JPH08142256A - Moistureproof composite vapor deposition film - Google Patents

Abstract

PURPOSE: To provide a moistureproof composite vapor deposition film excellent in gas barrier properties against oxygen, steam and helium and having high moistureproof properties. CONSTITUTION: A composite vapor deposition film contains at least one laminated structure wherein a vapor deposition film of an inorg. material is formed on at least the single surface of a polymeric film base material and a water- resistant film formed from a mixture containing polycarboxylic acid or a partially neutralized substance thereof and sugars in a wt. ratio of 95:5-20:80 is laminated on the vapor deposition film. A layer composed of a polymer compsn. containing a desiccant is arranged on at least one surface of the laminated structure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a moisture-proof composite vapor-deposited film, and more particularly to a moisture-proof composite vapor-deposited film having excellent gas barrier properties against oxygen, water vapor, helium and the like and having a high degree of moisture-proof property. INDUSTRIAL APPLICABILITY The moisture-proof composite vapor-deposited film of the present invention is useful in the field of foods, pharmaceuticals, packaging materials for daily sundries and the like, or sealing members, which are required to have a high degree of gas barrier property as well as gas barrier properties.

[0002]

2. Description of the Related Art In general, packaging materials are required to have a function of preventing quality deterioration of contents, but particularly in the field of food packaging where the contents are easily deteriorated or spoiled, oxygen gas barrier property, steam barrier property, etc. Is required to have excellent gas barrier properties. Conventionally, in order to provide gas barrier properties in packaging materials, for example, polyvinyl alcohol (PVA) film, ethylene / vinyl acetate copolymer partially saponified (EVOH) film, polyvinylidene chloride (PVDC) film, aluminum vapor deposition. Films, vapor-deposited silicon oxide films, etc. are used alone or in combination with various films.

These gas barrier films have advantages and disadvantages, and improvements have been made in each. For example, a PVA film has an excellent oxygen gas barrier property in a dry state, but under high humidity conditions, the oxygen gas barrier property is remarkably lowered due to moisture absorption, and further, it has a drawback that it dissolves in water or boiling water. ing. Therefore, P
It has been attempted to improve the crystallinity of a VA film by heat-treating it or biaxially stretching it, or to make it a laminated film having a multilayer structure to improve the humidity dependence of the oxygen gas barrier property.

EVOH is sensitive to humidity, and under high humidity conditions, the oxygen permeability coefficient remarkably increases. Therefore, conventionally, a multilayer plastic container having a laminated structure in which a layer of a composition containing a desiccant is sandwiched by a plurality of moisture-resistant thermoplastic resin layers is provided on at least one side of the EVOH layer (JP-A-61-249750). Issue), EVOH
A multi-layer container (at least one of JP-A-63-302017 and JP-A-63-302018) including at least one layer in which desiccant particles are dispersed in the matrix, and a metal having a desiccant mixed in the EVOH layer. Container with lid (JP-A-1-257)
No. 048) has been proposed. However,
In the conventional method, the effect of reducing oxygen gas barrier property due to moisture absorption and the effect of improving water resistance and moisture resistance are still insufficient.

On the other hand, the inventors of the present invention formed a film from a mixture of poly (meth) acrylic acid or a partially neutralized product thereof and a saccharide, and heat-treated the dried film to obtain a water resistant material having an excellent oxygen gas barrier property. It was found that a heat-resistant film was obtained (Japanese Patent Application No. 6-194940). This oxygen gas barrier material has a high oxygen gas barrier property even under high humidity conditions and is a water resistant film insoluble in boiling water. After that, the present inventors formed a vapor deposition film of an inorganic material on at least one surface of the polymer film substrate, and further, on the vapor deposition film, polycarboxylic acid or its partially neutralized product, starch, etc. By forming a dry film by applying a solution of the mixture with the saccharide of (1), and heat treating the dry film at a temperature of 100 ° C. (373 K) or higher to form a water resistant film having an oxygen gas barrier property. It has been found that a composite vapor deposition film having excellent gas barrier properties against oxygen, water vapor, helium, etc., and also excellent in flex fatigue resistance can be obtained (Japanese Patent Application No. 6-194942).

This composite vapor-deposited film has an oxygen gas barrier property of each layer of the vapor-deposited film and the water resistant film,
The steam barrier property and the helium gas barrier property are synergistically improved by the compounding. In addition, this composite vapor deposition film has excellent bending fatigue resistance because the film formed by the water resistant film prevents cracks from occurring in the vapor deposition film, and a decrease in gas barrier property due to destruction of the vapor deposition film is suppressed. . However, in fields such as packaging materials and seal members that require a high degree of moisture resistance, it is desirable that a high degree of moisture resistance be imparted while maintaining excellent gas barrier properties.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a moisture-proof composite vapor deposition film having excellent gas barrier properties against oxygen, water vapor, helium, etc. and having a high degree of moisture-proof property. As a result of diligent research, the present inventor has found that at least one surface of the polymer film substrate (A),
A vapor-deposited film (B) of an inorganic material is formed, and a water-resistant film (C) formed of a mixture of polycarboxylic acid or a partially neutralized product thereof and saccharide is further laminated on the vapor-deposited film (B). A composite film containing at least one laminated structure, wherein a layer (D) of a polymer composition containing a desiccant is disposed on at least one side of the laminated structure to obtain a high gas barrier. It has been found that a moisture-proof composite vapor-deposited film having properties and moisture-proof property can be obtained.
The present invention has been completed based on these findings.

[0008]

Thus, according to the present invention, the vapor deposition film (B) of an inorganic material is formed on at least one surface of the polymer film substrate (A), and the vapor deposition film (B) is further formed. A water resistant film (C) formed from a mixture containing polycarboxylic acid or a partially neutralized product thereof and saccharide in a ratio of 95: 5 to 20:80 (weight ratio) A composite film containing at least one structure, wherein a layer (D) of a polymer composition containing a desiccant is arranged on at least one side of the laminated structure. Will be provided.

The present invention will be described in detail below. (Vaporized film) As the polymer film substrate (A),
For example, polyamide such as nylon 6, nylon 66, nylon 12, nylon 6/66 copolymer, nylon 6/12 copolymer, polyethylene terephthalate (PE
T), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycarbonate, poly-4-methylpentene-1, polyphenylene sulfide, polypropylene (PP) and the like can be mentioned as a film. These films are unstretched films or stretched films,
It also includes a sheet.

The polymer film substrate may contain various additives in order to impart surface smoothness and stability.
If they bleed to the surface during vapor deposition, the adhesion between the base material and the vapor deposited film decreases, so it is preferable that the content of the additive is as small as possible. Also, the polymer film substrate is
It is preferable that the film has heat resistance enough to withstand the heat treatment conditions during production of the water resistant film. A polymer film having poor heat resistance that softens during heat treatment or impairs dimensional stability is not preferable as a substrate.

