JP2016093894A - Laminate and non-adsorbent packaging container made of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate capable of exhibiting excellent non-adsorbent and content-resistant properties, and a non-adsorbent packaging container including the laminate.SOLUTION: A laminate includes a substrate layer, an adhesive layer and a sealant layer in this order. The adhesive layer includes an adhesive resin composition including a terpolymer of alkene-(meth)acrylate-unsaturated carboxylic acid. The sealant layer is a layer including (a) cyclic polyolefin resin and (b) polyolefin resin. A non-adsorbent packaging container includes the laminate.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a non-adsorbent laminate in which the adsorption amount of active ingredients contained in the contents of chemical products, pharmaceuticals, foods and the like is reduced, and a non-adsorbent packaging container comprising the same, and more specifically, the contents The present invention relates to a laminate capable of maintaining a high content of an active ingredient in a product and preventing a decrease in interlayer adhesive strength due to penetration of the contents, and a non-adsorbing packaging container comprising the same.

  Conventionally, the innermost layer of a packaging material such as a packaging bag or a lid material is provided with a sealant layer made of a polyolefin resin such as polyethylene or polypropylene showing high sealing strength, or a copolymer resin such as ionomer or EMMA. These resins can achieve high adhesion strength by heat sealing, but are known to easily adsorb various organic compounds. Therefore, a packaging material having a sealant layer made of these resins as the innermost layer, that is, a layer in contact with the contents, is not suitable for packaging chemical products, pharmaceuticals, foods, etc. containing an organic compound as an active ingredient. It is necessary to take measures such as adding more active ingredients.

  Accordingly, development of a sealant layer that has a good seal strength and hardly adsorbs active ingredients has been made. Typically, a packaging material having a non-adsorptive sealant layer made of acrylonitrile resin as the innermost layer is used (Patent Document 1).

However, since an acrylonitrile-based resin does not provide good seal strength and is expensive, development of a more preferable non-adsorptive sealant is required.
On the other hand, for example, Patent Document 2 discloses a non-adsorbing packaging material in which the innermost layer is formed of an aluminum foil or an inorganic vapor-deposited film. The packaging material is used by making a bag by partially forming an adhesive resin layer on the aluminum foil or vapor deposition film. As the adhesive resin layer, urethane resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, and the like are disclosed. However, such a packaging material has a complicated manufacturing process.

  On the other hand, contents containing organic compounds, for example, mouthwashes containing various organic compounds such as alcohols such as concentrated glycerin, flavoring agents, solubilizers, preservatives, etc., are used to seal the sealant layer of the packaging container during storage. It is known that it penetrates and further erodes an adhesive layer made of various dry laminate adhesives or adhesive resins, causing delamination between the base film and the sealant film.

Therefore, as a packaging container for contents containing such an organic compound, a resin bottle having a wall thickness of 1 to 2 mm or more is often used. Such a resinous bottle can enclose and store the contents containing an organic compound, but its production requires a large amount of resin, and the production cost is high. Moreover, since it is hard and bulky, it requires a great deal of cost during transportation, storage and disposal, which is not preferable.
Therefore, it exhibits excellent non-adsorbability and content resistance, that is, it does not adsorb active ingredients in the contents while maintaining sufficient sealing strength as a packaging container, and further contains organic compounds and contents for a long time. There is a need for a flexible laminate that does not erode the adhesive layer even when in contact, and therefore does not cause delamination, and a packaging container comprising the same.

JP-A-7-132946 Japanese Patent Laid-Open No. 10-45176

  An object of the present invention is to solve the above-mentioned problems and to provide a laminate exhibiting excellent non-adsorbability and content resistance, and a non-adsorbable packaging container comprising the same.

  As a result of various studies, the present inventor is a laminate having a base material layer, an adhesive layer and a sealant layer in this order, and the adhesive layer is an alkene- (meth) acrylic ester-unsaturated carboxylic acid ternary. An adhesive resin composition containing a copolymer, wherein the sealant layer is (a) a cyclic polyolefin resin, and (b) a laminate containing a polyolefin resin. It has been found that the container achieves the above objective.

The present invention is characterized by the following points.
(1) A laminate having a base material layer, an adhesive layer and a sealant layer in this order, wherein the adhesive layer contains an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer. The said laminated body which consists of a resin composition, and this sealant layer is a layer containing (a) cyclic polyolefin resin and (b) polyolefin resin.
(2) The laminate according to (1) above, wherein the proportion of the component (a) cyclic polyolefin resin in the entire sealant layer is 5 to 70% by mass.
(3) The laminate according to (1) or (2) above, wherein the sealant layer has a single-layer structure composed of a resin composition containing the component (a) cyclic polyolefin resin and (b) polyolefin resin. .
(4) The above (1) or (1), wherein the sealant layer has a multilayer structure comprising two or more layers in which the component (a) cyclic polyolefin resin and (b) polyolefin resin are dispersed and mixed in each layer. The laminated body as described in 2).
(5) In the sealant layer having the multilayer structure, the layer forming the outermost surface of the laminate is a layer made of the component (b) polyolefin resin and does not contain the component (a) cyclic polyolefin resin. The laminate according to (4) above.

(6) In the sealant layer having the multilayer structure, the layer adjacent to the adhesive layer is a layer composed of the component (b) polyolefin resin, and does not include the component (a) cyclic polyolefin resin. (4) Or the laminated body as described in (5).
(7) The laminate according to any one of (1) to (6), wherein an amount of the unsaturated carboxylic acid component in the adhesive resin composition is 0.05% by mass or more and less than 1.0% by mass. .
(8) The laminate according to any one of (1) to (7), wherein the amount of the (meth) acrylic acid ester component in the adhesive resin composition is 5 to 40% by mass.
(9) A non-adsorptive packaging container in which the laminate according to any one of (1) to (8) above is overlapped so that the sealant layers face each other, and the ends thereof are heat-sealed.
(10) The non-adsorbing packaging container according to (9), which is a packaging container for mouthwash.
(11) The interlaminar adhesion strength between the base material layer or the barrier layer and the sealant layer after filling the mouthwash containing 10% by mass of glycerin and storing in a 25 ° C. atmosphere for 30 days is 3N / 15 mm width. As described above, the non-adsorbing packaging container according to (9) or (10), more preferably 5 N / 15 mm width or more, and further preferably 7 N / 15 mm width or more.
(12) The method for producing a laminate according to any one of (1) to (8) above, wherein the base material layer and the sealant layer are made of alkene- (meth) acrylate ester-unsaturated carboxylic acid. The said manufacturing method laminated | stacked by the sandwich lamination method through the adhesive resin composition containing an original copolymer.

The sealant layer consisting only of generally well-known polyolefin resin, its thickness,
The organic compound adsorption amount and the seal strength are proportional. Therefore, if the sealant layer of the packaging container is thinned to prevent the contents from being adsorbed, the sealing strength is lowered and the impact resistance of the container is lowered. Further, when the sealant layer is thickened to improve the impact resistance, the amount of content adsorbed increases.
In contrast, in the laminate of the present invention, the sealant layer is difficult to adsorb organic compounds. In addition, since the cyclic polyolefin resin contained in the sealant layer exhibits a high intermolecular force, it forms a dense surface structure with a close intermolecular distance and prevents the penetration of the contents. Thereby, erosion of the adhesive layer by the contents can be suppressed. At the same time, it can exhibit a sufficiently high sealing strength for use as a packaging material, and is suitably used as various packaging containers.
Furthermore, the laminate of the present invention can achieve extremely high interlayer adhesion strength between the base material layer and the sealant layer without using a dry laminate adhesive. Therefore, there is no concern regarding the elution of residual solvents and low molecular weight substances.

