JP2000301652A - Transparent laminated film containing antistatic layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film capable of answering respective demands for antistatic properties, gas barrier properties and transparency. SOLUTION: In a transparent laminated film wherein a plurality of layers are laminated on a plastic film substrate 21, an antistatic layer 400 comprising a resin material containing a crosslinkable copolymer having a carboxyl group and a quaternary ammonium base on its side chain is included between those layers. Gas barrier layers 11, 12 having at least steam cutting-off function are arranged on both upper and rear surfaces of the antistatic layer 400 in a sandwich state to protect the antistatic layer 400 from humidity penetrating from the upper and rear surface of the laminated film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent laminate film containing an antistatic layer, and more particularly to a resin having a crosslinkable copolymer polymer having a carboxyl group and a quaternary ammonium group in a side chain. It relates to technology made of materials.

[0002]

BACKGROUND OF THE INVENTION Generally, laminated films are widely used as materials for packaging bags. The properties required for this vary somewhat depending on the application. Here, for example, it is mainly intended to be one in which the contents to be packaged are required to have high drying properties, such as powdered medicine, dried sardines, and cup noodles. These applications require gas barrier properties and transparency in addition to antistatic properties. The antistatic property is a property that prevents accumulation of static electricity in a bag. The laminate film is obtained by laminating and integrating a plurality of plastic films. Since the plastic material of the film has dielectric properties, this antistatic measure is first required. Contents with high drying properties are liable to generate static electricity due to friction with a bag or the like. Therefore, sufficient antistatic measures should be taken from that point as well. Further, the gas barrier property is a property that the bag blocks moisture and the like, and is a property necessary for maintaining the contents under high drying. In addition, transparency is a necessary property to make the contents visible from the outside. From the viewpoint of transparency, a method using an opaque layer such as a general aluminum laminate cannot be used.

[0003] As one of the measures for preventing static electricity of a laminated film, there is known a technique of forming an antistatic layer on a laminated portion by using a resin material containing a crosslinkable copolymer polymer having a carboxyl group and a quaternary ammonium base in a side chain. (See, for example, Japanese Patent No. 2608383 or Japanese Patent Application Laid-Open No. H10-55894). In this technique, the layer made of the specific resin material is used as a primer layer,
On top of that, you can configure a layer of adhesive for lamination,
Alternatively, the layer of the specific resin material itself is used as an adhesive layer for lamination. The antistatic layer made of the specific resin material, which is located between a certain film and another film to be bonded thereto, neutralizes the charges in the films and effectively prevents the charges of both films. This technology is different from the general antistatic technology that puts a surfactant for antistatic in the film material itself,
The surfactant does not bleed to the surface of the film, and the outer surface of the film can be stabilized.

[0004]

Accordingly, an attempt has been made to develop a laminate film which can respond to antistatic properties by using such a specific resin material, and can also respond to gas barrier properties and transparency. After various studies, the specific resin material, while exhibiting an effective antistatic effect, is vulnerable to moisture, and may encounter peeling of the laminated film when it is encountered in a high-humidity environment or when immersed in water. It has been found.

[0005] Accordingly, an object of the present invention is to provide a laminate film which can meet each requirement of antistatic property, gas barrier property and transparency by using the above-mentioned specific resin material. Another object of the present invention is to effectively solve the difficulties of the antistatic layer by using a layer for obtaining gas barrier properties.

[0006]

SUMMARY OF THE INVENTION In the present invention, a gas barrier of a transparent metal oxide layer is used to make the specific resin material vulnerable to moisture while exhibiting an antistatic function by the specific resin material as described above. Supplement by function. Transparent metal oxides include oxides such as aluminum and silicon, which are superior in dechlorination as compared with vinylidene chloride-based materials well known as gas barrier materials. By arranging such a gas barrier metal oxide layer on the outer side of the bag rather than the antistatic layer, it is possible to prevent moisture from entering the inside of the bag from the outside of the bag from reaching the inner antistatic layer. I do. Preferable layer constitutions are roughly classified into two, a gas barrier layer composed of a metal oxide and an antistatic layer composed of a resin material containing a crosslinkable copolymer polymer having a carboxyl group and a quaternary ammonium group in a side chain. be able to. In the first type, by adjoining the first and second two metal oxide layers to each other, the gas barrier property of the metal oxide layer is more ensured, while the inner metal oxide layer is supported. On the plastic film substrate, an antistatic layer is disposed on the side near the heat seal layer to be laminated on the side opposite to the metal oxide layer. The adjoining first and second two metal oxide layers are smaller than the one metal oxide layer due to the empirical fact that cracks and the like do not occur in the same place of the two metal oxide layers. Very good gas barrier properties. In another second type, an antistatic layer is sandwiched between a first metal oxide layer and a second metal oxide layer. According to the second type, the antistatic layer can be protected not only from the outside of the bag but also from the inside.
After opening the packaging bag, the contents may not be completely used up and may be temporarily sealed with a rubber band and stored until the next use. At that time, it is affected by moisture from inside the packaging bag,
An antistatic layer that is sensitive to humidity may be adversely affected.
In the second type, such a fear can be avoided beforehand.

