JP2000248246A - Resin composition for adhesion and laminated material by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for adhesion, excellent in adhesive force, and a laminated material obtained by adhering a polyethylene layer with a layer of a saponified copolymer of an olefin with vinyl acetate, having an excellent falling resistance, bending resistance and barrier property and also a good interlayer adhesive force. SOLUTION: This resin composition for adhesion contains (a) an ethylene-α- olefin copolymer, (b) an ethylene-vinyl acetate copolymer, (c) a graft-modified polyethylene (density: 0.900-0.980 g/cm3, degree of crystallization by an X-ray: >=30%), and (d) a graft-modified polyethylene (density: >=0.850 g/cm3 and <0.900 g/cm3, degree of crystallization: <30%). By using the composition as an adhesive layer, it is possible to obtain a laminated material constituted of a polyethylene layer with a saponified layer of an olefin-vinyl acetate copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive resin composition and a laminate using the adhesive resin composition, and more particularly, to an adhesive resin composition having good adhesive strength and this adhesive resin composition. The present invention relates to a laminate which exhibits a good appearance using, is excellent in barrier properties, drop impact resistance, bending resistance, and pinhole resistance and is hard to generate voids and delamination.

[0002]

2. Description of the Related Art Polyethylene resins are excellent in mechanical strength, rigidity, heat resistance, chemical resistance, oil resistance, transparency, low-temperature impact strength, and the like. Widely used as packaging material. However, such a polyethylene resin has high permeability to gases such as oxygen, and thus cannot be used for packaging materials requiring high gas barrier properties such as foods, medicines, and cosmetics. In order to enhance the gas barrier properties of the polyethylene resin, a method has been proposed in which a resin having a higher gas barrier property than these resins, such as a saponified ethylene / vinyl acetate copolymer, is laminated on the polyethylene resin. At this time, since the adhesiveness between polyethylene and saponified olefin / vinyl acetate copolymer (hereinafter referred to as EVOH) is remarkably low, various adhesive resins such as ionomer, ethylene / vinyl acetate copolymer and carboxylic acid graft modified product are co-extruded. It was molded to obtain a multilayer structure. However, such a multilayer structure has a rigidity and lacks flexibility of the EVOH, so that the EVOH is not satisfactorily formed during secondary processing, dropping, and bending.
VOH and the adhesive resin may peel off, resulting in a defect in performance (strength, etc.) and appearance of the product. Also EVOH
When the EVOH layer is easily cracked due to the peeling of the adhesive resin layer, problems such as a decrease in barrier properties may occur.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an adhesive resin composition having an excellent adhesive strength, which is intended to solve the problems associated with the prior art as described above. . Also, using the adhesive composition as described above,
Polyethylene layer and a saponified ethylene-vinyl acetate copolymer layer, which have excellent barrier properties and good adhesion between layers. An object of the present invention is to provide a laminated body having good barrier properties and appearance by protecting EVOH from cracking by preventing the EVOH and the adhesive resin layer from peeling off.

[0004]

