JPH11342569A - Polyethylenic multilayered laminate, container and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyethylenic multilayered laminate and a container excellent in characteristics such as impact resistance, rigidity, gasoline barrier properties, interlaminar adhesion or the like and capable of being utilized as recyclable scraps. SOLUTION: A multilayered laminate includes a base layer (A1) containing a polyethylene resin (a1) with MFR of 0.001-0.5 g/10 min and a density of 0.940-0.980 g/cm<3> and an adhesive layer (A2) containing a modified ethylene/α- olefin copolymer (a2) with a density of 0.900-0.940 g/cm<3> graft-modified with an unsaturated carboxylic acid or a derivative thereof, a barrier layer (B) containing an ethylene/vinyl alcohol copolymer (b) and a compsn. layer (C) containing a polyethylenic resin compsn. (c) containing 80-99.5 wt.% of an ethylenic polymer (a) and 0.5-20 wt.% of an ethylene/vinyl alcohol copolymer (b) and having Izod impact strength (-40 deg.C, the presence of notches) of 100 J/m or more and a container is obtained from this laminate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyethylene multilayer laminate, a container comprising the multilayer laminate, and a polyethylene resin composition used in these or obtained as a regrind therefrom.

[0002]

2. Description of the Related Art Polyolefins such as polyethylene have excellent properties such as strength, impact resistance and heat resistance and are used for applications such as containers. However, gasoline barrier properties are not sufficient. It is used in combination with an ethylene-vinyl alcohol copolymer or polyamide resin having excellent properties.

For example, multilayer plastic bottles combining an ethylene / vinyl alcohol copolymer having excellent gasoline barrier properties and polyethylene having excellent strength and impact resistance are widely used as small pesticide bottles and large automobile gasoline tanks. It is used. In the multilayer structure, an adhesive resin layer is used between the polyethylene layer and the ethylene / vinyl alcohol copolymer layer to enhance the interlayer adhesion between the polyethylene layer and the ethylene / vinyl alcohol copolymer layer.

[0004] In the multilayer blow molding for producing such a bottle, about 30 to 40% of scraps and burrs are generally generated, and the recycling thereof is inevitable from an economic viewpoint. Therefore, a layer (regrind layer) for crushing scraps, burrs and the like or reusing grind is used as a special layer structure. This regrind layer is a three-component mixture of polyethylene, ethylene / vinyl alcohol copolymer, and adhesive resin. However, since the compatibility between polyethylene and ethylene / vinyl alcohol copolymer is generally poor, poor appearance of multilayer products and Mechanical strength such as impact strength was reduced. Therefore, conventionally, the layer containing regrind is usually diluted with unused polyethylene to such an extent that physical properties do not deteriorate, and it has been difficult to say that regrind is fully utilized effectively.

Here, the adhesive resin plays a certain role as a compatibilizer for improving the compatibility between polyethylene and an ethylene / vinyl alcohol copolymer, but the conventional adhesive polyethylene resin has an improved impact resistance. Had insufficient performance.

There have been many proposals for a regrind composition containing such a polyolefin and an ethylene / vinyl alcohol copolymer. For example, JP
JP-A-240429, JP-A-62-1748, JP-A-2-261863, JP-A-3-18034
No. 1 and Japanese Patent Laid-Open No. 5-125232 propose various proposals for improving the performance of a regrind composition containing a polyolefin and an ethylene / vinyl alcohol copolymer. However, these publications specifically aim at improving the process stability of a composition containing polypropylene, polyolefin, and ethylene / vinyl alcohol copolymer, or improving the adhesive strength with an ethylene / vinyl alcohol copolymer layer, It is different from the object of the present invention.

JP-A-57-11052 discloses a polyethylene layer / a regrind composition layer composed of polyethylene and an ethylene / vinyl alcohol copolymer / ethylene / vinyl alcohol copolymer.
A laminate comprising a vinyl alcohol copolymer layer is disclosed. However, the polyethylene used in this publication, the composition of the modified polyethylene is not clear, the purpose of the invention described in the publication is also intended to improve the delamination, moldability and appearance, the impact strength of the present invention There is no disclosure of providing a superior composition. JP-A-3-72
No. 539 discloses a regrind composition containing polyethylene and an ethylene / vinyl alcohol copolymer, but this publication only discloses a technique using a special ethylene / vinyl alcohol copolymer. is there. JP-A-3-227346 further discloses a regrind composition containing polyethylene and an ethylene / vinyl alcohol copolymer. In this publication, the ethylene / vinyl alcohol copolymer is contained in an amount of 50% by weight or more. Only compositions are disclosed.

Hitherto, it has been considered that the impact strength of a polyethylene composition containing an ethylene / vinyl alcohol copolymer is naturally lowered because the ethylene / vinyl alcohol copolymer is a foreign substance. However, as a result of intensive studies on the improvement of the impact strength of the polyethylene composition containing the ethylene / vinyl alcohol copolymer by the present inventors, a specific melt flow rate, a high-density polyethylene having a density as a main component, A polyethylene composition containing an ethylene / α-olefin copolymer and an ethylene / vinyl alcohol copolymer modified with an unsaturated carboxylic acid having a density, a graft ratio, and a melt flow rate or a derivative thereof,
It has been found that it has a high impact strength comparable to that of conventional polyethylene alone and is recyclable, and has reached the present invention.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyethylene-based multilayer laminate having excellent properties such as impact resistance, rigidity, gasoline barrier properties, and interlayer adhesion, and capable of recycling laminates and scraps. It is in. Other objects of the present invention are impact resistance, rigidity, gasoline barrier properties,
An object of the present invention is to provide a polyethylene-based container having excellent properties such as interlayer adhesiveness and capable of recycling a laminate and scrap. Still another object of the present invention is to provide a polyethylene resin composition which has excellent impact resistance and can be used as a regrind layer in a multilayer laminate.

