JP2003277677A - Gas-barrier coating composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a coating composition free from a compound with anxiety about harmful properties to a human body. <P>SOLUTION: The gas-barrier coating composition comprises (a) a polyvinyl alcoholic resin, and a cohydrolyzed product and/or cocondensed product of (b) at least one kind selected from the group consisting of a metal alcoholate represented by R<SP>1</SP><SB>m</SB>M(OR<SP>2</SP>)<SB>n</SB>(wherein, M is a metal atom selected from titanium, zirconium and aluminum; R<SP>1</SP>is the same or different and a 1-8C organic group; R<SP>2</SP>is the same or different and a 1-5C alkyl group, a 1-6C acyl group or a phenyl group; (m) and (n) are each an integer of ≥0; and m+n is the valence of M), a hydrolyzate, condensate or chelate compound of the metal alcoholate, a hydrolyzate, condensate or metal acylate of the metal chelate compound, and a hydrolyzate or condensate of the metal acylate, with (c) a silane coupling agent. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is used for packaging applications such as pharmaceuticals, foods, cosmetics, cigarettes, and toiletries, and is effective for preventing permeation of oxygen, water vapor, and other gases that alter contents. Gas barrier coating composition.

[0002]

2. Description of the Related Art In recent years, packaging materials used for packaging of pharmaceuticals, foods, cosmetics, cigarettes, toiletries, etc. prevent deterioration of contents such as oxidation of proteins and fats and oils for foods. , To maintain quality such as taste,
A material having a gas barrier property that does not allow oxygen, water vapor, and other gases that modify the contents to pass through is used.
In response to such conventional problems, for example, Japanese Patent Laid-Open No. 7-2
Japanese Patent No. 66485 discloses a mixed solution of one or more kinds of metal alkoxide or a hydrolyzate thereof and an isocyanate compound having at least two or more isocyanate groups in a molecule on a base material made of a polymer resin composition. A gas barrier material having a gas barrier coating layer formed by applying a coating agent as a main ingredient and heating and drying has been proposed. However, this gas barrier material contains melamine,
Since it contains formaldehyde, tin chloride, etc., it has a problem that it is harmful to the human body because it may be indirectly orally administered to the human body particularly in medical products and food applications.
On the other hand, Japanese Patent No. 1,476,209 proposes a coating material made of polyvinyl alcohol which does not contain isocyanate or the like and has low toxicity. However,
When used for retort packaging for foods, etc., the retort treatment is performed under high temperature and high humidity conditions of 120 ° C. or higher, and therefore requires an oxygen barrier property under high humidity. The gas barrier property of the coating material made of polyvinyl alcohol is significantly affected by humidity, and there is a problem that the gas barrier property is significantly reduced under high humidity. In addition, there is a problem that the adhesion between the barrier coat layer and the base film is significantly reduced under high humidity or in water.

[0003]

The present invention has been made against the background of the above-mentioned conventional technical problems, and does not impair the barrier property against gases such as oxygen and water vapor even under humid conditions, and also provides melamine, An object of the present invention is to provide a gas barrier coating composition which does not contain a compound such as formaldehyde or organic tin, which may be harmful to the human body, and is harmless to the human body.

[0004]

The present invention includes (a) a polyvinyl alcohol resin, and (b) a general formula (1) R ¹ _m M (OR ² ) _n (1) (wherein , M is a metal atom selected from titanium, zirconium, and aluminum, 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 to 1 carbon atoms.
A metal alcoholate represented by an alkyl group of 5 or an acyl group having 1 to 6 carbon atoms or a phenyl group, m and n are each an integer of 0 or more, and m + n is a valence of M; Metal alcoholate hydrolyzate, metal alcoholate condensate, metal alcoholate chelate compound, metal chelate compound hydrolyzate, metal chelate compound condensate, metal acylate, metal acylate hydrolyzate And a condensate of the metal acylate, a co-hydrolyzate and / or a co-condensate of at least one selected from the group of (c) a silane coupling agent (hereinafter also referred to as “co-hydrolyzed condensate”). A gas barrier coating composition containing In the present invention, the components (b) and (c) are cohydrolyzed and / or cocondensed in water or a mixed solvent containing water and a hydrophilic organic solvent, and then mixed with the component (a). The invention relates to a method for producing the above gas barrier coating composition. In the present invention, a gas barrier coating film can be obtained by laminating a coating film formed from the gas barrier coating composition of the present invention on the base resin film. Further, in the gas barrier coating film, on the base resin film,
A vapor deposited film of a metal and / or an inorganic compound may be provided, and a cured coating film formed from the above gas barrier coating composition may be further laminated. Here, the vapor deposition film is preferably an inorganic oxide vapor deposition film formed by a chemical vapor deposition method and / or a physical vapor deposition method.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Coating Composition (a) Component; As the polyvinyl alcohol resin as the (a) component, partially saponified polyvinyl alcohol in which tens of% of acetic acid groups remain, or acetic acid groups remain Not completely saponified polyvinyl alcohol or modified polyvinyl alcohol in which a hydroxyl group is modified may be used and is not particularly limited. Specific examples of the polyvinyl alcohol-based resin include RS-110 (saponification degree = 99%, polymerization degree =), which is an RS polymer manufactured by Kuraray Co., Ltd.
1,000), Kuraray Poval LM-20SO manufactured by the same company
(Saponification degree = 40%, degree of polymerization = 2,000), Goshenol NM-14 (saponification degree = 99%, degree of polymerization = 1400) manufactured by Nippon Synthetic Chemical Industry Co., Ltd., and the like. The ethylene / vinyl alcohol copolymer is a saponified product of a copolymer of ethylene and vinyl acetate, that is, an ethylene-vinyl acetate random copolymer obtained by saponification, and has an acetic acid group of several tens of mol%. From the remaining partial saponification product to the complete saponification product in which only a few mol% of acetic acid groups remain or acetic acid groups do not remain, it is not particularly limited, but in view of gas barrier properties, a preferred saponification product is preferable. The degree of conversion is 80 mol% or more, more preferably 90 mol% or more, and further preferably 95 mol% or more. The content of repeating units 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-produced by Kuraray Co., Ltd.
F101 (ethylene content; 32 mol%), manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908, D2935 (ethylene content; 29 mol%), D2630 (ethylene content;
26%), A4412 (ethylene content 44%) and the like.

The above (a) polyvinyl alcohol resin has a melt flow index of 210 ° C. and a load of 21.1.
Under 68 N conditions, 1 to 50 g / 10 min, preferably 5 to
It is 45 g / 10 minutes. Melt flow index is 1
If it is less than g / 10 minutes, the gas barrier property may deteriorate. On the other hand, if it exceeds 50 g / 10 minutes, the water resistance and solvent resistance may decrease, which is not preferable. these
The polyvinyl alcohol-based resin (a) may be used alone or in combination of two or more.

The ratio of the component (a) in the coating composition of the present invention is 10 to 10,000 with respect to 100 parts by weight of the component (b) before hydrolysis and / or condensation which will be described later.
It is 0 part by weight, preferably 20 to 5,000 parts by weight, more preferably 100 to 1,000 parts by weight. If it is less than 10 parts by weight, the resulting coating film tends to be cracked and the gas barrier property is deteriorated. It may decrease.