Means for Solving the Problems The present invention provides the following adhesive composition, and a laminate obtained by bonding a polyethylene layer and a saponified ethylene / vinyl acetate copolymer layer using the adhesive composition. It is. (1): (a) MFR: 0.1 to 50 g / 10 min Density: 0.850 to 0.900 g / cm ³ Ethylene content: 75 to 95 mol% Crystallinity by X-ray: less than 30% Ethylene ・ α
-Olefin copolymer: 93 to 50% by weight (b) MFR: 0.1 to 50 g / 10 minutes Vinyl acetate content: 5 to 40% by weight of ethylene
Vinyl acetate copolymer: 5 to 50% by weight (c) Graft amount of unsaturated carboxylic acid or derivative thereof: 0.05 to 15% by weight MFR: 0.1 to 50 g / 10 min Density: 0.900 to 0.1% 980 g / cm ³ X-ray crystallinity: 30% or more, partially or wholly graft-modified polyethylene:
1.0 to 30% by weight, and (d) Graft amount of unsaturated carboxylic acid or derivative thereof: 0.05 to 15% by weight MFR: 0.1 to 50 g / 10 min Density: 0.850 g / cm ³ or more 0 Less than 900 g / cm ³ Crystallinity by X-ray: less than 30%, partially or wholly graft-modified polyethylene:
(A) + (b) +
(C) + (d) with a total weight of 100% by weight, the graft amount of the whole composition being 0.01 to 3% by weight, and MF
R is 0.1 to 50 g / 10 min, and the degree of crystallinity is less than 35%. (2): A laminate including at least the three layers described below. (A) MFR: 0.1 to 50 g / 10 min Density: 0.850 to 0.900 g / cm ³ Ethylene content: 75 to 95 mol% X-ray crystallinity: 30 %, Ethylene-α
-Olefin copolymer: 93 to 50% by weight (b) MFR: 0.1 to 50 g / 10 minutes Vinyl acetate content: 5 to 40% by weight of ethylene
Vinyl acetate copolymer: 5 to 50% by weight (c) Graft amount of unsaturated carboxylic acid or derivative thereof: 0.05 to 15% by weight MFR: 0.1 to 50 g / 10 min Density: 0.900 to 0.1% 980 g / cm ³ X-ray crystallinity: 30% or more, partially or wholly graft-modified polyethylene:
1.0 to 30% by weight, and (d) Graft amount of unsaturated carboxylic acid or derivative thereof: 0.05 to 15% by weight MFR: 0.1 to 50 g / 10 min Density: 0.850 g / cm ³ or more 0 Less than 900 g / cm ³ Crystallinity by X-ray: less than 30%, partially or wholly graft-modified polyethylene:
(A) + (b) +
(C) + (d) with a total weight of 100% by weight, the graft amount of the whole composition being 0.01 to 3% by weight, and MF
An intermediate layer (B) of an adhesive resin composition having an R of 0.1 to 50 g / 10 min and a crystallinity of less than 35%;
Saponified layer of vinyl acetate copolymer (C). (3): A film comprising the laminate according to (2). (4): A tube comprising the laminate according to (2). (5): A bottle comprising the laminate according to (2).

Hereinafter, the adhesive resin composition according to the present invention and a laminate using the same will be specifically described. First, the adhesive resin composition according to the present invention will be described. This composition comprises (a) an ethylene / α-olefin copolymer,
(B) ethylene-vinyl acetate copolymer, (c) graft-modified polyethylene (density: 0.900 to 0.980 g /
cm ³ , crystallinity by X-ray: 30% or more) and (d) graft-modified polyethylene (density: 0.850 g)
/ Cm ³ or more and less than 0.900 g / cm ³ ; crystallinity by X-ray: less than 30%).

Hereinafter, each component will be described in detail. (A) Ethylene / α-olefin copolymer This ethylene / α-olefin copolymer is obtained by randomly copolymerizing ethylene and α-olefin.
R: 0.1 to 50 g / 10 min, preferably 0.2 to 40
g / 10 min, more preferably in the range of 0.3 to 30 g / 10 min, density: 0.850 to 0.900 g / cm
³ , preferably in the range of 0.850 to 0.895 g / cm ³ , ethylene content: 75 to 95 mol%, preferably in the range of 75 to 93 mol%, crystallinity by X-ray: less than 30%, Preferably it is in the range of less than 28%, more preferably less than 25%. Within the above range,
The adhesive strength of the obtained adhesive resin composition is good.

MFR is based on ASTM D1238 (190
C., 2.16 kg load).

The degree of crystallinity is measured using an X-ray diffractometer in the range of 2θ and 5 to 35 °, and is determined by separating a crystal peak from amorphous scattering by a peak separation method.

The α-olefin constituting the ethylene / α-olefin copolymer includes α-olefin having 3 to 20 carbon atoms.
Olefins, specifically, propylene,
-Butene, 1-hexene, 4-methyl-1-pentene,
1-octene, 1-decene, 1-tetradecene, 1-octadecene and the like are used, and these α-olefins are used alone or as a mixture of two or more. Such an ethylene / α-olefin copolymer has a melting point (ASTM D3418) of usually 100 ° C. or lower.

The ethylene / α-olefin copolymer is used in an amount of 93 to 50% by weight, preferably 90 to 60% by weight, based on the whole composition. Within this range, it is excellent in bending resistance and pinhole resistance.

(B) Ethylene / vinyl acetate copolymer The ethylene / vinyl acetate copolymer has an MFR of 0.1
５０50 g / 10 min, preferably 0.2-40 g / 10 min
Minutes, more preferably in the range of 0.3 to 30 g / 10 minutes, and the vinyl acetate content is in the range of 5 to 40% by weight, preferably 8 to 38% by weight, more preferably 10 to 35% by weight.