[0010]

The present invention provides the following polyethylene-based multilayer laminate, container and resin composition. (1) ASTM D1238 (190 ° C: 2160
g) has a melt flow rate (MFR) of 0.00
1-0.5 g / 10 min, density 0.945-0.980
g / cm ³ of the base layer containing the polyethylene resin (a1) (A
1) an adhesive layer (A2) containing a modified ethylene / α-olefin copolymer (a2) graft-modified with an unsaturated carboxylic acid or a derivative thereof and having a density of 0.900 to 0.940 g / cm ³ ; A multilayer laminate containing a barrier layer (B) containing a vinyl alcohol copolymer (b), wherein the laminate is mechanically pulverized and then granulated with a single screw extruder to produce a resin composition; The resin composition was press-molded at a set temperature of 230 ° C., a pressure of 50 kgf / cm ² ,
A sheet having a thickness of 3 mm was formed under cooling conditions in accordance with ASTM D1928, and a test piece was punched from the sheet.
A polyethylene multilayer laminate having an Izod impact strength of 100 J / m or more when measured at −40 ° C. by the method of STM D256 (with notch). (2) The multilayer laminate according to the above (1), wherein a bending test piece is cut from the sheet of the above (1) and the flexural modulus measured by the method of ASTM D790 is more than 3000 kgf / cm ² . (3) ASTM D1238 (190) containing 80 to 99.5% by weight of an ethylene-based polymer (a) and 0.5 to 20% by weight of an ethylene / vinyl alcohol copolymer (b), and C: 2160 g) at a melt flow rate (MFR) of 0.001 to 0.5.
g / 10 minutes, density 0.940 to 0.970 g / cm ³
And the Izod impact strength (with notch) measured at −40 ° C. by the method of ASTM D256 is 100 J.
The multilayer laminate according to the above (1) or (2), further comprising a composition layer (C) containing a polyethylene-based resin composition (c) having a molecular weight of at least / m. (4) ASTM D1238 (190 ° C: 2160
g) has a melt flow rate (MFR) of 0.00
1-0.5 g / 10 min, density 0.945-0.980
g / cm ³ polyethylene resin (a1): 99.3-5
0% by weight, density of 0.900 to 0.940 g / cm graft-modified with unsaturated carboxylic acid or its derivative
³ of the modified ethylene · alpha-olefin copolymer (a2):
ASTM D1238 (190 ° C .: 2160%) containing 0.2 to 20% by weight, and 0.5 to 30% by weight of ethylene / vinyl alcohol copolymer (b).
g) has a melt flow rate (MFR) of 0.00
1 to 0.2 g / 10 min, density 0.940 to 0.970
g / cm ³ , measured at −40 ° C. by ASTM D256 method (notched)
The multilayer laminate according to the above (1) or (2), further comprising a composition layer (C) containing a polyethylene-based resin composition (c) having a particle size of 100 J / m or more. (5) The multilayer laminate according to the above (3) or (4), wherein the polyethylene resin composition (c) is a multilayer laminate and / or a regrind of the scrap thereof. (6) The multilayer laminate according to any one of the above (3) to (5), wherein the composition layer (C) is formed between the base layer (A1) and the adhesive layer (A2). (7) A container comprising the multilayer laminate according to any one of (1) to (6). (8) ASTM D1238 (190 ° C: 2160
g) has a melt flow rate (MFR) of 0.00
1-0.5 g / 10 min, density 0.945-0.980
g / cm ³ polyethylene resin (a1): 99.3-5
0% by weight, density of 0.900 to 0.940 g / cm graft-modified with unsaturated carboxylic acid or its derivative
³ of the modified ethylene · alpha-olefin copolymer (a2):
ASTM D1238 (190 ° C .: 2160%) containing 0.2 to 20% by weight, and 0.5 to 30% by weight of ethylene / vinyl alcohol copolymer (b).
g) has a melt flow rate (MFR) of 0.00
1 to 0.2 g / 10 min, density 0.940 to 0.970
g / cm ³ , measured at −40 ° C. by ASTM D256 method (notched)
Is 100 J / m or more. (9) The polyethylene resin composition (c) according to the above (8), wherein the ratio of the graft-modifying component to the whole polyethylene resin composition (c) is 100 to 1500 ppm. (10) The polyethylene resin composition according to the above (8) or (9), which is a regrind of a multilayer laminate and / or a scrap thereof.

In the present invention, “scrap” is sometimes used to include “burr”. The polyethylene-based multilayer laminate of the present invention basically comprises a base layer (A1) containing a polyethylene resin (a1), an adhesive layer (A2) containing a modified ethylene / α-olefin copolymer (a2), and an ethylene / α-olefin copolymer (a2).
Although it is a multilayer laminate including a barrier layer (B) containing a vinyl alcohol copolymer (b), a multilayer laminate further including a composition layer (C) containing a polyethylene resin composition (c) is preferable. As the composition layer (C), a regrind layer can be used.

<< Base Layer (A1) >> The polyethylene resin (a1) used for the base layer (A1) in the present invention has a density of 0.9.
45 to 0.980 g / cm ³ , preferably 0.945 to 0.945 g / cm ³
0.970 g / cm ³ , particularly preferably 0.953 to
0.960 g / cm ³ , 1 according to ASTM D1238
A melt flow rate (MFR) at 90 ° C. and a load of 2.16 kg is 0.001 to 0.5 g / 10 min, preferably 0.01 to 0.2 g / 10 min, particularly preferably 0.0
High molecular weight and high density polyethylene of 2 to 0.05 g / 10 min. By using such a polyethylene resin (a1), a composition and a laminate having impact resistance, high rigidity and low gasoline permeability can be obtained for the first time.

Although the polyethylene resin used as the component (a1) is an ethylene homopolymer, ethylene and α-
It may be a random copolymer with an olefin. In the latter case, the structural unit derived from the α-olefin is at most 5 mol%, preferably at most 2 mol%. Examples of the α-olefin include propylene, 1-butene, 1-
Hexene, 4-methyl-1-pentene, 1-octene,
Α-olefins having 3 to 10 carbon atoms such as 1-decene are exemplified.

The polyethylene resin (a1) used in the present invention
It is preferable that Mw / Mn measured by gel permeation chromatography is 20 or more because moldability and impact strength are excellent. The base layer (A) used in the present invention
1) is a resin containing a polyethylene resin (a1) as a main component as described above, and may contain an antioxidant (d), a metal compound (e), and other known additives in addition to the resin. Good.

<< Adhesive Layer (A2) >> In the present invention, the adhesive layer (A2)
As 2) and / or as a dispersant for the ethylene / vinyl alcohol copolymer in the polyethylene resin composition (c) described below, a specific modified ethylene / α-olefin copolymer (a2) is used. Unmodified ethylene / α-olefin used in the modified ethylene / α-olefin copolymer (a2)
The olefin copolymer has a density of 0.900 to 0.940 g
/ Cm ³ , preferably 0.900 to 0.935 g / cm ³
Is an ethylene / α-olefin copolymer.

