JPH09249779A - Adhesive polyethylene composition and multilayer laminated film prepared by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyethylene composition having excellent adhesiveness characteristics and heat resistance by mixing a resin and/or an elastomer comprising a specified modified ethylene/α-olefin copolymer resin or elastomer and an unmodified gthylene/α-olefin copolymer with a tackifier. SOLUTION: This composition comprises a modified ethylene/α-olefin copolymer resin or elastomer prepared by modifying an unmodified ethylene/α-olefin copolymer resin or elastomer being an ethylene/3-20 C α-olefin copolymer having a density of 0.860-0.930g/cm<3> and a degree of crystallinity of 60% or below (as measured by an X-ray diffraction method) with an unsaturated carboxylic acid or its derivative and having a graft amount of 0.01-5wt.%, an unmodified ethylene/α-olefin copolymer resin and/or an elastomer and a tackifier.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an adhesive polyethylene composition and a multilayer laminated film using the composition,
More specifically, an adhesive polyethylene composition suitable for adhering an ethylene polymer layer and a layer made of a polyamide resin and / or an ethylene / vinyl alcohol copolymer, and a multi-layer laminate using the composition as an adhesive layer. Regarding film.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a laminated film of an ethylene polymer and a polyamide resin, and a laminated film of an ethylene polymer and an ethylene / vinyl alcohol copolymer have been known. Various materials for the adhesive layer used at that time have been proposed.
For example, in JP-A-57-165413, a modified polyethylene obtained by reacting a linear low-density polyethylene with an unsaturated carboxylic acid or a derivative thereof, and further a synthetic rubber and / or a linear low-density polyethylene are blended with the modified polyethylene. It is disclosed that the modified polyethylene composition described above can be used as a material for an adhesive layer. Further, JP-A-57-165469 discloses an adhesive resin composition obtained by modifying a mixture of linear low density polyethylene and synthetic rubber with an unsaturated carboxylic acid or a derivative thereof.

[0003] However, the conventionally proposed materials for the adhesive layer have an ethylene-based polymer layer and a polyamide resin layer or an ethylene / vinyl alcohol copolymer layer when subjected to a stretching treatment during the production of a shrink film, for example. There has been a problem that the interlayer adhesive strength is significantly reduced, and a laminated film that does not necessarily exhibit a sufficiently satisfactory adhesive strength cannot be obtained.

The shrink film is used for packaging an object to be packaged, such as ham, by using an automatic packaging machine.
The edges of the film are heat-sealed with each other, but it is required to exhibit high heat-sealing strength because stress is applied to the sealing portion in the subsequent heat shrinking step.

Furthermore, since shrink films are often subjected to boil sterilization treatment at a high temperature of 80 ° C. or higher after packaging of food contents, heat resistance of 80 ° C. or higher is required. Therefore, the appearance of an adhesive polyethylene composition having excellent adhesive strength characteristics, heat seal strength characteristics, and heat resistance with respect to an ethylene-based polymer, a polyamide resin, and an ethylene / vinyl alcohol copolymer, and an adhesive layer comprising the composition. There is a demand for the appearance of a multilayer laminated film in which the above is interposed between an ethylene-based polymer layer and a layer composed of a polyamide resin and / or an ethylene / vinyl alcohol copolymer.

[0006]

An object of the present invention is to provide an adhesive polyethylene composition which exhibits excellent adhesive strength characteristics, heat seal strength characteristics and heat resistance to ethylene-based polymers, polyamide resins and ethylene / vinyl alcohol copolymers. To do.

Another object of the present invention is to use the above adhesive polyethylene composition of the present invention between an ethylene polymer layer and a layer comprising a polyamide resin and / or an ethylene / vinyl alcohol copolymer. The object is to provide a multilayer laminated film having an adhesive layer.

Further, another object of the present invention is to exhibit excellent adhesive strength characteristics in both unstretched and stretched,
Another object of the present invention is to provide a multilayer laminated film having an adhesive layer made of the adhesive polyethylene composition of the present invention.

[0009]

SUMMARY OF THE INVENTION An adhesive polyethylene composition according to the present invention is a copolymer of [I] ethylene and an α-olefin having 3 to 20 carbon atoms, and (i) has a density of 0.860 to 0. ．
(Ii) Unmodified ethylene / α-olefin copolymer resin [A1] or unmodified ethylene / α-olefin having a crystallinity of 60% or less measured by X-ray diffractometry in the range of 930 g / cm ^3. Copolymer elastomer [B1]
Modified with unsaturated carboxylic acid or a derivative thereof, the amount of grafted ethylene / α- is 0.01 to 5% by weight.
Olefin copolymer resin [A2] or modified ethylene
α-olefin copolymer elastomer [B2] and [II] unmodified ethylene / α-olefin copolymer resin [C1] and / or unmodified ethylene / α-olefin copolymer elastomer [C2] and [III] The composition contains a tackifier [D], and the composition has a content of (a) the tackifier [D] of 0. 1-2
0% by weight, (b) the graft amount of the unsaturated carboxylic acid or its derivative is in the range of 0.01 to 1.0% by weight, and (c) the density. Is in the range of 0.880 to 0.920 g / cm ³ ,
(D) The crystallinity measured by X-ray diffraction is 15 to 50.
%, And (e) melt flow rate (ASTM
D 1238, 190 ° C, 2.16 kg load) is 0.1
It is characterized by being in the range of up to 50 g / 10 minutes.

The adhesive polyethylene composition according to the present invention as described above is suitable as an adhesive resin composition for shrink films. Further, the multilayer laminated film according to the present invention comprises an ethylene polymer layer [I] made of an ethylene polymer having an ethylene content of 70 mol% or more, and an adhesive layer [II] made of the adhesive polyethylene composition. A polyamide resin layer [III], an ethylene / vinyl alcohol copolymer layer [IV] or a mixed layer [V] of a polyamide resin and an ethylene / vinyl alcohol copolymer are laminated in this order to form three or more layers. It is characterized by being a laminated body.

As the ethylene polymer, low density polyethylene or ethylene / vinyl acetate copolymer is preferable.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The adhesive polyethylene composition according to the present invention and the multilayer laminated film using the composition will be specifically described below.