As the polymer film having heat resistance,
Either the crystal melting point or the Vicat softening point is usually 100 to 380 ° C, preferably 150 to 380 ° C.
More preferably, a resin formed of 180 to 380 ° C. is desirable. Among the polymer films, in particular,
A heat resistant film made of a resin having a crystal melting point or a Vicat softening point of 180 ° C. or higher, such as polyamide, PET or PEN, is preferable. The crystal melting point is JIS K7121.
Also, the Vicat softening point is determined by JIS K7206.
Can be measured by The thickness of the polymer film substrate is not particularly limited, but is usually 5 to 1000 μm, preferably 10 to 10 from the viewpoint of flexibility and economy.
0 μm.

As the inorganic material used as the vapor deposition source, there can be used metals, metal oxides, inorganic substances, and inorganic oxides which are usually used in the production of vapor deposited films. Specifically, aluminum (Al), aluminum oxide (Al ₂ O ₃ ), silicon oxide (SiO _x , x =
1-2), silicon oxynitride (SiO _x N _y , x = 0.6 to
0.8, y = 0.7 to 0.9) and the like. The thickness of the vapor deposition film (B) of an inorganic material can be arbitrarily determined according to desired transparency or opacity, color tone, gloss, flexibility, etc., but is usually 10 to 500 nm, preferably 10
˜300 nm, more preferably 10 to 150 nm. If the thickness of the vapor-deposited film is too thin, the gas barrier property will deteriorate, and it will easily peel off from the polymer film substrate. If it is too thick, the handleability will deteriorate.

The vapor deposition method includes a chemical vapor deposition method and a physical vapor deposition method. Usually, it is preferable to perform the vapor deposition using a vacuum vapor deposition method which is a physical vapor deposition method. In the vacuum evaporation method,
Place the polymer film as the base material in the vacuum evaporation system,
A method in which the inside of the vapor deposition apparatus is evacuated to about 10 ⁻⁴ Pa and a vapor deposition source such as aluminum is heated and vaporized to continuously form a vapor deposition film on the polymer film is preferably used. .

(Water-Resistant Film) In the present invention, a vapor deposition film (B) of an inorganic material is formed on at least one side of a polymer film substrate (A), and further, a poly-carbon film is deposited on the vapor deposition film (B). 95: 5 carboxylic acid or its partially neutralized product and sugar
By coating a solution of a mixture containing the mixture at a ratio of ˜20: 80 (weight ratio) to form a dry film, the obtained dry film is heat-treated at a temperature of 100 ° C. (373 K) or more, A water resistant film (C) is formed. A dry film formed from a mixture of polycarboxylic acid or a partially neutralized product thereof and a saccharide is water-soluble, but when heat-treated, it becomes a water-resistant film insoluble in water or boiling water. This water-resistant film, by itself, preferably has an oxygen permeability coefficient (measured under conditions of a temperature of 30 ° C. and a relative humidity of 80%) of 1.25 × 10 ⁻³ ml (STP) · cm / m ² · h ·. a
It has an excellent oxygen gas barrier property of tm {Pa} or less.

Polycarboxylic acid and partially neutralized product thereof The polycarboxylic acid used in the present invention is a polymer containing at least two carboxyl groups in the molecule,
Specifically, it is polyacrylic acid, polymethacrylic acid, acrylic acid-methacrylic acid copolymer, polymaleic acid, or a mixture of two or more thereof. Acrylic acid or methacrylic acid homopolymers or copolymers of both are preferred, and among these, homopolymers of acrylic acid and copolymers with methacrylic acid in which acrylic acid is the predominant amount are oxygen gas barrier properties, in particular, It is suitable. The number average molecular weight of the polycarboxylic acid is 2,000.
The range of 250,000 is preferable.

The partially neutralized polycarboxylic acid used in the present invention can be obtained by partially neutralizing the carboxyl group of the polycarboxylic acid as described above with an alkali to form a carboxylic acid salt. Examples of the alkali include sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia (including ammonia water), and the like. The partially neutralized product is usually prepared by adding an alkali to an aqueous solution of polycarboxylic acid and reacting them. A desired degree of neutralization can be achieved by adjusting the amount ratio of polycarboxylic acid and alkali.

When a partially neutralized product of a polycarboxylic acid is used, the oxygen gas barrier property is further improved by selecting the degree of neutralization, as compared with the case where an unneutralized polycarboxylic acid is used. You can However, when the degree of neutralization exceeds 20%, the oxygen gas barrier property tends to decrease, so that the partially neutralized product of polycarboxylic acid has a degree of neutralization of more than 0% and 20% or less. It is preferable. The degree of neutralization is more preferably in the range of more than 0% and 18% or less, and most preferably in the range of 5 to 15%. The degree of neutralization is
It can be calculated by the following formula. Neutralization degree = (A / B) × 100 (%) A: The number of moles of neutralized carboxyl groups in 1 g of partially neutralized polycarboxylic acid. B: The number of moles of carboxyl groups in 1 g of polycarboxylic acid before partial neutralization.

[0018] In the sugar acids present invention, as the saccharide (also referred to as sugar acids), monosaccharides,
Oligosaccharides and polysaccharides are used. These sugars also include sugar alcohols and various substitution products and derivatives. These sugars are preferably soluble in water.

<Monosaccharide> A monosaccharide is a basic substance that does not become a simpler molecule by hydrolysis among saccharides, and is a constituent unit of oligosaccharides and polysaccharides.
Monosaccharides is usually represented by the general formula C _n H _2n O _n, of which the number of carbon atoms (n) is 2,3,4,5,6,7,8,9
And 10 are referred to as diose, triose, tetrose, pentose, hexose, heptose, octose, nonose, and decose, respectively. Monosaccharides are classified into those having an aldehyde group as aldoses and those having a ketone group as ketose. Those having n = 3 or more have asymmetric carbon atoms, and there may be many stereoisomers depending on the number of asymmetric carbon atoms, but naturally known ones are a part thereof. Most naturally occurring substances are pentose and hexose. As the monosaccharide used in the present invention, n =
Aldose, which is an aldehyde of a chain polyhydric alcohol of 5 or more, is preferable because it is naturally abundant. Examples of such monosaccharides include glucose, mannose, galactose, xylose, and the like. Among them, glucose and galactose are more preferable.
The monosaccharides may be used alone or in combination of two or more.

<Sugar Alcohol> Sugar alcohol is a polyhydroxyalkane obtained by reducing aldose or ketose. As the sugar alcohol used in the present invention, a chain polyhydric alcohol is preferable. Such sugar alcohols may be represented by the general formula _{C n H 2n + 1 O n} .
When n is 3, 4, 5, 6, 7, 8, 9 and 10, they are called trititol, tetritol, pentitol, hexitol, heptitol, octitol, nonitol and decitol, respectively. Each sugar alcohol has many stereoisomers depending on the number of asymmetric carbon atoms. In the present invention, it is preferable to use a sugar alcohol of n = 3 to 6. Specific examples of the sugar alcohol include sorbitol, mannitol, dulcitol, xylitol, erythritol, glycerin and the like. The sugar alcohols may be used alone or in combination of two or more.

<Oligosaccharides> Oligosaccharides (oligosaccharides) have a structure in which 2 to 10 monosaccharides are linked by glycoside bonds. Depending on the number of monosaccharides, they are classified into disaccharides, trisaccharides, tetrasaccharides, pentasaccharides and the like. Specific examples include sucrose, lactose, trehalose, cellobiose, maltose, raffinose, stachyose and the like. Further, those obtained by alcoholizing the ends of these oligosaccharides (terminal alcoholized oligosaccharides) can also be used.