In the present invention, the ethylene / α-olefin copolymer before modification includes ethylene and another olefin such as propylene, 1-butene, 1-hexene, and 4-methyl-1.
-C3-C3 such as pentene, 1-octene, 1-decene, etc.
10 is a copolymer with an α-olefin.

As the ethylene / α-olefin copolymer before modification in the present invention, specifically, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene 1-octene copolymer, ethylene-4-methyl-1-pentene copolymer and the like. Among them, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-
Octene copolymers are preferred.

In the ethylene / α-olefin copolymer before modification used in the present invention, the structural unit derived from ethylene is 70 to 99.5 mol%, preferably 80 to 99 mol%, and the structural unit derived from α-olefin is The unit is 0.5-3
It is desirably 0 mol%, preferably 1 to 20 mol%.

The ethylene / α-olefin copolymer before modification was prepared at 190 ° C. and 2.16 according to ASTM D1238.
The melt flow rate (MFR) under a kg load is 0.
01-20 g / 10 min, preferably 0.05-20 g /
It is desirable that the time is 10 minutes.

The unmodified ethylene • α- used in the present invention
The method for producing the olefin copolymer is not particularly limited, and may be prepared by a known method using a transition metal catalyst such as a titanium (Ti) -based, chromium-based (Cr) -based, or zirconium (Zr) -based. it can.

The modified ethylene / α-olefin copolymer (a2) used in the present invention is the aforementioned ethylene / α-olefin copolymer before modification.
It is a graft-modified product obtained by graft-modifying an α-olefin copolymer with an unsaturated carboxylic acid or a derivative thereof.

Specific examples of the unsaturated carboxylic acids or derivatives thereof include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid. , Endocis-bicyclo [2,2,
1] Unsaturated carboxylic acids such as hept-5-ene-2,3-dicarboxylic acid (Nadic acid (trademark)) and derivatives thereof such as acid halides, amides, imides, acid anhydrides and esters. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid (trademark) or acid anhydrides thereof are particularly preferable.

The graft modification of the ethylene / α-olefin copolymer can be carried out by a known method, for example, by dissolving the ethylene / α-olefin copolymer in an organic solvent,
Next, an unsaturated carboxylic acid or a derivative thereof, a radical initiator, and the like are added to the obtained solution.
C., preferably at a temperature of 80-190.degree.
The reaction is carried out for a time, preferably 1 to 10 hours.

The above organic solvent can be used without any particular limitation as long as it can dissolve the ethylene / α-olefin copolymer. Examples of such an organic solvent include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, and heptane.

As another graft modification method, an ethylene / α-olefin copolymer is reacted with an unsaturated carboxylic acid or a derivative thereof without a solvent using an extruder or the like to modify the modified ethylene / α-olefin. Olefin copolymer (a
2) can be prepared. The reaction conditions in this case are:
The reaction temperature is usually equal to or higher than the melting point of the ethylene / α-olefin copolymer, specifically 100 to 350 ° C., and the reaction time is usually 0.5 to 10 minutes.

Regardless of the known graft modification method, the reaction is carried out in the presence of a radical initiator in order to efficiently graft copolymerize the unsaturated carboxylic acid or its derivative as the graft monomer. Is preferred.

Examples of the radical initiator include organic peroxides and organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide Benzoate) hexyne-3,1,4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di (t-
Butylperoxy) hexyne-3,2,5-dimethyl-
2,5-di (t-butylperoxy) hexane, t-butylperbenzoate, t-butylperphenylacetate, t-butylperisobutyrate, t-butylper-sec-octoate, t-butylperpivalate,
Cumyl perpivalate and t-butyl perdiethyl acetate; azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate are used.
Among them, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-
2,5-di (t-butylperoxy) hexane, 1,4
Dialkyl peroxides such as -bis (t-butylperoxyisopropyl) benzene are preferred. The radical initiator is ethylene / α-olefin copolymer 1 before modification.
It is usually used at a ratio of 0.001 to 1 part by weight with respect to 00 parts by weight.

The modified ethylene / α-olefin copolymer (a2) used in the present invention has a density of 0.900 to 0.940.
g / cm ³ , preferably 0.900 to 0.935 g / c
m is ^3. The graft amount (graft modification ratio) of the graft group derived from the unsaturated carboxylic acid or its derivative in the modified ethylene / α-olefin copolymer (a2) is usually 0.05 to 10% by weight, preferably 0.1 to 10% by weight.
An amount of grafting of from 0.5 to 5% by weight is desirable. Further, 135 of the modified ethylene / α-olefin copolymer (a2)
When the intrinsic viscosity [η] measured in a decalin (decahydronaphthalene) solution is 1.5 to 4.5 dl / g, preferably 1.6 to 3 dl / g, the impact strength is improved. Further, a modified ethylene / α-olefin copolymer (a
The crystallinity of 2) is 15 to 70%, preferably 35 to 70%.
%, Stable adhesive strength over a long period of time can be obtained even if gasoline permeates.

The adhesive layer (A2) is formed of the modified ethylene α-
The olefin copolymer (a2) can be used alone, or if necessary, the modified ethylene / α-olefin copolymer (a2) may be replaced with another ethylene-based polymer and / or an olefin-based elastomer-based resin. Can also be used. Here, the other ethylene-based polymer includes an ethylene homopolymer and an ethylene / α-olefin copolymer polymerized by a known method.

However, in order to achieve the object of the present invention, the modified ethylene / α-olefin copolymer (a2)
And the intrinsic viscosity [η] of the adhesive layer (A2) containing other components in a 135 ° C. decalin (decahydronaphthalene) solution is 1.0 to 4.5 dl / g, preferably 1.2 to 4.5 dl / g.
By being in the range of 3 dl / g, an improvement in impact strength can be achieved. The density of the adhesive layer (A2) is 0.900 to
0.940 g / cm ³ , preferably 0.900 to 0.9
When the weight is 35 g / cm ³ , the impact strength and the drop strength are increased. Further, the amount of graft modification in the entire adhesive layer (A2) is 0.2% by weight or more, preferably 0.1% by weight.
When the content is 2 to 2% by weight, an improvement in impact strength can be achieved. Further, when the n-decane-insoluble portion in the entire adhesive layer (A2) is 2% by weight or less, preferably 1.8% by weight or less, the adhesive strength of the recycled multilayer laminate can be improved.
Improved impact resistance can be achieved. Here, the n-decane-insoluble portion means that 8 g of the polymer of the adhesive layer was treated with n-decane 50 at 140 ° C.
This is a value obtained by completely dissolving in 0 ml and then lowering the temperature to 90 ° C., and filtering the precipitated component while hot.