Adhesive Polyethylene Composition First, the adhesive polyethylene composition according to the present invention will be described. The adhesive polyethylene composition according to the present invention,
Specific ethylene / α-olefin copolymer resin [A1]
Alternatively, a modified ethylene / α-olefin copolymer resin [A2] or a modified ethylene / α-olefin copolymer elastomer obtained by graft-modifying an ethylene / α-olefin copolymer elastomer [B1] with an unsaturated carboxylic acid or a derivative thereof. [B2] and unmodified ethylene / α-olefin copolymer resin [C1] and / or unmodified ethylene / α-olefin copolymer elastomer [C2]
And a tackifier [D].

<Unmodified ethylene / α-olefin copolymer resin [A1], [C1]> The unmodified ethylene / α-olefin copolymer resin [A1] used in the present invention comprises ethylene and 3 carbon atoms. .About.20 .alpha.-olefins.

The ethylene content of the ethylene / α-olefin copolymer resin [A1] is 70 mol% or more, preferably 75 to 95 mol%. As the α-olefin, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene,
1-decene and the like. Among them, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferably used. These α-olefins can be used alone or in combination of two or more.

The ethylene / α-olefin copolymer resin [A1] has a density of 0.860 to 0.930 g / c.
m ³ , preferably above 0.900 g / cm ³ and 0.93
0 g / cm ³ or less, more preferably 0.905 to 0.9
It is in the range of 25 g / cm ³ .

Further, the ethylene / α-olefin copolymer resin [A1] has a temperature (melting point; T at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC).
m) is 125 ° C. or lower, preferably 100 to 125 ° C.

Furthermore, the ethylene / α-olefin copolymer resin [A1] has a crystallinity of 60% or less, preferably 20 to 50%, more preferably 30 to 45%, as measured by an X-ray diffraction method. In range.

Further, the melt flow rate (MFR; ASTM D 1) of the ethylene / α-olefin copolymer resin [A1]
238, 190 ℃, 2.16kg load) is usually 0.01-100g
/ 10 minutes, preferably 0.1 to 50 g / 10 minutes, and more preferably 0.2 to 20 g / 10 minutes.

The unmodified ethylene / α-olefin copolymer resin [C1] preferably used in the present invention is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms and has (i) a density Exceeds 0.900 g / cm ³ ,
It is in the range of 0.930 g / cm ³ or less, and (ii) the temperature (melting point; Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) is 125 ° C. or less, preferably 100 to 125 ° C. And (iii) ethylene / α-having a crystallinity of 60% or less measured by an X-ray diffraction method.
It is an olefin copolymer resin [C1]. Ethylene / α
-The olefin copolymer resin [C1] may be the same as or different from [A1].

Ethylene / α-having the above physical properties
The olefin copolymer resin [A1] or [C1] can be produced by a conventionally known method using a catalyst such as titanium (Ti) type or zirconium (Zr) type. <Unmodified ethylene / α-olefin copolymer elastomer [B1], [C2]> The unmodified ethylene / α-olefin copolymer elastomer [B1] and [C2] used in the present invention are ethylene and carbon atoms, respectively. Number 3 to 2
0-α-olefin copolymer having a density of usually 0.860 to 0.930 g / cm ³ , preferably 0.860.
~ 0.900 g / cm ³ , more preferably 0.860 ~
0.895 g / cm ³ , especially 0.860 to 0.890 g
/ In the range of cm ^3, a melt flow rate (MFR; A
STM D 1238, 190 ℃, 2.16kg load) is usually 0.01-2
00 g / 10 minutes, preferably 0.01 to 100 g / 10
Min, more preferably 0.05 to 50 g / 10 min.

Further, such ethylene / α-olefin copolymer elastomers [B1] and [C2] have X
It is desirable that the crystallinity measured by the line diffraction method is less than 30% or that the crystallinity is amorphous.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-
Mention may be made of hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Of these, it is particularly preferable to use an α-olefin having 3 to 10 carbon atoms.

The ethylene / α-olefin copolymer elastomers [B1] and [C2] used in the present invention are
A constituent unit other than a constituent unit derived from an α-olefin, such as a constituent unit derived from a diene compound, may be contained within a range that does not impair the characteristics.

For example, ethylene used in the present invention
Specific examples of the constituent units that are allowed to be contained in the α-olefin copolymer elastomers [B1] and [C2] include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1, A structural unit derived from a chain non-conjugated diene such as 5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene; cyclohexadiene,
Dicyclopentadiene, methyltetrahydroindene,
5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene
-2-norbornene, 6-chloromethyl-5-isopropenyl
-2-Structural units derived from cyclic non-conjugated dienes such as norbornene; 2,3-diisopropylidene-5-norbornene,
2-ethylidene-3-isopropylidene-5-norbornene,
A structural unit derived from a diene compound such as 2-propenyl-2,2-norbornadiene can be mentioned.

Such dienes can be used alone or in combination. The content of the structural unit derived from such a diene is usually 10 mol% or less, preferably 0 to 5 mol%.

The ethylene / α-olefin copolymer elastomers [B1] and [C2] may be the same or different. These ethylene / α-olefin copolymer elastomers [B1] and [C2] can be prepared by a conventionally known method using a Ti-based catalyst, a vanadium (V) -based catalyst, a Zr-based catalyst, or the like.

<Modified ethylene / α-olefin copolymer resin [A2]> Modified ethylene / α-olefin used in the present invention
The olefin copolymer resin [A2] is obtained by graft-modifying the unmodified ethylene / α-olefin copolymer resin [A1] with an unsaturated carboxylic acid or a derivative thereof.

In the modified ethylene / α-olefin copolymer resin [A2] used in the present invention, the grafting amount of the unsaturated carboxylic acid or its derivative is 100% by weight of the modified ethylene / α-olefin copolymer resin [A2]. %,
It is in the range of 0.01 to 5% by weight, preferably 0.1 to 3% by weight.

Specific examples of the unsaturated carboxylic acid grafted to the unmodified ethylene / α-olefin copolymer resin [A1] include acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid. Can be mentioned. Examples of the derivative of the unsaturated carboxylic acid include acid anhydrides, esters, amides, imides, and metal salts. Specifically, maleic anhydride, hymic acid anhydride ^TD (endic acid anhydride), itaconic anhydride, citraconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, glycidyl acrylate, malein. Acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid monomethyl ester, itaconic acid diethyl ester, acrylamide, methacrylamide,
Maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid-
N, N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monobutylamide, fumaric acid-
Examples thereof include N, N-dibutylamide, maleimide, N-butylmaleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate and the like. Of these grafting monomers, it is most preferable to use maleic anhydride or hymic acid anhydride ^TD .

