JP2002047442A - Gas-barrier coating composition, its manufacturing method and gas-barrier coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a gas-barrier coating composition which is free from the deterioration of barrier properties to gases such as oxygen and a water vapor even under high-humidity conditions and is harmless to the human body, and a coating film made by using the composition and excellent in gas barrier properties. SOLUTION: The gas-barrier coating composition contains (a) a polyvinyl alcohol resin, (b) at least one compound selected from the group consisting of metal alcoholates represented by the formula: R1mM(OR2)n (wherein M is a metal atom; R1's may be the same or different and are each a 1-8C organic group; R2's may be the same or different and are each a 1-5C alkyl, a 1-6C acyl, or phenyl; and (m) and (n) are each an integer of 0 or greater, provided that m+n is the valence of M), hydrolyzates of the metal alcoholates, condensates of the metal alcoholates, chelate compounds of the metal alcoholates, hydrolyzates of the metal chelate compounds, condensates of the metal chelate compounds, metal acylates, hydrolyzates of the metal acylates, and condensates of the metal acylates, and (c) a boron compound. A gas-barrier coating film is prepared by using the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is used in packaging applications such as pharmaceuticals, foods, cosmetics, cigarettes, and toiletries, and is effective in preventing the permeation of oxygen, water vapor, and other gases that alter the contents. The present invention relates to a novel gas barrier coating composition and a coating film having excellent gas barrier properties using the same.

[0002]

2. Description of the Related Art In recent years, packaging materials used for packaging applications in the fields of pharmaceuticals, foods, cosmetics, tobacco, toiletries, etc., for foods, for example, prevent deterioration of contents such as oxidation of proteins and fats and oils. To maintain the quality of taste, etc.
A material having a gas barrier property that does not allow oxygen, water vapor, and other gas that alters contents to pass therethrough is used.
In response to such a conventional problem, see, for example,
No. 66485 discloses a mixed solution of one or more metal alkoxides or hydrolysates thereof and an isocyanate compound having at least two or more isocyanate groups in a molecule on a substrate made of a polymer resin composition. There has been proposed a gas barrier material in which a gas barrier material layer formed by applying a coating agent as a main agent and drying by heating is formed. However, this gas barrier material contains an isocyanate compound having an isocyanate group, melamine, formaldehyde, tin chloride and the like. There is a problem that it is. On the other hand, Japanese Patent No. 1,476,209 proposes a coating material that does not contain isocyanate or the like and is made of polyvinyl alcohol having low harm. However, when used in food retort packaging, etc., retort treatment is performed under high-temperature and high-humidity conditions of 120 ° C. or higher, so that oxygen barrier properties under high humidity are required. The gas barrier property of a coating material made of polyvinyl alcohol is significantly affected by humidity, and there is a problem that the gas barrier property is greatly reduced under high humidity.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional technical problems, and does not reduce the barrier property against gases such as oxygen and water vapor even under humid conditions. A gas barrier coating composition containing no isocyanate compound, melamine, formaldehyde, organotin and other compounds that are harmful to the human body, and harmless to the human body and excellent in storage stability, and gas barrier properties using the same An object of the present invention is to provide an excellent coating film.

[0004]

The present invention relates to (a) a polyvinyl alcohol-based resin (hereinafter also referred to as "component (a)"), (b) a general formula (1) (where M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different,
An alkyl group of 1 to 5 or an acyl group or phenyl group of 1 to 6 carbon atoms, m and n are each an integer of 0 or more, and m + n is a valence of M. Hydrolyzate of the metal alcoholate, condensate of the metal alcoholate, chelate compound of the metal alcoholate, hydrolyzate of the metal chelate compound, condensate of the metal chelate compound, metal acylate, hydrolysis of the metal acylate A gas barrier coating composition comprising: a decomposition product; and at least one selected from the group consisting of a condensate of the metal acylate (hereinafter also referred to as “component (b)”) and (c) a boron compound. (Hereinafter also referred to as “coating composition”). Here, as the (a) polyvinyl alcohol-based resin, at least one selected from the group consisting of polyvinyl alcohol and an ethylene / vinyl alcohol copolymer is exemplified. Further, when the coating composition of the present invention contains (d) a nitrogen-containing organic compound (hereinafter also referred to as “component (d)”) as needed, the gas barrier properties may be further improved. Further, the coating composition of the present invention comprises
If necessary, when (e) inorganic fine particles (hereinafter also referred to as “component (e)”) are further contained, the gas barrier properties may be further improved. Next, the present invention provides the coating composition, wherein the component (b) is hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent, and then mixed with the component (a). It relates to a manufacturing method. next,
The present invention relates to a gas barrier coating film, wherein a coating film formed from the above coating composition is laminated on a base resin film. Also,
The present invention relates to a gas barrier coating film comprising a substrate resin film, a metal and / or inorganic compound vapor-deposited film provided thereon, and a cured coating film formed from the above-mentioned coating composition laminated thereon. .
As the deposited film, a deposited film of an inorganic oxide formed by a chemical vapor deposition method and / or a physical vapor deposition method is preferable.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The coating composition (a) component; the polyvinyl alcohol resin used as the component (a) used in the present invention is selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymer. At least one kind is mentioned. Among the above components (a), polyvinyl alcohol is generally obtained by saponifying polyvinyl acetate. The polyvinyl alcohol may be a partially saponified polyvinyl alcohol in which acetic acid groups remain in several tens%, a completely saponified polyvinyl alcohol in which no acetic acid groups remain, or a modified polyvinyl alcohol in which an OH group is modified. It is not limited. Specific examples of the polyvinyl alcohol include RS-110, a RS polymer manufactured by Kuraray Co., Ltd. (degree of saponification = 99%, degree of polymerization =
1,000), Kuraray Poval LM-20SO manufactured by the company
(Degree of saponification = 40%, degree of polymerization = 2,000), and Gohsenol NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, degree of polymerization = 1,400). In addition, among the component (a), the ethylene / vinyl alcohol copolymer is a saponified product of a copolymer of ethylene and vinyl acetate, that is, a copolymer obtained by saponifying an ethylene-vinyl acetate random copolymer. , Acetic acid group is several tens mol%
From the remaining partially saponified substances, only a few mol% of acetic acid groups remain or completely saponified substances in which acetic acid groups do not remain, and are not particularly limited, but are preferably saponified from the viewpoint of gas barrier properties. The degree is at least 80 mol%, more preferably at least 90 mol%, further preferably at least 95 mol%. The content of the repeating unit derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Specific examples of the ethylene / vinyl alcohol copolymer include EVAL EP-F101 (ethylene content; 32 mol%) manufactured by Kuraray Co., Ltd., and Soarnol D290 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
8, D2935 (ethylene content; 29 mol%), D26
30 (ethylene content 26%), A3245 (ethylene content 3
2%).

The melt flow index of the above-mentioned (a) polyvinyl alcohol resin is 210 ° C., load 21.
Under 168N conditions, 1 to 50 g / 10 min, preferably 5
４５45 g / 10 min. If the melt flow index is less than 1 g / 10 minutes, the gas barrier properties may be significantly reduced. On the other hand, if it exceeds 50 g / 10 minutes, the solvent resistance may decrease, which is not preferable. These (a) polyvinyl alcohol-based resins can be used alone or in combination of two or more.

The polyvinyl alcohol resin constituting the component (a) itself has excellent gas barrier properties, weather resistance, organic solvent resistance, transparency, gas barrier properties after heat treatment, and the like. In addition, when the (a) polyvinyl alcohol-based resin cures a coating film obtained from the composition of the present invention, a hydroxyl group present in a repeating unit derived from polyvinyl alcohol has a component (b) described below, ) Components, metals and / or
Alternatively, by co-condensing with at least one selected from a vapor-deposited film of an inorganic compound, it is possible to obtain a coating film having excellent coating properties, particularly excellent gas barrier properties under high humidity and / or after heat treatment.

The proportion of the component (a) in the coating composition of the present invention is 10 to 10,000 parts by weight, preferably 20 to 5,5 parts by weight, based on 100 parts by weight of the component (b) before hydrolysis and / or condensation. 000 parts by weight, more preferably 100 to 1,000 parts by weight. If the amount is less than 10 parts by weight, cracks tend to occur in the obtained coating film, and the gas barrier property is lowered. May decrease.

Component (b): Component (b) used in the present invention is a metal alcoholate, a hydrolyzate of the metal alcoholate, or a condensate of the metal alcoholate represented by the general formula (1). A chelate compound of the metal alcoholate (hereinafter also referred to as a “metal chelate compound”), a hydrolyzate of the metal chelate compound, a condensate of the metal chelate compound, a metal acylate, a hydrolyzate of the metal acylate,
And at least one selected from the group of condensates of the metal acylate. That is, the component (b)
Only one of the species may be used, or a mixture of any two or more species may be used. Further, the metal chelate compound is a metal alcoholate and at least one compound selected from β-diketones, β-ketoesters, hydroxycarboxylic acids, hydroxycarboxylates, hydroxycarboxylates, keto alcohols and amino alcohols (Hereinafter also referred to as "chelating agent"). Among these chelating agents, it is preferable to use β-diketones or β-ketoesters,
Specific examples of these include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, and t-acetoacetate. Butyl, 2,4-hexane-dione, 2,4-heptane-
Examples thereof include dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione, and 5-methyl-hexane-dione. Here, the hydrolyzate of the metal alcoholate, a hydrolyzate of the metal chelate compound, and hydrolyzate of the metal acylate is not necessarily OR ² group is all hydrolysed contained in the metal alcoholate For example, one in which only one is hydrolyzed, one in which two or more are hydrolyzed, or a mixture thereof may be used. The condensate of the metal alcoholate, the condensate of the metal chelate compound, and the condensate of the metal acylate are formed by condensing the metal alcoholate, the metal chelate compound, and the M-OH group of the hydrolyzate of the metal acylate. However, in the present invention, it is not necessary that all M-OH groups are condensed, and only a small part of M-OH
It is a concept that includes those in which groups are condensed, those having different degrees of condensation, and mixtures of condensates in which M-OR groups and M-OH groups are mixed. When a condensate is used as the component (b), the above-mentioned metal alcoholate,
The metal chelate compound and the metal acylate which have been hydrolyzed and condensed in advance may be used, or a commercially available condensate may be used. Further, a condensate of a metal alcoholate may be used as it is, or may be reacted with the above chelating agent and used as a condensate of a metal chelate compound. Commercially available condensates of the above metal alcoholates include A-1 manufactured by Nippon Soda Co., Ltd.
0, B-2, B-4, B-7, B-10 and the like.
The component (b) comprises the component (a), the component (d), a metal and / or
Alternatively, it is considered that the compound acts to form a co-condensate with at least one selected from the components of a vapor-deposited film made of an inorganic compound.

As the metal atom represented by M in the general formula (1), zirconium, titanium and aluminum can be mentioned as preferred, and titanium is particularly preferred. The monovalent organic group having 1 to 8 carbon atoms of R ¹ differs depending on whether the compound represented by the general formula (1) is a metal alcoholate or a metal acylate. When it is a metal alcoholate, for example, methyl, ethyl, n-propyl, i-propyl, n-
Alkyl groups such as butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group; acetyl group, propionyl group and butyryl group , Valeryl group, benzoyl group, acyl group such as trioil group; vinyl group, allyl group, cyclohexyl group, phenyl group, glycidyl group,
In addition to (meth) acryloxy, ureido, amide, fluoracetamide, and isocyanate groups,
Substituted derivatives of these groups can be mentioned. R
Examples of the substituent in the substituted derivative ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group,
-An epoxycyclohexyl group, a (meth) acryloxy group, a ureido group, an ammonium base and the like. However, the carbon number of R ¹ composed of these substituted derivatives is 8 or less including the carbon atom in the substituent. In the case of metal acylate, R ¹ has 1 to ¹ carbon atoms.
As the monovalent organic group of 8, an acetoxyl group, a propionyloxyl group, a butyryloxyl group, a valeryloxyl group,
An acyloxyl group such as a benzoyloxyl group and a trioyloxyl group can be exemplified. When two R ¹ are present in the general formula (1), they may be the same or different from each other.

Examples of the alkyl group having 1 to 5 carbon atoms for R ² include a methyl group, an ethyl group, an n-propyl group,
i-propyl group, n-butyl group, sec-butyl group, t
-Butyl group, n-pentyl group and the like,
Examples of the acyl group having 1 to 6 carbon atoms include an acetyl group,
Examples include a propionyl group, a butyryl group, a valeryl group, and a caproyl group. A plurality of R ² in the general formula (1) may be mutually the same or different.