This ethylene / vinyl acetate copolymer is used in an amount of 5 to 50% by weight, preferably 5 to 20% by weight, based on the whole composition.
It is used in the range of weight%. Within this range, adhesive strength and film appearance are excellent.

(C) Graft-modified polyethylene This graft-modified polyethylene has the following properties. Grafting amount of unsaturated carboxylic acid or derivative thereof (grafting amount is a grafting amount to unmodified polyethylene): 0.05 to 15% by weight, preferably 0.08 to 12% by weight, more preferably 0.1 to 0.1% by weight. 10
Wt%, MFR: 0.1 to 50 g / 10
Min, preferably 0.2 to 40 g / 10 min, more preferably 0.3 to 30 g / 10 min.
900 to 0.980 g / cm ³ , preferably 0.903
０．９0.975 g / cm ³ , more preferably 0.905
In the range of ~0.970g / cm ^3, crystallinity by X-ray: 30% or more, preferably 33 to 80%, more preferably in the range 35 to 75%. In this graft-modified polyethylene, part or all of the polyethylene is graft-modified. Graft-modified polyethylene is
Ethylene and one or more other α-olefins such as propylene, 1-butene, 4-methyl-1-pentene, 1-
An ethylene / α-olefin copolymer which is a copolymer with hexene, 1-octene, 1-decene or the like may be graft-modified.

This graft-modified polyethylene is used in an amount of 1.0 to 30% by weight, preferably 5 to 20% by weight, based on the whole composition.
It is used in the range of weight%. Within this range, adhesive strength and film appearance are excellent.

(D) Graft-modified polyethylene This graft-modified polyethylene has the following properties. Graft amount of unsaturated carboxylic acid or derivative thereof (graft amount is a graft amount to unmodified polyethylene): 0.05 to 15% by weight, preferably 0.08 to 13% by weight, more preferably 0.1 to 13% by weight. 10
Wt%, MFR: 0.1 to 50 g / 10
Min, preferably 0.2 to 40 g / 10 min, more preferably 0.3 to 30 g / 10 min.
850 g / cm ³ or more 0.900 g / cm less than ^3, preferably 0.858 g / cm ³ or more 0.898 g / cm less than ^3, more preferably 0.855 g / cm ³ to 0.8
Crystallinity by X-ray: less than 95 g / cm ³ , preferably less than 28%, more preferably less than 25%. In this graft-modified polyethylene, part or all of the polyethylene is graft-modified. Graft-modified polyethylene is a copolymer of ethylene and one or more other α-olefins, such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and the like. It is obtained by graft-modifying an ethylene / α-olefin copolymer.

The graft-modified polyethylene is used in an amount of 1.0 to 30% by weight, preferably 5 to 30% by weight, based on the whole composition.
It is used in the range of weight%. In this range, the adhesive strength and the film appearance are excellent.

The above-mentioned graft-modified polyethylene (c) or (d) can be obtained by graft-modifying a part or all of polyethylene or an ethylene / α-olefin copolymer with an unsaturated carboxylic acid or a derivative thereof. However, as the unsaturated carboxylic acid or derivative thereof used in this case, specifically, acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid,
Citraconic acid, crotonic acid, isocrotonic acid, nadic acid ^R (endocis-bicyclo [2,2,1] hept-5-
Unsaturated carboxylic acids such as ene-2,3-dicarboxylic acid) or derivatives thereof such as acid halides, amides, imides, anhydrides and esters.
Maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like are used. Among them, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid ^R , hymic acid or acid anhydrides thereof are particularly preferably used. In order to produce a modified product by graft-copolymerizing a graft monomer selected from such unsaturated carboxylic acids or derivatives thereof with polyethylene, various conventionally known methods can be employed.

For example, there is a method in which polyethylene is melted and a graft monomer is added for graft copolymerization, or a method in which the polyethylene is dissolved in a solvent and the graft monomer is added for graft copolymerization. In any 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 proportion of the radical initiator used is polyethylene 1
It is usually in the range of 0.001 to 1 part by weight with respect to 00 parts by weight.

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, ter
t-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate, and other azo compounds such as azobisisobutyronitrile, dimethylazoiso Butyrate and the like are used. 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-butyl)
Butylperoxy) hexane, 1,4-bis (tert
Dialkyl peroxides such as -butylperoxyisopropyl) benzene are preferred.

