as molecular weight regulators.

[0008] The ethylene copolymer according to the present invention produced in this manner has excellent adhesiveness and thus firmly adheres to a polyolefin-based thermoplastic elastomer which is difficult to adhere, and at the same time, acid anhydride. By containing a material group, it shows a high dielectric constant and has extremely good high-frequency characteristics.
The ethylene copolymer according to the present invention produced as described above has a ratio of units derived from the radical polymerizable acid anhydride and a ratio of units derived from the radical polymerizable comonomer in the ethylene copolymer. Each in the range of 0.1 to 5% by weight, and in the range of 10 to 50% by weight, more preferably in the range of 0.5 to 4% by weight, based on the whole adhesive resin composition;
And 13 to 30% by weight. If the ratio of the unit derived from the radically polymerizable acid anhydride is less than 0.1% by weight based on the whole adhesive resin composition, the adhesive performance is insufficient and a good three-layer laminate cannot be produced, and the high frequency sealing property is also low. descend. Conversely, even if the unit derived from the radical polymerizable acid anhydride is contained in an amount of more than 5% by weight, it has no significant effect on the improvement of the adhesive property and the high-frequency sealing property, and is economically meaningless. Is not preferred. If the ratio of the unit derived from the radically polymerizable comonomer is less than 10% by weight based on the whole adhesive resin composition, the high-frequency characteristics which are the object of the present invention are lost, which is not preferable. Conversely, the content is 50% by weight.
Exceeding the range is not preferred because the handling of the resin becomes difficult and the heat resistance of the product decreases.

The ethylene copolymer according to the present invention is generally used without being blended with another resin, but can be blended with another polyolefin resin as long as the high-frequency sealing property is not impaired. Other polyolefin resins mentioned here include high-density polyethylene, linear low-density polyethylene, low-density polyethylene, EPR
And copolymers of ethylene and vinyl monomers other than the polyethylene copolymers related to the present invention, such as ethylene-vinyl acetate copolymer and ethylene-methyl methacrylate copolymer. The blending amount is not particularly limited as long as the high-frequency sealing property of the ethylene copolymer according to the present invention is not lost, but is generally preferably 50% by weight or less.

As the olefin-based thermoplastic elastomer according to the present invention, a mixture of a polyolefin and a partially cross-linked product of an ethylene / α-olefin-based copolymer rubber is desirable, and the following can be exemplified. (1) Various polyolefin resins represented by homopolymers of ethylene or propylene or copolymers with small amounts of other comonomers, and α-ethylene having 3 to 14 carbon atoms
Thermoplastic consisting of a binary copolymer rubber with olefin or a partially crosslinked product of ethylene / α-olefin copolymer rubber, which is a terpolymer rubber obtained by further copolymerizing various polyene compounds with the olefin. Resin composition. (2) A thermoplastic resin composition obtained by dynamically heat-treating a composition of a polyolefin resin and an ethylene / α-olefin-based copolymer rubber. (3) A thermoplastic resin composition obtained by blending a polyolefin resin and a composition obtained by dynamically heat-treating a composition of an ethylene / α-olefin-based copolymer rubber and a polyolefin. (4) Various peroxide-crosslinked polyolefin resins represented by homopolymers of ethylene or propylene, or copolymers thereof with a small amount of a comonomer, and ethylene / propylene.
A thermoplastic composition obtained by dynamically heat-treating a composition with an α-olefin copolymer rubber can be mentioned.

The olefin-based thermoplastic elastomer according to the present invention may contain a mineral oil-based softening agent as required. Mineral oil-based softeners usually weaken the intermolecular force of rubber when rolling rubber, facilitating processing and promoting the dispersion of carbon black, white carbon, etc., or reduce the hardness of vulcanized rubber. A petroleum fraction that is used to increase flexibility and rubber elasticity.
It is classified into paraffinic, naphthenic, aromatic and the like. Preferably, a paraffinic process oil is used. Such a mineral oil-based softener can be used in the range of 0 to 60% by weight. If you use more than this range,
The strength of the olefin-based thermoplastic elastomer is lowered, or a problem such as a mineral oil-based softening agent oozing out to impair the appearance occurs, which is not preferable. In the olefin-based thermoplastic elastomer according to the present invention, other additives, compounding agents, and fillers can be used as long as the characteristics of the composition are not impaired. If these are specifically shown, glass, carbon black, zinc oxide, clay, talc, heavy calcium carbonate, kaolin, diatomaceous earth, silica, alumina, asbestos, other inorganic fillers such as graphite, organic fillers,
Antioxidants (heat stabilizers), ultraviolet absorbers (light stabilizers), antistatic agents, flame retardants, lubricants (slip agents, antiblocking agents), reinforcing agents, coloring agents (dye, pigment),
Foaming agents, fragrances and the like can be mentioned.

