JP2001334621A - Laminated body and packaging material using the same - Google Patents

Abstract

(57) [Problem] To provide a laminate having good laminate strength and not decreasing the laminate strength even when packaging various highly permeable materials. The purpose is to provide. A resin composition layer obtained by forming a resin composition satisfying the following conditions by extrusion lamination on a metal surface or a vapor deposition surface of a barrier layer such as a metal foil or a metal vapor deposited film. A laminate having at least a configuration. The resin composition is a polyolefin-based resin having a specific copolymerization ratio and an adhesive polyolefin-based copolymer resin, wherein the functional group is selected from a carboxyl group, an acid anhydride group, an epoxy group, and a silane group. Or at least one copolymer resin having a specific amount capable of binding to the barrier layer surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for producing a metal foil layer, a metal-deposited film layer, or an inorganic compound-deposited film layer. The present invention relates to a laminate which includes at least a structure in which an applied resin composition layer is laminated, and which is preferably used as various packaging materials.

[0002]

2. Description of the Related Art In the field of packaging, aluminum foil, aluminum-deposited film or alumina-deposited film has been
It is used as one of barrier layers for protecting contents from water vapor and the like. In addition, it is possible to provide light-shielding properties for aluminum foil and aluminum-deposited films,
In addition, since aluminum foil can maintain its shape (having dead-holding properties) when it is folded, it is necessary to use aluminum foil to provide barrier properties and other functionalities to the packaging material (package). By laminating various thermoplastic resins on an aluminum surface or a vapor-deposited surface such as an aluminum-deposited film or an alumina-deposited film, it is used in various packaging forms.

[0003] Among these barrier layers, when manufacturing various packaging forms using an aluminum foil or an aluminum vapor-deposited film, a method of forming a laminate with a thermoplastic resin includes an aluminum foil or an aluminum surface of an aluminum vapor-deposited film or Ethylene-acrylic acid copolymer, ethylene-
A method of laminating an ethylene-α, β unsaturated carboxylic acid such as a methacrylic acid copolymer or an ionic cross-linked product of an ethylene-methacrylic acid copolymer or an ionic cross-linked product thereof by a method such as extrusion lamination is exemplified.

[0004] With respect to aluminum foil, aluminum-deposited film or alumina-deposited film, it is also possible to obtain a laminate with various thermoplastic resins by using various adhesives such as polyurethane or polyethyleneimine. However, the laminate thus obtained has the following problems.

First, the aluminum surface or the vapor-deposited surface of an aluminum foil or an aluminum-deposited film, and the alumina-deposited surface of an alumina-deposited film are oxidized with time,
When the above-mentioned ethylene-α, β unsaturated carboxylic acid or its ion cross-linked product is laminated on these barrier layers, aluminum foil supplied from aluminum foil manufacturer In the case of an aluminum-deposited film or an alumina-deposited film immediately after opening, it is preferable to laminate the above-mentioned ethylene-α, β-unsaturated carboxylic acid or its ion-crosslinked product immediately after the vapor deposition. However, depending on the manufacturing process of the laminate, an aluminum foil, an aluminum-deposited film, or an alumina-deposited film in which oxidation or contamination has progressed after the opening of the aluminum foil or after the vapor deposition may be used. When the above-mentioned ethylene-α, β-unsaturated carboxylic acid or its ion-crosslinked product is laminated using an aluminum foil, an aluminum-deposited film or an alumina-deposited film in such a state, it is difficult to obtain good lamination strength. there were.

As a second problem, in the case of a method of manufacturing a laminate using an adhesive, even if the surface of the barrier layer is oxidized or contaminated, the use of a solvent-type adhesive provides a good result. Although it is possible to obtain a high laminate strength, it requires an aging period at a high temperature of about several days to one week after bonding. As a result, a large amount of energy consumption, delivery time, deterioration of the work environment due to evaporation of the solvent and disaster prevention,
There was a problem such as odor due to the residual solvent in the laminated material.

Further, as a third problem, when a strongly permeable material is packaged by using a laminate obtained by laminating by the above-mentioned production method, the barrier of the laminate is formed by the strongly permeable content. The lamination strength of the layer and the thermoplastic resin layer is reduced. In general, a barrier layer such as an aluminum foil, an aluminum-deposited film or an alumina-deposited film has a good barrier property against various components, so that the highly permeable contents penetrate into a laminate interface between these barrier layers and various thermoplastic resins. As a result, it is considered that the laminate strength at the interface decreases. Examples of such a highly permeable substance include a fragrance of a bath agent and a component of a foaming agent.

