JP6404165B2 - LAMINATED FILM AND METHOD FOR PRODUCING LAMINATED FILM - Google Patents

Description

  The present invention relates to a laminated film and a method for producing the laminated film.

  The barrier film is widely used, for example, as a food packaging material in order to improve the storage stability of the contents. As such a film, a transparent barrier film in which a transparent thin film of a metal oxide is formed on a plastic film to achieve both transparency and barrier performance is known as a representative film.

  Examples of the technology relating to the transparent barrier film include those described in Patent Document 1 (Japanese Patent Laid-Open No. 63-265626).

Patent Document 1 describes a transparent barrier laminated film in which two or more transparent barrier films each having a metal oxide layer formed on one side of a plastic film are laminated with an adhesive.
Patent Document 1 describes that such a transparent barrier laminate film is excellent in barrier performance and transparency.

JP-A 63-265626

  However, in the conventional transparent barrier laminate film as described in Patent Document 1, moisture contained in the adhesive, carbon dioxide generated by a curing reaction, gas due to an uncured low molecular weight monomer, There was a phenomenon that many bubbles remained trapped in the laminated film and the appearance deteriorated.

  This invention is made | formed in view of the said situation, and it aims at providing the laminated | multilayer film with a favorable external appearance, having the outstanding water vapor | steam barrier performance.

  According to this invention, the manufacturing method of the laminated film and laminated film shown below is provided.

[1]
A first barrier film having a barrier resin layer (A), and a second barrier film having the same or different configuration from the first barrier film,
A laminated film in which the barrier resin layer (A) of the first barrier film and one surface of the second barrier film are directly heat-sealed.
[2]
In the laminated film according to the above [1],
A laminated film in which the barrier resin layer (A) contains a polyvinylidene chloride resin.
[3]
In the laminated film according to the above [2],
The barrier resin layer (A) is formed of a latex containing fine particles of the polyvinylidene chloride resin and the barrier resin formed of a solution in which the polyvinylidene chloride resin is dissolved. Having at least one layer selected from the layer (A2),
A laminated film in which the barrier resin layer (A1) or the barrier resin layer (A2) and one surface of the second barrier film are heat-sealed.
[4]
In the laminated film according to the above [3],
A laminated film in which the first barrier film is formed by laminating a resin film layer, an inorganic layer, the barrier resin layer (A2), and the barrier resin layer (A1) in this order.
[5]
In the laminated film according to the above [3] or [4],
The laminated film in which the second barrier film has a resin film layer and at least one barrier layer selected from an inorganic layer and a barrier resin layer (B).
[6]
In the laminated film according to the above [5],
The barrier resin layer (A1) or the barrier resin layer (A2) of the first barrier film and the inorganic layer or the barrier resin layer (B) of the second barrier film are thermally fused. Wearing laminated film.
[7]
In the laminated film according to the above [5],
A laminated film in which the barrier resin layer (A1) or the barrier resin layer (A2) of the first barrier film and the resin film layer of the second barrier film are heat-sealed.
[8]
In the laminated film according to any one of the above [4] to [7],
A laminated film in which the inorganic layer is composed of one or more inorganic materials selected from the group consisting of silicon oxide, aluminum oxide, and aluminum.
[9]
In the laminated film according to any one of [4] to [8] above,
A laminated film in which the resin film layer contains a thermoplastic resin.
[10]
In the laminated film according to any one of [1] to [9] above,
A laminated film having a water vapor permeability of 0.20 g / m ² · day or less measured at 40 ° C. and 90% RH.
[11]
A production method for producing the laminated film according to any one of the above [1] to [10],
The first barrier film having the barrier resin layer (A), and the second barrier film having the same or different configuration from the first barrier film, the barrier resin layer (A ) And one surface of the second barrier film are laminated so that they are in contact with each other;
Heat-sealing the barrier resin layer (A) of the first barrier film and one surface of the second barrier film;
The manufacturing method of the laminated | multilayer film containing.

  According to the present invention, it is possible to provide a laminated film having an excellent appearance while having excellent water vapor barrier performance.

It is sectional drawing which showed typically an example of the structure of the laminated film of this embodiment. It is sectional drawing which showed typically an example of the structure of the laminated film of this embodiment. It is sectional drawing which showed typically an example of the structure of the laminated film of this embodiment. It is sectional drawing which showed typically an example of the structure of the laminated film of this embodiment.

  Embodiments of the present invention will be described below with reference to the drawings. In addition, the figure is a schematic diagram and does not necessarily match the actual dimensional ratio. In addition, "-" between the numbers in a sentence represents the following from the above, unless there is particular notice.

[Laminated film]
1-4 is sectional drawing which showed typically an example of the structure of the laminated | multilayer film 100 of this embodiment.
The laminated film 100 includes a first barrier film 110 having a barrier resin layer (A), and a second barrier film 120 having the same or different configuration from the first barrier film 110. The barrier resin layer (A) of the first barrier film 110 and the one surface 125 of the second barrier film 120 are directly heat-sealed.