Examples of the olefin elastomer blended in the adhesive layer (A2) include polyisobutylene,
Examples include ethylene / propylene rubber, ethylene / 1-butene rubber, ethylene / 1-octene rubber, butyl rubber, butadiene rubber, styrene / butadiene rubber, ethylene / butadiene rubber, and isoprene rubber. Modified elastomers obtained by modifying these olefin-based elastomers with the above-mentioned unsaturated carboxylic acids or derivatives thereof can also be exemplified. Among these, polyisobutylene, ethylene propylene rubber, ethylene 1-butene rubber, ethylene 1-octene rubber, and modified products thereof are preferred.

Other ethylene-based polymers and / or olefin-based elastomers can be used as long as the performance of the present invention is not impaired, but the blending amount is usually 100 parts by weight of the modified ethylene / α-olefin copolymer. 30 for
It is not more than 20 parts by weight, preferably not more than 20 parts by weight. The adhesive layer (A2) may contain an antioxidant (d) described later, a metal compound (e), and other known additives.

<< Barrier Layer (B) >> The ethylene-vinyl alcohol copolymer (b) (hereinafter sometimes abbreviated as EVOH) used for the barrier layer (B) in the present invention is composed of ethylene and vinyl acetate. It is a saponified product of a copolymer with esters.

The structural unit derived from ethylene in the ethylene / vinyl alcohol copolymer (b) is 15 to 60.
Molar%, preferably 25 to 50% by mole, and the structural unit derived from the copolymerized monomer is 85 to 40% by mole, preferably 75 to 50% by mole.

The degree of saponification of the ethylene / vinyl alcohol copolymer (b) is 80 to 100%, preferably 90 to 100%.
Desirably, it is 100%. When the saponification degree is in the above range, the ethylene / vinyl alcohol copolymer (b) is excellent in mechanical properties, oil resistance, and water resistance.

When the ethylene content is within the above range,
The ethylene-vinyl alcohol copolymer (b) has a difference between the moldable temperature and the decomposition temperature, is easy to mold, and has excellent gasoline permeation resistance (gasoline barrier property) and mechanical properties. By laminating the barrier layer (B) made of such an ethylene / vinyl alcohol copolymer (b), a multilayer laminate excellent in gasoline permeation resistance described later can be obtained. In addition, it is possible to easily obtain a multilayer laminate by performing regrind, thereby enabling effective use of resources.

The ethylene / vinyl alcohol copolymer (b) used in the present invention may be modified with an epoxy compound, an isocyanate compound or the like. The barrier layer (B) contains the ethylene / vinyl alcohol copolymer (b) as a main component, but other polymers such as the ethylene / vinyl alcohol copolymer (b) as long as the object of the present invention is not impaired. Polyamide (nylon), polyester, polyolefin, polycarbonate, ionomer resin,
Polyvinyl acetate, polystyrene, ABS resin, acrylic resin, vinyl chloride resin and the like may be mixed. Further, it may contain an antioxidant (d), a metal compound (e) described below, and other known additives.

<< Composition Layer (C) >> The polyethylene resin composition (c) used in the composition layer (C) is 80 to 99.5% by weight, preferably 85 to 99% by weight of the ethylene polymer (a). Particularly preferably 90 to 98% by weight, and ethylene / vinyl alcohol copolymer (b) 0.5 to 20% by weight, preferably 1 to 15% by weight, particularly preferably 2 to 1% by weight.
ASTM D123 containing 0% by weight and of the total composition
8 (190 ° C .: 2160 g) has a melt flow rate (MFR) of 0.001 to 0.5 g / 10 min, preferably 0.01 to 0.2 g / 10 min, particularly preferably 0.1 to 0.2 g / 10 min.
03-0.1 g / 10 min, density 0.940-0.97
0 g / cm ³ , preferably 0.945 to 0.968 g /
cm ³ , particularly preferably 0.952 to 0.966 g / c
m ³ , and the Izod impact strength (−40 ° C., with notch) measured by the method of ASTM D256 is 100.
J / m or more, preferably 150 J / m or more, particularly preferably 200 J / m or more.

In the present invention, the ethylene polymer (a) may be a mixture of the polyethylene resin (a1) and the modified ethylene / α-olefin copolymer (a2). In this case, the polyethylene resin (a1) and the modified ethylene
The mixing ratio of the α-olefin copolymer (a2) and the ethylene / vinyl alcohol copolymer (b) is 99.3 to 50% by weight, preferably 99% by weight, of the polyethylene resin (a1).
65% by weight, particularly preferably 95-70% by weight, and the modified ethylene / α-olefin copolymer (a2) is 0.2-65% by weight.
20% by weight, preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight, and the ethylene / vinyl alcohol copolymer (b) is 0.5 to 30% by weight, preferably 1 to 2% by weight.
It is in the range of 5% by weight, particularly preferably 2 to 20% by weight.

When the polyethylene resin (a1) is within the above range, the polyethylene resin (a1) forms a matrix, and impact strength can be obtained. Modified ethylene α-
When the olefin copolymer (a2) is within the above range, the dispersion of the ethylene / vinyl alcohol copolymer (b) in the polyethylene resin (a1) is improved, and the impact strength of the polyethylene resin composition (c) is improved. Rigidity and gasoline permeability are increased. When the amount of the ethylene / vinyl alcohol copolymer (b) is within the above range, the impact strength of the polyethylene resin composition (c) does not decrease.

In the present invention, the blending ratio (weight ratio) of the modified ethylene / α-olefin copolymer (a2) and the ethylene / vinyl alcohol copolymer (b) is set to a range of 1/9 to 9/1. In this range, the composition can be harmonized with impact strength and rigidity and gasoline permeability resistance.

The polyethylene resin composition (c) of the present invention
Has an MFR of 0.001 to 5 g / 10 min, preferably 0.02 to 0.5 g / 10 min, particularly 0.03 to 0.1 g in ASTM D1238 (190 ° C .: 2160 g).
/ 10 minutes and a density of 0.940 to 0.970
g / cm ³ , preferably 0.945 to 0.968 g / c
m ³ , particularly preferably in the range of 0.952 to 0.966 g / cm ³ .

