JP2017124512A - Barrier film and barrier package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier film having excellent printing properties, particularly excellent printing properties on aqueous ink.SOLUTION: A barrier film 100 comprises at least comprise a polyvinylidene resin layer (A) predominantly composed of a polyvinylidene resin. The polyvinylidene resin layer (A) is an inhomogeneous layer and comprises a structure comprising a particle portion comprising a polyvinylidene resin.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a barrier film and a barrier package.

As a barrier film, a film having a polyvinylidene chloride resin layer is known.
Examples of the technology relating to such a barrier film include those described in Patent Document 1 (Japanese Patent Laid-Open No. 08-39718).

In Patent Document 1, a vapor deposition film (B) of an inorganic material is formed on at least one surface of a polymer film substrate (A), and a coating film of polyvinylidene chloride (B) is further formed on the vapor deposition film (B). A composite vapor deposition film characterized in that C) is laminated is described.
Patent Document 1 describes that such a composite vapor deposition film is excellent in gas barrier properties and bending fatigue resistance.

Japanese Patent Application Laid-Open No. 08-39718

  According to the study by the present inventors, it has been clarified that a barrier film provided with at least a polyvinylidene chloride-based resin layer is not preferable in printing characteristics, particularly printing characteristics for water-based ink.

  The present invention has been made in view of the above circumstances, and provides a barrier film excellent in printing characteristics, particularly printing characteristics for water-based ink.

  According to the present invention, the following barrier film and barrier package are provided.

[1]
A barrier film comprising at least a polyvinylidene chloride resin layer (A) containing a polyvinylidene chloride resin as a main component,
A barrier film comprising a structure in which the polyvinylidene chloride-based resin layer (A) is a heterogeneous layer and has a particle portion including the polyvinylidene chloride-based resin.
[2]
The barrier film according to the above [1], wherein a surfactant is unevenly distributed between particles in a particle portion containing the polyvinylidene chloride resin.
[3]
The surfactant includes one or more selected from the group consisting of alkyl sulfate ester salts, alkyl benzene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, and polyoxyalkylene unit-containing sulfate esters. The barrier film according to [2].
[4]
The barrier film according to any one of [1] to [3], further including a base film layer on at least one surface of the polyvinylidene chloride resin layer (A).
[5]
The barrier film according to [4], wherein the base film layer and the polyvinylidene chloride-based resin layer (A) are configured via an adhesive layer.
[6]
The barrier film according to [4] or [5], further including an inorganic layer on at least one surface of the base film layer.
[7]
The barrier film according to [6], wherein the inorganic layer contains one or more inorganic substances selected from the group consisting of silicon oxide, silicon oxynitride, silicon nitride, aluminum oxide, and aluminum.
[8]
The above [6] or [7] further comprising a polyvinylidene chloride resin layer (B) comprising a homogeneous layer containing a polyvinylidene chloride resin as a main component on at least one surface of the polyvinylidene chloride resin layer (A). ] The barrier film as described in any one of Claims 1-3.
[9]
The said base film layer, the said inorganic substance layer, the said polyvinylidene chloride resin layer (B), and the said polyvinylidene chloride resin layer (A) are laminated | stacked in this order in said [8] Barrier film.
[10]
The polyvinylidene chloride resin layer and the thickness of (B) and _{X 2,} the polyvinylidene chloride-based resin layer thickness of (A) when the _{X 1, X 1} / _{X 2} is 0.2 or more and 100 or less The barrier film according to the above [8] or [9].
[11]
The barrier film according to any one of [1] to [10], wherein an average particle diameter in a cross section of a particle portion containing the polyvinylidene chloride resin is 0.01 μm or more and 0.5 μm or less.
[12]
The polyvinylidene chloride resin layer (A) is one or more adhesives selected from the group consisting of silane coupling agents, urethane resins, urea resins, melamine resins, epoxy resins, and alkyd resins. The barrier film according to any one of the above [1] to [11], which contains a functional component.
[13]
The barrier packaging body containing the barrier film as described in any one of [1] to [12] above.

  ADVANTAGE OF THE INVENTION According to this invention, the barrier film excellent in the printing characteristic, especially the printing characteristic with respect to aqueous ink can be provided.

It is sectional drawing which showed typically an example of the structure of the barrier film of embodiment which concerns on this invention. It is sectional drawing which showed typically an example of the structure of the barrier film of embodiment which concerns on this invention. It is sectional drawing which showed typically an example of the structure of the barrier film of embodiment which concerns on this invention. It is sectional drawing which showed typically an example of the structure of the barrier film of embodiment which concerns on this invention. It is sectional drawing which shows the electron micrograph of the cross section which performed the ruthenium dyeing | staining process in the barrier film obtained in Example 1. FIG.

  Embodiments of the present invention will be described below with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate. Moreover, the figure is a schematic diagram and does not match the actual dimensional ratio. Unless otherwise specified, “˜” between numbers in the sentence represents the following.

[Barrier film]
1-4 is sectional drawing which showed typically an example of the structure of the barrier film 100 of embodiment which concerns on this invention. FIG. 5 is a cross-sectional view showing an electron micrograph of a cross section of the barrier film obtained in Example 1 subjected to ruthenium staining treatment.
The barrier film 100 according to this embodiment includes at least a polyvinylidene chloride resin layer (A) containing a polyvinylidene chloride resin as a main component. The polyvinylidene chloride-based resin layer (A) is a heterogeneous layer and includes a structure having a particle portion including the polyvinylidene chloride-based resin.
Here, FIG. 5 is a cross-sectional view showing an electron micrograph of a cross section of the barrier film obtained in Example 1 subjected to the ruthenium staining treatment. In the present embodiment, the heterogeneous layer is a layer having a non-uniform density or composition, such as the polyvinylidene chloride resin layer (A) in FIG.
In addition, the structure having a particle portion containing a polyvinylidene chloride resin is, for example, particles or particles containing a polyvinylidene chloride resin fused or bound as in the polyvinylidene chloride resin layer (A) in FIG. However, it refers to a structure that retains the particle shape to some extent.

