JP2018171807A - Gas barrier laminate film - Google Patents

Abstract

SOLUTION: There is provided a gas barrier laminate film which contains: an adhesive resin composition layer (A) formed of an adhesive resin composition that is modified with an unsaturated carboxylic acid or its derivative, and has a graft amount of 0.01-1.0 wt.%, a density of 900-930 kg/mand a melt flow rate of 0.5-3.0 g/10 min, contains a modified ethylene-α-olefin copolymer (A1) and an ethylene-α-olefin copolymer (A2), and has a content ratio of the component (A1) of 5-80 wt.% and a content ratio of the component (A2) of 20-95 wt.%; and a gas barrier resin layer (B).EFFECT: A gas barrier laminate film prevents a bag from being broken for a long time with peeling between an adhesive resin layer and a polyamide resin layer or an ethylene-vinyl alcohol copolymer layer as a starting point even at high temperature, for example, 70-95°C, and accordingly can be used as an air chain that is used as a packaging material of a food product subjected to boiling treatment and used during conveyance.SELECTED DRAWING: None

Description

The present invention relates to a gas barrier laminate film excellent in durability adhesiveness at high temperatures, and more specifically, it is suitably used for food packaging materials for boil, air chains, etc., and can be used without breaking in high temperature environments. The present invention relates to a gas barrier laminate film.
An air chain is a cushioning material in which two laminated films are heat sealed and filled with air.

  Conventionally, a laminated film of polyolefin and polyamide resin and a laminated film of polyolefin and ethylene / vinyl alcohol copolymer are known, and various adhesive resins used in the production of the laminated film have been proposed. ing. For example, Patent Document 1 discloses that a modified polyethylene obtained by reacting a linear low density polyethylene with an unsaturated carboxylic acid or a derivative thereof can be used as an adhesive resin. Further, synthetic rubber and / or linear low density polyethylene can be used as the modified polyethylene. It is disclosed that a modified polyethylene composition blended with can be used as an adhesive layer resin composition. Patent Document 2 discloses an adhesive resin composition obtained by modifying a mixture of linear low density polyethylene and synthetic rubber with an unsaturated carboxylic acid or a derivative thereof.

Japanese Patent No. 1597229 Japanese Patent No. 1640690

  However, with the conventionally proposed adhesive resins, for example, when used for a long boil sterilization treatment or an air chain used in a container with a high temperature atmosphere for a long time, an internal pressure is applied to the heat seal portion at a high temperature. Thus, it has been found that there is a problem that the bag breakage starts from peeling between the adhesive resin layer and the gas barrier resin layer.

  For this reason, the appearance of an adhesive resin composition exhibiting excellent heat-resistant and durable adhesion to polyolefin and gas barrier resin, and an adhesive layer made of the composition between the polyolefin layer and the layer made of gas barrier resin. The appearance of a gas barrier laminate film that can be used without breaking the bag for a long time in a high temperature environment is desired.

  The object of the present invention is to solve the above-mentioned problems of the prior art, and the object of the present invention is to provide an adhesive resin layer and a gas barrier resin, particularly a polyamide, in an environment where internal pressure is applied to the heat seal portion at high temperature. An object of the present invention is to provide a laminated film excellent in durability, in which bag breaking starting from peeling between the resin layer and the ethylene / vinyl alcohol copolymer layer does not occur for a long time.

  As a result of intensive studies to solve the above problems, it has been found that the above problems can be solved by using an adhesive resin composition having a specific composition, and the present invention has been completed.

The gas barrier laminate film according to the present invention is modified with an unsaturated carboxylic acid or a derivative thereof, and has a graft amount of 0.01 to 1.0% by weight,
The density is in the range of 900-930 kg / m ³ ;
According to ASTM D1238, the melt flow rate at 190 ° C. and 2.16 kg load is in the range of 0.5 to 3.0 g / 10 min.
Containing the following components (A1) and (A2),
The content of component (A1) is 5 to 80% by weight, and the content of component (A2) is 20 to 95% by weight (however, the total amount of (A1) and (A2) does not exceed 100% by weight) It is characterized by including an adhesive resin composition layer (A) made of an adhesive resin composition and a gas barrier resin layer (B).