According to the study by the present inventors, it was excellent by directly heat-sealing the barrier resin layer (A) of the first barrier film 110 and the one surface 125 of the second barrier film 120. The present inventors have found that a laminated film 100 having a water vapor barrier performance and a good appearance can be obtained, and have reached the present invention.
Here, since the first barrier film 110 and the second barrier film 120 are directly heat-sealed, for example, moisture contained in an adhesive such as a urethane-based adhesive or carbon dioxide resulting from a curing reaction, Generation | occurrence | production of an uncured low molecular weight monomer etc. can be suppressed. As a result, the generation of fine bubbles on the fusion surface between the first barrier film 110 and the second barrier film 120 can be suppressed, so that the overall appearance of the laminated film 100 can be improved.
In addition, since the first barrier film 110 and the second barrier film 120 are heat-sealed, it is possible to suppress the entry of water vapor at the interface between the first barrier film 110 and the second barrier film 120. In addition to being able to do so, the water vapor barrier performance of the laminated film 100 can be improved.
That is, according to the present embodiment, the barrier resin layer (A) and the one surface 125 of the second barrier film 120 are directly heat-sealed, so that the appearance is good while having excellent water vapor barrier performance. Can be realized.

The laminated film 100 is excellent in water vapor barrier performance and can be suitably used as a packaging film or a sealing film. Specifically, in the laminated film 100, the water vapor permeability measured under the conditions of a temperature of 40 ° C. and a humidity of 90% RH is preferably 0.20 g / m ² · day or less, more preferably 0.15 g / m. ² · day or less, more preferably 0.10 g / m ² · day or less, and particularly preferably 0.08 g / m ² · day or less.
Such water vapor permeability can be achieved, for example, by adjusting the thickness and type of the barrier resin layer (A), the barrier resin layer (B), the inorganic layer 103 described later, the manufacturing conditions of the laminated film 100, and the like. .

  Hereinafter, each member which comprises the laminated | multilayer film 100 is demonstrated.

<First barrier film>
The first barrier film 110 has a barrier resin layer (A) from the viewpoint of improving water vapor barrier performance. Moreover, it is preferable that the 1st barrier film 110 further has the resin film layer 101, the inorganic substance layer 103, etc. from a viewpoint which further improves the handleability of the laminated | multilayer film 100, oxygen barrier performance, and water vapor | steam barrier performance. In this case, as shown in FIG. 2, for example, the first barrier film 110 includes a resin film layer 101, an inorganic layer 103, and a barrier resin layer (A) laminated in this order.

(Barrier resin layer (A))
The barrier resin layer (A) contains a barrier resin. Examples of the barrier resin include polyvinyl alcohol resin, polyvinylidene chloride resin, polyacrylonitrile resin, polycarboxylic acid polyvalent metal salt resin, polycarboxylic acid resin, polyvinyl alcohol resin and polycarboxylic acid polyvalent resin. One or more selected from a resin comprising a metal salt resin, an organosilicon coating resin obtained by using a sol-gel method in which TEOS (tetraethoxysilane) or TMOS (tetramethoxysilane) is hydrolyzed and crosslinked Of resin.
Among these, it is preferable to include a polyvinylidene chloride resin from the viewpoint of production efficiency, water vapor barrier performance, transparency, and the like.
Moreover, it is preferable that the barrier resin layer (A) has a barrier resin layer (A1) formed of latex containing fine particles of polyvinylidene chloride resin from the viewpoint of excellent heat-fusibility. In this case, from the viewpoint of improving the adhesion between the first barrier film 110 and the second barrier film 120 and the water vapor barrier property, the barrier resin layer (A1) and one surface of the second barrier film 120 125 is preferably heat-sealed.
The barrier resin layer (A) may be composed of a single layer of a kind of barrier resin, or may be composed of a plurality of layers of two or more kinds of barrier resins.

  As a method for forming the barrier resin layer (A), for example, a method of forming the barrier resin layer (A) by laminating a resin film composed of the barrier resin on a laminate object, Examples include a method of forming a barrier resin layer (A) by coating a resin liquid obtained by dissolving or dispersing in a solvent on an object to be laminated and curing it. Among these, from the viewpoint of workability, a method of forming the barrier resin layer (A) by coating on a laminated object and curing it is preferable.

  The barrier resin layer (A) of the present embodiment is preferably composed of a polyvinylidene chloride resin. Hereinafter, the barrier resin layer (A) composed of the polyvinylidene chloride resin is also referred to as a polyvinylidene chloride resin layer.

  The polyvinylidene chloride-based resin of the present embodiment is not particularly limited as long as it mainly contains a vinylidene chloride monomer as a structural unit, and may be polyvinylidene chloride (PVDC), vinylidene chloride, and chloride. It may be a copolymer of a monomer copolymerizable with vinylidene.