Thus, the adhesive resin composition according to the present invention
Are (a) ethylene / α-olefin copolymers 93 to 5
0% by weight, (b) ethylene-vinyl acetate copolymer 5-5
0% by weight (c) graft-modified polyethylene (density: 0.
900-0.980 g / cm ^Three, X-ray crystallinity:
1.0 to 30% by weight and (d) graft
Modified polyethylene (density: 0.850 g / cm^Threethat's all
0.900 g / cm^Three, Crystallinity by X-ray: 30
%) Of 1.0 to 30% by weight.
Graft amount of the whole product is 0.01 to 3% by weight, preferably
0.02 to 2.8% by weight, more preferably 0.02 to 2.8% by weight.
It is in the range of 5-2.5% by weight.

The adhesive resin composition according to the present invention can be prepared by mixing the above-mentioned components (a), (b), (c) and (d) in various known methods within the above-mentioned range, for example, a Henschel mixer. , V-blender, ribbon blender, tumbler blender, etc., or a method of mixing and then kneading with a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, etc., followed by granulation or pulverization. .

The adhesive resin composition according to the present invention further comprises, in addition to the above components, a heat stabilizer, a weather stabilizer, an antistatic agent,
An anti-blocking agent, an antioxidant, an ultraviolet absorber, a stabilizer, a pigment, a dye, a rust inhibitor, a slip agent, a surface lubricant, and the like can be blended as long as the object of the present invention is not impaired.

Next, the laminate according to the present invention will be described. The polyethylene layer (A) constituting the laminate is, for example, a high-pressure low-density polyethylene, a linear low-density polyethylene, a medium-density polyethylene, a high-density polyethylene, an ethylene-propylene copolymer, or an ethylene-butene-1 copolymer. , An ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, or a mixture thereof.

The ethylene / α-olefin copolymer also includes a terpolymer obtained by copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated diene. Such non-conjugated dienes include 1,4 hexadiene, dicyclopentadiene, ethylidene norbornene and the like.

The layer (C) constituting the laminate according to the present invention comprises a saponified olefin / vinyl acetate copolymer. The saponified olefin / vinyl acetate copolymer has an olefin content of 15 to 60 mol.
%, Preferably 20 to 55 mol%, more preferably 25 to 50 mol%, having a saponification degree of 50% or more, preferably 70% or more.
%, More preferably 90% or more.

When the olefin content is in the range of 15% to 60%, thermal decomposition hardly occurs and melt moldability is good.
It has excellent stretchability, hardly absorbs water and swells, has excellent water resistance, and has excellent barrier properties. When the saponification degree is 50% or more, the barrier properties are excellent. Specific examples of the olefin copolymerized with vinyl acetate include ethylene, propylene, and olefin.
-Butene, 1-hexene, 4-methyl-1-pentene,
Examples thereof include 1-octene, 1-decene, 1-tetradecene, and 1-octadecene, and among them, ethylene is preferably used in terms of mechanical strength and moldability.

In order to produce the laminate according to the present invention, a polyethylene resin, an adhesive resin composition, and an olefin
A co-extrusion molding method in which saponified vinyl acetate copolymer is melted in separate extruders, and then supplied to a three-layer die, and co-extrusion molding is performed so that the adhesive resin composition becomes an intermediate layer. , A polyethylene resin layer and a saponified olefin / vinyl acetate copolymer layer, and a sandwich laminating method in which the adhesive resin composition is melt-extruded between these two layers. Of these, the coextrusion molding method is preferable in terms of interlayer adhesion. As the coextrusion molding method, there are a T-die method using a flat die and an inflation method using a circular die. The flat die may be either a single manifold type using a black box or a multi-manifold type. As the die used for the inflation method, any known die can be used.

The thickness of each layer in such a laminate is as follows:
Although it can be appropriately determined according to the application, usually, when the laminate is obtained as a sheet or a film, the polyethylene resin layer has a thickness of 0.02 to 5 mm, and the intermediate layer as an adhesive has a thickness of 0.1 to 5 mm.
The thickness of the saponified ethylene-vinyl acetate copolymer layer is preferably about 0.01 to 1 mm. Further, the laminate according to the present invention has a structure of (A) / (B) / (C) / (B) / (A) in which the layer (A) is disposed on both sides and a structure further including a polyolefin layer. For example, polypropylene / (B) / (C) / (B) /
A laminate such as (A) may be used.