(A1): 190 ° C. modified with an unsaturated carboxylic acid or derivative thereof, having a graft amount of 0.1 to 10% by weight, a density in the range of 915 to 970 kg / m ³ , and conforming to ASTM D1238 2. A modified ethylene / α-olefin copolymer having a melt flow rate in a range of 0.1 to 10.0 g / 10 min at a load of 2.16 kg.
(A2): The molecular weight distribution Mw / Mn is less than 4.0, the density is in the range of 900 to 930 kg / m ³ , and the melt flow rate at 190 ° C. and 2.16 kg load is 0.00 according to ASTM D1238. An ethylene / α-olefin copolymer having a graft amount of less than 0.1% by weight in the range of 1 to 2.0 g / 10 min.

The graft amount of the unsaturated carboxylic acid or derivative thereof in the adhesive resin composition is preferably in the range of 0.01 to 1.0% by weight with respect to 100% by weight of the entire composition.
The gas barrier resin layer (B) is preferably a layer comprising at least one selected from the group consisting of ethylene / vinyl alcohol copolymer and polyamide resin.

  The ethylene / vinyl alcohol copolymer preferably has a content of structural units derived from ethylene of 15 to 70 mol%.

  The polyamide resin is preferably selected from the group consisting of nylon 6, nylon 66, nylon 6,10, nylon 12, nylon 11, MXD nylon, amorphous nylon, and copolymer nylon.

The gas barrier laminate film preferably includes a polyolefin layer (C), and the gas barrier resin layer (B) and the polyolefin layer (C) are bonded via the adhesive resin composition layer (A). .
The food packaging material for boil and the air cushioning material according to the present invention include the gas barrier laminate film.

  The gas barrier laminate film of the present invention has a long bag breaking starting from peeling between the adhesive resin layer and the polyamide resin layer or the ethylene / vinyl alcohol copolymer layer even at high temperatures, for example, 70 ° C. to 95 ° C. Since it does not occur for a long time, it can be used, for example, as a packaging material for foods that are subjected to a boil treatment for a long time without breaking the bag. Further, the gas barrier laminate film of the present invention can be used as an air chain used when transporting electrical equipment or the like by ship without breaking the bag even when the environmental temperature becomes high under the equator.

The gas barrier laminate film according to the present invention is modified with an unsaturated carboxylic acid or a derivative thereof, has a graft amount of 0.01 to 1.0% by weight, and a density in the range of 900 to 930 kg / m ³ . In accordance with ASTM D1238, the melt flow rate at 190 ° C. and 2.16 kg load is in the range of 0.5 to 3.0 g / 10 minutes, and contains the following components (A1) and (A2), Adhesion having a content ratio of A1) of 5 to 80% by weight and a content ratio of component (A2) of 20 to 95% by weight (however, the total amount of (A1) and (A2) does not exceed 100% by weight) An adhesive resin composition layer (A) made of an adhesive resin composition and a gas barrier resin layer (B) are included.

(A1): 190 ° C. modified with an unsaturated carboxylic acid or derivative thereof, having a graft amount of 0.1 to 10% by weight, a density in the range of 915 to 970 kg / m ³ , and conforming to ASTM D1238 2. A modified ethylene / α-olefin copolymer having a melt flow rate in a range of 0.1 to 10.0 g / 10 min at a load of 2.16 kg.
(A2): The molecular weight distribution Mw / Mn is less than 4.0, the density is in the range of 900 to 930 kg / m ³ , and the melt flow rate at 190 ° C. and 2.16 kg load is 0.00 according to ASTM D1238. An ethylene / α-olefin copolymer having a graft amount of less than 0.1% by weight in the range of 1 to 2.0 g / 10 min.

  The gas barrier laminate according to the present invention includes a polyolefin layer (C), and the gas barrier resin layer (B) and the polyolefin layer (C) are bonded via the adhesive resin composition layer (A). It is preferable.