Specific examples of the metal alcoholate and the chelate compound of the metal alcoholate among the components (b) include (a) tetra-n-butoxyzirconium,
Zirconium tri-n-butoxyethylacetoacetate, zirconium di-n-butoxybis (ethylacetoacetate), zirconium zirconium n-butoxytris (ethylacetoacetate), zirconium tetrakis (n-propylacetoacetate), tetrakis (acetyl) Zirconium compounds such as acetoacetate) zirconium and tetrakis (ethylacetoacetate) zirconium;

(B) Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetra-t-butoxytitanium, di-i-propoxybis (ethylacetoacetate) titanium, di-i-propoxy.
Bis (acetylacetate) titanium, di-i-propoxybis (acetylacetonato) titanium, di-n-butoxybis (triethanolaminate) titanium, dihydroxybislactatetitanium, dihydroxytitanium lactate, tetrakis (2 −
Titanium compounds such as ethylhexyloxy) titanium;

(C) Aluminum tri-i-propoxy, aluminum di-i-propoxy ethyl acetoacetate, aluminum di-i-propoxy acetylacetonate, aluminum i-propoxy bis (ethyl acetoacetate), i-propoxy Aluminum compounds such as bis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, and monoacetylacetonate bis (ethylacetoacetate) aluminum; Among these metal alcoholates and chelate compounds of metal alcoholates, preferred are tri-n-butoxyethylacetoacetate zirconium, di-i-propoxybis (acetylacetonato) titanium, di-n-butoxy. Bis (triethanolaminato) titanium, dihydroxybislactatetitanium, di-i-propoxyethylacetoacetate aluminum and tris (ethylacetoacetate) aluminum can be mentioned, and particularly preferred compounds are di-i-propoxy. And titanium compounds such as bis (acetylacetonato) titanium, di-n-butoxybis (triethanolaminate) titanium, and dihydroxybislactatetotitanium.

Further, specific examples of the metal acylate include:
Dihydroxy titanium dibutyrate, di-i-propoxy titanium diacetate, di-i-propoxy titanium dipropionate, di-i-propoxy titanium dimallonate, di-i-propoxy titanium dibenzoylate, di -N-butoxy-zirconium diacetate, di-i-propylaluminum monomalonate, etc., and particularly preferred compounds are dihydroxy.
Titanium compounds such as titanium dibutyrate and di-i-propoxy titanium diacetate. These components (b) are used alone or in combination of two or more.

As the component (b), since the viscosity of the coating solution does not change with time and is easy to handle, the component (b) is hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent described in a hydrophilic solvent described below. It is preferable to use those subjected to a decomposition treatment. By performing such a hydrolysis treatment before mixing with the component (a), the unhydrolyzed component (b), partially hydrolyzed component (b), and partially condensed component (b) The mixture becomes a mixture, and a sharp increase in viscosity due to a shock or the like generated when the composition is mixed with the component (a) during preparation of the composition, and an increase in viscosity over time are suppressed. in this case,
The amount of water used is 0.1 mol per mol of R ¹ _mM (OR ² ) _n.
１，1,000 mol, preferably 0.5-500 mol. In the case of a mixed solvent, the mixing ratio of water and the hydrophilic organic solvent is such that water / hydrophilic organic solvent = 10-90 / 90-10
(Weight ratio), preferably 20-80 / 80-20, more preferably 30-70 / 70-30. As the component (b), particularly preferred are di-i-propoxybis (acetylacetonato) titanium, di-n-butoxybis (triethanolaminate) titanium,
It is obtained by hydrolyzing a titanium compound such as dihydroxybislactate to titanium with the above-mentioned mixed solvent.

Component (c): The gas barrier coating composition used in the present invention is added with a boron compound (c) for the purpose of improving the storage stability and curability of the coating composition. (C) Examples of the boron compound include boric acid, boron oxide, and borax. As the boron compound (e), boric acid is particularly preferable.

The proportion of the component (c) in the composition of the present invention is as follows:
Based on 100 parts by weight of the total of components (a) to (f), preferably 0.05 to 30 parts by weight, particularly preferably 0.1 to 30 parts by weight.
20 parts by weight. If the amount is less than 0.05 parts by weight, the storage stability at low temperatures becomes poor, and the white turbidity may occur quickly.
On the other hand, if it exceeds 30 parts by weight, the resulting coating film may be whitened, which is not preferred.

Component (d): The coating composition of the present invention preferably contains a nitrogen-containing compound as component (d), if necessary. As the nitrogen-containing compound of the component (d), for example, N, N-dimethylacetamide, N, N-
Hydrophilic nitrogen-containing organic solvents such as dimethylformamide, γ-butyrolactone, N-methylpyrrolidone and pyridine;
Nucleic acid bases such as thymine, glycine, cytosine, and guanine; hydrophilic nitrogen-containing polymers such as polyvinylpyrrolidone, polyacrylamide, and polymethacrylamide; and copolymers obtained by copolymerizing these components.
Among these, N, N-dimethylacetamide, N, N
-Dimethylformamide and polyvinylpyrrolidone are preferred. By mixing the component (d), a coating film having better transparency and good appearance can be obtained in coating with a thin film, and also exhibits a catalytic effect when condensing with inorganic particles and / or an inorganic laminate. The use ratio of the nitrogen-containing compound is usually 70% by weight or less in the total amount of the solvent,
It is preferably at most 50% by weight.

Component (e): The coating composition of the present invention preferably contains, if necessary, inorganic fine particles as component (e). The inorganic fine particles are a particulate inorganic substance having an average particle diameter of 0.2 μm or less and containing substantially no carbon atoms, and include metals or silicon oxides, metals or silicon nitrides, and metal borides. Methods for producing inorganic fine particles include, for example, a gas phase method in which silicon tetrachloride is obtained by hydrolysis of oxygen and hydrogen in a flame to obtain silicon oxide, a liquid phase method in which sodium silicate is ion-exchanged, a silica gel mill, and the like. Production methods such as a solid-phase method obtained by pulverization by a method described above, but are not limited to these methods.

Specific examples of compounds include SiO ₂ , A
l ₂ O ₃ , TiO ₂ , WO ₃ , Fe ₂ O ₃ , ZnO, NiO,
RuO ₂ , CdO, SnO ₂ , Bi ₂ O ₃ , 3Al ₂ O ₃ .2
_{SiO 2, Sn-In 2 O} 3, Sb-In 2 O 3, CoFe
Oxides such as O _x , Si ₃ N ₄ , Fe ₄ N, AlN, Ti
Nitrides such as N, ZrN, TaN, Ti ₂ B, ZrB ₂ ,
Borides such as TaB ₂ and W ₂ B are mentioned. Examples of the form of the inorganic fine particles include powder, colloid or sol dispersed in water or an organic solvent, but these are not limited. Among them, component (a) and / or
Or colloidal silica, colloidal alumina, alumina sol, tin sol, zirconium sol, antimony pentoxide sol, cerium oxide sol, zinc oxide sol, oxide A colloidal oxide having a hydroxyl group on the surface of a particle such as a titanium sol is used. The average particle diameter of the inorganic fine particles is 0.2 μm or less, preferably 0.1 μm or less. When the average particle diameter exceeds 0.2 μm, gas barrier properties may be poor from the viewpoint of the denseness of the film.

The proportion of the component (e) in the composition of the present invention is as follows:
900 parts by weight or less, particularly preferably 4 parts by weight, based on 100 parts by weight of the total of components (a) and (b).
Not more than 00 parts by weight. If the amount exceeds 900 parts by weight, the gas barrier properties of the obtained coating film may decrease.

Optional component: (f) a curing accelerator is used for the purpose of curing the composition of the present invention faster and for the purpose of facilitating the formation of a co-condensate of the components (a) and (b). It is more effective to use this curing accelerator (f) in combination to cure at a relatively low temperature and obtain a denser coating film.

As the (f) curing accelerator, inorganic acids such as hydrochloric acid; naphthenic acid, octylic acid, nitrous acid, sulfurous acid,
Alkali metal salts such as aluminate and carbonic acid; alkaline compounds such as sodium hydroxide and potassium hydroxide; alkyltitanic acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, phthalic acid, succinic acid, glutaric acid, oxalic acid , Acidic compounds such as malonic acid; ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine,
Piperazine, metaphenylenediamine, ethanolamine, triethylamine, various modified amines used as curing agents for epoxy resins, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ- (2 Amine-based compounds such as -aminoethyl) -aminopropylmethyldimethoxysilane and γ-anilinopropyltrimethoxysilane. The proportion of the (f) curing accelerator in the composition is usually 50 parts by weight or less, preferably 30 parts by weight or less, based on 100 parts by weight of the solid content of the composition of the present invention.

The composition of the present invention may further comprise, as a stability improver, β-diketones and / or β-diketones described above.
-Ketoesters can be added. That is,
By coordinating to a metal atom in the metal alcoholate present in the composition as the component (b), the component (a) acts to control the condensation reaction between the component (a) and the component (b) to obtain a composition obtained. It is considered that they act to improve the storage stability of the product. β-diketones and / or β
The amount of the ketoester to be used is preferably 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal atom in the component (b).

The coating composition of the present invention is usually obtained by dissolving and dispersing the above components (a) and (b) and optionally the above optional components in water and / or a hydrophilic organic solvent. Here, specific examples of the hydrophilic organic solvent include methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, and se.
c-butyl alcohol, tert-butyl alcohol,
1 carbon atoms such as diacetone alcohol, ethylene glycol, diethylene glycol, triethylene glycol, etc.
Saturated aliphatic monohydric alcohol or dihydric alcohol having 8 to 8 carbon atoms, such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether acetate;
Saturated aliphatic ether compounds; ester compounds of saturated aliphatic dihydric alcohols having 1 to 8 carbon atoms such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate; and dimethyl sulfoxide and the like. Sulfur compounds; examples include hydroxycarboxylic acids or hydroxycarboxylic esters such as lactic acid, methyl lactate, ethyl lactate, salicylic acid, and methyl salicylate. Of these, preferred are methanol, ethanol, n-propanol, i
-Saturated aliphatic monohydric alcohols having 1 to 8 carbon atoms such as -propanol, n-butyl alcohol, sec-butyl alcohol and tert-butyl alcohol. Further, the hydrophilic nitrogen-containing organic solvent exemplified as the component (d) may be used as part or all of the hydrophilic organic solvent.

These water and / or hydrophilic organic solvent are more preferably used by mixing water and a hydrophilic organic solvent.

The amount of water and / or hydrophilic organic solvent used is such that the total solid content of the composition is preferably 60% by weight or less. For example, when it is used for forming a thin film, it is usually 1 to 40% by weight, preferably 2 to 30% by weight. When it is used for forming a thick film, it is usually 5 to 50% by weight. %, Preferably 10-4
0% by weight. If the total solid content of the composition exceeds 60% by weight, the storage stability of the composition tends to decrease.

As the organic solvent, the above-mentioned water and / or hydrophilic organic solvent is preferable. Ethers, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate can also be used.

As described above, the coating composition of the present invention is obtained by mixing the above components (a) to (c) and optionally the above optional components (d) to (f) in water and / or a hydrophilic organic solvent. Preferably, the above components (a) to (c), and if necessary, components (d) to (f) are added, and the mixture is added to water and / or a hydrophilic organic solvent.
It is obtained by hydrolysis and / or (co) condensation of the component (b). At this time, the reaction conditions are as follows.
100 ° C, preferably 20-90 ° C, time 0.005
-20 hours, preferably 0.1-10 hours.

The coating composition of the present invention includes:
A filler may be separately added and dispersed in order to exhibit various properties such as coloring, thickening of the obtained coating film, prevention of ultraviolet transmission to the base, imparting corrosion resistance, and heat resistance. However, the filler excludes the components (e) to (f). As the filler, for example, organic pigments, other than water-insoluble pigments or pigments such as inorganic pigments, particulate, fibrous or flaky metals and alloys and oxides thereof,
Hydroxide, carbide, nitride, sulfide and the like.
Specific examples of the filler include particles, fibrous or scaly, iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, and chromium oxide. , Manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, Magnesium carbonate, barium sulfate, bentonite, mica, zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, shale green, green earth, manganese green, pigment green, ultramarine, navy blue, pigment green, rock ultramarine, Cobalt blue, cerulean blue, copper borate, molybdenum Down blue, copper sulfide, cobalt violet,
Mars purple, manganese purple, pigment violet, lead oxide, calcium lead, calcium zincate, lead sulfide, chrome yellow, loess, cadmium yellow, strontium yellow, titanium yellow, litharge, pigment yellow, cuprous oxide, cadmium red, selenium red , Chrome vermillion, red iron, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead zinc white, bunchesone white, lead phthalate, manganese white, lead sulfate,
Graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide and the like can be mentioned.