Component (b): The 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 “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 acylates. That is, the component (b) is
Only one of the species may be used, or a mixture of any two or more types 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, hydroxycarboxylic acid salts, hydroxycarboxylic acid esters, keto alcohols and amino alcohols. It is obtained by a reaction with (hereinafter also referred to as “chelating agent”). Among these chelating agents, it is preferable to use β-diketones or β-ketoesters,
Specific examples thereof include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate-sec-butyl, acetoacetate-t-. Butyl, 2,4-hexane-dione, 2,4-heptane-
Dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione, 5-methylhexane-dione and the like can be mentioned. Here, in the hydrolyzate of the metal alcoholate, the hydrolyzate of the metal chelate compound, and the hydrolyzate of the metal acylate, it is not necessary that all OR ² groups contained in the metal alcoholate be hydrolyzed. , For example, only one is hydrolyzed, two or more are hydrolyzed,
Alternatively, it may be a mixture thereof. Further, the condensate of the metal alcoholate, the condensate of the metal chelate compound, and the condensate of the metal acylate are condensed with the M-OH group of the hydrolyzate of the metal alcoholate, the metal chelate compound, and the metal acylate. However, in the present invention, it is not necessary that all the M-OH groups are condensed, and a small amount of the M-OH groups are condensed, and the degree of condensation. Are different,
The concept also includes a mixture of condensates in which M-OR groups and M-OH groups are mixed. When a condensate is used as the component (b), the metal alcoholate, the metal chelate compound, and the metal acylate may be previously hydrolyzed and condensed, or a commercially available condensate may be used. May be used. Further, the condensate of the metal alcoholate may be used as it is, or may be used as a condensate of the metal chelate compound by reacting with the above chelating agent. Commercially available products of the condensate of the metal alcoholate include A-10 and B manufactured by Nippon Soda Co., Ltd.
-2, B-4, B-7, B-10, etc.

As the metal atom represented by M in the general formula (1), zirconium, titanium and aluminum can be mentioned as preferable ones, and titanium is particularly preferable. 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. In the case of metal alcoholate, for example, methyl group, ethyl group, n-propyl group, i-propyl group, 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, 2-ethylhexyl group; acetyl group, propionyl group, butyryl group Acyl groups such as valeryl group, benzoyl group and trioyl group; vinyl group, allyl group, cyclohexyl group, phenyl group, glycidyl group,
In addition to (meth) acryloxy group, ureido group, amide group, fluoroacetamide group, isocyanate group, etc.,
Substituted derivatives of these groups and the like can be mentioned. R
Examples of the substituent in the substituted derivative of ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, 3,4
-Epoxy cyclohexyl group, (meth) acryloxy group, ureido group, ammonium base and the like can be mentioned. However, the carbon number of R ¹ including these substituted derivatives is 8 or less including the carbon atoms in the substituent. In the case of a metal acylate, R ¹ has 1 to ¹⁰ 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 mentioned. When two R ¹ 's are present in the general formula (1), they may be the same or different.

The alkyl group having 1 to 5 carbon atoms represented by R ² includes, for example, methyl group, ethyl group, 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 thereof include a propionyl group, a butyryl group, a valeryl group and a caproyl group. A plurality of R ^{2 s} in the general formula (1) may be the same or different from each other.

Of these components (b), specific examples of metal alcoholates and chelate compounds of metal alcoholates include (a) tetra-n-butoxyzirconium and tri-n-.
Butoxy / ethylacetoacetate zirconium, di-
n-butoxy bis (ethylacetoacetate) zirconium, n-butoxy tris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, etc. Zirconium compound;

(B) Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetra-t-butoxytitanium, di-i-propoxy.bis (ethylacetoacetate) titanium, di-i-propoxy.
Bis (acetylacetate) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (triethanolaminato) titanium, dihydroxybislactatertotitanium, dihydroxytitanium lactate, tetrakis (2 −
Titanium compounds such as ethylhexyloxy) titanium;

(C) tri-i-propoxy aluminum, di-i-propoxy ethyl acetoacetate aluminum, di-i-propoxy acetylacetonato aluminum, i-propoxy bis (ethyl acetoacetate) aluminum, i-propoxy Aluminum compounds such as bis (acetylacetonato) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonatobis (ethylacetoacetate) aluminum; and the like. Among these metal alcoholates and chelate compounds of metal alcoholates, preferred are tri-n-butoxyethyl acetoacetate zirconium, di-i-propoxy bis (acetylacetonato) titanium, and tri-i-propoxy. (Acetylacetonato) titanium, di-n-butoxybis (triethanolaminato) titanium, dihydroxybislactatertotitanium, di-i-propoxyethylacetoacetate aluminum and tris (ethylacetoacetate) aluminum. And particularly preferred compounds are di-i-propoxy bis (acetylacetonato) titanium, tri-i-propoxy. (Acetylacetonato) titanium, di-n-butoxy bis (triethanone). Aminato) titanium, dihydroxy
It is a titanium compound such as bislactetotitanium.

Specific examples of the metal acylate include:
Dihydroxy titanium dibutyrate, di-i-propoxy titanium diacetate, di-i-propoxy titanium dipropionate, di-i-propoxy titanium dimaloneate, di-i-propoxy titanium dibenzoylate, di -N-butoxy zirconium diacetate, di-i-propylaluminum monomaloniate and the like can be mentioned, and a particularly preferred compound is dihydroxy.
Titanium compounds such as titanium dibutyrate and di-i-propoxy titanium diacetate. These components (b) may be used alone or in combination of two or more.

The component (b) is mixed with the component (c) described below, and then cohydrolyzed and / or cocondensed in water and / or a hydrophilic organic solvent, and then mixed with the component (a). To do. By performing such a cohydrolysis and / or cocondensation treatment before mixing with the component (a),
A rapid increase in viscosity due to a shock or the like that occurs when the co-hydrolyzed condensate composed of the components (b) to (c) and the component (a) are mixed at the time of preparing the composition and a temporal increase in viscosity are suppressed. The temperature of co-hydrolysis and / or co-condensation is usually 0 ° C. to 90 ° C., and the treatment time is usually 0.1 to 12 hours, as described later. In this case, the amount of water used is
_{^{R 1 m M (OR 2)}} n 1 mole of 0.1 to 1,000 mol, preferably 0.5 to 500 moles. Further, in the case of the mixed solvent, the mixing ratio of water and the hydrophilic organic solvent is water / hydrophilic organic solvent = 10 to 90/90 to 10 (weight ratio), preferably 20 to 80/80 to 20, and more preferably Three
It is 0-70 / 70-30. As the one hydrolyzed with the above mixed solvent, particularly preferred are di-i-propoxy bis (acetylacetonato) titanium, tri-i-propoxy. (Acetylacetonato) titanium, and di-n-butoxy bis. (Triethanolaminato) Titanium compounds such as titanium and dihydroxy bislactate titanium are hydrolyzed with the above mixed solvent.

