JP7040212B2 - Multi-layer laminated film - Google Patents

Description

The present invention relates to a multilayer laminated film composed of at least 6 layers adjacent to each other in the order of a base material layer, an anchor coating agent layer, a sandrami layer, an adhesive layer, a barrier layer, and an adhesive layer.

Packaging materials made of thermoplastic resins for foods, beverages, pharmaceuticals, etc. are ethylene / vinyl alcohol-based copolymers with excellent gas barrier properties, fragrance retention, solvent resistance, etc. for the purpose of preventing deterioration of the contents (hereinafter referred to as , EVOH) is used for laminated films mainly for food packaging. However, since EVOH is hydrophilic and its gas barrier property is deteriorated due to moisture absorption and its heat-sealing property is poor, it is generally laminated with a base material such as biaxially stretched polypropylene or biaxially stretched polyester or a heat-sealing material such as polyethylene. And used (see, for example, Patent Document 1).

For example, in bonito pack pouch packaging, a multilayer film is manufactured by laminating biaxially stretched polypropylene and polyethylene on both sides of an EVOH film (see, for example, Non-Patent Document 1).

The laminating method is mainly produced by carrying out a dry laminating method via a polyurethane adhesive a plurality of times.

However, this method requires at least two laminating steps, which is uneconomical and has problems such as a large amount of residual solvent.

An adhesive-less thermal lamination technology (for example, see Patent Document 2) that heat-welds a film of another resin without using the above-mentioned adhesive for dry laminating has also been developed, and a molding technology that reduces residual solvent has been developed. It is desired.

Japanese Patent No. 4230007 Japanese Unexamined Patent Publication No. 2017-94591

Packaging ・ ・ ・ Knowledge to know 2012 Published by Japan Packaging Technology Association

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a multilayer laminated film containing EVOH by a highly versatile and simplified method.

The above-mentioned problem is composed of at least 6 layers adjacent to each other in the order of the base material layer (I), the anchor coating agent layer (II), the sandrami layer (III), the adhesive layer (IV), the barrier layer (V), and the adhesive layer (VI). The sandrami layer (III) is made of a polyolefin, and the adhesive layer (IV) and the (VI) layer are solved by a multilayer laminated film made of a resin composition containing an adhesive and a polyolefin that satisfy the following requirements (1) and (2). Will be done.

(1) A copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester having a vinyl ester and / or acrylic acid ester content of 5 mol% or more higher than that of the thermoplastic resin (A) and (A), and A hydrolyzate of a resin composition containing a modified product obtained by grafting (A) and (B).

(2) The vinyl alcohol content is 0.5 to 40 mol%, and the vinyl ester and / or acrylic acid ester content is 30 mol% or less.

The present invention will be described in detail below.

The base material (I) of the present invention is not particularly limited, but is, for example, polyester such as polyethylene terephthalate and polybutylene terephthalate, polyamide such as nylon 6 and nylon 66, polypropylene resin, acrylic resin and polymethyl. Examples thereof include a film made of a polymer polymer such as penten, polyvinyl chloride, polyvinylidene chloride, polycarbonate and a cellulose-based resin, and it is preferable that the film is at least one selected from the group consisting of polyester, polyamide and polypropylene. .. The thickness of the layer (I) can be selected depending on the intended use, but is generally 5 to 25 μm, preferably 10 to 15 μm.

The anchor coating agent layer (II) constituting the present invention is not particularly limited, but a general adhesive used for extrusion laminating molding is used. For example, polyurethane-based adhesives, isocyanate-based adhesives, polyethyleneimine-based adhesives, polybutadiene-based adhesives, and the like can be mentioned. The thickness of the layer (II) can be selected within a range in which the adhesiveness is not impaired, but is generally 2 to 10 μm, preferably 2 to 5 μm.

The sandrami layer (III) of the present invention is not particularly limited as long as it is a polyolefin, but for example, high-pressure low-density polyethylene, high-density polyethylene, medium-density polyethylene, ethylene / 1-butene copolymer, ethylene /. 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid ester copolymer, ethylene / methacrylic Ethylene-based polymers such as acid ester copolymers, polypropylene, propylene / ethylene copolymers, propylene / 1-butene copolymers, poly1-butene, poly1-hexene, poly4-methyl-1-pentene, etc. Can be mentioned. From the viewpoint of extrusion laminate formability, high pressure method low density polyethylene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene / 4-methyl-1- Pentene copolymers, ethylene / acrylic acid ester copolymers, and ethylene / methacrylate copolymers are preferable. The thickness of the layer (III) can be selected depending on the intended use as long as the adhesiveness is not impaired, but is generally 5 to 20 μm, preferably 5 to 15 μm.