As the polyolefin constituting the polyolefin layer (C), for example, an ethylene polymer is preferably exemplified. The ethylene polymer preferably has an ethylene content of 70 mol% or more, more preferably 70 to 100 mol%, and still more preferably 80 to 100 mol%. Specific examples of such ethylene polymers include high-density polyethylene, linear low-density polyethylene, high-pressure low-density polyethylene, ethylene / vinyl acetate copolymer (EVA), and ethylene / ethyl acrylate copolymer. , Ethylene / acrylic acid copolymer, ionomer resin and the like. Among these, low density polyethylene, EVA, and particularly linear low density polyethylene having a density of 930 kg / m ³ or less are preferably used.

  The gas barrier resin layer (B) is preferably a layer composed of at least one selected from the group consisting of polyamide resin and ethylene / vinyl alcohol copolymer. That is, the gas barrier resin layer (B) is a polyamide resin layer (B1), an ethylene / vinyl alcohol copolymer layer (B2), or a mixed layer (B3) of a polyamide resin and an ethylene / vinyl alcohol copolymer. preferable.

  Specific examples of the polyamide resin include nylon 6, nylon 66, nylon 6,10, nylon 12, nylon 11, MXD nylon, amorphous nylon, terephthalic acid / adipic acid / hexamethylenediamine copolymer, and the like. Nylon or the like is preferably used.

  The ethylene / vinyl alcohol copolymer is preferably a copolymer having a content of structural units derived from ethylene of preferably 15 to 70 mol%, more preferably 20 to 50 mol%. Such an ethylene / vinyl alcohol copolymer can be prepared by saponifying a copolymer of ethylene and vinyl acetate.

Specific examples of the gas barrier laminate film according to the present invention include the following aspects.
(1) Three-layer laminated film of polyolefin layer (C) / adhesive resin composition layer (A) / polyamide resin layer (B1)
(2) Three-layer laminated film of polyolefin layer (C) / adhesive resin composition layer (A) / ethylene / vinyl alcohol copolymer layer (B2)
(3) Polyolefin layer (C) / Adhesive resin composition layer (A) / Mixed layer of polyamide resin and ethylene / vinyl alcohol copolymer (B3) Three-layer laminated film
(4) Four-layer laminated film of polyolefin layer (C) / adhesive resin composition layer (A) / polyamide resin layer (B1) / ethylene-vinyl alcohol copolymer layer (B2)
(5) Four-layer laminated film of polyolefin layer (C) / adhesive resin composition layer (A) / ethylene-vinyl alcohol copolymer layer (B2) / polyamide resin layer (B1)
(6) Polyolefin layer (C) / Adhesive resin composition layer (A) / Mixed layer of polyamide resin and ethylene / vinyl alcohol copolymer (B3) / Polyamide resin layer (B1) 4 layer laminated film
(7) Polyolefin layer (C) / Adhesive resin composition layer (A) / Mixed layer of polyamide resin and ethylene / vinyl alcohol copolymer (B3) / Ethylene / vinyl alcohol copolymer layer (B2) 4 Layer laminated film
(8) 5-layer laminated film of polyolefin layer (C) / adhesive resin composition layer (A) / polyamide resin layer (B1) / adhesive resin composition layer (A) / polyolefin layer (C)
(9) Polyolefin layer (C) / Adhesive resin composition layer (A) / Ethylene / vinyl alcohol copolymer layer (B2) / Adhesive resin composition layer (A) / Polyolefin layer (C) the film
(10) Polyolefin layer (C) / Adhesive resin composition layer (A) / Mixed layer of polyamide resin and ethylene / vinyl alcohol copolymer (B3) / Adhesive resin composition layer (A) / Polyolefin layer ( C) 5-layer laminated film
(11) Four-layer laminated film of polyolefin layer (C) / adhesive resin composition layer (A) / ethylene / vinyl alcohol copolymer layer (B2) / adhesive resin composition layer (A)
(12) Four-layer laminated film of polyolefin layer (C) / adhesive resin composition layer (A) / polyamide resin layer (B1) / adhesive resin composition layer (A) The gas barrier laminated film according to the present invention comprises: For example, in the case of a three-layer laminated film, the polyolefin layer (C), the adhesive resin composition layer (A), and the gas barrier resin layer (B) made of polyamide resin and / or ethylene / vinyl alcohol copolymer are melted. It can manufacture by making it laminate in a state.