The average particle size or average length of these fillers is usually 50 to 50,000 nm, preferably 100 to 50,000 nm.
５，5,000 nm. The proportion of the filler in the composition is
Preferably 0 to 300 parts by weight, more preferably 0 to 200 parts by weight, based on 100 parts by weight of the total solid content of the components other than the filler.
Parts by weight.

The coating composition of the present invention includes:
Other known dehydrating agents such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, various surfactants,
Additives other than those described above, such as a silane coupling agent, a titanium coupling agent, a dye, a dispersant, a thickener, and a leveling agent can also be blended.

In preparing the coating composition of the present invention, the above components (a) to (c) or (a) to (c)
Component (d), or a composition containing components (a) to (c) and component (e), or components (a) to (e) may be prepared. Alternatively, after a hydrolysis treatment is performed in a mixed solvent containing water and a hydrophilic organic solvent, the mixture is mixed with the component (a). In this case, there is no change in viscosity of the coating composition over time, and a coating composition excellent in handleability can be obtained.

Specific examples of the method for preparing the coating composition of the present invention when the component (e) is used include the following. In these preparation methods,
As the component (b), a component which has been subjected to hydrolysis treatment in advance in water or a mixed solvent containing water and a hydrophilic organic solvent may be used. (A) dissolved in water and / or a hydrophilic organic solvent
And after adding the component (e) to the component (c),
How to add components. (A) dissolved in water and / or a hydrophilic organic solvent
And after adding the component (e) to the component (c),
A method in which components are added, and hydrolysis and / or condensation are performed. (B) dissolved in water and / or a hydrophilic organic solvent
A method in which the component (e) is added to the components, hydrolysis and / or condensation is performed, and then the components (a) and (c) are added. A method in which the components (a) to (e) are added all at once to water and / or a hydrophilic organic solvent and dissolved and dispersed. Alternatively, a method of performing hydrolysis and / or condensation after that. In addition,
The timing and method of adding the component (c) are not particularly limited, and any timing and method may be used.

As a specific example of the method for preparing the coating composition of the present invention when the component (e) is used, the component (e) previously dispersed in a mixed solvent containing water and / or a hydrophilic organic solvent is used. Is added to the components (a) and (c) dissolved in a mixed solvent containing water and / or a hydrophilic organic solvent, or (a) to (c), or (a) to (d) After the coating composition is prepared, a method of adding the component (e) dispersed in a mixed solvent containing water and / or a hydrophilic organic solvent is generally used, but the method is not limited thereto.

Coating Film The coating composition of the present invention is particularly useful for a gas barrier coating material. That is, on a base resin film, a cured coating film comprising the coating composition of the present invention,
Alternatively, a coating film having excellent gas barrier properties can be obtained by laminating a deposited film of an inorganic oxide and a cured coating film comprising the coating composition of the present invention.

The base film constituting the gas barrier coating film according to the present invention includes, for example, polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polyamide resins;
Polycarbonate resin, polystyrene resin, polyvinyl alcohol, polyvinyl alcohol resin such as saponified portion of ethylene-vinyl acetate copolymer, polyacrylonitrile resin, polyvinyl chloride resin, polyvinyl acetal resin, polyvinyl butyral resin, Fluorinated resins and other various resin films and sheets can be used. In the present invention, as a method for forming the resin film or sheet, for example, one or more of the above resins are used, and an inflation method, a T-die method,
Other methods of forming the above resin alone using a film forming method, or a method of forming a multilayer co-extrusion film using two or more different resins, and further, a method of forming two or more resins Using a method of mixing and forming a film before forming a film, a resin film or sheet is manufactured, and further,
For example, a resin film or sheet stretched in a uniaxial or biaxial direction using a tenter method or a tubular method can be formed. In the present invention, the thickness of the substrate film is preferably 5 to 2
It is about 00 μm, more preferably about 10 to 50 μm.
In the above, when forming a resin film, for example,
The purpose of improving and modifying the film's processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slip properties, mold release properties, flame retardancy, mold resistance, electrical properties, etc. Thus, various plastic compounding agents and additives can be added. The addition amount can be arbitrarily added from a very small amount to several tens% depending on the purpose. Also,
In the above, common additives include, for example, lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, fillers, reinforcing agents, reinforcing agents, antistatic agents, flame retardants, flame retardants, foaming agents, mold inhibitors Agents, pigments, and the like can be used, and further, a modifying resin and the like can be used.

In the present invention, the base film is
If necessary, for example, corona discharge treatment, ozone treatment,
A low-temperature plasma treatment using an oxygen gas or a nitrogen gas, a glow discharge treatment, an oxidation treatment using a chemical, or the like, and other pretreatments can be arbitrarily performed. The above-mentioned surface pretreatment may be performed in a separate step before forming an inorganic oxide vapor-deposited film.For example, in the case of a surface treatment such as a low-temperature plasma treatment or a glow discharge treatment, the above-mentioned inorganic oxidation treatment is performed. As a pre-process for forming a deposited film of an object, the pre-process can be performed by an in-line process, and in such a case, there is an advantage that the manufacturing cost can be reduced. The above-mentioned surface pretreatment is performed as a method for improving the adhesion between the base film and the deposited film of the inorganic oxide. However, as a method for improving the adhesion, other methods such as, for example, On the surface of the material film, a primer coating agent layer, an undercoating agent layer, a vapor-deposited anchor coating agent layer, or the like can be arbitrarily formed in advance. As the coating agent layer for the pretreatment, for example, a resin composition containing a polyester-based resin, a polyurethane-based resin, or the like as a main component of the vehicle can be used. Further, in the above, as a method of forming a coating agent layer, for example, using a coating agent such as a solvent type, an aqueous type, or an emulsion type, using a roll coating method, a gravure roll coating method, a kiss coating method, and other coating methods The coating can be performed as a post-step after the biaxial stretching of the base film, or in-line processing of the biaxial stretching. In the present invention, as the substrate film, specifically, a biaxially stretched polypropylene film,
Axially stretched polyethylene terephthalate film, or
It is preferable to use a biaxially stretched nylon film.

At this time, it is also possible to laminate a deposited film of a metal and / or an inorganic compound (hereinafter also referred to as a “deposited film”) on the substrate or the coating film of the present invention. By providing this deposited film, the gas barrier properties are further improved. When the vapor-deposited film is present, the vapor-deposited layer and the component (b) are chemically bonded by hydrolysis / co-condensation reaction,
A hydrogen bond or a coordination bond is formed, and the adhesion between the deposited layer and the gas barrier coating layer is improved. As the deposited film, a deposited film of an inorganic oxide formed by a chemical vapor deposition method and / or a physical vapor deposition method is preferable.

Here, the vapor-deposited inorganic oxide film formed by the chemical vapor deposition method which constitutes the gas barrier coating film of the present invention will be described. Examples of the deposited film of the inorganic oxide by the chemical vapor deposition method include a chemical vapor deposition method such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, and a photochemical vapor deposition method.
An inorganic oxide deposited film can be formed by an oxidation method, an oxidation method, or the like. In the present invention,
Specifically, on one surface of the base film, a monomer gas for vapor deposition such as an organosilicon compound is used as a raw material, and an inert gas such as an argon gas or a helium gas is used as a carrier gas. Can be manufactured by a method of forming a deposited film of an inorganic oxide such as silicon oxide by a plasma enhanced chemical vapor deposition (CVD) method using an oxygen gas or the like and a low-temperature plasma generator or the like. . In the above, as the low-temperature plasma generator, for example, high-frequency plasma, pulse wave plasma,
A generator such as a microwave plasma can be used. In the present invention, it is desirable to use a generator using a high-frequency plasma method in order to obtain highly active and stable plasma.

Specifically, a method of forming a deposited film of an inorganic oxide by the low-temperature plasma chemical vapor deposition method will be described with reference to an example. FIG. 1 is a schematic configuration diagram of a low-temperature plasma-enhanced chemical vapor deposition apparatus showing an outline of a method of forming a vapor-deposited film of an inorganic oxide by the plasma chemical vapor deposition method. As shown in FIG. 1 described above, in the present invention, the base film 2 is unwound from an unwind roll 13 disposed in a vacuum chamber 12 of a plasma enhanced chemical vapor deposition apparatus 11, and the base film 2 is further removed. The cooling / electrode drum 1 at a predetermined speed via the auxiliary roll 14
It is conveyed to 5 peripheral surfaces. Thus, in the present invention, an oxygen gas, an inert gas, a monomer gas for vapor deposition such as an organosilicon compound, and the like are supplied from the gas supply devices 16 and 17 and the raw material volatilization supply device 18 and the like, and the vapor deposition composed of them While preparing the mixed gas composition for vapor deposition, the mixed gas composition for vapor deposition is introduced into the chamber 12 through the raw material supply nozzle 19. And the above-mentioned cooling / electrode drum 1
Plasma is generated by the glow discharge plasma 20 on the base film 2 conveyed on the five peripheral surfaces, and the plasma is irradiated to form a continuous film of an inorganic oxide such as silicon oxide, thereby forming a film. . In the present invention, at that time,
A predetermined power is applied to the electrode drum 15 from a power source 21 disposed outside the chamber, and a magnet 22 is disposed near the cooling / electrode drum 15 so that the generation of plasma is promoted. It has become. Then
The base film 2 on which the continuous film of the inorganic oxide such as silicon oxide is formed as described above is wound on a winding roll 24 via an auxiliary roll 23, thereby forming the inorganic oxide by the chemical vapor deposition method of the present invention. Can be formed. In the figure, reference numeral 25 denotes a vacuum pump. The above exemplification is merely an example, and it goes without saying that the present invention is not limited thereby.
Although not shown, in the present invention, the inorganic oxide deposited film is not limited to one layer of a continuous inorganic oxide film, but may be a composite deposited film in which two or more layers are stacked. The material used may be one kind or a mixture of two or more kinds, and a vapor deposition film of an inorganic oxide in which different kinds of materials are mixed may be formed.

In the above, the pressure inside the vacuum chamber 12 is reduced by the vacuum pump 25, and the degree of vacuum is 1 × 10 ^-1 to 1 × 1.
About 0 ^-8 Torr, preferably a degree of vacuum of 1 × 10 ^-3 to 1
It is desirable to adjust to about 0 ^-7 Torr. Further, in the raw material volatilizing and supplying device 18, the organic silicon compound as the raw material is volatilized and mixed with oxygen gas, an inert gas or the like supplied from the gas supplying devices 16 and 17. It is introduced into the chamber 12 through. In this case, the content of the organic silicon compound in the mixed gas is about 1 to 40 mol%, and the content of the oxygen gas is 10%.
The content of the inert gas can be in the range of about 10 to 60 mol%, and the mixing ratio of the organosilicon compound, the oxygen gas, and the inert gas is 1: 1:
6: 5 to 1:17:14. On the other hand, since a predetermined voltage is applied to the cooling / electrode drum 15 from the power supply 21, a glow discharge plasma 20 is generated in the vicinity of the opening of the raw material supply nozzle 19 in the chamber 12 and the cooling / electrode drum 15. The glow discharge plasma 20 is derived from one or more gas components in the mixed gas. In this state, the base film 2 is transported at a constant speed, and a glow discharge plasma 20 forms a vapor-deposited film of an inorganic oxide such as silicon oxide on the base film 2 on the cooling / electrode drum 15 peripheral surface. can do. At this time, the degree of vacuum in the vacuum chamber 12 is preferably adjusted to about 1 × 10 ⁻¹ to 10 ⁻⁴ Torr, more preferably, to about 1 × 10 ⁻¹ to 10 ⁻² Torr. The transport speed of the base film 2 is about 10 to 300 m / min, preferably 50 to 15 m / min.
It is desirable to adjust to about 0 m / min.