Graft modification of the ethylene / α-olefin copolymer resin [A1] with the above-mentioned unsaturated carboxylic acid or its derivative (graft monomer) can be carried out by various conventionally known methods.

For example, a melt modification method in which an ethylene / α-olefin copolymer resin [A1] is melted using an extruder, and a graft monomer is added to carry out graft copolymerization,
Alternatively, ethylene / α-olefin copolymer resin [A
1] is dissolved in a solvent, a graft monomer is added, and graft copolymerization is carried out. Of these, the melt modification method using an extruder is preferable. In any of the modification methods, in order to efficiently graft-copolymerize the graft monomer, it is preferable to start the reaction in the presence of a radical initiator.

As the radical initiator, organic peroxide, organic perester and the like are preferably used. Specifically, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3,1,4-bis (tert -Butylperoxyisopropyl) Organic peroxides such as benzene and lauroyl peroxide; tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy)
Hexine-3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, ter
t-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate,
tert-butyl perpivalate, cumyl perpivalate,
Organic peresters such as tert-butyl perdiethyl acetate; azo compounds such as azoisobutyronitrile and dimethylazoisobutyrate are used. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3,2,5-dimethyl-2,5-di (tert-butyl Dialkyl peroxides such as peroxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

The above radical initiator is usually used in a proportion of 0.001 to 1 part by weight with respect to 100 parts by weight of the ethylene / α-olefin copolymer resin [A1]. In addition, another monomer such as styrene may be allowed to coexist in the graft reaction.

The amount of the unsaturated carboxylic acid or its derivative grafted onto the ethylene / α-olefin copolymer resin [A1] (referred to as "grafting amount") is the modified ethylene / α-olefin copolymer resin [A2]. ] In the range of 0.01 to 5% by weight with respect to 100% by weight.

<Modified Ethylene / α-Olefin Copolymer Elastomer [B2]> The modified ethylene / α-olefin copolymer elastomer [B2] used in the present invention is the above-mentioned unmodified ethylene / α-olefin copolymer elastomer [B1]. ] Is graft-modified with unsaturated carboxylic acid or its derivative.

The modified ethylene / α-olefin copolymer elastomer [B2] preferably used in the present invention is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms and has a density (i) of 0.860-0.900g
/ Cm ³ range, and (ii) the graft amount obtained by modifying an ethylene / α-olefin copolymer elastomer having a crystallinity of less than 30% measured by an X-ray diffraction method with an unsaturated carboxylic acid or a derivative thereof. Of 0.01 to 5% by weight is a modified ethylene / α-olefin copolymer elastomer.

For the graft modification of the ethylene / α-olefin copolymer elastomer [B1], the same unsaturated carboxylic acid or derivative thereof as used in the above-mentioned production of the ethylene / α-olefin copolymer resin [A2] can be used. Unsaturated carboxylic acids or their derivatives can be used. As the method for graft-modifying the ethylene / α-olefin copolymer elastomer [B1], the same method as the graft-modifying method for producing the ethylene / α-olefin copolymer resin [A2] described above may be adopted. it can.

<Tackifier [D]> The tackifier [D] used in the present invention is a solid amorphous polymer, and is usually used as a tackifier for adhesive tapes, paints, and hot melt adhesives. The following resins can be listed according to the difference in the type of monomer source used for polymerization.

[0040] For example, petroleum, C ₄ fraction obtained by decomposition of naphtha, C ₅ fraction, isoprene and 1,3-pentadiene mixtures thereof, or any of these fractions, for example, C ₅ distillate An aliphatic hydrocarbon resin whose main raw material is; etc .; an aromatic hydrocarbon resin whose main raw material is a styrene derivative and indene in a C ₉ fraction obtained by decomposing petroleum, naphtha, etc .; a C ₄ fraction and Aliphatic / Aromatic Copolymerized Hydrocarbon Resin Copolymerized with Any Fraction of C ₅ Fraction and C ₉ Fraction; Alicyclic Hydrocarbon Resin Hydrogenated with Aromatic Hydrocarbon Resin; Aliphatic , Synthetic terpene hydrocarbon resins having a structure containing alicyclic and aromatic hydrocarbon resins; terpene hydrocarbon resins starting from α, β-pinene in turpentine oil; indene and styrenes in coal tar naphtha The original Low molecular weight styrene resin; coumarone indene hydrocarbon resins and rosin-based hydrocarbon resins.

Among these tackifiers [D], an aliphatic hydrocarbon resin and an alicyclic hydrocarbon resin obtained by hydrogenating an aromatic hydrocarbon resin are modified ethylene / α-olefin copolymer resins. [A2] or modified ethylene / α
-Olefin copolymer elastomer [B2], unmodified ethylene / α-olefin copolymer resin [C1] or unmodified ethylene / α-olefin copolymer elastomer [C2] has good dispersibility and is preferably used. .
Further, an alicyclic hydrocarbon having a softening point (ring and ball method) of 105 to 150 ° C., preferably 110 to 140 ° C., and a hydrogenation rate to an aromatic nucleus of 80% or more, preferably 85% or more. Is particularly preferable.

<Adhesive Polyethylene Composition> The adhesive polyethylene composition according to the present invention has a density of 0.880 to
0.920 g / cm ³ , preferably 0.900 to 0.9
It is in the range of 20 g / cm ³ . Density is the melt flow rate (MFR) at 2.16 kg load at 190 ° C
The strand obtained at the time of measurement is heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and then measured with a density gradient tube.

The crystallinity of this composition as measured by the X-ray diffraction method is 15 to 50%, preferably 30 to 45.
% Range. Further, this composition has a graft amount of unsaturated carboxylic acid or a derivative thereof of 100 or less.
It is in the range of 0.01 to 1.0% by weight, preferably 0.1 to 0.8% by weight, based on the weight%.

The composition has a melt flow rate (ASTM D 1238, 190 ° C., 2.16 kg load) of 0.1 to 50.
g / 10 minutes, preferably 0.2 to 10 g / 10 minutes, more preferably 0.5 to 5 g / 10 minutes.

