JPH09187892A - Multilayer laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to simultaneously satisfy the flexibility, gas barrier properties, interlayer adhesive properties, heat sealability or high-frequency sealability and heat resistance by forming a crosslinkable ethylene copolymer composition layer to a composition layer obtained by kneading specific components. SOLUTION: As the component to be kneaded with a composition layer, first it is multi-component copolymer made of at least ethylene and radical polymerizable acid anhydride, and ethylene copolymer having 0.1 to 5wt.% of the ratio of the unit according to the radical polymerizable acid anhydride in the copolymer. Second, it is polyvalent alcohol compound having at least two hydroxyl groups in a molecule, but the molar ratio of the unit of the hydroxyl group in the polyvalent alcohol compound is in a range of 0.01 to 10 to the unit according to the radical polymerizable acid anhydride in the first ethylene copolymer. Third, it is reaction accelerator of a range of 0.01 to 20 pts.wt. to 100 pts.wt. of ethylene copolymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a multilayer laminate containing at least a crosslinkable ethylene-based copolymer composition layer and a gas barrier substrate layer, and in a particularly preferred embodiment, an ethylene-vinyl alcohol copolymer or The present invention relates to a multilayer laminate using a gas barrier substrate layer made of a polyamide resin, and a multilayer laminate having gas barrier properties and simultaneously satisfying both high frequency sealing properties and heat resistance.

[0002]

2. Description of the Related Art Conventionally, gas-barrier resins such as ethylene-vinyl alcohol copolymers and polyamide resins having excellent barrier properties against oxygen, nitrogen and carbon dioxide have been widely used as packaging materials for foods and the like. These gas barrier resins, except for acrylonitrile-based resin and vinylidene chloride resin, their gas barrier properties vary greatly depending on the water content, and in order to fully exert their performance, one side of the gas barrier resin film or It is often used as a composite film on both sides of which other moisture-proof films are laminated. Further, the gas barrier resin is poor in heat sealability and high frequency sealability except for acrylonitrile-based resin, and therefore, when used as a packaging material, the heat sealability or the outermost layer of the composite film including gas barrier property is used. It is used by laminating a resin film having a high frequency sealing property on the sealing layer side. In general, the seal layer often also functions as the moisture-proof film.

[0003]

In the case of forming a composite film as described above, since the gas barrier resin has poor adhesiveness, it is necessary to use a polyolefin resin grafted with maleic anhydride as an adhesive layer for coextrusion molding. Since it is necessary to carry out extrusion laminating molding through an adhesive and laminating the layers, there is a problem that the layer structure becomes complicated and the manufacturing equipment and working process become complicated, resulting in an increase in cost. Further, the film is variously selected according to the purpose, but when heat resistance is required, polypropylene resin, polycarbonate resin, polyester resin or the like is selected and laminated, but the problem that flexibility is often impaired have. In addition, the laminate has flexibility and low temperature heat sealability,
When it is desired to impart high-frequency sealability, etc., ethylene-vinyl acetate copolymer, in the seal layer of the composite film,
A method of laminating a flexible resin such as an ethylene- (meth) acrylic acid alkyl ester copolymer via an adhesive resin is adopted. However, when the laminated body is exposed to a high temperature environment of, for example, 80 ° C., there is a problem in heat resistance such as a remarkable change in appearance, sagging or peeling at a seal portion or an adhesive interface with a gas barrier resin. is there. Further, a flexible resin such as ethylene-vinyl acetate copolymer graft-modified with maleic anhydride or an ethylene-maleic anhydride- (meth) acrylic acid alkyl ester copolymer is laminated to form an adhesive layer with a gas barrier resin. Even when it is used also as the function of the sealing layer, the heat resistance is insufficient. As a method for imparting heat resistance, there is a method in which a soft resin such as the above-mentioned ethylene-vinyl acetate copolymer or a maleic anhydride graft modified product thereof is laminated and then crosslinked with an electron beam or an organic peroxide. Requires special cross-linking equipment, and the latter has a problem that the laminate is deformed due to heat history in the cross-linking process. Further, a method has been proposed in which ethylene-maleic anhydride- (meth) acrylic acid alkyl ester is crosslinked with a crosslinking agent such as an epoxy resin. In this case, however, thermal stability during molding is remarkably poor, and thus in an extruder. There is a problem that it is extremely difficult to obtain a laminated film having good appearance due to progress of crosslinking, and the sealing property is deteriorated by crosslinking. The object of the present invention is to solve various problems in the above-mentioned conventional techniques, have flexibility, gas barrier properties, etc., have excellent interlayer adhesiveness, and satisfy heat sealability or high frequency sealability and heat resistance at the same time. It is to provide a multilayer laminate having a good appearance.

[0004]

The inventors of the present invention have made extensive studies in order to solve the above problems, and as a result, have found that a specific ethylene-based multi-component copolymer and a polymer having at least two or more hydroxyl groups in the molecule. The crosslinkable ethylene-based copolymer composition consisting of a polyhydric alcohol compound and a reaction accelerator has high adhesiveness to a gas barrier resin, and the resulting laminate has good high-frequency sealing property and high heat resistance. Have been found. The present invention has been completed based on such findings.

The multilayer laminate of the present invention is a multilayer laminate containing at least a crosslinkable ethylene copolymer composition layer and a gas barrier substrate layer, wherein the crosslinkable ethylene copolymer composition layer is ) To (C) are kneaded to form a composition layer. (A) A multicomponent copolymer comprising at least ethylene and a radical-polymerizable acid anhydride, wherein the proportion of units derived from the radical-polymerizable acid anhydride in the copolymer is 0.1% by weight to 5%.
Ethylene copolymer, which is wt%. (B) A polyhydric alcohol compound having at least two hydroxyl groups in the molecule. However, the molar ratio of the unit of the hydroxyl group in the polyhydric alcohol compound to the unit derived from the radical-polymerizable acid anhydride in the ethylene copolymer (A) is 0.01.
-10. (C) A reaction accelerator in the range of 0.001 to 20 parts by weight based on 100 parts by weight of the ethylene copolymer.