<Polysaccharides> Polysaccharides is a general term for high molecular compounds (polymerization degree of 10 or more) in which monosaccharides are polyglycosylated, and homopolysaccharides (homoglycans) are used when the number of constituent sugars is one. More than one species are called heteropolysaccharides (heteroglycans). Polysaccharides are widely present in the animal, plant and microbial kingdoms as storage polysaccharides (such as starches), structural polysaccharides (such as cellulose) and functional polysaccharides (such as heparin). A natural polysaccharide is a polymer compound mainly composed of aldohexose and aldopentose, which are linked linearly, branched or cyclic by a glycoside bond. Aldopentose and aldohexose form a 6-membered ring structure called a pyranose ring by an intramolecular hemiacetal bond between an aldehyde at the C1 position and an alcohol at the C5 position. Aldohexose and aldopentose in the natural polysaccharide molecule mainly have this pyranose ring structure.

Aldohexose and aldopentose, which are constituent units of natural polysaccharides, include neutral monosaccharides, as well as neutral monosaccharide sulfates, phosphates, other organic acid esters, methyl ethers, and primary alcohol groups. C2 of uronic acid and aldohexose which are oxidized to carboxyl groups
Hexosamine in which the hydroxyl group at the position is substituted with an amino group or N-acetylhexosamine as a derivative thereof, C3 and C6
3,6-anhydrous aldohexose and the like in which ether is formed between the hydroxyl groups at the positions are included.

Natural polysaccharides are widely distributed in the animal and plant kingdoms, and exist in plants as cell wall constituents of higher plants and seaweeds, those not involved in cell wall composition, and cell constituents of microorganisms. Those that are not involved in the cell wall composition of higher plants and seaweeds include storage substances such as mucilage and starch contained in cell liquid. In animals, it exists as a storage substance such as glycogen and a constituent of mucus such as heparin and chondroitin sulfate.

When natural polysaccharides are classified according to their constituents, they are classified into neutral polysaccharides, acidic polysaccharides and basic polysaccharides.
The neutral polysaccharides include mannan and glucan as homopolysaccharides. As heteropolysaccharides, those consisting only of hexose are contained in konjac, guaran, etc., and those consisting only of pentose are contained in xylan, alaboxylan, etc. On the other hand, tamarind, pear and the like are known to contain hexose and pentose. The acidic polysaccharides include those containing only uronic acid, those that contain galaturonic acid and neutral sugars, such as Trolo mallow and pectin, and those that contain glucuronic acid and neutral sugars, such as chamomile and Xanthus quail, and other neutral sugars. There are acidic polysaccharides including sulfuric acid ester, phosphoric acid ester, organic acid ester, methyl ether and 3,6 anhydride. Some basic polysaccharides include glucosamine and galactosamine as constituent monosaccharides.

The polysaccharides used in the present invention include, in addition to these natural polysaccharides, these polysaccharides in the solid phase and in the liquid phase using an organic acid or an inorganic acid and a hydrolase of these polysaccharides as a catalyst. In the phase or solid-liquid mixed phase, by adding heat as needed, those obtained by hydrolysis, natural polysaccharides and those subjected to the above-mentioned hydrolysis treatment,
Those that have been further processed are also included.

Examples of the processing treatment for natural polysaccharides and their hydrolysates include the following. Esterification treatment with inorganic or organic acids, etherification treatment such as allyl etherification, methyl etherification, carboxymethyl etherification, etc. Cationization treatment: For example, natural polysaccharides or their hydrolysates, 2-diethylaminoethyl chloride or 2,
A method of reacting with 3-epoxypropyltrimethylammonium chloride can be mentioned. Cross-linking treatment: For example, a method of cross-linking using formaldehyde, epichlorohydrin, phosphoric acid, acrolein or the like can be mentioned. Grafting treatment: For example, a method of graft-polymerizing various monomers onto a natural polysaccharide or a hydrolyzate thereof. Examples of the monomer include vinyl acetate, vinyl propionate, t-butyl vinyl ether, (meth) acrylamide, (meth) acrylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic. Acid ethoxyalkyl ester, (meth) acrylic acid methoxy polyethylene glycol ester, (meth) acrylic acid 2-hydroxy-3-chloropropyl ester, (meth) acrylic acid dimethylaminoethyl ester, methacrylic acid glycidyl ester, acrylonitrile, styrene, anhydrous Examples thereof include maleic acid and itaconic acid.

Among these natural polysaccharides, their hydrolysis products and their processed products, those soluble in water are preferred. Further, among the water-soluble natural polysaccharides, their hydrolysis products, and their processed products, homopolysaccharides whose constituent monosaccharide is glucose are more preferable. Examples of glucose homopolysaccharides include starches, celluloses, dextran, pullulan, water-soluble chitins and chitosans.

In the present invention, sugar sugars thereof may be used in place of the natural polysaccharides and hydrolysis products thereof and processing products thereof. As used herein, the sugar alcohols of the natural polysaccharides, their hydrolysis products and their processed products are the alcohols obtained by reducing the carbonyl group at the C ₁ -position at their reducing ends. In addition to this, in the present invention, saccharides such as cyclodextrin in which the sugar molecular chains are linked in a ring shape can also be used. The polysaccharides used in the present invention can be used alone or in combination of two or more.

<Starches> Starches are included in the above-mentioned polysaccharides, and the starches used in the present invention will be described in more detail below. As the starches used in the present invention,
Wheat starch, corn starch, waxy corn starch,
Raw starch (unmodified starch) such as potato starch, tapioca starch, rice starch, sweet potato starch, sago starch, and various processed starches are available.

Examples of the modified starch include pregelatinized starch, separated and purified amylose, separated and purified amylopectin, physically modified starch such as heat-moisture treated starch, hydrolyzed dextrin, enzyme-degraded dextrin, enzyme-modified starch such as amylose, and acid-treated starch. , Chemically decomposed modified starch such as hypochlorous acid oxidized starch, dialdehyde starch, etc., esterified starch (acetic acid esterified starch, succinic acid esterified starch,
Nitric acid esterified starch, phosphoric acid esterified starch, urea phosphoric acid esterified starch, xanthogenic acid esterified starch, acetoacetic acid esterified starch, etc., etherified starch (allyl etherified starch, methyl etherified starch, carboxymethyl etherified starch) Starch, hydroxyethyl etherified starch, hydroxypropyl etherified starch, etc.), cationized starch (reaction product of starch and 2-diethylaminoethyl chloride, reaction product of starch and 2,3-epoxypropyltrimethylammonium chloride, etc.), Chemically modified starch such as cross-linked starch (formaldehyde cross-linked starch, epichlorohydrin cross-linked starch, phosphoric acid cross-linked starch, acrolein cross-linked starch, etc.), grafted starch obtained by graft-polymerizing various starches with a monomer (for example, vinyl acetate, propion Acid vinyl Le, t- butyl vinyl ether, (meth) acrylamide, (meth) acrylic acid,
(Meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid ethoxyalkyl ester, (meth) acrylic acid methoxy polyethylene glycol ester, (meth) acrylic acid 2-hydroxy-3-chloropropyl ester , (Meth) acrylic acid dimethylaminoethyl ester, methacrylic acid glycidyl ester, acrylonitrile, styrene, maleic anhydride, itaconic acid and the like. ] Etc. are mentioned. Among these starches, modified starch that is soluble in water is preferable. The starches may be hydrous. Further, these starches can be used alone or in combination of two or more kinds.