[0029]

By using such an adhesive resin composition according to the present invention, it is possible to provide a laminate that does not peel off during secondary processing, dropping, or bending. In detail, the adhesive resin composition according to the present invention,
Even if the polyethylene layer (A) and the EVOH layer (C) exhibit strong adhesion, they do not peel off during secondary processing, dropping, or bending, and maintain the strength, appearance, and barrier properties of the laminate. ing.

[0030]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited by the examples.

[0031]

Example 1 (a) Ethylene / propylene random copolymer (hereinafter referred to as EPR; MFR: 1.0 g / 10 min,
Ethylene content: 80 mol%, density: 0.865 g /
cm ³ , crystallinity: 4%), 70% by weight, and (b) an ethylene / vinyl acetate copolymer (hereinafter referred to as EVA; MFR:
2.5 g / 10 min, vinyl acetate content: 25% by weight) 1
0% by weight and (c) maleic anhydride graft-modified polyethylene (hereinafter referred to as MAH-PE; MFR: 0.3 g /
10 minutes, density: 0.925 g / cm ³ , crystallinity: 51
%, Maleic anhydride graft amount: 0.8% by weight) and 5% by weight, and (d) maleic anhydride graft-modified ethylene butene random copolymer (hereinafter referred to as MAH-EBR; MF
R: 2.0 g / 10 min, density: 0.885 g / cm ³ ,
(Crystallinity: 15%, ethylene content: 88 mol%, maleic anhydride graft amount: 0.5% by weight) Composition (I) mixed with 15% by weight (maleic anhydride graft amount of composition (I): 0.12% by weight, crystallinity: 9%, MF
R: 1.1 g / 10 min), linear low density polyethylene (hereinafter referred to as LLDPE-1; MFR: 2.2 g / 10 min,
Density: 0.920 g / cm ³ , 4-methyl-pentene-
1 content: 4 mol%), saponified ethylene / vinyl acetate copolymer (hereinafter referred to as EVOH; MFR: 5.5 g / 1)
0 minutes, density: 1.14 g / cm ³ , ethylene content: 4
Using 4 mol%, trade name EVAL, manufactured by Kuraray Co., Ltd., a five-layer laminated film was formed under the following conditions.

[Film Structure] Film thickness of each layer (μm) LLDPE-1 / (I) / EVOH / (I) / LLDP
E-1 = 30/10/20/10/30 [Extruder] 40 mmφ extruder 220 ° C. (for EVOH) 40 mmφ extruder 220 ° C (for adhesive resin composition) 40 mmφ extruder 220 ° C (for LLDPE-1) [Adhesive strength] The interface adhesion limit between the EVOH layer and the (I) layer of the obtained five-layer film was determined by T-peeling at a peeling speed of 300 mm / min. Table 2 shows the results. [Falling bag test] The obtained film was sealed in a bag shape, and after 200 ml of water was sealed, a drop test was repeated three times from 1.5 m above the ground, and the state change of the bag was examined. Table 2 shows the results. [Bending Fatigue Test] The obtained film was subjected to a gelbo flex test, and the test was performed until a pinhole was recognized in the film sample. Table 2 shows the results.

[0033]

Example 2 The composition ratio of the composition (I) used in Example 1 was (a) 60% by weight of EPR and (b) 10% of EVA.
(C) MAH-PE: 15% by weight, and (d)
Composition (II) mixed with MAH-EBR: 15% by weight
(Amount of grafted maleic anhydride of composition (II): 0.2% by weight, crystallinity: 13%, MFR: 1.0 g / 10 minutes)
The procedure was performed in the same manner as in Example 1 except that Table 2 shows the results.

[0034]

Comparative Example 1 In place of the composition (I) used in Example 1, (e) a high-pressure low-density polyethylene (hereinafter referred to as LDPE; MFR: 3.0 g / 10 min, density: 0.929 g)
/ Cm ³ , crystallinity: 58%) 70% by weight, and (a) E
PR: 15% by weight, and (c) MAH-PE: 15% by weight
(III) (maleic anhydride graft amount of composition (III): 0.12% by weight, crystallinity: 45)
%, MFR: 1.8 g / 10 min). Table 2 shows the results.