The gas barrier laminate film can be produced, for example, by coextrusion molding, cast film molding, inflation film molding, and a tenter or tubular biaxial stretching method.
The adhesive resin composition layer (A) is made of an adhesive resin composition.

  The adhesive resin composition is modified with an unsaturated carboxylic acid or a derivative thereof, and has a graft amount of 0.01 to 1.0% by weight, preferably 0.5 to 5.0% by weight. If the graft amount is too low, the adhesive force is not sufficient, and if it is too high, a crosslinking reaction tends to occur and the quality becomes difficult to stabilize.

The adhesive resin composition has a density in the range of 900 to 930 kg / m ³ , preferably in the range of 905 to 925 kg / m ³ . When the density is too low, the interlayer adhesion at a high temperature of 80 ° C. or more tends to decrease. On the other hand, if it is too high, the interlayer adhesion tends to become unstable.

  The adhesive resin composition has a melt flow rate in the range of 0.5 to 3.0 g / 10 min at 190 ° C. and 2.16 kg load, preferably 1.0 to 2.0 g, in accordance with ASTM D1238. / 10 min. If the MFR is too low, the moldability tends to deteriorate, and if it is too high, the durable adhesiveness at high temperatures tends to deteriorate.

  The adhesive resin composition includes a modified ethylene / α-olefin copolymer (A1) modified with an unsaturated carboxylic acid or a derivative thereof and having a graft amount of 0.1 to 10% by weight, and a graft amount of 0. It contains less than 1% by weight of ethylene / α-olefin copolymer (A2).

  The modified ethylene / α-olefin copolymer (A1) has a graft amount of 0.1 to 10% by weight, preferably 0.1 to 5.0% by weight, more preferably 0.1 to 3.0% by weight. %.

The modified ethylene / α-olefin copolymer (A1) has a density in the range of 915 to 970 kg / m ³ , preferably 915 to 945 kg / m ³ , more preferably 915 to 930 kg / m ³ .

  The modified ethylene / α-olefin copolymer (A1) has a melt flow rate in the range of 0.1 to 10.0 g / 10 min at 190 ° C. and 2.16 kg load, preferably 0, in accordance with ASTM D1238. 0.1 to 7.0 g / 10 min, more preferably 0.1 to 5.0 g / 10 min.

The ethylene / α-olefin copolymer (A2) has a graft amount of less than 0.1% by weight and is preferably unmodified.
The ethylene / α-olefin copolymer (A2) has a molecular weight distribution Mw / Mn of less than 4.0, preferably 2.0 to 4.0, more preferably 2.5 to 3.5.

The ethylene / α-olefin copolymer (A2) has a density in the range of 900 to 930 kg / m ³ , preferably 903 to 928 kg / m ³ , more preferably 905 to 925 kg / m ³ .

  The ethylene / α-olefin copolymer (A2) has a melt flow rate in the range of 0.1 to 2.0 g / 10 min at 190 ° C. and a load of 2.16 kg in accordance with ASTM D1238, preferably 0.8. It is in the range of 3 to 2.0 g / 10 minutes, more preferably 0.5 to 2.0 g / 10 minutes.

  In the adhesive resin composition, the content of the modified ethylene / α-olefin copolymer (A1) is 5 to 80% by weight, and the content of the ethylene / α-olefin copolymer (A2) is 20 to 95% by weight. The content of the modified ethylene / α-olefin copolymer (A1) is 5 to 50% by weight, and the content of the ethylene / α-olefin copolymer (A2) is 30 to 95% by weight. More preferably, the content of the modified ethylene / α-olefin copolymer (A1) is 10 to 30% by weight, and the content of the ethylene / α-olefin copolymer (A2) is 50 to 90% by weight. Is more preferable. However, the total amount of the component (A1) and the component (A2) does not exceed 100% by weight.

  The ethylene / α-olefin copolymer that is graft-modified to obtain the modified ethylene / α-olefin copolymer (A1) is a crystalline resin mainly composed of ethylene units. In the ethylene / α-olefin copolymer, the structural unit derived from ethylene is preferably contained in an amount of 70 to 100 mol%, particularly preferably 90 to 98 mol%. The monomer other than ethylene constituting the ethylene / α-olefin copolymer is preferably an α-olefin having 3 to 10 carbon atoms. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and combinations of two or more thereof. .

