JPH0615789A - Multilayered laminate - Google Patents

Abstract

PURPOSE:To inexpensively provide a multilayered laminate excellent in gas barrier properties and mechanical strength, not lowered in gas barrier properties even by retorting or boiling treatment and excellent in the preservability of content. CONSTITUTION:A multilayered laminate is constituted by laminating at least one resin layer containing an ethylenic copolymer containing an ethylene unit and an acrylic derivative unit and/or a methacrylamide derivative unit and other thermoplastic resin layer using a hygroscopic gas barrier layer as an intermediate layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel multilayer laminate, and more specifically, it has excellent gas barrier properties and does not deteriorate in gas barrier properties even when subjected to retort treatment or boil treatment. The present invention relates to a multilayer laminate suitably used for a packaging film for articles and containers.

[0002]

2. Description of the Related Art Conventional multilayer laminates having gas barrier properties used for packaging films and containers for foods, medical products, etc. include, for example, saponified ethylene-vinyl acetate copolymer resin (hereinafter referred to as EVOH). Abbreviated), acrylonitrile copolymer resin, polyvinyl alcohol resin, polyamide resin (hereinafter abbreviated as PA), vinylidene chloride copolymer resin having a high oxygen barrier property, or metal foil such as aluminum foil is used as a gas barrier layer. Further, a layer obtained by laminating a hydrophobic polyolefin resin such as polyethylene, polypropylene or ethylene / α-olefin copolymer on this layer is used.

Among these, a multilayer laminate using a hygroscopic gas barrier resin such as EVOH, PA, polyvinyl alcohol resin, etc., has a gas barrier layer sufficiently suppressing permeation of gas such as oxygen under low humidity, so that the contents of Although it has the feature that the quality of the contents is stable over a long period of time by preventing oxidation, when this multilayer laminate is used by boiling in high temperature water of 90 to 135 ° C, such as a retort food packaging material. Water penetrates through the outer layer and is adsorbed by the gas barrier layer, and the gas barrier layer is made of a resin having a high water absorbing property such as an olefin-vinyl acetate copolymer saponified resin, a polyvinyl alcohol resin, or a polyamide resin. In this case, this moisture causes a rapid decrease in the gas permeation resistance of the gas barrier layer, and the function of the gas barrier layer is lost. There are, for applications such as retort food there is a problem that can not be used.

For example, when a multi-layer laminate having a thickness of about 100 μm and made of polypropylene, an adhesive resin layer and EVOH is retort-treated, EV is obtained under retort conditions of 120 ° C. or higher.
The water content adsorbed on OH becomes 7% by weight or more, and the oxygen permeation amount before retort treatment may increase 1000 times or more. Therefore, as a method to improve such inconvenience,
For example, a method has been proposed in which a desiccant composed of an inorganic metal salt is added to the adhesive layer for adhering the gas barrier layer and the outer layer, and the invading water is captured by this layer to prevent the deterioration of the gas barrier performance. . (European Patent No. 59274,
U.S. Pat. Nos. 4,407,897, 4,464,443 and JP-A-57-170748). However, in this method, there is a problem in that the interlayer adhesion strength between the adhesive layer and the gas barrier layer may be reduced, or the inorganic metal salt may be present as a foreign substance, so that the application may be unavoidable. .

Further, a method for improving water resistance by adding a phenol compound (US Pat. No. 4,347,337,
No. 4,289,830), a method of laminating a polyamide resin or a mixture thereof as an outermost layer adjacent to a polycarbonate resin having good water vapor permeability or an EVOH layer (JP-A-1-253442 and JP-A-1-308626). Publication, European Patent No. 322891) is disclosed. However, although these methods may be effective for thin products such as films, they are not effective for thick products such as sheets and bottles, and cost is high, and polycarbonate resins and the like are not suitable for multilayer extrusion. It is difficult and requires special extrusion equipment.

On the other hand, in a multi-layer laminate including an EVOH layer, a method has been attempted in which the EVOH layer is arranged at an outer position to accelerate recovery of gas barrier property after retort treatment ["Paper, Film and Foil. Converter (Paper, Film & Foil Converter) "October issue, No. 5
Page 4 (1985), "Food Package" November issue, page 82 (1985), December issue, 67
Page (1985), "COEX'89", Page 267 (1989) (Schotland Business Research In
c. (USA) sponsorship)). However, in this method, since the multilayer thickness is a non-symmetrical multilayer structure, the target shape has the same multilayer thickness in coextrusion molding and the like.
Where only one extruder for the resin for the outer layer is required, an extra extruder is required, which is disadvantageous in terms of cost and has problems such as insufficient recovery of gas barrier properties. There is.