Component (c): The silane coupling agent of component (c) is an amino group-containing silane coupling agent,
Epoxy group-containing silane coupling agents, and isocyanurate group-containing silane coupling agents are preferred. Specific examples of the amino group-containing silane coupling agent include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldimethoxysilane, aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-butyl-γ-aminopropyltrimethoxysilane, N-β
-(Aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N- (6-aminohexyl ) Γ-Aminopropyltrimethoxysilane, N-
(6-aminohexyl) γ-aminopropylmethyldimethoxysilane, N- (6-aminohexyl) γ-aminopropyltriethoxysilane, N- [styryl (aminomethyl)] γ-aminopropyltrimethoxysilane, N
-[Styryl (aminomethyl)] γ-aminopropylmethyldimethoxysilane, N- [styryl (aminomethyl)] γ-aminopropyltriethoxysilane, N [N
-Β (aminoethyl) aminoethyl] γ-aminopropyltrimethoxysilane, N [N-β (aminoethyl) aminoethyl] γ-aminopropylmethyldimethoxysilane, N [N-β (aminoethyl) aminoethyl] γ -Aminopropyltriethoxysilane, N [N- (benzylmethyl) aminoethyl] γ-aminopropyltrimethoxysilane, N [N- (benzylmethyl) aminoethyl]
γ-aminopropylmethyldimethoxysilane, N [N-
(Benzylmethyl) aminoethyl] γ-aminopropyltriethoxysilane, N [N- (benzyl) aminoethyl] γ-aminopropyltrimethoxysilane, N [N-
(Benzyl) aminoethyl] γ-aminopropylmethyldimethoxysilane, N [N- (benzyl) aminoethyl] γ-aminopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropylmethyldimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminomethyltrimethoxysilane, N-phenylaminomethylmethyldimethoxysilane, N-phenylaminomethyltriethoxysilane, bis (trimethoxysilylpropyl) amine, P- [N- (2-aminoethyl) aminomethyl] phenethyltrimethoxysilane, N-[(3-trimethoxysilyl) propyl] diethylenetriamine,
Examples thereof include N-[(3-trimethoxysilyl) propyl] triethylenetetramine and N-3-trimethoxysilylpropyl-m-phenylenediamine. Of these, particularly preferred are aminopropyltrimethoxysilane, aminopropyltriethoxysilane, N-β-
(Aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, and N-β (aminoethyl) γ-
Examples include aminopropyltriethoxysilane.
Further, as specific examples of the epoxy group-containing silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane,
γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldietoxysilane, β- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Of these, γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane are particularly preferable. Specific examples of the isocyanurate group-containing silane coupling agent include (trimethoxysilylpropyl)
Isocyanurate, (triethoxysilylpropyl) isocyanurate, (triisopropoxysilylpropyl) isocyanurate, 1,3-bis (trimethoxysilylpropyl) isocyanurate, 1,3-bis (triethoxysilylpropyl) isocyanurate, 1,3-
Bis (triisopropoxysilylpropyl) isocyanurate, 1,5-bis (trimethoxysilylpropyl)
Isocyanurate, 1,5-bis (triethoxysilylpropyl) isocyanurate, 1,5-bis (triisopropoxysilylpropyl) isocyanurate, 1,
3,5-tris (trimethoxysilylpropyl) isocyanurate, 1,3,5-tris (triethoxysilylpropyl) isocyanurate, 1,3,5-tris (triisopropoxysilylpropyl) isocyanurate and the like can be mentioned. . Among these, 1,3,5-tris (trimethoxysilylpropyl) isocyanurate and 1,3,5-tris (triethoxysilylpropyl) isocyanurate are particularly preferable.
These components (c) are mixed with the components (b) and then cohydrolyzed and / or co-hydrolyzed in water and / or a hydrophilic organic solvent.
Alternatively, after cocondensation, it is mixed with the component (a). The temperature of co-hydrolysis and / or co-condensation is usually 0 ° C to 90 ° C.
The treatment time is usually 0.1 to 12 hours.

Here, specific examples of the hydrophilic organic solvent include methanol, ethanol, n-propanol and i-.
Propanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, diacetone alcohol, ethylene glycol, diethylene glycol, triethylene glycol and other saturated aliphatic monohydric alcohols or dihydric alcohols having 1 to 8 carbon atoms; ethylene Saturated aliphatic ether compounds having 1 to 8 carbon atoms such as glycol monobutyl ether and ethylene glycol monoethyl ether acetate; 1 to 8 carbon atoms such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether acetate Ester compounds of saturated aliphatic dihydric alcohols; sulfur-containing compounds such as dimethyl sulfoxide; lactic acid, methyl lactate, ethyl lactate, salicylic acid, salicyl In addition to hydrophilic organic solvents such as hydroxycarboxylic acid or hydroxycarboxylic acid ester such as methyl, for example, ethers such as tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, cyclohexanone and isophorone, esters such as ethyl acetate and butyl acetate. In addition to the group, methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethyl sulfoxide and the like can be mentioned. Of these, preferred are methanol, ethanol,
Examples thereof include saturated aliphatic monohydric alcohols having 1 to 8 carbon atoms such as n-propanol, i-propanol, n-butyl alcohol, sec-butyl alcohol and tert-butyl alcohol. Further, the hydrophilic nitrogen-containing organic solvent exemplified as the component (d) described below may be used as a part or all of the hydrophilic organic solvent.

These water and / or hydrophilic organic solvent are more preferably used as a mixture of water and a hydrophilic organic solvent.

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

The ratio of the component (c) in the coating composition of the present invention is 1 to 10,000 parts by weight, preferably 5 to 5,000 parts by weight, and more preferably 100 to 100 parts by weight of the polyvinyl alcohol resin (a). Preferably 10
It is 1000 parts by weight. If the amount is less than 1 part by weight, the resulting coating film may have poor adhesion to the underlying substrate under high humidity and gas barrier properties may not be exhibited, which is not preferable.

The co-hydrolyzate and / or co-condensate of the components (b) and (c) are selected from the component (a), the component (e) described below, and a vapor deposition film component composed of a metal and / or an inorganic compound. It is considered to act to form a co-condensate with at least one. The (a) polyvinyl alcohol-based resin itself is excellent in gas barrier properties, weather resistance, organic solvent resistance, transparency, gas barrier properties after heat treatment, and the like, and in addition, it is a co-hydrolyzed component (b) and component (c). The combined use with the decomposed product and / or the cocondensed product makes it possible to obtain a coating film having excellent gas barrier properties and adhesiveness particularly under high humidity and / or after heat treatment.

Component (d): The coating composition of the present invention can optionally contain a nitrogen-containing compound which is the component (d). Examples of the nitrogen-containing compound as the component (d) include N, N-dimethylacetamide, N, N-
Hydrophilic nitrogen-containing organic solvents such as dimethylformamide, γ-butyrolactone, N-methyl-2-pyrrolidone and pyridine; nucleobases such as thymine, glycine, cytosine and guanine; hydrophilicity such as polyvinylpyrrolidone, polyacrylamide and polymethacrylamide And nitrogen-containing polymers and copolymers obtained by copolymerizing these components. Among these, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-
Pyrrolidone and polyvinylpyrrolidone are preferred.
By mixing the component (d), in coating with a thin film, a coating film having a more transparent appearance and a good appearance can be obtained, and a catalytic effect at the time of condensation with an inorganic vapor deposition layer is exhibited. The proportion of the nitrogen-containing compound used is usually 70% by weight or less, preferably 50% by weight or less, based on the total amount of the solvent.

Component (e): The coating composition of the present invention preferably contains inorganic fine particles as the component (e), if necessary. The above-mentioned (e) inorganic fine particles are particulate inorganic substances having an average particle size of 0.2 μm or less and substantially not containing carbon atoms, and examples thereof include metals or silicon oxides, metals or silicon nitrides, and metal borides. . (E) The method for producing the inorganic fine particles includes, for example, a vapor phase method for obtaining silicon oxide by hydrolysis of silicon tetrachloride in a flame of oxygen and hydrogen, a liquid phase method for obtaining ion exchange of sodium silicate,
A production method such as a solid phase method obtained by pulverizing silica gel with a mill or the like can be mentioned, but the method is not limited to these methods.