  Specific examples of the unsaturated carboxylic acid grafted onto the ethylene / α-olefin copolymer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid. Examples of the unsaturated carboxylic acid derivative include acid anhydrides, esters, amides, imides, and metal salts. Specifically, maleic anhydride, endic acid anhydride, itaconic anhydride, citraconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, glycidyl acrylate, maleic acid monoethyl ester, maleic Acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid monomethyl ester, itaconic acid diethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N , N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-dibutyramide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-dibutyramide , Maleimide, N-butylmer Imide, N- phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, and potassium methacrylate. Of these graft monomers, maleic acid or maleic anhydride is preferred.

  Graft modification of the ethylene / α-olefin copolymer using the unsaturated carboxylic acid or derivative thereof (graft monomer) as described above can be performed by various conventionally known methods.

  For example, an ethylene / α-olefin copolymer is melted using an extruder, a graft modification is performed by adding a graft monomer, or an ethylene / α-olefin copolymer resin is dissolved in a solvent, There is a solution modification method in which a graft monomer is added to perform graft copolymerization. Among these, the melt modification method using an extruder is preferable. In any modification method, in order to efficiently graft copolymerize the graft monomer, it is preferable to start the reaction in the presence of a radical initiator.

  As the radical initiator, organic peroxides, organic peresters and the like are preferably used. Specifically, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3, 1,4-bis (tert -Butylperoxyisopropyl) Organic peroxides such as benzene and lauroyl peroxide; tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5 -Di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylperisobutyrate, tert-butylper-sec-octoate, tert-butylperpivalate, cumylperpi Organic peresters such as valerate and tert-butylperdiethyl acetate; azoisobutyronitrile, dimethylazoy And azo compounds such as butylate are used. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3, 2,5-dimethyl-2,5-di (tert-butyl) Peroxy) Dialkyl peroxides such as hexane, 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

  The radical initiator as described above is usually used at a ratio of 0.001 to 1.0 part by weight with respect to 100 parts by weight of the ethylene / α-olefin copolymer resin.

  The amount of unsaturated carboxylic acid or its derivative grafted in the modified ethylene / α-olefin copolymer (A1) (hereinafter referred to as “grafting amount”) is the same as that of the modified ethylene / α-olefin copolymer (A1). The range is preferably 0.1 to 10% by weight with respect to 100% by weight.

  Examples of the ethylene / α-olefin copolymer (A2) include a crystalline resin mainly composed of ethylene units polymerized using a metallocene catalyst. In the ethylene / α-olefin copolymer (A2), the structural unit derived from ethylene is preferably contained in an amount of 70 to 100 mol%, particularly preferably 90 to 98 mol%. As the monomer other than ethylene constituting the ethylene / α-olefin copolymer (A2), an α-olefin having 3 to 10 carbon atoms is preferable. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and combinations of two or more thereof. .

  As the metallocene catalyst used for the production of the ethylene / α-olefin copolymer (A2), a conventionally known single-site catalyst can be used. Such a metallocene catalyst is usually a metallocene catalyst component (a) comprising a transition metal compound of group IVB of the periodic table having at least one ligand having a cyclopentadienyl skeleton, and an organoaluminum oxy compound catalyst It is formed from component (b), if necessary, particulate carrier (c), organoaluminum compound catalyst component (d), and ionized ionic compound catalyst component (e).

As the metallocene catalyst component (a) used for the production of the ethylene / α-olefin copolymer (A2), a transition metal compound of group IVB of the periodic table having at least one ligand having a cyclopentadienyl skeleton is used. Can be mentioned. Examples of such a transition metal compound include a transition metal compound represented by the following general formula [I].
ML ¹ _X ... [I]
[I] In the formula, x is the valence of the transition metal atom M. M is a transition metal atom selected from Group IVB of the periodic table, and zirconium is preferred.

L ¹ is a ligand coordinated to the transition metal atom M. Among these, at least one ligand L ¹ is a ligand having a cyclopentadienyl group skeleton, and the cyclopenta The dienyl group skeleton may have a substituent.