[0008] Such strongly permeable contents are, in particular, α, β
In the case of a resin having a polarity such as an adhesive resin obtained by copolymerizing an unsaturated carboxylic acid or the like, these strongly permeable contents are adsorbed by the thermoplastic resin, and significantly reduce the strength physical properties of the thermoplastic resin. Sometimes.

A laminate comprising a barrier layer of an aluminum foil, an aluminum-deposited film or an alumina-deposited film and various thermoplastic resin layers is indispensable in various packaging forms because of its excellent barrier properties and functionality. Even when a highly permeable material is packaged using these laminates, the adhesive strength of the laminate interface between the barrier layer and various thermoplastic resins is improved to reduce the laminate strength and the thermoplastic resin. There is a demand for a laminate that does not cause deterioration in strength properties.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and the metal used as the barrier layer is a metal foil such as aluminum, a metal surface of a metal-deposited film or a metal-deposited surface. Or, the inorganic compound surface of the inorganic compound vapor deposition film such as alumina has good laminating strength without being affected by the state of oxidation or contamination, and is packed with various highly permeable materials. Even in such a case, an object of the present invention is to provide a laminate in which the laminate strength does not decrease.

[0011]

In order to solve the above-mentioned problems, the invention according to claim 1 provides a barrier layer comprising any one layer selected from a metal foil layer, a metal vapor-deposited film layer and an inorganic compound vapor-deposited film layer. A laminate having at least a structure in which a resin composition layer satisfying the following conditions is formed by extrusion lamination on a metal surface or a vapor deposition surface. The resin composition comprises a polyolefin-based resin and an adhesive polyolefin-based copolymer resin, and the ratio of the adhesive polyolefin-based copolymer resin in the composition is 25 to 1
The ratio of the functional group capable of forming a bond with the metal surface or the vapor deposition surface of the barrier layer in the resin composition is 0.1 to 40% by weight. The functional group is a functional group composed of at least one selected from a carboxyl group, an acid anhydride group, an epoxy group, and a silane group.

According to a second aspect of the present invention, in the laminate according to the first aspect, the metal foil layer, the metal-deposited film layer, or the inorganic compound-deposited film layer as the barrier layer is an aluminum foil layer, an aluminum-deposited film layer, or It is characterized by being an alumina deposited film layer.

According to a third aspect of the present invention, in the laminate according to the first or second aspect, a surface treatment is performed on a metal surface or a vapor-deposited surface of the metal foil layer, the metal-deposited film layer, or the inorganic compound-deposited film layer which is a barrier layer. And the surface treatment is a boehmite treatment.

According to a fourth aspect of the present invention, there is provided the first or second aspect.
In the laminate described above, a surface treatment is performed on a metal surface or a vapor-deposited surface of the metal foil layer, the metal-deposited film layer, or the inorganic compound-deposited film layer that is a barrier layer, and the surface treatment is an epoxy coat treatment. It is characterized by.

According to a fifth aspect of the present invention, there is provided various packaging materials using the laminate according to any one of the first to fourth aspects.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. The laminate of the present invention, a metal foil layer, a metal vapor deposition film layer or an inorganic compound vapor deposition film layer on the metal surface or vapor deposition surface of the barrier layer consisting of any layer selected from the resin composition satisfying the following conditions A laminate having at least a structure in which the resin composition layers formed by extrusion lamination are laminated. The resin composition comprises a polyolefin-based resin and an adhesive polyolefin-based copolymer resin, and the ratio of the adhesive polyolefin-based copolymer resin in the composition is 25 to 1
The ratio of the functional group capable of forming a bond with the metal surface or the vapor deposition surface of the barrier layer in the resin composition is 1 to 40% by weight. The functional group is a functional group composed of at least one selected from a carboxyl group, an acid anhydride group, an epoxy group, and a silane group.

The resin composition used in the present invention comprises a polyolefin resin and an adhesive polyolefin copolymer resin. Examples of the polyolefin resin include a low-density polyethylene resin, a medium-density polyethylene resin, a high-density polyethylene resin, -α olefin copolymer, poly α
Resins such as olefins, polypropylene resins, propylene-α-olefin copolymers, propylene-ethylene-α-olefin terpolymers, and the like, or blends thereof, may be used. Since the polyolefin resin is laminated by extrusion lamination on a barrier layer composed of the above-mentioned metal foil layer, metal-deposited film layer or inorganic compound-deposited film layer, it is necessary to use a resin modified for extrusion lamination as necessary. Can also. For example, a polypropylene resin having a long-chain branch introduced by irradiating an electron beam to the polypropylene resin may be used. Further, the melt index of the polyolefin resin is 0.1.
Those satisfying the range of 5 to 100 g / 10 minutes are used, and preferably, the range of 1 to 50 g / 10 minutes is desirable.