Here, the polyhydric alcohol compound (B) is
The following general formula (I) (R ¹ ) _a C (CH ₂ OH) _b (I) [wherein R ¹ represents hydrogen or a chain or cyclic alkyl group having 1 to 12 carbon atoms or an aralkyl group, and a is 0
~ 2 represents an integer, b represents an integer of 2 to 4, and a +
It is selected to satisfy b = 4. Or the following general formula _{(II) CH 2 (OH)} CH (OH) CH 2 O [CH 2 CHOHCH 2 O] m H (II) [ wherein, m is an integer of 0. Polyhydric polyoxyalkylene compound having a structure obtained by adding ethylene oxide or propylene oxide to an alcohol compound, or the following general formula (III) in R ² -COOH (III) [represented by the formula], R ² is 2 carbon atoms 25 chain alkyl groups, cyclic alkyl groups, aralkyl groups or alkenyl groups are shown. ] One or more of polyglycerin esters having two or more hydroxyl groups in the molecule, which are obtained by dehydration condensation of the organic carboxylic acid compound represented by the above and the polyglycerin represented by the general formula (II). It is preferable. Further, the reaction accelerator of the component (C) is preferably a metal salt of a polymer containing a carboxyl group or a metal salt of an organic carboxylic acid. The gas barrier substrate is preferably a polyamide resin or a copolymer of ethylene and vinyl alcohol.

The ethylene-based copolymer (A) is a multi-component copolymer composed of ethylene, a radical-polymerizable acid anhydride and a radical-polymerizable comonomer other than the radical-polymerizable acid anhydride. The proportion of the units derived from the radical-polymerizable acid anhydride is 0.1% by weight to 5% by weight, and the proportion of the units derived from the radical-polymerizable comonomer other than the radical-polymerizable acid anhydride is 5% by weight to It is preferably 50% by weight.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The ethylene copolymer which is the component (A) according to the present invention is a multi-component copolymer containing at least ethylene and a radical-polymerizable acid anhydride. here,
The radical-polymerizable acid anhydride means a compound having one or more radical-polymerizable unsaturated bond and one or more acid anhydride group in the molecule, and capable of introducing an acid anhydride group into the molecule by polymerization. . The acid anhydride group is preferably cyclic. Such compounds include, for example, maleic anhydride, itaconic anhydride, citraconic anhydride, endic anhydride,
Examples thereof include dodecenyl succinic anhydride, 1-butene-3,4-dicarboxylic acid anhydride, and alkadienyl succinic anhydride having a double bond at the terminal having at most 18 carbon atoms. These may be used alone or in combination of two or more kinds. Among these, maleic anhydride and itaconic anhydride are particularly preferable. The proportion of the units derived from the radical-polymerizable acid anhydride in the ethylene copolymer as the component (A) needs to be in the range of 0.1 to 5% by weight, preferably 0.5 to 5. It is in the range of 4.5% by weight, particularly preferably in the range of 1.0 to 3.5% by weight. Radical polymerizable acid anhydride content is 0.1% by weight
If it is less than the above range, sufficient adhesive strength is not obtained and good adhesive strength cannot be obtained, and sufficient crosslink density cannot be obtained, so sufficient heat resistance cannot be obtained. On the other hand, if it exceeds 5% by weight, there is almost no effect of improving the adhesive strength, and further, it becomes difficult to manufacture it commercially, which is not preferable.

If desired, a radical-polymerizable comonomer other than the radical-polymerizable acid anhydride may be used in the ethylene copolymer as the component (A). There are various compounds as radical-polymerizable comonomers other than radical-polymerizable acid anhydrides, and examples thereof include ethylenically unsaturated ester compounds, ethylenically unsaturated amide compounds, ethylenically unsaturated acid compounds, and ethylenically unsaturated ether compounds. , Ethylenically unsaturated hydrocarbon compounds, other compounds and the like. If these are specifically described, examples of the ethylenically unsaturated ester compound include vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylate.
Propyl acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, methyl fumarate, ethyl fumarate, propyl fumarate , Butyl fumarate, dimethyl fumarate, diethyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, methyl maleate, ethyl maleate, propyl maleate, butyl maleate, dimethyl maleate, maleate Diethyl acid,
Examples thereof include dipropyl maleate and dibutyl maleate. Examples of the ethylenically unsaturated amide compound include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-
Propyl (meth) acrylamide, N-butyl (meth)
Examples thereof include acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like. Examples of the ethylenically unsaturated acid compound include (meth) acrylic acid, maleic acid, fumaric acid and the like. Examples of the ethylenically unsaturated ether compound include methyl vinyl ether,
Examples thereof include ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octadecyl vinyl ether and phenyl vinyl ether. Examples of the ethylenically unsaturated hydrocarbon compound include styrene, α-methylstyrene, norbornene, butadiene and the like. Examples of other compounds include (meth) acrylonitrile, acrolein, crotonaldehyde, trimethoxyvinylsilane, vinyl chloride, vinylidene chloride,
N-vinyl acetamide etc. are mentioned. Among these, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate are mentioned as particularly preferable compounds. These monomers may be used alone or in combination of two or more.

In the multi-layer laminate of the present invention, particularly in applications where high-frequency sealing property is required, the proportion of units derived from the radical-polymerizable comonomer in the ethylene copolymer (A) is 5 to 50% by weight. Ranges are preferred. More preferably in the range of 8-40% by weight, and further preferably 10-3.
It is in the range of 5% by weight. Here, if the proportion of the radical-polymerizable comonomer is less than 5% by weight, the crystal melting point of the ethylene-based copolymer will not be sufficiently lowered, and the low-temperature heat-sealing property and the high-frequency sealing property cannot be sufficiently exhibited. Also,
If it exceeds 50% by weight, handling of the resin becomes difficult due to mutual adhesion and the heat resistance of the product decreases. As a method for producing the ethylene-based copolymer (A), various methods such as radical solution polymerization can be used, but in general, ordinary high-pressure process low-density polyethylene production equipment is used. Manufactured. The ethylene-based copolymer which is the component (A) is rich in physicochemical interaction and reactivity with the gas barrier resin, and therefore is large in exhibiting high interlayer adhesion strength in the multilayer laminate of the present invention. Play a role. In addition, since it melts at a relatively low temperature and has a large dielectric loss, it plays a major role in exhibiting low-temperature heat sealability and high-frequency sealability.

