JPH10286912A - Laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated body excellent in gas barrier properties, impact resistance, and heat-sealing strength, and excellent in interlaminer adhesion between a polyolefin layer and a polyketone layer, and having good appearance, and easy for laminating and manufacturing. SOLUTION: A laminated body, which is formed by laminating a polyolefin layer (A) and a polyketone layer (B) with a bonding composition layer (C) therebetween, where the bonding composition (C) contains 99-60 wt.% polyplefin (C-1) containing 0.01-10 wt.% grafted unsaturated carboxylic acid or its derivative, and 1-40 wt.% tackifier (C-2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate in which a polyolefin layer and a polyketone layer are laminated via an adhesive layer, and can be suitably used for packaging food or medicine.

[0002]

2. Description of the Related Art Polyketones are expected to be used as food preservation or food packaging materials because of their excellent gas barrier properties. However, since the polyketone is inferior in heat seal properties and impact strength as it is, it is usually used as a laminate with polyolefin. However, since the polyketone and the polyolefin do not adhere as they are, some kind of adhesive layer is required.

[0003] For this reason, conventionally, as an adhesive layer between a polyketone and a polyolefin, a polyolefin modified with an unsaturated carboxylic acid and further modified with an amine has been proposed (for example, JP-A-8-503996). . However, conventional adhesives do not have sufficient adhesive strength at the time of high-speed thin film forming such as film forming, and there are many denaturation steps, and furthermore, a gel is generated or the fluidity is reduced to obtain a laminate having a good appearance. There are problems such as not being able to be done.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide not only excellent gas barrier properties, impact resistance and heat seal strength, but also excellent interlayer adhesion strength between a polyolefin layer and a polyketone layer, and a good appearance. Another object of the present invention is to provide a laminate that can be easily laminated and manufactured.

[0005]

The present invention relates to the following laminate. (1) In a laminate in which a polyolefin (A) layer and a polyketone (B) layer are laminated via a bonding composition (C) layer, the bonding composition (C) is crystallized by (C-1) Degree is 40% or less, 99-60% by weight of a modified polyolefin containing 0.01-10% by weight of a grafted unsaturated carboxylic acid or a derivative thereof, and (C-2) 1-40% by weight of a tackifier A laminate comprising: (2) Polyolefin (A) layer / adhesive composition (C)
The laminate according to the above (1), comprising a three-layer structure of a layer / polyketone (B) layer. (3) The laminate according to the above (1) or (2), wherein the polyolefin (A) is an ethylene copolymer containing ethylene as a main component. (4) The laminate according to the above (3), wherein the polyolefin (A) is an ethylene / propylene copolymer, an ethylene / 1-butene copolymer or an ethylene / 1-octene copolymer. (5) The laminate according to any one of the above (1) to (4), wherein the laminate is laminated by a co-extrusion method.

<< Polyolefin (A) >> The polyolefin (A) used in the present invention is an α-olefin having 2 to 20 carbon atoms.
-Olefin homopolymers or copolymers. Here, specific examples of the α-olefin include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. The polyolefin (A) may be copolymerized with a small amount of another monomer, for example, 10 mol% or less, in addition to the α-olefin.

[0007] Specific examples of the polyolefin (A) include the following polymers or copolymers. (1) Ethylene homopolymer (manufacturing method may be either low-pressure method or high-pressure method) (2) Ethylene 99-80 mol% and propylene 1-2
Ethylene / propylene copolymer with 0 mol% (3) 99-80 mol% of ethylene and 1-butene 1-2
Ethylene / 1-butene copolymer with 0 mol% (4) 99-80 mol% of ethylene and 1-octene 1-
20 mol% of ethylene / 1-octene copolymer (5) Copolymer of ethylene and 10 mol% or less of other α-olefin or vinyl monomer such as vinyl acetate and ethyl acrylate (6) Propylene homopolymer Combined (7) Random copolymer of propylene and 30 mol% or less of other α-olefin (8) Block copolymer of propylene and 40 mol% or less of other α-olefin (9) 1-butene alone Polymer (10) Random copolymer of 1-butene and 10 mol% or less of other α-olefin (11) 4-methyl-1-pentene homopolymer (12) 4-methyl-1-pentene and 20 Random copolymer with not more than mol% of other α-olefin