The polyethylene resin composition (c) of the present invention
Has an impact strength of at least 100 J / measured at -40 ° C.
The feature is that it is extremely large as m. This impact strength is higher than that of polyethylene alone, and the same M
Compared to the impact strength of polyethylene having FR, it is 1/3 or more. The impact strength of a resin composition similar to the heretofore known application is 1/1 compared to polyethylene alone.
This is higher than the value of 0 or less.

The composition layer (C) contains a polyethylene resin composition (c) containing the ethylene copolymer (a) and the ethylene / vinyl alcohol copolymer (b) as a main component. If necessary, an antioxidant (d), a metal compound (e) and other known additives described below may be contained. The composition layer (C) may be composed of new components containing these components, or may be composed of regrind containing these components. When a regrind is used, all of the components (A1), (A2), and (B) can be supplied entirely from a regrind, or can be used as a mixture with a new product.

The regrind is obtained by pulverizing unnecessary portions which have been subjected to a heating history, such as scraps and burrs, generated when a multilayer laminate is formed by using the base layer (A1), the adhesive layer (A2) and the barrier layer (B). . The average particle size of the ethylene / vinyl alcohol copolymer (b) in the regrind is 0.1.
1 to 10 μm, preferably 0.1 to 5 μm, particularly preferably 0.1 to 3 μm, and the composition of the ethylene / vinyl alcohol copolymer (b) is 0.5 to 10% by weight, preferably 2 to 8% by weight. By doing so, a composition layer (C) having a high impact strength can be obtained.

<< Antioxidant (d) >> In the present invention, the antioxidant (d) preferably blended in the base layer (A1), the adhesive layer (A2), the barrier layer (B), and the composition layer (C) is as follows. Phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, etc., which are commonly used in polyolefins, can be used alone or in combination. Phenolic antioxidants and phosphorus-based antioxidants It is preferable to use in combination with

The phenolic antioxidants include 2,2
6-di-tert-butyl-p-cresol (BH
T), o-tert-butyl-p-cresol (BH
A), tetrakis [methylene-3- (3,5-di-te
rt-butyl-4-hydroxyphenyl) propionate] methane (Irganox 1010, trademark), 1,1
-Bis (4-oxyphenyl) cyclohexane, 1,
3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzene), 2,
6-bis (2'-hydroxy-3'-tert-butyl-5'-methylbenzyl) -4-methylphenol,
Examples thereof include hydroxy chroman derivatives such as 2,2-thiobis (4-methyl-6-tert-butylphenol), p-hydroxy-diphenylamine, and tocopherol.

As the phosphorus antioxidant, tris (2,
4-di-tert-butylphenyl) phosphite (Irgafos 168, trademark), bis (2,6-di-t)
tert-butyl-4-methylphenyl) pentaerythritol-diphosphite (Mark PEP-3)
6, trademark), tetrakis (2,4-di-tert-butylphenyl) 4,4-biphenylenediphosphite (P-EPQ) and the like.

Examples of the sulfur-based antioxidant include dilauryl-thiodipropionate (DLTP), distearylthiodipropionate (DSTP) and the like. The compounding amount of the antioxidant (d) is (a1), (a2), (b)
Alternatively, it is preferably 0.01 to 0.5 part by weight, more preferably 0.01 to 0.5 part by weight, per 100 parts by weight of (c).
０．３0.3 parts by weight. When two or more antioxidants (d) are used in combination, they are blended so that the total amount falls within the above range. In the present invention, it is preferable to use a phenolic antioxidant and a phosphorus antioxidant in combination. In this case, the weight ratio of the phenolic antioxidant to the phosphorus antioxidant is 5: 1 to 1: 5. Is preferred.

<< Metal Compound (e) >> In the present invention, the metal of the metal compound (e) preferably blended in the base layer (A1), the adhesive layer (A2), the barrier layer (B) and the composition layer (C) is , IUPAC Inorganic Chemical Nomenclature Revised Edition (198
In the periodic table of long-period type elements represented by group numbers 1 to 18 according to 9), elements belonging to groups 1, 2, 3, 4, 5, 12, 13 or 14 are mentioned, and sodium, potassium, magnesium , Calcium, strontium, barium, zinc, cadmium, aluminum, silicon, tin, lead, titanium and the like are preferably used.

Suitable examples of the metal compound (e) include metal oxides such as magnesium oxide, calcium oxide, aluminum oxide, silicon dioxide and titanium dioxide; magnesium hydroxide, calcium hydroxide, and water. Metal hydroxides such as aluminum oxide and orthotitanic acid; metal carbonates such as potassium carbonate, sodium hydrogen carbonate, sodium carbonate, magnesium carbonate and calcium carbonate; metal sulfates such as magnesium sulfate, calcium sulfate, barium sulfate and aluminum sulfate Silicates such as sodium metasilicate, anhydrous sodium silicate, lithium metasilicate, anhydrous lithium silicate, potassium metasilicate, anhydrous potassium silicate, magnesium silicate, magnesium metasilicate, calcium silicate, etc., and aluminum silicate Salt etc. It is. These may be natural products or synthetic products, or may be a mixture of two or more. Examples of natural products include talc, bentonite, and hydrotalcite.

Examples of the metal salts of higher fatty acids include metal salts of carboxylic acids having 7 to 23 carbon atoms, particularly 11 to 21 carbon atoms, and straight-chain aliphatic carboxylic acids such as lauric acid, palmitic acid, stearic acid and behenic acid. Sodium, magnesium, calcium and zinc salts of acids can be suitably used.

These metal compounds (e) are preferably solid when the particle size is small, but it is sufficient if the metal compound (e) has an average particle size of at least 150 μm or less, especially 40 μm or less.
The shape may be flat, massive, needle-like, or any other shape, but is preferably a rounded shape, particularly a spherical shape.

The compounding amount of the metal compound (e) is (a1)
(A2), (b), (c) 0.0 to 100 parts by weight
It is preferably from 1 to 0.4 parts by weight. When two or more metal compounds (e) are used in combination, they are blended so that the total amount is within the above range.

<< Multilayer Laminate >> The multilayer laminate of the present invention has a basic layer structure in which the above-mentioned base layer (A1), adhesive layer (A2) and barrier layer (B) are laminated. Generally, a multilayer laminate in which the composition layer (C) is laminated is used. As the resin composition used for the layer C, a new resin composition may be used, but it is preferable to use regrind. In some cases, both may be used in combination.