The polyhydric alcohol compound having at least two hydroxyl groups in the molecule, which is the component (B) relating to the present invention, means a compound having two or more hydroxyl groups, and has a function as a so-called crosslinking agent. It is a thing. Examples of such polyhydric alcohol compounds include ethylene glycol, glycerin, 1,4-butanediol, 1,6
Alcohol compounds such as hexanediol, 1,8-octanediol, 1,10-decanediol, trimethylolmethane, trimethylolethane, trimethylolpropane and pentaerythritol; polyethylene glycols such as diethylene glycol, triethylene glycol and tetraethylene glycol; di Polyglycerin such as glycerin, triglycerin and tetraglycerin; saccharides such as albitol, sorbitol, xylose, arabinose, glucose, galactose, sorbose, fructose, palatinose, maltotriose, malezitose and sorbitan; dehydration condensation products of these saccharides; Polyoxyalkylene compounds obtained by adding ethylene oxide or propylene oxide to various compounds of Compounds partially esterified in;
A compound obtained by partially esterifying the above polyoxyalkenylene compound with a carboxylic acid; a polyoxyalkylene compound obtained by further adding ethylene oxide or propylene oxide to the above partially esterified compound;
Examples thereof include saponified products of ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyolefin-based oligomers having two or more hydroxyl groups, and polymers having two or more hydroxyl groups such as ethylene-hydroxyethyl (meth) acrylate copolymer. The melting point of the polyhydric alcohol compound is 3
It is preferably 00 ° C or lower. Further, these polyhydric alcohol compounds may be used in combination of two or more kinds at the same time. Particularly preferred as the polyhydric alcohol compound (B) is at least one compound selected from the following polyhydric alcohols. These compounds, in addition to having a function as a so-called cross-linking agent, impart heat stability to the cross-linkable ethylene copolymer constituting the multilayer laminate of the present invention, and when molded at a relatively high temperature, It has the effect of preventing the formation of gel, lumps and the like on the body.

First, the following general formula (I) (R ¹ ) _a C (CH ₂ OH) _b (I) [wherein R ¹ is hydrogen or a chain or cyclic alkyl group having 1 to 12 carbon atoms] Or represents an aralkyl group,
Represents an integer of 0 to 2, b represents an integer of 2 to 4, and is selected so as to satisfy a + b = 4. ]

Alternatively, the following general formula (II) CH ₂ (OH) CH (OH) CH ₂ O [CH ₂ CHOHCH ₂ O] _m H (II) [wherein, m is an integer of 0 to 10]. ] The polyoxyalkylene compound which has the structure which added ethylene oxide or propylene oxide to the polyhydric alcohol compound shown by these,

Alternatively, the following general formula (III) R ² —COOH (III) [wherein, R ² represents a chain alkyl group having 2 to 25 carbon atoms, a cyclic alkyl group, an aralkyl group or an alkenyl group. ] One or more of polyglycerin esters having two or more hydroxyl groups in the molecule, which are obtained by dehydration condensation of the organic carboxylic acid compound represented by the above and the polyglycerin represented by the general formula (II). .

The above polyoxyalkylene compound can be easily obtained by adding ethylene oxide or propylene oxide to the polymethylol represented by the general formula (I) or the polyglycerin represented by (II) by an ordinary method. To be Here, as the polymethylol represented by the general formula (I), for example, 1,3-dihydroxypropane; 2,2-dimethyl-1,3-dihydroxypropane; trimethylolethane: 1,1,1-tri Methylol propane; 1,1,1-trimethylol hexane; 1,1,
1-trimethylol dodecane; 2-cyclohexyl-2
-Methylol-1,3-dihydroxypropane; 2-
(P-methylphenyl) -2-methylol-1,3-dihydroxypropane; pentaerythritol and the like.

Examples of the polyglycerin represented by the general formula (II) include glycerin, diglycerin, hexaglycerin, octaglycerin, decaglycerin and the like. Polyoxyalkylene compounds obtained by adding ethylene oxide or propylene oxide to these compounds are usually extremely difficult to obtain as a single compound, and are generally obtained as a mixture of compounds having a plurality of different structures. It can be used without any problem for the purpose of the invention. Furthermore, a polyoxyalkylene compound obtained by simultaneously adding ethylene oxide or propylene oxide to two or more polyhydric alcohol compounds represented by the general formulas (I) and / or (II) may be used. The amount of ethylene oxide or propylene oxide added to the compound represented by the general formula (I) or (II) depends on the number of hydroxyl groups contained in the above compound used, and therefore cannot be unconditionally specified.
It is preferable to add at least 2 mol of ethylene oxide or propylene oxide to at least 1 mol of the above compound. The upper limit of the addition amount is not particularly limited, but in general, when the addition amount exceeds 50 mols relative to 1 mol of the polyhydric alcohol represented by the general formula (I) or (II), the polyoxyalkylene compound obtained is This is not preferable because the molecular weight becomes too large, the mixing property at the time of adjusting the composition decreases, and problems such as bleeding after molding occur.

The polyglycerol ester has the general formula (II
By subjecting the organic carboxylic acid represented by I) or its equivalent (eg, alkali metal salt, acid halide, etc.) and polyglycerol represented by the general formula (II) to dehydration condensation by a generally known method. It can be easily manufactured. Examples of the organic carboxylic acid represented by the general formula (III) include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, hexanoic acid, caprylic acid, capric acid, stearic acid, oleic acid, lauric acid, phenylacetic acid, and phenylpropione. Acid, phenylbutyric acid, etc. are mentioned. The polyglycerin ester compound used must have two or more hydroxyl groups in the molecule. Therefore, the amount of the organic carboxylic acid used for esterifying the polyglycerin of the general formula (II) needs to be determined in consideration of the number of hydroxyl groups contained in the polyglycerin.