A mixed system of a polycarboxylic acid or a partially neutralized product thereof and a saccharide is excellent in compatibility, and a uniform mixed solution can be obtained at an arbitrary mixing ratio, for example, when it is made into an aqueous solution. In order to form a water resistant film from a film of these mixtures, generally, a method of coating an aqueous solution of the mixture on a support by a casting method or the like and forming a film by drying is a dry method having excellent transparency. It is preferable because a film can be easily obtained. In the present invention, a vapor deposition film is used as the support. On the vapor-deposited film, a film composed of a mixture of polycarboxylic acid or its partially neutralized product and saccharide is formed, and then a water-resistant film is formed by heat-treating the film to melt the ordinary thermoplastic resin film. Unlike the case of lamination by extrusion lamination or dry lamination, cracks are not generated in the vapor deposition film, and the flexural fatigue resistance of the obtained composite vapor deposition film is improved.

The mixture of a polycarboxylic acid or a partially neutralized product thereof and a saccharide can be obtained by dissolving each component in water, mixing an aqueous solution of each component, or (meth) acrylic acid or maleic acid in an aqueous saccharide solution. To polymerize (meth) acrylic acid or maleic acid in an aqueous solution of sugar,
It can be prepared by a method of neutralizing with an alkali or the like. The mixture may be prepared using a solvent other than water. The solid content concentration in the solution is usually about 1 to 30% by weight. When preparing an aqueous solution, a solvent other than water, such as alcohol, a softening agent, etc. may be appropriately added, if desired.

The thickness of the water resistant film can be appropriately determined according to the purpose of use and is not particularly limited, but the thickness after drying is usually 0.5 to 100 μm, preferably 1 to 50 μm, more preferably 1 It is about 25 μm. In the moisture-proof composite vapor deposition film of the present invention, an excellent effect can be obtained even if the thickness of the water resistant film layer is about 1 to 15 μm, and further about 1 to 5 μm. From the viewpoint of oxygen gas barrier properties under high humidity conditions, the mixing ratio of the polycarboxylic acid or partially neutralized product thereof and the saccharide is 9 by weight.
It is 5: 5 to 20:80. Outside the range of this mixing ratio, good oxygen gas barrier properties cannot be obtained under high humidity conditions. This mixing ratio is preferably 90:10.
-40: 60, more preferably 85: 15-50: 50
Is.

In order to form a water resistant film having an excellent oxygen gas barrier property from a mixture of polycarboxylic acid or a partially neutralized product thereof and a saccharide, a solution of the mixture is used to form a film, and then a dry film is heat treated. It is necessary to do. The mixture film was subjected to heat treatment at various temperatures and times after film formation. As a result, by heat treating the film having a thickness of 3 μm, the oxygen permeability at a temperature of 30 ° C. and a relative humidity (RH) of 80% was 100 ml (STP). ) / M ² · day · a
It was found that a water-resistant film having a tm {Pa} or less and insoluble in boiling water can be obtained. This oxygen permeability is
Converted to an oxygen permeability coefficient, 1.25 × 10 ^-3 ml (S
TP) · cm / m ² · h · atm {Pa}. Further, this oxygen permeability is the same as or better than the oxygen permeability obtained by heat-treating the PVA simple film.

A dried film prepared from a mixture of polycarboxylic acid or its partially neutralized product and saccharide is heat treated to give 30
The oxygen permeability coefficient measured under the conditions of 80 ° C. and 80% RH is 1.
25 × 10 ^-3 ml (STP) ・ cm / m ²・ h ・ atm
In order to obtain a water resistant film having an oxygen gas barrier property of {Pa} or less, the following heat treatment conditions may be adopted in a dry heat atmosphere. (A) 373 ≦ T ≦ 623 (b) logt ≧ −0.0631 × T + 29.32 [In the formula, T is the heat treatment temperature (K), and t is the heat treatment time (minutes). ]

A dry film prepared from a mixture of polycarboxylic acid or its partially neutralized product and saccharide is heat-treated to obtain an oxygen permeability of 10 ml (STP) / m ^{2 at} a film thickness of 3 μm, 30 ° C. and 80% RH. In order to obtain a water resistant film having an oxygen gas barrier property of not more than day · atm {Pa}, heat treatment may be performed under the condition that the following relational expression (c) is satisfied instead of the above expression (b). However, T is assumed to satisfy the above relational expression (a). (C) logt ≧ −0.0645 × T + 30.71 According to the heat treatment conditions (a) and (c), 30 ° C., 80
Oxygen permeability coefficient measured under conditions of% RH is 1.25 × 1
0 ^-4 ml (STP) · cm / m ² · h · atm {Pa}
The following oxygen gas barrier film is obtained.

A dried film prepared from a mixture of polycarboxylic acid or its partially neutralized product and saccharide is heat-treated to give an oxygen permeability of 1 ml (STP) / m ^{2 at} a film thickness of 3 μm, 30 ° C. and 80% RH. In order to obtain a water resistant film having an oxygen gas barrier property of not more than day · atm {Pa}, heat treatment may be performed under the condition that the following relational expression (d) is satisfied instead of the above expression (b). However, T is assumed to satisfy the above relational expression (a). (D) logt ≧ −0.0659 × T + 32.11 According to the heat treatment conditions (a) and (d), 30 ° C., 80
Oxygen permeability coefficient measured under conditions of% RH is 1.25 × 1
0 ^-5 ml (STP) · cm / m ² · h · atm {Pa}
The following oxygen gas barrier film is obtained.

As the heat treatment means, not only a dry heat atmosphere such as an oven but also a method of contacting with a heat roll or a heat roll group can be adopted. When the dry film is brought into contact with the hot roll, the heat treatment can be efficiently performed in a shorter time, as compared with the case where the dry film is in a dry heat atmosphere. When the heat treatment is performed using a hot roll, according to the results of studies by the present inventors, a dry film formed from a mixture of a polycarboxylic acid or a partially neutralized product thereof and a saccharide is formed by the following relational expression (1) and By heat treatment under the conditions satisfying (2), the oxygen permeability coefficient measured under the conditions of 30 ° C. and 80% RH is 1.25 × 10 ⁻³ ml (STP) · cm / m ^2.
An oxygen gas barrier film having a h · atm {Pa} or less can be obtained. (1) 373 ≦ T ≦ 623 (2) logt ≧ −0.122 × T + 11.3 [where T is the heat treatment temperature (K) and t is the heat treatment time (seconds). ]

The oxygen permeability coefficient measured under the conditions of 30 ° C. and 80% RH is 1.25 × 10 ⁻⁴ ml (STP) · cm /
In order to obtain an oxygen gas barrier film having m ² · h · atm {Pa} or less, heat treatment may be performed under the condition that the following relational expression (3) is satisfied instead of the above relational expression (2). However, T is assumed to satisfy the above relational expression (1). (3) logt ≧ −0.0966 × T + 24.1 has an oxygen permeability coefficient of 1.25 × 10 ⁻⁵ ml (STP) · cm / m ² · h · a measured at 30 ° C. and 80% RH.
In order to obtain an oxygen gas barrier film having a thickness of tm {Pa} or less, the heat treatment may be performed under the condition that the following relational expression (4) is satisfied instead of the relational expression (2). However, T is assumed to satisfy the above relational expression (1). (4) logt ≧ −0.0712 × T + 36.7 Oxygen permeability coefficient [ml (STP) · cm / m ² · h · at
m {Pa}] is the oxygen permeability [ml (STP) / m ² · day · atm {Pa}] at a film thickness of 3 μm.
Can be obtained by multiplying by 1.25 × 10 ⁻⁵ · cm.