[0007] Since the antistatic layer has a certain degree of adhesive function, it can itself be used as a layer for adhesion. However, preferably, for the adhesive function,
It is preferably obtained by an adhesive layer applied on the antistatic layer. When a two-layer structure of an antistatic layer and an adhesive layer is used, the adhesive layer is applied in a solid pattern over the entire surface. On the other hand, by forming the antistatic layer in a pattern, even if moisture invades, adverse effects may occur. Can be prevented. The pattern shape is a shape or arrangement in which there is a gap between adjacent patterns, such as a stripe or a mesh. The adhesive layer enters the gaps between the patterned antistatic layers, and performs an adhesive function without the interposition of a resin material layer for antistatic. As the adhesive, an adhesive having higher water resistance and higher adhesive strength than a resin material for preventing static charge is used. In that regard, urethane-based ones are preferred. The adhesive layer covers the entire surface to be laminated to each other, whereas the patterned antistatic layer occupies a part of one surface in area because of the pattern. In other words, the area of the adhesive layer is 100% in area, whereas the area ratio of the patterned antistatic layer is, for example, 10 to 60%. If the area ratio of the antistatic layer is high, it is advantageous in terms of antistatic, but the adhesive strength is weakened. However, at least in the above range, there is no practical problem in terms of the antistatic effect and the adhesive strength. Therefore, the area ratio can be appropriately changed according to the application. Generally, the area ratio of the antistatic layer is suitably from 25 to 40%. In addition, when used as a packaging material that is kept in a particularly strong dry state as a content (for example, a drug or other powdery material), in order to obtain a stronger antistatic effect, The area ratio can be set to 50% or more. By patterning the antistatic layer,
In consideration of securing a gap into which the adhesive enters, the area ratio of the antistatic layer is up to 95%. The antistatic effect of the antistatic layer is almost the same as the case where the area ratio is 100% when the area ratio of the layer is 80 to 95%. Therefore, when an antistatic effect equivalent to that of an antistatic layer with an area ratio of 100% is to be obtained, for example, when applied to a material kept in a strong dry state, the area ratio of the antistatic layer is set to 80 to 95. % Value can be set. Thereby, a stable adhesive effect by the adhesive can be reliably obtained. It is preferable that both the thickness of the patterned antistatic layer and the thickness of the adhesive layer be equal or that the thickness of the adhesive layer is greater. Thereby, the gap between the adjacent patterns of the antistatic layer can be sufficiently filled with the adhesive, and an effective adhesive function can be obtained.

Further, the present invention can be considered as a technique for covering the point that the specific resin material constituting the antistatic layer is weak to moisture. In other words, the present invention can be regarded as a technique for protecting the antistatic layer made of a specific resin material from moisture not only from the outside of the bag but also from the inside. From that point of view, the second
Can be interpreted as a gas barrier layer in a broad sense. Thereby, the present invention
This is a technique in which the antistatic layer, which is weak to moisture, is arranged in a sandwich between the first and second gas barrier layers.

As the specific layer structure, the following three structures can be applied in relation to the outside and inside of the bag. First layer structure: Outside bag | Metal oxide deposited film | Antistatic layer | Gas barrier resin layer | (sealant layer) | Inside bag Second layer structure: Outside bag | Gas barrier resin layer | Oxide deposited film | (sealant layer) | in the bag Third layer structure: outside the bag | first gas barrier resin layer | antistatic layer | second gas barrier layer | (sealant layer) | in the bag

The metal oxide serving as the gas barrier layer is an oxide such as aluminum or silicon described above, and can be formed by vapor deposition. The resin layer, which is another gas barrier layer, can be formed in the form of a film or a coating. In the case of a film form, an adhesive is applied to the surface. These gas barrier layers are layers having a function of blocking oxygen and / or water vapor, and in a coating form, by combining different layers, a barrier property against both oxygen and water vapor or a gas barrier function is formed. Can be obtained. From the viewpoint of the object of the invention, it is necessary that the gas barrier layer has at least a barrier function against water vapor (that is, a barrier function).