On the other hand, examples of the adhesive ethylene copolymer resin used in the present invention include the following. First, a polyolefin copolymer in which at least one kind of α, β unsaturated carboxylic acid or its esterified product or ionic crosslinked product is copolymerized in a polyolefin resin such as ethylene or propylene in a graft or main chain. And ethylene-acrylic acid copolymers and ethylene-methacrylic acid copolymers.
(Meth) acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-
Ethylene- (meth) acrylate such as ethyl methacrylate copolymer, ethylene-methacrylic acid-ethyl methacrylate copolymer, ethylene-methacrylic acid-methyl methacrylate copolymer, ethylene-acrylic acid-acrylic acid Ethylene- (meth) acrylic acid such as methyl copolymer, ethylene-acrylic acid-ethyl acrylate copolymer
(Meth) acrylic acid ester copolymers, and ionically crosslinked products obtained by neutralizing a part of the acid sites of the above-mentioned copolymers with zinc ions, sodium ions, or magnesium ions are exemplified.

Second, there may be mentioned those obtained by copolymerizing the above-mentioned polyolefin resin with an acid anhydride such as maleic anhydride. Examples thereof include an ethylene-maleic anhydride graft copolymer and a propylene-maleic anhydride copolymer. Acid anhydride graft copolymers such as ethylene-ethyl acrylate-
Examples include an ethylene- (meth) acrylate-acid anhydride terpolymer such as a maleic anhydride copolymer.

Third, a copolymer in which an epoxy group is introduced into the above-mentioned polyolefin resin may be mentioned.
Examples include glycidyl methacrylate copolymers and copolymers of monomers containing an epoxy group such as ethylene-epoxidized vegetable oil.

Fourth, copolymers obtained by introducing a silane group into the above-mentioned polyolefin-based resin include ethylene-vinyltrimethoxysilane graft copolymer, ethylene-
Ethylene-vinylsilane copolymer such as vinyltriethoxysilane-graft copolymer, ethylene-acrylsilane such as ethylene-acryloxypropyltrimethoxysilane-graft copolymer, ethylene-methacryloxypropyltrimethoxysilane-graft copolymer Copolymers, ethylene-vinyl acetate-glycidyl methacrylate
-Ethylene resin-vinylalkoxysilane copolymer or ethylene resin- (meth) acryloxysilane copolymer can be used, such as multi-component copolymers such as methacryloxypropyltrimethoxysilane copolymer. It is.

The resin composition used in the present invention is, as described above, a resin composition comprising a polyolefin-based resin and an adhesive polyolefin-based copolymer. The proportion of the system copolymer resin is 25 to 100% by weight. When the polyolefin-based resin is more than 75% by weight, the suitability for extrusion lamination is improved, but the content of the adhesive ethylene-based copolymer is reduced, so that the metal foil layer, the metal-deposited film layer or the inorganic compound-deposited film layer may be used. Poor adhesion to the barrier layer.

When the contents packaged using the laminate of the present invention include a non-polar hydrocarbon component or a component having a polar group, the components of the content are adsorbed and permeated into the thermoplastic resin. Permeation occurs, and the strength properties of the thermoplastic resin, which are considered to be caused by the effect of these components as a plasticizer on the thermoplastic resin, decrease. In the laminate of the present invention, the resin composition can be designed so as to reduce the affinity of the resin composition for the components of the contents. If the components of the contents selectively attack the adhesive ethylene copolymer resin into which various functional groups are introduced, increase the compounding ratio of the non-polar polyolefin resin or, conversely, the non-polar polyolefin resin. If the resin is selectively attacked, it is possible to increase the compounding ratio of the adhesive ethylene copolymer into which various functional groups are introduced. However, from the viewpoint of adhesiveness, the resin composition is such that the ratio of the adhesive polyolefin copolymer resin in the resin composition comprising the polyolefin resin and the adhesive polyolefin copolymer resin satisfies the range of 25 to 100% by weight. Need to be designed. More preferably, 40 to
It is desirable to design in the range of 70% by weight.