The composition ratio of the adhesive polyethylene composition according to the present invention is as follows. (1) The adhesive polyethylene composition according to the present invention comprises a modified ethylene / α-olefin copolymer resin [A2], an unmodified ethylene / α-olefin copolymer resin [C1] and a tackifier [D]. In this case, this composition comprises a modified ethylene / α-olefin copolymer resin [A2] and an unmodified ethylene / α-olefin copolymer resin [C1],
10/90 to 70/30, preferably 20/80 to 60
It is contained in a weight ratio ([A2] / [C1]) of / 40. (2) The adhesive polyethylene composition according to the present invention comprises a modified ethylene / α-olefin copolymer resin [A2] and an unmodified ethylene / α-olefin copolymer elastomer [C
2] and a tackifier [D], the composition is a modified ethylene / α-olefin copolymer resin [A
2] and the unmodified ethylene / α-olefin copolymer elastomer [C2] are 95/5 to 5/95, preferably 90/10 to 10/90, and particularly preferably 80/20 to
It is contained in a weight ratio of 20/80 ([A2] / [C2]). (3) The adhesive polyethylene composition according to the present invention is modified ethylene / α-olefin copolymer resin [A2], unmodified ethylene / α-olefin copolymer resin [C1], unmodified ethylene / α-olefin. When composed of a copolymer elastomer [C2] and a tackifier [D], the composition comprises a modified ethylene / α-olefin copolymer resin [A2] and an unmodified ethylene / α-olefin copolymer resin [C1. ] And an unmodified ethylene / α-olefin copolymer elastomer [C2], 95/5 to 5/95,
Preferably 90/10 to 10/90, particularly preferably 8
It is contained in a weight ratio of 0/20 to 20/80 ([A2] + [C1] / [C2]), and is a modified ethylene / α-olefin copolymer resin [A2] and unmodified ethylene / α. -Weight ratio ([A2] / [C1]) of olefin copolymer resin [C1] is 1
0/90 to 70/30, preferably 20/80 to 60 /
40. (4) The adhesive polyethylene composition according to the present invention is a modified ethylene / α-olefin copolymer elastomer [B
2], an unmodified ethylene / α-olefin copolymer resin [C1] and a tackifier [D], the composition is modified ethylene / α-olefin copolymer resin [B2] and unmodified ethylene. .Alpha.-Olefin copolymer resin [C1], 5/95 to 95/5, preferably 90
/ 10 to 10/90, particularly preferably 80/20 to 20
It is contained in a weight ratio ([B2] / [C1]) of / 80. (5) The adhesive polyethylene composition according to the present invention is a modified ethylene / α-olefin copolymer elastomer [B
2], an unmodified ethylene / α-olefin copolymer resin [C1], an unmodified ethylene / α-olefin copolymer elastomer [C2] and a tackifier [D], the composition is modified ethylene.・ Α-Olefin copolymer elastomer [B2] and unmodified ethylene ・ α-
The olefin copolymer elastomer [C2] and the unmodified ethylene / α-olefin copolymer resin [C1] were mixed with 95
/ 5 to 5/95, preferably 90/10 to 10/90,
The weight ratio ([B2] + [C2] / [C] is more preferably 80/20 to 20/80, particularly preferably 75/25 to 50/50.
1]) and modified ethylene / α-olefin copolymer elastomer [B2] and unmodified ethylene /
The weight ratio ([B2] / [C2]) with the α-olefin copolymer elastomer [C2] is 100/0 to 30/70, preferably 100/0 to 40/60.

In the compositions (1) to (5), the tackifier [D] is used in an amount of 100% by weight of the entire composition.
It is used in a proportion of 0.5 to 30% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight.

Among the adhesive polyethylene compositions according to the present invention, modified ethylene / α-olefin copolymer elastomer [B2], unmodified ethylene / α-olefin copolymer resin [C1] and tackifier [D]. The polyethylene composition consisting of (3) is most preferable because it has the best adhesion. In this polyethylene composition, the modified ethylene / α-olefin copolymer elastomer [B2] is the entire composition 10
5 to 95% by weight, preferably 10 to 0% by weight
It is contained in an amount of 50% by weight, more preferably 20 to 40% by weight.

<Preparation of Adhesive Polyethylene Composition> In the adhesive polyethylene composition of the present invention, the above components are mixed by a conventionally known method, for example, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender or the like. Alternatively, the mixture obtained by such a method is further melt-kneaded with a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, etc., and then granulated or by crushing the obtained resin mass. Obtainable.

In the present invention, various compounding agents such as heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, nucleating agents, pigments, dyes and the like, which are usually added to polyolefins in the composition, and other components. Polyolefins, saponified products of ethylene / α-olefin copolymers, polyester resins, polyamide resins, waxes and the like can be added within a range that does not impair the object of the present invention.

The adhesive polyethylene composition according to the present invention comprising the above components is an ethylene-based polymer,
Exhibits high adhesion to polyamide resins and ethylene / vinyl alcohol copolymers.

Multilayer Laminated Film Next, the multilayer laminated film according to the present invention will be described. The multilayer laminated film according to the present invention comprises an ethylene polymer layer [I] made of an ethylene polymer, an adhesive layer [II] made of the adhesive polyethylene composition according to the present invention, and a polyamide resin layer [III], Ethylene / vinyl alcohol copolymer layer [IV] or mixed layer of polyamide resin and ethylene / vinyl alcohol copolymer [V]
And is a laminated body of three or more layers laminated in this order.

The ethylene polymer has an ethylene content of 70 mol% or more, usually 70 to 100 mol%, preferably 80 to 100 mol%. Specific examples of such an ethylene polymer include high-density polyethylene, linear low-density polyethylene, high-pressure low-density polyethylene, ethylene-vinyl acetate copolymer (EVA),
Examples thereof include ethylene / ethyl acrylate copolymer, ethylene / acrylic acid copolymer, and ionomer resin. Among them, low-density polyethylene, EVA, particularly linear low-density polyethylene or EVA having a density of 0.930 g / cm ³ or less is preferably used.

As the polyamide resin, specifically, nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, MXD nylon, amorphous nylon, terephthalic acid / adipic acid / hexamethylenediamine copolymer and the like are preferable. Used.