According to the study by the present inventors, it has been clarified that a barrier film provided with at least a polyvinylidene chloride-based resin layer is inferior in printing characteristics, particularly printing characteristics for water-based ink containing water as a main solvent.
Therefore, as a result of intensive studies, the present inventors have made the polyvinylidene chloride resin layer an inhomogeneous layer and further include a layer having a structure having a particle portion containing the polyvinylidene chloride resin. It has been found that a barrier film excellent in printing characteristics for aqueous ink can be obtained.
The barrier film 100 according to the present embodiment can exhibit excellent printing characteristics because the ink easily penetrates into the gaps between the particle portions containing the polyvinylidene chloride resin in the polyvinylidene chloride resin layer (A). That is, according to the present embodiment, the barrier performance is provided by providing at least the polyvinylidene chloride resin layer (A) which is a heterogeneous layer and includes a structure having a particle portion containing a polyvinylidene chloride resin. While having it, the barrier film 100 excellent in printing characteristics can be realized.
In addition, the quality of said printing characteristic can be judged by the wetting tension measured according to JISK6768, for example. In general, oil-based inks that use solvents as the main solvent are familiar with the resin and are easy to paste, but water-based inks are easy to repel the resin, making it difficult to stick to the resin, and as a result, ink loss etc. can easily occur. Often difficult. Therefore, the wetting tension can be used as an index for determining the quality of the printing characteristics of the water-based ink.

In the barrier film 100, the surface specific resistance value in an environment of a temperature of 23 ° C. and a humidity of 50% RH is preferably 1.0 × 10 ¹⁴ Ω / □ or less, more preferably 1.0 × 10 ¹² Ω. / □ or less.
By setting the surface specific resistance value to be equal to or lower than the upper limit value, the antistatic performance and printing characteristics of the barrier film 100 can be further improved.
In addition, the said surface specific resistance value is a value when it measures about the surface of a polyvinylidene chloride type-resin layer (A).

Moreover, it can prevent that dust etc. adhere to the surface of the barrier film 100 by making the said surface specific resistance value below into the said upper limit. Thereby, the barrier film 100 can be suitably used as a packaging film for foods and pharmaceuticals.
The surface specific resistance value can be controlled, for example, by adjusting the thickness of the polyvinylidene chloride resin layer (A). In addition, the barrier film 100 of the present embodiment can realize the surface specific resistance value without separately providing an antistatic layer on the surface or adding an antistatic agent.

  The barrier film 100 has a small amount of residual organic solvent and is excellent as a packaging film or a sealing film. Specifically, the amount of residual organic solvent in the barrier film 100 is preferably 5.0 ppm or less, more preferably 3.0 ppm or less, and further preferably 1.0 ppm or less.

The amount of the residual organic solvent can be measured, for example, as follows. First, three 5 cm × 5 cm samples are produced from the barrier film 100. Put three prepared samples into a 20 mL vial and seal tightly. Subsequently, it heats at 90 degreeC for 30 minute (s) using a head space sampler. Next, 1 mL of the space gas in the heated vial is analyzed using gas chromatography and a flame ionization detector, and the amount of the organic solvent in the space gas is quantified. This amount of organic solvent is the amount of residual organic solvent in the barrier film 100.
The amount of the residual organic solvent can be controlled, for example, by adjusting the thickness of the polyvinylidene chloride resin layer (A) or the polyvinylidene chloride resin layer (B) described later.

The barrier film 100 of the present embodiment includes at least a polyvinylidene chloride resin layer (A) containing a polyvinylidene chloride resin as a main component from the viewpoint of improving printing characteristics while maintaining excellent barrier performance.
The polyvinylidene chloride resin layer (A) is a heterogeneous layer and includes a structure having a particle portion containing a polyvinylidene chloride resin.

  The polyvinylidene chloride-based resin layer (A) may be composed of one polyvinylidene chloride-based resin layer, or may be composed of two or more polyvinylidene chloride-based resin layers. At this time, the two or more polyvinylidene chloride-based resin layers may be the same type of polyvinylidene chloride-based resin layers or different types of polyvinylidene chloride-based resin layers.

Here, containing polyvinylidene chloride resin as a main component means that the polyvinylidene chloride resin layer (A) contains 50% by mass or more of polyvinylidene chloride resin. The polyvinylidene chloride resin layer (A) is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, still more preferably 90% by mass or more, particularly preferably polyvinylidene chloride resin. Contains 95% by mass or more.
This is because if the content of the polyvinylidene chloride resin in the polyvinylidene chloride resin layer (A) is within the above range, the performance balance of printing characteristics and barrier properties will be further improved.

In the polyvinylidene chloride resin layer (A) according to this embodiment, it is preferable that the surfactant is unevenly distributed between the particles of the particle portion containing the polyvinylidene chloride resin. Thereby, it is possible to further improve the antistatic performance and the printing characteristics, particularly the printing characteristics for water-based ink, while maintaining excellent barrier performance.
That is, the barrier film 100 according to the present embodiment has good transferability of water-based ink due to the hydrophilic group of the surfactant exposed on the surface of the water-based ink in the polyvinylidene chloride resin layer (A). And the synergistic effect that ink easily permeates into the gaps between the particle portions containing the polyvinylidene chloride resin, it is considered that extremely excellent printing characteristics can be realized. Further, it is more preferable that the surfactant is unevenly distributed on the surface to be printed from the viewpoint of antistatic performance and printing characteristics.
Here, in the polyvinylidene chloride-based resin layer (A), the surfactant is dyed by the ruthenium dyeing treatment, and the portion where the surfactant is present becomes visible as a dark portion as shown in FIG. On the other hand, the white part which was not dye | stained by the ruthenium dyeing | staining process forms the particle | grain part containing a polyvinylidene chloride resin.
In this embodiment, between the particles of the particle portion is, for example, a dark portion between the particle portions in the polyvinylidene chloride resin layer (A) in FIG. As apparent from FIG. 5, the surfactant is unevenly distributed between the particles including the polyvinylidene chloride resin and between the surfaces of the polyvinylidene chloride resin layer (A) and in the vicinity thereof.