When a barrier function against both water vapor and oxygen is obtained by coating, polyvinylidene chloride or a composite layer of an inorganic layered compound and a resin composition can be applied. When obtaining an oxygen barrier function, polyvinyl alcohol or an ethylene-vinyl alcohol copolymer can be used. On the other hand, as a film having both barrier functions of water vapor and oxygen, polyvinylidene chloride, stretched polypropylene coated with an ethylene-vinyl alcohol copolymer, stretched polypropylene coated with polyvinyl alcohol, polyvinyl alcohol coated with polyvinylidene chloride, Polypropylene by coextrusion | ethylene-vinyl alcohol copolymer | polypropylene. The films having a water vapor barrier function include stretched polypropylene, non-stretched polypropylene, and high-density polyethylene, and the films having an oxygen barrier function include stretched nylon | ethylene-vinyl alcohol copolymer | stretched nylon and stretched Nylon | Polyimide formed from meta-xylylenediamine and adipic acid | Coextruded film of stretched nylon and the like, blended film of nylon, meta-xylylenediamine and polyimide formed from adipic acid, and ethylene-vinyl alcohol There are simple films of polymers, polyacrylonitrile, polyvinyl alcohol, meta-xylylenediamine-based polyimide, polyethylene naphthalate, and the like.

Such a gas barrier resin layer is less likely to generate cracks than a metal oxide layer, has an excellent barrier function, is advantageous in terms of cost, and is also excellent in the strength of lamination or bonding. I have. Further, when viewed from the inside of the bag, the inside is doubly shielded from the outside by the gas barrier layer, so that a more reliable gas barrier function can be obtained.

In particular, in order to provide a barrier function of both water vapor and oxygen, in the case of the first layer structure, in addition to using a composite layer, an olefin resin having a water vapor barrier property as a sealant (for example, non-stretched resin) It is preferable to select a resin having an oxygen barrier property as the gas barrier resin layer while using polypropylene. In the case of the second layer structure, since the gas barrier resin layer is directly exposed to a high humidity environment, a resin layer having both a water vapor and oxygen barrier function should be selected as the layer. is there. Furthermore, in the case of the third layer structure, since the first gas barrier resin layer is directly exposed to a high humidity environment, the layer functions as a barrier function for both water vapor and oxygen as before. You should choose a resin layer that has For the second gas barrier resin layer, it is sufficient to select a resin having an oxygen barrier property for the same reason as in the case of the first layer structure. However, more preferably, a resin layer having a barrier function against both water vapor and oxygen is preferably used.

[0014]

The first plastic film substrate 21 including the 1 ... first metal oxide layer 11 transparent 1 one surface [embodiment of the invention, a similar, second transparent metal oxide layer 12 Is laminated with an adhesive layer 30 so that the first and second metal oxide layers 11 and 12 face each other. An antistatic layer 40 is provided on the inner surface of the second metal oxide layer 12 on the second plastic film substrate 22 on the opposite side of the first plastic film substrate 21 from the outside of the packaging bag. The heat seal layer 50 is laminated as an anchor layer. According to the first embodiment, the first and second metal oxide layers 11 and 12 adjacent to each other can more reliably block moisture and protect the inner antistatic layer 40 that prevents moisture. The first embodiment includes a first plastic film substrate 21 including a first metal oxide layer 11.
And a second plastic film substrate 22 including the second metal oxide layer 12 are dry-laminated with the adhesive layer 30, and then an antistatic layer 40 is applied on the second plastic film substrate 22, Then, the antistatic layer 4
, And can be obtained by extrusion-coating the heat-sealing layer 50 on the top. Part 2 ... FIG. 2 This is a modification of the first embodiment, and the solid antistatic layer 40 as the anchor layer is replaced with a patterned antistatic layer 42. The heat seal layer 50 to be extrusion-coated on the antistatic layer 42 is the same as in the first embodiment. In the second embodiment, after a gravure printing of a patterned antistatic layer 42 on the back surface of the second plastic film substrate 22 (the surface on the side without the second metal oxide layer 12), the second Of the first plastic film base 21 against another plastic film base 22
Can be obtained by dry laminating and then forming the heat seal layer 50 directly on the antistatic layer 42 or via an anchor layer (not shown). Part 3 ... FIG. 3 This is also a modification of the first embodiment, in which the inner heat seal layer 50 ′ is formed of a heat sealable film, and the pattern-like charging is performed on the heat seal layer 50 ′. The prevention layer 42 is first gravure printed. Then, the heat seal layer 50 ′ including the antistatic layer 42 is dry-laminated with the adhesive layer 33 on the second plastic film substrate 22 side. In this case, the antistatic layer 42 is directly applied to the plastic film base including the metal oxide layer.
Is not formed, it is possible to avoid the possibility that cracks may occur in the metal oxide layer in the processing step when forming the antistatic layer 42. In addition, the antistatic layer 42 itself may be solid in addition to the pattern.