In any case, the heat treatment temperature T is 373.
It is performed in the range of K (100 ° C) to 623K (350 ° C).
When the heat treatment temperature is low, a long heat treatment time is required to obtain the desired oxygen gas barrier property, and conversely, when the heat treatment temperature is high, the desired oxygen gas barrier property is obtained by a short heat treatment time. It is possible to obtain a water resistant film having However, if the heat treatment temperature is too high, the film may be discolored or decomposed. The preferred heat treatment temperature is 4
It is 33K (160 degreeC) -523K (250 degreeC).

The lower limit of the heat treatment time is preferably an oxygen permeability coefficient (measured at a temperature of 30 ° C. and 80% RH) of 1.25 × 1.
0 ^-3 ml (STP) · cm / m ² · h · atm {Pa}
The following water-resistant film is obtained, but the upper limit of the heat treatment time is within a range in which discoloration or decomposition of the film does not occur. The heat treatment conditions in a dry heat atmosphere are preferably 160 to 250 ° C., 4 hours to 1 minute, more preferably 180 to 250 ° C., 2 hours to 1 minute, most preferably 200 to 250 ° C., 30 to 1 It's a minute. The heat treatment conditions under contact with a heating body such as a heat roll are preferably 160 to 250 ° C., 180 to 3 seconds, more preferably 180 to 250 ° C., 120 to 3 seconds, and most preferably 200 to 250 ° C. , 60 to 3 seconds.

Under any of the heat treatment conditions, when the heat treatment temperature is low, the heat treatment is performed for a long heat treatment time, and the heat treatment time is shortened as the heat treatment temperature is increased. Then, a desired oxygen gas barrier property and water resistance are achieved, while a treatment time that does not cause discoloration or decomposition of the film at a predetermined heat treatment temperature is adopted. From the viewpoint of productivity, it is desirable to adopt a relatively high heat treatment temperature and a short heat treatment time within the preferable heat treatment conditions.

By carrying out such heat treatment, it is possible to obtain a water resistant film which is a film formed from a mixture of a polycarboxylic acid or a partially neutralized product thereof and a saccharide and which has an excellent oxygen gas barrier property. . Oxygen gas barrier property of this water resistant film is heat treated PVA.
Same as or better than single film. Moreover, the film formed from the mixture can obtain water resistance by heat treatment and becomes insoluble in water and boiling water.

Desiccant- Containing Polymer Composition Layer In the moisture-proof composite vapor-deposited film of the present invention, a composite film having a laminated structure of a polymer film substrate (A) / vapor-deposited film (B) / water-resistant film (C) is used. Further, a layer (D) of the polymer composition containing a desiccant is arranged. The desiccant is not particularly limited, but examples thereof include metal chlorides such as calcium chloride, sodium chloride, and zinc chloride; phosphates such as monosodium phosphate, disodium phosphate, trisodium phosphate, and sodium pyrophosphate; Salts such as calcium sulfate, sodium sulfate, sodium borate, sodium nitrate and potassium carbonate; metal oxides such as calcium oxide and magnesium oxide; other activated alumina, silica gel, bentonite, molecular sieve,
Examples thereof include synthetic crystalline zeolite, synthetic crystalline metal aluminosilicate, and super absorbent resin. These desiccants can be used alone or in combination of two or more kinds. These desiccants are usually used in the form of particles or powder. Further, these desiccants may be treated with a silane coupling agent or the like, if desired.

Examples of the polymer include low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, ethylene / vinyl acetate copolymer, polypropylene, ethylene / propylene copolymer, Ethylene / acrylic acid copolymer, ethylene / acrylic acid salt copolymer, ethylene / ethyl acrylate copolymer, polybutene-1, ethylene /
Polyolefin resins such as butene-1 copolymer, propylene / butene-1 copolymer, ethylene / propylene / butene-1 copolymer and ionomer; nylon 6.66
Polyamide resins such as copolymers, nylon 6/12 copolymers, nylon 6, nylon 66; styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, polybutadiene, polyisoprene, polyisobutylene , Styrene-butadiene copolymer rubber and other elastomers; saturated polyester resin, polystyrene resin, polyvinyl chloride resin, acrylic resin, polyvinylidene chloride resin, polyurethane resin, polycarbonate resin, polyacetal resin, etc. Can be mentioned. These polymers may be used alone or in combination of two or more as needed. Among these polymers, a polyolefin resin and a nylon copolymer are particularly preferable because they have heat sealability.

The mixing ratio of the desiccant varies depending on the kind of the desiccant, the kind of the polymer, the required performance and the like, but is usually 3 to 100 relative to 100 parts by weight of the polymer.
Parts by weight, preferably 5 to 60 parts by weight, more preferably 8
~ 30 parts by weight. The layer (D) of the polymer composition containing a desiccant is an essential layer having a laminated structure of a polymer film substrate (A) / vapor-deposited film (B) / water resistant film (C) after being melt-extruded to form a film. It is laminated by a method such as laminating with a composite film having the constitution or directly melt-extruding on the composite film. The thickness of the layer (D) of the polymer composition containing a desiccant can be appropriately determined as desired. In applications such as packaging materials, it is usually 10 to 1000 μm, preferably 30 to 500 μm.
m, more preferably 50 to 200 μm. For applications such as sealing members, a large amount of desiccant can be blended to form a relatively thick layer up to several mm.

Moisture-Proof Composite Vapor Deposition Film The moisture-proof composite vapor deposition film of the present invention has a laminated structure of a polymer film substrate (A) / vapor deposition film (B) / water resistant film (C) as an essential layer structure, and further, By arranging the layer (D) of the polymer composition containing a desiccant, both high gas barrier property and high moisture resistance are achieved. The moisture-proof composite vapor deposition film of the present invention has a laminated structure of a polymer film substrate (A) / vapor deposition film (B) / water resistant film (C) as an essential layer structure. It is necessary that the vapor deposition film of the inorganic material and the layer of the water resistant film are adjacent to each other. When the vapor-deposited film and the water-resistant film layer are not provided adjacent to each other, it is not possible to obtain a synergistic improvement effect on gas barrier properties and an improvement effect on bending fatigue resistance. .