Further, recently, it has been attempted to use EVOH having a high ethylene unit content and to preliminarily set the thickness of the EVOH layer to a large thickness in anticipation of a decrease in gas barrier property due to the retort treatment. ["Future-PAK'90" page 125 (1990), Ryder Associates. Inc.
(USA)]. However, this method has the disadvantage that it is unavoidably expensive. Further, a method of blending a polymer network structure such as a vinyl alcohol-acrylate copolymer network structure with either the oxygen barrier layer or the outer layer or the adhesive layer (JP-A-62-182030).
JP-A-62-208344), and a method of blending an inorganic powder such as mica or sericite with the outer layer and the EVOH layer (JP-A-2-47139). However, in the former method, the polymer network structure is inferior in melt moldability and thermal stability, so that there is a problem in molding, and in the latter method, since the inorganic powder is blended, it becomes hard and brittle. There was a problem.

[0008]

Under these circumstances, the present invention does not require a special extrusion device, has an excellent gas barrier property, and has a reduced gas barrier property even by a retort process or a boil process. The purpose of the invention is to provide a multi-layer laminate that does not do so at low cost.

[0009]

DISCLOSURE OF THE INVENTION As a result of intensive studies to develop a multilayer laminate having the above-mentioned preferable properties, the present inventors have found that a hygroscopic gas barrier layer is an intermediate layer and at least one ethylene layer is formed. It has been found that the object can be achieved by laminating a resin layer containing an ethylene-based copolymer containing a unit and an acrylamide derivative and / or a methacrylamide derivative unit and another thermoplastic resin layer. The present invention has been made based on such findings. That is, the present invention provides a resin layer comprising (A) a hygroscopic gas barrier layer as an intermediate layer and at least one layer (B) an ethylene-based copolymer containing ethylene units and acrylamide derivative and / or methacrylamide derivative units. And (C) a multilayer laminate formed by laminating other thermoplastic resin layers.

In the multilayer laminate of the present invention, the hygroscopic gas barrier layer (A) is used as the intermediate layer. For this hygroscopic gas barrier layer, saponified olefin-vinyl acetate copolymer and / or polyamide resin is preferably used. Examples of the olefin-vinyl acetate copolymer saponified resin include EVOH and propylene-vinyl acetate copolymer saponified resin, and EVOH is preferably used because polymerization is particularly easy. It is preferable that the EVOH contains ethylene units in an amount of 15 mol% or more, preferably 15 to 60 mol% and the vinyl acetate component has a saponification degree of 90 mol% or more. If the ethylene unit content is less than 15 mol%, the melt moldability will be insufficient, and if it exceeds 60 mol%, the gas barrier property will decrease. Further, if the saponification degree is less than 90 mol%, the gas barrier property is deteriorated. Especially when the ethylene unit content is 25
EVOH with a saponification degree of 96 mol% or more at 50 mol%
Is good. In addition to ethylene units, vinyl acetate units, and vinyl alcohol units formed by saponifying them, unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, and maleic acid, alkyl esters thereof, or propylene, butene, α -Α-such as decene and α-octadecene
It may contain a unit of a monomer such as an olefin.

On the other hand, examples of the polyamide resin include lactam, ε-amino acid, and polycondensation product of dibasic acid and diamine. Specifically, polymers such as ε-caprolactam, aminolactam, enanthlactam, 11-aminoundecanoic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, α-pyrrolidone and α-piperidone, and hexamethylenediamine and nonamethylene. Polycondensation products of diamines such as diamine, undecamethylenediamine, dodecamethylenediamine, metaxylylenediamine and dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid and glutaric acid, or these A copolymer is mentioned. Furthermore, specifically, nylon 4, nylon 6, nylon 7, nylon 8, nylon 11, nylon 12, nylon 6.6, nylon 6
・ 9, nylon 6/10, nylon 6/11, nylon 6/12, nylon MXD, etc.

In the multi-layer laminate of the present invention, at least one resin layer containing (B) an ethylene-based copolymer containing ethylene units and acrylamide derivative and / or methacrylamide derivative units is provided. Regarding the ethylene-based copolymer containing the ethylene unit and the acrylamide derivative and / or methacrylamide derivative unit, "Polymer Thesis Collection", Vol. 35, No. 12, p. 795 (1
978), U.S. Pat. No. 3,629,209, Japanese Patent Publication No. 4
3-21655, Japanese Patent Publication No. 44-19537, Japanese Patent Publication No. 43-23766, Japanese Patent Publication No. 43-90.
It can be obtained by a usual method described in JP-A-63, JP-A-63-304010, or the like.