The functional group content of the adhesive polyolefin copolymer resin contained in the resin composition greatly affects the adhesiveness. The functional group contained in the adhesive polyolefin-based copolymer resin has a functional group ratio of 0.1 to 40% by weight.
Must be satisfied. When the amount is less than 0.1% by weight, the adhesiveness becomes insufficient because the amount of the functional group is small. When the amount is more than 40% by weight, an unnecessary functional group is introduced. Goes up. Furthermore, the fact that the content of the comonomer, which is a functional group, is large is influenced by the residual monomer, and the adhesive strength may be reduced due to the residual monomer.

The adhesive polyolefin copolymer resin used in the present invention has at least one functional group selected from a carboxyl group, an acid anhydride group, an epoxy group and a silane group. If necessary, a plurality of the above-mentioned adhesive ethylene-based copolymers can be blended and used. The content of the functional group contained in the adhesive polyolefin-based copolymer resin is one of the factors that determine the compatibility with the polyolefin-based resin. If the proportion of the functional group is more than 40% by weight, the compatibility of the polyolefin-based resin and the adhesive polyolefin-based copolymer resin is reduced, phase separation occurs, and the cohesive strength of the resin composition itself is reduced. Therefore, the interfacial adhesion decreases.

When the above resin composition layer is laminated on a barrier layer such as a metal foil layer, a metal vapor deposited film layer or an inorganic compound vapor deposited film layer, according to the theory of adhesion, the wettability with the material surface and the adhesive strength are determined. It is known that there is a high correlation. It is important that the adhesive, which is the resin composition layer, wets the adherend to the barrier layer. In general, extruded laminate grade resins have low melt index (MI) and high melt viscosity, so these resins have low wettability to adherends. In order to improve the wettability of extruded laminate grade resin, use an adhesive polyolefin copolymer resin having a functional group with a high melt index (MI) and a low melt viscosity, or use a resin such as acrylic acid. In the case of a resin having a carboxyl group, it can be locally esterified with various alcohols to impart tackiness or wettability. Furthermore, it is also possible to improve the wettability by imparting a hydrogen bonding property by forming an amide bond of a carboxyl group with various amines such as alkanolamines.

The resin composition of the present invention may contain various additives such as various polymers, antioxidants, tackifiers, fillers and various fillers, if necessary.

The laminate of the present invention is characterized in that the metal foil layer, the metal-deposited film layer or the inorganic compound-deposited film layer as the barrier layer is an aluminum foil layer, an aluminum-deposited film layer or an alumina-deposited film layer, respectively. These barrier layers can be formed by a known method. In particular, in the case of an aluminum-deposited film layer or an alumina-deposited film layer, various substrates such as a stretched polyester film, a stretched polypropylene film, and a stretched nylon film can be used as the base material for the deposition, and various primers for the deposition are also available It is possible to select one according to the base material.

In the laminate of the present invention, the metal surface or the metallized surface of the metal foil layer or the metallized film layer or the inorganic compound vapor-deposited film layer as the barrier layer is subjected to a surface treatment, and the surface treatment is carried out by boehmite treatment. When the surface of these barrier layers is subjected to boehmite treatment and a strong adhesive or strongly permeable material is wrapped, the barrier layer of the laminate and the resin are bonded by the highly permeable content. A decrease in the lamination strength of the composition layer can be prevented. The boehmite treatment method can be performed by a conventional method. For example, the method can be carried out by immersing an aluminum foil or the like in boiling water which is made alkaline by adding ammonia or triethanolamine to distilled water or the like.

As an index of the boehmite treatment, when the boehmite treated surface was measured by X-ray photoelectron spectroscopy, Al12p
The orbital aluminum oxide-derived spectral peak has a binding energy of 75.4 eV or less, an oxygen (O) / aluminum (Al) ratio of 1.7 or more, and a time-of-flight secondary ion mass. When analyzed and measured, the ratio of hydroxyl (OH) / oxygen (O) may be 0.9 or more. The measurement data obtained by the X-ray photoelectron spectroscopy is data serving as an index of the degree of oxidation of aluminum (including oxygen of hydroxide). The higher the degree of oxidation, the better the bonding state such as hydrogen bond with various functional groups. . The time-of-flight secondary ion mass spectrometry results can further separate the degree of oxidation and the degree of hydroxylation.
When the ratio of H) / oxygen (O) is 0.9 or more, it is possible to provide a bond utilizing a hydroxyl group (a hydrogen bond or a primary bond can be formed if a reaction occurs). It is. In addition, by performing the boehmite treatment, fine irregularities are generated on the treated surface, and the resin composition is laminated on the fine irregularities, so that the adhesive area is improved by an effect such as an improvement of an adhesion area and an anchoring effect. Is improved. However, the range of the above-mentioned boehmite index is not necessarily limited to these ranges, and if the boehmite-treated surface is oxidized or hydroxylated, it is effective for adhesion.