In the polyvinylidene chloride resin layer (A) according to the present embodiment, the average particle diameter in the cross section of the particle portion containing the polyvinylidene chloride resin is preferably 0.01 μm or more and 0.5 μm or less, more preferably 0.05 μm. It is not less than 0.45 μm, more preferably not less than 0.07 μm and not more than 0.40 μm, still more preferably not less than 0.08 μm and not more than 0.35 μm. Thereby, antistatic performance and printing characteristics can be further improved while maintaining excellent barrier performance.
Here, the average particle diameter in the cross section of the particle part containing the polyvinylidene chloride resin can be measured by an electron micrograph. For example, the measurement is performed according to the following procedure. First, the barrier film 100 is cut with a microtome or the like to produce a cross section. Next, several cross-sectional photographs of the barrier film 100 are taken with an electron microscope. Subsequently, the particle part containing arbitrary polyvinylidene chloride resin is selected, and the particle size is measured from the photograph. At this time, it measures about 10 or more particle diameters in a cross section, and makes those average values into the average particle diameter in a cross section.

  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.

As said copolymer, the content rate of vinylidene chloride is 60 mass% or more and less than 100 mass%, and the content rate of the monomer copolymerizable with vinylidene chloride exceeds 0 mass% and is 40 mass% or less. A copolymer can be illustrated.
Examples of monomers copolymerizable with vinylidene chloride include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylate-n-butyl, and (meth) acrylic. Isobutyl acid, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate-n-octyl, (meth) C1-C18 alkyl ester or cycloalkyl ester of (meth) acrylic acid such as lauryl acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, methoxybutyl (meth) acrylate, (meth) acrylic Of (meth) acrylic acid such as methoxyethyl acid and ethoxybutyl (meth) acrylate (Meth) acrylic acid esters such as alkoxyalkyl esters having 2 to 18 primes; carboxyl groups such as (meth) acrylic acid, crotonic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid, citraconic acid Ethylene-based α, β-unsaturated carboxylic acids and salts thereof; unsaturated amide compounds such as (meth) acrylamide and diacetone acrylamide; nitrile group-containing monomers such as acrylonitrile and methacrylonitrile; (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, acrylic acid such as hydroxybutyl (meth) acrylate or (meth) acrylic acid having 2 to 2 carbon atoms 8 hydroxyalkyl esters; polyoxyethylene monoacyl Hydroxyl group-containing monomers such as rate, polyoxyethylene monomethacrylate, N-methylol (meth) acrylamide, and allyl alcohol; styrene, α-methylstyrene, vinyl chloride, butadiene, vinyl toluene, vinyl acetate, itaconic acid alkyl ester, One type or two or more types selected from other polymerizable unsaturated monomers such as ethylene, propylene, and isobutylene can be used.

The polyvinylidene chloride-based resin layer (A) can be formed of, for example, a latex containing fine particles of a polyvinylidene chloride-based resin.
The latex containing the fine particles of the polyvinylidene chloride resin used for the polyvinylidene chloride resin layer (A) can be produced by conventionally known emulsion polymerization.

In the barrier film 100 of the present embodiment, the surfactant contained in the polyvinylidene chloride resin layer (A) is not particularly limited, and a surfactant generally used in emulsion polymerization can be used. Examples thereof include a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. An anionic surfactant is particularly preferred from the viewpoint of ease of bleeding out.
Moreover, content of surfactant is 0.3-2.5 mass% with respect to the whole polyvinylidene chloride resin layer (A) from a viewpoint of barrier performance and printing characteristics, for example.
Examples of the cationic surfactant include alkyl ammonium salts such as dodecyl ammonium chloride or quaternary ammonium salts.
Examples of the anionic surfactant include alkyl diphenyl ether disulfonates such as diammonium dodecyl diphenyl ether disulfonate, sodium dodecyl diphenyl ether disulfonate, calcium dodecyl diphenyl ether disulfonate, sodium alkyl diphenyl ether disulfonate; sodium dodecylbenzene sulfonate, dodecylbenzene Alkyl benzene sulfonates such as ammonium sulfonate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; aliphatic carboxylates such as fatty acid sodium and potassium oleate; sulfate salts containing polyoxyalkylene units (eg, polyoxy Sodium ethylene alkyl ether sulfate, polyoxyethylene alkyl ether Polyoxyethylene alkyl ether sulfate such as ammonium sulfate; polyoxyethylene alkyl phenyl ether sulfate sodium, polyoxyethylene alkyl phenyl ether sulfate such as ammonium polyoxyethylene alkyl phenyl ether sulfate; polyoxyethylene polycyclic sodium phenyl ether sulfate; Polyoxyethylene polycyclic phenyl ether ammonium sulfate such as polyoxyethylene polycyclic phenyl ether sulfate); naphthalene sulfonic acid formalin condensate such as sodium naphthalene sulfonic acid formalin condensate salt; sodium dialkyl sulfosuccinate, dialkyl sulfosuccinic acid di Alkylsulfosuccinates such as sodium; polyoxyethylene-polyoxypropylene glycol ester Ether sulfates; sulfonates or sulfate group and a polymerizable carbon - carbon (unsaturated) double bond and the anti-surfactants having in the molecule thereof.
Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyalkylene alkyl ether compounds such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, A polyoxyalkylene unit-containing ether compound such as a polyoxyalkylene alkyl phenyl ether compound such as polyoxyethylene nonylphenyl ether, a polyoxyalkylene polycyclic phenyl ether compound such as polyoxyethylene polycyclic phenyl ether; a polyoxyethylene monolaurate; Polyoxyalkylene alkyl ester compounds such as polyoxyethylene monostearate and polyoxyethylene monooleate; Polyoxyalkylene alkylamine compounds such as polyoxyethylene alkyl amine; sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, sorbitan compounds such as polyoxyethylene sorbitan monooleate and the like.
Examples of amphoteric surfactants include lauryl betaine and lauryl dimethylamine oxide.
These surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.
Among these, as the surfactant contained in the polyvinylidene chloride-based resin layer (A), it is preferable to include at least one selected from anionic surfactants and nonionic surfactants, alkyl sulfate salts, More preferably, it contains one or more selected from alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, and polyoxyalkylene unit-containing sulfate ester salt.