Examples of the acrylamide derivative or methacrylamide derivative constituting the ethylene copolymer include N-alkyl acrylamide; N, N-dialkyl acrylamide; N-alkyl methacrylamide; and N, N-dialkyl methacrylamide. Specifically, N-methyl acrylamide; N-ethyl acrylamide; N-n-
Propylacrylamide; N-isopropylacrylamide; Nn-butylacrylamide; N-isobutylacrylamide; Nt-butylacrylamide; N,
N-dimethyl acrylamide; N, N-diethyl acrylamide; N-ethyl methacrylamide; Nn-propyl methacrylamide; Nt-butyl methacrylamide; N, N-dimethyl methacrylamide; N, N-diethyl methacrylamide, etc. These can be used alone or as a mixture. Of these, N-ethyl acrylamide; N-isopropyl acrylamide; Nt-butyl acrylamide; N, N-
Dimethyl acrylamide; N; N-diethyl acrylamide; Nn-propyl methacrylamide; Nt-butyl methacrylamide and the like are preferable.

The content of the acrylamide derivative and / or methacrylamide derivative unit in the ethylene copolymer is usually 0.1 to 50% by weight, preferably 1 to 45% by weight. If the content is less than 0.1% by weight, the effect of preventing the deterioration of the barrier property is not sufficiently exerted by the retort treatment, but if it exceeds 50% by weight, the copolymer loses its flexibility and becomes a multilayer laminate. However, there is a risk of causing an unfavorable situation such as insufficient rigidity. The ethylene-based copolymer resin may contain units derived from other polymerizable monomers, in addition to the ethylene unit and the acrylamide derivative and / or methacrylamide derivative unit. Here, as other polymerizable monomers, ester compounds each having an unsaturated bond,
Examples thereof include acid compounds, ether compounds and hydrocarbon compounds.

Examples of the ester compound having an unsaturated bond include vinyl acetate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate,
Hexyl acrylate, octyl acrylate, lauryl acrylate, benzyl acrylate, N, N-dimethylaminoethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, Lauryl methacrylate, N, N-dimethylaminoethyl methacrylate, methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, methyl maleate, Examples thereof include ethyl maleate, propyl maleate, butyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate and dibutyl maleate.

Examples of the acid compound having an unsaturated bond include acrylic acid, methacrylic acid, maleic acid and fumaric acid. Examples of the ether compound having an unsaturated bond include methyl vinyl ether,
Examples include ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octadecyl vinyl ether, and phenyl vinyl ether. Furthermore, examples of the hydrocarbon compound having an unsaturated bond include styrene, norbornene, butadiene, acrylonitrile, methacrylonitrile, acrolein, crotonaldehyde, trimethoxyvinylsilane, vinyl chloride, and the like.
Examples thereof include vinylidene chloride. These third component monomers may be used alone or in combination of two or more depending on the intended use. The content of the units derived from the monomer of the third component in the copolymer is preferably 40% by weight at most. The content is 40
When the content exceeds the weight%, the inherent properties of the ethylene copolymer may be impaired.

Basically, it is preferable that the above-mentioned third component monomer does not react with the acrylamide derivative and the methacrylamide derivative, but if the amount used is selected in consideration of the stoichiometry, these derivatives will not react. It is also possible to use reactive monomers. Particularly for applications requiring transparency, it is preferable to contain at least 3% by weight of the monomer of the third component in order to reduce the crystallinity of the ethylene-based copolymer. More preferably at least 5% by weight, particularly preferably at least 10% by weight is used. Further, when used in a field requiring oil resistance in industrial material applications, it is preferable to select and copolymerize a monomer having a high polarity as the third component. In particular, acrylonitrile, acrylic acid, acrylic acid ester and the like can be given as specific preferred monomers.

Furthermore, in the field of food packaging, where the application is hygienic, low odor and low taste are strongly required. The odor caused by the monomer of the third component usually depends on the amount remaining in the copolymer and cannot be unconditionally limited, but it is preferably 3% by weight at most. Particularly, in a laminate for which strict odorlessness and tastelessness are required, there is no or very little use of the third component monomer having a strong odor, and the amount of the monomer is at most 1% by weight. desirable. The resin containing the ethylene copolymer used as the component (B) has a melting index (MFR, load of 2.61 according to JIS-K6758).
There is no particular limitation on the measurement (kg, temperature 230 ° C.), and it may be appropriately selected depending on the molding method, but in the case of extrusion molding, the range of 0.1 to 50 g / 10 minutes is suitable.