(E) Specific examples of compounds in the inorganic particles include SiO ₂ , Al ₂ O ₃ , TiO ₂ , WO ₃ , and Fe _2.
O ₃ , ZnO, NiO, RuO ₂ , CdO, SnO ₂ , B
_{i 2 O 3, 3Al 2 O} 3 · 2SiO 2, Sn-In 2 O 3, S
b-In ₂ O _3, oxides such CoFeO _x, Si ₃ N _4,
Examples thereof include nitrides such as Fe ₄ N, AlN, TiN, ZrN, and TaN, and borides such as Ti ₂ B, ZrB ₂ , TaB ₂ , and W ₂ B. Examples of the form of the (e) inorganic fine particles include powder, colloid or sol dispersed in water or an organic solvent, but are not limited thereto. Of these, colloidal silica, colloidal alumina, and alumina sol are preferable in order to obtain excellent coating performance by cocondensing the components (a) and the cohydrolysis condensates of the components (b) to (c). , Tin sol, zirconium sol, antimony pentoxide sol, cerium oxide sol, zinc oxide sol, titanium oxide sol, colloidal oxides having a hydroxyl group on the particle surface are used. (E) The average particle size of the inorganic fine particles is 0.2 μm or less, preferably 0.1 μm
When the average particle size is less than m and the average particle size exceeds 0.2 μm, the gas barrier property may be deteriorated from the viewpoint of the denseness of the film.
The ratio of the component (e) in the composition of the present invention is as follows:
The total amount of the components (b) and (c) is 100 parts by weight, preferably 900 parts by weight or less, particularly preferably 400 parts by weight or less. If it exceeds 900 parts by weight, the gas barrier properties of the obtained coating film may deteriorate.

For the purpose of curing the composition of the present invention faster and facilitating formation of a cocondensate of the component (a) and the cohydrolysis condensate of the components (b) to (c), (f ) A curing accelerator may be used to cure at relatively low temperatures,
It is more effective to use this (f) curing accelerator together in order to obtain a more dense coating film.

The (f) curing accelerator includes inorganic acids such as hydrochloric acid; naphthenic acid, octylic acid, nitrous acid, sulfurous acid,
Alkali metal salts such as aluminic acid and carbonic acid; alkaline compounds such as sodium hydroxide and potassium hydroxide; alkyl titanic acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, phthalic acid, succinic acid, glutaric acid, oxalic acid , Acid 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 compounds such as -aminoethyl) -aminopropylmethyldimethoxysilane and γ-anilinopropyltrimethoxysilane are used. The proportion of these (f) curing accelerators 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.

Furthermore, in the composition of the present invention, the above-mentioned β-diketones and / or β can be used as stability improvers.
-Ketoesters can be added. That is,
Condensation reaction between the component (a) and the co-hydrolyzed condensate of the components (b) to (c) by coordinating to the metal atom in the metal alcoholate present in the composition as the component (b). It is considered that it has the function of controlling the storage stability and improving the storage stability of the resulting composition. β-
The amount of diketones and / or β-ketoesters used is preferably 2 moles or more, and more preferably 3 to 20 moles, relative to 1 mole of the metal atom in the component (b).

The coating composition of the present invention contains
A filler may be added and dispersed separately in order to develop various properties such as coloring of the resulting coating film, thickening of the film, prevention of ultraviolet ray transmission to the base, provision of corrosion resistance, and heat resistance. However, the filler excludes the components (e) to (f). As the filler, for example, organic pigments, water-insoluble pigments such as inorganic pigments or other than pigments, particulate, fibrous or scale-like metals and alloys and oxides thereof,
Examples thereof include hydroxides, carbides, nitrides and sulfides.
Specific examples of this filler include iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide and chromium oxide in the form of particles, fibers or flakes. , 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, schele green, green soil, manganese green, pigment green, ultramarine blue, dark 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 suboxide, calcium leadate, zinc yellow, lead sulfide, chromium yellow, ocher, cadmium yellow, strontium yellow, titanium yellow, litharge, pigment yellow, cuprous oxide, cadmium red, selenium red , Chrome vermillion, red iron oxide, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead zinc white, bunchson white, lead phthalate, manganese white, lead sulfate,
Graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whiskers, 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.
~ 5,000 nm. The proportion of the filler in the composition is
It 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 components other than the filler.
Parts by weight.

The coating composition of the present invention contains
Other known dehydrating agents such as methyl orthoformate, methyl orthoacetate, and tetraethoxysilane, various surfactants,
Additives other than the above, such as a silane coupling agent, a titanium coupling agent, a dye, a dispersant, a thickener, and a leveling agent, may be added.

In preparing the coating composition of the present invention, a composition containing the above essential components (a) to (c) and optional components (d) to (f) may be prepared, but it is essential. Regarding the components, the components (b) to (c) are subjected to a cohydrolysis treatment and / or a cocondensation treatment in water or a mixed solvent containing water and a hydrophilic organic solvent, and (b) to
After preparing the co-hydrolyzate and / or co-condensate of the component (c), it is mixed with the component (a). By doing so, the coating composition does not change in viscosity over time, and a coating composition having excellent handleability can be obtained.

Specific examples of the method for preparing the coating composition of the present invention in the case of using the component (e) include the following. In these preparation methods,
As the component (b), those which have been previously hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent may be used. Further, the components (b) to (c) are previously subjected to a cohydrolysis treatment and / or a cocondensation treatment in water or a mixed solvent containing water and a hydrophilic organic solvent, to obtain the components (b) to (c). Component) as a cohydrolyzate and / or a cocondensate. Dissolved in water and / or hydrophilic organic solvent (a)
After adding (e) component to the components, (b) component and (c)
A method of adding a cohydrolyzate with a component and / or a cocondensate thereof. Dissolved in water and / or hydrophilic organic solvent (a)
A method comprising adding a co-hydrolyzate of component (b) and component (c) and / or a co-condensate thereof to the component, and then adding component (e) to carry out hydrolysis and / or condensation. Dissolved in water and / or hydrophilic organic solvent (b)
~ A method of adding the component (e) to the component (c), performing hydrolysis and / or condensation, and then adding the component (a). Component (a) in water and / or hydrophilic organic solvent,
A method in which the co-hydrolyzate of the component (b) and the component (c) and / or its co-condensate and the component (e) are added all at once and dissolved / dispersed. Alternatively, a method of performing hydrolysis and / or condensation after that.

The coating composition of the present invention has a gel content after being formed into a film. Specifically, the coating composition of the present invention is applied on a PET film so that the film thickness is 1 μm, and then dried at 140 ° C. for 2 minutes to form a film, and 0.25 g of the film is n-propanol / water ( Weight ratio) =
After dissolving in 1/183 ml at 60 ° C. for 1 hour, the insoluble content is filtered and dried, and the insoluble content calculated from the insoluble content (hereinafter referred to as “heat gelation rate”) is preferably 1 to 90%,
More preferably, it is 5 to 70%. Heat gelation rate is 1
If it is less than%, the water resistance is significantly lowered and the gas barrier property is lowered, which is not preferable. On the other hand, if it exceeds 90%, the water absorption is improved and the gas barrier property is deteriorated, which is not preferable.