To produce the moisture-proof composite vapor deposition film of the present invention, first, an inorganic material vapor deposition source is used to form a vapor deposition film (B) of an inorganic material on at least one surface of a polymer film substrate (A). Next, a mixed solution of polycarboxylic acid or a partially neutralized product thereof and a saccharide is applied onto the vapor-deposited film (B) of the obtained vapor-deposited film and dried to form a film. Then, the dry film is heat-treated at a temperature of 100 ° C. (373 K) or higher to form a water resistant film (C) having excellent oxygen gas barrier properties.

To apply a mixture solution of a polycarboxylic acid or a partially neutralized product thereof and a saccharide onto a vapor-deposited film, the mixture solution may be applied, for example, with an air knife coater, a kiss roll coater, a metering bar coater, a gravure roll coater. , Reverse roll coater, dip coater, die coater, or the like, or using a combination thereof, on the vapor deposition film of the vapor deposition film, coating to a desired thickness, then arch dryer, straight bath dryer, A device such as a tower drier or a drum drier or a device in which these are combined is used to evaporate and dry water by blowing hot air or irradiating infrared rays to form a film. Then, the film is heat-treated.

The moisture-proof composite vapor-deposited film of the present invention has a laminated structure of a polymer film substrate (A) / vapor-deposited film (B) / water-resistant film (C) as an essential layer structure, and further,
A layer (D) of a polymer composition containing a desiccant is arranged on at least one side of the laminated structure. For example,
The composite film having a laminated structure of the polymer film substrate (A) / vapor-deposited film (B) / water resistant film (C) is preferably a polymer composition containing a desiccant on the water resistant film (C) side. Place the object layer (D).

Further, in order to enhance the gas barrier property, for example, a polymer film substrate (A) / vapor deposited film (B) / water resistant film (C) / polymer film substrate (A) / water resistant film ( For a composite film having a laminated structure of (C) / vapor-deposited film (B) / polymer film substrate (A), a desiccant is contained on one side of the polymer film substrate (A). It is preferred to arrange the layer (D) of the polymer composition. Of course, the above laminated structure is merely an example, and if desired, a composite film containing three or more laminated structures of a polymer film substrate (A) / a vapor deposition film (B) / a water resistant film (C). The layer (D) of the polymer composition which has been formed and contains a desiccant can be disposed on at least one side thereof. In some cases, a layer of thermoplastic resin can be provided outside the layer (D) of the polymer composition containing the desiccant.

The layer (D) of the polymer composition containing the desiccant comprises a polymer film substrate (A) / a vapor deposition film (B) /
The composite film having the laminated structure of the water resistant film (C) is heat-sealed or laminated with an adhesive. In particular, a method of dry laminating with an adhesive is preferable. Examples of the adhesive include various adhesives such as urethane-based, acrylic-based and polyester-based adhesives which are generally used for dry laminating various films. If desired, various additives such as an antioxidant, a lubricant, an ultraviolet absorber, a pigment, a filler and an antistatic agent can be added to each layer of the moisture-proof composite film of the present invention.

[0054]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Example 1] As a saccharide, soluble starch manufactured by Wako Pure Chemical Industries, Ltd. (potato starch was hydrolyzed by acid to be water-soluble) was used, and polycarboxylic acid was produced by Wako Pure Chemical Industries ( A 25 wt% aqueous solution of polyacrylic acid (PAA; number average molecular weight 150,000) manufactured by K.K. was used. A PAA partially neutralized product having a neutralization degree of 10% was prepared by adding a calculated amount of sodium hydroxide to the PAA aqueous solution. Next, starch: PAA partially neutralized product = 30: 70
An aqueous solution (concentration: 10% by weight) containing a mixture (weight ratio) was prepared.

As aluminum vapor-deposited film, thickness 1
A film in which a vapor deposition film of aluminum (Al) having a thickness of 80 nm was formed on a 2 μm polyethylene terephthalate (PET; crystal melting point = 250 ° C.) film was used. The above aqueous solution was applied on the vapor-deposited film of this Al vapor-deposited film using a reverse coater method using a multi coater-200L (improved type) manufactured by Hirano Techseed Co., Ltd., and further dried to obtain a dry film having a thickness of 2 μm. Was formed. By contacting the vapor deposition film on which this dry film is formed with a hot roll having a surface temperature of 230 ° C. for 37 seconds,
Heat treatment was performed (Film 1). The film obtained after the heat treatment was insoluble in water. In addition, the film is boiled with water (95
However, it was insoluble. Therefore, it was confirmed that the water resistant film was formed.

Film 1 : PET / Al vapor-deposited layer / coat layer (water resistant film) Calcium chloride (CaCl ₂ ) manufactured by Wako Pure Chemical Industries, Ltd. was used as a desiccant, and after pulverization, it was heated in an oven at 150 ° C.
It was dried for 2 hours. Next, this CaCl ₂ and polypropylene (Ace Polypro E401 manufactured by Tonen Chemical Co., Ltd.)
ET: PP) pellets and CaCl ₂ : PP = 10:
Dry blending was performed so as to be 90 (weight ratio). A film having a thickness of 100 μm was molded from the thus obtained desiccant-containing PP using an extruder, a T-die, and a cooling winding device (film 2).

Film 2 : Calcium chloride-containing PP film Further, Multicoater 20 manufactured by Hirano Techseed Co., Ltd.
0L (improved type) is used to form the film 1 and the film 2
On the water resistant film (coat layer) side of the film 1,
Dry lamination was performed via an adhesive to obtain a film having the following constitution. As the adhesive, a mixture of adhesives AD590 and CAT56 manufactured by Toyo Morton Co., Ltd. was used. The thickness of the adhesive was 3 μm. In the following examples and comparative examples, the same adhesive was used with the same thickness, unless otherwise specified. PET / Al vapor-deposited layer / coat layer // CaCl ₂ -containing PP Note that // here means an adhesive layer. The water vapor permeability of the obtained laminated film was evaluated by the method described below.

Example 2 The film 1 prepared in Example 1 was applied to both sides of a PET film having a thickness of 12 μm by using a multi coater 200L (improved type) manufactured by Hirano Techseed Co., Ltd. The layers were sequentially dry-laminated with an adhesive to obtain a film having the following constitution (Film 3). Film 3 : PET / Al vapor deposition layer / coat layer // PET
// Coat layer / Al vapor-deposited layer / PET This film 3 and the film 2 of Example 1 were further dried on the PET / PP surface with an adhesive using a multi coater 200L (improved type) manufactured by Hirano Techseed Co., Ltd. Lamination was performed to obtain a film having the following constitution. PET / Al vapor-deposited layer / coat layer // PET // coat layer / Al vapor-deposited layer / PET // CaCl ₂ -containing PP The water vapor permeability of the obtained laminated film was evaluated.