  In particular, the adhesive layer of the laminate of the present invention is a content containing an organic compound, for example, a mouthwash containing various organic compounds such as alcohols such as concentrated glycerin, flavoring agents, solubilizers, and preservatives. Since it exhibits excellent content resistance and is not easily eroded even when in contact with these, high interlayer adhesion strength can be maintained over a long period of time. Furthermore, since the sealant layer of the laminate of the present invention is difficult for such organic compounds to penetrate, the interlaminar adhesive strength of the adhesive layer is maintained at a high level for an extremely long time combined with this effect. The Rukoto.

It is a schematic sectional drawing which shows an example about the layer structure of the laminated body of this invention. It is a schematic sectional drawing which shows another example about the layer structure of the laminated body of this invention. It is a schematic sectional drawing which shows another example about the layer structure of the laminated body of this invention. It is a schematic sectional drawing which shows another example about the layer structure of the laminated body of this invention.

The above-described present invention will be described in more detail below.
<1> Layer Configuration of Laminate of the Present Invention FIGS. 1 to 4 are schematic cross-sectional views showing an example of the layer configuration of the laminate of the present invention.
As shown in FIG. 1, the laminated body of the present invention has a basic structure of three layers of a base material layer 1, an adhesive layer 2 and a heat sealable resin layer 3. Various functional layers such as a barrier layer may be provided between the base material layer 1 and the adhesive layer 2 as desired.
In the following, regarding the heat-sealable resin layer 3, the surface in contact with the adhesive layer 2 is referred to as “adhesive layer laminated surface”, and the surface on the opposite side that is in contact with the contents as the innermost layer of the container is referred to as “heat seal surface” "
Here, the heat-sealable resin layer 3 is a layer containing the component (a) cyclic polyolefin resin and (b) polyolefin resin, and has a single layer structure made of a resin composition obtained by mixing them. It's okay.

In another aspect, the heat-sealable resin layer 3 may have a multilayer structure in which the components (a) and (b) are dispersed and blended in each layer. That is, each layer may have a multilayer structure of two or more layers containing the components (a) and (b) in different proportions.
Specifically, as shown in FIG. 2, the layer 3x forming the adhesive layer lamination surface of the heat-sealable resin layer 3 is composed of only the component (a) or the components (a) and (b) are mixed. The layer 3z may be a layer composed of a resin composition obtained in this manner, and the layer 3z forming the heat seal surface may be a two-layer structure in which the component (a) is not included and the layer 3z is composed of only the component (b). With this configuration, high sealing strength and sealing performance can be obtained when heat-sealing.
Or the reverse structure may be sufficient and the layer 3x which forms the contact bonding layer lamination surface of the heat-sealable resin layer 3 is a layer which does not contain a component (a) but consists only of a component (b), and heat-seal surface The layer 3z forming the layer may be composed of only the component (a) or a layer composed of a resin composition obtained by mixing the components (a) and (b). With this configuration, the interlayer adhesive strength between the adhesive layer 2 and the heat-sealable resin layer 3 is further increased, and the low adsorptivity of the contents is further increased.

  Alternatively, as shown in FIG. 3, the layer 3x that forms the adhesive layer lamination surface and the layer 3z that forms the heat seal surface are layers that do not contain the component (a) and consist only of the component (b). The intermediate layer 3y may have a three-layer structure which is a layer made of only the component (a) or a resin composition obtained by mixing the components (a) and (b). With this configuration, high sealing strength, sealing performance, and interlayer adhesion strength can be obtained.

  Alternatively, as illustrated in FIG. 4, a four-layer configuration in which layers including the component (a) and layers including only the component (b) but not the component (a) are alternately stacked may be employed. With this configuration, there is an advantage that adhesion with the adhesive layer can be improved.

  In any configuration, the proportion of the component (a) cyclic polyolefin-based resin in the entire heat-sealable resin layer 3 is preferably 5 to 70% by mass, and more preferably 10 to 40% by mass. Due to the presence of cyclic polyolefin resin in this ratio in the heat-sealable resin layer, it maintains excellent sealing strength and sealing properties, and film formability while maintaining excellent low adsorptivity to the contents. In addition, it is possible to prevent the contents from entering the laminate and prevent the adhesive layer from being eroded.

<2> Base material layer In this invention, the film which comprises a normal packaging material can be used suitably as a base material layer. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, polyvinyl alcohol, polyacrylonitrile, polycarbonate, ethylene-vinyl acetate copolymer, ionomer, ethylene- (meth) acrylic acid Copolymer, ethylene- (meth) ethyl acrylate copolymer, ethylene-propylene copolymer, methylpentene, polybutene, acid-modified polyolefin resin, polyamide resin, polystyrene resin, low crystalline saturated polyester or non-crystalline Crystalline polyester resin, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), tetrafluoroethylene-ethylene copolymer (ETFE), polytetrafluoroethylene (PTFE) It can be used a film made of MXD6 like. Or the multilayer film which laminated | stacked two or more layers of these films may be sufficient. In the case of a multilayer film, each layer may have the same composition or a different composition.

  In the present invention, these resin films may be films formed by any method such as extrusion film formation and inflation film formation. Further, a resin film obtained by coating polyvinylidene chloride called K coat on these films, for example, K coat polypropylene film, K coat nylon film and the like may be used. These may be unstretched films or may be stretched in a uniaxial or biaxial direction. In addition, for example, a film such as cellophane, a synthetic paper, or the like can be used.

Among the above films, a film made of a gas barrier resin such as polyvinylidene chloride, polyvinyl alcohol, MXD6 or the like can exhibit good gas barrier properties without further providing a barrier layer.
In the present invention, the thickness of the base material layer may be arbitrary, but is preferably 5 to 300 μm and more preferably 10 to 100 μm from the viewpoint of moldability and transparency.
The film constituting the base material layer may be subjected to pretreatment for improving wettability such as corona treatment, ozone treatment, and frame treatment on the surface on which the adhesive layer is laminated.

<3> Barrier layer In the present invention, various functional layers can be provided between the base material layer and the adhesive layer as desired. For example, by providing a gas barrier layer with respect to oxygen and water vapor, it is possible to prevent the ingress of oxygen and water vapor from the outside, to prevent evaporation of water from the inside, and to suitably prevent deterioration of the contents.
In the present invention, the barrier layer is, for example, a metal foil made of aluminum foil or the like, a vapor deposition film of an inorganic substance or an inorganic oxide, a vapor deposition film having the vapor deposition film on a resin film, or an ethylene-vinyl alcohol copolymer, It may be a layer made of a gas barrier resin such as vinylidene chloride, polyvinyl alcohol, MXD6, or a combination thereof.
Usually, the thickness of the barrier layer is preferably 0.01 to 500 μm, more preferably 1 to 300 μm from the viewpoint of gas barrier properties and transparency. The barrier layer may be subjected to surface treatment for improving wettability, such as corona treatment, ozone treatment, and flame treatment, on at least one surface thereof.
In particular, since it exhibits excellent gas barrier properties, transparency, and interlayer adhesion strength, in the present invention, an inorganic oxide vapor-deposited film or an inorganic oxide vapor-deposited film formed by providing the vapor-deposited film on a plastic film is provided. Particularly preferably used.