In the laminate of the present invention, a surface treatment is performed on the metal surface or the vapor deposition surface of the metal foil layer, the metal vapor deposition film layer, or the inorganic compound vapor deposition film layer which is the barrier layer. It is characterized by being an epoxy coat treatment. By applying the epoxy coat, the reactivity with various functional groups present in the resin composition is improved, and the adhesiveness is improved. Further, when a highly permeable material is packaged using the laminate of the present invention, a decrease in the laminate strength between the barrier layer and the resin composition layer of the laminate can be prevented by the highly permeable content.

The laminate of the present invention can be used as various types of packaging materials. The configuration is shown below as an example of a lid material as a packaging material. (1) Lid material: paper layer / thermoplastic resin layer (I) / barrier layer /
Resin composition layer (2) Lid material: paper layer / thermoplastic resin layer (II) / barrier layer / resin composition layer / thermoplastic resin layer (III) (3) Lid material: thermoplastic resin layer (IV) / Barrier layer / resin composition layer (4) Lid material: thermoplastic resin layer (V) / barrier layer / resin composition layer / thermoplastic resin layer (VI)

[0033] In the case of (1) and (2) above, the paper layer is formed
The paper to be formed is not particularly limited to its type. Ma
Further, basically, the resin composition layer in the present invention itself is
Used as a sealant layer due to its heat sealing properties
Although it is also possible to do the above, (2)
Or heat as a sealant layer as in the configuration shown in (4).
Plastic resin layers (III) and (VI) can be provided.
You. Further, if necessary, a thermoplastic resin (III),
(VI) includes heat resistance, low temperature sealing, easy opening, etc.
Various functions can be provided. In addition, the above (1)
Or the thermoplastic resin layers (I) and (II) in the configuration of (2).
Used to laminate the paper layer and barrier layer
Because, polyethylene resin and ethylene-α-olefin
Polyolefin resin such as copolymer
Extrusion, preferably at high temperatures above 320 ° C
By doing so, it is possible to laminate. Also, Bali
A) Depending on the type of layer, the barrier layer and the thermoplastic resin (I),
(II) is replaced with various types such as urethane type and imine type
Gravure coating with reverse adhesive
By known methods such as coating and roll coating
Dry lamination, wet lamination and non-solvent
It can also be laminated by lamination.

In the case of the above (4), the thermoplastic resin layers (IV) and (V) can be selected from a stretched polyester film, a stretched polyamide film, a stretched polyethylene film, a stretched polypropylene film and the like. It is possible. These laminating methods can also use the conventional method described above. Also, if necessary,
Various ink layers can be provided by a known method such as gravure coating in order to impart design properties. The lid is not limited to the above configuration as long as it is a laminate including at least a configuration in which a barrier layer and a resin composition layer are laminated.

As a packaging material using the laminate of the present invention, the structure is shown below as an example of a soft packaging. (5) Flexible packaging: thermoplastic resin layer (VII) / barrier layer /
Resin composition layer (6) Flexible packaging: thermoplastic resin layer (VIII) / barrier layer / resin composition layer / thermoplastic resin layer (IX)

Although the above example has a relatively simple structure used as a soft packaging material, other layers may be interposed depending on the function. Thermoplastic resin layer (V
Various films such as the above-mentioned stretched polyester film, stretched propylene film, stretched nylon film and the like can be used as the base material as II) and (VIII), and the conventional laminating method can be used. The thermoplastic resin layer (IX) may be provided as a sealant layer on the resin composition side. This soft wrapping material can be used in various forms such as primary wrapping such as a sachet stored in a paper secondary wrapping container and a pouch filled with a liquid material.