The layers (IV) to (VI) of the present invention are composed of layers (IV) and (VI) containing a specific adhesive and polyolefin, and a barrier material layer (V), such as three-layer cast molding and inflation molding. It can be manufactured by the general-purpose molding method of.

The adhesive used for the layers (IV) and (VI) is a hydrolyzate of a resin composition that satisfies the following requirements (1) and (2).

(1) A copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester having a vinyl ester and / or acrylic acid ester content of 5 mol% or more higher than that of the thermoplastic resin (A) and (A), and A hydrolyzate of a resin composition containing a modified product obtained by grafting (A) and (B).

(2) The vinyl alcohol content is 0.5 to 40 mol%, and the vinyl ester and / or acrylic acid ester content is 30 mol% or less.

Examples of the thermoplastic resin (A) (hereinafter, may be abbreviated as (A) or component (A)) constituting the adhesive used for the (IV) and (VI) layers include ethylene, propylene, and 1-butene. Examples thereof include homopolymers of α-olefins having 2 to 12 carbon atoms, copolymers thereof, and copolymers of ethylene and vinyl esters and / or acrylic acid esters.

For example, high-pressure method low-density polyethylene, high-density polyethylene, medium-density polyethylene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene / 4-methyl- 1-Penten copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid ester copolymer, ethylene / methacrylate copolymer and other ethylene-based polymers, polypropylene, propylene / ethylene copolymer, propylene / Examples thereof include 1-butene copolymer, poly1-butene, poly1-hexene, poly4-methyl-1-pentene, etc., and the thermoplastic resin (A) may be used alone or in combination of two or more. May be good. Among them, high-pressure low-density polyethylene, high-density polyethylene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / vinyl acetate copolymer, and polypropylene are preferable from the viewpoint of adhesiveness and cost. These compositions are most preferable because they are also excellent in moldability.

The method for producing low-density polyethylene by the high-pressure method can exemplify high-pressure radical polymerization, and such a resin can be conveniently selected from commercially available products, and is commercially available from, for example, Tosoh Corporation under the trade name of Petrosen. ing. The method for producing high-density polyethylene, ethylene / 1-butene copolymer and ethylene / 1-hexene copolymer is not particularly limited, but high / medium using a Ziegler-Natta catalyst, a Phillips catalyst, or a metallocene catalyst is used. -A low-pressure ion polymerization method or the like can be exemplified, and such a resin can be conveniently selected from commercially available products. For example, it is commercially available from Tosoh Corporation under the trade names of Niporon Hard, Niporon-L, and Niporon-Z.

The method for producing the ethylene-vinyl acetate copolymer is not particularly limited as long as the ethylene-vinyl acetate copolymer can be produced, but known high-pressure radical polymerization methods and ionic polymerization methods can be exemplified. can. As an ethylene-vinyl acetate copolymer produced by a high-pressure radical polymerization method, it is commercially available from Tosoh Corporation under the trade name of Ultrasen.

A copolymer (B) of ethylene constituting the adhesive used for the layers (IV) and (VI) and a vinyl ester and / or an acrylic acid ester (hereinafter, may be abbreviated as (B) or component (B). ) Has a vinyl ester and / or acrylic acid ester content of 5 mol% or more higher than that of the thermoplastic resin (A).

The vinyl ester and / or acrylic acid ester of the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester includes vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate and vinyl isobutyrate. , An aliphatic vinyl ester such as vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, aromatic vinyl ester such as vinyl benzoate, methyl acrylate, ethyl acrylate, butyl acrylate and the like can be mentioned. From the viewpoint of adhesiveness to EVOH, the vinyl ester and / or acrylic ester content is preferably 10 to 80 mol%.

Examples of the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester include ethylene / vinyl acetate copolymer, ethylene / acrylic acid ester copolymer, ethylene / methacrylic acid ester copolymer and the like. It may be used alone or in combination of two or more. Above all, it is preferable to use an ethylene-vinyl acetate copolymer from the viewpoint of cost. Further, from the viewpoint of adhesiveness to EVOH, the vinyl ester and / or acrylic acid ester content is preferably 10 to 80 mol%.

The vinyl acetate content in the ethylene-vinyl acetate copolymer in the component (B) is preferably 12 mol% or more, and when used in combination with the above-mentioned component (A), the adhesiveness of the resin composition in the present invention to EVOH. Becomes good. When the vinyl acetate content of the component (B) is less than 10 mol%, the adhesiveness of the adhesive in the present invention to EVOH deteriorates.