As the polyglycerin ester compound,
For example, glycerin monostearate, glycerin monooleate, glycerin monolaurate, glycerin monocaprylate, glycerin monohexanoate, glycerin monophenethyl ester, glycerin monopropionate, diglycerin monostearate, diglycerin distearate. , Diglycerin monooleate, diglycerin monohexanoate, diglycerin dioctanoate, tetraglycerin monostearate, tetraglycerin tristearate, tetraglycerin tetrastearate, tetraglycerin trihexanoate, tetraglycerin monophenethyl Ester, hexaglycerin monostearate, hexaglycerin distearate, hexaglycerin pentastearate, hexaglycerin triolee Door, hexa-glycerin monolaurate, hexa-glycerin penta laurate, decaglycerol monostearate, decaglycerol octa stearate, decaglycerol pentaoleate, decaglycerol dilaurate, penta decaglycerol distearate,
Examples include pentadecaglycerin decaoleate and octadecaglycerin tetrastearate. Two or more of these polyglycerin esters can be used in combination.

The amount of the polyhydric alcohol compound used as the component (B) is such that the polyhydric alcohol compound is used with respect to the unit derived from the radical-polymerizable acid anhydride contained in the ethylene-based copolymer of the component (A). It is necessary that the molar ratio of the units of the hydroxyl groups contained in 0.01 to be in the range of 0.01 to 10,
It is preferably in the range of -5. This molar ratio is 0.0
When it is less than 1, it is insufficient to introduce the crosslinked structure into the crosslinkable ethylene copolymer in an effective amount. On the other hand, when the molar ratio exceeds 10, it is not preferable because it is meaningless in effectively introducing the crosslinked structure and also the cost becomes high.

The reaction accelerator which is the component (C) relating to the present invention means a carbonyl group contained in the unit derived from the radically polymerizable carboxylic acid anhydride contained in the ethylene-based copolymer to activate the hydroxyl group and the acid. It is a compound that accelerates the reaction with an anhydride. There are various kinds of reaction accelerators, and an example thereof is a metal salt of an organic carboxylic acid. As the metal salt of an organic carboxylic acid, a metal salt of a fatty acid having 1 to 30 carbon atoms, for example, acetic acid, butyric acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, Aliphatic carboxylic acids such as octenoic acid, erucic acid, elaidic acid, adipic acid, malonic acid, succinic acid, glutaric acid, citric acid, tartaric acid, malic acid, diglycolic acid; benzoic acid, chlorobenzoic acid, anisic acid, amino Aromatic carboxylic acids such as benzoic acid, phthalic acid, terephthalic acid, naphthoic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid and the like, and metals of Group IA, IIA, IIB and IIIB of the periodic table (eg Li, Na, K , Mg, Ca, Zn, Al
Etc.). More specific examples are lithium acetate, sodium acetate, magnesium acetate, aluminum acetate, potassium butyrate, calcium butyrate, zinc butyrate, sodium octanoate, calcium octanoate, potassium decanoate, magnesium decanoate, zinc decanoate, and lauric acid. Lithium, sodium laurate, calcium laurate, aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, magnesium palmitate, sodium stearate, potassium stearate, calcium stearate, stearic acid Metal salts of aliphatic carboxylic acids such as zinc, sodium oleate and sodium behenate; sodium benzoate, zinc benzoate, sodium phthalate Aluminum phthalic acid, magnesium terephthalate, and metal salts of aromatic carboxylic acids such as naphthalene calcium dicarboxylic acid. Among these, lithium laurate, sodium laurate, calcium laurate,
Aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, magnesium palmitate, sodium stearate, potassium stearate, calcium stearate, zinc stearate, sodium oleate are preferred. .

Another example of the metal salt of an organic carboxylic acid is a polymer having a metal salt structure of a carboxylic acid. Examples of such a polymer include metals of Group IA, Group IIA, Group IIB, and Group IIIB of ethylene and radically polymerizable carboxylic acid (for example, Li, Na, K, Mg, Ca, Zn, Al, etc.).
Examples thereof include those having a structure in which a salt is copolymerized, and those having a structure in which a metal salt of ethylene and a radical-polymerizable carboxylic acid and another radical-polymerizable carboxylic acid and / or a derivative thereof are multi-component copolymerized.

Further, a metal salt of the radical-polymerizable unsaturated carboxylic acid (free unsaturated carboxylic acid is graft-polymerized on a polyolefin resin such as polyethylene, polypropylene or ethylene-propylene copolymer) and then neutralized. Which has a structure obtained by graft polymerization of
One having a structure in which a metal salt of a radically polymerizable carboxylic acid and another radically polymerizable carboxylic acid and / or a derivative thereof are simultaneously co-grafted with a polyolefin polymer is mentioned. As the radical-polymerizable carboxylic acid derivative used here, (meth) acrylic acid, maleic acid, fumaric acid, monomethyl maleate, monomethyl fumarate, monoethyl maleate, monoethyl fumarate,
Monobutyl maleate, monobutyl fumarate, (meth)
Examples thereof include methyl acrylate, dimethyl maleate, dimethyl fumarate, diethyl maleate, diethyl fumarate, dibutyl maleate, dibutyl fumarate and the like.

Other examples of the reaction accelerator relating to the present invention include tertiary amine compounds such as trimethylamine, triethylamine, dimethylethylamine and diethylcyclohexylamine. Other examples of the reaction accelerator relating to the present invention include, for example, tetramethylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetramethylammonium bromide, tetraethylammonium bromide, tetraethylammonium iodide, methyltri-n-butylammonium. Examples thereof include quaternary ammonium salts such as chloride, tetrabutylammonium bromide and tetrahexyl ammonium bromide.

Further, as another example of the reaction accelerator according to the present invention, for example, metal hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide, calcium chloride, calcium bromide, magnesium chloride and the like can be used. Metal halide, sodium nitrate, calcium nitrate,
Metal salts of oxo acids such as calcium phosphate, sodium carbonate, calcium carbonate, magnesium carbonate, sodium sulfate, zinc sulfate, potassium chlorate, sodium iodate, and further NaBF ₄ , KPF ₆ , NaPCl ₆ , NaFeCl ₄ , NaSnCl ₄ , NaSb
Lewis acid metal salts such as F ₆ , NaAsF ₆ and KAsCl ₆ and organic sulfonic acids such as sodium paratoluate sulfonate, potassium paratoluate sulfonate, aluminum chloroethane sulfonate, calcium ethyl methane sulfonate and zinc ethyl ethane sulfonate The metal salts of

Among the reaction accelerators exemplified above, metal salts of polymers containing a carboxyl group, metal salts of organic carboxylic acids are preferably used. Further, two or more of the above-mentioned various reaction accelerators may be used in combination, if necessary. The amount of the reaction accelerator used in the present invention is 10% by weight of the ethylene-based copolymer.
It is necessary to be in the range of 0.001 to 20 parts by weight with respect to 0 parts by weight, and preferably in the range of 0.01 to 15 parts by weight. If this amount is less than 0.001 part by weight, the reaction becomes too slow and it becomes difficult to effectively introduce a crosslinked structure into the composition. If it exceeds 20 parts by weight, the reaction rate is improved. Not only is it meaningful, but it is also economically unfavorable.