The copolymer is a copolymer having a vinylidene chloride content of 60% to 99% by mass and a monomer copolymerizable with vinylidene chloride of 1% to 40% by mass. A coalescence can be illustrated.
Examples of monomers copolymerizable with vinylidene chloride include, for example, vinyl chloride, acrylonitrile, acrylic acid, acrylic acid alkyl ester (alkyl group having 1 to 18 carbon atoms), methacrylic acid, methacrylic acid alkyl ester (alkyl group carbon). And 1 type or 2 types selected from maleic anhydride, itaconic acid, itaconic acid alkyl ester, vinyl acetate, ethylene, propylene, isobutylene, butadiene and the like.

  The polyvinylidene chloride resin of the present embodiment can be produced by a conventionally known method, but various commercially available products can also be used. As commercially available products, the Saran Resin series manufactured by Asahi Kasei Co., Ltd., the Saran latex series manufactured by Asahi Kasei Co., Ltd. and the like can be preferably used.

The polyvinylidene chloride-based resin layer of the present embodiment is not particularly limited. For example, a resin film composed of a polyvinylidene chloride-based resin, a barrier resin layer formed of latex containing fine particles of a polyvinylidene chloride-based resin ( A1), a barrier resin layer (A2) formed of a polyvinylidene chloride resin solution obtained by dissolving a polyvinylidene chloride resin in an organic solvent, and the like. The barrier resin layer (A1) and the barrier resin layer (A2) may each be provided alone as the barrier resin layer (A), or the barrier resin layer (A1) and the barrier resin layer (A2). Both may be provided as the barrier resin layer (A). Moreover, the barrier resin layer (A1) and the barrier resin layer (A2) constituting the barrier resin layer (A) may be a single layer or may be composed of two or more layers.
In this case, from the viewpoint of improving the adhesion between the first barrier film 110 and the second barrier film 120 and the water vapor barrier property, the barrier resin layer (A1) or the barrier resin layer (A2), and the second It is preferable that the one surface 125 of the barrier film 120 is heat-sealed.
The barrier resin layer (A) of the present embodiment has a barrier resin layer (A2) from the viewpoint of further improving the antistatic performance while reducing the amount of residual organic solvent while maintaining excellent barrier performance. ) Is preferably provided with a barrier resin layer (A1). Further, when an inorganic layer 103, particularly a layer made of aluminum oxide, is provided in order to further improve the barrier performance, the viewpoint of stabilizing the barrier performance and maintaining the peel strength between the inorganic layer 103 and the barrier resin layer It is preferable to provide a barrier resin layer (A2) on the surface of the inorganic layer 103.

The organic solvent for dissolving the polyvinylidene chloride-based resin is not particularly limited because it is appropriately selected depending on the type of the polyvinylidene chloride-based resin to be used. For example, ketones such as acetone, methyl ethyl ketone, cyclohexanone; dioxane, diethyl Examples include ethers such as ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate; amides such as dimethylformamide; mixed solvents thereof.
Among these, a mixed solvent of tetrahydrofuran and toluene, a mixed solvent of methyl ethyl ketone and toluene, and a mixed solvent of tetrahydrofuran, toluene and methyl ethyl ketone are preferable.

  As a method for forming a polyvinylidene chloride resin layer, for example, a method of laminating a polyvinylidene chloride resin film formed of a polyvinylidene chloride resin on a laminate object, a polyvinylidene chloride resin solution on a laminate object Examples thereof include a method of forming by applying and drying, and a method of forming by drying a latex containing fine particles of polyvinylidene chloride resin on a layered object and drying.

Further, in the first barrier film 110, the coating amount of the barrier resin layer (A) is from the viewpoint of a balance of barrier properties, transparency, residual organic solvent amount, antistatic performance, adhesion, handling properties, etc. Usually 0.05 g / ^{m 2} or more, 20.0 g / ^{m 2} or less, preferably 0.07 g / ^{m 2} or more, 15.0 g / ^{m 2} or less, more preferably 0.10 g / ^{m 2} or more, 8.0 g / m ² or less, particularly preferably 0.15 g / m ² or more and 5.0 g / m ² or less, most preferably 0.18 g / m ² or more and 3.0 g / m ² or less.

The barrier resin layer (A) may further contain an adhesive from the viewpoint of improving adhesiveness with the resin film layer 101 and the inorganic layer 103. In particular, when a layer formed of silicon oxide is used as the inorganic layer 103, the adhesive property between the barrier resin layer (A) and the inorganic layer 103 is inferior, so that the barrier resin layer (A) further contains an adhesive. Is preferred.
As the adhesive, one or more selected from the group consisting of silane coupling agents; adhesive resins such as urethane resins, urea resins, melamine resins, epoxy resins, alkyd resins, etc. are used. It is preferable.