The method for producing the ethylene-vinyl acetate copolymer in the component (B) is not limited, but known production methods such as high-pressure radical polymerization, solution polymerization and latex polymerization can be mentioned, and Tosoh Corporation has given the trade name of Ultrasen. , Lanxess Co., Ltd. marketed under the trade name of Revaplen.

Further, as a constituent component of the adhesive used for the (IV) and (VI) layers, the compatibilizer (C) (hereinafter, (C) or component (C) of the component (A) and the component (B) may be abbreviated. ) May be included.

Examples of the component (C) include a copolymer of ethylene and a vinyl ester and / or an acrylic acid ester, and the vinyl ester content and / or the acrylic acid ester of the component (C) is higher than that of the component (A). A polymer of ethylene and vinyl ester and / or acrylic acid ester having a lower vinyl ester and / or acrylic acid ester content than the component (B) is preferable. Examples of the vinyl ester and / or acrylic acid ester include fats such as vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl capricate, vinyl laurate, and vinyl stearate. Examples thereof include group vinyl esters, aromatic vinyl esters such as vinyl benzoate, methyl acrylate, ethyl acrylate, butyl acrylate, and the like.

Among them, it is preferable to use an ethylene-vinyl acetate copolymer because it is excellent in economy, and one kind alone or two or more kinds may be used in combination. In particular, by using two or more kinds of compatibilizers in combination, the dispersibility of the component (A) and the component (B) is improved, and the compatibility of the adhesive with the polyolefin and the adhesive strength with respect to EVOH are improved.

When a copolymer of ethylene and vinyl ester is used as the compatibilizer (C), the vinyl ester content differs between the compatibilizer (C) and the component (A) or the component (B) by 1. A copolymer of ethylene and vinyl ester having an amount of about 40% by weight is preferable, and a copolymer of ethylene and vinyl ester having a vinyl ester content difference of 1 to 30% by weight is more preferable, and a vinyl ester content difference is most preferable. Is a polymer of ethylene and vinyl ester in an amount of 1 to 20% by weight.

When a copolymer of a plurality of ethylenes and vinyl esters is used as the component (C), the difference in vinyl ester content is preferably 1 to 20% by weight, more preferably 1 to 15% by weight, and most preferably 1 to 15% by weight. It is preferably within 1 to 10% by weight.

The method for producing the ethylene / vinyl acetate copolymer in the component (C) is not limited, but known production methods such as high-pressure method radical polymerization, solution polymerization and latex polymerization can be mentioned, and such resins can be obtained from commercially available products. It can be selected for convenience, and is commercially available under the trade name of Ultrasen from Tosoh Corporation and the trade name of Revaplen from LANXESS CO., LTD.

The method for graft-modifying the thermoplastic resin (A), ethylene, vinyl ester and / or acrylic acid ester (B) is not particularly limited as long as it can be graft-modified, and is appropriately selected in consideration of reactivity and the like. A method of graft-copolymerizing ethylene and vinyl acetate to (A), a method of graft-copolymerizing ethylene alone or ethylene and α-olefin to (B), prepolymerizing (A) and (B), and graft-modifying them. However, from the viewpoint of productivity, it is preferable to add the cross-linking agent (D) to the composition containing the above-mentioned components (A) and (B).

When the thermoplastic resin (A) is polyethylene or polyproprene, it is most preferable to use an organic oxide as the cross-linking agent (D).

The organic peroxide of the cross-linking agent (D) is not particularly limited as long as it is an organic peroxide, and for example, dicumyl peroxide, dit-butyl peroxide, 2,5-dimethyl-2,5-di (t-). Butylperoxy) hexane, 1,1-di (t-butylperoxy) cyclohexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3,1,3-bis (t-butylperoxyisopropyl) ) Benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,3-di- (t-butylperoxy) -diisopropylbenzene, n-butyl-4,4-bis ( t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, diacetylperoxide, lauroyl peroxide, t-butylcumyl peroxide, etc. Can be mentioned. These can be used alone or in combination of two or more.

Of these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 1,1-di (t-butylperoxy) cyclohexane are preferably used from the viewpoint of reactivity. Further, a cross-linking aid such as triallyl isocyanurate or divinylbenzene may be used together with the cross-linking agent, if necessary.