The crosslinkable ethylene-based copolymer composition constituting the multi-layer laminate of the present invention is obtained by adding a polyolefin resin to the composition comprising the component (A), the component (B) and the component (C). Can be used. Specific examples of the polyolefin-based resin here include low-density polyethylene,
A homopolymer of a saturated hydrocarbon monomer having 2 to 10 carbon atoms such as high density polyethylene, polypropylene, polyisoprene, polyisobutylene, polybutene, poly-3-methylbutene-1, poly-4-methylpentene-1, polybutadiene, etc. Can be mentioned. Further, a copolymer of two or more kinds of monomers selected from the monomers and other olefins constituting these homocopolymers, or the monomers or other olefins constituting the above homocopolymers. And a copolymer of another radically polymerizable monomer having no acid anhydride, for example, ethylene-
Propylene; styrene-butadiene copolymer; ethylene-propylene-diene terpolymer; linear low-density polyethylene using butene-1, hexene-1, octene-1,4-methylpentene-1 as comonomer; propylene-ethylene Block copolymers of ethylene; copolymers of ethylene with unsaturated carboxylic acids or their derivatives (for example, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid ester copolymers, etc.) and the like.
Furthermore, a mixture of each of the above resins can be used.

The polyolefin-based resin used here is used as a resin for diluting the crosslinkable ethylene-based copolymer composition consisting of (A), (B) and (C), and also at the time of molding at high temperature. Is added for the purpose of improving the moldability of. The amount of polyolefin resin used is the amount of component (A)
The amount is in the range of 5 to 300 parts by weight based on 100 parts by weight of the total of the resin compositions (B) and (C). When the amount of the polyolefin used exceeds 300 parts by weight, the amount of the ethylene copolymer, which is the component (A) capable of exhibiting adhesion with the gas barrier resin, becomes too small in the crosslinkable ethylene copolymer. Therefore, the adhesive heat resistance of the obtained crosslinkable ethylene-based copolymer composition is significantly lowered, which is not preferable. When the amount is less than 5 parts by weight, it is meaningless to mix the polyolefin resin.

In the crosslinkable ethylene copolymer composition constituting the present invention, a tackifier may be further added to the composition comprising the component (A), the component (B) and the component (C). it can. If a specific example of such a tackifier is shown,
Examples thereof include aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, polyterpene resins, rosins, styrene resins and the like. When these are specifically shown, butene-1, as the aliphatic hydrocarbon resin,
Homopolymers and copolymers of monoolefins having 4 or 5 carbon atoms such as isobutylene Copolymers containing these monoolefins as main components; butadiene, 1,3-pentadiene having 4 or 5 carbon atoms Examples include homopolymers and copolymers of certain diolefins, and copolymers containing these diolefins as main components.

Examples of the alicyclic hydrocarbon resin include C4 to C
Examples thereof include a resin obtained by polymerizing a diene component in 5 fractions by cyclization dimerization and then polymerizing the resin, and a resin obtained by intra-nuclearly hydrogenating the following aromatic hydrocarbon resin. As the aromatic hydrocarbon resin,
Homopolymers and copolymers of vinyl aromatic hydrocarbons having 8 to 9 carbon atoms such as styrene, vinyltoluene, indene, α-methylstyrene, etc. (vinyltoluene-methylstyrene, etc.) Mainly these vinyl aromatic hydrocarbons The copolymer (styrene-olefin copolymer etc.) etc. which are used as a component are mentioned. As the polyterpene resin, α-pinene polymer, β
-Pinene polymer, dipentene polymer, terpene-phenol polymer, α-pinene-phenol copolymer and the like. Examples of the rosins include rosin, polymerized rosin, hydrogenated rosin, rosin glycerin ester and its hydrogenated products or polymers. Among these, terpene phenol resin and hydrogenated petroleum resin are preferable. These may be used alone or in combination of two or more.

The purpose of adding the tackifier used here is, from the tackifiers exemplified above, to a softening point of 80 ° C. or higher (softening point here) in applications requiring heat resistance at high temperatures. And those that have a ring-and-ball method). That is, by adding a tackifier, the crosslinkable ethylene-based copolymer is provided with tackiness, which has low-temperature heat-sealing property or high-frequency sealing property and heat-resistant shape-retaining property. It is possible to make it. The softening point of the tackifier used here (the softening point here means that measured by the ring and ball method) is preferably from 80 to 200 ° C. 120-180 degreeC is especially preferable. If the softening point of the tackifier is less than 80 ° C, the heat resistance of the heat-sensitive adhesive becomes insufficient, and if it exceeds 200 ° C, the adhesiveness becomes insufficient, which is not preferable. The amount of tackifier used is preferably 1 to 80 parts by weight, and more preferably 3 to 60 parts by weight, based on 100 parts by weight of the ethylene copolymer (A). If this amount is less than 1 part by weight, it is meaningless to add it substantially and the effect of improving the adhesive performance is lost, which is not preferable. On the other hand, if it exceeds 80 parts by weight, the heat resistance is lowered and the tackiness of the crosslinkable ethylene-based copolymer is too strong, which makes handling difficult, which is not preferable.

Further, various additives, compounding agents and fillers can be used in the crosslinkable ethylene copolymer composition of the present invention as long as the characteristics of the copolymer composition are not impaired. is there. Specific examples of these are antioxidants (heat stabilizers), ultraviolet absorbers (light stabilizers), antistatic agents, antifogging agents, flame retardants, lubricants (slip agents, antiblocking agents), glass fillers, etc. Inorganic fillers, organic fillers, reinforcing agents, colorants (dyes, pigments), foaming agents, fragrances, and the like.