  Although it does not specifically limit as said silane coupling agent, For example, halogen-containing silanes, such as 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane Coupling agent: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 2 -Epoxy group-containing silane coupling agents such as glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and 3-glycidyloxypropyltriethoxysilane; 2 Aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- [N- (2-aminoethyl) amino] ethyltrimethoxysilane, 3- [N- (2-aminoethyl) 2) amino group-containing silane coupling agents such as amino] propyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- [N- (2-aminoethyl) amino] propylmethyldimethoxysilane; -Mercapto group-containing silane coupling agents such as mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane; Vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane ; 2-metak Royloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxy Examples include (meth) acryloyl group-containing silane coupling agents such as silane.

When the adhesive is a silane coupling agent, the blending amount of the adhesive used for the barrier resin layer (A) is preferably when the total of the polyvinylidene chloride resin and the silane coupling agent is 100% by mass. Is 0.5 mass% or more and 10 mass% or less, More preferably, it is 1.0 mass% or more and 5.0 mass% or less.
The amount of the adhesive used for the barrier resin layer (A) is preferably 3 when the total of the polyvinylidene chloride resin and the adhesive resin is 100% by mass when the adhesive is an adhesive resin. It is not less than 40% by mass, more preferably not less than 3% by mass and not more than 20% by mass, particularly preferably not less than 5% by mass and not more than 10% by mass.
It is preferable that the blending amount of the adhesive is in the above range because the performance balance between adhesiveness and barrier property is particularly excellent.

(Resin film layer)
The resin film layer 101 of the present embodiment usually contains a thermoplastic resin, and is preferably composed of a sheet-like or film-like substrate formed of a thermoplastic resin. A known thermoplastic resin can be used as the thermoplastic resin. For example, polyolefins such as polyethylene, polypropylene, poly (4-methyl-1-pentene), poly (1-butene); polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; nylon-6, nylon-66, poly Polyamide such as meta-xylene adipamide, polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer, polyacrylonitrile, polycarbonate, polystyrene, ionomer, and the like can be used.
Among these, polypropylene, polyethylene terephthalate, and polyamide are preferable from the viewpoint of good stretchability and transparency.

Further, the film-like substrate formed of the thermoplastic resin may be an unstretched film or a stretched film.
Moreover, in order to improve the adhesiveness with the barrier resin layer (A) or the inorganic material layer 103 to be described later on one side or both sides of the resin film layer 101, for example, corona treatment, flame treatment, plasma treatment, undercoat treatment. In addition, surface activation treatment such as primer coating treatment or frame treatment may be performed.
The thickness of the resin film layer 101 is usually 1 μm or more and 200 μm or less, preferably 5 μm or more and 150 μm or less.

(Inorganic layer)
In the laminated film 100 of the present embodiment, the first barrier film 110 preferably further includes an inorganic layer 103 from the viewpoint of further improving the balance between transparency and barrier performance.

As for the inorganic substance which comprises the inorganic substance layer 103 of this embodiment, the metal which can form the thin film which has barrier property, a metal oxide, etc. are mentioned, for example.
Examples of inorganic substances constituting the inorganic layer 103 include periodic table 2A elements such as beryllium, magnesium, calcium, strontium, and barium; periodic table transition elements such as titanium, zirconium, ruthenium, hafnium, and tantalum; and a periodic table such as zinc. 2B group element; periodic table 3B element such as aluminum, gallium, indium, thallium; periodic table 4B element such as silicon, germanium, tin; simple substance or oxide of periodic table 6B element such as selenium, tellurium, etc. One type or two or more types may be mentioned.

Furthermore, among the inorganic materials, one or two or more inorganic materials selected from the group consisting of silicon oxide, aluminum oxide, and aluminum are preferable because of excellent balance between barrier properties and cost.
In addition to silicon dioxide, silicon oxide may contain silicon monoxide and silicon suboxide.

  The inorganic layer 103 is made of the above inorganic material. The inorganic layer 103 may be composed of a single inorganic layer or may be composed of a plurality of inorganic layers. Further, when the inorganic layer 103 is composed of a plurality of inorganic layers, it may be composed of the same kind of inorganic layer or may be composed of different kinds of inorganic layers.

The thickness of the inorganic layer 103 is usually from 1 nm to 500 nm, preferably from 2 nm to 300 nm, more preferably from 5 nm to 150 nm, from the viewpoint of the balance of barrier properties, adhesion, handling, and the like.
In the present embodiment, the thickness of the inorganic layer 103 can be obtained from an observation image obtained by a transmission electron microscope or a scanning electron microscope.

  The formation method of the inorganic layer 103 is not particularly limited. For example, the inorganic layer 103 may be formed on one or both surfaces of the resin film layer 101 by a vacuum process such as a vacuum deposition method, a sputtering method, a plasma vapor deposition method (CVD method), a sol-gel process, or the like. Layer 103 can be formed.