Among these, (2) 95 to 85 mol% of ethylene and propylene 5 to 1
Ethylene / propylene copolymer with 5 mol% (3) 95 to 85 mol% of ethylene and 5-1 to 1-butene
Ethylene / 1-butene copolymer with 5 mol% (4) 97 to 85 mol% of ethylene and 1-octene 3 to
15 mol% of ethylene / 1-octene copolymer (5) Ethylene copolymers such as copolymers of ethylene with 10 mol% or less of other α-olefin or vinyl monomer such as vinyl acetate, ethyl acrylate, etc. (6) Propylene homopolymer (7) Random copolymer of propylene and 20 mol% or less of other α-olefin (8) Block copolymer of propylene and 40 mol% or less of other α-olefin A propylene-based polymer or copolymer such as a coalescence is preferred.

Among them, ethylene copolymers are more preferable, and in particular, the ethylene-propylene copolymer (2), the ethylene-1-butene copolymer (3), and the ethylene-1-octene (4) Preferred are ethylene copolymers of the copolymer.

<< Polyketone (B) >> The polyketone (B) used in the present invention is a linear polymer in which a carbonyl group (CO) and a divalent organic group derived from an ethylenically unsaturated compound are alternately bonded. And the general formula (1)

Embedded image [In the formula, A represents a divalent organic group derived from an ethylenically unsaturated compound, m represents a number of 1 to 6, and n represents a number of 2 to 6000 or more. ] Is represented. Such a polyketone (B) is known, and is a polymer usually obtained by polymerizing carbon monoxide and an ethylenically unsaturated compound.

Specific examples of the above ethylenically unsaturated compounds include α-C2-C12 such as ethylene, propylene, 1-butene, isobutylene and 1-pentene.
Olefins; diene compounds such as butadiene, isoprene and 2-chlorobutadiene-1,3; vinylidene compounds such as vinylidene chloride; tetrafluoroethylene;
Vinyl halides, esters or acetals such as vinyl acetate, vinyl chloride, vinyl chloroacetate, dimethyl vinyl acetate and trimethyl vinyl acetate; vinyl ketones such as vinyl methyl ketone and vinyl ethyl ketone; styrene, chlorostyrene and α-methyl styrene Styrene or a derivative thereof; acrylic acid, methacrylic acid, esters, amides, nitriles and acid halides thereof; vinyl esters of unsaturated carboxylic acids such as vinyl hexenoate and vinyl crotonic acid.

Among them, linear α having 2 to 6 carbon atoms is preferred.
-Olefins are preferred, especially ethylene. Ethylenically unsaturated compounds can be used alone or in combination of two or more. In the latter case, it is preferable to use a combination of ethylene and a linear α-olefin having 3 to 6 carbon atoms, particularly propylene. In this case, it is desirable that the molar ratio of ethylene / α-olefin having 3 to 6 carbon atoms is larger than 1, preferably 2 to 30.

The polyketone (B) has a melting point of 175.
The intrinsic viscosity number (IV) measured by a standard capillary viscometer in m-cresol at 0.5 to 300 ° C., preferably 210 to 270 ° C., is 0.5 to 10 dl / g, preferably 0.8 to 4 dl / g. Are preferred.

Polyketones (B) are known; for example, US Pat. No. 4,880,903 discloses carbon monoxide, ethylene and other ethylenically unsaturated compounds such as propylene.
Are described.
The polyketone (B) can be produced by polymerizing carbon monoxide and the ethylenically unsaturated compound by a known method. For details of the production method, see JP-A-47-32
No. 100, Tokuhei 5-87527, Tokuhei 6-136
No. 08 and the like.

As the polyketone (B), commercially available products can be used. For example, Carilon (manufactured by Shell Inc.) and the like can be mentioned.