[0035]

Comparative Example 2 In place of the composition (I) used in Example 1, (f) a linear low-density polyethylene (hereinafter LLDPE-
2. Copolymerized monomer: butene-1, MFR: 2.
2 g / 10 min, density: 0.922 g / cm ³ , crystallinity: 51%): 65% by weight, (a) EPR: 20% by weight, and (c) MAH-PE: 15% by weight Composition (IV) (maleic anhydride graft amount of composition (IV): 0.12% by weight, crystallinity: 40%, MFR: 1.
(5 g / 10 minutes), except that the reaction was performed in the same manner as in Example 1. Table 2 shows the results.

[0036]

Comparative Example 3 In place of the composition (I) used in Example 1, (g) high density polyethylene (hereinafter referred to as HDPE;
MFR: 0.3 g / 10 min, density: 0.960 g / cm
³ , crystallinity: 78%): 70% by weight, and (a) EP
Composition (V) in which R: 15% by weight and (c) MAH-PE: 15% by weight (maleic anhydride graft amount of composition (V): 0.12% by weight, crystallinity: 50) %, M
FR: 0.4 g / 10 min) was used in the same manner as in Example 1. Table 2 shows the results.

[0037]

[Table 1]

[0038]

[Table 2]

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Claims (5)

[Claims] (1) MFR: 0.1 to 50 g / 10 min Density: 0.850 to 0.900 g / cm ³ Ethylene content: 75 to 95 mol% Crystallinity by X-ray: less than 30% , Ethylene ・ α
-Olefin copolymer: 93 to 50% by weight (b) MFR: 0.1 to 50 g / 10 minutes Vinyl acetate content: 5 to 40% by weight of ethylene
Vinyl acetate copolymer: 5 to 50% by weight (c) Graft amount of unsaturated carboxylic acid or derivative thereof: 0.05 to 15% by weight MFR: 0.1 to 50 g / 10 min Density: 0.900 to 0.1% 980 g / cm ³ X-ray crystallinity: 30% or more, partially or wholly graft-modified polyethylene:
1.0 to 30% by weight, and (d) Graft amount of unsaturated carboxylic acid or derivative thereof: 0.05 to 15% by weight MFR: 0.1 to 50 g / 10 min Density: 0.850 g / cm ³ or more 0 Less than 900 g / cm ³ Crystallinity by X-ray: less than 30%, partially or wholly graft-modified polyethylene:
(A) + (b) +
(C) + (d) with a total weight of 100% by weight, the graft amount of the whole composition being 0.01 to 3% by weight, and MF
R is 0.1 to 50 g / 10 min, and the degree of crystallinity is less than 35%. 2. A laminate comprising at least the three layers described below. Layer (A) made of polyethylene, (a) MFR: 0.1 to 50 g / 10 min Density: 0.850 to 0.900 g / cm ³ Ethylene content: 75 to 95 mol% Crystallinity by X-ray: 30 %, Ethylene-α
-Olefin copolymer: 93 to 50% by weight (b) MFR: 0.1 to 50 g / 10 minutes Vinyl acetate content: 5 to 40% by weight of ethylene
Vinyl acetate copolymer: 5 to 50% by weight (c) Graft amount of unsaturated carboxylic acid or derivative thereof: 0.05 to 15% by weight MFR: 0.1 to 50 g / 10 min Density: 0.900 to 0.1% 980 g / cm ³ X-ray crystallinity: 30% or more, partially or wholly graft-modified polyethylene:
1.0 to 30% by weight, and (d) Graft amount of unsaturated carboxylic acid or derivative thereof: 0.05 to 15% by weight MFR: 0.1 to 50 g / 10 min Density: 0.850 g / cm ³ or more 0 Less than 900 g / cm ³ Crystallinity by X-ray: less than 30%, partially or wholly graft-modified polyethylene:
(A) + (b) +
(C) + (d) with a total weight of 100% by weight, the graft amount of the whole composition being 0.01 to 3% by weight, and MF
An intermediate layer (B) of an adhesive resin composition having an R of 0.1 to 50 g / 10 min and a crystallinity of less than 35%;
Saponified vinyl acetate copolymer layer (C). 3. A film comprising the laminate according to claim 2. 4. A tube comprising the laminate according to claim 2. 5. A bottle comprising the laminate according to claim 2.