<Second barrier film>
The second barrier film 120 preferably has at least one barrier layer selected from the inorganic layer 103 and the barrier resin layer (B) from the viewpoint of improving the water vapor barrier performance.
The second barrier film 120 preferably has an inorganic layer 103 in order to further improve the handleability, oxygen barrier performance, and water vapor barrier performance of the laminated film 100. Moreover, it is preferable to further have the resin film layer 101 from a viewpoint of the ease of forming the barrier resin layer (B). In this case, as for the 2nd barrier film 120, the resin film layer 101, the inorganic substance layer 103, and the barrier resin layer (B) are laminated | stacked in this order, for example. For example, it is preferable that the barrier resin layer (A) of the first barrier film 110 and the inorganic layer 103 or the barrier resin layer (B) of the second barrier film 120 are heat-sealed. From the viewpoint of further improving the adhesiveness between the first barrier film 110 and the second barrier film 120 and the water vapor barrier property, as shown in FIG. More preferably, the barrier resin layer (A) and the barrier resin layer (B) of the second barrier film 120 are heat-sealed. Alternatively, from the viewpoint of further improving the adhesiveness between the first barrier film 110 and the second barrier film 120 and the water vapor barrier property with excellent heat-fusibility, for example, as shown in FIG. It is preferable that the barrier resin layer (A) of the conductive film 110 and the resin film layer 101 of the second barrier film 120 are heat-sealed.

(Barrier resin layer (B))
The barrier resin layer (B) contains a barrier resin. Examples of the barrier resin include the same ones as mentioned in the above-described barrier resin layer (A).
Among these, it is preferable to include a polyvinylidene chloride resin from the viewpoint of production efficiency, water vapor barrier performance, transparency, and the like.
Moreover, it is preferable that the barrier resin layer (B) has a barrier resin layer (B1) formed of latex containing fine particles of polyvinylidene chloride resin from the viewpoint of excellent heat-fusibility. In this case, from the viewpoint of improving the adhesion between the first barrier film 110 and the second barrier film 120 and the water vapor barrier property, the barrier resin layer (A) of the first barrier film 110 and the barrier resin The layer (B1) is preferably heat-sealed.
The barrier resin layer (B) may be composed of a single layer of a kind of barrier resin, or may be composed of a plurality of layers of two or more kinds of barrier resins.

  Examples of the method for forming the barrier resin layer (B) include the same method as the method for forming the barrier resin layer (A) described above.

  The barrier resin layer (B) of this embodiment is preferably composed of a polyvinylidene chloride resin. Hereinafter, examples of the barrier resin layer (B) made of the polyvinylidene chloride resin include the same structure as the barrier resin layer (A) made of the vinylidene resin.

  Moreover, in the 2nd barrier film 120, the range similar to the barrier resin layer (A) mentioned above can be employ | adopted for the coating amount and thickness of a barrier resin layer (B).

  The barrier resin layer (B) may further contain an adhesive from the viewpoint of improving adhesion with the resin film layer 101 and the inorganic layer 103. As an adhesive agent, the thing similar to what was mentioned by the barrier resin layer (A) mentioned above can be mentioned.

(Resin film layer)
Examples of the resin film layer 101 of the second barrier film 120 include the same ones as those described for the first barrier film 110 described above.

(Inorganic layer)
In the laminated film 100 of the present embodiment, the second barrier film 120 preferably further includes an inorganic layer 103 from the viewpoint of further improving the balance between transparency and barrier performance.

  The inorganic substance which comprises the inorganic substance layer 103 of the 2nd barrier film 120 can mention the thing similar to what was mentioned by the inorganic substance layer 103 of the 1st barrier film 110 mentioned above.

  Examples of the layer configuration, thickness, and formation method of the inorganic layer 103 include the same layer configuration, thickness, and formation method as those of the inorganic layer 103 of the first barrier film 110 described above.

<Heat-fusion layer>
The laminated film 100 of the present embodiment may be provided with a heat fusion layer on at least one side in order to impart heat sealability.
As the heat sealing layer, those known as heat sealing layers can be used. For example, homopolymers or copolymers of α-olefins such as ethylene, propylene, butene-1, hexene-1, 4-methyl-pentene-1, octene-1, high pressure method low density polyethylene, linear low density polyethylene (So-called LLDPE), high density polyethylene, polypropylene, polypropylene random copolymer, low crystalline or amorphous ethylene / propylene random copolymer, ethylene / butene-1 random copolymer, propylene / butene-1 random copolymer A layer formed of a resin composition containing one or two or more polyolefins selected from polymers, a layer formed of a resin composition containing an ethylene / vinyl acetate copolymer (EVA), EVA and polyolefin Examples thereof include a layer formed of the resin composition that is included.

<Other layers>
The laminated film 100 of this embodiment may further be provided with various coating layers and laminate layers such as a slipping layer and an antistatic layer.