<< Adhesive Composition (C) >> The polyolefin (C-1) used as a component of the adhesive composition (C) in the present invention has a crystallinity of 4 as measured by an X-ray diffraction method.
0% or less, preferably 20 to 0%, and the grafted unsaturated carboxylic acid or its derivative is contained in an amount of 0.01 to 1%.
It is a polyolefin containing 0% by weight, preferably 0.05 to 3% by weight. When the amount of the unsaturated carboxylic acid or its derivative (hereinafter sometimes referred to as graft amount) and the crystallinity are in the above ranges, the adhesiveness to the polyketone (B) is excellent.

The polyolefin (C-1) may be a single type or a mixture of two or more types. In the case of a mixture of two or more, the degree of crystallinity and the amount of graft as a mixture may be within the above-mentioned range, and the graft-modified polyolefin having a degree of crystallinity and / or the amount of graft outside the above-mentioned range, and / or a graft-modified polyolefin. No polyolefin may be included.

Specific examples of the mixture include: 1) a mixture of two or more kinds of graft-modified polyolefins having a crystallinity and a graft amount within the above-mentioned range; A mixture of the above-mentioned graft-modified polyolefin and one or more kinds of graft-modified polyolefins having a crystallinity and / or a graft amount outside the above-mentioned range. 3) Graft-modification having a crystallinity and / or a graft amount outside the above-mentioned range. A mixture of two or more polyolefins, 4) a mixture of one or more graft-modified polyolefins having a crystallinity and a graft amount within the above range, and one or more non-graft-modified polyolefins, 5) a crystallinity and And / or one or more graft-modified polyolefins having a graft amount outside the above range, A mixture of one or more polyolefins is not, 6) the 1) such as a mixture to the mixture was further mixed with one or more polyolefins that are not graft-modified of -3) and the like.

The polyolefin before graft modification or without graft modification includes α 2 -C 20.
-An olefin homopolymer or a copolymer of two or more types. As the α-olefin, ethylene,
Propylene, 1-butene, 1-hexene, 4-methyl-
Examples thereof include 1-pentene, 1-octene, 1-decene, 1-tetradecene, and 1-octadecene. The polyolefin may be copolymerized with a small amount of a monomer other than the α-olefin, for example, 10 mol% or less.

As the polyolefin before the graft modification or without the graft modification, an ethylene homopolymer or an ethylene / α-olefin random copolymer is preferable. Specific examples include linear low-density polyethylene (L-LDPE), ethylene-propylene copolymer,
Ethylene / butene copolymer and the like. Among these, especially the melt flow rate (MFR: ASTM)
D 1238, L) is 0.1 to 50 g / 10 min, preferably 0.2 to 20 g / 10 min, and the density is 0.85
0 to 0.900 g / cm ³ , preferably 0.855 to
0.895 g / cm ³ , an ethylene content of 30 to 95 mol%, preferably 40 to 92 mol%, and a crystallinity measured by X-ray diffraction of 40% or less, preferably 30
% Or less is desirable. When the MFR is in the above range, the moldability and the adhesive strength are excellent. When the density is in the above range, the adhesive strength to the polyketone (B) is excellent. When the crystallinity is in the above range, the adhesive strength with the polyketone (B) is excellent.

The ethylene / α-olefin is a low-crystalline or amorphous polyolefin, and the low-crystalline copolymer usually has a melting point (ASTM D 3418) of 1
It is below 00 ° C. Examples of the α-olefin constituting the ethylene / α-olefin random copolymer include the same α-olefins having 3 to 20 carbon atoms as described above.

Examples of the unsaturated carboxylic acid used in graft modification of the polyolefin (graft monomer), acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, Nadic ^TM (Endoshisu -Bicyclo [2.
2.1] hept-5-ene-2,3-dicarboxylic acid). Examples of unsaturated carboxylic acid derivatives include acid halides, amides, imides, anhydrides, and esters. Specific examples include maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, and maleic acid. Examples include dimethyl and glycidyl maleate. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid ^TM or acid anhydrides thereof are particularly preferable.