The structure of a composite paper container as an example of a packaging material using the laminate of the present invention is shown below. (7) Composite paper container: thermoplastic resin layer (X) / paper layer / thermoplastic resin layer (XI) / barrier layer / resin composition layer (8) Composite paper container: thermoplastic resin layer (XII) / paper layer /
Thermoplastic resin layer (XIII) / barrier layer / resin composition layer / thermoplastic resin layer (XIV)

In the above example, the configuration is in consideration of a composite paper container typified by a liquid paper container or the like.
For example, a composite paper container filled with a bath agent powder can be used, and the present invention is not particularly limited to the above configuration. Since the thermoplastic resin layers (X) and (XII) are used as the outermost layers, it is possible to use a polyolefin-based resin such as a polyethylene resin or a polypropylene resin in consideration of moisture resistance and waterproof of the paper layer. There is no particular limitation. The thermoplastic resin layer (XIV) of the example of the above (8) is
Although the above-mentioned polyolefin-based resin can be used, it is also possible to use a polyester-based sealant so that various components such as flavor components and medicinal components of the contents are not adsorbed.

The method for producing such a laminate is not particularly limited, but is basically a method in which a resin composition layer blended under the above conditions is laminated by an extrusion lamination method on a barrier layer satisfying the above conditions. It is.

The laminate thus obtained can be developed in various packaging forms such as the above-mentioned lid material, flexible packaging and composite paper container, and the lamination strength is not reduced even for a strongly permeable substance. In addition, it is possible to obtain a laminate capable of preventing the deterioration of the resin due to the contents.

[0041]

Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 An aluminum foil (thickness: 7 μm) subjected to a boehmite treatment was used as a barrier layer. The aluminum foil was preliminarily dried and laminated with a polyester film substrate (12 μm) using a urethane-based adhesive. Laminated. Low density polyethylene (LDPE,
MI = 5.1) and an ethylene-ethyl acrylate-maleic anhydride copolymer (MI = 65, ethylene: 80% by weight, ethyl acrylate: 17% by weight, maleic anhydride:
3% by weight), and adjusted so as to have the following composition ratio of the resin composition, and an evaluation sample was prepared based on the following evaluation sample preparation method. The obtained sample was evaluated based on the following evaluation method. The results are shown in Table 1. Low-density polyethylene 40% by weight Ethylene-ethyl acrylate-maleic anhydride copolymer 60% by weight

[Evaluation Sample Preparation Method] Using a resin composition adjusted at the compounding ratio shown in the examples, these barrier layers were processed at a processing temperature of 240 to 240 as shown in the table according to each resin composition. A film was formed at 320 ° C., and at that time, the cut sample of the barrier layer was bonded in advance to a through substrate of an extrusion laminator, whereby a resin composition layer was laminated on the barrier layer. The processing speed at this time is 50 m / mi
n. The thickness of the resin composition layer is 30 μm. The thus obtained barrier layer / resin composition layer laminate is
A sample for measurement (pouch) was prepared by sealing the entire surface.

[0044] [Evaluation method] Pouch sun obtained by the above method
Measure the peel strength between the pull barrier layer / resin composition layer
Was. In that case, the peeling speed is 300 mm / mi by T-type peeling.
n. I went in. In addition, a strong osmosis resistance test
Propellant, bath agent, turf fungicide (solvent-based)
Select and pack in each of the above pouches.
The peel strength after storage for a week was measured and evaluated.

Example 2 Aluminum foil (thickness: 7 μm) treated with boehmite as a barrier layer, low-density polyethylene (LDPE, MI = 5.1) as a resin composition and an ethylene-acrylic acid copolymer (MI) = 35, ethylene: 9
A sample was prepared and evaluated in the same manner as in Example 1 except that 0% by weight and acrylic acid: 10% by weight) were used. The results are shown in Table 1.

Example 3 Boehmite-treated aluminum foil (thickness 7 μm) as a barrier layer, low-density polyethylene (LDPE, MI = 5.1) as a resin composition, ethylene-ethyl acrylate / ethylene-acetic acid Vinyl-glycidyl methacrylate-methacryloxypropyltrimethoxysilane copolymer (MI = 23, silane 0.1 ~
2% by weight), and a sample was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4 A sample was prepared and evaluated in the same manner as in Example 1 except that an aluminum foil (7 μm in thickness) subjected to an epoxy coating treatment was used as a barrier layer. The results are shown in Table 1.

Example 5 A sample was prepared and evaluated in the same manner as in Example 1 except that an aluminum-deposited polyethylene terephthalate film (thickness: 12 μm) subjected to boehmite treatment was used as a barrier layer. The results are shown in Table 1.