  When the compound represented by the general formula [I] includes two or more groups having a cyclopentadienyl skeleton, the groups having two cyclopentadienyl skeletons are each a (substituted) alkylene group, or It may be bonded via a (substituted) silylene group or the like. Moreover, these two cyclopentadienyl group skeletons may have two or more substituents such as a methyl group and an ethyl group.

The ligand L ¹ other than the ligand having a cyclopentadienyl skeleton is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a sulfonate group-containing hydrocarbon group, A halogen atom or a hydrogen atom.

  As the organoaluminum oxy compound catalyst component (b), a conventionally known aluminoxane is preferably used. The fine particle carrier (c) is a conventionally known inorganic or organic compound, preferably a granular or fine particle solid having a particle size of preferably 20 to 200 μm.

  As the organoaluminum compound catalyst component (d), trialkylaluminum, alkenylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide and the like are used.

  As the ionized ionic compound catalyst component (e), Lewis acids, ionic compounds such as triphenylcarbenium tetrakis (pentafluorophenyl) borate, carborane compounds such as dodecaborane, and the like are used.

  The adhesive resin composition is prepared by a method known per se, for example, the polymers (A1) and (A2) are kneaded in a molten state using an extruder, a Banbury mixer or the like, or stirred and mixed in the presence of a solvent. Can be prepared. The adhesive resin composition can contain, for example, other polymers, rubbers, or various additives as long as the object of the present invention is not impaired.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by these Examples.

The resins used in the examples are shown in Table 1.
[Example 1]
[Production of modified ethylene / 1-butene copolymer (modified PE-1)]
Ethylene / 1-butene copolymer resin prepared using a Ti-based catalyst (density: 0.920 g / m ³ , melting point (Tm): 124 ° C., MFR (ASTM D 1238, 190 ° C., 2.16 kg load) : 2.0 g / 10 min, ethylene content: 96 mol%) 100 parts by weight, maleic anhydride (MAH) 0.8 part by weight, peroxide (trade name Perhexin 25B, manufactured by NOF Corporation) 0 0.07 parts by weight was mixed with a Henschel mixer, and the resulting mixture was melt graft-modified with a 65 mmφ single screw extruder set at 230 ° C. to give a modified ethylene / 1-butene copolymer (hereinafter, modified PE). (Abbreviated as −1).

When the graft amount of this modified ethylene / 1-butene copolymer (modified PE-1) was measured by IR analysis, the maleic anhydride graft amount was 0.8% by weight. The MFR at 190 ° C. under a 2.16 kg load was 1.0 g / 10 min, the melting point was 122 ° C., and the density was 920 kg / m ³ according to ASTM D1238.
[Manufacture of adhesive resin composition]
As copolymer (A1), 15% by weight of the modified ethylene / 1-butene copolymer (modified PE-1) obtained as described above, and as copolymer (A2), the density was 905 kg / m ^3. In accordance with ASTM D1238, the MFR at 190 ° C. and the load of 2.16 kg is 1.0 g / 10 min, the molecular weight distribution Mw / Mn is 3.1, and the graft amount is 0% by weight. A mixture blended with 85% by weight of 1-hexene copolymer (PE-1) was melt mixed with a single screw extruder to obtain an adhesive resin composition (1).

The obtained adhesive resin composition (1) has a density of 907 kg / m ³ , MFR at 190 ° C. and a load of 2.16 kg of 1.0 g / 10 min in accordance with ASTM D1238, and maleic anhydride ( The MAH) graft amount was 0.15% by weight.

Next, a laminated film was produced using this adhesive resin composition (1), and the adhesive strength with polyamide (PA6) and the durability of the heat seal part were tested.
(I) Test Method for Adhesive Strength with Polyamide Polyamide (PA6; trade name: Amilan CM1021XF, manufactured by Toray Industries, Inc.), the above adhesive resin composition (1) and ethylene / 1-hexene copolymer resin (LLDPE; trade name) Using Evolu SP2540 (manufactured by Prime Polymer Co., Ltd.), a 5-layer laminated film was molded under the following conditions.