As a method for producing a three-layer laminate of the ethylene copolymer and the thermoplastic elastomer of the present invention, a method usually called a coextrusion molding method is used. Specifically, this is a method in which an ethylene copolymer and a thermoplastic elastomer are simultaneously multilayer-extruded using a T-die having a three-layer structure and two extruders directly connected to the T-die. According to this production method, it is possible to produce a three-layer laminate having extremely high adhesive strength between the ethylene-based copolymer layer and the thermoplastic elastomer layer. The molding temperature at the time of coextrusion molding is not particularly limited, but is generally performed under the condition that the resin temperature is in the range of 160 ° C to 280 ° C, more preferably 180 ° C.
~ 250 ° C. The thickness configuration of the three-layer laminate can be freely selected depending on the application, and according to the thickness configuration,
Conditions such as the screw rotation speed of the extruder, the resin discharge amount, and the winding speed of the winding machine are selected. The thickness of the two adhesive layers made of the ethylene copolymer forming the outer layer of the three-layer laminate is not particularly limited, but if it is too thin, the sealing strength after high-frequency sealing may be reduced.
It is desirable to be thicker than m.

Other methods for producing a three-layer laminate include a method of simultaneously multilayer injection-molding an ethylene-based copolymer and a thermoplastic elastomer, and a method in which an adhesive resin is inserted in a mold in advance and then heated. It can also be produced by a two-stage injection molding method in which a plastic elastomer is injection-molded so that an ethylene-based copolymer forms an outer layer. As another molding method, after forming an ethylene copolymer and a thermoplastic elastomer into a film or a sheet by inflation molding or T-die molding, the polyolefin resin composition and the thermoplastic elastomer are heated and pressed by a hot press or a hot roll. And a method in which an ethylene-based copolymer is laminated on both sides of a thermoplastic elastomer film or sheet. However, in these methods, the interfacial adhesive strength between the thermoplastic elastomer containing a mineral oil-based softener and the ethylene-based copolymer is lower than that of a laminate produced by co-extrusion molding, and the production method is also low. It becomes extremely complicated.

The three-layer laminate manufactured as described above has high-frequency sealing properties and sufficient flexibility and strength due to the effect of the thermoplastic elastomer of the intermediate layer. It can be used for various application fields used after sealing. Specific examples of applications include, for example, seat covers for automobiles, ships, trains, etc., skin materials for office chairs, skin materials for sofas, sun visor skin materials for automobiles, sheet materials for various notebook covers, and various accessories. And sheet materials for flexible containers, skin materials for bags and the like.

[0015]

The ethylene copolymer according to the present invention is excellent in high-frequency sealability and also has good adhesiveness to a thermoplastic elastomer containing a large amount of a mineral oil-based softener. Therefore, a three-layer laminate having a thermoplastic elastomer as an intermediate layer, which is obtained by co-extrusion of a thermoplastic elastomer originally having no high-frequency sealing property and the ethylene copolymer according to the present invention, has high-frequency sealing properties. It is a useful material that can be used for a wide range of applications as a flexible sheet material.

[0016]

EXAMPLES The present invention will be described below with reference to Reference Examples, Examples, and Comparative Examples.

Reference Example 1 Using a high-pressure method low-density polyethylene plant facility, a polymerization temperature of 240 ° C. and a polymerization pressure of 1
Under the condition of 900 kg / cm ² , ethylene-vinyl acetate-
An ethylene copolymer (A), which is a terpolymer of maleic anhydride, was produced. MFR of this ethylene copolymer
(JIS-K7210, Table 1, Condition 4) was 30, the content of units derived from vinyl acetate was 15% by weight, and the content of units derived from maleic anhydride was 0.8% by weight. The composition of the comonomer was determined by infrared absorption spectrum.

REFERENCE EXAMPLE 2 A polymerization temperature of 200.degree.
An ethylene copolymer (B), which is an ethylene-methyl methacrylate-maleic anhydride terpolymer, was produced under the conditions of 900 kg / cm ² . The MFR (JIS-K7210, Table 1, condition 4) of this ethylene copolymer is 80,
The content of units derived from methyl methacrylate was 25% by weight, and the content of units derived from maleic anhydride was 3.8% by weight. The composition of the comonomer was determined by infrared absorption spectrum.