A suitable blending ratio of the adhesive used for the layers (IV) and (VI) is that the thermoplastic resin (A) is 5 to 95 parts by weight and ethylene and vinyl ester and / or from the viewpoint of improving the adhesiveness to polyethylene and EVOH. The acrylic acid ester (B) contains 5 to 95 parts by weight (the total of (A) and (B) is 100 parts by weight), and more preferably the thermoplastic resin (A) contains 15 to 85 parts by weight and polyethylene. And vinyl ester and / or acrylic acid ester (B) in an amount of 15 to 85 parts by weight (the total of (A) and (B) is 100 parts by weight), and most preferably thermoplastic resin (A) is in an amount of 20 to 80 parts by weight. Polyethylene and vinyl ester and / or acrylic acid ester (B) contain 20 to 80 parts by weight (the total of (A) and (B) is 100 parts by weight).

When the adhesive used for the (IV) and (VI) layers contains the compatibilizer (C), the blending amount of the compatibilizer (C) is (A) and from the viewpoint of improving the adhesiveness to polyethylene and EVOH. The total of (B) contains 1 to 50 parts by weight of the compatibilizer (C) with respect to 100 parts by weight, more preferably 5 to 45 parts by weight, and most preferably 10 to 40 parts by weight.

When the adhesive used for the (IV) and (VI) layers contains a cross-linking agent (D), the total amount of the thermoplastic resin (A) and the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester. The blending amount of the cross-linking agent (D) with respect to 100 parts by weight is preferably in the range of 0.005 to 1 part by weight from the viewpoint of improving adhesiveness to EVOH and moldability.

In addition to the above ingredients, if necessary, antioxidants, lubricants, neutralizers, blocking inhibitors, surfactants, slip agents, silicon oil, UV absorbers, flame retardants, mold release agents, foaming agents, fragrances, etc. It may contain one or more commonly used additives of.

The adhesive used for the layers (IV) and (VI) can be produced by kneading the components (A) to (D) and hydrolyzing them. The method of melt-kneading the components (A) to (D) is not particularly limited as long as it is a melt-kneading device capable of uniformly dispersing each component, and can be produced by a commonly used resin mixing device. Examples thereof include melt kneading devices such as single-screw extruders, multi-screw extruders, Banbury mixers, pressurized kneaders, and rotary rolls. Among them, a twin-screw extruder having a high degree of kneading and capable of continuous operation is preferable because the dispersed state can be finely and uniformly. The melting temperature is preferably about 260 ° C. from the melting point of the thermoplastic resin (A).

Specific examples of the manufacturing process of the adhesive used for the (IV) and (VI) layers are as follows.

The dry blend of the components (A) to (D) is charged into the hopper of the extruder. At least a part of the thermoplastic resin (A), the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester, and the cross-linking agent (E) may be added from a side feeder or the like. Further, two or more extruders may be used to sequentially melt and knead in stages. A Henschel mixer, a V blender, a ribbon blender, a tumbler, or the like may be used for mixing the components (A) to (D).

The method for hydrolyzing the resin composition containing the components (A) to (D) constituting the adhesive used for the layers (IV) and (VI) is not particularly limited, but the resin composition is described from the viewpoint of productivity. It is preferable to hydrolyze the pellets or powders of the above directly in an alkali. The adhesive used for the (IV) and (VI) layers preferably has a saponification degree of 10% by weight or more of the vinyl ester and / or acrylic acid ester component. If it is 10% by weight mol% or more, the adhesiveness to EVOH is sufficient.

The polyolefin to be blended with the adhesive used for the (IV) and (VI) layers is not particularly limited, and for example, high-pressure low-density polyethylene, high-density polyethylene, medium-density polyethylene, ethylene / 1-butene copolymer, and the like. Ethylene 1-hexene copolymer, ethylene 1-octene copolymer, ethylene 4-methyl-1-pentene copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid ester copolymer, ethylene・ Ethylene-based polymers such as methacrylic acid ester copolymers, polypropylene, propylene / ethylene copolymers, propylene / 1-butene copolymers, poly1-butene, poly1-hexene, poly4-methyl-1-pentene. However, from the viewpoint of dispersibility of the adhesive, the ethylene / vinyl acetate copolymer is most preferable.

A suitable blending ratio of the adhesive and the polyolefin used for the (IV) and (VI) layers is 5 to 95 parts by weight for the adhesive and 5 to 95 parts by weight for the polyolefin (the total of the adhesive and the polyolefin is 100 parts by weight). From the viewpoint of adhesiveness to EVOH, the adhesive contains 30 to 95 parts by weight and the polyolefin contains 30 to 95 parts by weight (the total of the adhesive and the polyolefin is 100 parts by weight). The thickness of the (IV) layer and the (VI) layer can be selected within a range in which the adhesiveness and the like are not impaired, but are generally 3 to 20 μm, preferably 5 to 10 μm.