In order to produce the crosslinkable ethylene-based copolymer composition of the present invention, various components (A) to (C), a polyolefin-based resin, a tackifier, or additives used as necessary are variously added. It may be mixed by means of. As a mixing method, a generally known mixing method of various resins can be used. For example, dry blending may be performed using a mixer such as a Henschel mixer or a tumbler, and melt kneading may be performed using a mixer such as a Banbury mixer, a static mixer, a pressure kneader, or an extruder roll mill. At this time, a uniform composition can be obtained by previously dry blending and melt-kneading the resulting mixture. Further, by utilizing the step of molding the crosslinkable ethylene-based copolymer composition of the present invention into the multilayer laminate of the present invention or a single film, the respective components are mixed in the form of pellets or powder (dry blending). Then
It is also possible to perform melt mixing in an extruder or an injection molding machine.

The use of the crosslinkable ethylene copolymer composition according to the present invention makes it possible to obtain a multi-layer laminate by adhering it to a gas barrier resin. Further, when used as a seal layer, it has a low-temperature heat-sealing property and a high-frequency sealing property, and can exhibit the contradictory performance of exhibiting heat distortion resistance at a high temperature.

Examples of the gas barrier substrate that constitutes the multilayer laminate of the present invention include polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer, polyamide resin,
Vinylidene chloride resin, acrylonitrile resin, resins such as polyester resin, metal foil such as aluminum foil can be used, but especially polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer, polyamide resin,
A gas barrier resin such as an acrylonitrile resin or a vinylidene chloride resin is preferable.

The polyvinyl alcohol which can be used in the present invention is a saponified product of a homo- or copolymer of vinyl ester of carboxylic acid such as vinyl acetate and vinyl propionate.

The ethylene-vinyl alcohol copolymer which can be used in the present invention is a copolymer containing ethylene units and vinyl alcohol units as main components, and has an ethylene component content of 20 to 55 mol% and a saponification degree of 90 mol%. It is a saponified product of a copolymer of ethylene and a vinyl ester of a carboxylic acid such as the above ethylene-vinyl acetate copolymer, ethylene-vinyl formate copolymer or ethylene-vinyl propionate copolymer. If the content of the ethylene component is less than 20 mol%, the extrudability of the obtained saponified resin is difficult,
If it exceeds 55 mol%, the gas barrier property tends to deteriorate, which is not preferable. The degree of saponification of the vinyl ester component of carboxylic acid must be 90 mol% or more. When it is less than 90 mol%, the gas barrier property is low and various physical properties such as heat resistance and water resistance tend to be deteriorated, which is not preferable.

The polyamide resin usable in the present invention is obtained by ring-opening condensation of a cyclic lactam or condensation polymerization of an aliphatic aminocarboxylic acid, for example, ring-opening condensation product of ε-caprolactam or condensation of 6-aminocaproic acid. Nylon 6, obtained by condensation polymerization of 11-aminoundecaic acid by polymerization, ring-opening condensation polymerization of ω-laurolactam or nylon 12 obtained by condensation polymerization of 12-aminododecaic acid; aliphatic diamine and aliphatic dicarboxylic acid A polycondensation polymer of, for example, 66-nylon by cocondensation of hexamethylenediamine and adipic acid, nylon 610 by cocondensation of hexamethylenediamine and sebacic acid; cocondensation polymer of aromatic diamine and aliphatic dicarboxylic acid For example, a condensation polymer of metaxylenediamine and adipic acid, A polycondensation product of taxylenediamine and sebacic acid can be mentioned. A copolymer with the monomer constituting the above-mentioned polycondensation polymer can also be used. Among these, nylon 6, nylon 66, and a copolymer of metaxylenediamine and adipic acid are particularly preferable.

As the acrylonitrile resin, a homopolymer of acrylonitrile or a copolymer with at least one of vinyl acetate, vinyl chloride, styrene, alkyl methacrylate, butadiene and the like is used for the purpose of improving moldability. I can do things.

The vinylidene chloride resin that can be used in the present invention is, for example, a homopolymer of vinylidene chloride, or a copolymer of vinylidene chloride and vinyl chloride, a (meth) acrylic acid alkyl ester or acrylonitrile for the purpose of improving extrusion moldability. Mention may be made of polymers. Moreover, you may use what added the plasticizer as needed. Among the above gas barrier resins, ethylene-vinyl alcohol copolymer and polyamide resin are particularly preferable.

The gas barrier resin MFR (JIS
K-7210 Table 1 condition 14) is 0.5 to 50 g / 10.
Minutes, preferably 2 to 25 g / 10 minutes.
If it is less than 0.5 g / 10 minutes, the melt flowability is insufficient and molding cannot be performed at a normal speed, which is not preferable.
If it exceeds / 10 minutes, melt tension becomes insufficient and moldability deteriorates, which is not preferable.

In producing the multilayer laminate of the present invention, various molding methods can be adopted. For example, a coextrusion molding method in which a crosslinkable ethylene-based copolymer composition and a gas barrier resin are simultaneously extrusion-molded in a molten state by inflation molding or T-die molding; crosslinking on a gas barrier resin film or a gas barrier substrate sheet. Extrusion Lamination Method of Extrudable Ethylene Copolymer Composition; Gas Barrier Substrate and Crosslinkable Ethylene Copolymer Composition Film or Sheet Overlaid, Hot Pressed,
Alternatively, there may be mentioned a method of melt-pressing with a hot roll. In the above-described method for producing the multilayer laminate of the present invention, the molding temperature cannot be unconditionally specified because it depends on the softening point of the gas barrier resin used, or the crystal melting point, and the composition of the crosslinkable ethylene-based copolymer. The temperature is at least the softening point of the crosslinkable ethylene-based copolymer composition and the gas barrier resin and is not higher than the temperature at which thermal decomposition does not occur.

The thickness of each layer of the multi-layer laminate of the present invention varies depending on the use, required physical properties and the like and is not particularly limited, but 10 layers of the crosslinkable ethylene copolymer composition according to the present invention. To 200 μm, preferably 20 to 100
μm. If it is less than 10 μm, the heat resistance of the multilayer laminate is insufficient, which is not preferable, and if it exceeds 200 μm, the thermal conductivity decreases and the sealing strength cannot be obtained, which is not practical. The layer made of gas barrier resin is 5-100μ
m, preferably 20 to 80 μm. Here, if it is less than 5 μm, the gas barrier property becomes insufficient, which is not preferable, and if it exceeds 100 μm, it is meaningless in the sense that the gas barrier property is maintained, and the cost increases.
Originally, if the ratio of the thickness of the barrier resin having high rigidity is increased, the flexibility of the multilayer laminate is lowered, which is not preferable.