Further, the above-mentioned plasma chemical vapor deposition apparatus 1
In (1), a continuous film of an inorganic oxide such as silicon oxide is formed on the base film 2 in the form of SiO _{x in} the form of a thin film while oxidizing a plasma-converted raw material gas with oxygen gas. The formed deposited film of an inorganic oxide such as silicon oxide is a continuous layer that is dense, has few gaps, and is highly flexible. Therefore, the gas barrier property of a deposited film of an inorganic oxide such as silicon oxide is much higher than that of a deposited film of an inorganic oxide such as silicon oxide formed by a conventional vacuum deposition method or the like, and the thin film thickness is small. And a sufficient gas barrier property can be obtained. Further, in the present invention, the surface of the base film 2 is cleaned by the SiOx plasma, and a polar group or a free radical is generated on the surface of the base film 2. This has the advantage that the adhesion between the deposited film of the substance and the substrate film is high. further,
As described above, the degree of vacuum at the time of forming a deposited film of an inorganic oxide such as silicon oxide is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably, 1 × 10 ⁻¹ to 1 × 10 ^−. Adjust to about ² Torr. Therefore, the degree of vacuum when forming a deposited film of an inorganic oxide such as silicon oxide by a conventional vacuum deposition method,
The degree of vacuum is lower than about 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, and the vacuum state setting time at the time of exchanging the base film of the base film 2 can be shortened, and the degree of vacuum is easily stabilized. This stabilizes the film forming process.

In the present invention, a deposited silicon oxide film formed using a vaporized monomer gas such as an organosilicon compound chemically reacts with a vaporized monomer gas such as an organosilicon compound and oxygen gas to form a reaction product. The substance adheres to one surface of the base film to form a dense and flexible thin film.
X is a number from 0 to 2), and is a continuous thin film mainly composed of silicon oxide. The above silicon oxide vapor-deposited film has a general formula of SiO from the viewpoints of transparency, gas barrier properties, and the like.
The thin film is preferably a thin film mainly composed of a continuous silicon oxide film represented by x (where X represents a number of 1.3 to 1.9). In the above, the value of X changes depending on the molar ratio of the vaporized monomer gas to the oxygen gas, the energy of the plasma, and the like. Generally, as the value of X decreases, the gas permeability decreases, but the film itself becomes yellow. Tinged with transparency.

The silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further contains at least one compound of one or more of carbon, hydrogen, silicon and oxygen, or two or more thereof. , By a chemical bond or the like.
For example, when the compound having a C—H bond, the compound having a Si—H bond, or the carbon unit is in a graphite shape, a diamond shape, a fullerene shape, or the like, an organic silicon compound or a derivative thereof as a raw material is further added. May be contained due to chemical bonding. Specific examples include hydrocarbon having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, SiH ₂
Examples include a hydroxyl group derivative such as OH silanol. In addition to the above, the kind and amount of the compound contained in the deposited silicon oxide film can be changed by changing the conditions of the deposition process and the like. The content of the above compound contained in the deposited silicon oxide film is 0.1%.
About 1 to 50 mol%, preferably about 5 to 20 mol% is desirable. If it is less than 0.1 mol%, the impact resistance, spreadability, flexibility, etc. of the deposited silicon oxide film become insufficient, and scratches, cracks, etc. are easily generated by bending and the like,
It is difficult to stably maintain high gas barrier properties. On the other hand, if it exceeds 50 mol%, the gas barrier properties are undesirably reduced. Further, in the present invention, it is preferable that the content of the above compound is reduced in the depth direction from the surface of the deposited silicon oxide film in the deposited silicon oxide film. Thereby, on the surface of the silicon oxide vapor-deposited film, the impact resistance is enhanced by the above-mentioned compound and the like, while, at the interface with the base film, the content of the above-mentioned compound is small, so that the base film and This has the advantage that the adhesion to the deposited silicon oxide film becomes strong.

In the present invention, the above-mentioned deposited film of silicon oxide is, for example, an X-ray photoelectron spectrometer (Xray).
Photoelectron Spectroscope
y, XPS), secondary ion mass spectrometer (Second
ary Ion Mass Spectroscopy,
Confirming the physical properties as described above by performing elemental analysis of the deposited silicon oxide film using a method of performing ion etching in the depth direction or the like using a surface analyzer such as SIMS. Can be. Further, in the present invention, the thickness of the silicon oxide deposited film is preferably about 5 to 400 nm, more preferably 10 to 100 nm.
nm. If the film thickness is 10 nm or less than 5 nm, it is difficult to achieve the gas barrier effect, which is not preferable. On the other hand, when the film thickness is 100 nm,
When the thickness is larger than 00 nm, cracks and the like are easily generated in the film, which is not preferable. In the above description, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name: RIX2000 type) manufactured by Rigaku Corporation. Further, in the above, as means for changing the thickness of the deposited film of silicon oxide, increasing the volume velocity of the deposited film, that is, a method of increasing the amount of monomer gas and oxygen gas, or reducing the deposition rate It can be performed by a method or the like.

In the above description, examples of the monomer gas for vapor deposition such as an organic silicon compound for forming a vapor-deposited film of an inorganic oxide such as silicon oxide include 1,1,3,3-tetramethyldisiloxane and hexamethyldisiloxane. , Vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrisilane Methoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. In the present invention, among the above-mentioned organosilicon compounds, the use of 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material can improve the handling property and the formed continuous film. From the viewpoint of properties and the like, it is a particularly preferable raw material.
In the above, for example, an argon gas, a helium gas, or the like can be used as the inert gas.

Next, as the vapor-deposited inorganic oxide film formed by the physical vapor deposition method to constitute the gas barrier coating film of the present invention, for example, a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method and an ion plating method. (P
physical VaporDeposition method,
(PVD method). Specifically, a vacuum deposition method in which a metal oxide is used as a raw material, which is heated and vapor-deposited on a substrate film, a metal or a metal oxide is used as a raw material, and oxygen is introduced and oxidized to form a base. The deposited film can be formed by using an oxidation reaction deposition method of depositing on a material film, a plasma-assisted oxidation reaction deposition method of assisting an oxidation reaction by plasma, or the like.

An example of a method for forming a deposited film of an inorganic oxide by physical vapor deposition according to the present invention will be described with reference to the drawings. FIG. 2 is a schematic configuration diagram of a take-up type vacuum evaporation apparatus.
As shown in FIG. 2, in a vacuum chamber 52 of a take-up type vacuum evaporation apparatus 51, a base film 2 having a vapor-deposited inorganic oxide film formed by a chemical vapor deposition method unwound from an unwind roll 53 is formed by a guide roll. It is guided to the cooled coating drum 56 via 54 and 55. The base film 2 having a vapor-deposited inorganic oxide film formed by chemical vapor deposition guided on the cooled coating drum 56
The vapor deposition source 58 heated by the crucible 57, for example, metal aluminum, aluminum oxide, or the like is evaporated on the inorganic oxide vapor deposition film, and an oxygen gas outlet 59 is provided as necessary.
While supplying oxygen gas and the like, a vapor-deposited film of an inorganic oxide such as aluminum oxide is formed through the masks 60 and 60 while supplying the gas, and then a vapor-deposited film of an inorganic oxide such as aluminum oxide is formed. The base film 2 formed on the inorganic oxide vapor-deposited film by the chemical vapor deposition method is fed through guide rolls 55 ′ and 54 ′ and wound up by a take-up roll 61, whereby the physical properties of the present invention are obtained. An inorganic oxide deposited film can be formed by a vapor deposition method.

The inorganic oxide deposited film may be any thin film on which a metal oxide is deposited.
For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb) ), Zirconium (Zr), yttrium (Y), and other metal oxide deposited films. Suitable materials for the packaging material include metal oxides such as silicon (Si) and aluminum (Al). Deposited film of the metal oxide include silicon oxide, aluminum oxide, as magnesium oxide, can be called as a metal oxide, the title is SiO _X, AlO _X, MO such as MgO _{X X} (where M represents a metal element, and the value of X varies depending on the metal element).
Further, as a range of the value of X, silicon (Si) is 0%.
2, aluminum (Al) is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, potassium (K) is 0 to 0.5, and tin (Sn) is 0 to 1. 2, sodium (Na) is 0-0.5, boron (B) is 0-0.5
1.5, 0 for titanium (Ti), 0 for lead (Pb)
1, zirconium (Zr) can take a value of 0-2, and yttrium (Y) can take a value of 0-1.5. In the above, when X = 1, it is a perfect metal, is not transparent and cannot be used at all. Further, the upper limit of the range of X is a value that is completely oxidized. In the present invention, examples other than silicon (Si) and aluminum (Al) are generally rarely used as packaging materials. Silicon (S
i) is 1.0 to 2.0, aluminum (Al) is 0.5
Those having a range of ~ 1.5 can be preferably used. In the present invention, the thickness of the inorganic oxide thin film,
It depends on the type of metal and metal oxide used,
For example, 5 to 200 nm, preferably 10 to 100 n
It is desirable to arbitrarily select and form within the range of m.
Further, the deposited film of the inorganic oxide of the present invention may be not only one layer of the deposited film of the inorganic oxide but also a laminated body in which two or more layers are laminated. Also, the metal used,
The metal oxide is used in one kind or a mixture of two or more kinds,
It is also possible to form a thin film of an inorganic oxide mixed with different materials.

Specific examples of the method for forming the coating film of the present invention using the coating composition of the present invention include the following methods. A method for forming a coating film of the present invention on a substrate surface. If necessary, the primer of the present invention may be applied on the surface of the base material in advance to form the coating film of the present invention. A method of forming a coating film of the present invention on a surface of a base material, on which a deposited film of an inorganic oxide is formed by a chemical vapor deposition method and / or a physical vapor deposition method. In addition, when forming a vapor deposition film on a base material surface, you may apply a primer in advance on a base material surface as needed. A method of forming a vapor-deposited film on the surface of the coating film of the present invention by a chemical vapor deposition method and / or a physical vapor deposition method. A method of forming a vapor-deposited film on the surface of the coating film of the present invention by a chemical vapor deposition method and / or a physical vapor deposition method. A method for further forming a coating film of the present invention on the surface of the above-mentioned deposited film. A method for further forming a coating film of the present invention on the surface of the above-mentioned deposited film. The method of the above-mentioned, wherein the surface of the substrate is one or both sides.

On a substrate such as a synthetic resin film (including a substrate on which the above-mentioned vapor-deposited film is laminated), a cured coating film formed from the gas barrier coating composition of the present invention (hereinafter also referred to as “the coating film of the present invention”) To laminate), on the surface of the substrate,
Roll coat such as gravure coater, spray coat, spin coat, dipping, brush, bar code,
The coating film of the present invention having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm can be formed by one or more coatings by a coating means such as an applicator. Below, 50-300 ° C, preferably 70-
By heating and drying at a temperature of 200 ° C. for 0.005 to 60 minutes, preferably 0.01 to 10 minutes, condensation is carried out and the coating film of the present invention can be formed. If necessary, a printed pattern layer may be provided on the gas barrier coating film of the present invention, and if necessary, a heat-sealing resin layer may be formed on the printed pattern layer.

As the print pattern layer, for example, a usual gravure ink composition, offset ink composition, letterpress ink composition, screen ink composition, and other ink compositions can be coated on the above-mentioned cured coating film. Use, for example, gravure printing method, offset printing method,
It can be configured by using a letterpress printing method, a silk screen printing method, or another printing method, and forming a desired printing pattern composed of, for example, characters, figures, pictures, symbols, and the like. In the above ink composition, as a vehicle constituting the ink composition, for example, a polyolefin resin such as a polyethylene resin, a chlorinated polypropylene resin, a poly (meth) acrylic resin, a polyvinyl chloride resin, a polyvinyl acetate Resin, vinyl chloride
Vinyl acetate copolymer, polystyrene resin, styrene
Butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin,
Polyvinyl butyral resin, polybutadiene resin,
Polyester resin, polyamide resin, alkyd resin, epoxy resin, unsaturated polyester resin, thermosetting poly (meth) acrylic resin, melamine resin,
Urea resin, polyurethane resin, phenolic resin,
Xylene resin, maleic resin, nitrocellulose,
Cellulose resins such as ethylcellulose, acetylbutylcellulose and ethyloxyethylcellulose, rubber resins such as chlorinated rubber and cyclized rubber, petroleum resins, rosin,
Mixtures of one or more of natural resins such as casein, oils and fats such as linseed oil and soybean oil, and other resins can be used. In the present invention, one or more kinds of the above-mentioned vehicles are used as a main component, and one or more kinds of coloring agents such as dyes and pigments are added thereto. Stabilizers, plasticizers, antioxidants, light stabilizers such as ultraviolet absorbers, dispersants, thickeners, desiccants, lubricants, antistatic agents, crosslinking agents, and other optional additives, solvents, Ink compositions of various forms which are sufficiently kneaded with a diluent or the like can be used.