Coating Film The coating composition of the present invention is particularly useful as a gas barrier coating material. That is, on the 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 vapor deposition film of an inorganic oxide and a cured coating film made of the coating composition of the present invention.

Examples of the base film that constitutes the gas barrier coating film according to the present invention include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins,
Polycarbonate-based resin, polystyrene-based resin, polyvinyl alcohol, polyvinyl alcohol-based resin such as saponified portion of ethylene-vinyl acetate copolymer, polyacrylonitrile-based resin, polyvinyl chloride-based resin, polyvinyl acetal-based resin, polyvinyl butyral-based resin, Fluorine-based resin 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,
A method of independently forming the above resin by using another film forming method, a method of forming a multilayer coextrusion film by using two or more different resins, and further a method of forming two or more kinds of films. A resin film or sheet is produced by using a resin and mixing it before forming into a film to form a film, and further, for example, a uniaxial method using a tenter system or a tubular system. Or, a resin film or sheet formed by biaxial stretching can be formed. In the present invention, the thickness of the substrate film is preferably 5
˜200 μm, more preferably 10 to 50 μm. In the above, in forming the resin film, for example, the processability of the film, heat resistance, weather resistance, mechanical properties,
Various plastic compounding agents and additives may be added for the purpose of improving and modifying dimensional stability, anti-oxidation property, slipperiness, releasability, flame retardancy, anti-mold property, electrical properties and others. it can. The amount of addition thereof can be arbitrarily added from a very small amount to several tens of% depending on the purpose. Also,
In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a filler other than the above, a reinforcing agent, a reinforcing agent, an antistatic agent, a flame retardant, a flameproofing agent,
A foaming agent, an antifungal agent, a pigment, and the like can be used, and further, a modifying resin and the like can also be used.

In the present invention, the base film is
If necessary, for example, corona discharge treatment, ozone treatment,
Low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals or the like, and other pretreatments can be arbitrarily performed. The above surface pretreatment may be carried out in a separate step before forming a vapor deposition film of inorganic oxide, and, for example, in the case of surface treatment such as low temperature plasma treatment or glow discharge treatment, the above inorganic oxidation treatment is carried out. As a pretreatment for forming a vapor deposition film of a substance, the pretreatment can be performed by an in-line treatment, and in such a case, there is an advantage that the manufacturing cost can be reduced. The surface pretreatment is carried out as a method for improving the adhesion between the substrate film and the vapor deposition film of the inorganic oxide, but as a method for improving the above adhesion, other, for example, A primer coat agent layer, an undercoat agent layer, a vapor deposition anchor coat agent layer, or the like can be optionally formed in advance on the surface of the material film. As the coating agent layer for the above pretreatment, for example, a resin composition containing a polyester resin, a polyurethane resin, or the like as a main component of the vehicle can be used. Further, in the above, as a method for forming the coating agent layer, for example, a solvent type, an aqueous type, or an emulsion type coating agent is used, and a roll coating method, a gravure roll coating method, a kiss coating method, and other coating methods are used. Can be used to coat,
It can be carried out as a post-process after the biaxial stretching treatment of the base material film, or as an in-line treatment of the biaxial stretching treatment. In the present invention, as the base film, specifically, a biaxially stretched polypropylene film, 2
Axial 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 vapor deposition film of a metal and / or an inorganic compound (hereinafter also referred to as "vapor deposition film") on the substrate or the coating film of the present invention. By providing this vapor deposition film, the gas barrier property is further improved. When the vapor deposition film exists, the vapor deposition film and the above (a)
The co-hydrolyzed condensate of the component and the components (b) to (c) forms a chemical bond, a hydrogen bond, or a coordinate bond due to a hydrolysis / co-condensation reaction, and adheres the vapor deposition film and the gas barrier coating layer. The property is improved. As the vapor deposition film,
A vapor deposited film of an inorganic oxide by a chemical vapor deposition method and / or a physical vapor deposition method is preferable.

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

A method for forming a vapor deposition film of an inorganic oxide by the above-mentioned low temperature plasma chemical vapor deposition method will be specifically described with reference to an example thereof. FIG. 1 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of the method for forming a vapor deposition film of an inorganic oxide by the plasma chemical vapor deposition method described above. As shown in FIG. 1 above, in the present invention, the substrate film 2 is fed from the unwinding roll 13 arranged in the vacuum chamber 12 of the plasma enhanced chemical vapor deposition apparatus 11, and the substrate film 2 is further fed. , The cooling / electrode drum 1 at a predetermined speed through the auxiliary roll 14.
It is transported to the 5th circumferential surface. Thus, in the present invention, oxygen gas, inert gas, monomer gas for vapor deposition such as organosilicon compound, and the like are supplied from the gas supply devices 16 and 17, the raw material volatilization supply device 18, etc. 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 cooling / electrode drum 1 described above
Plasma is generated by the glow discharge plasma 20 on the base material film 2 conveyed on the five peripheral surfaces, and this is irradiated to form a continuous film of an inorganic oxide such as silicon oxide to form a film. . In the present invention, at that time, cooling /
A predetermined power is applied to the electrode drum 15 from a power source 21 arranged outside the chamber, and a magnet 22 is arranged in the vicinity of the cooling / electrode drum 15 so as to promote generation of plasma. It has become. Then
The base film 2 on which a continuous film of an inorganic oxide such as silicon oxide is formed is wound around a winding roll 24 via an auxiliary roll 23, so that the inorganic oxide produced by the chemical vapor deposition method of the present invention. It is possible to form a vapor deposition film of In the figure, 25 indicates a vacuum pump. It goes without saying that the above-mentioned exemplification is one example, and the present invention is not limited thereby.
Further, although not shown, in the present invention, the vapor deposition film of the inorganic oxide may be not only one layer of the continuous film of the inorganic oxide but also a composite vapor deposition film in which two or more layers are laminated. The materials to be used can also be used alone or as a mixture of two or more kinds, and further, a vapor deposition film of an inorganic oxide can be formed by mixing different materials.

In the above, the inside of the vacuum chamber 12 is decompressed by the vacuum pump 25, and the degree of vacuum is 1 × 10 ^-1 to 1 × 1.
About 0 ^-8 Torr, preferably a vacuum degree of 1 × 10 ^{-3 -1}
It is desirable to adjust it to about 0 ^-7 Torr. Further, in the raw material volatilization supply device 18, the organosilicon compound which is the raw material is volatilized and mixed with the oxygen gas, the inert gas and the like supplied from the gas supply devices 16 and 17, and this mixed gas is supplied to the raw material supply nozzle 19. It is introduced into the chamber 12 through. In this case, the content of the organosilicon compound in the mixed gas is about 1 to 40 mol%, and the content of the oxygen gas is 10%.
˜70 mol%, the content of the inert gas may be in the range of 10 to 60 mol%, and the mixing ratio of the organosilicon compound, the oxygen gas and the inert gas is 1: 1.
It can be about 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 source 21, the glow discharge plasma 20 is generated near 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 material film 2 is conveyed at a constant speed, and the glow discharge plasma 20 forms a vapor deposition film of an inorganic oxide such as silicon oxide on the base material film 2 on the peripheral surface of the cooling / electrode drum 15. can do. The degree of vacuum in the vacuum chamber 12 at this time is preferably adjusted to about 1 × 10 ⁻¹ to 10 ⁻⁴ Torr, preferably about 1 × 10 ⁻¹ to 10 ⁻² Torr, and The transport speed of the base film 2 is about 10 to 300 m / min, preferably 50 to 15 m.
It is desirable to adjust to about 0 m / min.