A preferred embodiment of the multilayer laminate of the present invention is a multilayer laminate in which the composition layer (C) is provided between the base layer (A1) and the barrier layer (B). Another preferred embodiment of the multilayer laminate of the present invention is a multilayer laminate in which the composition layer (C) is laminated between the base layer (A1) and the adhesive layer (A2).

Examples of embodiments of the multilayer laminate include: A1 / A2 / B A1 / C / A2 / B A1 / C / A2 / B / A2 A1 / A2 / B / C A1 / C / A2 / B / C / A1 A1 / A2 / B / A2 / C, A1 / C / A2 / B / A2 / A1 A1 / C / A2 / B / A2 / C A1 / C / A2 / B / A2 / C / A1, etc. Laminates.

Of these, the composition layer (C) is laminated on one or both sides of the barrier layer (B), and the composition layer (C) is laminated between the base layer (A1) and the adhesive layer (A2). Multilayer laminates are preferred.

The ratio of the thickness of each layer to the total thickness of the multilayer laminate is not particularly limited.
%, The content of the barrier layer (B) is in the range of 1 to 25%, and the content of the composition layer (C) is in the range of 20 to 60%, from the viewpoint of the balance between impact strength, rigidity and gasoline barrier properties. In this case, the thickness of each layer is preferably such that the regrind has the composition of the composition layer (C).

In the above multilayer laminate, the adhesive layer (A) containing the modified ethylene / α-olefin copolymer (a2)
2) serves as an adhesive to bond the base layer (A1) or the composition layer (C) and the barrier layer (B). A1 layer and C
The layer or the A2 layer has good adhesiveness, and can be directly laminated by a method such as coextrusion.

In general, in a commercial production, when a regrind resin is used as the composition layer (C), the regrind layer receives heat history many times and is liable to undergo oxidative deterioration. It is preferable to blend (d). The antioxidant (d) can be added directly to the C layer,
Moreover, you may add to A1 layer, A2 layer, and C layer. In normal production, it is added to the A1 and / or A2 and / or C layers.

In general, the ethylene / vinyl alcohol copolymer (b) is a resin which is more likely to be thermally degraded than polyethylene or a modified polyethylene resin composition, and is liable to cause yellowing and gelation. When used as a regrind resin, gelation of the ethylene-vinyl alcohol copolymer (b) is promoted by hydrochloric acid generated due to the catalyst residue of polyethylene in the outer layer. Therefore, it is preferable to mix the metal compound (e) as a hydrochloric acid absorbent in the adhesive layer (A2) adjacent to the barrier layer (B). Although the metal compound (e) is added to the A1 layer and / or the A2 layer, it is more effective to add it to the A2 layer.

The multilayer laminate of the present invention is obtained by pulverizing the laminate,
A re-grind was made through a mesh having an opening of 7 mm, and after granulating it with a single screw extruder, compression molding was performed with a press molding machine at a set temperature of 230 ° C. and a pressure of 50 kgf / cm ² ,
The cooling is performed under the condition of slow cooling according to ASTM D1928, a test piece having a thickness of 3 mm is prepared, and the Izod impact strength measured at −40 ° C. by the method of ASTM D256 (with a notch) is 50 J / m or more, preferably 80 J / m. m or more. The value of the Izod impact strength of the pulverized multilayer laminate is also significantly superior to the conventionally known polyolefin / ethylene / vinyl alcohol copolymer laminate, and by evaluating the Izod impact strength, the regrind can be reduced. It is possible to estimate the impact strength of the multilayer laminate laminated as the composition layer (C).

The multilayer laminate of the present invention can be formed into a film by extrusion sheet molding, cast molding, blow molding or the like.
It can be formed into a desired form such as a sheet or a container.

<< Container >> The container of the present invention is obtained by molding the above-mentioned multilayer laminate into a container. The shape of the container can be any shape such as a tank, a bottle, a cup, and a tray. These containers are preferably used as the outer layer as the base layer (A1) or the composition layer (C), whereby a container having high impact strength can be obtained. By laminating the barrier layer (B), a barrier property against gasoline and other solvents can be obtained.

The above-mentioned container can be formed by blow molding, compressed air or vacuum molding, injection molding or the like.
In the case of a large bottle or the like, it can be formed by blow molding. INDUSTRIAL APPLICABILITY The container of the present invention is rigid, has excellent gasoline barrier resistance, and is extremely excellent in impact resistance, particularly low-temperature impact resistance, so that it can be advantageously used particularly as a large container. it can.
When used as a gasoline tank, it can be used for a long period of time without causing delamination or deterioration of the regrind layer even if it is filled with gasoline or gasohol because of its excellent interlayer adhesion.

[0067]

As described above, the polyethylene-based multilayer laminate of the present invention comprises a base layer containing a specific polyethylene resin, an adhesive layer containing a specific modified ethylene / α-olefin copolymer, and a specific ethylene / vinyl alcohol. Since the barrier layer containing the copolymer is laminated, a polyethylene-based multilayer laminate having excellent properties such as impact resistance, rigidity, gasoline barrier properties, interlayer adhesion, etc., and in which the laminate and scrap can be recycled can be obtained. .

The above polyethylene resin, modified ethylene / α
-By further laminating a layer containing a polyethylene resin composition containing an olefin copolymer and an ethylene / vinyl alcohol copolymer, the scrap can be recycled as a regrind layer, thereby providing a multilayer laminate having a high impact strength. You can get the body.

Since the polyethylene container of the present invention comprises the above-mentioned multilayer laminate, the polyethylene container has excellent properties such as impact resistance, rigidity, gasoline barrier properties, interlayer adhesion and the like, and the laminate and scrap can be recycled. Is obtained.

Since the polyethylene resin composition of the present invention comprises the above components, it has excellent impact resistance, and a polyethylene resin composition which can be used as a regrind layer in a multilayer laminate is obtained.