The heat-sealable resin forming the heat-sealable resin layer may be any heat-sealable resin that can be melted by heat and fused to each other. For example, low-density polyethylene, medium-density polyethylene, High density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-
Acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyolefin resin such as polyethylene and polypropylene, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, It is possible to use a resin composed of one or more of itaconic acid, another acid-modified polyolefin resin modified with an unsaturated carboxylic acid, a polyvinyl acetate resin, a polyester resin, a polystyrene resin, and other resins. . In the present invention, as the heat-sealable resin layer, one or more of the above resins are used, and for example, a resin film or sheet formed into a film by an inflation method, a T-die method, or another method. Or one of the above resins
It can be used in the form of a coating film or the like made of a resin composition containing a seed or more as a main component of the vehicle. The thickness is about 5 to 100 μm, preferably about 10 to 50 μm.

In the present invention, among the above resins, it is particularly preferable to use linear (linear) low-density polyethylene. The linear low density polyethylene,
Adhesiveness has the advantage of reducing the propagation of fracture and improving impact resistance. In addition, since the inner layer is in constant contact with the contents, deterioration of environmental stress cracking resistance is prevented. It is also effective for Further, in the present invention, other resins can be blended with the linear low-density polyethylene, for example, by blending an ethylene-butene copolymer or the like.
Although the heat resistance is slightly inferior and the seal stability tends to deteriorate in a high temperature environment, there is an advantage that the tearing property is improved and the easy opening property is contributed. As the linear low-density polyethylene as the heat sealable resin as described above, specifically, ethylene-polymerized using a metallocene catalyst
α-Olefin copolymer can be used. Specifically, the product name "Kernel" manufactured by Mitsubishi Chemical Corporation, the product name "Evolu" manufactured by Mitsui Petrochemical Industry Co., Ltd., Exxon Chemical (USA)
L), a metallocene catalyst such as "AFFINITY", a product name "AFFINITY", a product name, "ENGAGE", a product name, manufactured by DOW CHEMICAL, USA A polymerized ethylene-α-olefin copolymer can be used. The use of the ethylene-α-olefin copolymer polymerized using the above-mentioned metallocene catalyst has an advantage that low-temperature heat sealability is possible when a bag is manufactured.

In the laminated material using the gas barrier coating film of the present invention, since the packaging container is usually subjected to severe physical and chemical conditions, the packaging material is used for the laminated material constituting the packaging container. The strict requirements for packaging suitability, that is, deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing property, quality maintenance, workability, hygiene, and other various conditions are required. For this reason, in the present invention, a material that satisfies the above-described conditions can be arbitrarily selected, and a desired laminated material can be formed in addition to the material that forms the laminated material. For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene -Acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic Resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin , Arbitrarily selected from known resin films or sheets such as polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, etc. Can be used. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used. In the present invention, any of the above-mentioned films or sheets, such as unstretched or uniaxially or biaxially stretched, can be used. Also,
Although the thickness is arbitrary, it can be selected from a range of several μm to about 300 μm. The film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.

In the present invention, the method for producing the laminate according to the present invention using the barrier film, the printed picture layer, the heat-sealing resin layer, and other materials according to the present invention includes, for example, lamination. It can be performed by a dry lamination method in which the layers are laminated via an adhesive layer for lamination with a bonding adhesive, or an extrusion lamination method in which the layers are laminated via a melt-extruded resin layer with a melt-extruded adhesive resin. In the above, as the laminating adhesive, for example, one-component or two-component curing or non-curing type vinyl, (meth) acrylic, polyamide, polyester, polyether,
Adhesives for lamination such as solvent type, aqueous type, and emulsion type such as polyurethane type, epoxy type, rubber type and the like can be used. As a coating method of the laminating adhesive, for example, direct gravure roll coating method, gravure roll coating method,
It can be applied by a kiss coat method, a reverse roll coat method, a Fonten method, a transfer roll coat method, or other methods. The coating amount is preferably about 0.1 to 10 g / m ² (dry state), more preferably about 1 to 5 g / m ² (dry state). In addition,
An adhesion promoter such as a silane coupling agent can be optionally added to the laminating adhesive. Further, in the above, as the melt-extruded adhesive resin, the heat-sealable resin forming the heat-sealable resin layer can be similarly used, and low-density polyethylene, particularly linear low-density polyethylene, acid-modified polyethylene may be used. It is preferred to use. The thickness of the melt-extruded resin layer made of the melt-extruded adhesive resin is preferably 5
About 100 μm, more preferably about 10 to 50 μm. In the present invention, when it is necessary to obtain a stronger adhesive strength when performing the lamination, an adhesive improving agent such as an anchor coat agent may be coated. Examples of the anchor coating agent include, for example, organic titanium-based anchor coating agents such as alkyl titanates, isocyanate-based anchor coating agents, polyethyleneimine-based anchor coating agents, polybutadiene-based anchor coating agents, and various other aqueous or oil-based anchor coating agents. Can be used. In the present invention, the anchor coating agent is coated by roll coating, gravure coating, knife coating, dip coating, spray coating, or another coating method, and the solvent, diluent, etc. are dried to form an anchor coating agent layer. can do. The coating amount of the anchor coating agent is 0.1 to
It is preferably about 5 g / m ² (dry state).

Of the chemical vapor deposition method and physical vapor deposition method described above, when vapor deposition is performed by chemical vapor deposition method, functionalities such as organic components and hydroxyl groups are larger than when vapor deposition is performed by physical vapor deposition method. It contains more groups and the adhesion between the gas barrier coating layer and the deposited film becomes higher.

The oxygen permeability of the gas barrier coating film of the present invention produced as described above is 1.5 cm ³ / m ² · atm at a temperature of 23 ° C. and a relative humidity of 90% RH.
・ It is 24 hours or less. The measurement of the oxygen permeability is carried out, for example, using an oxygen permeability measuring instrument [model name, OX-TRAN 2/2, manufactured by MOCON, USA]
0] can be measured at 23 ° C. and 90% RH.

The gas barrier coating film of the present invention and the laminated material thereof are formed into a bag and a box by using the film.
It is possible to manufacture a packaging container suitable for filling and packaging various forms of articles. The packaging container obtained by using the gas barrier coating film of the present invention is excellent in gas barrier properties against oxygen, water vapor, etc., transparency, heat resistance, impact resistance, etc., lamination processing, printing processing, bag making, box making processing. Has post-processing suitability, such as food and drink, pharmaceuticals,
It has excellent suitability for packing, preservation, etc. of chemicals such as detergents, shampoos, oils, toothpastes, adhesives and adhesives, cosmetics, and various other articles. The above bag making,
To explain the method of making a box, for example, in the case of a soft packaging bag, using a laminated material of the gas barrier coating film, facing the surface of the heat-sealing resin layer of the inner layer, or fold it or A bag body can be formed by superposing two sheets and heat sealing the peripheral end thereof to provide a seal portion. As the bag making method, the above-mentioned laminated material is bent with its inner layer surface opposed, or two of them are overlapped, and the peripheral edge of the outer periphery is further sealed with a side seal type, a two-side seal type, a three-side seal type. Various types of packaging containers that are heat-sealed, including four-sided seal type, envelope-attached seal type, gasket-attached seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, and other heat seal forms. To manufacture. Also,
The laminated material is a self-supporting packaging bag (stand-up pouch),
Tube containers and the like can also be manufactured. The heat sealing can be performed by a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal. Furthermore, for example, a one-piece type, a two-piece type, another spout, an opening / closing zipper, and the like can be arbitrarily attached to the packaging container.

In the case of manufacturing a packaging container including a paper base, a laminated material in which paper bases are laminated is manufactured, and a blank plate for manufacturing a desired paper container is manufactured from the laminated material. Using a blank plate, a body, a bottom, a head, and the like can be manufactured to produce a liquid paper container of a brick type, a flat type, a goebel top type, and the like.
In addition, any shape can be manufactured, such as a rectangular container or a round or other cylindrical paper can. The packaging container manufactured as described above can be used for filling and packaging of various foods and drinks, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods, and other various articles. The gas barrier coating film of the present invention thus obtained is excellent in gas barrier properties even under humid conditions, so that it is useful not only for food, tobacco, and packaging materials in the toiletry field, but also for solar cells, protective films, moisture-proof films, and the like. Used for applications.

[0063]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. In the examples, parts and% are based on weight unless otherwise specified. Each evaluation item in the examples was measured as follows.

The appearance of the coating film was visually evaluated. Viscosity of coating liquid The viscosity at a liquid temperature of 25 ° C. was measured by a B-type viscometer. The viscosity measurement was performed immediately after the preparation of the coating composition and 24 hours later. MOCON OXTRAN2 made by Oxygen Permeability Modern Control
/ 20 was measured in an atmosphere at a temperature of 25 ° C. and a humidity of 90 RH%.

Reference Example 1 (Preparation of Titanium Chelate Compound) To a reactor equipped with a reflux condenser and a stirrer, 100 parts of tetra-i-propoxytitanium and 70 parts of acetylacetone were added, and the mixture was stirred at 60 ° C. for 30 minutes. Compound (b-1) was obtained. The purity of the reaction product was 75%.

Reference Example 2 (Preparation of zirconium chelate compound) 100 parts of tetra-n-butoxyzirconium (purity 100%) and 68 parts of ethyl acetoacetate were added to a reactor equipped with a reflux condenser and a stirrer. The mixture was stirred for 30 minutes to obtain a zirconium chelate compound (b-2). The purity of the reaction product was 77%.

Example 1 As the component (a), an ethylene / vinyl alcohol copolymer [Soarnol D2630, manufactured by Nippon Synthetic Chemical Co., Ltd., saponification degree: 98% or more, ethylene content: 26 mol%, melt flow index: 30 g / 10 min] 15% water / n
In 100 parts of a -propyl alcohol solution (water / n-propyl alcohol weight ratio = 6/4), 10 parts of boric acid was added as a component (c) and dissolved, and then prepared as a component (b) in Reference Example 1. Titanium chelate compound (b-1) 10
Were mixed to obtain a coating composition (A) of the present invention.

Example 2 As the component (a), an ethylene / vinyl alcohol copolymer [manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol D2630, degree of saponification: 98% or more, ethylene content: 26 mol%, melt flow index: 30 g / 10 min] 15% water / n
100 parts of -propyl alcohol / N, N-dimethylformamide solution (water / n-propyl alcohol / N, N-dimethylformamide weight ratio = 6/3/1) and 5 parts of boric acid as the component (c) were added. After dissolving,
As the component (b), 10 parts of the titanium chelate compound (b-1) prepared in Reference Example 1 was mixed to obtain a coating composition (B) of the present invention.

Example 3 Ethylene / vinyl alcohol copolymer (Soarnol D2908, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree: 98% or more, ethylene content: 29 mol%, melt flow index: 8 g) / 10 min] of 15% water / n-
In 100 parts of propyl alcohol / N, N-dimethylformamide solution (water / n-propyl alcohol / N, N-dimethylformamide weight ratio = 6/3/1), 10 parts of boric acid is added as a component (c) and dissolved. After that, 10 parts of the titanium chelate compound (b-1) prepared in Reference Example 1 previously prepared as the component (b) and 10 parts of water were mixed, and the mixture was stirred at room temperature for 1 hour, and then mixed. C) was obtained.

Example 4 In Example 1, colloidal silica [Nissan Chemical Industry Co., Ltd., Snowtex IPA] was added as a component (d).
-ST, dispersion medium; isopropyl alcohol, average particle diameter: 10 nm, solid content: 30%] A coating composition (D) of the present invention was obtained in the same manner as in Example 1 except for adding 50 parts. .

Example 5 A coating of the present invention was prepared in the same manner as in Example 1 except that 10 parts of the zirconium chelate compound (b-2) prepared in Reference Example 2 was used as the component (b). A composition (E) was obtained.

Example 6 As the component (a), an ethylene / vinyl alcohol copolymer [manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol A3245, degree of saponification: 98% or more, ethylene content: 32 mol%, melt flow index: 45 g / 10 min] 15% water / n
100 parts of -propyl alcohol (water / n-propyl alcohol weight ratio = 3/7) and 5 parts of boric acid as the component (c) were added and dissolved, and then the titanium chelate prepared in Reference Example 1 was used as the component (b). 10 parts of the compound (b-1) was mixed to obtain a coating composition (F) of the present invention.