As the ethylene / vinyl alcohol copolymer, a copolymer having an ethylene content of 20 to 50 mol% is preferably used. Such an ethylene / vinyl alcohol copolymer can be prepared by saponifying a copolymer of ethylene and vinyl acetate.

Specific examples of the multilayer laminated film according to the present invention include the following modes. (1) Three-layer laminated film of ethylene polymer layer [I] / adhesive layer [II] / polyamide resin layer [III] (2) Ethylene polymer layer [I] / adhesive layer [II] / ethylene vinyl alcohol Three-layer laminated film of polymer layer [IV] (3) Ethylene polymer layer [I] / adhesive layer [II] / three-layer laminated film of mixed layer [V] of polyamide resin and ethylene / vinyl alcohol copolymer (4) 4-layer laminated film of ethylene-based polymer layer [I] / adhesive layer [II] / polyamide resin layer [III] / ethylene / vinyl alcohol copolymer layer [IV] (5) ethylene-based polymer layer [I] / Adhesive layer [II] / Ethylene / vinyl alcohol copolymer layer [IV] / Polyamide resin layer [III] 4-layer laminated film (6) Ethylene polymer layer [I] / Adhesive layer [II] / Polyamide resin Copolymerization of ethylene and vinyl alcohol 4-layer laminated film of mixed layer with polymer [V] / polyamide resin layer [III] (7) Ethylene polymer layer [I] / adhesive layer [II] / mixture of polyamide resin and ethylene / vinyl alcohol copolymer 4-layer laminated film of layer [V] / ethylene / vinyl alcohol copolymer layer [IV] (8) Ethylene polymer layer [I] / adhesive layer [II] / polyamide resin layer [III] / adhesive layer [II] ] / 5-layer laminated film of ethylene polymer layer [I] (9) Ethylene polymer layer [I] / adhesive layer [II] / ethylene / vinyl alcohol copolymer layer [IV] / adhesive layer [II] / Five-layer laminated film of ethylene polymer layer [I] (10) Ethylene polymer layer [I] / adhesive layer [II] / mixed layer [V] of polyamide resin and ethylene / vinyl alcohol copolymer / adhesive layer 5 of [II] / ethylene polymer layer [I] Layer Laminated Film (11) Ethylene polymer layer [I] / Adhesive layer [II] / Ethylene / vinyl alcohol copolymer layer [IV] / Adhesive layer [I
I] 4-layer laminated film (12) Ethylene polymer layer [I] / adhesive layer [II] / polyamide resin layer [III] / adhesive layer [II] 4-layer laminated film Multi-layer laminated film according to the present invention, for example The three-layer laminated film can be produced by laminating an ethylene polymer layer, an adhesive layer, and a layer made of a polyamide resin and / or an ethylene / vinyl alcohol copolymer in a molten state.

The multilayer laminated film can be produced by, for example, coextrusion molding, cast film molding, inflation film molding, and tenter or tubular biaxial stretching method.

When the multilayer laminated film according to the present invention is cast by the T-die method, if the molding speed is set to a high speed of, for example, 20 m / min or more, preferably 20 to 150 m / min, a high adhesive force is obtained. The multilayer laminated film shown can be obtained. The multilayer laminated film according to the present invention may be in an unstretched state as it is after molding, or may be in a state stretched in at least uniaxial direction, preferably biaxial direction after molding. When the polyamide resin layer [III] is contained in the multilayer laminated film, it is preferably stretched before use. When the multilayer laminated film contains the ethylene / vinyl alcohol copolymer layer [IV], it can be used in either unstretched or stretched state.
Since a high-strength film can be obtained by stretching,
When high strength is required for the film, a stretched multilayer laminated film is preferable. Generally, when the film is stretched, the adhesive strength of the adhesive layer is greatly reduced, but the multilayer laminated film according to the present invention does not have a large decrease in the adhesive strength even when stretched, and has a sufficiently practical adhesiveness. Holding power. Stretching is preferably carried out at a uniaxial direction at a stretch ratio of 1.5 to 6 times. In the biaxial stretching, it is preferable to stretch in the biaxial direction at a stretching ratio of 1.5 to 6 times.

The stretching conditions for producing a multilayer laminated film as a shrink film are usually a stretching temperature of 70 to 130 ° C. and a stretching ratio (longitudinal direction × horizontal direction) of 2 × 2 to 5 × 5 times. is there. The thickness of the film produced under such conditions is 10 to 200 μm. The film is heat shrinkable between 70 and 130 ° C. with a length or width of 5% to 50%.

[0059]

The adhesive polyethylene composition according to the present invention exhibits excellent adhesive strength characteristics, heat seal strength characteristics and heat resistance with respect to ethylene polymers, polyamide resins and ethylene / vinyl alcohol copolymers.

Further, the multilayer laminated film according to the present invention is
Excellent adhesive strength characteristics in both unstretched and stretched, excellent strength, heat resistance and gas barrier properties,
Also, it has excellent heat shrinkage characteristics.

Therefore, the multilayer film according to the present invention can be suitably used as a shrink film, for general food packaging and meat packaging such as ham.

[0062]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0063]

Example 1 [Modified ethylene / 1-butene copolymer resin (MAH-PE
-1) Production] Ethylene prepared using a Ti-based catalyst
1-butene copolymer resin [abbreviated as PE-1; density = 0.9
20 g / cm ³ , melting point (Tm) = 124 ° C., crystallinity =
48%, MFR (ASTM D 1238, 190 ° C, 2.16kg load)
= 2.0 g / 10 minutes, ethylene content = 96 mol%] 1
00 parts by weight, maleic anhydride 0.8 parts by weight, and peroxide [trade name Perhexin-25B, NOF Corporation]
Made] 0.07 parts by weight with a hexshell mixer,
The resulting mixture was melt-graft modified with a 65 mmφ uniaxial extruder set at 230 ° C. to obtain a modified ethylene / 1-butene copolymer resin [abbreviated as MAH-PE-1].
I got