[0071]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 << Modification of Ethylene / α-Olefin Copolymer >> Density =
0.921 g / cm ³ , M according to ASTM D1238
FR (190 ° C .: 2160 g) = 2.0 g / 10 min, 1
-100 parts by weight of an ethylene / 1-butene copolymer (PE-1) having a butene content of 4 mol% was added to maleic anhydride 0.8%.
Parts by weight and 0.07 parts by weight of peroxide [Perhexin 25B, manufactured by NOF CORPORATION], and the resulting mixture is subjected to melt graft modification with a single screw extruder set at 230 ° C. A modified ethylene / 1-butene copolymer (MAH-PE-1) was obtained. This modified ethylene-1
When the grafting amount of the butene copolymer was examined by IR analysis, the maleic anhydride grafting modification amount was 0.80% by weight. The intrinsic viscosity [η] measured in a decalin solution at 135 ° C. was 1.86 dl / g. Table 1 shows the results
Shown in

<< Production of Modified Ethylene / α-Olefin Copolymer (a2) >> 50 parts by weight of the above modified ethylene / 1-butene copolymer (MAH-PE-1), density = 0.92 g
/ Cm ³ , MFR according to ASTM D1238 (190
C: 2160 g) = 2.0 g / 10 min, ethylene / 1-butene copolymer having 1-butene content of 4 mol% (PE-
1) 50 parts by weight, 0.1 part by weight of Irganox 1010 (Ciba-Geigy), a phenolic stabilizer, 0.1 part by weight of Irgafos 168 (Ciba-Geigy), a phosphorus-based stabilizer, and 0.1 parts by weight of synthetic hydrotalcite (average particle size: 1 μm) is uniformly mixed with a Henschel mixer, and this mixture is melt-mixed with a single screw extruder set at 230 ° C. and used as an adhesive layer (A2). Modified ethylene / 1-butene copolymer composition (AD-
1) was obtained. The MFR of AD-1 was 0.7 g / 10 min, the density was 0.921 g / cm ³ , and the amount of maleic anhydride grafted was 0.43% by weight. Table 2 shows the results.

<< Production of Laminate >> From the outermost layer to the base layer (A
1) High-density polyethylene [HDPE: Hyzex 8200B, manufactured by Mitsui Chemicals, Inc., trademark, density = 0.9
56 g / cm ³ , MFR according to ASTM D1238
(190 ° C .: 2160 g) = 0.03 g / 10 min], a modified ethylene / α-olefin copolymer AD-1 as the adhesive layer (A2), and an ethylene / vinyl alcohol copolymer [EVOH] as the barrier layer (B) : EVAL EP-F
101A, manufactured by Kuraray Co., Ltd., trademark, MFR (ASTM
D1238, 190 ° C, 2160 g) = 1.3 g / 10
Min, density 1.19 g / cm ³ , ethylene content = 32 mol%, degree of saponification = 100%], modified ethylene / α-olefin copolymer (AD-1) as adhesive layer (A2),
High-density polyethylene [HDPE: Hyzex 8200B, manufactured by Mitsui Chemicals, Inc., trade name, density = 0.956 g / cm ³ , MFR by ASTM D1238 (190 ° C .: 2160 g) = 0.03 g / 10 as the base layer (A1)
4) provided so as to be stacked in the die in the order of
Using a seed 6-layer blow molding machine, a bottle having a height of 150 mm and a content of 500 ml was molded at a molding temperature of 230 ° C. so as to have the following thickness ratio (weight conversion). A1 / A2 / B / A2 / A1 = 45/2/5/2/46
(%)

<< Production of Polyethylene Composition (c) >> This bottle was pulverized using a pulverizer, and this was compressed to a compression ratio of 4.0.
Using a full flight screw single screw extruder
The resulting mixture was melt-mixed at a temperature of ° C to obtain a polyethylene resin composition (c). This was named C-1.

<< Evaluation of Performance of Polyethylene Resin Composition (c) >> Next, the pellet (C-1) obtained by the above method was melted at a heating mold temperature of 230 ° C. using a hot-melt press molding machine, and subjected to ASTM D1928. And cooled and solidified under the slow cooling conditions specified in (1) to form a 3 mm press sheet. A test piece punched out from the obtained 3 mm sheet into a dumbbell shape was subjected to an Izod impact test (AST
MD256, notched). Table 3 shows the results.

<< Production of Laminate and Evaluation Thereof >> From the outermost layer, a high-density polyethylene [HDP] was used as the base layer (A1).
E: Hyzex 8200B, manufactured by Mitsui Chemicals, Inc., trademark, density = 0.956 g / cm ³ , ASTM D123
MFR according to 8 (190 ° C .: 2160 g) = 0.03 g
/ 10 min], C-1 as composition layer (C), modified ethylene / α-olefin copolymer AD-1 as adhesive layer (A2), ethylene / vinyl alcohol copolymer as barrier layer (B) [EVOH: EVAL EP-F10
1A, manufactured by Kuraray Co., Ltd., trademark, MFR (ASTM D1
238, 190 ° C., 2160 g) = 1.3 g / 10 min,
Density 1.19 g / cm ³ , ethylene content = 32 mol%, degree of saponification = 100%], modified ethylene / α-olefin copolymer AD-1 as adhesive layer (A2), high as base layer (A1) Density polyethylene [HDPE: Hyzex 8200B, manufactured by Mitsui Chemicals, Inc., trademark, density =
0.956 g / cm ³ , M according to ASTM D1238
FR (190 ° C .: 2160 g) = 0.03 g / 10 minutes]
4 types 6 provided so as to be laminated in a die in the order of
Using a layer blow molding machine, a bottle having a height of 150 mm and a content of 500 ml was molded at a molding temperature of 230 ° C. so as to have the following thickness ratio (weight conversion). A1 / C / A2 / B / A2 / A1 = 13/40/2/3
/ 2/40 (%)

<< Evaluation of Interlaminar Adhesive Strength of Laminate >> A sample was cut out from the side of the blow bottle with a width of 15 mm, and A2
The adhesive strength between the layer and layer B (vs. EVOH adhesion) was measured by the T-peel method at a peel rate of 50 mm / min. The results are shown in Table 5.

<< Method of Producing Recycled Material and Its Evaluation >> The above blow bottle was pulverized using a pulverizer, and melted and mixed at 220 ° C. using a single screw extruder with a full flight screw having a compression ratio of 4.0. Thus, a recycled pellet (C-1) of the polyethylene resin composition (c) was obtained. Next, the pellet (C-1) obtained by the above method was melted at a heating mold temperature of 230 ° C. using a hot melt press molding machine.
It was cooled and solidified under slow cooling conditions specified by STM to form a 3 mm press sheet. An Izod impact test (ASTM D256, with a notch) was performed on a test piece punched out in a dumbbell shape from the obtained 3 mm sheet in an atmosphere at -40 ° C. Table 5 shows the results.

Example 2 The procedure of Example 1 was repeated, except that the composition of the modified ethylene / α-olefin copolymer (a2) was changed as shown in Table 2. The results are shown in Tables 3 and 5.