Example 7 As the component (a), an ethylene / vinyl alcohol copolymer [manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol D2935, degree of saponification: 98% or more, ethylene content: 29 mol%, melt flow index: 35 g / 10 min] 5% water / n-
100 parts of a propyl alcohol / i-propyl alcohol solution (water / n-propyl alcohol / i-propyl alcohol weight ratio = 38/41/21), 2 parts of the titanium chelate compound (b-1) prepared in Reference Example 1, and n 6.6 parts of propyl alcohol, 3.3 parts of i-propyl alcohol
Part, 6 parts of water, 12.1 parts of N, N-dimethylformamide as a component (d), and the mixture was hydrolyzed at room temperature for 30 minutes, and a 5% aqueous solution of boric acid 10 as a component (c) Parts were mixed at room temperature to obtain a coating composition (G) of the present invention.

Example 8 An ethylene / vinyl alcohol copolymer containing 2% boric acid as the component (c) [component (a)] [Nippon Synthetic Chemical Co., Ltd.
Manufactured by Soarnol D2935, degree of saponification: 98% or more, ethylene content: 29 mol%, melt flow index;
35 g / 10 min] of 5% water / n-propyl alcohol /
i-propyl alcohol solution (water / n-propyl alcohol / i-propyl alcohol weight ratio = 38/41/2)
1) 100 parts, 2 parts of the titanium chelate compound (b-1) prepared in Reference Example 1, and 18.7 of n-propyl alcohol
Part, 3.3 parts of i-propyl alcohol and 6 parts of water were mixed and hydrolyzed at room temperature for 30 minutes, and the component (b) was mixed at room temperature to obtain a coating composition (H) of the present invention.

Example 9 An ethylene / vinyl alcohol copolymer containing 5% boric acid as the component (c) [component (a)] [Nippon Gohsei Chemical Co., Ltd.
Manufactured by Soarnol D2935, degree of saponification: 98% or more, ethylene content: 29 mol%, melt flow index;
35 g / 10 min] of 5% water / n-propyl alcohol /
i-propyl alcohol solution (water / n-propyl alcohol / i-propyl alcohol weight ratio = 38/41/2)
1) 100 parts, 2 parts of the titanium chelate compound (b-1) prepared in Reference Example 1 and n-propyl alcohol 12.5
(B), which was mixed with 1.3 parts of i-propyl alcohol and 4 parts of water and hydrolyzed at room temperature for 30 minutes, was mixed at room temperature to obtain a coating composition (I) of the present invention.

Example 10 An ethylene / vinyl alcohol copolymer containing 5% boric acid as the component (c) [component (a)] [Nippon Gohsei Chemical Co., Ltd.
Manufactured by Soarnol D2935, degree of saponification: 98% or more, ethylene content: 29 mol%, melt flow index;
35 g / 10 min] of 5% water / n-propyl alcohol /
i-propyl alcohol solution (water / n-propyl alcohol / i-propyl alcohol weight ratio = 38/41/2)
1) 100 parts, 0.7 part of the titanium chelate compound (b-1) prepared in Reference Example 1, and n-propyl alcohol 6.4
Part, i-propyl alcohol and 1.1 parts of water and 2 parts of water were mixed and hydrolyzed at room temperature for 30 minutes. Component (b) and component (d) were N, N-dimethylformamide.
One part was mixed at room temperature to obtain a coating composition (J) of the present invention.

Example 11 An ethylene / vinyl alcohol copolymer containing 5% boric acid as the component (c) [component (a)] [Nippon Synthetic Chemical Co., Ltd.
Manufactured by Soarnol D2935, degree of saponification: 98% or more, ethylene content: 29 mol%, melt flow index;
Water / n-propyl alcohol / i-propyl alcohol solution (water / n-35 g) containing 5% each of polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., Mw = 25,000) as a component (d). Propyl alcohol / i-
Propyl alcohol weight ratio = 38/41/21) 100
Part of the titanium chelate compound (b-
1) 2 parts, 18.7 parts of n-propyl alcohol, 3.3 parts of i-propyl alcohol, and 6 parts of water were mixed and hydrolyzed at room temperature for 30 minutes. An inventive coating composition (K) was obtained.

Example 12 Ethylene / vinyl alcohol copolymer containing 10% boric acid as the component (c) [Component (a)] [manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol D2935, degree of saponification: 98% or more; Ethylene content: 29 mol%, melt flow index: 35 g / 10 min] in 5% water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio 40/6)
0) 100 parts, 2 parts of the titanium chelate compound (b-1) prepared in Reference Example 1 and n-propyl alcohol 16.8
(B) hydrolyzed at 55 ° C. for 4 hours by mixing and then mixing at 40 ° C. and stirring for 2 hours to obtain a coating composition (L) of the present invention.

Example 13 Ethylene / vinyl alcohol copolymer containing 5% of boric acid as the component (c) [Component (a)] [Nippon Synthetic Chemical Co., Ltd.
Manufactured by Soarnol D2935, degree of saponification: 98% or more, ethylene content: 29 mol%, melt flow index;
35 g / 10 min] 5% water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio 40/60) 1
00 parts of the titanium chelate compound (b) prepared in Reference Example 1.
-1) 2 parts, n-propyl alcohol 16.8 parts, water 1
1.2 parts were mixed and hydrolyzed at 55 ° C. for 4 hours (b)
The component and 12.1 parts of N, N-dimethylformamide as the component (d) were mixed at 40 ° C. and stirred for 2 hours to obtain a coating composition (M) of the present invention.

Example 14 In Example 12, as the component (a), polyvinyl alcohol [RS polymer RS-110 manufactured by Kuraray Co., Ltd.] was used.
(Saponification degree = 99%, polymerization degree = 1,000)], except that the gas barrier coating composition (N) was obtained in the same manner as in Example 12 above.

Comparative Example 1 A 15% water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio = 6/4) of the ethylene-vinyl alcohol copolymer used in Example 1 was used as a coating composition for comparison. (Α).

Comparative Example 2 In Example 1, 100 parts of a 15% aqueous solution of a polyvinyl alcohol polymer [Gosenol NL-05 manufactured by Nippon Synthetic Chemical Co., Ltd.] in which ethylene was not copolymerized was used in place of the component (a). Except for using, a coating composition (β) for comparison was obtained in the same manner as in Example 1.

Comparative Example 3 A comparative coating composition (γ) was prepared in the same manner as in Example 1 except that the component (c) was not added.
I got

Evaluation Examples 1 to 13, Comparative Evaluation Examples 1 to 3 Measurements of the viscosity of the compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 3 at the initial stage and after 24 hours, and a film thickness of 12 μm subjected to corona discharge treatment Is coated on a polyethylene terephthalate (PET) film by a bar coater and dried at 120 ° C. for 1 minute with a hot air drier to form a 1 μm-thick coating film. A gas barrier coating material (coating film)
I got The gas barrier property of the obtained gas barrier coating material was measured using an oxygen permeability measuring device (M Modern Control Co., Ltd., M
OCON OXTRAN 2/20) at room temperature under a 90% humidity condition. The transparency of the coating film was evaluated by visual observation. Tables 1 and 2 show these results.

[0085]

[Table 1]

[0086]

[Table 2]

* 1) The unit of viscosity is mPa · s * 2) The unit of oxygen permeability is cc / m ² · atm · 24
hr

Example 15 (1) As a substrate, a biaxially stretched polyethylene having a thickness of 12 μm was used.
Use of terephthalate film and turn it into plasma
Attached to the delivery roll of the chemical vapor deposition equipment, the following conditions
A silicon oxide deposited film having a thickness of 0.012 μm
On one side of stretched polyethylene terephthalate film
Formed. (Evaporation conditions) Reaction gas mixture ratio: hexamethyl
Disiloxane: oxygen gas: helium = 1: 10: 10
(Unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10^-6mbar Degree of vacuum in the deposition chamber: 6.5 × 10^-2mbar Cooling / electrode drum supply power: 18 kW Film transport speed: 80 m / min Evaporation surface: Corona treated surface (2) Next, the above-described biaxial silicon oxide evaporated film was formed
Silicon oxide in stretched polyethylene terephthalate film
Was subjected to a corona treatment under the following conditions. The result
As a result, the surface tension of the silicon oxide deposited film surface is 35 dyn
To 62 dyn. Output: 10 kW Processing speed: 100 m / min (3) Next, the above-mentioned corona-treated silicon oxide vapor-deposited film
-Formed biaxially stretched polyethylene terephthalate fill
Corona treated surface of the deposited silicon oxide film
, Using a gravure printing machine, the first color gravure
A coating roll was placed, and the coating obtained in Example 12 was removed.
Using a barrier coating composition (L),
Coated by lab roll coat method, thickness
0.5g / m ^Two(Dry state) to form a coating film
Was. Next, heat-treat at 120 ° C for 2 minutes to coat
Gas barrier coating of the present invention by forming a cured film
A film was produced. Next, the gas barrier coating
On the cured film of the film
Using a gravure printing machine, using a gravure ink composition
Thus, a desired multicolor printed pattern layer was formed. (4) Next, the biaxially stretched po
Dry lamination of polyethylene terephthalate film
Attached to the first delivery roll of the machine, and its printed pattern layer surface
And two-part curable poly using the gravure roll coating method
4.5 g / m of urethane-based laminating adhesive^Two(Dry
State) to form an adhesive layer for lamination
did. Next, a thickness of 7
Dry laminating 0μm low density polyethylene film
To produce a laminated material. Oxygen permeability of this laminate
Is 0.2cm^Three/ M^TwoAtm · 24 hr.

Example 16 (1) As a substrate, a biaxially oriented polypropylene film having a thickness of 20 μm (trade name, GH, manufactured by Nimura Chemical Industry Co., Ltd.)
-I, a single-sided corona-treated product), which was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and a silicon oxide deposited film having a thickness of 0.015 μm was formed on the biaxially stretched polypropylene film under the following conditions. Formed on one side. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.2 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber : 5.1 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transport speed: 70 m / min Evaporation surface: Corona treated surface (2) Next, biaxial stretching on which a silicon oxide evaporation film was formed as described above A corona treatment was applied to the surface of the silicon oxide vapor-deposited film of the polypropylene film under the following conditions. As a result, the surface tension of the silicon oxide deposited film surface was changed from 42 dyn to 65 d.
yn. Output: 10 kW Processing speed: 100 m / min (3) Next, using a biaxially stretched polypropylene film on which a corona-treated silicon oxide vapor-deposited film was formed,
On the corona-treated surface of the deposited silicon oxide film, using a gravure printing machine, arranging a gravure coating roll for the first color, using the gas barrier coating composition (H) obtained in Example 8, This was coated by a gravure roll coating method to form a coating film having a thickness of 0.9 g / m ² (dry state). Then 100
The coating was cured by heating at a temperature of 3 ° C. for 3 minutes to produce a gas barrier coating film of the present invention. Next, a desired multicolor printed picture layer was formed on the cured coating of the gas barrier coating film using the gravure printing machine and the gravure ink composition. (4) Next, the biaxially stretched polypropylene film having the printed pattern surface formed thereon is mounted on a first delivery roll of a dry laminating machine, and a two-component curing type polyurethane is applied to the printed pattern layer surface using a gravure roll coating method. An adhesive for system lamination was applied at a rate of 4.5 g / m ² (dry state) to form an adhesive layer for lamination. Then
A 70 μm-thick unstretched polypropylene film was dry-laminated on the laminating adhesive layer surface to produce a laminated material. The oxygen transmission rate of this laminated material is 0.6 cm
³ / m ² · atm · 24 hr.

Example 17 (1) A 15 μm-thick biaxially stretched nylon film was used as a base material, and was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus.
m of silicon oxide was formed on one surface of the biaxially stretched nylon film. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.2 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber : 5.1 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transport speed: 70 m / min Evaporation surface: Corona treated surface (2) Next, biaxial stretching on which a silicon oxide evaporation film was formed as described above A corona treatment was performed on the surface of the nylon film on which the silicon oxide was deposited, under the following conditions. As a result, the surface tension of the surface of the deposited silicon oxide film was improved from 42 dyn to 65 dyn. Output: 10 kW Processing speed: 100 m / min (3) Next, using a biaxially stretched nylon film on which a corona-treated silicon oxide vapor-deposited film was formed, a gravure was applied to the corona-treated surface of the silicon oxide vapor-deposited film. Using a printing machine, a gravure coating roll was placed in the first color, and the gas barrier coating composition (M) obtained in Example 13 was used. A coating film of 0.5 g / m ² (dry state) was formed. Subsequently, the coating was cured by heating at 120 ° C. for 1 minute to form a gas barrier coating film of the present invention. Next, on the coating cured film of the gas barrier coating film, subsequently using the gravure printing machine,
The gravure ink composition was used to form the desired multicolor printed picture layer. (4) Next, the biaxially stretched nylon film having the printed pattern surface formed thereon is mounted on a first delivery roll of a dry laminating machine, and the two-component curing type polyurethane is coated on the printed pattern layer surface using a gravure roll coating method. An adhesive for system lamination was applied at a rate of 4.5 g / m ² (dry state) to form an adhesive layer for lamination. Next, a 70 μm-thick unstretched polypropylene film was dry-laminated on the surface of the laminating adhesive layer to produce a laminated material. The oxygen transmission rate of this laminated material is 0.5 cm ³ / m ²
Atm · 24 hr.