The gas barrier material used for the layer (V) of the present invention is not particularly limited, and is, for example, polyester such as polyethylene terephthalate and polybutylene terephthalate, polyamide 6 such as nylon 6 and nylon 66, polyvinylidene chloride, polyvinyl alcohol, and the like. EVOH is mentioned, and it is preferable to use EVOH because it has a high oxygen barrier property and excellent adhesion between the adhesive of the present invention and a layer containing a polyolefin. EVOH is a copolymer composed of an ethylene unit and a vinyl alcohol unit. The EVOH used in the present invention is not particularly limited, and examples thereof include known ones used in molding applications. The method for producing EVOH is not particularly limited, and for example, EVOH can be produced by producing an ethylene-vinyl ester copolymer according to a known method and then saponifying it. However, the ethylene unit content of EVOH is preferably 55 mol% or less, more preferably 10 to 55 mol%, from the viewpoint of high barrier property against gas, organic liquid and the like and molding processability. Such a resin can be conveniently selected from commercially available products, and is commercially available, for example, under the trade name of Eval from Kuraray Co., Ltd. and under the trade name of Soanol from Nippon Synthetic Chemical Industry Co., Ltd. The thickness of the layer (V) can be selected within a range in which the gas barrier property is not impaired, but is generally 5 to 20 μm, preferably 10 to 15 μm.

It is preferable to have at least one sealing layer (VII) on the (VI) layer constituting the multilayer laminated film of the present invention because the heat sealing property is improved.

The material used for the (VII) layer is not particularly limited as long as it is a thermoplastic resin, and examples thereof include polyolefins, soft vinyl chloride, polystyrene, and polyurethane-based materials. Among these, polyolefin is preferable from the viewpoint of adhesiveness, and for example, high-pressure method low-density polyethylene, high-density polyethylene, medium-density polyethylene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1- Ethylene-based polymers such as octene copolymers, ethylene / 4-methyl-1-pentene copolymers, ethylene / vinyl acetate copolymers, ethylene / acrylic acid ester copolymers, ethylene / methacrylic acid ester copolymers, etc. Examples thereof include polypropylene, propylene / ethylene copolymer, propylene / 1-butene copolymer, poly1-butene, poly1-hexene, poly4-methyl-1-pentene and the like. The thickness of the (VII) layer can be selected within a range in which the sealing property is not impaired, but is generally 5 to 50 μm, preferably 10 to 30 μm.

Since the multilayer laminate film of the present invention and the multilayer laminate film containing the (VII) layer are excellent in gas barrier properties and heat seal properties, packaging materials and containers made of thermoplastic resins for foods, beverages, pharmaceuticals, etc. It can be used for a wide range of purposes such as.

Further, as an example of use of the multilayer laminated film of the present invention and the multilayer laminated film including the (VII) layer, not only general food packaging film applications but also various functions can be imparted by using a specific polyolefin. can.

For example, by using an easy peel resin that can impart a good opening feeling after heat sealing as the polyolefin of the (VII) layer, it can be used in applications that require easy peeling properties such as a lid material for food packaging. Such an easy peel resin is commercially available from Tosoh Corporation under the trade name of Mercen M.

As another example, it can be applied to a packaging material for powder by adding an antistatic agent capable of preventing static electricity of the contents from being applied to the polyolefin of the (VII) layer. It is preferable to use a polyolefin layer containing an antistatic agent because the productivity when filling the packaging material with powder is improved. As the polyolefin, an ethylene / vinyl acetate polymer and an ethylene / 1-hexene copolymer are preferable. , Ethylene / 1-octene copolymer is preferable, and ethylene / vinyl acetate polymer is most preferable because high heat seal strength can be obtained. Such an ethylene-vinyl acetate polymer is commercially available from Tosoh Corporation under the trade name of Ultrasen.
As the antistatic agent, any antistatic agent can be used as long as it belongs to the category of antistatic agent and has a function of preventing the film from being charged. Examples of the antistatic agent include nonionic interfaces such as glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyethylene glycol crude acid ester, polyoxyethylene sorbitan fatty acid ester, and fatty acid alkanolamide. Examples thereof include activators, polyglycerin fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyethylene alkyls with polyethylene oxide, alkylamines, stearyl alcohols and the like. These can be used alone or in combination of two or more. The compounding ratio of the antistatic agent is 0.1 to 1% by weight, and is preferably 0.3 to 0.6% by weight because it is particularly excellent in antistatic performance and heat seal strength.

For the (IV) to (VI) layers of the present invention, a three-layer film can be produced by a general-purpose molding method such as three-layer cast molding or inflation molding.

The multilayer laminated film of the present invention can be produced by a one-step single extrusion laminator by using the above three-layer film as a base material for sandwich laminating, and in the case of a laminated body having a (VII) layer, one step. It can be manufactured by a tandem type extrusion laminator.