Examples 3 to 5 Using various ethylene / α-olefin copolymers shown in Table 1, modification with maleic anhydride was carried out by the method described in Example 1. However, some of them are modified by changing the modification rate partially. This was mixed with ethylene / α-
The modified ethylene / α-olefin copolymer (a2) was synthesized by blending with the olefin copolymer.
Using this modified ethylene / α-olefin copolymer, a multilayer laminate was formed in the same manner as in Example 1, and this was pulverized to obtain a multilayer laminate.
The mixture was melt-mixed with a screw extruder to obtain a polyethylene resin composition (c). Table 3 shows the results. A multilayer laminate is formed using this polyethylene resin composition,
The adhesive strength and the Izod impact strength of the recycled material were measured. Table 5 shows the results.

Comparative Examples 1 to 3 Using the various ethylene / α-olefin copolymers shown in Table 1, maleic anhydride modification was carried out in the manner described in Example 1. However, some of them are modified by changing the modification rate partially. This was mixed with ethylene / α-
The modified ethylene / α-olefin copolymer (a2) was synthesized by blending with the olefin copolymer.
Using this modified ethylene / α-olefin copolymer, a multilayer laminate was formed in the same manner as in Example 1, and this was pulverized to obtain a multilayer laminate.
The mixture was melt-mixed with a screw extruder to obtain a polyethylene resin composition (c). Table 4 shows the results. A multilayer laminate is formed using this polyethylene resin composition,
The adhesive strength and the Izod impact strength of the recycled material were measured. Table 6 shows the results.

Example 6 Using the modified ethylene / α-olefin copolymer (a2) AD-1 synthesized in Example 1, a multilayer bottle was molded in the same composition ratio as shown in Table 3 as in Example 1. As in Example 1, the bottle was pulverized and melt-mixed with a single screw extruder to obtain a polyethylene resin composition (c). Table 4 shows the results.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

[0088]

[Table 5]

[0089]

[Table 6]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 23:26 29:04)

Claims (10)

[Claims] 1. ASTM D1238 (190 ° C .: 21
60g) has a melt flow rate (MFR) of 0.
001 to 0.5 g / 10 min, density 0.945 to 0.9
Base layer comprising polyethylene resin (a1) of 80g / cm ³ (A1), an unsaturated carboxylic acid or a graft-modified density 0.900~0.940g / cm ³ of the modified ethylene · alpha-olefin copolymer heavy derivatives thereof A multi-layer laminate comprising an adhesive layer (A2) containing a coalescence (a2) and a barrier layer (B) containing an ethylene / vinyl alcohol copolymer (b), wherein the laminate is mechanically pulverized and then subjected to a single-screw extruder. To produce a resin composition. Then, the resin composition is subjected to a press molding machine at a set temperature of 230 ° C., a pressure of 50 kgf / cm ² , and an ASTM.
A sheet having a thickness of 3 mm was formed under cooling conditions in accordance with D1928, and a test piece was punched out of the sheet to form an ASTM D sheet.
A polyethylene multilayer laminate having an Izod impact strength of 100 J / m or more when measured at −40 ° C. by the method of 256 (with notch). ^2. The multilayer laminate according to claim 1, wherein a bending test piece is cut from the sheet according to claim 1, and a flexural modulus measured by a method according to ASTM D790 is greater than 3000 kgf / cm ² . 3. Ethylene polymer (a): 80 to 99.
5% by weight, and 0.5 to 20% by weight of an ethylene / vinyl alcohol copolymer (b), and ASTM D1238 (190 ° C .: 2
160g) has a melt flow rate (MFR) of 0.001 to 0.5 g / 10 min and a density of 0.940 to
ASTM D25 in the range of 0.970 g / cm ³
The composition layer (C) containing the polyethylene-based resin composition (c) having an Izod impact strength (with notch) of not less than 100 J / m measured at -40 ° C by the method of claim 6, further comprising: Multilayer laminate. 4. ASTM D1238 (190 ° C .: 21
60g) has a melt flow rate (MFR) of 0.
001 to 0.5 g / 10 min, density 0.945 to 0.9
80 g / cm ³ polyethylene resin (a1): 99.3
Modified ethylene / α-olefin copolymer (a2) having a density of from 0.900 to 0.940 g / cm ³ , graft-modified with an unsaturated carboxylic acid or a derivative thereof, from 0.2 to 50% by weight.
0% by weight and ethylene / vinyl alcohol copolymer (b): 0.5 to 30% by weight, and ASTM D1238 (190 ° C .: 2
160g) has a melt flow rate (MFR) of 0.001 to 0.2 g / 10 min and a density of 0.940 to
ASTM D25 in the range of 0.970 g / cm ³
The composition layer (C) containing the polyethylene resin composition (c) having an Izod impact strength (notched) measured at −40 ° C. by the method of No. 6 of 100 J / m or more, further comprising: Multilayer laminate. 5. The multilayer laminate according to claim 3, wherein the polyethylene resin composition (c) is a multilayer laminate and / or a regrind of the scrap thereof. 6. The composition layer (C) is formed between the base layer (A1) and the adhesive layer (A2).
The multilayer laminate according to any one of the above. 7. A container comprising the multilayer laminate according to any one of claims 1 to 6. 8. ASTM D1238 (190 ° C .: 21
60g) has a melt flow rate (MFR) of 0.
001 to 0.5 g / 10 min, density 0.945 to 0.9
80 g / cm ³ polyethylene resin (a1): 99.3
Modified ethylene / α-olefin copolymer (a2) having a density of from 0.900 to 0.940 g / cm ³ , graft-modified with an unsaturated carboxylic acid or a derivative thereof, from 0.2 to 50% by weight.
0% by weight and ethylene / vinyl alcohol copolymer (b): 0.5 to 30% by weight, and ASTM D1238 (190 ° C .: 2
160g) has a melt flow rate (MFR) of 0.001 to 0.2 g / 10 min and a density of 0.940 to
ASTM D25 in the range of 0.970 g / cm ³
A polyethylene resin composition (c) having an Izod impact strength (with a notch) of not less than 100 J / m measured at -40 ° C by the method of 6. 9. The ratio of the graft-modified component to the whole polyethylene resin composition (c) is 100 to 1500 pp.
The polyethylene resin composition (c) according to claim 8, wherein m is m. 10. The polyethylene resin composition according to claim 8, which is a regrind of a multilayer laminate and / or a scrap thereof.