A vapor deposition film and a vapor deposition film are demonstrated in detail. As the plastic film for forming the vapor deposition film, a plastic film that has excellent chemical or physical strength, can withstand the conditions for forming the vapor deposition film, etc., and can be well maintained without impairing the characteristics of the vapor deposition film is used. be able to.
As such a plastic film, for example, a polyolefin film such as polypropylene or polyethylene, a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate, a film or sheet made of various resins such as a polyamide film or a polyimide film is used. can do.
Plastic film is treated with corona treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc. as necessary before providing a vapor deposition film. The pre-treatment can be arbitrarily performed. In addition, the surface pretreatment is performed as a method for improving the adhesion between the plastic film and the vapor deposition film. As a method for improving the adhesion, for example, the surface of the plastic film is preliminarily formed. In addition, a primer coating agent layer, an undercoat agent layer, an anchor coating agent layer, or the like can be arbitrarily formed.

  The material for forming the vapor deposition film may be an inorganic oxide having transparency and gas barrier properties such as oxygen and water vapor, such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, Although oxides such as titanium oxide, boron oxide, hafnium oxide, and barium oxide are used, aluminum oxide and silicon oxide are particularly preferably used from the viewpoint of gas barrier properties and production efficiency.

  As a method for forming a deposited film, physical vapor deposition methods (Physical Vapor Deposition method, PVD method) such as vacuum deposition method, sputtering method and ion plating method, plasma chemical vapor deposition method, thermal chemical vapor deposition method, etc. And film forming methods such as chemical vapor deposition (chemical vapor deposition, CVD) such as photochemical vapor deposition.

Moreover, the vapor deposition film may consist of a single layer formed by a single vapor deposition process, or may have a multilayer structure formed by repeating the vapor deposition process a plurality of times. In the case of a multilayer structure, each layer may be made of the same material or different materials, and may be formed by the same forming method or by different forming methods. Good. For example, a vapor deposition film made of silicon oxide may be formed on a plastic film by chemical vapor deposition, and then a vapor deposition film made of aluminum oxide may be formed by physical vapor deposition.

  The layer thickness of the deposited film can be appropriately set within the range of 1 to 200 nm, preferably 1 to 100 nm, more preferably 1 to 50 nm, and still more preferably 1 to 30 nm as the thickness of the entire layer. For example, if it exceeds 200 nm, the flexibility is lowered, and there is a possibility that the deposited film may be cracked by an external force such as bending or pulling after film formation, transparency may be lowered, and the stress of the material itself may be reduced. It becomes undesirably large and colored. On the other hand, when the thickness of the deposited film is less than 1 nm, the transparency is good, but it is difficult to obtain a uniform layer and it is difficult to sufficiently perform the gas barrier function.

Hereinafter, as a preferred embodiment of the present invention, a deposited film of silicon oxide will be described in more detail. The vapor-deposited film (thin film) of silicon oxide is represented by the general formula: SiO _x (wherein x represents a number from 0 to 2), and the value of x is preferably 1.3 to 1.9. The silicon oxide thin film may be mainly composed of silicon oxide, and may further contain at least one kind of compound composed of one kind of carbon, hydrogen, silicon or oxygen, or two or more kinds of elements by chemical bonding or the like. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. As content which said compound contains in the vapor deposition film | membrane of a silicon oxide, it is 0.1-50 mass%, Preferably it is 5-20 mass%. Moreover, when a silicon oxide thin film contains the said compound, it is preferable that content of a compound is reducing toward the depth direction from the surface of the vapor deposition film | membrane of a silicon oxide.

  As a result, the impact resistance and the like are enhanced by the above compound on the surface of the silicon oxide vapor deposition film, and on the other hand, at the interface with the plastic film, the plastic film and the silicon oxide vapor deposition film The tight adhesion is strong.

  When forming a silicon oxide vapor-deposited film containing carbon as described above, the organic silicon compound used as a raw material is 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane (HMDSO) , Vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltri Methoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane and the like can be used.

In the present invention, by further providing a gas barrier coating film as described below on the vapor deposition film, not only a further excellent gas barrier property can be obtained, but also a close adhesion with an adhesive layer described later is enhanced. .
In the present invention, the gas barrier coating film is a film obtained by applying and drying a gas barrier composition obtained by polycondensation of an alkoxide and a water-soluble polymer by a sol-gel method.
The alkoxide used in the gas barrier composition has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and M is a metal An atom is represented, n represents an integer greater than or equal to 0, m represents an integer greater than or equal to 1, n + m represents the valence of M.) At least 1 type or more alkoxide represented by this can be mentioned. .
As the water-soluble polymer, either a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer or both can be preferably used.

In the present invention, as the metal atom M, silicon, zirconium, titanium, aluminum or the like can be used as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m . Moreover, in this invention, the alkoxide of a single or 2 or more types of different metal atoms can be mixed and used in the same solution.
In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples include -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and other alkyl groups.
In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ² include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group and the like.
In the present invention, these alkyl groups may be the same or different in the same molecule.

In the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, an alkoxysilane in which M is Si can be used. As the alkoxysilane, for example, tetramethoxy Examples thereof include silane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si (OC ₄ H ₉ ) _{4 and the} like.
Moreover, in this invention, it is preferable that content of a polyvinyl alcohol-type resin and / or an ethylene vinyl alcohol copolymer is the range of 5-500 weight part with respect to 100 weight part of total amounts of said alkoxide. In the above, when it exceeds 500 weight part, since the brittleness of the gas-barrier coating film formed becomes large and the weather resistance etc. fall, it is unpreferable.

  In the present invention, as the polyvinyl alcohol-based resin, generally obtained by saponifying polyvinyl acetate can be used. Specific examples of the polyvinyl alcohol resin include PVA110 (degree of saponification = 98 to 99%, degree of polymerization = 1100), PVA117 (degree of saponification = 98 to 99%, degree of polymerization = 1700), PVA124 (made by Kuraray Co., Ltd.) Degree of saponification = 98-99%, degree of polymerization = 2400), PVA135H (degree of saponification = 99.7% or more, degree of polymerization = 3500), RS-110 (degree of saponification = 99%) manufactured by the same company , Degree of polymerization = 1000), Kuraray Poval LM-20SO manufactured by the same company (degree of saponification = 40%, degree of polymerization = 2000), GOHSENOL NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, polymerization) Degree = 1400) and Gohsenol NH-18 (degree of saponification = 98-99%, degree of polymerization = 1700) and the like can be used.

In the present invention, as the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer should be used. Can do. Such saponification products include partial saponification products in which several tens mol% of acetic acid groups remain to complete saponification products in which only several mol% of acetic acid groups remain or no acetic acid groups remain. The Although not particularly limited, it is desirable to use a saponification degree of 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Is preferably used.
Specific examples of the ethylene / vinyl alcohol copolymer include Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%). ) Etc. can be used.