In the multilayer laminate of the present invention, another thermoplastic resin layer is provided as the (C) layer. Examples of the other thermoplastic resins include polyolefin resins represented by polypropylene and polyethylene, polycarbonate resins, polyamito resins, and the like. The polyolefin resin is medium / high density polyethylene, homopolypropylene, ethylene-propylene random copolymer, ethylene-propylene block copolymer,
It refers to an α-olefin copolymer having 3 to 12 carbon atoms with ethylene. Examples of the ethylene-α-olefin copolymer having 3 to 12 carbon atoms include ethylene-butene-1 copolymer,
Ethylene-4 methylpentene-1 copolymer, ethylene-
Examples include hexene-1 copolymer, ethylene-butene-1 copolymer, modified polypropylene obtained by blending ethylene-propylene rubber and the like, modified polybutene, modified ethylene-4 methylpentene and the like. Further, as the polyolefin resin, an unsaturated carboxylic acid or its acid anhydride is grafted onto the above polyolefin polymer in the presence of an organic peroxide or copolymerized with another monomer (for example, methyl methacrylate, ethyl acrylate, etc.). You can list things such as things. Of these, polypropylene resin and polyester resin such as homopolypropylene, ethylene-propylene random copolymer, ethylene-propylene block copolymer, etc. preferable. Further, in view of cost and versatility, polypropylene resin is particularly preferable.

Next, regarding the layer structure of the multilayer laminate of the present invention, at least one layer (B) of a resin layer containing an ethylene-based copolymer containing an ethylene unit and an acrylamide derivative and / or a methacrylamide derivative unit is laminated. However, the effect of the present invention cannot be exhibited without this layer. The (B) layer may be adjacent to the hygroscopic gas barrier layer of the (A) layer or may be provided separately. When adjoining, the hygroscopic gas barrier layer is EVOH.
When it has excellent compatibility with the ethylene-based copolymer, such as PA or PA, the ethylene-based copolymer may be used as the layer (B) and laminated directly adjacent to each other. on the other hand,
When the layer (B) is provided separately from the hygroscopic gas barrier layer, the ethylene-based copolymer may be mixed in the adhesive resin layer in the coextrusion molding. In this case, EVOH
The adhesive peel strength with PA and PA is improved, which is particularly preferable. Further, it may be mixed with a layer containing scrap. In this case, the content of the ethylene copolymer is preferably in the range of 2 to 80% by weight. If this content is less than 2% by weight, the effect of trapping water entering during retort treatment or sterilization of boil tends to be small. On the other hand, 80% by weight
If it exceeds, the rigidity is lowered, which is not preferable. More preferably, it is in the range of 5 to 70% by weight. The layer (B) is preferably laminated on the outer side of the hygroscopic gas barrier layer of the layer (A) because the effect of the present invention is remarkably exhibited.

The method for processing the multilayer laminate of the present invention includes:
Generally, it is carried out by so-called co-extrusion molding (feed block, multi-manifold) in which a number of extruders corresponding to the resin is used and the molten resin flows are co-extruded in a multi-layered state. The multilayer laminate is prepared by a co-injection molding method, a co-extrusion pipe molding method, and a dry lamination molding method or a sandwich lamination molding method using a dry laminating adhesive such as polyethyleneimine, a titanate coupling agent, or an isocyanate acrylic. Alternatively, it can be obtained by various molding methods such as a coextrusion lamination molding method. The multilayer laminate thus obtained can be reheated using a vacuum forming machine, a compressed air forming machine, a stretch blow molding machine, or the like, and subjected to a stretching operation.
Alternatively, the above-mentioned multilayer laminate can be subjected to a heat stretching operation using a uniaxial or biaxial stretching machine.

[0022]

Although the reason for the multilayer laminate of the present invention is not clear,
Since the water entering through the retort treatment is adsorbed by the ethylene copolymer of the layer (B) which is also a hygroscopic material before being adsorbed by the hygroscopic gas barrier layer of the intermediate layer, the gas barrier layer is It seems that the gas barrier performance originally possessed can be maintained without impairing it.