[Comparative Example 1] Polypropylene (Ace Polypro E401ET) manufactured by Tonen Kagaku KK was pelletized using an extruder, a T-die, and a cooling winding device to obtain a thickness of 100 μm.
m PP monolayer film was molded (Film 4). Film 4 : PP single-layer film This film 4 and film 1 were processed in the same manner as in Example 1 by Hiranotecseed Co., Ltd. Multi Coater 200L (improved type).
Using the above, the water-resistant film (coat layer) side of the film 1 was dry-laminated with an adhesive to obtain a film having the following constitution. PET / Al vapor-deposited layer / coat layer // PP The water vapor permeability of the obtained film was evaluated.

Comparative Example 2 A vapor deposition film (film 5) was prepared by forming a vapor deposition film of aluminum having a thickness of 80 nm on a PET film having a thickness of 12 μm. Film 5 : PET / Al vapor deposition layer The film 5 and the film 2 were dry-laminated on the surface of the Al vapor deposition layer of the film 5 via an adhesive to obtain a film having the following constitution. PET / Al vapor deposition layer // CaCl ₂ -containing PP The water vapor permeability of the obtained film was evaluated.

Comparative Example 3 Biaxially stretched nylon 6 (crystal melting point = 225 ° C.) film (emblem: thickness 25 μm) manufactured by Unitika Ltd. is used and dry laminated with the film 2 of Example 1 via an adhesive. As a result, a film having the following constitution was created. Nylon 6 // CaCl ₂ -containing PP The water vapor permeability of the obtained film was evaluated.

[Example 3] Silica gel (silica gel medium particles) manufactured by Wako Pure Chemical Industries, Ltd. was used as a desiccant. Silica gel was used after being pulverized and dried in an oven at 150 ° C. for 2 hours. This silica gel and polypropylene manufactured by Tonen Chemical Co., Ltd. (Ace Polypro E401E
The pellets of T) were dry blended with silica gel: PP = 10: 90 (weight ratio). A film having a thickness of 100 μm was formed from the thus obtained desiccant-containing PP using an extruder, a T-die and a cooling winding device (film 6). Film 6 : Silica gel-containing PP film Next, using Film 1 and Film 6 using a multi coater 200L (improved type) manufactured by Hirano Techseed Co., Ltd.,
The water-resistant film (coat layer) side of the film 1 was dry-laminated via an adhesive to obtain a film having the following constitution. PET / Al vapor-deposited layer / coat layer // silica gel containing PP The water vapor permeability of the obtained film was evaluated.

[Example 4] The film 3 of Example 2 and the film 6 of Example 3 were dried with an adhesive on the PET / PP side using a multicoater 200L (improved type) manufactured by Hirano Techseed Co., Ltd. After laminating, a film having the following constitution was obtained. PET / Al vapor deposition layer / coat layer // PET // coat layer / Al vapor deposition layer / PET // silica gel-containing PP The water vapor permeability of the obtained laminated film was evaluated.

[Comparative Example 4] The film 5 of Comparative Example 2 and the film 6 of Example 3 were mixed with Al of Film 5 by using a multi coater 200L (improved type) manufactured by Hirano Techseed Co., Ltd.
On the surface of the vapor deposition layer, dry laminate with an adhesive,
A film having the following constitution was obtained. PET / Al vapor deposition layer // PP containing silica gel The water vapor permeability of the obtained film was evaluated.

[Comparative Example 5] A biaxially stretched nylon 6 film (emblem: thickness 25 µm) manufactured by Unitika Ltd. was used, and the film 6 of Example 3 and Multicoater 200L (improved type) manufactured by Hirano Techseed Co., Ltd. were used. Then, it was dry laminated through an adhesive to obtain a film having the following constitution. Nylon 6 // PP containing silica gel The water vapor permeability of the obtained film was evaluated.

[Example 5] As the saccharide, soluble starch (made by hydrolyzing potato starch with acid to make it water-soluble) manufactured by Wako Pure Chemical Industries, Ltd. was used, while Wako Pure Chemical was used as polycarboxylic acid. PAA manufactured by Kogyo Co., Ltd. (number average molecular weight 1
50,000) 25% by weight aqueous solution was used. A PAA partially neutralized product having a neutralization degree of 10% was prepared by adding a calculated amount of sodium hydroxide to the PAA aqueous solution. Then, an aqueous solution (concentration: 10% by weight) containing a mixture of starch: PAA partially neutralized product = 30: 70 (weight ratio) was prepared.

As a silicon oxide vapor-deposited film, a silicon oxide (SiO _x ) vapor-deposited PET film (thickness PET 12 μm, SiO _x vapor-deposited film 80 nm: MO manufactured by Oike Industry Co., Ltd.) was used.
S-TH) was used. On the vapor-deposited film of this silicon oxide vapor-deposited film, the above aqueous solution was applied by a reverse roll coating method using Multicoater-200L (improved type) manufactured by Hirano Techseed Co., Ltd., and further dried,
A dry film having a thickness of 2 μm was formed. The vapor-deposited film on which this dry film was formed was brought into contact with a hot roll having a surface temperature of 230 ° C. for 37 seconds to perform heat treatment (film 7). The film obtained after the heat treatment was insoluble in cold water. Further, the film was immersed in boiling water (95 ° C.) for 10 minutes, but it was insoluble. Therefore, it was confirmed that the water resistant film was formed.

Film 7 : PET / SiO _x vapor-deposition layer / coat layer (water-resistant film) The films 7 and 2 were replaced by Hirano Techseed Co., Ltd.
Using a multi coater 200L (improved type) manufactured by Dry Co., Ltd., the surface of the water resistant film (coat layer) of the film 7 was dry laminated through an adhesive to obtain a film having the following constitution. PET / SiO _x deposition layer / coat layer // CaCl ₂ -containing P
P The water vapor permeability of the obtained laminated film was evaluated.

Example 6 The film 7 of Example 5 was applied to both sides of a PET film having a thickness of 12 μm using a multi coater 200L (improved type) manufactured by Hirano Techseed Co., Ltd.
The coat layer surface of the film 7 was sequentially dry laminated via an adhesive to obtain a film having the following constitution (film 8). Film 8 : PET / SiO _x vapor deposition layer / coat layer // P
ET // coat layer / SiO _x vapor deposition layer / PET This film 8 and the film 2 of Example 1 were mixed with PET / P
Dry lamination was performed on the P surface via an adhesive to obtain a film having the following constitution. PET / SiO _x vapor deposition layer / coat layer // PET // coat layer / SiO _x vapor deposition layer / PET // CaCl ₂ -containing PP The water vapor permeability of the obtained laminated film was evaluated.

[Comparative Example 6] The film 4 and the film 7 of Comparative Example 1 were prepared by Multicoater 20 manufactured by Hirano Techseed Co., Ltd.
Using 0 L (improved type), the surface of the water resistant film (coat layer) of the film 7 was dry laminated with an adhesive to obtain a film having the following constitution. PET / SiO _x vapor deposition layer / coat layer // PP The water vapor permeability of the obtained film was evaluated.

[Comparative Example 7] Silicon oxide (SiO _x ) vapor-deposited PET film (MOS-TH) manufactured by Oike Kogyo Co., Ltd. and Film 2 were used by using a multi coater 200L (improved type) manufactured by Hirano Techseed Co., Ltd. The film having the following constitution was obtained by dry-laminating with a silicon oxide vapor deposition surface via an adhesive. PET / SiO _x vapor deposition layer // CaCl ₂ -containing PP The water vapor permeability of the obtained film was evaluated.