As a method for forming the polyvinylidene chloride-based resin layer (A), a polyvinylidene chloride-based resin film formed of a latex containing fine particles of polyvinylidene chloride-based resin is used as a base film layer 101, an inorganic material layer 102, and a poly-layer, which will be described later. A method of forming a polyvinylidene chloride resin layer (B) and a polyvinylidene chloride resin layer (A) by laminating on another substrate; latex containing fine particles of a polyvinylidene chloride resin; Examples include a method of forming the polyvinylidene chloride resin layer (A) by applying the inorganic material layer 102, the polyvinylidene chloride resin layer (B), and other substrates and drying. Among these, from the viewpoints of barrier properties, adhesion, and productivity, latex containing fine particles of polyvinylidene chloride resin is used as the base film layer 101, the inorganic layer 102, the polyvinylidene chloride resin layer (B), and other groups. A method of forming the polyvinylidene chloride resin layer (A) by applying on a material and drying is preferable.
In addition, the above-mentioned method of forming a polyvinylidene chloride resin layer using a latex containing fine particles of polyvinylidene chloride resin is repeated two times or more, or is combined with two or more polyvinylidene chloride resin layers. A polyvinylidene chloride resin layer (A) can be formed.

  The thickness of the polyvinylidene chloride-based resin layer (A) is such that the barrier film 100 does not include the base film layer 101 from the viewpoint of the balance of barrier properties, transparency, printing characteristics, antistatic properties, handling properties, etc. The thickness is preferably from 0.1 μm to 100 μm, more preferably from 0.2 μm to 50 μm, more preferably from 0.5 μm to 30 μm, and even more preferably from 1 μm to 20 μm.

  The thickness of the polyvinylidene chloride resin layer (A) is such that the barrier film 100 is a base material from the viewpoint of the balance of barrier properties, transparency, printing characteristics, residual organic solvent amount, antistatic performance, adhesion, handling properties, etc. When the film layer 101 is included, it is preferably 0.1 μm or more and 10 μm or less, more preferably 0.1 μm or more and 5 μm or less, further preferably 0.1 μm or more and 3.5 μm or less, and even more preferably 0.2 μm or more and 2.0 μm or less. Hereinafter, it is particularly preferably 0.5 μm or more and 2.0 μm or less, and most preferably 0.5 μm or more and 1.0 μm or less.

  As shown in FIG. 2, the barrier film 100 according to this embodiment may further include a base film layer 101 laminated on at least one surface of the polyvinylidene chloride resin layer (A).

The base film layer 101 of the present embodiment preferably includes a thermoplastic resin, and more preferably includes a sheet-like or film-like base 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, polybutylene terephthalate, polyethylene naphthalate, 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.
Further, in order to improve the adhesion with the polyvinylidene chloride resin layer (A), the polyvinylidene chloride resin layer (B) or the inorganic layer 102 described later on one or both surfaces of the base film layer 101, for example, Surface activation treatment such as corona treatment, flame treatment, plasma treatment, and primer coating treatment may be performed.
The thickness of the base film layer 101 is preferably 1 μm or more and 200 μm or less, more preferably 5 μm or more and 150 μm or less.

  From the viewpoint of improving interlayer adhesion, an adhesive layer may be provided between the base film layer 101 and the polyvinylidene chloride resin layer (A). In particular, a polyester-based adhesive layer is preferable as the adhesive layer from the viewpoint of improvement in delamination strength and stability.

  The polyester-based adhesive layer is preferably formed from, for example, a curing agent such as polyester polyol and polyvalent isocyanate.

  The polyester polyol is a polyester obtained by a reaction between a polyvalent carboxylic acid and a polyol. The polyol used as a raw material is a compound having at least two or more hydroxyl groups in the molecule, and examples thereof include a low molecular weight polyol and a high molecular weight polyol.

  Examples of the low molecular weight polyol include ethylene glycol, propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,6-hexanediol, neopentyl glycol, alkane (C7- C22) Diol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanedimethanol, alkane-1,2-diol (C17 to C20), bisphenol A, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2 , 6-dimethyl-1-octene-3,8-diol, bishydroxyethoxybenzene, xylene glycol, bishydroxyethylene terephthalate and other low molecular weight diols; glycerin, 2-methyl-2-hydroxymethyl 1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, 1,1,1-tris (hydroxymethyl) propane, 2,2-bis (hydroxymethyl) Low molecular weight triols such as -3-butanol and other aliphatic triols (C8 to C24); low molecular weights having 4 or more hydroxyl groups such as tetramethylolmethane, D-sorbitol, xylitol, D-mannitol, D-mannitol A polyol etc. are mentioned.

  Examples of the high molecular weight polyol include polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, epoxy polyol, natural oil polyol, silicon polyol, fluorine polyol, and polyolefin polyol.

  Examples of the polyester polyol include one or more of the above-described low molecular weight polyols, or one or more of the high molecular weight polyols, for example, oxalic acid, malonic acid, succinic acid, methyl succinic acid, and glutar. Acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, azelaic acid, sebacic acid, other aliphatic dicarboxylic acids (C11 to C13), hydrogenated Carboxylic acids such as dimer acid, maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, dimer acid, het acid, and acid anhydrides derived from these carboxylic acids; Oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl anhydride (C1 ~ C18) Obtained by reaction with succinic acid, tetrahydrophthalic anhydride, trimellitic anhydride, acid halides derived from these carboxylic acids, etc .; oxalic acid dichloride, adipic acid dichloride, sebacic acid dichloride, etc. A polyester polyol etc. are mentioned.

  The polyvalent isocyanate, which is a curing agent for forming the polyester-based adhesive layer according to the present embodiment, is a compound having at least two or more isocyanate groups in the molecule, for example, aromatic polyisocyanate, aromatic fat Group polyisocyanate, alicyclic polyisocyanate, aliphatic polyisocyanate and the like.

  Examples of the aromatic polyisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4- or Aromatic diisocyanates such as 2,6-tolylene diisocyanate (TDI) or mixtures thereof, 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate; triphenylmethane-4,4 ′, 4 ″ -triisocyanate Aromatic triisocyanates such as 1,3,5-triisocyanatebenzene and 2,4,6-triisocyanate toluene; aromatics such as 4,4′-diphenylmethane-2,2 ′, 5,5′-tetraisocyanate Tetraisocyanate And the like.

  Examples of the araliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate (XDI) or a mixture thereof, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4. -Aroaliphatic diisocyanates such as bis (1-isocyanate-1-methylethyl) benzene (TMXDI) or a mixture thereof; and araliphatic triisocyanates such as 1,3,5-triisocyanate methylbenzene.

  Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 4,4'-methylenebis (cyclohexyl isocyanate) (H12MDI), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane (H6XDI) Or an alicyclic diisocyanate such as a mixture thereof; 1,3,5-triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 2- (3-isocyanate (Lopyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2.2.1) Heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3- Isocyanatopropyl) -bicyclo (2.2.1) heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 5- ( 2-Isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) -hept Emissions, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanate propyl) - bicyclo (2.2.1) alicyclic triisocyanates such heptane, and the like.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1, Aliphatic diisocyanates such as 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate; lysine ester triisocyanate, 1,4,8- Triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-triisocyanate Hexane, 2,5,7 aliphatic triisocyanate such as trimethyl-1,8-diisocyanate-5-isocyanatomethyl octane.

These polyisocyanates may be used alone or in combination of two or more.
Preferably, aromatic, araliphatic, alicyclic and aliphatic diisocyanates are used.

As shown in FIG. 3, the barrier film 100 may further include an inorganic layer 102 laminated on at least one surface of the base film layer 101. Thereby, barrier performance, such as oxygen barrier property and water vapor | steam barrier property, can further be improved, maintaining a favorable printing characteristic. The inorganic layer 102 is preferably laminated between the base film layer 101 and the polyvinylidene chloride resin layer (A) or a polyvinylidene chloride resin layer (B) described later.
As for the inorganic substance which comprises the inorganic substance layer 102 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 the inorganic substance constituting the inorganic layer 102 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 3A group element such as aluminum, gallium, indium, thallium; periodic table 4A group element such as silicon, germanium, tin; simple substance or oxide such as 6A group element of periodic table such as selenium, tellurium, etc. One type or two or more types may be mentioned.
In the present embodiment, the family name of the periodic table is shown by the old CAS formula.

Furthermore, among the above inorganic substances, one or two or more kinds of inorganic substances selected from the group consisting of silicon oxide, silicon oxynitride, silicon nitride, aluminum oxide, and aluminum are used because of their excellent balance of barrier properties, cost, etc. Is preferred.
In addition to silicon dioxide, silicon oxide may contain silicon monoxide and silicon suboxide.

  The inorganic layer 102 is formed of the above inorganic material. The inorganic layer 102 may be composed of a single inorganic layer or a plurality of inorganic layers. Further, when the inorganic layer 102 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 102 is preferably 1 nm or more and 500 nm or less, more preferably 2 nm or more and 300 nm or less, and further preferably 5 nm or more and 150 nm or less, from the viewpoint of the balance of barrier properties, adhesion, handling, and the like.
In the present embodiment, the thickness of the inorganic layer 102 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 102 is not particularly limited, and may be formed on one surface or both surfaces of the base 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. The inorganic layer 102 can be formed.

As shown in FIG. 4, the barrier film 100 of the present embodiment has a polyvinylidene chloride on at least one surface of the polyvinylidene chloride resin layer (A) from the viewpoint of protecting the inorganic layer 102 and improving the barrier property. It is preferable to further have a polyvinylidene chloride resin layer (B) comprising a homogeneous layer containing a resin as a main component.
The polyvinylidene chloride-based resin layer (B) is a homogeneous layer, and can be formed by, for example, a polyvinylidene chloride-based resin solution obtained by dissolving a polyvinylidene chloride-based resin in an organic solvent.
In the present embodiment, the homogeneous layer is a layer having a uniform density and composition, for example, as shown in the polyvinylidene chloride resin layer (B) in FIG. In the polyvinylidene chloride resin layer (B) in FIG. 5, the polyvinylidene chloride resin layer (B) has a uniform density and composition.

  As shown in FIG. 4, the barrier film 100 includes a base film layer 101, an inorganic layer 102, a polyvinylidene chloride resin layer (B), and a polyvinylidene chloride resin layer (A) in this order. It is preferable to be laminated. By doing so, the performance balance such as barrier performance, residual organic solvent amount, printing characteristics and antistatic performance is further improved.

  The polyvinylidene chloride-based resin layer (B) may be composed of one polyvinylidene chloride-based resin layer, or may be composed of two or more polyvinylidene chloride-based resin layers. At this time, the two or more polyvinylidene chloride-based resin layers may be the same type of polyvinylidene chloride-based resin layers or different types of polyvinylidene chloride-based resin layers.

Here, the phrase “containing a polyvinylidene chloride-based resin as a main component” means that the polyvinylidene chloride-based resin layer (B) contains 50% by mass or more of the polyvinylidene chloride-based resin. The polyvinylidene chloride resin layer (B) is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, still more preferably 90% by mass or more, particularly preferably polyvinylidene chloride resin. Contains 95% by mass or more.
This is because when the content of the polyvinylidene chloride-based resin in the polyvinylidene chloride-based resin layer (B) is within the above range, the barrier property is further improved.

  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. Specifically, the same thing as the polyvinylidene chloride-type resin used by the polyvinylidene chloride-type resin layer (A) mentioned above can be mentioned. The description is omitted here.

  The polyvinylidene chloride resin used for the polyvinylidene chloride resin layer (B) can be produced by a conventionally known method, but various commercially available products can also be used. As a commercially available product, the Saran Resin series manufactured by Asahi Kasei Corporation can be preferably used.

The organic solvent for dissolving the polyvinylidene chloride-based resin is not particularly limited because it is appropriately selected according to 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. These organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type.
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 the polyvinylidene chloride resin layer (B), for example, a polyvinylidene chloride resin film formed from a polyvinylidene chloride resin solution is used as a base film layer 101, an inorganic material layer 102, a polyvinylidene chloride resin layer. (A) A method of forming a polyvinylidene chloride-based resin layer (B) by laminating on, a base film layer 101, an inorganic layer 102, a polyvinylidene chloride-based resin layer (A), a polyvinylidene chloride-based resin solution, Examples include a method of forming a polyvinylidene chloride-based resin layer (B) by coating on another substrate and drying. Among these, from the viewpoint of barrier properties, adhesion, productivity, etc., the polyvinylidene chloride resin solution is applied to the base film layer 101, the inorganic layer 102, the polyvinylidene chloride resin layer (A), and other base materials. A method of forming the polyvinylidene chloride resin layer (B) by coating and drying is preferred.
Also, a polyvinylidene chloride-based resin layer composed of two or more polyvinylidene chloride-based resin layers by repeating or combining the above-described method of forming a polyvinylidene chloride-based resin layer using the polyvinylidene chloride-based resin solution two or more times. A resin layer (B) can be formed.