The multilayer laminated film of the present invention can be used as a packaging material having excellent gas barrier properties by a highly versatile and simplified method.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[Saponification degree]
Using each resin composition obtained from Examples, the vinyl ester content was measured according to JIS K7192 (1999), and the saponification degree (% by weight) was determined according to the following formula.
Degree of saponification (% by weight) = 100 × {(vinyl ester content of resin composition before hydrolysis)-(vinyl ester content of resin composition after hydrolysis)} / (vinyl of resin composition before hydrolysis) Ester content)
[Heat seal strength]
Using the laminate obtained from the examples, the heat seal strength between the (VII) layers was evaluated by the following procedure. Using a hot tack tester manufactured by Tester Sangyo Co., Ltd., the (VII) layers of each laminate were heat-sealed with a sealing temperature of 130 ° C., a sealing pressure of 0.2 MPa, a sealing time of 1 second, and vertical heating. Using ORIENTEC's Tencilon RTE-1210), the adhesive strength (N / 15 mm width) in T-type peeling was measured at a sample width of 15 mm and a tensile speed of 300 mm / min. The measurement was repeated 3-5 times for the same sample.

Production Example of Adhesive The component (A), component (B), component (C), and component (D) were melt-kneaded with a twin-screw extruder at a molten resin temperature of 190 ° C. to obtain a pellet-shaped resin composition. .. Subsequently, the present resin composition was hydrolyzed with 1 part by weight of a sodium hydroxide methanol solution at a temperature of 55 ° C. to prepare the present adhesive.

Production Example of Adhesive 1 As an adhesive component (A), an ethylene-vinyl acetate copolymer (manufactured by Toso Co., Ltd., product) having a melt mass flow rate of 14/10 minutes, a density of 935 kg / m ³ , and a vinyl acetate content of 15% by weight. Name Ultrasen 625) (hereinafter, may be abbreviated as component (A-1)) is 50 parts by weight, melt mass flow rate as component (B) is 70 g / 10 minutes, density is 968 kg / m ³ , vinyl acetate content is 42% by weight. Ethylene-vinyl acetate copolymer (manufactured by Toso Co., Ltd., trade name Ultrasen 760) (hereinafter, may be abbreviated as component (B-1)) is 50 parts by weight, and an organic peroxide is used as component (D). (Manufactured by Nichiyu Co., Ltd., trade name: Perhexa 25B) was dry-blended at a ratio of 0.02 parts by weight, melt-kneaded with a twin-screw extruder at a molten resin temperature of 190 ° C., and pelletized with the composition shown in Table 1. Resin composition of. Subsequently, the resin composition was hydrolyzed with 1 part by weight of a sodium hydroxide methanol solution at a reaction temperature of 55 ° C., and adhered with a vinyl alcohol content of 7 mol% and a vinyl ester and / or acrylic acid ester content of 5 mol%. Agent 1 was obtained.

Production Example of Adhesive 2 It was produced by the same method as Production Example 1 except that the component (A-1) of the adhesive was 75 parts by weight and the component (B-1) was 25 parts by weight, and the vinyl alcohol content was high. Adhesive 2 having a 5 mol% vinyl ester and / or acrylic acid ester content of 3 mol% was obtained.

Production Example of Adhesive 3 Ethylene-vinyl acetate copolymer with 75 parts by weight of adhesive component (A-1), melt mass flow rate of 5 g / 10 minutes as component (B), and vinyl acetate content of 80% by weight (Rankses (Rankses) Same as Production Example 1 except that 25 parts by weight of the product (trade name: Revaplen 800) (hereinafter, may be abbreviated as component (B-2)) manufactured by Co., Ltd. and 20 parts by weight of the following component as component (C) are used. To obtain an adhesive 3 having a vinyl alcohol content of 8 mol% and a vinyl ester and / or acrylic acid ester content of 5 mol%.
[Structure of component (C)]
A dry blend of 4 parts by weight of the following 5 types of ethylene-vinyl acetate copolymers-Ethylene-vinyl acetate copolymer with melt mass flow rate of 20 g / 10 minutes, density of 940 kg / m ³ , and vinyl acetate content of 20% by weight ( Tosoh Co., Ltd., trade name Ultrasen 633)
-Ethylene-vinyl acetate copolymer with melt mass flow rate 18 g / 10 minutes, density 949 kg / m ³ , vinyl acetate content 28% by weight (manufactured by Tosoh Corporation, trade name Ultrasen 710)
-Ethylene-vinyl acetate copolymer with melt mass flow rate 30 g / 10 minutes, density 954 kg / m ³ , vinyl acetate content 32% by weight (manufactured by Tosoh Corporation, trade name Ultrasen 750)
-Ethylene-vinyl acetate copolymer with melt mass flow rate 70 g / 10 minutes, density 968 kg / m ³ , vinyl acetate content 42% by weight (manufactured by Tosoh Corporation, trade name Ultrasen 760)
-Ethylene-vinyl acetate copolymer with melt mass flux rate of 5 g / 10 minutes and vinyl acetate content of 50% by weight (manufactured by LANXESS Co., Ltd., trade name: Revaprene 500)
Production Example of Adhesive 4 100 parts by weight of the adhesive component (A-1) and 0.02 parts by weight of the organic peroxide (manufactured by NOF CORPORATION, trade name Perhexa 25B) as the component (D). The resin composition was dry-blended at 190 ° C. and melt-kneaded with a twin-screw extruder to obtain a pellet-shaped resin composition having the composition shown in Table 1. Subsequently, the resin composition was hydrolyzed with 1 part by weight of a sodium hydroxide methanol solution at a reaction temperature of 55 ° C., and adhered with a vinyl alcohol content of 2 mol% and a vinyl ester and / or acrylic acid ester content of 4 mol%. Agent 4 was obtained.