Part 4 ... FIG. 4 This embodiment 4 is based on the first plastic film substrate 2.
The antistatic layer 400 is interposed between the first metal oxide layer 11 and the second metal oxide layer 12 of the second plastic film substrate 22. Antistatic layer 4
00 performs an antistatic function and also has an adhesive function for laminating the first and second plastic film substrates 21 and 22. The heat seal layer 500 is extrusion-coated on the second plastic film substrate 22 side via a general anchor layer 60 having no antistatic function. Part 5 ... FIG. 5 A modification of the fourth embodiment, in which the antistatic layer 400 and the antistatic layer 400 are covered between the first metal oxide layer 11 and the second metal oxide layer 12. The adhesive layer 300 is located. The antistatic layer 400 performs an antistatic function and also functions as an anchor layer for the adhesive layer 300. 6 ... FIG. 6 A modification of the fifth embodiment, in which the antistatic layer is patterned. The patterned antistatic layer 420 can be formed on one of the first and second metal oxide layers 11 and 12 by gravure printing. If the function of blocking moisture from the outside of the packaging bag is considered first, a patterned antistatic layer 420 is formed on the second metal oxide layer 12 as shown in FIG. When forming 420, it is preferable to avoid generation of cracks in the first metal oxide layer 11 located further outside. Here, since the antistatic layer 420 is patterned, a part of the adhesive layer 300 for lamination enters into the gap between the antistatic layers 420, and the first metal oxide layer 11 and the second metal This is a mode in which the oxide layer 12 is directly adhered without the interposition of the antistatic layer 420. 7 ... FIG. 7 A further modification of the sixth embodiment. In order to achieve more effective antistatic, a patterned antistatic layer 420 is formed on both the first and second metal oxide layers 11 and 12. I have.

Further, in addition to the above, the laminated film of the present invention can be used as a part of a laminated structure used for a packaging material. For example, when the light-shielding property is required, the transparent laminate film of the present invention may be used as a part of the laminated structure, and further, a light-shielding milky polyethylene film may be laminated.

Next, each layer or substrate in each embodiment will be described. First and second plastic film substrates 21 and 22 These film substrates 21 and 22 have excellent transparency,
It is in the form of a sheet or film, and has a thickness of 3 to 1
00 μm is preferred. Examples of the material include polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, etc.), polyvinyl chloride, polyimide, etc. Such as copolymers,
Unstretched or stretched films can be used. From the viewpoint of forming the metal oxide layers 11 and 12, biaxially stretched polyethylene terephthalate is most suitable. The first and second plastic film substrates 21 and 22 can be formed of different materials, but usually the same material is used. In that respect, the first and second metal oxide layers 1
The same applies to 1 and 12.

Metal oxide layers 11 and 12 These metal oxide layers are transparent and provide a gas barrier property. A deposited layer of silicon oxide or aluminum oxide is preferred, and the deposited layer is formed to a thickness of 50 to 5000 Å, preferably 400 to 700 Å by a vacuum deposition method, a sputtering method, a plasma vapor deposition method, or the like. .