In order to produce a modified product by graft-copolymerizing a graft monomer selected from an unsaturated carboxylic acid or a derivative thereof with a polyolefin before modification, various known methods can be employed. For example, there is a method in which a polyolefin before modification is melted and a graft monomer is added to carry out graft copolymerization, or a method in which the polyolefin is dissolved in a solvent and the graft monomer is added to carry out graft copolymerization. In either case, it is preferable to carry out the reaction in the presence of a radical initiator in order to efficiently graft-copolymerize the graft monomer. The grafting reaction is usually performed at a temperature of 60 to 350 ° C. The usage ratio of the radical initiator is usually in the range of 0.001 to 1 part by weight based on 100 parts by weight of the polyolefin before modification.

Examples of the radical initiator include organic peroxides and organic peroxides such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-
Dimethyl-2,5-di (peroxidebenzoate) hexyne-3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide,
tert-butyl peracetate, 2,5-dimethyl-
2,5-di (tert-butylperoxy) hexyne-
3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, te
tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate, and other azo compounds such as azobisisobutyronitrile, dimethylazo Isobutyrate and the like. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert)
-Butylperoxy) hexane, 1,4-bis (ter
Dialkyl peroxides such as (t-butylperoxyisopropyl) benzene are preferred.

In the present invention, as the tackifier (C-2) used as a component of the adhesive composition (C), an aliphatic hydrocarbon resin or an alicyclic hydrocarbon obtained by hydrogenating an aromatic hydrocarbon resin is used. Hydrogen resin, α-pinene resin, terpene resin,
Rosin, modified rosin, mixtures thereof and the like are used. Such a tackifier (C-2) is a solid amorphous polymer conventionally used as a tackifier resin in the fields of pressure-sensitive adhesive tapes, paints, hot melt adhesives, and the like.

Among such tackifiers (C-2), the softening point (ring and ball method) is 105 to 150 ° C., preferably 110 to 140 ° C., and the hydrogenation rate to the aromatic nucleus is 8
0% or more, preferably 85% or more, of alicyclic hydrocarbons are particularly preferred. A commercial item can also be used as an adhesion imparting agent (C-2). For example, Alcon P-125 manufactured by Arakawa Chemical Industry Co., Ltd. may be mentioned.

The amount of the polyolefin (C-1) and the tackifier (C-2) is 9
It is 9 to 60% by weight, preferably 95 to 80% by weight, and 1 to 40% by weight, preferably 5 to 20% by weight of the tackifier (C-2). When the compounding amount is in the above range, the bonding composition (C) has excellent adhesion to the polyolefin (A) and the polyketone (B).

In the adhesive composition (C), in addition to the components (C-1) and (C-2), other resins, heat stabilizers, weather stabilizers, antistatic agents, pigments, dyes, rusting Additives, such as inhibitors, may be incorporated within the range that does not impair the purpose of the present invention. As the other resin, polyethylene, polypropylene, polyamide, polyester, polycarbonate,
Examples include polystyrene, AS resin, and ABS resin.

In order to obtain the bonding composition (C), the polyolefin (C-1) and the tackifier (C-2) and, if necessary, additives to be added are mixed in various known methods within the above range, for example, A method of mixing with a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, or the like, or a method of mixing and then kneading with a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or the like, followed by granulation or pulverization. can do.

<< Laminate >> The laminate of the present invention comprises a polyolefin (A) layer composed of the polyolefin (A) and a polyketone (B) layer composed of the polyketone (B). It is a laminated body laminated via an adhesive composition (C) layer composed of: The laminate of the present invention has a three-layer structure of (A) layer / (C) layer / (B) layer and (A) layer / (C) layer / (B) layer / (C) layer / (A). A laminate having a five-layer structure of layers is preferable, but not limited thereto.

The thickness of the polyolefin (A) layer is 0.01
１００100 mm, preferably 0.03 to 2 mm. The thickness of the polyketone (B) layer is 0.005 to 3
mm, preferably 0.01 to 0.5 mm. The thickness of the bonding composition (C) layer is 0.005 to 3 m.
m, preferably 0.01 to 0.5 mm. The thickness of the laminate is desirably 0.02 to 106 mm, preferably 0.05 to 3 mm. (A)-(C)
When there are a plurality of layers, the above thickness is the total thickness of these.