  The thickness of the polyvinylidene chloride-based resin layer (B) is not particularly limited as long as the effect of the present invention is exhibited, but is preferable from the viewpoint of balance of barrier properties, transparency, residual organic solvent amount, adhesion, handling properties, and the like. Is from 0.02 μm to 1.5 μm, more preferably from 0.02 μm to 1.3 μm, still more preferably from 0.05 μm to 0.7 μm.

At least one of the polyvinylidene chloride-based resin layer (A) and the polyvinylidene chloride-based resin layer (B) further includes an adhesive component from the viewpoint of improving the adhesion with the base film layer 101 and the inorganic layer 102. May be. In particular, when a layer formed of silicon oxide is used as the inorganic layer 102, from the viewpoint of improving the adhesion between the polyvinylidene chloride resin layer (A) or the polyvinylidene chloride resin layer (B) and the inorganic layer 102, It is preferable that the vinylidene chloride resin layer (A) and the polyvinylidene chloride resin layer (B) further contain an adhesive component.
The adhesive component includes 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; It is preferable to use it.

  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. These silane coupling agents may be used individually by 1 type, and may be used in combination of 2 or more type.

  The total thickness of the polyvinylidene chloride-based resin layer (A) and the polyvinylidene chloride-based resin layer (B) is not particularly limited as long as the effects of the present invention are exhibited, but barrier properties, transparency, printing characteristics, and residual organic solvent amount From the viewpoint of the balance of antistatic performance, adhesion, handleability, etc., preferably from 0.12 μm to 4.8 μm, more preferably from 0.25 μm to 2.7 μm, and even more preferably from 0.40 μm to 2.0 μm. Hereinafter, it is still more preferably 0.50 μm or more and 1.5 μm or less.

In the barrier film 100, a polyvinylidene chloride resin layer and the thickness of (B) and _{X 2,} when the polyvinylidene chloride-based resin layer thickness of (A) and the _{X 1,} is preferably _X 1 / X ₂ 0. 2 or more and 100 or less, more preferably 0.2 or more and 30 or less, further preferably 1.0 or more and 20 or less, and still more preferably 3.0 or more and 10 or less. By setting X ₁ / X ₂ within the above range, the performance balance such as barrier performance, residual organic solvent amount, printing characteristics and antistatic performance is further improved.

  Further, the overall thickness of the barrier film 100 according to the present embodiment is not particularly limited as long as the effects of the present invention are exhibited. However, since the barrier film 100 has excellent barrier properties, the thickness of the film can be reduced. It becomes possible. Specifically, a barrier film having a total thickness of 15 μm or less is also possible.

The barrier film 100 of the present embodiment may be provided with a heat-sealing 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.

  The barrier 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.

The barrier film 100 is excellent in water vapor barrier properties and can be suitably used as a packaging film or a sealing film. Specifically, in the barrier film 100, the water vapor transmission coefficient measured under the conditions of 40 ° C. and 90% RH is preferably 1.0 g / m ² · day or less, more preferably 0.5 g / m ^2. · Day or less, particularly preferably 0.3 g / m ² · day or less.
Such a water vapor transmission coefficient can be achieved, for example, by adjusting the thicknesses of the inorganic layer 102, the polyvinylidene chloride-based resin layer (A), and the polyvinylidene chloride-based resin layer (B).

The barrier film 100 is excellent in oxygen barrier properties and can be suitably used as a packaging film or a sealing film. Specifically, in the barrier film 100, the oxygen permeability measured under the conditions of a temperature of 20 ° C. and a humidity of 90% RH in accordance with JISK7126-2: 2006 is preferably 5.0 ml / m ² · day ·. MPa or less, more preferably 2.0 ml / m ² · day · MPa or less, still more preferably 1.0 ml / m ² · day · MPa or less, and even more preferably 0.5 ml / m ² · day · MPa or less. It is.
Such oxygen permeability can be achieved, for example, by adjusting the thicknesses of the inorganic layer 102, the polyvinylidene chloride resin layer (A), and the polyvinylidene chloride resin layer (B).

The barrier film 100 of the present embodiment is, for example, a packaging film for packaging foods, pharmaceuticals, daily miscellaneous goods, etc. that require printing characteristics, barrier performance, low residual organic solvent amount, antistatic performance, etc .; vacuum It can be suitably used as a film for heat insulation panel; a film for sealing for sealing electroluminescent elements, solar cells and the like;
Moreover, the barrier film 100 of this embodiment can also be used suitably as a barrier film which comprises a barrier packaging body. The barrier packaging body according to the present embodiment is filled with the contents in the barrier packaging bag itself or the bag made of the barrier film 100 of the present embodiment used for the purpose of filling the contents, for example. It is a thing. Moreover, the barriering packaging bag according to the present embodiment may use the barriering film 100 for a part of the barriering packaging bag, or may use the barriering film 100 for the entire barriering packaging bag.

[Method for producing barrier film]
Hereinafter, production of the barrier film 100 in which the base film layer 101, the inorganic layer 102, the polyvinylidene chloride resin layer (B), and the polyvinylidene chloride resin layer (A) are laminated in this order. A method will be described.
The manufacturing method of this barrier film 100 includes the following steps.
(1) A step of forming a polyvinylidene chloride-based resin layer (B) by applying a polyvinylidene chloride-based resin solution obtained by dissolving a polyvinylidene chloride-based resin in an organic solvent on the inorganic layer 102 and drying it ( 2) A step of forming a polyvinylidene chloride resin layer (A) by applying a latex containing fine particles of polyvinylidene chloride resin on the polyvinylidene chloride resin layer (B) and drying it.