<Application>
The laminated film 100 of the present embodiment includes, for example, a packaging film for packaging foods, pharmaceuticals, daily miscellaneous goods, and the like that require water vapor barrier performance and transparency; a film for vacuum insulation; an electroluminescence element, and a solar cell. The film for sealing for sealing etc .; etc. can be used conveniently.

[Production method of laminated film]
The manufacturing method of the laminated film 100 according to the present embodiment includes a first barrier film 110 having a barrier resin layer (A), a second barrier film 120 having the same or different configuration from the first barrier film 110, and Are laminated so that the barrier resin layer (A) of the first barrier film 110 and one surface 125 of the second barrier film 120 are in contact with each other, and the barrier resin layer of the first barrier film 110 ( A) and the step of heat-sealing one surface 125 of the second barrier film 120.

  The first barrier film 110 and the second barrier film 120 are preferably laminated by heating and pressing. Thereby, the barrier resin layer (A) and the one surface 125 of the second barrier film 120 can be heat-sealed. By carrying out like this, the balance with the water vapor | steam barrier performance and transparency of the laminated | multilayer film 100 obtained can be improved more effectively.

As a method of laminating the first barrier film 110 and the second barrier film 120, it is preferable to use a laminator that heats and pressurizes the films while keeping the films in close contact with each other so as not to entrain air.
The heating temperature is not particularly limited and can be appropriately selected depending on the fusion temperature of the barrier resin to be thermally fused and the heat resistance temperature of the base film, but when the barrier resin is a polyvinylidene chloride resin, it is 100. The temperature is preferably from 150 ° C. to 150 ° C., more preferably from 110 ° C. to 140 ° C.

  Said laminator process can be performed using the commercially available vacuum laminator. For example, a home office laminator SP230 manufactured by Inajin Co., Ltd. or an equivalent thereof can be used.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.

  Hereinafter, the present embodiment will be described in detail with reference to Examples, Comparative Examples, and Reference Examples. In addition, this embodiment is not limited to description of these Examples, Comparative Examples, and Reference Examples.

  Each evaluation in an Example, a comparative example, and a reference example is as follows.

(Water vapor permeability)
The water vapor permeability in Examples, Comparative Examples and Reference Examples was measured by the following measuring method.
For the laminated films obtained in Examples, Comparative Examples, and Reference Examples, an LLDPE film having a thickness of 50 μm (manufactured by Mitsui Chemicals, Inc., TUX (registered trademark) FCS) and an adhesive (manufactured by Mitsui Chemicals) , Takerak (registered trademark) A-310 / Takenate (registered trademark) A-3 = 12/1 (weight ratio)) is applied at 3.0 g / m ² , and the surface of the laminated film is an LLDPE film adhesive coated surface. They were laminated so as to be in contact.
Next, using the obtained laminated film, a bag was made so that the inner surface area was 0.01 m ² , 10 g of calcium chloride was put as the contents in the obtained bag, and the entrance of the bag was heat-sealed.
Next, the obtained bag was stored for 72 hours in an environment of a temperature of 40 ° C. and a humidity of 90% RH.
The weight of calcium chloride before and after storage was measured, and the water vapor permeability was calculated from the difference.

(appearance)
The appearance of the laminated films obtained in Examples, Comparative Examples and Reference Examples was evaluated according to the following criteria.
◯: Fine bubbles were not generated on the adhesive surface, and the overall appearance of the laminated film was good. Or, a small amount of fine bubbles were generated on the adhesive surface, but the overall appearance of the laminated film was good. X: Many fine bubbles were generated on the adhesive surface, and the overall appearance of the laminated film was clearly poor

Example 1
A 12 μm biaxially stretched polyethylene terephthalate film (manufactured by Unitika Ltd., Emblet (registered trademark) PET12) was used as the base film. Oxygen was introduced into the corona-treated surface of this base film while heating and evaporating aluminum using a high frequency induction heating method. Thereby, an aluminum oxide layer having a thickness of 10 nm was formed on the base film.
A first barrier film was obtained by sequentially forming a polyvinylidene chloride-based resin layer 1 and a polyvinylidene chloride-based resin layer 2 on the aluminum oxide layer of the obtained aluminum oxide vapor-deposited film.
Here, the formation method of the polyvinylidene chloride resin layer 1 and the polyvinylidene chloride resin layer 2 is as follows. First, a polyvinylidene chloride resin (Saran Resin F216, manufactured by Asahi Kasei Co., Ltd.) is dissolved in a mixed organic solvent of toluene and methyl ethyl ketone (weight ratio: toluene / methyl ethyl ketone = 1/2) to obtain a polyvinylidene chloride resin solution (solid content 5 mass). %) Was prepared.
Next, this polyvinylidene chloride resin solution is coated on the aluminum oxide layer with an applicator so that the coating amount after drying is 0.2 g / m ² , and is dried to remove the solvent. A vinylidene resin layer 1 was formed.
Subsequently, a latex containing fine particles of polyvinylidene chloride resin (Asahi Kasei Co., Ltd., Saran Latex L536B) was neutralized with 10 w / v% ammonia water, and the coating amount after drying was 2.5 g / m. ² was coated on the polyvinylidene chloride resin layer 1 with an applicator and dried to remove the solvent, thereby forming the polyvinylidene chloride resin layer 2 to obtain a first barrier film.
Subsequently, the 2nd barrier film was produced by the method similar to this 1st barrier film.
Next, the first barrier film and the second barrier film are laminated so that the polyvinylidene chloride-based resin layers 2 are in contact with each other, and a setting temperature of 130 ° C. is used using a laminator (Home Office Laminator SP230, manufactured by Inajin Co., Ltd.). The laminated film 1 was obtained by heat-sealing. The evaluation results of the obtained laminated film 1 are shown in Table 1.