Production Example of Adhesive 5 100 parts by weight of the adhesive component (B-1) and 0.02 parts by weight of the organic peroxide (manufactured by NOF CORPORATION, trade name Perhexa 25B) as the component (D). The resin composition was dry-blended at 190 ° C. and melt-kneaded with a twin-screw extruder to obtain a pellet-shaped resin composition having the composition shown in Table 1. Subsequently, the resin composition was hydrolyzed with 1 part by weight of a sodium hydroxide methanol solution at a reaction temperature of 55 ° C., and adhered with a vinyl alcohol content of 11 mol% and a vinyl ester and / or acrylic acid ester content of 8 mol%. Agent 5 was obtained.

Production Example of Adhesive 6 The vinyl alcohol content of the composition shown in Table 1 is 0 mol%, and the vinyl ester and / or acrylic acid ester content is the same as that of Adhesive 1 except that the resin composition is not hydrolyzed. Made a 12 mol% adhesive 6.

Example 1
Dry blend 50 parts by weight of adhesive 1, melt mass flow rate 7 g / 10 minutes as polyolefin, and 50 parts by weight of low density polyethylene (manufactured by Tosoh Corporation, trade name Petrosen 204) with a density of 922 kg / m ³ and extrude uniaxially. Melt blended using a machine at a molten resin temperature of 180 ° C.

The above-mentioned compound was supplied to the inner and outer layer extruders of a three-layer cast film forming machine (manufactured by Plastic Engineering Laboratory Co., Ltd.) having a screw of 20/20 / 32 mmΦ and equipped with a T-die. An ethylene / vinyl alcohol copolymer (Kuraray Co., Ltd., trade name EVAL E105B) having a melt mass flow rate of 5.7 g / 10 minutes and an ethylene content of 44 mol% was supplied to the intermediate layer extruder as a barrier material at a temperature of 200 ° C. It was co-extruded from a T-die and cast on a casting roll surface to obtain a three-layer film ((IV) to (VI) layer) having a thickness of 0.035 mm having an inner layer / intermediate layer / outer layer = 10 μm / 15 μm / 10 μm.

After applying a polyurethane adhesive as an anchor coating agent to the biaxially stretched polypropylene film ((I) layer) ((II) layer), the melt mass flow rate as the (III) layer is 7 g / 10 min, and the density is as low as 922 kg / m ³ . A laminate obtained by sandwich-laminating the above-mentioned three-layer film with a thickness of 15 μm using a density polyethylene (manufactured by Tosoh Corporation, trade name Petrosen 204) using an extruded laminator (screw diameter 25 mmΦ manufactured by Placo Co., Ltd.). An ethylene-vinyl acetate copolymer containing an antistatic agent having a melt mass flow rate of 8.5 g / 10 minutes and a density of 925 kg / m ³ as a polyolefin layer (VII) on the surface of the (VI) layer of this laminate (manufactured by Tosoh Corporation). , Trade name Ultrasen 537S-2) (hereinafter, may be abbreviated as component (PO-1)) was extruded and laminated to a thickness of 30 μm to obtain a laminate. When the heat sealability of the obtained laminate was evaluated, it was as shown in Table 2.

Example 2
A laminate was obtained in the same manner as in Example 1 except that the adhesive 2 was used as the adhesive. When evaluated using the obtained laminate, it was as shown in Table 2.