The plasma chemical vapor deposition apparatus 1 described above is also used.
In 1, a continuous film of an inorganic oxide such as silicon oxide is formed on the base film 2 in the form of a thin film in the form of SiO _x while oxidizing the raw material gas turned into plasma with oxygen gas. The formed vapor-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 the vapor deposited film of inorganic oxide such as silicon oxide is much higher than that of the vapor deposited film of inorganic oxide such as silicon oxide formed by the conventional vacuum vapor deposition method, etc. It is possible to obtain sufficient gas barrier properties. Further, in the present invention, the surface of the base film 2 is cleaned by SiO _x plasma, and polar groups and free radicals are generated on the surface of the base film 2. Therefore, inorganic substances such as silicon oxide formed are formed. This has the advantage that the adhesion between the vapor-deposited oxide film 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 ^{−. 2} Adjust to about Torr. Therefore, the degree of vacuum when forming a vapor deposition film of an inorganic oxide such as silicon oxide by the conventional vacuum vapor deposition method,
The degree of vacuum is lower than that of about 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, and the vacuum state setting time can be shortened when the base film 2 is replaced with a new one, and the degree of vacuum is easily stabilized. The film forming process is stabilized.

In the present invention, the vapor deposition film of silicon oxide formed by using the vapor deposition monomer gas such as the organosilicon compound chemically reacts with the vapor deposition monomer gas such as the organosilicon compound and oxygen gas to produce the reaction product. The material adheres to one side of the substrate film to form a dense and flexible thin film, and is usually of the general formula SiO _x (however,
X represents a number of 0 to 2) and is a continuous thin film mainly composed of silicon oxide. The above-mentioned vapor-deposited film of silicon oxide has a general formula SiO in terms of transparency, gas barrier properties, and the like.
It is preferably a thin film mainly composed of a continuous film of silicon oxide 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 vapor deposition monomer gas and oxygen gas, the energy of plasma, etc. Generally, the smaller the value of X, the lower the gas permeability, but the film itself becomes yellow. It becomes more transparent and becomes less transparent.

The vapor-deposited film of silicon oxide is mainly composed of silicon oxide, and further contains at least one kind of carbon, hydrogen, silicon or oxygen, or at least one kind of compound consisting of two or more kinds of elements. It is characterized by comprising a continuous film containing a by a chemical bond or the like.
For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit having a graphite shape, a diamond shape, a fullerene shape, or the like, a raw material organosilicon compound or a derivative thereof is used. It may be contained by a chemical bond. Specific examples include hydrocarbons having a CH ₃ moiety, SiH ₃ silyl, hydrosilica such as SiH ₂ silylene, SiH ₂ O.
A hydroxyl group derivative such as H-silanol can be used. In addition to the above, the kind and amount of the compound contained in the vapor deposition film of silicon oxide can be changed by changing the conditions of the vapor deposition process. The content of the above compound contained in the vapor-deposited film of silicon oxide was 0.1.
˜50 mol%, preferably about 5-20 mol%. If it is less than 0.1 mol%, the impact resistance, spreadability, flexibility, etc. of the vapor-deposited film of silicon oxide will be insufficient, and scratches, cracks, etc. will easily occur due to bending, etc., and high gas barrier properties will be stably maintained. Will be difficult to do.
On the other hand, when it exceeds 50 mol%, the gas barrier property is deteriorated, which is not preferable. Further, in the present invention, it is preferable that the content of the above compound in the vapor-deposited film of silicon oxide be decreased in the depth direction from the surface of the vapor-deposited film of silicon oxide. Thereby, on the surface of the vapor-deposited film of silicon oxide, the impact resistance is enhanced by the above compound and the like, while at the interface with the base film, the content of the above compound is small, so that It has the advantage that the adhesion of silicon oxide to the vapor deposited film becomes strong.

In the present invention, the vapor deposition film of silicon oxide is, for example, an X-ray photoelectron spectrometer (Xray).
Photoelectron Spectroscop
y, XPS), secondary ion mass spectrometer (Second)
ary Ion Mass Spectroscopy,
Confirm the above physical properties by performing elemental analysis of the vapor-deposited film of silicon oxide by using a surface analysis device such as SIMS) and analyzing by performing ion etching in the depth direction. You can Further, in the present invention, the film thickness of the vapor deposition film of silicon oxide is preferably about 5 to 400 nm, more preferably 10 to 100 nm.
It is about nm. If the film thickness is 10 nm, or even less than 5 nm, it is difficult to exert the effect of gas barrier property, which is not preferable. On the other hand, the film thickness is 100 nm, and further 4
When the thickness is more than 00 nm, cracks and the like are likely to occur in the film, which is not preferable. In the above, the film thickness can be measured by the fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name: RIX2000 type) manufactured by Rigaku Co., Ltd. Further, in the above, as a means for changing the film thickness of the vapor deposition film of silicon oxide, increasing the volume velocity of the vapor deposition film, that is, a method of increasing the amount of monomer gas and oxygen gas, or slowing the vapor deposition rate It can be performed by a method or the like.

In the above, examples of the vapor deposition monomer gas such as an organic silicon compound which forms a vapor deposition film of an inorganic oxide such as silicon oxide include, for example, 1,1,3,3-tetramethyldisiloxane and hexamethyldisiloxane. , Vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltri Methoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. 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 makes it easier to handle and to form a continuous film. It is a particularly preferable raw material because of its characteristics.
Further, in the above, as the inert gas, for example, argon gas, helium gas or the like can be used.

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

An example of a method of forming a vapor deposition film of an inorganic oxide by the physical vapor deposition method of the present invention will be illustrated and described. FIG. 2 is a schematic configuration diagram of a roll-up type vacuum vapor deposition device.
As shown in FIG. 2, in the vacuum chamber 52 of the take-up type vacuum vapor deposition apparatus 51, the substrate film 2 having the vapor deposition film of the inorganic oxide by the chemical vapor deposition method fed from the unwinding roll 53 is a guide roll. It is guided to the cooled coating drum 56 via 54 and 55. Base film 2 having a vapor deposited film of inorganic oxide by chemical vapor deposition guided on the cooled coating drum 56
The vapor deposition source 58 heated by the crucible 57, for example, metallic aluminum, aluminum oxide or the like is evaporated on the vapor deposition film of the inorganic oxide of, and an oxygen gas outlet 59 is provided if necessary.
Oxygen gas or the like is further ejected, and while supplying the same, a vapor deposition film of an inorganic oxide such as aluminum oxide is formed through the masks 60 and 60, and then a vapor deposition film of an inorganic oxide such as aluminum oxide is formed. The base film 2 formed on the vapor deposition film of the inorganic oxide by the above chemical vapor deposition method is sent out through the guide rolls 55 'and 54' and wound on the take-up roll 61 to obtain the physical properties of the present invention. A vapor-deposited film of an inorganic oxide can be formed.