In the multilayer laminate of the present invention, at least the above-mentioned two layers or both outer layers are composed of a crosslinkable ethylene-based copolymer composition and the intermediate layer is a three-layer structure comprising a gas barrier substrate, or if necessary. Further, a layer comprising a crosslinkable ethylene-based copolymer composition or a gas barrier substrate layer according to the present invention, other material such as a polyolefin-based resin, through an adhesive layer or without an adhesive layer, It may be a laminated body. The multilayer laminate of the present invention can be suitably used for applications requiring long-term gas barrier properties, heat sealing properties or high frequency sealing properties, and heat resistance, such as air pillows and cushioning materials.

[0044]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. Of course, the present invention is not limited by the examples given below.

In producing the multilayer laminate, the following were used as the ethylene-based copolymer which is the component (A). (1) Ethylene-based copolymer (a) Ethylene-methyl methacrylate-maleic anhydride terpolymer: MFR (JIS-K7210) 8 g / 10 minutes Content of units derived from methyl methacrylate 8% by weight Anhydrous Content of units derived from maleic acid 3.0% by weight (2) Ethylene copolymer (b) Ethylene-butyl acrylate-itaconic anhydride terpolymer: MFR (JIS-K7210) 20 g / 10 min Content of units derived from butyl acrylate 20% by weight Content of units derived from itaconic anhydride 3.5% by weight (3) Ethylene-based copolymer (c) Ethylene-methyl acrylate-maleic anhydride ternary Copolymer: MFR (JIS-K7210) 8 g / 10 minutes Content of units derived from methyl acrylate 16% by weight Content of units derived from maleic anhydride Amount 2.5 wt% (4) Ethylene-based copolymer (d) Ethylene-vinyl acetate-maleic anhydride terpolymer: MFR (JIS-K7210) 15 g / 10 min Content of units derived from vinyl acetate 20 wt% Content of units derived from maleic anhydride 2.0 wt% (5) Ethylene copolymer (e) Ethylene-maleic anhydride binary copolymer: MFR (JIS-K7210) 10 g / 10 min Content of units derived from maleic anhydride 2.0% by weight (6) Ethylene-based copolymer (f) Ethylene-methyl acrylate-maleic anhydride terpolymer: MFR (JIS-K7210) 10 g / 10 Component Content of units derived from methyl acrylate 25% by weight Content of units derived from maleic anhydride 1.6% by weight (7) Ethylene copolymer (g) Ethylene-methac Methyl phosphate binary copolymer MFR (JIS-K7210) 3 g / 10 min Content of units derived from methyl methacrylate 20% by weight

As the polyhydric alcohol which is the component (B), those described in Table 1 were used.

[Table 1]

As the reaction accelerator which is the component (C), those listed in Table 2 were used.

[Table 2]

The following resins were used as the polyolefin resin. (1) High-pressure low-density polyethylene resin (LDPE) J-LEX LDPE L211 manufactured by Nippon Polyolefin Co., Ltd. Density 0.916 g / cc MFR (JIS-K7210) 10 g / 10 min (2) Low-pressure high-density polyethylene resin (HDPE) J-LEX HDPE 5080 manufactured by Nippon Polyolefin Co., Ltd. density 0.948 g / cc MFR (JIS-K7210) 7.5 g / 10 min (3) ethylene-vinyl acetate copolymer (EVA) J-LEX EVA DL19-8 manufactured by Nippon Polyolefin Co., Ltd. Content of units derived from vinyl acetate 10% by weight MFR (JIS-K7210) 10 g / 10 minutes (4) Propylene-ethylene random copolymer (PP) J-Aroma FD432 Nippon Polyolefin Co., Ltd.
Production Content of units derived from ethylene 7% by weight MFR (JIS-K7210) 9 g / 10 minutes

The tackifier used was a terpene phenol resin (Tamanor 803L, manufactured by Arakawa Chemical Co., Ltd., softening point (ring and ball method) = 145 ° C.).

<Production of Crosslinked Ethylene Copolymer Composition> (Composition 1) 0.5% by weight of trimethylolpropane as a polyhydric alcohol was reacted with 100 parts by weight of the ethylene copolymer (a). Zn of ethylene-methacrylic acid copolymer (methacrylic acid content 10% by weight) as an accelerator
Salt (neutralize 10 mol% of units derived from methacrylic acid)
After 10% by weight was dry blended with a Henschel mixer, the mixture was melt-kneaded at 220 ° C. using a 37 mmφ co-directional twin-screw extruder to obtain pellets of the crosslinkable ethylene copolymer composition. The contents of this formulation are shown in Table 3. (Compositions 2 to 8) As shown in Table 3, component (A), component (B), component (C), a polyolefin resin or a tackifier is used in the same manner as in composition 1 to perform crosslinking. The pellets of a soluble ethylene copolymer were obtained. (Comparative compositions 1 to 4) In the same manner, pellets of a crosslinkable ethylene copolymer were obtained according to the formulation shown in Table 3. That is, in Comparative composition 1, the reaction accelerator (C) was not blended, in Comparative composition 2, the polyhydric alcohol (B) was not blended, and in Comparative composition 3, ethylene-methyl methacrylate was used as the component (A). A binary copolymer (methyl methacrylate content = 20% by weight, MFR = 3) was used, and in Comparative Composition 4, each ethylene-based copolymer alone was used to obtain each crosslinkable ethylene-based copolymer.

[0051]

[Table 3] In Table 3, "OH / acid anhydride" indicates the molar ratio of the unit of the hydroxyl group in the polyhydric alcohol (B) to the unit derived from the acid anhydride in the ethylene copolymer (A).