Example 3
A laminate was obtained in the same manner as in Example 1 except that the adhesive 3 was used as the adhesive. When evaluated using the obtained laminate, it was as shown in Table 2.

Example 4
Ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation, product) having a melt mass flow rate of 14/10 minutes, a density of 935 kg / m ³ , and a vinyl acetate content of 15% by weight as the polyolefin to be blended in the (IV) layer and the (VI) layer. A laminated body was obtained in the same manner as in Example 1 except that the name Ultrasen 625) was used. When evaluated using the obtained laminate, it was as shown in Table 2.

Example 5
A laminate was obtained in the same manner as in Example 1 except that 30 parts by weight of polyolefin and 70 parts by weight of an adhesive were blended as the (IV) layer and the (VI) layer. When evaluated using the obtained laminate, it was as shown in Table 2.

Example 6
A laminated body was obtained by the same method as in Example 1 except that the thickness of the three-layer film was (IV) layer / (V) layer / (VI) layer = 5 μm / 15 μm / 5 μm. When evaluated using the obtained laminate, it was as shown in Table 2.

Example 7
(III) The same method as in Example 1 except that a linear low-density polyethylene (manufactured by Tosoh Corporation, trade name Niporon TZ420) having a melt mass flow rate of 10 g / 10 minutes and a density of 913 kg / m ³ was used as the layer. Obtained a laminate. When evaluated using the obtained laminate, it was as shown in Table 3.

Example 8
As the (VII) layer, a polyolefin-based adhesive polymer having a melt mass flow rate of 9 g / 10 minutes and a density of 930 kg / m ³ (manufactured by Tosoh Corporation, trade name: Mercen MX02) (hereinafter, may be abbreviated as component (PO-2)). ) Was laminated, and a laminated body was obtained in the same manner as in Example 1. When evaluated using the obtained laminate, it was as shown in Table 3.

Comparative Example 1
A laminate was obtained in the same manner as in Example 1 except that the component (A-1) of the adhesive was 100 parts by weight and the component (B-1) was 0 parts by weight. When evaluated using the obtained laminate, the adhesiveness to EVOH was low. It was as shown in Table 4.

Comparative Example 2
A laminate was obtained in the same manner as in Example 1 except that the component (A-1) of the adhesive was 0 parts by weight and the component (B-1) was 100 parts by weight. When evaluated using the obtained laminate, the adhesiveness to EVOH was low. It was as shown in Table 4.

Comparative Example 3
A laminate was obtained in the same manner as in Example 1 except that the adhesive was not hydrolyzed. When evaluated using the obtained laminate, the adhesiveness to EVOH was low. It was as shown in Table 4.

Claims (7)

It is composed of at least 6 layers adjacent to the base material layer (I), the anchor coating agent layer (II), the sandrami layer (III), the adhesive layer (IV), the barrier layer (V), and the adhesive layer (VI) in this order. A multilayer laminated film comprising a resin composition containing an adhesive and a polyolefin in which the layer (III) is made of a polyolefin and the adhesive layer (IV) and the (VI) layer satisfy the following requirements (1) and (2).
(1) A thermoplastic resin (A ) containing at least one homopolymer of α-olefin having 2 to 12 carbon atoms or a copolymer thereof, or a copolymer of ethylene and vinyl ester and / or acrylic acid ester. ), The polymer (B) of ethylene and vinyl ester and / or acrylic acid ester having a vinyl ester and / or acrylic acid ester content of 5 mol% or more more than that of (A), and (A) and (B). A hydrolyzate of a resin composition containing a grafted polymer.
(2) The vinyl alcohol content is 0.5 to 40 mol%, and the vinyl ester and / or acrylic acid ester content is 30 mol% or less. The first aspect of claim 1, wherein the adhesive layers (IV) and (VI) are resin compositions containing 10 to 90 parts by weight of an adhesive and 10 to 90 parts by weight of a polyolefin (the total of the adhesive and the polyolefin is 100 parts by weight). Multilayer laminated film. The multilayer laminated film according to claim 1 or 2 , wherein the barrier material used for the barrier layer (V) is an ethylene-vinyl alcohol copolymer. The multilayer laminated film according to any one of claims 1 to 3 , further comprising a sealing layer (VII) on the adhesive layer (VI) layer. A food packaging film comprising the multilayer laminated film according to claim 4 . A multi-layer laminating film for a lid, which comprises the multi-layer laminating film according to claim 4 , and contains an easy peel resin in the (VII) layer. A multilayer laminating film for powder packaging, comprising the multilayer laminating film according to claim 4 , wherein the (VII) layer contains an antistatic agent.