(Example 2)
A laminated film 2 was obtained in the same manner as in Example 1 except that the coating amount after drying of the polyvinylidene chloride resin layer 2 was changed to 0.8 g / m ² . The evaluation results of the obtained laminated film 2 are shown in Table 1.

(Example 3)
A laminated film 3 was obtained in the same manner as in Example 1 except that the coating amount after drying of the polyvinylidene chloride resin layer 2 was 0.4 g / m ² . The evaluation results of the obtained laminated film 3 are shown in Table 1.

Example 4
A 12 μm biaxially stretched polyethylene terephthalate film (manufactured by Unitika Ltd., Emblet (registered trademark) PET12) was used as the base film. Oxygen was introduced into the corona-treated surface of this base film while heating and evaporating aluminum using a high frequency induction heating method. Thereby, an aluminum oxide layer having a thickness of 10 nm was formed on the base film.
A first barrier film was obtained by forming a polyvinylidene chloride resin layer 1 on the aluminum oxide layer of the obtained aluminum oxide vapor-deposited film.
Here, the formation method of the polyvinylidene chloride resin layer 1 is as follows. First, a polyvinylidene chloride resin (Saran Resin F216, manufactured by Asahi Kasei Co., Ltd.) is dissolved in a mixed organic solvent of toluene and methyl ethyl ketone (weight ratio: toluene / methyl ethyl ketone = 1/2) to obtain a polyvinylidene chloride resin solution (solid content 5 mass). %) Was prepared.
Next, this polyvinylidene chloride resin solution is coated on the aluminum oxide layer with an applicator so that the coating amount after drying is 0.2 g / m ² , and is dried to remove the solvent. A vinylidene resin layer 1 was formed to obtain a first barrier film.
Next, the first barrier film and the second barrier film prepared in Example 2 are laminated so that the polyvinylidene chloride resin layers are in contact with each other, and a laminator (Inashishin, home office laminator SP230) is used. The laminated film 4 was obtained by heat-sealing under the condition of a set temperature of 130 ° C. The evaluation results of the obtained laminated film 4 are shown in Table 1.

(Example 5)
A 12 μm biaxially stretched polyethylene terephthalate film (manufactured by Unitika Ltd., Emblet (registered trademark) PET12) was used as the base film. Oxygen was introduced into the corona-treated surface of this base film while heating and evaporating aluminum using a high frequency induction heating method. Thereby, an aluminum oxide layer having a thickness of 10 nm was formed on the base film.
Implementation with the aluminum oxide vapor deposition film so that the polyethylene terephthalate film side surface of the obtained aluminum oxide vapor deposition film and the polyvinylidene chloride resin layer 2 side surface of the first barrier film produced in Example 2 were in contact with each other. The laminated film 5 was obtained by laminating | stacking with the 1st barrier property film produced in Example 2, and heat-sealing on the conditions of the setting temperature of 130 degreeC using a laminator (Inashinsha make, home office laminator SP230). The evaluation results of the obtained laminated film 5 are shown in Table 1.

(Comparative Example 1)
A first barrier film and a second barrier film were produced in the same manner as in Example 1. Next, a urethane-based adhesive (Mitsui Chemicals Takenate A-3, Takelac A-310, and ethyl acetate mixed in a ratio of 1: 12: 7) is coated on the polyvinylidene chloride resin layer 2 of the first barrier film. It apply | coated so that it might become 3 g / m < ² > by solid content using a Mayer bar, and it dried for 30 second at the temperature of 70 degreeC using the dryer, and formed the urethane type adhesive bond layer. Next, the second barrier film was bonded to the urethane adhesive layer and pressed with a rubber roller, and the second barrier film was bonded and laminated on the urethane adhesive layer of the first barrier film. This was aged in an oven at 40 ° C. for 2 days to obtain a laminated film 6. The evaluation results of the obtained laminated film 6 are shown in Table 1.