The laminate of the present invention can be easily laminated and manufactured by a known molding method such as a coextrusion molding method or a sandwich lamination method. For example, (A) / (C) /
The laminate having the three-layer structure of the layer (B) can be manufactured by the following molding method. That is, the polyolefin (A), the polyketone (B), and the bonding composition (C) are each melted by a separate extruder and then supplied to a three-layer die, and the bonding composition (C) is used as an intermediate layer. Extrusion molding method: a method in which a polyolefin (A) layer and a polyketone (B) layer are formed in advance, and the adhesive composition (C) is melt-extruded between the polyolefin (A) layer and the polyketone (B) layer (so-called so-called extrusion method). (Sandwich lamination method) or the like. Among these, the co-extrusion molding method is preferable from the viewpoint of interlayer adhesion. As the coextrusion method, there are a T-die method using a flat die and an inflation method using a circular die, and any of these methods can be adopted. Flat die is black
Either a single manifold format using a box or a multi-manifold format may be used. As the die used for the inflation method, any known die can be used.

The laminate of the present invention is excellent in gas barrier properties, impact resistance and heat sealing strength, and also excellent in interlayer adhesion strength between the polyolefin (A) layer and the polyketone (B) layer, and has a good appearance. And it can be easily laminated and manufactured. Therefore, the laminate of the present invention can be suitably used as a material for preservation or packaging of foods or medicines, or as a material for pressure-formed cups, hollow bottles and the like.

[0034]

According to the laminate of the present invention, the polyolefin (A) layer and the polyketone (B) layer are bonded by the specific bonding composition (C) layer, so that the gas barrier property is improved.
It is excellent in impact resistance and heat seal strength, has excellent interlayer adhesion strength between the polyolefin (A) layer and the polyketone (B) layer, has a good appearance, and can be easily laminated and manufactured.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION

Example 1 Using the following polyolefin (A), polyketone (B) and adhesive composition (C), the following method (A) /
A laminate having a three-layer structure of (C) / (B) layers was obtained. The interlayer adhesion of this laminate was measured. Table 1 shows the results.

<< Polyolefin (A) >> Neo23H: High-pressure polyethylene, MFR = 3.3 g
/ 10 min, density = 0.921 g / cm ³ , manufactured by Mitsui Dupont Chemical Co., Ltd. << Polyketone (B) >> Carilon: P-1000 (grade name), MFR
= 6 g / 10 min (240 ° C, load 2 kg), density = 1.
240 g / cm ³ , manufactured by Shell

<< Adhesive Composition (C) >> EPR-1 / tackifier / modified polyethylene A = 85/10/5 (weight ratio) was mixed with a Henschel mixer and mixed with a single screw extruder.
Granulation was performed at 00 ° C. to obtain pellets of the composition. The density of the adhesive composition (C) was 0.880 g / cm ³ . EPR-1: ethylene propylene rubber, ethylene content =
80 mol%, propylene content = 20 mol%, MFR =
2.9 g / 10 min, density = 0.870 g / cm ³ , crystallinity = 5% or less Tackifier: Alcon P-125 manufactured by Arakawa Chemical Industries, density = 0.999 g / cm ³ , softening point (ring and ball) Mod) = 125
Modified polyethylene A: maleic anhydride-modified polyethylene, density = 0.965 g / cm ³ , melt index = 4.4 g / 10 min, maleic anhydride graft amount = 2.
2% by weight

The adhesive composition (C), the polyolefin (A), and the polyketone (B) obtained by the above method were classified into three types, 3
Using a layer cast molding machine, at a molding temperature of 230 ° C., the configuration of the laminate was (A) / (C) / (B) = 160 μm / 40.
A μm / 40 μm laminate was formed.