REFERENCE EXAMPLE 3 A polymerization temperature of 190.degree.
Under the conditions of 900 kg / cm ² , an ethylene copolymer (C), which is an ethylene-methyl acrylate-maleic anhydride terpolymer, was produced. M of this ethylene copolymer
The FR (JIS-K7210, Table 1, condition 4) was 12, the content of units derived from methyl acrylate was 16% by weight, and the content of units derived from maleic anhydride was 2.5% by weight. The composition of the comonomer was determined by infrared absorption spectrum.

Reference Example 4 A polymerization temperature of 220.degree.
An ethylene copolymer (D), which is an ethylene-ethyl acrylate-maleic anhydride terpolymer, was produced under the conditions of 800 kg / cm ² . M of this ethylene copolymer
The FR (JIS-K7210, Table 1, condition 4) was 8, the content of units derived from ethyl acrylate was 35% by weight, and the content of units derived from maleic anhydride was 1.8% by weight. The composition of the comonomer was determined by infrared absorption spectrum.

Reference Example 5 A polymerization temperature of 220.degree. C. and a polymerization pressure of 2 was utilized using equipment of a high-pressure low-density polyethylene plant.
2,000 kg / cm ² , ethylene-vinyl acetate-
An ethylene copolymer (E), which is a maleic anhydride terpolymer, was produced. MFR of this ethylene copolymer
(JIS-K7210, Table 1, Condition 4) was 10, the content of units derived from vinyl acetate was 5% by weight, and the content of units derived from maleic anhydride was 2.4% by weight. The composition of the comonomer was determined by infrared absorption spectrum.

Reference Example 6 Ethylene / propylene / ethylidene norbornene terpolymer (ethylene / propylene molar ratio: 70/30, iodine value: 14, Mooney viscosity (M
L _{1 + 4} , 121 ° C.) 59) 49% by weight, polypropylene (MFR (JIS K7210, Table 1, condition 14) 15
g / 10 minutes) 20% by weight, naphthenic process oil 3
0% by weight and 1% by weight of a mixture of 1,3-bis (tert-butylperoxyisopropyl) benzene / trimethylolpropane triacrylate in a weight ratio of 4/6 are mixed in a Henschel mixer, and the mixture is then mixed with 120%
Into a Banbury mixer preheated to ~ 140 ° C,
The mixture was kneaded at 180 to 190 ° C. for 10 minutes to perform a crosslinking reaction.
This was designated as thermoplastic elastomer (1).

Reference Example 7 Terpolymer of ethylene / propylene / ethylidene norbornene (ethylene / propylene molar ratio: 70/30, iodine value: 14, Mooney viscosity (M
L _{1 + 4} , 121 ° C.) 59) 69% by weight, polypropylene (MFR (JIS K7210, Table 1, condition 14) 15
g / 10 minutes) and 1% by weight of a mixture of 1,3-bis (tert-butylperoxyisopropyl) benzene / trimethylolpropane triacrylate in a weight ratio of 4/6 were mixed with a Henschel mixer, Thereafter, this mixture was put into a Banbury mixer preheated to 120 to 140 ° C., and kneaded at 180 to 190 ° C. for 10 minutes to perform a crosslinking reaction. This was designated as thermoplastic elastomer (2).

Reference Example 8 Ethylene / propylene binary copolymer [ethylene / propylene molar ratio 70/30, M
FR (JIS K7210, Table 1, condition 14) 0.02
g / 10 min, Mw / Mn = 5.3, 135 ° C. in decalin
Has an intrinsic viscosity of 5.4 dl / g] 43% by weight, polypropylene [MFR (JIS K7210, Table 1, condition 14)]
0.5 g / 10 min, crystal melting point 160 ° C.] 19 wt%, paraffin-based process oil 36 wt%, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane / triallyl isocyanurate 2% by weight of a mixture having a ratio of 5/5 was mixed with a Henschel mixer, and then the mixture was put into a Banbury mixer preheated to 120 to 140 ° C, and kneaded at 180 to 190 ° C for 10 minutes to perform a crosslinking reaction. . This is a thermoplastic elastomer (3)
And

Example 1 An adhesive resin comprising the ethylene copolymer (A) of Reference Example 1 and the thermoplastic elastomer (1) of Reference Example 6 were combined with two extruders equipped with a 35 mmφ screw to form an extruder. Using a sheet forming machine having a layer T-die, at a T-die temperature of 190 ° C., a thickness of 400 μm
(Thickness configuration: (A) / (1) / (A) = 50 μm / 30
(0 μm / 50 μm). The peel strength at the interface between the ethylene-based copolymer and the thermoplastic elastomer layer of the obtained three-layer sheet could not be measured because the peeling was impossible. This three-layer sheet is formed by stacking two sheets, and a high-frequency sealing device (seal bar: length 30 cm, width 5 mm, sealing pressure: 2 kg / c)
m ² ), high-frequency sealing was performed at a current value of 0.35 A and a sealing time of 4 seconds. This sample was placed in a thermostatic chamber at 23 ° C,
After conditioning for 24 hours at 60% humidity, cut into 15mm width,
Measure 180 ° peel strength with a tensile tester (tensile speed =
300 mm / min). As a result, the peel strength was 2580.
g / 15 mm, which proved to have extremely good suitability for high-frequency sealing.