  In the present invention, a silane coupling agent or the like can also be added to prepare a gas barrier composition for forming a gas barrier coating film according to the present invention. Suitable silane coupling agents include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2- Amino group-containing silane coupling agents such as aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2 -Epoxy group-containing silanes such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Coupling agent, 3-mercaptopro Examples include mercapto group-containing silane coupling agents such as rumethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, and isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane. .

The gas barrier composition used in the present invention can be prepared by hydrolyzing and polycondensing an alkoxide and a water-soluble polymer by a sol-gel method in the presence of an acid, water and an organic solvent.
The gas barrier coating film is formed by applying the gas barrier composition on the vapor deposition film, and is 10 to 10 seconds at a temperature of 20 to 200 ° C., preferably 140 ° C. or more and below the melting point of the plastic film constituting the base material layer. It can be formed by heat treatment for minutes.
Moreover, as an acid used in preparation of said gas-barrier composition, organic acids, such as mineral acids, such as a sulfuric acid, hydrochloric acid, nitric acid, and an acetic acid, tartaric acid, etc. can be used, for example. Furthermore, as an organic solvent, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, etc. can be used, for example.

Further, regarding the gas barrier composition, the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer is preferably in a state of being dissolved in a coating solution containing the alkoxide, the silane coupling agent, or the like. Therefore, the type of the organic solvent is appropriately selected. In the present invention, as the ethylene / vinyl alcohol copolymer solubilized in a solvent, for example, those commercially available as Soarnol (manufactured by Nippon Synthetic Chemical Co., Ltd.) can be used.
When the gas barrier composition is applied onto the vapor deposition film and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed, and a transparent gas barrier coating film is formed.
Furthermore, since the hydroxyl group generated by hydrolysis and the silanol group derived from the silane coupling agent are bonded to the hydroxyl group on the surface of the deposited film, the tight adhesion between the deposited film and the gas barrier coating film is improved. .

  By being formed as described above, the gas barrier coating film of the present invention includes a linear polymer having crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous portion. . Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the cohesive energy of the molecule is high. Good gas barrier properties.

In the present invention, the vapor deposition film and the gas barrier coating film form, for example, a chemical bond, hydrogen bond, or coordination bond by hydrolysis / co-condensation, and the adhesion between these two layers is improved, synergistically. Due to the effect, a better gas barrier property can be exhibited.
In the present invention, the gas barrier composition may be applied by one or more times by a coating means such as a roll coat such as a gravure roll coater, a spray coat, dipping, a brush, a bar coat, or an applicator. With this coating, it is possible to form a gas barrier coating film having a dry film thickness of 0.01 to 100 μm, preferably 0.1 to 50 μm. If the dry film thickness exceeds 100 μm, cracks may occur, which is not preferable.
In the present invention, in order to obtain a higher gas barrier property, after providing a gas barrier coating film, a vapor deposition film and a gas barrier coating film are alternately laminated in this order one or more times. Preferably, the gas barrier coating film may be formed as an outermost layer to form a transparent gas barrier film.

<4> Adhesive layer In the present invention, the adhesive layer located between the base material layer or barrier layer and the heat-sealable resin layer is an alkene- (meth) acrylate-unsaturated carboxylic acid ternary copolymer. An adhesive resin composition containing a polymer (hereinafter referred to as “adhesive resin composition of the present invention”). The adhesive resin composition of the present invention exhibits high interlayer adhesive strength with these by being laminated on a base material layer or a barrier layer by an extrusion coating method. Here, the base material layer or the barrier layer may be made of any of the above-described materials, for example, a vapor film or a film made of various gas barrier resins.
In particular, by extruding the adhesive resin composition of the present invention onto the surface comprising a vapor-deposited film of inorganic oxide or the above-mentioned surface comprising a gas barrier coating film, extremely high interlayer adhesion strength is exhibited, and Even after contact with contents containing alcohols and various organic substances over a long period of time, high interlayer adhesion strength is maintained.

  The adhesive resin composition of the present invention has a functional group such as a carboxyl group, so that it has chemical groups and chemical groups on the surface of the base material layer or the barrier layer and the surface of the heat-sealable resin layer (adhesive layer lamination surface). It is possible to improve the laminate strength between the layers.

In the present invention, an anchor coat agent layer or the like provided in advance during normal extrusion coating on the base material layer or barrier layer is not necessarily required. Moreover, the adhesive resin composition of this invention does not contain an organic solvent. Therefore, according to this invention, the elution of the residual solvent and low molecular-weight substance originating in an anchor coating agent or an organic solvent can be prevented. Further, there is no problem of a decrease in laminate strength due to deterioration of the adhesive layer over time, and it can be applied to a wide variety of uses. In particular, the adhesive resin composition of the present invention is excellent in content resistance, can maintain a high laminate strength even after storing the content for a long time, and deterioration of the adhesive layer due to erosion of the content. Can be prevented.
The adhesive resin composition of the present invention may be composed of only an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer.

In another embodiment, the adhesive resin composition of the present invention may further comprise a polyolefin resin, a polyamide resin, a polyester resin, an ethylene-vinyl alcohol copolymer, as desired, in addition to the ternary copolymer. And a modifying resin such as polyvinyl chloride and polyvinylidene chloride. However, the amount of the unsaturated carboxylic acid component and the amount of the (meth) acrylic acid ester component in the composition are adjusted so as to be within the prescribed ranges described later.
In addition, the adhesive resin composition of the present invention has, for example, processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, electrical properties, Various plastic compounding agents and additives can be added for the purpose of improving and improving the mechanical properties, strength, etc., and the addition amount is from a very small amount to several tens of percent depending on the purpose. , Can be optionally added. As a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment and the like can be used.

In the production of the terpolymer, the alkene as a comonomer includes ethylene, propylene, butene, isobutene, pentene, hexene and the like, and in particular, α-olefins such as ethylene and propylene are preferably used.
Moreover, (meth) acrylic acid ester used as a comonomer includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, ( Examples include tert-butyl (meth) acrylate, ethyl-2-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and methyl acrylate, ethyl acrylate, and butyl acrylate are preferred, and methyl acrylate is more preferred. It is.
Examples of the unsaturated carboxylic acid serving as a comonomer include acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, and derivatives thereof such as acid anhydrides, esters, amides, imides, and the like. Examples thereof include monomethyl maleate, maleic anhydride, citraconic anhydride, itaconic anhydride and the like. In particular, unsaturated dicarboxylic acid, maleic anhydride and the like can be preferably used. These may be used alone or in a mixture of two or more.

The ternary copolymer is obtained by graft polymerization or ternary copolymerization of the alkene, (meth) acrylic acid ester, and unsaturated carboxylic acid. The ternary copolymer may contain a comonomer other than the above as long as the object of the present invention is not impaired. For example, an ethylene- (meth) acrylic acid ester-maleic anhydride terpolymer resin can be preferably used.
In the present invention, the polymerization reaction can be produced by various conventional methods using a comonomer as a raw material.
For example, a polymer consisting of an alkene is dry blended with an unsaturated carboxylic acid and, if necessary, an organic peroxide and a radical initiator at a predetermined mixing ratio using a Henschel mixer, etc., and the system is purged with nitrogen gas. It is obtained by charging into a kneading machine such as a Banbury mixer, a double screw mixer or the like, and melt-kneading at a temperature of 120 to 300 ° C. for 0.1 to 30 minutes. At the time of the grafting reaction, the reaction can be carried out efficiently by adding a conventional radical generator.