Antistatic layers 40, 42, 400, 420 These antistatic layers have a thickness of about several μm to 5 μm. Commercially available bond dip PW, bond dip P, bond dip P100
Resin paints containing a crosslinkable copolymer polymer having a carboxyl group and a quaternary ammonium base in the side chain, such as (all trade names manufactured by Altec Co.) can be used. The composition of the paint is as follows. And the monomer has an antistatic function, a function of obtaining a crosslinked product as a resin,
And are for obtaining a crosslinking function, respectively. Monomer having terminal -COOH group: 3 to 13 mol
% Acrylic acid (including meth), acroyloxyether succinic acid, phthalic acid, hexahydrophthalic acid (including meth) and the like. Monomer with quaternary ammonium base: 15 to 40 m
ol% dimethylaminoether acrylate 4 oxide (including anions such as chloride, sulfate, sulfonate, and alkylsulfonate as counter ions). Other monomers: 63.5 to 79.5 mol% Examples thereof include alkyl acrylates, alkyl methacrylates, styrene, vinyl acetate, vinyl halides, and vinyl derivatives such as olefins. Monomer as cross-linking curing agent: 0.5 to 1.5 mol
% Polyglycidyl ethers of aliphatic alcohols having 2 to 4 valences, such as bifunctional monomers such as glycerin diglycidyl ether, diethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; Trifunctional monomers include trimethylolpropane triglycidyl ether, and tetrafunctional monomers include epoxy derivatives such as tetraglycidyl ether such as pentaerythritol and neopentyl. The epoxy derivative is used as a mixture with polyethyleneimine, and has an average molecular weight of 20.
0 to 70000. Polyethyleneimine is linear, but may be partially branched. Catalyst: 1 to 25% (weight ratio) with 10 as a crosslinking curing agent As a ring-opening reaction catalyst for an epoxy derivative of a bifunctional or trifunctional monomer, 2-methylimidazole, 2-ethyl-4-
Imidazole derivatives such as methylimidazole; polyamines and polyethyleneimine derivatives.

An anchor layer 60 (a layer having no antistatic function)
Of) This is a layer for enhancing adhesion between the heat seal layer and the substrate film. An adhesive for dry lamination and an adhesive for extrusion lamination are used depending on the method of forming the heat seal layer. Isocyanate-based (polyurethane-based) is a suitable material because it has good suitability for a base material and excellent moisture resistance, water resistance, oil resistance, and the like. In the case of extrusion lamination, examples of the isocyanate-based anchoring agent include a polyurethane polyisocyanate-based, a polyurethane polyol-based and a curing agent, or a polyurethane isocyanate-based and a curing agent. On the other hand, in the case of dry lamination, a polyether polyurethane polyisocyanate-based, polyester polyurethane polyisocyanate-based, or a combination of an adhesive main agent having a hydroxy group and an isocyanate-based curing agent can be used. Examples of a combination of an adhesive main agent having a hydroxy group and an isocyanate-based curing agent include a combination of a polyester polyol-based and a curing agent and a combination of a polyurethane polyol-based and a curing agent. In addition, the thing for dry lamination can also be used as the adhesive layer 300 of Embodiments 5-7.

Heat seal layer 50, 50'500 This is an extruded laminate layer of a heat seal resin or a layer obtained by dry laminating a heat seal film. As the heat sealing resin, low density polyethylene (LDPE), linear low density polyethylene (LLDP)
E), ethylene vinyl acetate and the like can be used. When formed by extrusion lamination, such a resin layer is formed by melt extrusion via an anchor layer as necessary,
In the case of dry lamination, a film made of these resins is formed using an adhesive for dry lamination. In particular, when formed by extrusion coating, low density polyethylene is preferred, and when formed by dry lamination, a linear low density polyethylene film is preferred.

[0022]

Example 1 Two polyethylene terephthalate films (transparent plastic film base materials) each containing a silica (silicon oxide) vapor deposited layer (metal oxide layer) (MOS-TR of Oike Kogyo Co., Ltd.) were prepared. The silica deposition layers were dry-laminated. For dry lamination, Takelac A-536: hydroxy group-containing adhesive main agent for dry lamination, 100 parts manufactured by Takeda Pharmaceutical Co., Ltd. Taketake A-50: adhesive for dry lamination isocyanate-based curing agent, manufactured by Takeda Pharmaceutical Co., Ltd. An adhesive consisting of 10 parts and 50 parts of ethyl acetate was used. After the dry lamination, a coating layer having the following composition and having an antistatic function was used as an anchor layer (100% area ratio) on a film, and a polyethylene resin was extruded and laminated to form a heat seal layer. Ink (paint) for anchor layer: Bondip P100 (product made by Altec) Base agent 100 parts Bondip P100 (product made by Altec) Hardener 100 parts Isopropyl alcohol 100 parts Water 50 parts

[0023]

Example 2 As in Example 1, when the same two polyethylene terephthalate films were dry-laminated,
Layer with the paint of Example 1 having antistatic function (area ratio 1
00%). On the other hand, when extruding and laminating a polyethylene resin in forming the heat seal layer, Takelac A-
An adhesive containing 536, Takenate A-50, and ethyl acetate (having no antistatic function itself) was used.