<Molding conditions>
Film layer configuration and thickness of each layer:
LLDPE / adhesive resin composition / PA6 / adhesive resin composition / LLDPE = 60/10/10/10/10/60 micrometer
Molding machine: Die diameter 40mmφ Extruder (for LLDPE layer)
Set temperature: 230 ° C
Die diameter 40mmφ Extruder (for PA6 layer)
Set temperature: 260 ° C
Die diameter 40mmφ Extruder (for adhesive resin layer)
Set temperature: 230 ° C
Molding speed: 10 m / min Subsequently, the interlayer adhesion strength (peel strength) between the PA6 layer and the adhesive resin layer of this five-layer film was peeled off at 23 ° C. and 80 ° C. at a peel rate of 300 mm / min. The adhesive strength was determined.

(II) Durability test method Two layers of the above five-layer laminated film are overlapped, and heat sealing is performed under the following conditions using a heat sealer (trade name: Heat Seal Tester TP-701B) manufactured by Tester Sangyo Co., Ltd. In the state of T-peeling, a constant load (1 kgf) was applied to the seal portion, and the seal portion was held at 80 ° C., and the time until the seal portion broke was measured.

<Heat seal conditions>
・ Temperature: 120 ℃
Seal pressure: 2kg / cm ²
Seal time: 1 second Table 2 shows the test results.

[Examples 2 and 3]
In Examples 4 and 5, the copolymer (PE-1) and the ethylene / 1-butene copolymer (PE-6) were used in the proportions shown in Table 2 as the copolymer (A2), respectively. In the same manner as in Example 1, adhesive resin compositions (2) and (3) were obtained.
Table 2 shows the density, MFR (ASTM D1238, 190 ° C., 2.16 kg load), and maleic anhydride graft amount of these compositions.
Using these compositions, a five-layer laminated film was prepared in the same manner as in Example 1, and the above test was performed.
The results are shown in Table 2.

[Examples 4 and 5]
In Examples 4 and 5, Example 1 and Example 3 were prepared, respectively, except that ethylene / 1-hexene copolymer resin (PE-3) was used instead of PE-1 as the copolymer (A2). In the same manner, adhesive resin compositions (4) and (5) were obtained.
Table 2 shows the density, MFR (ASTM D1238, 190 ° C., 2.16 kg load), and maleic anhydride graft amount of these compositions.
Using these compositions, a five-layer laminated film was prepared in the same manner as in Example 1, and the above test was performed.
The results are shown in Table 2.

[Comparative Example 1]
An adhesive resin composition (6) was obtained in the same manner as in Example 1 except that the copolymer (PE-6) was used instead of PE-1 as the copolymer (A2).
Table 2 shows the density, MFR (ASTM D1238, 190 ° C., 2.16 kg load), and maleic anhydride graft amount of this composition.
Using this composition, a 5-layer laminated film was prepared in the same manner as in Example 1, and the above test was performed.
The results are shown in Table 2.

[Comparative Examples 2, 3, 4]
In Comparative Examples 2, 3 and 4, instead of PE-1 as the copolymer (A2), an ethylene / 1-butene copolymer (PE-5) and an ethylene / 1-hexene copolymer (PE-4), respectively. ), Ethylene / 1-hexene copolymer (PE-2) in the proportions shown in Table 2, and in the same manner as in Example 3, the adhesive resin compositions (7), (8) and (9 )

Table 2 shows the density, MFR (ASTM D1238, 190 ° C., 2.16 kg load), and maleic anhydride graft amount of these compositions.
Using these compositions, a five-layer laminated film was prepared in the same manner as in Example 1, and the above test was performed.
The results are shown in Table 2.

[Comparative Example 5]
An adhesive resin composition (10) was obtained in the same manner as in Example 1 except that PE-1 and PE-6 were used as the copolymer (A2) in the proportions shown in Table 2.
Table 2 shows the density, MFR (ASTM D1238, 190 ° C., 2.16 kg load), and maleic anhydride graft amount of this composition.
Using this composition, a 5-layer laminated film was prepared in the same manner as in Example 1, and the above test was performed.
The results are shown in Table 2.