  In the steps (1) and (2), a method of applying a polyvinylidene chloride resin solution on the inorganic layer 102, or a latex containing fine particles of a polyvinylidene chloride resin on the polyvinylidene chloride resin layer (B) There is no particular limitation on the method of applying to the substrate, and ordinary methods can be used. Examples thereof include a coating method using a known coating machine such as an air knife coater, kiss roll coater, metering bar coater, gravure roll coater, reverse roll coater, dip coater or die coater.

In the steps (1) and (2), the drying method after coating is not particularly limited, and a normal method can be used. For example, the method of drying using well-known dryers, such as an arch dryer, a straight bath dryer, a tower dryer, a drum dryer, a floating dryer, is mentioned.
The drying temperature is preferably 50 ° C. or higher and 200 ° C. or lower, more preferably 70 ° C. or higher and 150 ° C. or lower, more preferably 90 ° C. or higher and 130 ° C. or lower, and the drying time is preferably 5 seconds or longer and 10 minutes or shorter, more preferably Is from 5 seconds to 3 minutes, more preferably from 5 seconds to 1 minute.

  After drying, it is preferable to perform a heat treatment with an oven or the like if necessary. For example, the dried film is preferably 35 to 60 ° C., more preferably 40 to 50 ° C. in an oven, preferably 5 to 70 hours, more preferably 10 to 50 hours. Heat treatment. By such heat treatment, crystallization of the polyvinylidene chloride resin is promoted, and the barrier performance of the barrier film 100 can be further improved.

  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 and comparative examples. In addition, this embodiment is not limited to description of these Examples at all.

  Each evaluation in an Example and a comparative example was performed with the following method.

(1) Measurement of water vapor transmission coefficient An LLDPE film having a thickness of 50 μm (trade name: TUXFCS, manufactured by Mitsui Chemicals, Inc.) and an adhesive (Mitsui Chemicals, Takelac A-310 (trade name) / Takenate A) −3 (trade name) = 12/1 (weight ratio)) was applied at 3.0 g / m ² . Next, the barrier film and the LLDPE film are laminated so that the surface opposite to the base film layer of the barrier film obtained in Examples and Comparative Examples and the adhesive application surface of the LLDPE film are in contact with each other, A barrier laminate film was obtained.
Next, using the obtained barrier laminate 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 bag entrance 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 transmission coefficient (g · mm / (m ² · 24h)) was calculated from the difference.

(2) Measurement of oxygen permeability The oxygen permeability was measured according to JIS K7126-2: 2006.
LLDPE film with a thickness of 50 μm (trade name: TUXFCS, manufactured by Mitsui Chemicals, Inc.) and adhesive (Mitsui Chemicals, Takelac A-310 (trade name) / Takenate A-3 (trade name)) = 12 / 1 (weight ratio)) was applied at 3.0 g / m ² . Next, the barrier film and the LLDPE film are laminated so that the surface opposite to the base film layer of the barrier film obtained in Examples and Comparative Examples and the adhesive application surface of the LLDPE film are in contact with each other, A barrier laminate film was obtained.
Subsequently, the oxygen permeability of the obtained barrier laminate film was measured under the conditions of a temperature of 20 ° C. and a humidity of 90% RH using an oxygen permeability measuring machine (manufactured by MOCON: OXTRAN 2/21).

(3) Measurement of printing characteristics The printing characteristics of the obtained barrier film were evaluated by the following methods.
According to JIS K6768, the wetting tension of the surface to be printed (polyvinylidene chloride resin layer (A) surface) was measured. If the wetting tension is 60 mN / cm or more, printing with a good condition with water-based ink and no ink omission is possible.
(Criteria)
○: Wetting tension is 60 mN / cm or more ×: Wetting tension is less than 60 mN / cm

(4) Measurement of surface resistivity The substrate resistivity of the obtained barrier film was measured using R83340 (digital ultra-high resistance / microammeter) and R12704 (resistivity chamber) manufactured by Advantest. The surface on the opposite side was measured in an environment of 23 ° C. and 50% RH.

(5) Measurement of residual organic solvent amount The residual organic solvent amount of the obtained barrier film was measured by the following procedure. First, three 5 cm x 5 cm samples were produced from the barrier film. Three prepared samples were put into a 20 mL vial and sealed. Subsequently, it heated at 90 degreeC for 30 minutes using the headspace sampler (G1888 by Agilent). Subsequently, 1 mL of space gas in the vial after heating was analyzed using a gas chromatography equipped with a flame ionization detector (HP 6890 manufactured by Agilent), and the amount of the organic solvent in the space gas was quantified. This amount of organic solvent was defined as the amount of residual organic solvent in the barrier film.

(6) Measurement of average particle diameter of particle part containing polyvinylidene chloride resin and confirmation of presence / absence of uneven distribution of surfactant between particles of polyvinylidene chloride resin particle part containing polyvinylidene chloride resin The average particle size of was measured by a transmission electron micrograph. First, the barrier film was cut with a microtome to prepare a cross section. Next, after ruthenium staining, several cross-sectional photographs of the barrier film were taken with a transmission electron microscope at a magnification of 150,000 times. Next, an arbitrary particle portion was selected, and the particle size of the particle portion containing the polyvinylidene chloride resin was measured from the photograph. At this time, 10 or more particle sizes were measured, and the average value thereof was defined as the average particle size.
Further, the distribution state of the surfactant dyed by ruthenium dyeing was observed with a transmission electron microscope at a magnification of 150,000, and the cross section of the barrier film was observed.