  Although it does not specifically limit as a radical generator, For example, hydroperoxides, such as diisopropyl benzene hydroperoxide and 2, 5- dimethyl- 2, 5- di (hydroperoxy) hexane; Di-t-butyl peroxide Dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane; organic peroxides such as diacyl peroxides such as benzoyl peroxide, or azobisisobutyronitrile An azo compound such as These radical generators may be used alone or as a mixture of two or more. The addition amount of the radical generator is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of the comonomer components.

In the present invention, in order to obtain good handling while suppressing hygroscopicity, a suitable blending ratio of each component is a component (residue) derived from a (meth) acrylate ester with respect to the total mass of the adhesive resin composition. ) Is preferably 5 to 40% by mass, more preferably 10 to 30% by mass.
Further, the unsaturated carboxylic acid-derived component (residue) is contained in an amount of 0.05 to 3.0% by mass, more preferably 0.05% by mass to less than 1.0% by mass, and the rest is derived from an alkene. It is a component (residue), a modifying resin, an additive, and the like.

When the amount of unsaturated carboxylic acid component in the adhesive resin composition containing the terpolymer of the present invention is more than the above range, the acid content of the laminate increases, so that the hygroscopicity is increased, and foaming occurs during extrusion coating. there's a possibility that. Moreover, since the residual monomer of unsaturated carboxylic acid elutes from an adhesion layer, we are anxious about hygiene. Furthermore, it is inferior to bending resistance. Furthermore, since it is highly corrosive to metals, problems are likely to occur in the manufacturing process.

On the other hand, when the amount of the unsaturated carboxylic acid component is too small, chemical interaction with the transparent gas barrier film or the heat-sealable resin is difficult to occur, which may cause a decrease in interlayer adhesive strength.
When the content of the (meth) acrylic acid ester-derived component is more than the above range, the resin itself is liable to be liquefied, resulting in poor handling. Moreover, when content of the component derived from (meth) acrylic acid ester is less than the said range, the adhesion | attachment by reaction of an acrylate becomes difficult to generate | occur | produce and the adhesive strength with the layer which consists of polypropylene, PET, etc. falls.

  It is preferable that MFR of the adhesive resin composition of this invention is 3-100 g / 10min in 190 degreeC, More preferably, it is 5-20 g / 10min. When the MFR is outside the above range, there is a problem that extrusion becomes difficult.

  Moreover, it is preferable that the thickness of the contact bonding layer which consists of adhesive resin compositions is 0.1-200 micrometers, More preferably, it is 1-100 micrometers. When the film thickness is not more than the above range, it is difficult to extrude easily and the adhesive strength is not exhibited. When the film thickness exceeds the range, problems such as adhesive strength are solved, but the packaging material cost increases due to excessive use of the resin.

The adhesion mechanism of the adhesive layer comprising the adhesive resin composition of the present invention includes a mechanism for adhering by the flexibility of the adhesive resin composition, a mechanism for adhering by compatibilization with the resin, the surface of the counterpart substrate and the unsaturated carboxylic acid There are a mechanism for adhering by chemical interaction with the substrate, a mechanism for adhering by chemical interaction of unsaturated carboxylic acid and acrylate to the surface of the counterpart substrate, and a mechanism for adhering by radical generation by extrusion at high temperature.
The adhesive layer made of the adhesive resin composition of the present invention is not necessarily bonded by one bonding mechanism, and is bonded by utilizing at least two or more of the above reactions. For example, for polyethylene and ethylene copolymers, the compatibility mainly due to the alkene moiety contributes to bonding. In addition, the reaction between the polar groups of the unsaturated carboxylic acid and the counterpart substrate contributes to the binding to the vapor deposition film or metal of the gas barrier film. In addition, for a layer made of polypropylene or PET, chemical interaction between the acrylate and the unsaturated carboxylic acid contributes to bonding.
In the present invention, the adhesive layer is a layer obtained by co-extrusion coating in this order on the base material layer or the barrier layer with the layer made of the adhesive resin composition of the present invention and the heat-sealable resin layer. Also good. By laminating the base material layer and the heat-sealable resin layer in this order, that is, through the layer made of the adhesive resin composition of the present invention, high interlayer adhesive strength can be obtained.

<5> Heat-sealable resin layer In the present invention, the heat-sealable resin layer is a layer containing the component (a) cyclic polyolefin-based resin and (b) polyolefin-based resin, and has a single-layer configuration as described above. Or it may be a multi-layered structure composed of two or more layers.
In the present invention, the component (a) cyclic polyolefin-based resin includes a ring-opening metathesis polymer (COP) obtained by polymerizing a cyclic olefin by a metathesis ring-opening polymerization reaction, and a copolymer of a cyclic olefin and an α-olefin (chain olefin). Includes polymers, ie cyclic olefin copolymers (COC).

As the cyclic olefin, any cyclic hydrocarbon having an ethylenically unsaturated bond and a bicyclo ring can be used, particularly those having a bicyclo [2.2.1] hept-2-ene (norbornene) skeleton. preferable.
Specifically, bicyclo [2.2.1] hept-2-ene and derivatives thereof, tricyclo [4.3.0.1 ^2.5 ] -3-decene and derivatives thereof, tricyclo [4.4.0.1 ^2.5] -3-undecene and derivatives thereof, tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3-dodecene and derivatives thereof, pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} - 4 pentadecene and its derivatives, pentacyclo ^{[7.4.0.1 2.5 .1 9.12 .0 8.13]} -3- pentadecene and its derivatives, pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} - 4,10 penta decadiene and its derivatives, pentacyclo ^{[8.4.0.1 2.5 .1 9.12 .0 8.13]} -3- hexadecene and it derivatives, and the like, without limitation. The cyclic olefin may have a polar group such as an ester group, a carboxyl group, and a carboxylic anhydride group as a substituent.

  As the α-olefin copolymerized with the cyclic olefin, ethylene, an α-olefin having 3 to 20 carbon atoms can be used, and specifically, ethylene, propylene, 1-butene, 1-pentene, 3-methyl. Examples include -1-butene, 1-hexene, 4-methyl-1-pentene, and preferably ethylene.

In the present invention, the production of the ring-opening metathesis polymer is not particularly limited as long as it is a known ring-opening metathesis polymerization reaction, and can be produced by ring-opening polymerization of the above cyclic olefin using a polymerization catalyst. .
In the production of the cyclic olefin copolymer, 25 to 45 mol% of α-olefin and 55 to 75 mol% of cyclic olefin are randomly polymerized using a single site catalyst such as a metallocene catalyst or a multisite catalyst. Is made by

Ring-opening metathesis polymer and a cyclic olefin copolymer are preferably used in the present invention, some are commercially available, for example, Nippon Zeon Co., Ltd. of "ZEONOR ^(R)" and manufactured by Polyplastics Co., Ltd., "TOPAS ^{(R )} "And the like.