When the grafting amount of the modified ethylene / 1-butene copolymer resin (MAH-PE-1) was measured by IR analysis, the maleic anhydride grafting amount was 0.8% by weight. MFR (190 ℃, 2.16kg load) is 0.27
g / 10 min, melting point 122 ° C. [Production of Modified Polyethylene Composition (1)] Modified ethylene / 1-butene copolymer resin (M
AH-PE-1) 10 parts by weight, and unmodified ethylene 1-
30 parts by weight of butene copolymer resin (PE-1) and ethylene / propylene copolymer rubber prepared using a V-based catalyst [abbreviated as EPR; density = 0.865 g / cm ³ , MFR
(190 ° C., 2.16 kg load) = 2.9 g / 10 minutes, ethylene content = 80 mol%] 30 parts by weight, and ethylene / 1-butene copolymer rubber prepared by using a V-based catalyst [abbreviated as EBR Density = 0.885 g / cm ³ , MFR (ASTM D 123
8, 190 ° C., 2.16 kg load) = 3.6 g / 10 minutes, 25 parts by weight of ethylene content: 90 mol%, and 5 parts by weight of tackifier [trade name: Alcon P125, manufactured by Arakawa Chemical Co., Ltd.]
Irganox 1010 [trade name, manufactured by Ciba-Geigy Japan, stabilizer] 0.05 parts by weight, and Irgafos 168
[Brand name, manufactured by Ciba-Geigy Japan, Stabilizer] 0.10 parts by weight, synthetic hydrotalcite [Brand name DHT-4
A, Kyowa Chemical Co., Ltd., stabilizer] 0.03 part by weight was mixed and mixed with a uniaxial extruder to obtain a modified polyethylene composition (1).

The composition (1) thus obtained had a density of 0.90.
4 g / cm ³ , MFR (ASTMD 1238, 190 ° C, 2.
16 kg load) is 2.0 g / 10 minutes, the amount of maleic anhydride grafted is 0.08% by weight, and the crystallinity is 35.
%Met.

Then, a multi-layer stretched film was prepared using this composition (1) and tested for its adhesive strength with an ethylene / vinyl acrole copolymer (EVOH), heat seal strength and heat resistance. (I) Method for testing adhesive strength with ethylene / vinyl alcohol copolymer Ethylene / vinyl alcohol copolymer (EVOH; trade name Eval EP-E105, manufactured by Kuraray Co., Ltd., MFR
(ASTM D 1238, 190 ° C., 2.165 kg load) = 5.
5 g / 10 min, ethylene content = 44 mol%), the modified polyethylene composition (1) and unmodified ethylene.
Using 1-butene copolymer resin (PE-1), a three-layer coextrusion cast film was molded under the following conditions.

<Molding conditions> Film layer constitution and thickness of each layer: EVOH (outer layer) / composition (1) (middle layer) / PE-1 (inner layer) = 40/40 /
160μm Molding machine: Die diameter 40mmφ Extruder (for outer layer) Set temperature ・ ・ ・ 220 ℃ Die diameter 40mmφ Extruder (for intermediate layer) Set temperature ・ ・ ・ 220 ℃ Die diameter 40mmφ Extruder (for inner layer) Set temperature ・ ・220 ° C. Molding speed: 5 m / min The three-layer film obtained as described above was heated at 80 ° C. for 10 minutes using a biaxial stretching device manufactured by Toyo Seiki Seisakusho, and then at that temperature. A three-layer stretched film was produced by simultaneously biaxially stretching three times in the machine direction and three times in the transverse direction.

Subsequently, this three-layer stretched film was cooled to room temperature, and the interlayer adhesion strength (peel strength) between the EVOH layer and the composition layer of the three-layer stretched film was T-shaped peeled at a peeling speed of 300 mm / min. I asked. (II) Method for testing heat-sealing strength Two sheets of the above-mentioned three-layer stretched film are superposed and heat-sealed under the following conditions using a heat sealer [trade name: Heat Seal Tester TP-701B] manufactured by Tester Sangyo Co., Ltd. The adhesive strength is the same as that of (I) above.
A mold peeling test was performed and measured.

<Heat Sealing Conditions> Temperature: 140 ° C. Sealing pressure: 2 kg / cm ² Sealing time: 1 second (III) Test method for heat resistance Between two sheets of the above biaxially stretched film (square of 15 cm on a side) Then, a wooden rectangular parallelepiped (10 cm × 10 cm × 2 cm) was sandwiched, and four sides of the film were heat-sealed under the above conditions.

Next, the heat-sealed film was immersed in warm water at 90 ° C. for 10 minutes to shrink the film, and the broken state of the film was observed.

The test results are shown in Table 1.

[0072]

[Examples 2 and 3] In Example 1, MAH-PE-
1, PE-1, EPR, EBR and tackifier first
In the same manner as in Example 1 except that the proportions shown in the table were used,
Modified polyethylene compositions (2) and (3) were obtained.

The density of these compositions, MFR (ASTM D 1
238, 190 ℃, 2.16kg load), maleic anhydride graft amount and crystallinity are shown in Table 1. Hereinafter, using these compositions, a three-layer stretched film was prepared in the same manner as in Example 1, and the above test was conducted.

The results are shown in Table 1.

[0075]

Examples 4 and 5 In Example 1, an ethylene / 1-octene copolymer rubber prepared by using a Zr-based catalyst instead of EBR [abbreviated as EOR; density = 0.870 g / c
m ³ , MFR (ASTM D 1238, 190 ℃, 2.16kg load) =
5.8 g / 10 min, ethylene content = 85 mol%] in the proportions shown in Table 1, and tackifier Alcon P1
Tackifier Escoletz 53 instead of 25 (trade name)
Modified polyethylene compositions (4) and (5) were obtained in the same manner as in Example 1 except that 20 [trade name, manufactured by Tonex Corporation] was used in the proportions shown in Table 1.

The density of these compositions, MFR (ASTM D 1
238, 190 ℃, 2.16kg load), maleic anhydride graft amount and crystallinity are shown in Table 1. Hereinafter, using these compositions, a three-layer stretched film was prepared in the same manner as in Example 1, and the above test was conducted.

The results are shown in Table 1.