<Example 1>
A 12 μm biaxially stretched polyethylene terephthalate film (manufactured by Unitika Ltd., trade name: Emblet PET12) was used as the base film. On the corona-treated surface of this base film, aluminum is heated and evaporated by high-frequency induction heating method, oxygen is further introduced, and aluminum oxide is deposited on the base film so as to have a thickness of 10 nm. Got.
A barrier film was obtained by sequentially forming a polyvinylidene chloride-based resin layer (B) and a polyvinylidene chloride-based resin layer (A) on the aluminum oxide layer of the obtained aluminum oxide vapor-deposited film.
Here, the method for forming the polyvinylidene chloride-based resin layer (B) and the polyvinylidene chloride-based resin layer (A) is as follows. First, polyvinylidene chloride resin (product name: 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), and a polyvinylidene chloride resin solution (solid) 5% by mass) was prepared.
Next, the polyvinylidene chloride resin solution (B) having a thickness of 0.13 μm was formed by applying the polyvinylidene chloride resin solution on the aluminum oxide layer with an applicator and drying to remove the solvent.
Subsequently, a latex (trade name: Saran Latex L536B (manufactured by Asahi Kasei Chemicals)) containing polyvinylidene chloride fine particles and a surfactant (sulfur and sodium-containing anionic surfactant) is used as a polyvinylidene chloride resin layer. (B) A polyvinylidene chloride-based resin layer (A) having a thickness of 0.56 μm was formed by coating on an applicator and drying to remove the solvent.
Here, FIG. 5 is a view showing an electron micrograph showing a cross section of the barrier film obtained in Example 1. FIG. As can be seen from FIG. 5, in the obtained barrier film, the polyvinylidene chloride-based resin layer (A) was a heterogeneous layer and included a structure having a particle portion containing the polyvinylidene chloride-based resin. . The polyvinylidene chloride resin layer (B) was a homogeneous layer.
Moreover, the average particle diameter of the particle part containing the polyvinylidene chloride resin in the polyvinylidene chloride resin layer (A) was 0.15 μm. Furthermore, by observing the ruthenium-stained section at 150,000 times with a TEM, between the particles of the polyvinylidene chloride-based resin layer (A) containing the polyvinylidene chloride-based resin and between the polyvinylidene chloride-based resin layers ( It was confirmed that the surfactant was unevenly distributed on the surface of A) and in the vicinity thereof.
The evaluation results of the obtained barrier film are shown in Tables 1 and 2.

<Example 2>
A barrier film was obtained in the same manner as in Example 1 except that the polyvinylidene chloride resin layer (B) was not formed and the thickness after drying of the polyvinylidene chloride resin layer (A) was 0.56 μm. It was.
From the cross-sectional photograph of the obtained barrier film by a transmission electron microscope, in the obtained barrier film, the polyvinylidene chloride resin layer (A) is a heterogeneous layer and contains a polyvinylidene chloride resin. It was confirmed that a structure having a particle portion was included.
Moreover, the average particle diameter of the particle part containing the polyvinylidene chloride resin in the polyvinylidene chloride resin layer (A) was 0.15 μm. Furthermore, by observing the ruthenium-stained section at 150,000 times with a TEM, between the particles of the polyvinylidene chloride-based resin layer (A) containing the polyvinylidene chloride-based resin and between the polyvinylidene chloride-based resin layers ( It was confirmed that the surfactant was unevenly distributed on the surface of A) and in the vicinity thereof.
The evaluation results of the obtained barrier film are shown in Tables 1 and 2.

<Comparative Example 1>
A barrier film was obtained in the same manner as in Example 1 except that the polyvinylidene chloride resin layer (A) and the polyvinylidene chloride resin layer (B) were not formed. The evaluation results of the obtained barrier film are shown in Tables 1 and 2.

<Comparative example 2>
A barrier film was obtained in the same manner as in Example 1 except that the polyvinylidene chloride resin layer (A) was not formed and the thickness after drying of the polyvinylidene chloride resin layer (B) was 0.13 μm. . The evaluation results of the obtained barrier film are shown in Tables 1 and 2.
Moreover, from the cross-sectional photograph by the transmission electron microscope of the obtained barrier film, it has confirmed that the polyvinylidene chloride resin layer (B) was a homogeneous layer in the obtained barrier film.

The barrier films of Examples 1 and 2 were excellent in the performance balance of barrier performance, printing characteristics, low residual organic solvent amount, and antistatic performance.
In contrast, the barrier films obtained in Comparative Examples 1 and 2 were inferior in the performance balance of barrier performance, printing characteristics, low residual organic solvent amount, and antistatic performance.

DESCRIPTION OF SYMBOLS 100 Barrier film 101 Base film layer 102 Inorganic layer A Polyvinylidene chloride resin layer B Polyvinylidene chloride resin layer

Claims (13)

A barrier film comprising at least a polyvinylidene chloride resin layer (A) containing a polyvinylidene chloride resin as a main component,
A barrier film comprising a structure in which the polyvinylidene chloride-based resin layer (A) is a heterogeneous layer and has a particle portion including the polyvinylidene chloride-based resin.   The barrier film according to claim 1, wherein a surfactant is unevenly distributed between particles in a particle portion containing the polyvinylidene chloride resin.   The surfactant comprises one or more selected from the group consisting of alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, and polyoxyalkylene unit-containing sulfates. Item 3. The barrier film according to Item 2.   The barrier film according to any one of claims 1 to 3, further comprising a base film layer on at least one surface of the polyvinylidene chloride resin layer (A).   The barrier film according to claim 4, wherein the base film layer and the polyvinylidene chloride resin layer (A) are configured with an adhesive layer interposed therebetween.   The barrier film according to claim 4 or 5, further comprising an inorganic layer on at least one surface of the base film layer.   The barrier film according to claim 6, wherein the inorganic layer contains one or more inorganic substances selected from the group consisting of silicon oxide, silicon oxynitride, silicon nitride, aluminum oxide, and aluminum.   The polyvinylidene chloride resin layer (B) comprising a homogeneous layer containing a polyvinylidene chloride resin as a main component on at least one surface of the polyvinylidene chloride resin layer (A). Barrier film.   The said base film layer, the said inorganic substance layer, the said polyvinylidene chloride type-resin layer (B), and the said polyvinylidene chloride type-resin layer (A) are laminated | stacked in this order. Barrier film. The polyvinylidene chloride-based resin layer and the thickness of (B) and _{X 2,} when the polyvinylidene chloride resin layer thickness of (A) and the _{X 1, X 1} / _{X 2} is 0.2 or more and 100 or less The barrier film according to claim 8 or 9.   11. The barrier film according to claim 1, wherein an average particle diameter in a cross section of a particle portion containing the polyvinylidene chloride resin is 0.01 μm or more and 0.5 μm or less.   The polyvinylidene chloride resin layer (A) is one or more adhesives selected from the group consisting of silane coupling agents, urethane resins, urea resins, melamine resins, epoxy resins, and alkyd resins. The barrier film as described in any one of Claims 1 thru | or 11 containing a sex component.   The barrier property package body containing the barrier property film as described in any one of Claims 1 thru | or 12.