試験の結果、実施例１〜５は、何れの評価とも良好であった。共重合体(Ａ２)として、Ｍｗ/Ｍｎが４以上のエチレン・α−オレフィン共重合体を使用した比較例１は、破断時間が短かった。比較例１では、破断は接着樹脂層とＰＡ６層との剥離を起点に発生していた。共重合体（Ａ２)として、密度またはＭＦＲが規定の範囲を外れる、エチレン・α−オレフィン共重合体を使用した比較例２、３および４は、何れも破断時間が短かった。比較例２〜４では、破断は接着樹脂層とＰＡ６層との剥離を起点に発生していた。共重合体(Ａ２)として、Ｍｗ/Ｍｎが４未満のエチレン・α−オレフィン共重合体が規定の含有量を下回る比較例５は、破断時間が短かった。比較例５では、破断は接着樹脂層とＰＡ６層との剥離を起点に発生していた。

As a result of the test, Examples 1 to 5 were good in any evaluation. Comparative Example 1 using an ethylene / α-olefin copolymer having Mw / Mn of 4 or more as the copolymer (A2) had a short breaking time. In Comparative Example 1, the fracture occurred starting from peeling between the adhesive resin layer and the PA6 layer. Comparative Examples 2, 3 and 4 using an ethylene / α-olefin copolymer having a density or MFR outside the specified range as the copolymer (A2) all had a short breaking time. In Comparative Examples 2 to 4, the fracture occurred starting from the separation between the adhesive resin layer and the PA6 layer. As the copolymer (A2), the comparative example 5 in which the ethylene / α-olefin copolymer having an Mw / Mn of less than 4 was less than the specified content had a short breaking time. In Comparative Example 5, the fracture occurred starting from peeling between the adhesive resin layer and the PA6 layer.

  The gas barrier laminate film of the present invention is excellent in durability of a heat seal part under high temperature, can provide a laminate film suitably used for food packaging materials for boil and air chains, packaging and transportation of food, electronic devices, etc. , In storage and sales, can greatly contribute to food safety and hygiene, cost control and efficiency.

Claims (7)

It is modified with an unsaturated carboxylic acid or derivative thereof, the graft amount is 0.01 to 1.0% by weight,
The density is in the range of 900-930 kg / m ³ ;
According to ASTM D1238, the melt flow rate at 190 ° C. and 2.16 kg load is in the range of 0.5 to 3.0 g / 10 min.
Containing the following components (A1) and (A2),
The content of component (A1) is 5 to 80% by weight, the content of component (A2) is 20 to 95% by weight (however, the total amount of component (A1) and component (A2) does not exceed 100% by weight) A gas barrier laminate film comprising an adhesive resin composition layer (A) comprising an adhesive resin composition and a gas barrier resin layer (B).
(A1): 190 ° C. modified with an unsaturated carboxylic acid or derivative thereof, having a graft amount of 0.1 to 10% by weight, a density in the range of 915 to 970 kg / m ³ , and conforming to ASTM D1238 2. A modified ethylene / α-olefin copolymer having a melt flow rate in a range of 0.1 to 10.0 g / 10 min at a load of 2.16 kg.
(A2): The molecular weight distribution Mw / Mn is less than 4.0, the density is in the range of 900 to 930 kg / m ³ , and the melt flow rate at 190 ° C. and 2.16 kg load is 0.00 according to ASTM D1238. An ethylene / α-olefin copolymer having a graft amount of less than 0.1% by weight in the range of 1 to 2.0 g / 10 min.   The gas barrier laminate film according to claim 1, wherein the gas barrier resin layer (B) is a layer comprising at least one selected from the group consisting of ethylene / vinyl alcohol copolymer and polyamide resin.   The gas barrier laminate film according to claim 2, wherein the ethylene-vinyl alcohol copolymer has a content of structural units derived from ethylene of 15 to 70 mol%.   The gas barrier laminate film according to claim 2 or 3, wherein the polyamide resin is selected from the group consisting of nylon 6, nylon 66, nylon 6, 10, nylon 12, nylon 11, MXD nylon, amorphous nylon, and copolymer nylon.   The gas barrier resin layer (B) and the polyolefin layer (C) containing the polyolefin layer (C) are bonded to each other via the adhesive resin composition layer (A). Gas barrier laminate film.   A food packaging material for boil comprising the gas barrier laminate film according to any one of claims 1 to 5.   An air cushioning material comprising the gas barrier laminate film according to claim 1.