Example 18 In (4) of Example 15 described above, the thickness of the biaxially stretched polyethylene terephthalate film on which the print pattern layer was formed was set to a thickness of 70 through a laminating adhesive layer.
Instead of dry laminating a low-density polyethylene film of μm to produce a laminated material, a biaxially stretched polyethylene terephthalate film having a printed pattern layer is mounted on a first delivery roll of an extrusion laminating machine, and the printed pattern layer surface is Using a low-density polyethylene for melt extrusion, a 70 μm-thick low-density polyethylene film was extruded and laminated while being melt-extruded to a thickness of 20 μm. Manufactured. The oxygen permeability of this laminate is
0.3 cm ³ / m ² · atm · 24 hr.

Example 19 In (4) of Example 16 described above, the biaxially stretched polypropylene film on which the print pattern layer was formed,
Instead of dry laminating an unstretched polypropylene film having a thickness of 70 μm via a laminating adhesive layer to produce a laminated material, a biaxially stretched polypropylene film having a printed picture layer formed thereon is extruded into a first delivery roll of a laminating machine. , The printed pattern layer surface, using a low-density polyethylene for melt extrusion, while extruding this to a thickness of 20μm, extruding a 70μm-thick low-density polyethylene film, laminating, otherwise,
A laminated material was manufactured in exactly the same manner as in Example 16 above.
The oxygen transmission rate of this laminated material is 0.8 cm ³ / m ² · atm.
-It was 24 hours.

Example 20 In Example 17 (4), a printed pattern layer was formed.
Laminate is applied to the printed pattern layer of the biaxially stretched nylon film.
Non-stretched polyp with a thickness of 70 μm via the adhesive layer
Produce laminated material by dry laminating propylene film
Biaxially stretched nylon with printed pattern layer
The first delivery roll of a laminating machine that extrudes a film
On the surface of the printed picture layer, low density for melt extrusion
Using polyethylene, melt-press this to a thickness of 20μm
70μm thick low density polyethylene fill
Extruded and laminated, and otherwise the above Example 1
In the same manner as in 7, a laminated material was produced. Of this laminate
Oxygen permeability is 0.6cm ^Three/ M^Two・ Atm ・ 24hr
there were.

Example 21 (1) A 12 μm-thick biaxially stretched polyethylene terephthalate film was used as a base material, and was mounted on a delivery roll of a take-up type vacuum evaporation apparatus. The aluminum film was fed out, and while supplying oxygen gas, an oxidation reaction vacuum evaporation method using an electron beam (EB) heating method was used to deposit a film having a thickness of 0.02 μm on the biaxially stretched polyethylene terephthalate film. Of aluminum oxide was formed. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 5.2 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 1.1 × 10 ⁻⁶ mbar EB output: 40 kW Film transport speed: 600 m / min Vapor deposition surface: Corona treated surface (2) Next, the aluminum oxide deposited film surface of the biaxially stretched polyethylene terephthalate film having the aluminum oxide deposited film formed thereon was subjected to corona treatment under the following conditions. As a result, the surface tension of the surface of the deposited aluminum oxide film was improved from 45 dyn to 60 dyn. Output: 10 kW Processing speed: 100 m / min (3) Next, using a biaxially stretched polyethylene terephthalate film on which a vapor-deposited aluminum oxide film subjected to the above-described corona treatment was formed, the corona-treated surface of the vapor-deposited aluminum oxide film was A gravure printing machine is used, a gravure coating roll is arranged on the first color, and the gas barrier coating composition (L) obtained in Example 12 is used. A coating film having a thickness of 0.9 g / m ² (dry state) was formed. Subsequently, the coating was cured by heating at 120 ° C. for 1 minute to form a gas barrier coating film of the present invention. Next, a desired multicolor printed picture layer was formed on the cured coating of the gas barrier coating film using the gravure printing machine and the gravure ink composition. (4) Next, the biaxially stretched polyethylene terephthalate film having the printed pattern layer formed thereon is mounted on a first delivery roll of a dry laminating machine, and the printed pattern layer surface is cured by a two-component curing method using a gravure roll coating method. The polyurethane-based laminating adhesive was applied at a rate of 4.5 g / m ² (dry state) to form a laminating adhesive layer. Next, a thickness of 7
A low-density polyethylene film of 0 μm was dry-laminated to produce a laminated material. The oxygen transmission rate of this laminated material was 0.2 cm ³ / m ² · atm · 24 hr.

Example 22 (1) As a substrate, a biaxially stretched polypropylene having a thickness of 20 μm was used.
Renfilm (made by Nimura Chemical Co., Ltd., trade name, GH
-I, single-sided corona treated product) and take-up type
Attached to the delivery roll of the vacuum evaporation device, then
Unwind the film onto the coating drum and
Using minium as the deposition source, while supplying oxygen gas,
Oxidation reaction vacuum by lectron beam (EB) heating method
By the vapor deposition method, the biaxially stretched polypropylene film
On top, a deposited film of aluminum oxide with a thickness of 0.02 μm
Formed. (Evaporation conditions) Evaporation source: Aluminum Vacuum degree in vacuum chamber: 8.2 × 10^-6mbar Degree of vacuum in evaporation chamber: 1.0 × 10^-6mbar EB output: 40 kW Film transport speed: 500 m / min (2) Next, a vapor-deposited film of aluminum oxide was formed as described above.
Aluminum oxide of biaxially oriented polypropylene film
Was subjected to a corona treatment under the following conditions. The result
As a result, the surface tension of the evaporated aluminum oxide film surface is 47
dyn was improved to 62 dyn. Output: 10 kW Processing speed: 100 m / min (3) Next, the above-mentioned corona-treated aluminum oxide
Use a biaxially stretched polypropylene film with a deposited film
Corona treated surface of the deposited aluminum oxide film
, Using a gravure printing machine, the first color gravure
A coating roll was placed, and the coating obtained in Example 13 was removed.
Using the barrier coating composition (M),
Coated by lab roll coat method, thickness
0.5g / m ^Two(Dry state) to form a coating film
Was. Next, heat-treat at 100 ° C for 3 minutes to coat
Gas barrier coating of the present invention by forming a cured film
A film was produced. Next, the gas barrier coating
On the cured film of the film
Using a gravure printing machine, using a gravure ink composition
Thus, a desired multicolor printed pattern layer was formed. (4) Next, the biaxially stretched po
First feed of propylene film to dry laminating machine
Gravure roll on the print pattern layer
Two-component curing type polyurethane laminating
4.5 g / m of adhesive for nate^Two(Dry) ratio
Coating was performed to form an adhesive layer for lamination. Then
On the laminating adhesive layer surface, non-stretched with a thickness of 70 μm
Dry lamination of polypropylene film and lamination
Lumber was manufactured. The oxygen transmission rate of this laminated material is 0.6 cm
^Three/ M^TwoAtm · 24 hr.

Example 23 (1) A biaxially stretched nylon film having a thickness of 15 μm was used as a base material, and this was mounted on a delivery roll of a take-up type vacuum evaporation apparatus. Using an aluminum as a vapor deposition source and supplying oxygen gas, an oxidation reaction vacuum vapor deposition method using an electron beam (EB) heating method is used to form a film having a thickness of 0.02 μm on the biaxially stretched nylon film.
Of aluminum oxide was formed. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.2 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 1.0 × 10 ⁻⁶ mbar EB output: 40 kW Film transport speed: 500 m / min Vapor deposition surface: Corona treated surface (2) Next, the aluminum oxide deposited film surface of the biaxially stretched nylon film on which the aluminum oxide deposited film was formed was subjected to corona treatment under the following conditions. As a result, the surface tension of the aluminum oxide deposited film surface was 45 dyn.
To 60 dyn. Output: 10 kW Processing speed: 100 m / min (3) Next, using a biaxially stretched nylon film on which a vapor-deposited film of aluminum oxide subjected to the above corona treatment was formed,
Using a gravure printing machine, a gravure coating roll for the first color is placed on the corona-treated surface of the aluminum oxide deposited film, and the gas barrier coating composition (H) obtained in Example 8 is used. This is coated by the gravure roll coating method, and the thickness is 1.2 g / m.
² (dry state) of the coating film was formed. Then
The coating was cured by heating at 120 ° C. for 2 minutes to form a gas barrier coating film of the present invention. Next, a desired multicolor printed picture layer was formed on the cured coating of the gas barrier coating film using the gravure printing machine and the gravure ink composition. (4) Next, the biaxially stretched nylon film having the printed pattern layer formed thereon is mounted on a first delivery roll of a dry laminator, and a two-component curable polyurethane is applied to the printed pattern layer surface using a gravure roll coating method. An adhesive for system lamination was applied at a rate of 4.5 g / m ² (dry state) to form an adhesive layer for lamination. Next, a 70 μm-thick unstretched polypropylene film was dry-laminated on the surface of the adhesive layer for lamination to produce a laminated material. The oxygen transmission rate of this laminated material is 0.5 cm ³ / m ²
Atm · 24 hr.

Example 24 In Example 21 (4), the thickness of the biaxially stretched polyethylene terephthalate film on which the print pattern layer was formed was set to a thickness of 70 through a laminating adhesive layer.
Instead of dry laminating a low-density polyethylene film of μm to produce a laminated material, a biaxially stretched polyethylene terephthalate film on which a printed picture layer is formed is mounted on a first delivery roll of an extrusion laminating machine, and the printed picture layer is Using a low-density polyethylene for melt extrusion, a 70 μm-thick low-density polyethylene film was extruded and laminated while being melt-extruded to a thickness of 20 μm. Manufactured. The oxygen permeability of this laminate is
0.3 cm ³ / m ² · atm · 24 hr.

Example 25 In (4) of Example 22, a biaxially stretched polypropylene film having a print pattern layer formed thereon was printed on the print pattern layer surface.
Instead of dry laminating an unstretched polypropylene film having a thickness of 70 μm via a laminating adhesive layer to produce a laminated material, a biaxially stretched polypropylene film having a printed picture layer formed thereon is extruded into a first delivery roll of a laminating machine. , The printed pattern layer surface, using a low-density polyethylene for melt extrusion, while extruding this to a thickness of 20μm, extruding a 70μm-thick low-density polyethylene film, laminating, otherwise,
A laminated material was manufactured in exactly the same manner as in Example 22 above.
The oxygen transmission rate of this laminated material is 0.8 cm ³ / m ² · atm.
-It was 24 hours.

Example 26 In (4) of Example 23, a printed pattern layer was formed.
Laminate is applied to the printed pattern layer of a biaxially stretched nylon film
Non-stretched polyp with a thickness of 70 μm via the adhesive layer
Produce laminated material by dry laminating propylene film
Biaxially stretched nylon with printed pattern layer
The first delivery roll of a laminating machine that extrudes a film
On the surface of the printed picture layer, low density for melt extrusion
Using polyethylene, melt-press this to a thickness of 20μm
70μm thick low density polyethylene fill
Extruded and laminated, and otherwise the above Example 2
In the same manner as in Example 3, a laminated material was produced. Of this laminate
Oxygen permeability is 0.6cm ^Three/ M^Two・ Atm ・ 24hr
there were.