[0024]

Example 3 A coating having the same antistatic function as in Example 1 (the main agent of Bondip P100, the curing agent of Bondip P100, and the like) was applied to the silica-deposited surface of a polyethylene terephthalate film having a silica-deposited layer on one side in Example 1.
A coating containing isopropyl alcohol and water) was applied (100% area ratio). Then, the coated film and a polyethylene terephthalate film containing a silica layer were dry-laminated with an adhesive containing Takelac A-536, Takenate A-50, and ethyl acetate in Example 1. A heat seal layer was further formed on the dry-laminated film in the same manner as in Example 2.

[0025]

Embodiment 4 In Example 1, a paint having the same antistatic function as in Example 1 (the base material of Bondip P100, the base material of Bondip P100) was applied to each of two sheets of polyethylene terephthalate film including a silica vapor deposition layer on one surface. A coating containing a curing agent, isopropyl alcohol, and water) was applied (100% area ratio). Using these two coated films, a heat-sealing layer is formed by extruding and laminating a polyethylene resin using the layer made of adhesive containing Takelac A-536, Takenate A-50 and ethyl acetate in Example 1 as an anchor layer. did.

[0026]

Example 5 The anti-static function in Example 1 was applied to the silica-deposited surface of the first polyethylene terephthalate film having a silica-deposited layer on one side and the silica-deposited surface of the second polyethylene terephthalate film having a silica-deposited layer on one side. The antistatic layer surface of the film in which the antistatic layer was formed into a uniform halftone dot pattern having an area ratio of 10% with the paint having the same composition as the adhesive containing Takelac A-536, Takenate A-50, and methyl acetate in Example 1. And laminated. Further, the polyethylene resin was formed on the surface of the second polyethylene terephthalate film on which the antistatic layer was not formed, via an anchor layer formed using the material containing Takelac A-536, Takenate A-50, and ethyl acetate in Example 1. Was extruded and laminated to form a heat seal layer.

[0027]

Example 6 The area ratio of the antistatic layer in Example 5 was 4
A laminate film was prepared in the same manner except that the content was set to 0%.

[0028]

Example 7 The area ratio of the antistatic layer in Example 5 was set to 6
A laminate film was prepared in the same manner except that the content was set to 0%.

[0029]

Example 8 The area ratio of the antistatic layer in Example 5 was set to 8
A laminate film was prepared in the same manner except that the content was set to 0%.

[0030]

Example 9 The area ratio of the antistatic layer in Example 5 was 9
A laminate film was prepared in the same manner except that the content was 5%.

[0031]

Example 10 A laminated film was produced in the same manner as in Example 4, except that the area ratio of the antistatic layer was changed to 10%.

[0032]

Example 11 A laminate film was produced in the same manner as in Example 4 except that the area ratio of the antistatic layer was changed to 40%.

[0033]

Example 12 A laminate film was produced in the same manner as in Example 4 except that the area ratio of the antistatic layer was changed to 60%.

[0034]

Example 13 A laminated film was produced in the same manner as in Example 4, except that the area ratio of the antistatic layer was changed to 80%.

[0035]

Example 14 A laminate film was produced in the same manner as in Example 4 except that the area ratio of the antistatic layer was changed to 95%.

[0036]

Example 15 An antistatic layer was formed on the silica-deposited surface of a polyethylene terephthalate film having a silica-deposited layer on one side by using the antistatic paint used in Example 1. Next, apply a polyvinylidene chloride resin on the antistatic layer,
Drying to form a gas barrier layer, and further, Taketake A-536 used in Example 1 on the gas barrier layer,
A heat seal layer was formed by extruding and laminating a polyethylene resin via an anchor layer formed using a material containing Takenate A-50 and ethyl acetate.

[0037]

Example 16 A laminate film was produced in the same manner as in Example 15 except that the antistatic layer was formed into a uniform halftone dot pattern having an area ratio of 50%.

[0038]

Example 17 In Example 1, the antistatic layer was formed into a uniform halftone dot pattern having an area ratio of 50%, and an antistatic layer containing Takelac A-536, Takenate A-50, and ethyl acetate was placed on the antistatic layer. A laminate film was produced in the same manner except that a heat seal layer was formed.

[0039]

COMPARATIVE EXAMPLE 1 A laminate structure similar to that of Example 1 was used, but instead of a paint having an antistatic function (a paint containing Bondip P100, a curing agent for Bondip P100, isopropyl alcohol and water), a charge was applied. An adhesive containing Takelac A-536, Takenate A-50, and ethyl acetate, which does not have a prevention function, was used.