In the present invention, the component (b) polyolefin resin includes, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene (LLDPE), ethylene / vinyl acetate copolymer, ethylene / acrylic acid. Copolymers, ethylene / acrylic acid ester copolymers, ethylene-methacrylic acid copolymers, ethylene-methacrylic acid ester copolymers, ionomers, polypropylene and the like are used.
It is particularly preferable to use LLDPE in order to have high adhesion to the cyclic polyolefin-based resin composition layer and to further improve the film-forming stability when coextruded with the layer. In addition, when the layer forming the heat seal surface of the heat sealable resin layer (the innermost layer of the packaging container) is made of only LLDPE, excellent low temperature sealability, seal strength, sealability, and interlayer adhesion strength Is particularly preferable.

  In the present invention, LLDPE is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, which can be obtained from a single site catalyst such as a metallocene catalyst or a multisite catalyst. Here, specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, and the like. These monomers are polymerized using a polymerization method such as a low pressure method, a slurry method, a solution method, or a gas phase method. Usually, the short chain distribution has 3 to 25 short chain branches per 1000 carbons, but does not have long chain branches exceeding about 20 carbon atoms. Usually, in LLDPE, the structural unit derived from ethylene is about 99.9 to 90 mol%, and the structural unit derived from α-olefin is about 0.1 to 10 mol%. In the present invention, LLDPE prepared with a metallocene catalyst can be suitably used because of excellent structural uniformity.

Suitable LLDPE for use in the present invention includes “Sumikasen” manufactured by Sumitomo Chemical Co., Ltd.
Furthermore, in the present invention, the main component is the polyolefin resin as described above, and if necessary, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antiblocking agent, a lubricant (fatty acid amide, etc.). ), A flame retardant, an inorganic or organic filler, a crosslinking agent, a colorant such as a dye or a pigment, and one or more additives such as a modifying resin may be added.

  In the laminate of the present invention, even if the heat-sealable resin layer has a single-layer structure composed of a resin composition containing components (a) and (b), components (a) and (b) are dispersed and blended in each layer. It may be a multi-layered structure composed of two or more layers.

In any case, the total thickness of the heat-sealable resin layer is not particularly limited, but is 5 to 500 μm, more preferably 10 to 250 μm. When the heat-sealable resin layer has a multilayer structure, the thickness of each layer can be appropriately determined by those skilled in the art according to the required seal strength and low adsorptivity. For example, in the heat-sealable resin layer, when the layer that forms the heat-seal surface (the layer that becomes the innermost layer) is a layer that is made only of a polyolefin-based resin, this layer thickness is reduced to increase the low adsorptivity. be able to. Conversely, by increasing the layer thickness, the sealing strength and adhesiveness during bag making can be increased.
The surface of the heat-sealable resin layer in contact with the adhesive layer can further enhance the interlayer adhesive strength with the adhesive layer by increasing the wettability by corona treatment, flame treatment, ozone treatment or the like.

<6> Lamination A laminate of the present invention is obtained by laminating the base material layer, the (barrier layer), and the heat-sealable resin layer via the adhesive layer. As a lamination method, the laminate of the present invention can be suitably produced by sandwich-laminating the films constituting each layer via an adhesive layer.
For example, a heat-sealable resin is formed as a heat-sealable resin film by an arbitrary method, for example, by a T-die method or an inflation method, and this is sandwiched by an adhesive layer and a base material layer. Or it can be laminated with a barrier layer.
Or you may laminate | stack the adhesive resin composition of this invention and the resin composition which comprises a heat-sealable resin layer on a base material layer or a barrier layer by a coextrusion coating method.
In a further aspect of the present invention, in the layer structure of the laminate of the present invention, for example, a printing layer such as characters, figures, symbols, and patterns is provided between the base material layer and the barrier layer. Also good.

<7> Packaging container Using the laminate of the present invention, it is possible to produce a packaging container such as a packaging bag by making a bag so that the heat-sealable resin layer becomes the innermost layer.
In order to produce a packaging container, the laminate is folded in two, or two laminates are prepared, the heat-sealable resin layers face to face each other, and the peripheral edge is, for example, Standing pouch type, side seal type, two-side seal type, three-side seal type, four-side seal type, envelope-attached seal type, joint-attached seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, Heat sealing is performed by a heat sealing form such as a gusset type to form various types of packaging containers.
In the above, as a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.

The packaging container composed of the above laminate can be suitably used for packaging chemical products, pharmaceuticals, quasi drugs, cosmetics, foods and the like containing an organic compound as an active ingredient.
In particular, the mouthwash can be used for various active ingredients such as cleaning, bactericidal or anti-inflammatory effects, flavoring agents such as herb mint, peppermint and sodium saccharin, preservatives such as parabens and sodium benzoate, and polyoxyethylene hydrogenated castor oil. Contains a solubilizer, a Ph adjuster such as sodium citrate, sodium phosphate phosphate, and a wetting agent such as glycerin, sorbitol, and propylene glycol, that is, an organic compound that is easily adsorbed by a conventional sealant layer, and the sealant layer. Contains an organic solvent that permeates and erodes the adhesive layer. Therefore, when a conventional packaging container made of a flexible laminate is filled, the concentration of active ingredients, etc. changes, and the laminate is likely to delaminate, so that it cannot be stored stably for a long time. there were.
However, these problems are solved by filling the packaging container comprising the laminate of the present invention. Furthermore, since the packaging container comprising the laminate of the present invention has no problem that a low molecular weight substance elutes from the inside of the laminate into the contents, it can be preferably used for packaging mouthwashes that are oral compositions. it can.
Next, the present invention will be specifically described with reference to examples.

[Example 1]
(1) Cyclic olefin copolymer (COC) (TOPAS ^(R) 8007F-500 manufactured by Polyplastics Co., Ltd.) and low density polyethylene (LLDPE) (SP-1540, Prime Polymer Co., Ltd.) manufactured by multilayer inflation The film was coextruded to produce a sealant film having a structure of LDPE layer (thickness 10 μm) / COC layer (thickness 20 μm).
(2) As a base material layer, a biaxially stretched PET film (T-4102 manufactured by Toyobo Co., Ltd.) having a thickness of 12 m with a corona treatment on one side is set in a primary paper feeding unit of an extrusion tandem laminating machine, and a barrier layer As a result, an aluminum foil having a thickness of 7 μm (1N30 manufactured by Toyo Aluminum Co., Ltd.) was set in the secondary paper feeding unit. Next, from the die 1, an adhesive resin composition comprising an ethylene-methyl acrylate-maleic acid terpolymer (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd., maleic anhydride component amount: 0.3% by mass, (Methyl acrylate component: 19% by mass) was melt extruded at 310 ° C. to a thickness of 7 μm, and the corona-treated surface of the biaxially stretched PET film and aluminum foil were laminated by sandwich lamination while performing ozone treatment. A laminated film was obtained.
(3) On the surface of the aluminum foil of the laminated film obtained in (2) above, an adhesive resin composition made of ethylene-methyl acrylate-maleic terpolymer (Lotader ^(R ) manufactured by Arkema Co., Ltd.) ⁾ 4503) was melt-extruded at 310 ° C. to a thickness of 20 μm, and at the same time, the sealant film obtained in (1) above was drawn out and laminated by sandwich lamination, and PET film / adhesive layer / aluminum foil / adhesion A laminate of the present invention having a layer configuration of layer / LLDPE layer / COC layer was obtained.
The laminated body obtained above was overlapped so that the sealant layers faced each other, and a 10 cm × 10 cm packaging bag was created.