[0023]

EXAMPLES Next, the present invention will be described in more detail by way of examples. Production Example 1 (Production of ethylene-N, N'-dimethylacrylamide copolymer) Polymerization was carried out at a temperature of 190 to 210 ° C and a pressure of 1 in an autoclave type reactor divided into 2 zones with an internal volume of 4 liters.
It was carried out using t-butyl peroxide as an initiator under the conditions of 100 to 1300 atm. N, N′-dimethylacrylamide and acrylamide were used as the acrylamide component, and these and other monomers and / or solvents were injected upstream of the second stage compressor and fed with ethylene to the first zone of the reactor. The produced copolymer was separated into unreacted monomers by a high-pressure separator and a low-pressure separator and pelletized by using an extruder to produce the copolymers shown in (a) to (e) below. The contents of N, N'-dimethylacrylamide and acrylamide were measured by an infrared spectrometer and ¹³ C.
-Determined using NMR. (A) Ethylene-N, N'-dimethylacrylamide copolymer (MFR 3.5 g / 10 min, N, N'-dimethylacrylamide = 19.2 wt%) (b) Ethylene-N, N'-dimethylacrylamide copolymer Polymer (MFR 3.7 g / 10 min, N, N'-dimethylacrylamide = 37 wt%) (c) Ethylene-acrylamide copolymer (MFR 4.6 g / 10 min, acrylamide = 11.4 wt%) (d) Ethylene-methylmethacrylate-N, N'-dimethylacrylamide copolymer (MFR 5.1 g / 10 min, methylmethacrylate content = 6.2% by weight, N, N'-dimethylacrylamide = 9.
1% by weight) (e) Ethylene-vinyl acetate-N, N'-dimethylacrylamide copolymer (MFR 4.4 g / 10 min, vinyl acetate content = 3.4% by weight, N, N'-dimethylacrylamide = 24) 0.1% by weight)

Example 1 As a hygroscopic gas barrier resin, "Asonol A" manufactured by Nippon Synthetic Chemical Industry Co., Ltd., which is an EVOH having an ethylene unit content of 44 mol%, was used as an adhesive resin with an adhesive resin of polypropylene and EVOH. Showa Denko KK "ER3
21P "(MFR 5.5g / 10 minutes, JIS-K6758
(Measured at 230 ° C. in accordance with the above) was used as a resin for forming the surface layer, polypropylene “Show Allomer SA510” manufactured by Showa Denko KK. Further, the (b) copolymer obtained in Production Example 1 was used as the ethylene-based copolymer of the (B) layer. Using a feedblock type multi-layer sheet forming machine with a die temperature of 220 ° C., a multi-layer sheet is prepared, and then the multi-layer sheet is subjected to a vacuum forming machine to obtain a drawing ratio of 0.
5, a container with an internal capacity of 100 cc was prepared. This container 12
After performing retort treatment at 5 ℃ for 30 minutes, use Modern Con
Using OXTRAN-10 / 50A manufactured by trol, oxygen gas barrier properties of three containers were measured before and after the retort treatment under the conditions of 23 ° C. and 65% RH, and an average value was obtained. The layer structure and thickness of this container were as follows. Polypropylene is PP, adhesive resin is AD, EV
OH is EV, and the (b) copolymer is represented by the symbol B. In the PP layer, the PP on the outside of the container is shown outside and the PP on the inside is shown inside. Inner PP / AD / B / AD / EV / AD / B / AD / Outer P
P = 425/10/20/10/10/30/10/20/1
0/425 μm The oxygen transmission rate of this container was 0.01 (cc /
Container / day / atm), 0.013 after retort treatment
(Cc / container / day / atm).

Comparative Example 1 In Example 1, the layer (B) was not provided, and the layer structure and thickness were: inner PP / AD / EV / AD / outer PP = 455/10 /
Example 1 was carried out in the same manner as in Example 1 except that the thickness was 30/10/455 μm. As a result, the amount of oxygen permeation was 0.01 (cc / container · day · atm) before the retort treatment and 0.84 (cc / container · day · atm) after the retort treatment.

Example 2 Using the same material as in Example 1, in the layer structure, the inner PP / AD / B / AD / E is made so that the outer PP layer becomes thin.
V / AD / B / AD / outer PP = 610/10/20/1
The same procedure as in Example 1 was carried out except that the thickness was 0/30/10/20/10/240 μm. As a result, the oxygen permeation amount was 0.01 (cc / container / day / at) before the retort treatment.
m), 0.06 after retort treatment (cc / container / day / a
tm). The oxygen permeation amount after one month is 0.02.
(Cc / container / day / atm).