(Comparative Example 2)
A first barrier film and a second barrier film were produced in the same manner as in Example 2. Next, a urethane-based adhesive (Mitsui Chemicals Takenate A-3, Takelac A-310, and ethyl acetate mixed in a ratio of 1: 12: 7) is coated on the polyvinylidene chloride resin layer 2 of the first barrier film. It apply | coated so that it might become 3 g / m < ² > by solid content using a Mayer bar, and it dried for 30 second at the temperature of 70 degreeC using the dryer, and formed the urethane type adhesive bond layer. Next, the second barrier film was bonded to the urethane adhesive layer and pressure-bonded with a rubber roller, and the second barrier film was bonded and laminated on the urethane adhesive layer of the first barrier film. This was aged in an oven at 40 ° C. for 2 days to obtain a laminated film 7. The evaluation results of the obtained laminated film 7 are shown in Table 1.

(Comparative Example 3)
A first barrier film and a second barrier film were produced in the same manner as in Example 2. The polyvinylidene chloride resin layer 2 of the first barrier film and the surface of the second barrier film on the polyethylene terephthalate film side were bonded and laminated in the same manner as in Comparative Example 1 to obtain a laminated film 8. The evaluation results of the obtained laminated film 8 are shown in Table 1.

(Reference Example 1)
A first barrier film was produced in the same manner as in Example 1. With respect to this first barrier film, the water vapor permeability was measured. The obtained evaluation results are shown in Table 1.

(Reference Example 2)
A first barrier film was produced in the same manner as in Example 2. With respect to this first barrier film, the water vapor permeability was measured. The obtained evaluation results are shown in Table 1.

  The laminated films of Examples 1 to 5 had good appearance while having excellent water vapor barrier performance. On the other hand, the laminated films obtained in Comparative Examples 1 to 3 were inferior in appearance.

DESCRIPTION OF SYMBOLS 100 Laminated film 101 Resin film layer 103 Inorganic layer 110 First barrier film 120 Second barrier film 125 One side A Barrier resin layer B Barrier resin layer

Claims (10)

A first barrier film having a barrier resin layer (A), and a second barrier film having the same or different configuration from the first barrier film,
The barrier resin layer (A) of the first barrier film and one surface of the second barrier film are directly heat-sealed ,
The barrier resin layer (A) contains a polyvinylidene chloride resin,
The barrier resin layer (A) is a barrier resin layer (A1) formed of a latex containing fine particles of the polyvinylidene chloride resin, and a barrier resin formed of a solution in which the polyvinylidene chloride resin is dissolved. Having a layer (A2),
A laminated film in which the barrier resin layer (A1) is in contact with the barrier resin layer (A2) . In the laminated film according to claim 1 ,
A laminated film in which the first barrier film is a resin film layer, an inorganic layer, the barrier resin layer (A2), and the barrier resin layer (A1) laminated in this order. In the laminated film according to claim 1 or 2 ,
The laminated film in which the second barrier film has a resin film layer and at least one barrier layer selected from an inorganic layer and a barrier resin layer (B). In the laminated film according to claim 3 ,
A laminated film in which the barrier resin layer (A) of the first barrier film and the inorganic layer or the barrier resin layer (B) of the second barrier film are heat-sealed. In the laminated film according to claim 3 ,
A laminated film in which the barrier resin layer (A) of the first barrier film and the resin film layer of the second barrier film are heat-sealed. In the laminated film according to any one of claims 2 to 5 ,
A laminated film in which the inorganic layer is composed of one or more inorganic materials selected from the group consisting of silicon oxide, aluminum oxide, and aluminum. In the laminated film according to any one of claims 2 to 6 ,
A laminated film in which the resin film layer contains a thermoplastic resin. In the laminated film according to any one of claims 1 to 7 ,
A laminated film having a water vapor permeability of 0.20 g / m ² · day or less measured at 40 ° C. and 90% RH. A manufacturing method for manufacturing a laminated film as claimed in any one claims 1 to 8,
A first barrier film having a barrier resin layer (A), and a second barrier film having the same or different configuration from the first barrier film, the barrier resin layer (A of the first barrier film) ) And one surface of the second barrier film are laminated so as to be in contact with each other;
Heat-sealing the barrier resin layer (A) of the first barrier film and one surface of the second barrier film;
The manufacturing method of the laminated | multilayer film containing.   In the manufacturing method of the laminated | multilayer film of Claim 9,
  Further comprising the step of forming the barrier resin layer (A),
  The step of forming the barrier resin layer (A)
    Applying and drying a polyvinylidene chloride resin solution obtained by dissolving a polyvinylidene chloride resin in an organic solvent to form the barrier resin layer (A2);
    Applying and drying latex containing fine particles of polyvinylidene chloride resin to form the barrier resin layer (A1);
The manufacturing method of the laminated | multilayer film containing this.

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