[0078]

Examples 6 and 7 [Modified ethylene / 1-butene copolymer elastomer (MA
Production of H-PE-2)] EBR of Example 1 prepared using a V-based catalyst [density = 0.885 g / cm ³ , MFR
(ASTM D 1238, 190 ° C, 2.16kg load) = 3.6g / 10
Min, ethylene content = 90 mol%, melting point (Tm) = 72
C, crystallinity = 16%] 100 parts by weight, maleic anhydride 0.5 parts by weight, peroxide [trade name Perhexin-
25B, manufactured by Nippon Oil & Fats Co., Ltd.] with 0.045 parts by weight with a hexhel mixer, and the resulting mixture is subjected to melt graft modification with a 65 mmφ uniaxial extruder set at 230 ° C. to obtain modified ethylene / 1. A butene copolymer elastomer [abbreviated as MAH-PE-2] was obtained.

When the graft amount of this modified ethylene / 1-butene copolymer elastomer (MAH-PE-2) was measured by IR analysis, the maleic anhydride graft amount was 0.5.
% By weight. MFR (ASTM D 1238, 190 ℃,
2.16kg load) is 2.1g / 10min, melting point is 71
° C. [Production of modified polyethylene composition (6), (7)] MAH-PE-2, PE-1, E obtained as described above
Modified polyethylene compositions (6) and (7) were obtained in the same manner as in Example 1 except that the PR and tackifier Escoletz 5320 were used in the proportions shown in Table 1.

The density of these compositions, MFR (ASTM D 1
238, 190 ℃, 2.16kg load), maleic anhydride graft amount and crystallinity are shown in Table 1. Hereinafter, using these compositions, a three-layer stretched film was prepared in the same manner as in Example 1, and the above test was conducted.

The results are shown in Table 1.

[0082]

Example 8 In Example 7, instead of PE-1,
Ethylene / 1-hexene copolymer resin prepared using Zr-based catalyst [abbreviated as PE-2; density = 0.923 g / cm
³ , MFR (ASTM D 1238, 190 ℃, 2.16kg load) =
2.1 g / 10 minutes] was used to obtain a modified polyethylene composition (8) in the same manner as in Example 7.

The density of this composition (8), MFR (ASTM D
Table 1 shows 1238, 190 ° C, 2.16 kg load), the amount of maleic anhydride grafted and the degree of crystallinity. Hereinafter, using this composition (8), a three-layer stretched film was prepared in the same manner as in Example 1, and the above test was conducted.

The results are shown in Table 1.

[0085]

[Comparative Example 1] [Production of modified high-density polyethylene resin (MAH-PE-3)] High-density polyethylene prepared using a Ti-based catalyst [abbreviated as HDPE; density = 0.965 g / cm ³ , MF
R (ASTM D 1238, 190 ° C, 2.16kg load) = 15g / 1
0 minutes, melting point (Tm) = 132 ° C., crystallinity = 75%)
Is graft-modified with maleic anhydride by a solution modification method in a toluene solvent to obtain a modified high-density polyethylene resin [M
Abbreviated as AH-PE-3].

This modified high-density polyethylene resin (MAH
-PE-3) had a maleic anhydride graft amount of 2.2% by weight, MFR (ASTM D 1238, 190 ° C, 2.16 kg load) of 4.2 g / 10 minutes, and a melting point of 127 ° C. . [Production of modified polyethylene composition (9)] 5 parts by weight of the modified high-density polyethylene resin (MAH-PE-3),
Unmodified ethylene / 1-butene copolymer resin (PE-1)
A modified polyethylene composition (9) was obtained in the same manner as in Example 1 except that the composition was 65 parts by weight and 30 parts by weight of unmodified EPR.

The density of this composition (9), MFR (ASTM D
Table 1 shows 1238, 190 ° C, 2.16 kg load), the amount of maleic anhydride grafted and the degree of crystallinity. Hereinafter, using this composition (9), a three-layer stretched film was prepared in the same manner as in Example 1, and the above test was performed.

The interlayer adhesion between the modified polyethylene composition (9) layer and the ethylene / vinyl alcohol copolymer and the heat seal strength were both low and insufficient. The results are shown in Table 1.

[0089]

[Comparative Example 2] In Example 1, the amount of the modified ethylene / 1-butene copolymer resin (MAH-PE-1) was changed to 15 parts by weight to obtain an unmodified ethylene / 1-butene copolymer resin. (PE-1) Instead of 65 parts by weight, an unmodified medium density polyethylene resin [abbreviated as PE-3; density = 0.940]
g / cm ³ , MFR (ASTM D 1238, 190 ° C., 2.16 kg load) = 2.2 g / 10 min, crystallinity = 60%] and 85 parts by weight, and EPR, EBR and tackifier are not used. A modified polyethylene composition (10) was obtained in the same manner as in Example 1 except for the above.

The density of this composition (10), MFR (ASTM
D 1238, 190 ° C., 2.16 kg load), the amount of maleic anhydride grafted and the crystallinity are shown in Table 1. Hereinafter, using this composition (10), a three-layer stretched film was prepared in the same manner as in Example 1, and the above test was performed.

The composition (10) had a density of 0.938.
Since the g / cm ³ and the crystallinity were as high as 59%, the interlayer adhesion between the modified polyethylene composition (10) layer and the ethylene / vinyl alcohol copolymer and the heat seal strength were both low and insufficient. .

The results are shown in Table 1.

[0093]

Comparative Example 3 Instead of 10 parts by weight of the modified ethylene / 1-butene copolymer resin (MAH-PE-1) in Example 1, the modified ethylene / 1-butene copolymer elastomer (MAH of Example 6) was used. -PE-2) using 30 parts by weight, EP
The amount of R was changed to 70 parts by weight, and PE-1, E
Example 1 except that BR and tackifier were not used
A modified polyethylene composition (11) was obtained in the same manner as in.

The density of this composition (11), MFR (ASTM
D 1238, 190 ° C., 2.16 kg load), the amount of maleic anhydride grafted and the crystallinity are shown in Table 1. Hereinafter, using this composition (11), a three-layer stretched film was prepared in the same manner as in Example 1, and the above test was performed.

This composition (11) has a density of 0.870.
Since the g / cm ³ and crystallinity of 13% are too low, the interlayer adhesion between the modified polyethylene composition (11) layer and the ethylene / vinyl alcohol copolymer and the heat seal strength are good, but the heat resistance is high. The film was torn due to insufficient pressure.

The results are shown in Table 1.