[0040]

Comparative Example 2 When a laminate structure similar to that of Comparative Example 1 is obtained, a polyethylene resin to which an antistatic agent has been added is used as the polyethylene resin to be extruded and laminated when forming a heat seal layer by extruding and laminating a polyethylene resin. Was.

[0041]

Comparative Example 3 A laminated film was produced in the same manner as in Example 1, except that the first and second polyethylene terephthalate films including the silica-deposited layer were replaced by polyethylene terephthalate films without the silica-deposited layer.

With respect to the films of Examples 1 to 17 and Comparative Examples 1 to 3 described above, the charge amount after 10 reciprocations with human silk and the water vapor barrier property (40 ° C., 90
% RH was measured for 24 hours in an environment of% RH. The results are as follows. Charge amount (kV) Surface impurities Water vapor barrier property (cc) Example 1 -0.2 None 0.39 Example 2 -0.2 None 0.40 Example 3 -0.2 None 0.35 Example 4- 0.2 None 0.34 Example 5-5.4 None 0.33 Example 6-4.5 None 0.37 Example 7-1.5 None 0.36 Example 8-0.2 None 0. 34 Example 9 -0.2 None 0.34 Example 10 -3.6 None 0.35 Example 11 -2.1 None 0.33 Example 12 -0.7 None 0.35 Example 13-0 0.2 None 0.35 Example 14 -0.2 None 0.36 Example 15 -0.2 None 0.37 Example 16 -1.7 None 0.37 Example 17 -3.3 None 0.36 Comparative Example 1-14.8 No 0.37 Comparative Example 2-1.2 Yes 0.48 Comparative Example 3 -1.2 No 25 3 Silica-deposited polyethylene terephthalate film 0.83 From these results, according to Examples 1 to 17 of the present invention, even when the contents are extremely dried, there is a high water vapor barrier property and the antistatic function It can be seen that it can be effectively performed. Focusing on the antistatic function, by setting the area ratio of the antistatic layer to 60 to 95%, a particularly strong dry state such as a medicine or other powdery substance is maintained, and a higher antistatic property is obtained. It can be seen that the present invention can be effectively applied to those requiring effects.

Further, each of the laminated films of Example 1, Example 17 and Comparative Example 3 was sealed in a three-sided shape to form a bag, and after standing for 24 hours in an environment of 80% RH, an antistatic layer was formed. The adhesive strength between the film surface on the side and the heat seal layer was examined by a T-peel test. According to the results, in the bag using the film of Comparative Example 3, peeling occurred on the surface of the antistatic layer, whereas in the bag using the film of Example 1, although the end portion was slightly peeled, the film material was broken. In addition, in the bag using the film of Example 17, the film material was broken without peeling, and it was found that there was sufficient adhesive strength. Next, Examples 1 and 1
7, the antistatic layer was sandwiched between the laminated films of Examples 2 to 14 in which the antistatic layer was sandwiched between the silica-deposited layers, and the silica-deposited layer and the gas barrier layer of polyvinylidene chloride resin. Embodiment 1 of the embodiment
After leaving each of the laminated films 5 and 16 in an environment of a humidity of 80% RH for 24 hours in the state of the film,
The film surface on the side where the antistatic layer is formed, the heat seal layer (Examples 1 and 17), and the two polyethylene terephthalate films provided with the silica vapor deposition layer (Example 2)
To 14), and the respective adhesive strengths between the polyethylene terephthalate film having a silica vapor-deposited layer and the gas barrier layer of the polyvinylidene chloride resin (Examples 15 and 16) were examined by a T-peel test. According to the results, in the case of Example 1, peeling occurred on the surface of the antistatic layer.
In Examples 4 and 17, the film material was broken, and in Examples 15 and 16, the polyvinylidene chloride resin layer was broken. Therefore, as in Examples 2 to 16, the form in which the antistatic layer is sandwiched between gas barrier layers in a sandwich-like manner to suppress the influence of humidity penetrating from both sides of the laminate film is used in a humid environment. It can be said that it is particularly preferable from the viewpoint of maintaining a sufficient adhesive strength of the laminate film underneath.