Example 2 The procedure of Example 1 was repeated except that the following composition was used as the bonding composition (C). Table 1 shows the results
Shown in << Adhesive composition (C) >> modified polyethylene B / tackifier / modified polyethylene A = 85/10/5 (weight ratio),
Density = 0.902 g / cm ³ Modified polyethylene B: maleic anhydride-modified ethylene / butene copolymer, density = 0.886 g / cm ³ , melt index = 2.0 g / 10 min, maleic anhydride graft amount = 0. 4% by weight, crystallinity = 15% Tackifier: Same as in Example 1 Modified polyethylene A: See Example 1

Comparative Example 1 The procedure of Example 1 was repeated, except that the diamine-modified adhesive prepared as described below was used instead of the bonding composition (C). Table 1 shows the results. << Diamine-modified adhesive >> Extruder: Single, full flight screw, 40mm
φ, L / D = 26 Temperature condition: 200 ° C. Extrusion amount: 10.6 kg / hr Rotation speed: 63 rpm Composition: 2021 L / EPR-1 / modified polyethylene A /
Diamine = 60/30/10 / 0.3 (weight ratio) [2021L] Linear low-density polyethylene (L-LDPE) manufactured by Mitsui Petrochemical Industries, density = 0.922 g / cm
^3. Melt index = 2.1 g / 10 min [EPR-1] See Example 1 [Modified polyethylene A] See Example 1 [Diamine] 4,9-dioxidedecane-1,12-diamine Blend method: Modified polyethylene A (powder) and diamine (liquid) are pre-blended, and then the pellets are blended. Density: 0.909 g / cm ³ MFR: 1.61 g / 10 min

Comparative Example 2 The procedure of Example 1 was repeated, except that the following adhesive was used instead of the bonding composition (C). Table 1 shows the results. << Adhesive >> 25100J / EPR-2 / EPR-1 / modified polyethylene C = 56/20/8/16 (weight ratio),
Density = 0.914 g / cm ³ 25100J: Linear low density polyethylene (L-LDPE) manufactured by Mitsui Petrochemical Industries, Ltd., melt index = 10
g / 10 min, density = 0.925 g / cm ³ EPR-2: ethylene propylene rubber, ethylene content =
80 mol%, propylene content = 20 mol%, melt index = 4.5 g / 10 min, density = 0.870 g / c
m ³ EPR-1: see Example 1 Modified polyethylene C: maleic anhydride-modified polyethylene, density = 0.965 g / cm ³ , melt index = 7 g / 10 min, maleic anhydride graft amount = 1.6% by weight

Comparative Example 3 The procedure of Example 1 was repeated, except that the following adhesive was used instead of the bonding composition (C). Table 1 shows the results. << Adhesive >> 2021 L / EPR-1 / modified polyethylene D = 40/20/40 (weight ratio), density = 0.910 g
/ Cm ³ 2021 L: Refer to Comparative Example 1 EPR-1: Refer to Example 1 Modified polyethylene D: Maleic anhydride-modified ethylene / butene copolymer (L-LDPE), density = 0.922 g /
cm ³ , melt index = 0.3 g / 10 min, maleic anhydride graft amount = 0.8% by weight

[0043]

[Table 1] * 1 Interlayer adhesive strength is 300m by T-peel method at room temperature
It was measured under the condition of m / min.

Claims (5)

[Claims] 1. A laminate in which a polyolefin (A) layer and a polyketone (B) layer are laminated via a bonding composition (C) layer, wherein the bonding composition (C) is: The crystallinity is 40% or less, and the grafted unsaturated carboxylic acid or a derivative thereof is 0.01 to 1%.
A laminate comprising 99 to 60% by weight of a modified polyolefin containing 0% by weight and (C-2) 1 to 40% by weight of a tackifier. 2. The laminate according to claim 1, which has a three-layer structure of a polyolefin (A) layer / adhesive composition (C) layer / polyketone (B) layer. 3. The laminate according to claim 1, wherein the polyolefin (A) is an ethylene copolymer containing ethylene as a main component. 4. The laminate according to claim 3, wherein the polyolefin (A) is an ethylene / propylene copolymer, an ethylene / 1-butene copolymer or an ethylene / 1-octene copolymer. 5. The laminate according to claim 1, wherein the laminate is laminated by a co-extrusion method.