[0097]

Comparative Example 4 The modified ethylene / 1-butene copolymer resin (MAH-PE-1) and the unmodified P in Example 1 were used.
A modified polyethylene composition (12) was obtained in the same manner as in Example 1 except that the blending amount of E-1 was changed to 15 parts by weight and 55 parts by weight, respectively, and EBR and the tackifier were not used. It was

The density of this composition (12), MFR (ASTM
D 1238, 190 ° C., 2.16 kg load), the amount of maleic anhydride grafted and the crystallinity are shown in Table 1. Hereinafter, using this composition (12), a three-layer stretched film was prepared in the same manner as in Example 1, and the above test was performed.

The results are shown in Table 1.

[0100]

Comparative Example 5 70 parts by weight of PE-1 used in Example 1, 30 parts by weight of EPR used in Example 6, 0.2 parts by weight of maleic anhydride, and peroxide (trade name Perhexin-25B, 0.01 parts by weight of Nippon Oil & Fats Co., Ltd.) was mixed with a Henschel mixer, and the resulting mixture was melt-graft modified with a 65 mmφ extruder set at 230 ° C. to obtain a modified polyethylene mixture (MAH-PE-4). )
I got When the graft amount of this product was measured by IR analysis, the graft amount of maleic anhydride was 0.2% by weight. The MFR (190 ° C, 2.165kg load) is 1.2.
The melting point was 122 ° C at g / 10 minutes.

95 parts by weight of the modified product and Escoletz 5
5 parts by weight of 320, 0.05 parts by weight of Irganox 1010 (trade name, manufactured by Japan Ciba-Geigy Co., Ltd.), and 0.10 parts by weight of Irgafos 168 (stabilizer, manufactured by Nippon Ciba-Geigy Co., Ltd.) And synthetic hydrotalcite (trade name: DHT-4A, manufactured by Kyowa Chemical Co., Ltd.,
Stabilizer) 0.03 parts by weight was mixed with a Henschel mixer, and the resulting mixture was melt-blended with a 65 mmφ extruder set at 200 ° C. to obtain a modified polyethylene resin composition (13). When the graft amount of this product was measured by IR analysis, the maleic anhydride graft amount was found to be 0.
It was 2% by weight. MFR (190 ℃, 2.165kg load) is 1.3g / 10min, density is 0.903g / cm
³ , the crystallinity was 35%.

Then, using this composition (13), a three-layer stretched film was prepared in the same manner as in Example 1, and the above-mentioned test was conducted.

[0103]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location B32B 27/32 103 B32B 27/32 103 27/34 27/34 C08L 23/00 C08L 23/00 23 / 04 LCD 23/04 LCD 51/06 LLE 51/06 LLE // B29C 55/02 B29C 55/02 B29K 23:00 B29L 9:00 (72) Inventor Sawata Yufumi 3 Chikusaigan, Ichihara, Chiba Prefecture Mitsui Oil Chemicals Co., Ltd.

Claims (10)

[Claims] 1. [I] ethylene and α having 3 to 20 carbon atoms
-A copolymer with an olefin, wherein (i) the density is 0.
In the range of 860 to 0.930 g / cm ³ , (ii) X
An unmodified ethylene / α-olefin copolymer resin [A1] or an unmodified ethylene / α-olefin copolymer elastomer [B1] having a crystallinity of 60% or less measured by a line diffraction method is used as an unsaturated carboxylic acid. Alternatively, a modified ethylene / α-olefin copolymer resin [A2] or a modified ethylene / α-olefin copolymer elastomer [B] modified with a derivative thereof in an amount of 0.01 to 5% by weight.
2] and [II] unmodified ethylene / α-olefin copolymer resin [C1] and / or unmodified ethylene / α-olefin copolymer elastomer [C2] and [III] tackifier [D]. In the composition, the content of the (a) tackifier [D] is 0.1 to 2 with respect to 100% by weight of the entire composition.
0% by weight, (b) the graft amount of the unsaturated carboxylic acid or its derivative is in the range of 0.01 to 1.0% by weight, and (c) the density. Is in the range of 0.880 to 0.920 g / cm ³ ,
(D) The crystallinity measured by X-ray diffraction is 15 to 50.
%, And (e) melt flow rate (ASTM
D 1238, 190 ° C, 2.16 kg load) is 0.1
The adhesive polyethylene composition is in the range of 50 g / 10 minutes. 2. The component [I] is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and (i) has a density of 0.860 to 0.900.
g / cm ³ and (ii) an ethylene / α-olefin copolymer elastomer [B1] having a crystallinity of less than 30% measured by an X-ray diffraction method with an unsaturated carboxylic acid or a derivative thereof. The modified graft amount is 0.01-
5. The modified ethylene / α-olefin copolymer elastomer [B2] of 5% by weight.
The adhesive polyethylene composition according to item 1. 3. The component [II] is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, wherein (i) the density exceeds 0.900 g / cm ³ and 0.930 g. / Cm ³ or less, (ii)
The temperature (melting point; Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) is 100 ° C. or higher 1
2. The ethylene / α-olefin copolymer resin [C1] having a temperature of 25 ° C. or lower and (iii) a crystallinity of 60% or less measured by an X-ray diffraction method.
Or the adhesive polyethylene composition according to the item 2. 4. An ethylene polymer layer [I] comprising an ethylene polymer having an ethylene content of 70 mol% or more,
An adhesive layer [II] comprising the adhesive polyethylene composition according to any one of claims 1 to 3, and a polyamide resin layer [II].
I], an ethylene / vinyl alcohol copolymer layer [IV] or a mixed layer [V] of a polyamide resin and an ethylene / vinyl alcohol copolymer is a laminate of three or more layers laminated in this order. A multilayer laminated film characterized in that. 5. The multilayer laminated film according to claim 4, wherein the ethylene-based polymer is low density polyethylene or an ethylene / vinyl acetate copolymer. 6. The multilayer laminated film according to claim 4, which is stretched in at least a uniaxial direction. 7. The multilayer laminated film according to claim 6, which is stretched in at least a uniaxial direction at a stretch ratio of 1.5 to 6 times. 8. The multilayer laminated film according to claim 4, which is biaxially stretched. 9. The multilayer laminated film according to claim 8, which is biaxially stretched at a stretching ratio of 1.5 to 6 times in each axial direction. 10. The multilayer laminated film according to claim 4, which is for shrink film.