Example 6 Alumina-deposited polyethylene terephthalate film (12 μm) treated with boehmite as a barrier layer A sample was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Comparative Examples 1 to 6> Each of Examples 1 to 6 was performed except that an untreated aluminum foil (7 μm) was used as a barrier layer.
Samples were prepared and evaluated in the same manner for Nos. To 6 above. The results are shown in Table 1.

Example 7 A sample was prepared and evaluated in the same manner as in Example 1 except that the mixing ratio of the resin composition was adjusted to the following ratio. The results are shown in Table 1. Low-density polyethylene 60% by weight Ethylene-ethyl acrylate-maleic anhydride copolymer 40% by weight

Comparative Example 7 A sample was prepared and evaluated in the same manner as in Example 1 except that the mixing ratio of the resin composition was adjusted to the following ratio. The results are shown in Table 1. Low-density polyethylene 90% by weight Ethylene-ethyl acrylate-maleic anhydride copolymer 10% by weight

Example 8 Using the same material as in Example 1, a sample was prepared based on the following Preparation of Packaging Material-1. The container was actually sealed as a lid, and the storage test was conducted at 40 ° C-90% R.C. H. For 4 weeks. Thereafter, as a result of opening, the adhesion between the barrier layer and the resin composition layer was very good, and no obstacle (double lid) in lowering the laminate strength due to the effect of the contents occurred.

[0054] [Preparation of packaging material-1] Configuration example as lid material
A laminate having the configuration shown in the above (2) was prepared (see FIG. 1).
See). At that time, paper layer / low density polyethylene
Layer (16 μm) / Al foil (7 μm)
Thereafter, a resin composition layer and a sheet having easy peelability
The runt layer is formed into a film by co-extrusion.
Plastic resin layer (low density polyethylene layer) / barrier layer / tree
Fat composition layer / thermoplastic layer (has easy peel properties)
Sealant layer III). Like this
The lid material created is obtained by combining paper and plastic.
Used as a lid material for composite containers
Used a bath agent (powder form).

<Comparative Example 8> Using the same material as in Comparative Example 1, a lid material was prepared in the same manner as in Example 8, and after a storage test,
evaluated. The lamination strength of the barrier layer / resin composition layer was significantly reduced, and the problem of a double lid occurred.

Example 9 Using the same materials as in Example 1, a sample was prepared based on Preparation of Packaging Material-2 shown below. Storage test at 40 ° C-90% R. H.
For 4 weeks. Thereafter, as a result of opening, no peeling of the barrier layer / resin composition layer due to the contents was observed.

[0057] [Preparation of packaging material-2]
Example A laminate having the structure shown in the above (5) was prepared. (Figure
2). This laminate is composed of a paper layer / a thermoplastic resin layer (low density)
Polyethylene layer) / barrier layer / resin composition layer
Will be successful. However, the barrier layer in this case is made of boehmite
A treated aluminum vapor-deposited film is used. This product
The layer is sealed in a pouch-like manner and issued as a content.
The agent was used.

<Comparative Example 9> Using the same materials as in Comparative Example 1, a soft package was prepared in the same manner as in Example 9 and evaluated after a storage test. When the soft package is opened to take out the contents, peeling occurs between the barrier layer / resin composition layer,
The contents could not be easily taken out.

Example 10 Using the same materials as in Example 1, a sample was prepared based on Preparation of Packaging Material-3 shown below. A bactericide for turf was used as the contents of the container. Storage test at 40 ° C-90% R. H. For 4 weeks. As a result, no peeling of the barrier layer / resin composition layer due to the contents was observed.

[Preparation of Packaging Material-3] As a composite paper container, a laminate having the configuration shown in the above (7) was prepared. The composition was a thermoplastic resin layer (X) / paper layer / thermoplastic resin layer (XI) / barrier layer / resin composition layer, and an alumina vapor-deposited film layer was used as the barrier layer. A layer obtained by laminating a thermoplastic resin layer (X) and a paper layer on the barrier layer that has been subjected to the above-described treatment in advance is converted into a thermoplastic resin layer (X
Lamination was performed by sand lamination using I). At that time, the thermoplastic resin layer (X) is made of low-density polyethylene,
By performing high-temperature extrusion on the thermoplastic resin layer (XI),
An ethylene-acrylate-acrylic acid terpolymer, which can be laminated with corona-treated PET without an adhesive, was used. This laminate was used as a gobel-top type liquid container, and was prepared using an end face processing technique such as skiving.