As the vapor deposition film of the above-mentioned inorganic oxide, any film can be used as long as it is a thin film obtained by vapor-depositing a metal oxide.
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 the like can be used as a vapor deposition film of a metal oxide. Suitable examples of the packaging material include metal oxides such as silicon (Si) and aluminum (Al). The deposited film of the metal oxide can be referred to as a metal oxide such as silicon oxide, aluminum oxide, and magnesium oxide, and its title is MO _x such as SiO _x , AlO _x , and MgO _{x. X} (however, M represents a metal element, and the value of X has a different range depending on the metal element).
The range of the value of X is 0 for silicon (Si).
~ 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 0. 2, sodium (Na) 0-0.5, boron (B) 0-
1.5, 0 for titanium (Ti), 0 for lead (Pb)
1, zirconium (Zr) can take a value of 0 to 2, and yttrium (Y) can take a value of 0 to 1.5. In the above, when X = 1, it is a perfect metal and is not transparent and cannot be used at all. Further, the upper limit of the range of X is a completely oxidized value. In the present invention, as the packaging material, generally, there are few examples other than silicon (Si) and aluminum (Al). Silicon (Si) in the range of 1.0 to 2.0 and aluminum (Al) in the range of 0.5 to 1.5 can be preferably used. In the present invention, the thickness of the thin film of the inorganic oxide varies depending on the metal used, the type of the metal oxide, etc., but is, for example, 5 to 200 nm, preferably 10 to 1.
It is desirable to arbitrarily select and form it within the range of 00 nm. Further, the vapor deposition film of the inorganic oxide of the present invention may be not only one layer of the vapor deposition film of the inorganic oxide but also a laminated body in which two or more layers are laminated. Further, the metal or metal oxide used may be used alone or in a mixture of two or more kinds to form a thin film of an inorganic oxide mixed with different materials.

Specific examples of the method of forming the coating film of the present invention using the coating composition of the present invention include the following methods. A method of forming the coating film of the present invention on the surface of a substrate. If necessary, a primer may be applied beforehand on the surface of the base material to form the coating film of the present invention. A method of forming a vapor deposition film of an inorganic oxide by a chemical vapor deposition method and / or a physical vapor deposition method on the surface of a substrate, and forming the coating film of the present invention on the surface of the vapor deposition film. When forming a vapor deposition film on the surface of a base material, a primer may be applied on the surface of the base material in advance, if necessary. A method of forming a vapor deposition 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 deposition 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 the coating film of the present invention on the surface of the above vapor deposition film. A method for further forming the coating film of the present invention on the surface of the above vapor deposition film. The method according to any one of (1) to (3) above, wherein the surface of the substrate is one side or both sides.

A cured coating film (hereinafter referred to as "coating film of the present invention") formed from the gas barrier coating composition of the present invention on a base material such as a synthetic resin film (including a base material on which the above vapor deposition film is laminated). In order to stack
Roll coat such as gravure coater, spray coat, spin coat, dipping, brush, barcode,
With a coating means such as an applicator, 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 coating once or a plurality of times. Lower, 50 to 300 ° C., preferably 70 to
By heating and drying at a temperature of 200 ° C. for 0.005 to 60 minutes, preferably 0.01 to 10 minutes, condensation is performed and the coating film of the present invention can be formed. Further, an adhesion improving agent such as an anchor coating agent may be coated prior to laminating a cured coating film formed from the gas barrier coating composition. Examples of the anchor coating agent include organic titanium-based anchor coating agents such as alkyl titanates, isocyanate-based anchor coating agents, polyethyleneimine-based anchor coating agents,
A polybutadiene-based anchor coating agent and other various water-based or oil-based anchor coating agents can be used. If necessary, a print pattern layer can be provided on the gas barrier coating film of the present invention, and if necessary, a heat-sealable resin layer can be formed on the print pattern layer.

As the above-mentioned printed pattern layer, for example, a conventional gravure ink composition, offset ink composition, letterpress ink composition, screen ink composition, and other ink composition are provided on the above-mentioned cured coating film. Used, 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, for example, by forming a desired printed picture pattern including characters, figures, patterns, symbols, and the like. Regarding the above ink composition, as a vehicle constituting the ink composition, for example, polyolefin resin such as polyethylene resin, chlorinated polypropylene resin, poly (meth) acrylic resin, polyvinyl chloride resin, polyvinyl acetate, etc. 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, phenol resin,
Xylene resin, maleic acid resin, nitrocellulose,
Fiber-based resins such as ethyl cellulose, acetylbutyl cellulose, ethyloxyethyl cellulose, rubber-based resins such as chlorinated rubber and cyclized rubber, petroleum-based resins, rosin,
A natural resin such as casein, oils and fats such as linseed oil and soybean oil, and a mixture of one or more kinds of 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 colorants such as dyes and pigments are added thereto, and if necessary, a filler and a stabilizer are added. Agent, plasticizer, antioxidant,
A light stabilizer such as an ultraviolet absorber, a dispersant, a thickener, a drying agent, a lubricant, an antistatic agent, a cross-linking agent, and other additives are optionally added, and sufficiently kneaded with a solvent, a diluent, etc. Ink compositions having various forms can be used.

Next, as the heat-sealable resin for forming the heat-sealable resin layer, any heat-sealable resin may be used as long as it 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 resins 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 acid-modified polyolefin resin modified with itaconic acid and other unsaturated carboxylic acids, polyvinyl acetate resin, polyester resin, polystyrene resin, and other resins. . In the present invention, as the heat-sealable resin layer, one or more of the above resins are used, for example, a resin film or sheet formed 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 of a resin composition containing one or more species as the main component of the vehicle. The film thickness is preferably about 5 to 100 μm, and more preferably 10 to 50 μm.

In the present invention, it is particularly preferable to use linear (linear) low density polyethylene among the above resins. The linear low density polyethylene is
Since it has adhesiveness, it has the advantage that there is little propagation of breakage and improves impact resistance, and since the inner layer is constantly in contact with the contents, it prevents deterioration of environmental stress cracking resistance. It is also effective for. In the present invention, the linear low density polyethylene may be blended with another resin, for example, by blending an ethylene-butene copolymer or the like,
Although it is slightly inferior in heat resistance and tends to deteriorate seal stability in a high temperature environment, it has an advantage that tearability is improved and contributes to easy opening. As the linear low density polyethylene as the heat-sealable resin as described above, specifically, ethylene-polymerized using a metallocene catalyst is used.
An α-olefin copolymer can be used. Specifically, the product name “Kernel” manufactured by Mitsubishi Chemical Co., Ltd., the product name “Evolue” manufactured by Mitsui Petrochemical Industry Co., Ltd., and EXXON CHEMICA
L) using a metallocene catalyst such as “EXACT”, a trade name “AFFINITY” manufactured by DOW CHEMICAL, and “ENGAGE” A polymerized ethylene-α-olefin copolymer can be used. When the ethylene-α-olefin copolymer polymerized using the metallocene catalyst is used, there is an advantage that low-temperature heat sealability is possible when the bag is manufactured.