<Production of Multilayer Laminate> The crosslinkable ethylene copolymer composition obtained in the composition 1 is a coextruded film having two 25 mmφ extruders and a T-type die for two-layer three-layer coextrusion. In the molding machine, both outer layers were a crosslinkable ethylene copolymer, and the intermediate layer was an ethylene-vinyl alcohol copolymer (Kuraray Co., Ltd., Eval EP-H101, ethylene content 38 mol%, MFR (190 ° C) = A multilayer laminate having the constitution of 1.6) was manufactured. The molding temperature was 230 ° C., and the molding speed was 5 m / min. The thickness of both outer layers was 20 μm, the thickness of the intermediate layer was 30 μm, and the total thickness was 70 μm. After film formation, after conditioning for 24 hours at 23 ° C. and 50% relative humidity, it was cut into 15 mm wide test pieces, and a 180 ° peeling test at room temperature (23 ° C.) using a tensile tester (peeling speed 200 mm / min. ) Was carried out to measure the adhesive strength.
As for the oxygen barrier property test, MOKO (MOKO
N) method (Oxygen permeability measuring device “OX-TRAN 10 / 50A” (Mode
rn Contorols INC.)))
According to D3985 (JIS K-7126B method), temperature 23 ℃,
It was measured at a relative humidity of 50%. In addition, two multi-layer laminates are overlaid and high-frequency seal (current value 0.4A, 2kg / cm ² , 2
Seconds), cut into 15 mm wide test pieces, and measured the adhesive strength (kg / 15 mm) of the seal portion at room temperature (23 ° C.) and 90 ° C. using a tensile tester (pulling speed 200
mm / min). Further, as a heat resistance test, an external appearance test was performed by leaving it in an atmosphere of 120 ° C. for 24 hours to evaluate the heat resistance. Table 4 shows the evaluation results.

Compositions 2 to 8 and comparative composition 1 were similarly prepared.
To 4 were used to manufacture the multilayer laminates of Examples 2 to 8 and Comparative Examples 1 to 4 using the gas barrier resins shown in Table 4, and each test was performed in the same manner as in Example 1.

[0054]

[Table 4]

From Table 4, the multilayer laminates of Examples 1-8 are
All have excellent moldability and appearance, and also have excellent interlayer adhesion strength that can withstand practical use, oxygen barrier property, high frequency sealing property,
It can be seen that it has heat resistance. On the other hand, the multilayer laminate of Comparative Example 1 having the crosslinkable ethylene-based copolymer composition layer having no reaction accelerator has a moldability due to poor crosslinking,
The appearance is poor, the layers are easily peeled off, and the seal strength and heat resistance are low. Further, since the multilayer laminate of Comparative Example 2 having the crosslinkable ethylene-based copolymer composition layer having no polyhydric alcohol does not crosslink,
The seal strength at high temperature is low and the heat resistance is poor. Further, the multilayer laminate of Comparative Example 3 also has low seal strength at high temperature and poor heat resistance, and the multilayer laminate of Comparative Example 4 easily peels between layers and has low seal strength and poor heat resistance.

[0056]

As described above, the multi-layer laminate according to the present invention exhibits high interlayer adhesion strength, has excellent gas barrier properties, and can be heat-sealed at a relatively low temperature or high-frequency sealed and high in temperature. Has heat-resistant shape retention. Therefore, the multi-layer laminate is excellent in bag-making processability, does not escape the enclosed gas for a long period of time, and is suitable as an air pillow or cushioning material that is required to retain its shape even in a relatively high temperature environment. Can be used.

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Claims (5)

[Claims] 1. A multilayer laminate comprising at least a crosslinkable ethylene-based copolymer composition layer and a gas barrier substrate layer, wherein the crosslinkable ethylene-based copolymer composition layer has the following (A) to (C). A multilayer laminate, which is a composition layer obtained by kneading the components. (A) A multicomponent copolymer comprising at least ethylene and a radical-polymerizable acid anhydride, wherein the proportion of units derived from the radical-polymerizable acid anhydride in the copolymer is 0.1% by weight to 5%.
Ethylene copolymer, which is wt%. (B) A polyhydric alcohol compound having at least two hydroxyl groups in the molecule. However, the molar ratio of the unit of the hydroxyl group in the polyhydric alcohol compound to the unit derived from the radical-polymerizable acid anhydride in the ethylene copolymer (A) is 0.01.
-10. (C) A reaction accelerator in the range of 0.001 to 20 parts by weight based on 100 parts by weight of the ethylene copolymer. 2. The multi-layer laminate according to claim 1, wherein the polyhydric alcohol compound (B) has the following general formula (I) (R ¹ ) _a C (CH ₂ OH) _b (I) ¹ represents hydrogen or a chain or cyclic alkyl group having 1 to 12 carbon atoms or an aralkyl group, and a is 0
~ 2 represents an integer, b represents an integer of 2 to 4, and a +
It is selected to satisfy b = 4. Or the following general formula _{(II) CH 2 (OH)} CH (OH) CH 2 O [CH 2 CHOHCH 2 O] m H (II) [ wherein, m is an integer of 0. Polyhydric polyoxyalkylene compound having a structure obtained by adding ethylene oxide or propylene oxide to an alcohol compound, or the following general formula (III) in R ² -COOH (III) [represented by the formula], R ² is 2 carbon atoms 25 chain alkyl groups, cyclic alkyl groups, aralkyl groups or alkenyl groups are shown. ] One or more of polyglycerin esters having two or more hydroxyl groups in the molecule, which are obtained by dehydration condensation of the organic carboxylic acid compound represented by the above and the polyglycerin represented by the general formula (II). A multilayer laminate characterized by the above. 3. The multilayer laminate according to claim 1, wherein the reaction accelerator as the component (C) is a metal salt of a polymer containing a carboxyl group or a metal salt of an organic carboxylic acid. 4. The multilayer laminate according to claim 1, wherein the gas barrier substrate is a polyamide resin or a copolymer of ethylene and vinyl alcohol. 5. The ethylene-based copolymer (A) is a multi-component copolymer comprising ethylene, a radical-polymerizable acid anhydride and a radical-polymerizable comonomer other than the radical-polymerizable acid anhydride, and the ethylene-based copolymer The ratio of the units derived from the radical-polymerizable acid anhydride in the combined product is 0.1% by weight to 5% by weight, and the ratio of the units derived from the radical-polymerizable comonomer other than the radical-polymerizable acid anhydride is 5% by weight. It is -50 weight%, The multilayer laminated body in any one of Claims 1-4.