<Evaluation Method of Water Vapor Permeability> Regarding the evaluation of water vapor permeability, for each sample prepared in each Example and Comparative Example, the inside of the pouch prepared by using the PP layer as a sealant was replaced with dry air and sealed. After that, when the temperature was kept at constant temperature and humidity, the change in relative humidity inside was checked and the temperature was 40 ° C.
, The relative humidity inside the pouch is 50 at atmospheric pressure.
The time required to reach% RH was used as an index of water vapor permeability.

Preparation of Pouch The composite film is cut into a rectangle of 30 cm × 13 cm. Two of these rectangles are overlapped so that the PP faces are aligned. One side is left and three sides are sealed using a high frequency sealer, and the remaining one side is sealed while degassing the inside. At that time, the injection needle is sandwiched so as to traverse the sealing surface, and one end of the injection needle protruding to the outside of the pouch is closed so as not to leak during deaeration. The inside of the sealed portion thus sealed is formed into a rectangle of 21 cm × 10 cm. Using a gas tight syringe, 50 cm ³ of dry air is introduced into the pouch at room temperature under 1 atm.
After that, quickly remove the injection needle and re-seal inside the sealing surface that sandwiched the injection needle. Finally, the inside of the seal part is a rectangle of 20 cm × 10 cm, and the inside of it is dried at 50 cm ³ at room temperature under 1 atmosphere. Create a pouch containing air.
In this way, a large number of pouches were prepared using each composite film sample, and used for evaluation of water vapor permeability.

Measurement of Relative Humidity in Pouch The above pouch was placed in a thermo-hygrostat at a temperature of 40 ° C. and a relative humidity of 9
Hold under conditions of 0% RH. After a certain period of time, a certain amount of gas inside the pouch is taken out using a gas tight syringe, and the amount of water in a certain volume of air, that is, absolute humidity is obtained by using gas chromatography. The relative humidity at 40 ° C. is calculated from the absolute humidity value using the following formula. The measurement was performed using one pouch for each measurement. e / mmHg = 0.945 {1 + 0.00367 (t /
℃)} ・ (f / gm ^-3 ) e: Vapor pressure of water f: Absolute humidity 40 ℃, saturated vapor pressure under atmospheric pressure is 55.33m
Since it is mHg, the relative humidity at 40 ° C. can be obtained from the following equation. RH (%) = 1.959 × f The relative humidity inside the pouch thus obtained is 50% at 40 ° C.
The time (days) required to reach RH was used as an index of water vapor permeability. Water vapor pressure at 40 ° C and 50% RH is 2
It is 7.67 mmHg, and if the water content corresponding to this value exists under atmospheric pressure, the dew point becomes about 27 ° C. Therefore, when sampling the gas in the pouch, it is necessary to warm the gas tight syringe to prevent condensation.

[0076]

[Table 1]

<Oxygen Gas Permeability and Water Vapor Permeability of Each Film> Table 2 shows the measurement results of the oxygen gas permeability and water vapor permeability of each film used in the above-mentioned Examples and Comparative Examples. Measurement of oxygen gas permeability According to ASTM D-3985, Modern Co
oxygen permeation tester OX-TRAN 2 /
It was measured using a 20-type under the conditions of 30 ° C. and 80% RH. Measurement of water vapor transmission rate According to JIS Z-0280, it was measured under the conditions of 40 ° C and 90% RH.

[0078]

[Table 2]

[0079]

EFFECTS OF THE INVENTION According to the present invention, there is provided a moisture-proof composite film having excellent gas barrier properties against oxygen, water vapor, helium, etc. and having a high degree of moisture-proof property. INDUSTRIAL APPLICABILITY The moisture-proof composite film of the present invention is particularly useful in fields such as packaging materials and seal members, which are required to have a high degree of moisture-proof property as well as gas barrier properties.

Claims (10)

[Claims] 1. A vapor deposition film (B) of an inorganic material is formed on at least one surface of a polymer film substrate (A), and further,
A water resistant film (C) formed from a mixture containing a polycarboxylic acid or a partially neutralized product thereof and a saccharide in a ratio of 95: 5 to 20:80 (weight ratio) on the deposited film (B). A composite film containing at least one laminated structure in which is laminated, wherein a layer (D) of a polymer composition containing a desiccant on at least one side of the laminated structure.
Moisture-proof composite vapor deposition film, characterized in that 2. The moisture-proof composite vapor deposition film according to claim 1, wherein the polymer film substrate (A) is a heat-resistant film made of a resin having a crystal melting point or a Vicat softening point of 180 ° C. or higher. 3. The vapor-deposited film (B) is made of aluminum (A
l), aluminum oxide (Al ₂ O ₃ ), silicon oxide (SiO _x , x = 1 to 2), or silicon oxynitride (Si)
_{O x N y, x = 0.6~0.8} , y = 0.7~0.9) is one formed by depositing claim 1 or 2 moistureproof composite deposited film according. 4. The water resistant film (C) is a vapor deposition film (B).
It is formed by applying a solution of a mixture containing polycarboxylic acid or a partially neutralized product thereof and a saccharide onto the above to form a dry film, and then heat-treating at a temperature of 100 ° C. (373 K) or more. The moisture-proof composite vapor deposition film according to any one of claims 1 to 3, which is a film insoluble in water and boiling water. 5. The water resistant film (C) has an oxygen permeability coefficient (measured at a temperature of 30 ° C. and a relative humidity of 80%) of 1.25 × 10.
The moisture-proof composite vapor deposition film according to any one of claims 1 to 4, which has a volume of ^-3 ml (STP) · cm / m ² · h · atm {Pa} or less. 6. The polycarboxylic acid is polyacrylic acid, polymethacrylic acid, an acrylic acid-methacrylic acid copolymer,
Polymaleic acid, or a mixture of two or more thereof, wherein the partially neutralized polycarboxylic acid has a degree of neutralization of the carboxyl groups of these polycarboxylic acids with an alkali of 20%.
6. A partially neutralized product according to the following ratios.
The moisture-proof composite vapor deposition film according to any one of 1. 7. The moisture-proof composite vapor deposition film according to claim 1, wherein the saccharide is at least one selected from the group consisting of monosaccharides, sugar alcohols, oligosaccharides, and polysaccharides. 8. The moisture-proof composite according to claim 1, wherein the layer (D) of the polymer composition containing a desiccant is a layer formed from a polyolefin resin containing a desiccant. Evaporated film. 9. A laminate structure comprising a polymer film substrate (A) / vapor-deposited film (B) / water resistant film (C) / layer (D) of a polymer composition containing a desiccant. 9. The moisture-proof composite vapor deposition film according to any one of 8 above. 10. A polymer film substrate (A) / vapor deposited film (B) / water resistant film (C) / polymer film substrate (A) / water resistant film (C) / vapor deposited film (B) / high 9. A laminated structure comprising a molecular film substrate (A) / a layer (D) of a polymer composition containing a desiccant.
The moisture-proof composite vapor deposition film according to any one of 1.