<Comparative Example 10> A container was prepared in the same manner as in Example 10 using the same materials as in Comparative Example 1, and after a storage test, evaluation was made. As a result, peeling occurred between the barrier layer and the resin composition layer, resulting in inferior functionality and appearance as a container.

The results of Examples 1 to 7 are shown in the table.

[0063]

[Table 1]

The layer structure of each of the laminates of Examples 1 to 7 shows that the peeling strength of the resin composition layer was out of the sealant from the results of the peel strength measurement, and the lamination strength between the barrier layer and the resin composition layer was good. Can be confirmed. On the other hand, in the layer configurations of the laminates of Comparative Examples 1 to 6, a decrease in resin physical properties due to the contents has been confirmed. The results reflect the surface state of the barrier layer, and it is confirmed that the surface treatment state of the barrier layer greatly affects the adhesion. In addition, in the configuration of the laminate of Comparative Example 7, a decrease in resin physical properties due to the contents was confirmed from the effect of the mixing ratio of the resin composition.

[0065]

The laminate of the present invention is obtained by subjecting a metal layer or a vapor-deposited surface of a barrier layer such as a metal foil layer, a metal-deposited film layer, or an inorganic compound-deposited film layer to a boehmite treatment or an epoxy coat treatment. By including at least a configuration in which a resin composition layer having adhesiveness is laminated, even if a highly permeable material is packaged using this laminate as various packaging materials, The laminate strength between the barrier layer and the thermoplastic resin layer does not decrease without being affected by the object. Therefore, the laminate of the present invention can be conventionally developed as a packaging material in a field that cannot be used depending on the type of contents, and is used as a wide variety of packaging materials such as a lid material, a soft packaging material, and a composite paper container. Things.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a configuration of a laminate as one embodiment of the present invention.

FIG. 2 is a cross-sectional view showing a configuration of a laminate as one embodiment of the present invention.

FIG. 3 is a cross-sectional view showing a configuration of a laminate as one embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Thermoplastic resin layer 2 ... Resin composition layer 3 ... Barrier layer 4 ... Thermoplastic resin layer 5 ... Paper layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/02 C08L 23/02 23/08 23/08 23/26 23/26 F-term (Reference) 3E086 AB01 AD01 AD02 AD23 BA04 BA13 BA14 BA15 BA24 BB01 BB52 CA28 DA01 4F100 AA01A AA19A AB01A AB10A AB33A AK03B AK06 AK41 AK51G AK53A AK70 AK80 AL01B AL05B BA02 CB02 DG10 EH66A EJ65A EJ68A GB15 GB16 GB18 JD01A JL11B 4J002 BB032 BB052 BB071 BB081 BB101 BB122 BB142 BB152 BB172 BB211 BB231 BN051 GF00

Claims (5)

[Claims] 1. A resin composition satisfying the following conditions is extrusion-laminated on a metal surface or a vapor deposition surface of a barrier layer composed of any one selected from a metal foil layer, a metal vapor deposition film layer and an inorganic compound vapor deposition film layer. A laminate having at least a structure in which the resin composition layers formed by a method are laminated. The resin composition comprises a polyolefin-based resin and an adhesive polyolefin-based copolymer resin, and the ratio of the adhesive polyolefin-based copolymer resin in the composition is 25 to 1
00% by weight. The ratio of the functional group capable of forming a bond with the metal surface or the vapor deposition surface of the barrier layer in the resin composition is 0.1 to 40% by weight. The functional group is a functional group consisting of at least one selected from a carboxyl group, an acid anhydride group, an epoxy group, and a silane group. 2. A metal foil layer, a metal vapor-deposited film layer or an inorganic compound vapor-deposited film layer which is the barrier layer is an aluminum foil layer, an aluminum vapor-deposited film layer or an alumina vapor-deposited film layer, respectively. The laminate according to the above. 3. A surface treatment is performed on a metal surface or a vapor deposition surface of the metal foil layer, the metal vapor deposition film layer or the inorganic compound vapor deposition film layer as the barrier layer, and the surface treatment is a boehmite treatment. The laminate according to claim 1 or 2, wherein 4. A surface treatment is performed on a metal surface or a vapor deposition surface of the metal foil layer, the metal vapor deposition film layer, or the inorganic compound vapor deposition film layer which is the barrier layer, and the surface treatment is an epoxy coating process. The laminate according to claim 1 or 2, wherein: 5. A packaging material using the laminate according to any one of claims 1 to 4.