Further, the antistatic layer having an area ratio of 100% exerts a larger antistatic function. According to the experimental results, the area ratio of the antistatic layer is set to 80% or more. %, It is possible to obtain substantially the same effect as the antistatic function of the antistatic layer. On the other hand, a film of Example 1 and a film having a uniform halftone dot pattern in which the area ratio of the antistatic layer in the film of Example 1 was 95% were prepared, and these were subjected to 40 ° C., 90% RH,
It was stored under the condition of 4 hours, and the adhesive strength between the film surface on which the antistatic layer was formed and the heat seal layer was examined by a T-peel test. Caused peeling, and a material having an area ratio of 95% did not peel, resulting in material destruction. Therefore, by setting the area ratio of the antistatic layer to 80 to 95%, it is possible to obtain an antistatic function equivalent to that of the case where the area ratio of the antistatic layer is 100%, and to obtain a sufficient adhesive strength to moisture. Can be.

[Brief description of the drawings]

FIG. 1 is a sectional view showing Embodiment 1 of the present invention.

FIG. 2 is a sectional view showing Embodiment 2 of the present invention.

FIG. 3 is a sectional view showing a third embodiment of the present invention.

FIG. 4 is a sectional view showing Embodiment 4 of the present invention.

FIG. 5 is a sectional view showing a fifth embodiment of the present invention.

FIG. 6 is a sectional view showing Embodiment 6 of the present invention.

FIG. 7 is a sectional view showing Embodiment 7 of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 1st metal oxide layer 12 2nd metal oxide layer 21 1st plastic film base material 22 2nd plastic film base material 30 Adhesive layer 40,42,400,420 Antistatic layer 50,50 ' , 500 heat seal layer

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 4F100 AA17A AA17B AA20A AA20B AK01C AK04D AK42A AK42B AK51G AL01C BA04 BA07 BA10A BA10D BA32C CB00 CC00C EH23D EH66A EH66B GB15 JB12JJD01 JD01 JD01

Claims (7)

[Claims] 1. An antistatic layer comprising a resin film containing a cross-linkable copolymer having a carboxyl group and a quaternary ammonium group in a side chain between a plurality of layers laminated on a plastic film substrate. A transparent laminate film containing, on both the front side and the back side of the antistatic layer, a gas barrier layer having at least a function of blocking water vapor is arranged in a sandwich form, and the antistatic layer is disposed on the front side of the laminate film and A laminated film characterized by being protected from moisture from the back side, that is, from inside and outside. 2. The laminated film according to claim 1, wherein at least one of said gas barrier layers is formed of a resin layer. 3. A transparent laminated film including an antistatic layer for preventing electrification, which comprises the following A to D: A. B. First plastic film substrate including a transparent first metal oxide layer on one side A transparent second metal oxide layer on one side, the second
B. a second plastic substrate laminated to said first plastic substrate with the side of said metal oxide layer adjacent to said first metal oxide layer; B. a heat-sealing heat-sealable layer, which is a layer portion laminated on one surface of the second plastic substrate on the side opposite to the second metal oxide layer; An antistatic layer located closer to the heat seal layer than both the first and second metal oxide layers when viewed from the first plastic substrate, wherein the side chain has a carboxyl group Antistatic layer made of resin material containing crosslinkable copolymer polymer having quaternary ammonium base 4. The antistatic layer is located between the heat seal layer and the second plastic substrate, and has a pattern such as a stripe or a mesh having a gap between adjacent patterns. 4. The laminate film according to claim 3, wherein there is a portion where the heat seal layer and the second plastic substrate adhere to each other without interposing the antistatic layer. 5. A transparent laminated film including an antistatic layer for preventing electrification, comprising the following A, B, C and E: A. B. First plastic film substrate including a transparent first metal oxide layer on one side A transparent second metal oxide layer on one side, the second
B. a second plastic substrate laminated to said first plastic substrate with the side of said metal oxide layer adjacent to said first metal oxide layer; B. a heat-sealing heat-sealable layer, which is a layer portion laminated on one surface of the second plastic substrate on the side opposite to the second metal oxide layer; An antistatic layer located between the first metal oxide layer and the second metal oxide layer, the crosslinkable copolymer having a carboxyl group and a quaternary ammonium base in a side chain; Antistatic layer made of resin material containing molecules 6. The antistatic layer and an adhesive layer covering the antistatic layer are located between the first metal oxide layer and the second metal oxide layer. 5 laminated film. 7. The adhesive layer extends over the entire surface of the first and second metal oxide layers, while the antistatic layer has an adjacent pattern such as a stripe or a mesh. A pattern having a gap between them, occupying a part of the surface of the first and second metal oxide layers in terms of area, and the adhesive layer enters the gap between the antistatic layers. 6 laminated film.