[Example 2]
As a base material layer, a biaxially stretched PET film having a thickness of 12 μm, which is corona-treated on one side, is mounted on a feeding roll of a plasma chemical vapor deposition apparatus, and hexagonal silicon compound, which is an organosilicon compound, is attached to the corona-treated surface. A 200-nm-thick silicon oxide vapor deposition film was provided using methyldisiloxane (HMDSO) as a raw material. Next, plasma treatment was performed on the surface of the deposited film.
On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution prepared by dissolving EVOH (ethylene copolymerization ratio 29%) in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed liquid composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixed solution composed of an aqueous polyvinyl alcohol solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.

Next, the plasma-treated surface on the deposited film surface is coated with the gas barrier composition produced above, and heat-treated at 100 ° C. for 30 seconds to form a gas barrier having a thickness of 0.4 g / m ² (dry operation state). An adhesive coating film was formed.
Next, the transparent gas barrier film formed above is set in an extrusion laminating machine, and the adhesive resin composition comprising an ethylene-methyl acrylate-maleic acid terpolymer is formed on the surface of the gas barrier coating film from a die. A product (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd.) was melt-extruded to a thickness of 20 μm at 310 ° C., and at the same time, the sealant film obtained in (1) of Example 1 above was fed out and sandwiched laminate Thus, a laminate of the present invention having a layer configuration of PET film / silicon oxide vapor deposition film / gas barrier coating film / adhesive layer / LLDPE layer / COC layer was obtained.
The laminate obtained above was overlapped so that the sealant layers faced each other, and a packaging bag of 10 cm × 10 cm was produced in the same manner as in Example 1.

[Example 3]
40% by mass of cyclic olefin copolymer (COC) (TOPAS ^(R) 8007F-500 manufactured by Polyplastics Co., Ltd.) and 60% by mass of low density polyethylene (LDPE) (LC600A manufactured by Nippon Polyethylene Co., Ltd.) The film was extruded to a thickness of 20 μm by inflation film formation to produce a sealant film having a single layer structure.
An adhesive resin composition (manufactured by Arkema Co., Ltd.) composed of an ethylene-methyl acrylate-maleic acid terpolymer is obtained by combining the obtained sealant film and the laminated film obtained in (2) of Example 1 above. The laminate of the present invention having a layer structure of PET film / adhesive layer / aluminum foil / adhesive layer / sealant film was obtained through Lotader ^(R) 4503) in the same manner as in Example 1.
The laminate obtained above was overlapped so that the sealant layers faced each other, and a packaging bag of 10 cm × 10 cm was produced in the same manner as in Example 1.

[Example 4]
Cyclic olefin copolymer (COC) (TOPAS ^(R) 8007F-500 manufactured by Polyplastics Co., Ltd.) and low density polyethylene (LDPE) (LC600A manufactured by Nippon Polyethylene Co., Ltd.) were coextruded by multilayer inflation film formation, A sealant film having a configuration of COC layer (thickness 10 μm) / LDPE layer (thickness 20 μm) was produced.
An adhesive resin composition (manufactured by Arkema Co., Ltd.) composed of an ethylene-methyl acrylate-maleic acid terpolymer is obtained by combining the obtained sealant film and the laminated film obtained in (2) of Example 1 above. Lotader ^(R) 4503) was laminated in the same manner as in Example 1 to obtain a laminate of the present invention having a layer structure of PET film / adhesive layer / aluminum foil / adhesive layer / COC layer / LDPE layer. .
The laminate obtained above was overlapped so that the sealant layers faced each other, and a packaging bag of 10 cm × 10 cm was produced in the same manner as in Example 1.

[Example 5]
Cyclic olefin copolymer (COC) (TOPAS ^(R) 8007F-500 manufactured by Polyplastics Co., Ltd.) and linear low density polyethylene (LLDPE) (SP-1540, Prime Polymer Co., Ltd.) manufactured by multilayer inflation The film was co-extruded to produce a sealant film having a four-layer structure of COC layer (thickness 5 μm) / LLDPE layer (thickness 10 μm) / COC layer (thickness 5 μm) / LLDPE layer (thickness 10 μm).
An adhesive resin composition (manufactured by Arkema Co., Ltd.) composed of an ethylene-methyl acrylate-maleic acid terpolymer is obtained by combining the obtained sealant film and the laminated film obtained in (2) of Example 1 above. via Lotader ^(R) 4503), and laminated in the same manner as in example 1, the present invention having a layer construction of PET film / adhesive layer / aluminum foil / adhesive layer / COC layer / LLDPE layer / COC layer / LLDPE layer A laminate was obtained.
The laminate obtained above was overlapped so that the sealant layers faced each other, and a packaging bag of 10 cm × 10 cm was produced in the same manner as in Example 1.

[Example 6]
Cyclic olefin copolymer (COC) (TOPAS ^(R) 8007F-500 manufactured by Polyplastics Co., Ltd.) and linear low density polyethylene (LLDPE) (SP-1540, Prime Polymer Co., Ltd.) manufactured by multilayer inflation The film was co-extruded to produce a sealant film having a three-layer structure of LLDPE layer (thickness 10 μm) / COC layer (thickness 10 μm) / LLDPE layer (thickness 10 μm).
An adhesive resin composition (manufactured by Arkema Co., Ltd.) composed of an ethylene-methyl acrylate-maleic acid terpolymer is obtained by combining the obtained sealant film and the laminated film obtained in (2) of Example 1 above. Lotader ^(R) 4503) and laminated in the same manner as in Example 1 and has a layer structure of PET film / adhesive layer / aluminum foil / adhesive layer / LLDPE layer / COC layer / LLDPE layer. Got.
The laminate obtained above was overlapped so that the sealant layers faced each other, and a packaging bag of 10 cm × 10 cm was produced in the same manner as in Example 1.

[Example 7]
As an adhesive resin composition, ethylene-methyl acrylate-maleic acid terpolymer (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd.) was used as an ethylene-methyl acrylate (Arkema Co., Ltd. LOTRYL 18MA02, methyl acrylate component). The amount of the unsaturated carboxylic acid component in the adhesive resin composition is 0.08% by mass and the amount of the acrylate component is 19% by mass. Except that was used, a laminate of the present invention was obtained in the same manner as in Example 1, and a packaging bag was prepared therefrom.

[Example 8]
As an adhesive resin composition, ethylene-methyl acrylate-maleic acid terpolymer (Lotader ^(R) 4210 manufactured by Arkema Co., Ltd., unsaturated carboxylic acid 3.6% by mass, acrylic ester component amount 4.5) Mass%) is diluted 4.5 times with ethylene-methyl acrylate (Arkema Co., Ltd. LOTRYL 18MA02), the amount of unsaturated carboxylic acid component in the adhesive resin composition is 0.8% by mass, acrylic ester component Except having used the adhesive resin composition which made the quantity 15 mass%, it carried out similarly to Example 1, and obtained the laminated body of this invention, and created the packaging bag from this.