Example 27 (1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base material, and was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus. A 012 μm deposited silicon oxide film was formed on one surface of the biaxially stretched polyethylene terephthalate film. (Deposition conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10 ⁻⁶ mbar Degree of vacuum in deposition chamber : 6.5 × 10 ^-2 mbar Cooling / supply power of the electrode drum: 18 kW Film transport speed: 80 m / min Evaporation surface: Corona treated surface (2) Next, the above-described biaxial film on which a silicon oxide evaporation film was formed Using a stretched polyethylene terephthalate film, this is mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and is fed out onto a coating drum. Using an aluminum as an evaporation source and supplying oxygen gas, an electron beam ( EB) Biaxially stretched polyethylene terephthalate film on which a silicon oxide vapor-deposited film was formed by a reactive vacuum vapor deposition method using a heating method. An aluminum oxide deposited film having a thickness of 0.02 μm was formed on the deposited silicon oxide film of the film. Further, a corona treatment was performed on the surface of the deposited aluminum oxide film under the following conditions. As a result, the surface tension of the surface of the deposited aluminum oxide film was 40 dyn.
To 65 dyn. Output: 10 kW Processing speed: 100 m / min (3) Next, using a biaxially stretched polyethylene terephthalate film on which a deposited film of aluminum oxide and a deposited film of silicon oxide were formed as described above, the surface of the deposited film of aluminum oxide was used. A gravure printing machine is used, a gravure coating roll is arranged in the first color, and the gas barrier coating composition (L) obtained in Example 12 is used in the first color, and the gravure roll coating method is used. To form a coating film having a thickness of 1.0 g / m ² (dry state). Then at 120 ° C for 1 minute,
The coating was cured by heating to form a gas barrier coating film of the present invention. Next, a desired multicolor printed picture layer was formed on the cured coating of the gas barrier coating film using the gravure printing machine and the gravure ink composition. (4) Next, the biaxially stretched polyethylene terephthalate film having the printed pattern layer formed thereon is mounted on a first delivery roll of a dry laminating machine, and the printed pattern layer surface is cured by a two-component curing method using a gravure roll coating method. The polyurethane-based laminating adhesive was applied at a rate of 4.5 g / m ² (dry state) to form a laminating adhesive layer. Next, a thickness of 7
A low-density polyethylene film of 0 μm was dry-laminated to produce a laminated material. The oxygen transmission rate of this laminated material was 0.2 cm ³ / m ² · atm · 24 hr.

Example 28 (1) As a substrate, a biaxially oriented polypropylene film having a thickness of 20 μm (trade name, GH, manufactured by Nimura Chemical Industry Co., Ltd.)
-I, a single-sided corona-treated product), attached to a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and deposited a 0.015 μm-thick silicon oxide vapor-deposited film of the biaxially stretched polypropylene film under the following conditions. Formed on one side. (Evaporation conditions) Mixing ratio of reaction gas: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.2 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber : 5.1 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transport speed: 70 m / min Evaporation surface: Corona treated surface (2) Next, biaxial stretching on which a silicon oxide evaporation film was formed as described above Using a polypropylene film, this is mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and is fed out onto a coating drum. While using aluminum as an evaporation source and supplying oxygen gas, an electron beam (EB) is used. Silicon oxide deposited film of a biaxially stretched polypropylene film formed with the above silicon oxide deposited film by a reactive vacuum deposition method using a heating method. A thickness of 0.02μ
m of aluminum oxide was deposited. Further, a corona treatment was performed on the surface of the deposited aluminum oxide film under the following conditions. As a result, the surface tension of the surface of the deposited aluminum oxide film was improved from 42 dyn to 65 dyn. Output: 10 kW Processing speed: 100 m / min (3) Next, using a biaxially stretched polypropylene film on which a deposited film of aluminum oxide and a deposited film of silicon oxide were formed as described above, A gravure printing machine is used, a gravure coating roll is arranged in the first color, and the gas barrier coating composition (G) obtained in Example 7 is used. 0.8g /
An m ² (dry state) coating film was formed. Subsequently, the coating was cured by heating at 120 ° C. for 1 minute to form a gas barrier coating film of the present invention. Next, on the cured coating film of the gas barrier coating film, using the gravure printing machine, a gravure ink composition was used to form a desired multicolor printing pattern layer. (4) Next, the biaxially stretched polypropylene film on which the print pattern layer is formed is mounted on a first delivery roll of a dry laminator, and a two-component curing type polyurethane is applied to the print pattern layer surface by using a gravure roll coat method. An adhesive for system lamination was applied at a rate of 4.5 g / m ² (dry state) to form an adhesive layer for lamination. Then
An unstretched polypropylene film having a thickness of 70 μm was dry-laminated on the surface of the adhesive layer for lamination to produce a laminated material. The oxygen transmission rate of this laminated material is 0.5 cm
³ / m ² · atm · 24 hr.

Example 29 (1) A 15 μm-thick biaxially stretched nylon film was used as a base material, and this was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus.
m of silicon oxide was formed on one surface of the biaxially stretched nylon film. (Evaporation conditions) Mixing ratio of reaction gas: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.2 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber : 5.1 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transport speed: 70 m / min Evaporation surface: Corona treated surface (2) Next, biaxial stretching on which a silicon oxide evaporation film was formed as described above Using a nylon film, it is mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and is fed out onto a coating drum. While using aluminum as an evaporation source and supplying oxygen gas, an electron beam (E) is used.
B) A 0.02 μm-thick aluminum oxide vapor-deposited film was formed on the silicon oxide vapor-deposited film of the biaxially stretched nylon film on which the silicon oxide vapor-deposited film was formed by a reactive vacuum vapor deposition method using a heating method. Further, a corona treatment was performed on the surface of the deposited aluminum oxide film under the following conditions.
As a result, the surface tension of the surface of the deposited aluminum oxide film was improved from 45 dyn to 65 dyn. Output: 10 kW Processing speed: 100 m / min (3) Next, using a biaxially stretched nylon film on which a deposited film of aluminum oxide and a deposited film of silicon oxide were formed as described above, A gravure printing machine is used, a gravure coating roll is arranged in the first color, and the gas barrier coating composition (L) obtained in Example 12 is used. 1.2 g / m ²
A (dry) coating film was formed. Then 1
A coating cured film was formed by heat treatment at 20 ° C. for 2 minutes to produce a gas barrier coating film of the present invention. Next, a desired multicolor printing pattern layer was formed on the cured coating film of the gas barrier coating film by using the gravure ink composition using the gravure printing machine. (4) Next, the biaxially stretched nylon film having the printed pattern layer formed thereon is mounted on a first delivery roll of a dry laminator, and a two-component curable polyurethane is applied to the printed pattern layer surface using a gravure roll coating method. An adhesive for system lamination was applied at a rate of 4.5 g / m ² (dry state) to form an adhesive layer for lamination. Next, a 70 μm-thick unstretched polypropylene film was dry-laminated on the surface of the adhesive layer for lamination to produce a laminated material. The oxygen transmission rate of this laminated material is 0.4 cm ³ / m ²
Atm · 24 hr.

Example 30 In the above (27) of Example 27, the thickness of the biaxially stretched polyethylene terephthalate film having the printed pattern layer formed on the surface of the printed pattern layer was increased by 70% through a laminating adhesive layer.
Instead of dry laminating a low-density polyethylene film of μm to produce a laminated material, a biaxially stretched polyethylene terephthalate film on which a printed picture layer is formed is mounted on a first delivery roll of an extrusion laminating machine, and the printed picture layer is Using a low-density polyethylene for melt extrusion, a 70 μm-thick low-density polyethylene film was extruded and laminated while being melt-extruded to a thickness of 20 μm. Manufactured. The oxygen permeability of this laminate is
0.2 cm ³ / m ² · atm · 24 hr.

Example 31 In (4) of Example 28, the biaxially stretched polypropylene film on which the print pattern layer was formed,
Instead of dry laminating an unstretched polypropylene film having a thickness of 70 μm via a laminating adhesive layer to produce a laminated material, a biaxially stretched polypropylene film having a printed picture layer formed thereon is extruded into a first delivery roll of a laminating machine. , The printed pattern layer surface, using a low-density polyethylene for melt extrusion, while extruding this to a thickness of 20μm, extruding a 70μm-thick low-density polyethylene film, laminating, otherwise,
A laminated material was manufactured in exactly the same manner as in Example 28.
The oxygen transmission rate of this laminated material is 0.6 cm ³ / m ² · atm.
-It was 24 hours.

Example 32 In (4) of Example 29, a printed pattern layer was formed.
Laminate is applied to the printed pattern layer of a biaxially stretched nylon film
Non-stretched polyp with a thickness of 70 μm via the adhesive layer
Produce laminated material by dry laminating propylene film
Biaxially stretched nylon with printed pattern layer
The first delivery roll of a laminating machine that extrudes a film
On the surface of the printed picture layer, low density for melt extrusion
Using polyethylene, melt-press this to a thickness of 20μm
70μm thick low density polyethylene fill
Extruded and laminated, and otherwise the above Example 2
A laminate was produced in exactly the same manner as in No. 9. Of this laminate
Oxygen permeability is 0.5cm ^Three/ M^Two・ Atm ・ 24hr
there were.

Example 33 A laminated material was manufactured in the same manner as in Example 28 except that the gas barrier coating composition (N) was used in (3) of Example 28. The oxygen transmission rate of this laminated material was 0.4 cm ³ / m ² · atm · 24 hr.

[0107]

According to the present invention, a gas barrier coating composition having an extremely low oxygen permeability even under high humidity and harmless to the human body can be obtained. By coating on a synthetic resin film provided with, a coating material having more excellent gas barrier properties can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of a plasma enhanced chemical vapor deposition apparatus.

FIG. 2 is a schematic configuration diagram of a take-up type vacuum evaporation apparatus.

[Explanation of symbols]

 2: Base film 11: Plasma chemical vapor deposition apparatus 15: Cooling / electrode drum 20: Glow discharge plasma 51: Winding vacuum evaporation apparatus 56: Coating drum 58: Evaporation source

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) // C08L 23:00 C08L 23:00 (72) Inventor Koji Shibo 2- 11-24 Tsukiji, Chuo-ku, Tokyo No. within JSR Co., Ltd. (72) Inventor Hiroshi Yamamoto 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Within Dai Nippon Printing Co., Ltd. (72) Takuya Yamazaki 1-1, Ichigaga-cho, Shinjuku-ku, Tokyo No. 1 Inside Dai Nippon Printing Co., Ltd. (72) Inventor Hideki Izawa 1-1-1 Ichigaya Kagacho, Shinjuku-ku, Tokyo F-term inside Dai Nippon Printing Co., Ltd. 4F006 AA12 AB20 AB64 AB73 BA05 CA07 DA04 4F100 AA01B AA01C AA17C AA20 AA31B AB01C AH03B AH08B AK01A AK21B AK42 AK68 AL05B BA02 BA03 BA07 BA10A BA10C CC00B DE01B EH462 EH66C EH662 EJ08B EJ082 GB15 GB23 GB66 JD02B JL00 4J038 CE021 CE031 CG172 CK032 DM002 HA216 HA446 HA476 JB12 JB26 KA08 MA07 NA08 PB03 PB04 PC08

Claims (8)

[Claims] (A) a polyvinyl alcohol-based resin, (b) a general formula (1) R ¹ _mM (OR ² ) _n (1) wherein M is a metal atom and R ¹ is The same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different and has 1 carbon atom
An alkyl group of 1 to 5 or an acyl group or phenyl group of 1 to 6 carbon atoms, m and n are each an integer of 0 or more, and m + n is a valence of M. Hydrolyzate of the metal alcoholate, condensate of the metal alcoholate, chelate compound of the metal alcoholate, hydrolyzate of the metal chelate compound, condensate of the metal chelate compound, metal acylate, hydrolysis of the metal acylate A gas barrier coating composition comprising: a decomposition product; and at least one selected from the group consisting of a condensate of the metal acylate; and (c) a boron compound. 2. The method according to claim 1, wherein (a) the polyvinyl alcohol resin is
The gas barrier coating composition according to claim 1, which is at least one member selected from the group consisting of polyvinyl alcohol and an ethylene / vinyl alcohol copolymer. 3. The gas barrier coating composition according to claim 1, further comprising (d) a nitrogen-containing organic compound. 4. The gas barrier coating composition according to claim 1, further comprising (e) inorganic fine particles. 5. The method according to claim 1, wherein the component (b) is hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent, and then mixed with the component (a). 1
A method for producing a gas barrier coating composition according to any one of claims 1 to 4. 6. A cured resin film formed from the gas barrier coating composition according to any one of claims 1 to 4, which is laminated on a base resin film,
Gas barrier coating film. 7. A base material resin film is provided with a metal and / or inorganic compound vapor-deposited film, and a cured coating film formed from the gas barrier coating composition according to claim 1 is laminated. A gas barrier coating film comprising: 8. The method according to claim 1, wherein the deposited film is formed by a chemical vapor deposition method and / or
8. The gas barrier coating film according to claim 7, which is a deposited film of an inorganic oxide formed by a physical vapor deposition method.