Examples 3 to 6 In Example 1, as the hygroscopic gas barrier resin, "Soarnol DT" manufactured by Nippon Synthetic Chemical Industry Co., Ltd., which is EVOH having an ethylene unit content of 29 mol%, is used (B )
Example 1 was carried out in the same manner as in Example 1 except that the ethylene-based copolymer constituting the layers was the one obtained in Production Example 1 shown in Table 1. The results are shown in Table 1.

[0028]

[Table 1]

Comparative Example 2 In Example 1, the layer structure was changed to an inner PP / AD / EV / A so that the outer PP layer was thinned without providing the (B) layer.
D / outer PP = 610/10/30/10/240 μm, but the same procedure as in Example 1 was performed. As a result, the amount of oxygen permeation before the retort treatment was 0.01 (cc / container / container /
after the retort treatment was 3.08 (cc / container · day · atm). The oxygen permeation amount after one month was 0.68 (cc / container · day · atm).

Examples 7 to 12 and Comparative Examples 3 to 4 ER3 manufactured by Showa Denko KK having an MFR (value measured at 230 ° C. according to JIS-K6758) of 5.5 g / 10 min.
21P and the ethylene-based copolymer obtained in Production Example 1 of the type shown in Table 2 using a 40 mmφ single screw extruder at a temperature of 2
Pelletization was carried out at 20 ° C by changing the mixing ratio as shown in Table 2. This resin molded product was used as an adhesive resin [referred to as B (AD)], and the same layer structure as shown in Example 1 was used. The results are shown in Table 2. Inner PP / B (AD) / EV / B (AD) / Outer PP = 42
5/20/30/20/425 μm

[0031]

[Table 2]

Comparative Example 5 In Example 1, the EVOH was changed to "Soarnol DT", and the (B) layer was not provided, and the inner PP / AD / EV / AD / outer PP =
Other than 610/10/30/10/240 μm,
It carried out like Example 1. As a result, the amount of oxygen permeation before the retort treatment was 0.01 (cc / container / day / at
m), after retort treatment is 4.58 (cc / container / day / a
tm). The oxygen transmission rate after one month is 0.43.
(Cc / container / day / atm).

[0033]

EFFECTS OF THE INVENTION According to the present invention, a multi-layer laminate having excellent gas barrier properties and mechanical strength, and having a gas barrier property not deteriorated by retort treatment or boil treatment and having excellent storage stability of contents is specially prepared. It is possible to obtain a low cost without the need for a special extrusion device. The multilayer laminate of the present invention is suitable for use as a packaging film or container for foods, medical products and the like.

Claims (9)

[Claims] 1. A resin layer comprising (A) a hygroscopic gas barrier layer as an intermediate layer and containing at least one layer (B) an ethylene-based copolymer containing an ethylene unit and an acrylamide derivative and / or a methacrylamide derivative unit, and (C) A multilayer laminate formed by laminating other thermoplastic resin layers. 2. The multilayer laminate according to claim 1, wherein the layer (B) is a layer composed only of an ethylene-based copolymer containing an ethylene unit and an acrylamide derivative and / or a methacrylamide derivative unit. 3. A mixture of the ethylene-based copolymer, wherein the layer (B) contains 2 to 80% by weight of the ethylene-based copolymer containing an ethylene unit and an acrylamide derivative and / or a methacrylamide derivative unit, and an adhesive resin. The multilayer laminate according to claim 1, which is a layer made of a resin. 4. An ethylene-based copolymer containing an ethylene unit and an acrylamide derivative and / or a methacrylamide derivative unit contains the acrylamide derivative and / or a methacrylamide derivative unit in a proportion of 0.1 to 50% by weight. A multilayer laminate according to any one of claims 1 to 3. 5. The multilayer laminate according to claim 1, wherein the acrylamide derivative unit is an N-alkyl-substituted acrylamide derivative unit. 6. The acrylamide derivative unit is N, N ′.
-The multilayer laminate according to claim 1, which is a dimethyl acrylamide unit. 7. The multilayer laminate according to claim 1, wherein the hygroscopic gas barrier layer (A) is an olefin-vinyl acetate copolymer saponified resin and / or a polyamide resin. 8. The multilayer laminate according to claim 7, wherein the olefin-vinyl acetate copolymer saponified resin is an ethylene-vinyl acetate copolymer saponified resin. 9. The multilayer laminate according to claim 8, wherein the saponified ethylene-vinyl acetate copolymer resin has an ethylene unit content of 15 mol% or more and a saponification degree of 90 mol% or more.