[Comparative Example 1]
As a laminating method, instead of melting and extruding an adhesive resin composition composed of ethylene-methyl acrylate-maleic acid terpolymer and laminating by sandwich lamination, a two-component curable urethane adhesive (manufactured by Rock Paint Co., Ltd.) Lamination having a layer structure of PET film / adhesive layer / aluminum foil / adhesive layer / LLDPE layer / COC layer in the same manner as in Example 1 except that the laminate was laminated by dry lamination using RU-40 / H-4). Got the body. The application amount of the two-component curable urethane adhesive was 3 to 5 μm (dry film thickness).
The laminate obtained above was overlapped so that the sealant layers faced each other, and a packaging bag of 10 cm × 10 cm was produced in the same manner as in Example 1.

[Comparative Example 2]
An adhesive resin composition comprising an LLDPE film having a thickness of 30 μm (TUX-FCS manufactured by Mitsui Chemicals, Inc.) as a sealant film, and comprising an ethylene-methyl acrylate-maleic acid terpolymer as a lamination method. Instead of melt extrusion and laminating by sandwich lamination, the same as Example 1 except that laminating by dry lamination using a two-component curable urethane adhesive (RU-40 / H-4 manufactured by Rock Paint Co., Ltd.) Thus, a laminate having a layer configuration of PET film / adhesive layer / aluminum foil / adhesive layer / LLDPE layer was obtained. The application amount of the two-component curable urethane adhesive was 3 to 5 μm (dry film thickness).
The laminate obtained above was overlapped so that the sealant layers faced each other, and a packaging bag of 10 cm × 10 cm was produced in the same manner as in Example 1.

[Comparative Example 3]
As a sealant film, an unstretched polypropylene (CPP) film (P-1128 manufactured by Toyobo Co., Ltd.) having a thickness of 30 μm is used, and an adhesive property comprising an ethylene-methyl acrylate-maleic acid terpolymer as a lamination method. Example except that the resin composition was melt extruded and laminated by sandwich lamination instead of laminating by dry lamination using a two-component curable urethane adhesive (RU-40 / H-4 manufactured by Rock Paint Co., Ltd.) 1 to obtain a laminate having a layer structure of PET film / adhesive layer / aluminum foil / adhesive layer / CPP layer. The application amount of the two-component curable urethane adhesive was 3 to 5 μm (dry film thickness).
The laminate obtained above was overlapped so that the sealant layers faced each other, and a packaging bag of 10 cm × 10 cm was produced in the same manner as in Example 1.

[Comparative Example 4]
PET film / adhesive layer / aluminum foil / adhesive layer / LLDPE layer in the same manner as in Example 1 except that an LLDPE film having a thickness of 30 μm (TUX-FCS manufactured by Mitsui Chemical Tosero Co., Ltd.) was used as the sealant film. A layered product having the layer structure was obtained.
The laminate obtained above was overlapped so that the sealant layers faced each other, and a packaging bag of 10 cm × 10 cm was produced in the same manner as in Example 1.

[Evaluation test]
(Interlayer adhesion strength test)
The laminates of Examples 1 to 8 and Comparative Examples 1 to 4 were cut into strips having a width of 15 mm and JISK.
In accordance with No. 6854, using a Tensilon tensile tester, the adhesive part between the base material / barrier layer and the sealant layer was peeled off in a direction of 90 ° at a tensile rate of 50 mm / min in an atmosphere of 25 ° C. ) Was measured.
Next, 100 ml of mouthwash containing 10% by mass of glycerin, 1% by mass of triclosan and 30% by mass of ethanol as an active ingredient was enclosed in a packaging bag made of the laminates of Examples and Comparative Examples, and this was placed in a 25 ° C. atmosphere. Stored under 30 days. A strip-shaped test piece having a width of 15 mm was cut out from each packaging bag after 30 days storage, and the interlayer adhesion strength was measured in the same manner as described above. The results are shown in Table 2.

(Non-adsorption test)
The laminates of Examples 1 to 8 and Comparative Examples 1 to 4 were cut into 10 cm × 10 cm squares, and their initial weights were measured.
Put 10 g of isopropylmethylphenol (IPMP) solid (Wako Pure Chemical Industries, Ltd.) in a stainless steel container with a capacity of 18 liters, fill the container with IPMP vapor with a lid, and suspend the laminated body cut out in it. And stored at 40 ° C. for 7 days.
After storage, the laminate was taken out and weighed, and the amount of IPMP adsorbed was calculated from the difference from the initial weight. The results are shown in Table 3.

1. Base material layer 2. 2. Adhesive layer Heat-sealable resin layer 3x. Layers 3y, 3y ', 3y "forming the adhesive layer lamination surface of the heat sealable resin layer 3. Intermediate layer 3z of the heat sealable resin layer 3. Layer forming the heat seal surface of the heat sealable resin layer 3

Claims (12)

A laminate having a base material layer, an adhesive layer and a sealant layer in this order,
The adhesive layer comprises an adhesive resin composition containing a terpolymer of alkene- (meth) acrylic acid ester-unsaturated carboxylic acid,
The above-mentioned laminate, wherein the sealant layer is a layer containing (a) a cyclic polyolefin resin and (b) a polyolefin resin.   The laminate according to claim 1, wherein the proportion of the component (a) cyclic polyolefin resin in the entire sealant layer is 5 to 70 mass%.   The laminate according to claim 1 or 2, wherein the sealant layer has a single-layer structure composed of a resin composition containing the component (a) a cyclic polyolefin resin and (b) a polyolefin resin.   The laminate according to claim 1 or 2, wherein the sealant layer has a multilayer structure composed of two or more layers in which the component (a) cyclic polyolefin resin and (b) polyolefin resin are dispersed and blended in each layer. body.   The layer forming the outermost surface of the laminate in the sealant layer having the multilayer structure is a layer made of the component (b) polyolefin resin, and does not contain the component (a) cyclic polyolefin resin. 4. The laminate according to 4.   The sealant layer having the multilayer structure, wherein the layer adjacent to the adhesive layer is a layer made of the component (b) polyolefin resin and does not contain the component (a) cyclic polyolefin resin. 5. The laminate according to 5.   The laminated body of any one of Claims 1-6 whose amount of unsaturated carboxylic acid components in the said adhesive resin composition is 0.05 mass% or more and less than 1.0 mass%.   The laminate according to any one of claims 1 to 7, wherein an amount of the (meth) acrylic acid ester component in the adhesive resin composition is 5 to 40% by mass.   A non-adsorptive packaging container formed by stacking the laminate according to any one of claims 1 to 8 so that the sealant layers face each other and heat-sealing the end portion.   The non-adsorbing packaging container according to claim 9, which is a packaging container for mouthwash.   The interlayer adhesion strength between the base material layer or the barrier layer and the sealant layer after being filled with a mouthwash containing 10% by mass of glycerin and stored at 25 ° C. for 30 days is 3 N / 15 mm width or more. The non-adsorbent packaging container according to claim 9 or 10.   It is a manufacturing method of the laminated body of any one of Claims 1-8, Comprising: A ternary copolymer of alkene- (meth) acrylic ester-unsaturated carboxylic acid is used for a base material layer and a sealant layer. The said manufacturing method laminated | stacked by the sandwich lamination method through the adhesive resin composition containing this.

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