<Examples 2 to 10> In the layer structure shown in Table 1,
A three-layer sheet was prepared in the same manner as in Example 1. Table 1 summarizes the results of measuring the delamination strength and the high-frequency sealing property of the obtained three-layer sheet.

<Comparative Example 1> In Example 1, instead of the ethylene copolymer (A), an ethylene-vinyl acetate binary copolymer (EVA: MFR (JIS-K7210, Table 1, condition 14)) 12, 12 units derived from vinyl acetate
Wt%) in the same manner as in Example 1 except that
0 μm (thickness configuration: EVA / (1) / EVA = 50 μm
/ 300 μm / 50 μm). The resulting three-layer sheet is placed in a thermostatic chamber at a temperature of 23 ° C and a humidity of 60% for 24 hours.
After adjusting the time condition, cut to a width of 15 mm, and
80 ° Measure peel strength (pulling speed = 300mm / min)
did. As a result, the peel strength at the interface between EVA and the thermoplastic elastomer layer was 720 g / 15 mm, and the interlayer adhesive strength was insufficient. Next, two sheets of the three-layer sheet are stacked, and a high-frequency sealing device (seal bar: length 30c)
m, width 5 mm, sealing pressure: 2 kg / cm ² )
High-frequency sealing was performed with a current value of 0.35 A and a sealing time of 4 seconds. This sample was cut in a 15 mm width after conditioning for 24 hours at a temperature of 23 ° C. and a humidity of 60% in a constant temperature chamber, and a 180 ° peel strength was measured with a tensile tester (tensile speed = 300 mm /
Minute). As a result, it was found that the peel strength at the interface between the EVA and the thermoplastic elastomer layer was as weak as 360 g / 15 mm, which was not suitable for high-frequency sealing.

Comparative Examples 2 to 4 Three-layer sheets were prepared in the same manner as in Example 1 with the layer configuration shown in Table 1. Table 1 summarizes the results of measuring the delamination strength and the high-frequency sealing property of the obtained three-layer sheet. It was found that none of the three-layer sheets was suitable for high-frequency sealing.

[0029]

[Table 1]

[0030]

As specifically shown in each of the examples, when co-extrusion molding is performed using the ethylene-based copolymer according to the present invention, it is possible to obtain an adhesive which is extremely strongly adhered to a thermoplastic elastomer having poor adhesion. A layer stack is obtained. In addition, the three-layer laminate has a good high-frequency sealing property, and is a useful material that can replace the soft polyvinyl chloride material, which has recently become a particular problem due to environmental problems and the like.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00

Claims (4)

(57) [Claims] The intermediate layer is (1) partially crosslinked ethylene-α-olefin copolymer rubber.
Olefin-based thermoplastic elastomer comprising a blend of a polymer and a polyolefin-based resin, wherein the other two layers adjacent to the intermediate layer comprise (2) ethylene and a radical polymerizable acid anhydride and other radicals. An ethylene copolymer which is a multicomponent copolymer comprising a polymerizable comonomer, wherein (a) a unit derived from ethylene is 50 to 99% by weight; and (b) a unit derived from a radically polymerizable acid anhydride is 0.1 to 5%. wt% (c) characterized in that it consists of units 10 to 50% by weight derived from other radical polymerizable comonomers trilayer laminate. 2. An olefin-based thermoplastic elastomer comprising: (a) 100 to 40% by weight of a blend of a partially crosslinked product of an ethylene-α-olefin copolymer rubber and a polyolefin-based resin; and (b) a mineral oil-based softener. 2. The three-layer laminate according to claim 1, comprising 60% by weight. 3. Co-extrusion of (1) an olefin-based thermoplastic elastomer and (2) an ethylene-based copolymer which is a multi-component copolymer composed of ethylene, a radical-polymerizable acid anhydride and other radical-polymerizable comonomers. The method for producing a three-layer laminate according to claim 1, wherein the molding is performed. 4. An olefin-based thermoplastic elastomer comprising: (a) 100 to 40% by weight of a blend of a partially crosslinked product of an ethylene-α-olefin copolymer rubber and a polyolefin-based resin; and (b) a mineral oil-based softener. The method for producing a three-layer laminate according to claim 3 , which comprises 60% by weight.