In the laminated material using the gas barrier coating film of the present invention, the packaging container is usually subjected to severe physical and chemical conditions. Requires strict packaging suitability, that is, various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing performance, quality maintenance, workability, hygiene and the like. Therefore, in the present invention, it is possible to arbitrarily select a material that satisfies the above-mentioned various conditions, and to form a desired laminated material in addition to the material that constitutes 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 -Based resin, polyacrylonitrile-based resin, polystyrene-based resin, acrylonitrile-styrene copolymer (AS-based resin), acrylonitrile-butadiene-styrene copolymer (ABS-based resin), polyester-based resin, polyamide-based resin, polycarbonate-based resin , Polyvinyl alcohol-based resin, saponified ethylene-vinyl acetate copolymer, fluorine-based resin, diene-based resin, polyacetal-based resin, polyurethane-based 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, the film or sheet may be unstretched or uniaxially or biaxially stretched. Also,
Although its thickness is arbitrary, it can be selected from a range of several μm to 300 μm and used. 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 laminated material according to the present invention using the gas barrier film according to the present invention, the printed pattern layer, the heat-sealable resin layer, and other materials is, for example, a laminate. Lamination method of laminating via a laminating adhesive layer using an adhesive for molding, or extrusion lamination method of laminating via a melt-extruded resin layer of a melt-extruded adhesive resin. In the above, examples of the laminating adhesive include, for example, one-component or two-component curing or non-curing type vinyl-based, (meth) acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based adhesives. A solvent-based adhesive such as a rubber-based adhesive, a water-based adhesive, or an emulsion adhesive can be used. As a coating method of the above-mentioned laminating adhesive, for example, a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a Fonten method, a transfer roll coating method and the like can be applied. As the coating amount,
It is preferably from 0.1 to 10 g / m ² (dry state), more preferably from 1 to 5 g / m ² (dry state). In addition, for example, 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 can be used. Preference is given to using. The thickness of the melt-extruded resin layer formed of the melt-extruded adhesive resin is preferably about 5 to 100 μm, more preferably about 10 to 50 μm. In the present invention, when the above-mentioned lamination is performed,
When it is necessary to obtain stronger adhesive strength, an adhesion improver such as an anchor coat agent can be coated. Examples of the anchor coating agent include 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 other water-based or oil-based anchor coating agents. Can be used. In the present invention, the anchor coating agent is coated by a roll coating method, a gravure coating method, a knife coating method, a dip coating method, a spray coating method, or another coating method, and a solvent or a diluent is 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 above-mentioned chemical vapor deposition method and physical vapor deposition method, when chemical vapor deposition is used, the organic components and functional groups such as hydroxyl groups are higher than those when physical vapor deposition is used. By containing a larger amount of the group, the adhesion between the gas barrier coating layer and the vapor deposition 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 oxygen permeability is measured, for example, by an oxygen permeability measuring device [model name, OX-TRAN] 2/2 manufactured by MOCON, USA.
0], and can be measured under the conditions of 23 ° C. and 90% RH.

The gas barrier coating film and the laminated material thereof of the present invention are used for bag making and box making,
It enables the production of packaging containers suitable for filling and packaging various forms of articles. The packaging container obtained by using the gas barrier coating film of the present invention has excellent gas barrier properties against oxygen, water vapor, etc., transparency, heat resistance, impact resistance, etc., and is laminated, printed, bag-made, box-made. It has post-processing suitability such as food and drink, pharmaceuticals,
It is excellent in filling and packaging suitability, storage suitability and the like of detergents, shampoos, oils, toothpaste, chemicals such as adhesives and adhesives, cosmetics and various other articles. Bag making,
Explaining the method for box making, for example, in the case of a soft packaging bag, using the laminated material of the gas barrier coating film, the surfaces of the heat-sealing resin layer of the inner layer are opposed to each other, or they are folded or folded. It is possible to construct a bag body by stacking two sheets and further heat-sealing the peripheral end portions thereof to provide a seal portion. As the bag-making method, the above laminated material is bent with the inner layer surfaces thereof facing each other, or two sheets thereof are stacked, and the peripheral edge portion of the outer periphery thereof is a side seal type, a two-side seal type, a three-side seal type. , Four-sided seal type, envelope sticker seal type, joint sticker seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, and other heat seal forms, and various packaging containers To manufacture. Also,
The laminated material is a self-supporting packaging bag (stand-up pouch),
It is also possible to manufacture tube containers and the like. As the heat sealing method, known methods such as bar sealing, rotating roll sealing, belt sealing, impulse sealing, high frequency sealing, and ultrasonic sealing can be used. Furthermore, for example, one-piece type, two-piece type, other spouts, zipper for opening and closing, etc. can be optionally attached to the packaging container.

Further, in the case of producing a packaging container containing a paper base material, a laminated material in which paper base materials are laminated is produced, and a blank plate for producing a desired paper container is produced from the laminated material. A blank plate can be used to make a box, a bottom, a head, and the like to manufacture a liquid paper container of a brick type, a flat type, a gobel top type, or the like.
Further, any shape such as a rectangular container and a cylindrical paper can such as a round shape can be manufactured. The packaging container produced as described above can be used for filling and packaging 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 not only in gas barrier properties even under high humidity conditions, so that it is useful as a packaging material for foods, cigarettes, toiletries, etc., as well as solar cells, protective films, moisture-proof films, etc. Used for.

[0060]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. In the examples, parts and% are based on weight unless otherwise specified. In addition, each evaluation item in the examples was measured according to the following.

Heat Gelation Rate The coating composition was coated on a PET film using a 40 / 10,000 inch applicator and dried at 140 ° C. for 2 minutes using a Tabay dryer. The obtained film was isolated with tweezers and then collected in a 0.25 g sample bottle, and the n-propanol / water weight ratio = 1/1.
Was adjusted to a concentration of 0.3% with a magnetic stirrer at 60 ° C. for 1 hour. The obtained dispersion was filtered with a filter paper (No. 2), and the filtered product was vacuum dried at 120 ° C. for 1 hour. The insoluble content (heated gelation rate) was calculated from the obtained residue.

Appearance of coating film The appearance of the coating film was visually evaluated. Viscosity of coating liquid (composition) The viscosity at a liquid temperature of 25 ° C was measured with a B type viscometer. The viscosity was measured immediately after the coating composition was prepared and 24 hours later. Oxygen permeability Modern Control Co., MOCON OXTRAN2
/ 20 at a temperature of 25 ° C. and a humidity of 90 RH%. Water-Resistant Adhesion Property The coating film was immersed in hot water at 90 ° C. for 30 minutes and then taken out, and it was tested whether the coating layer was peeled off by hand rubbing.

Reference Example 1 (Preparation of titanium chelate compound) 100 parts of tetra-i-propoxy titanium and 70 parts of acetylacetone were added to a reactor equipped with a reflux condenser and a stirrer, and the mixture was stirred at 60 ° C. for 30 minutes to prepare a titanium chelate. The compound (b-1) was obtained. The purity of this reaction product was 75%.

Reference Example 2 (Preparation of zirconium chelate compound) To a reactor equipped with a reflux condenser and a stirrer, 100 parts of tetra-n-butoxyzirconium (purity 100%) and 68 parts of ethyl acetoacetate were added, and the mixture was heated at 60 ° C. The mixture was stirred for 30 minutes to obtain a zirconium chelate compound (b-2). The purity of this reaction product was 77%.

Example 1 As a component (a), an ethylene / vinyl alcohol copolymer [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908, saponification degree: 98% or more, ethylene content: 29 mol%, melt flow index; 8 g / 10 minutes] of 4% (water / n
-Propyl alcohol = 40/60) 100 parts of solution was prepared. Then, 2 parts of the titanium chelate compound (b-1) prepared in Reference Example 1 as the component (b), 1 part of γ-glycyloxypropyltrimethoxysilane as the component (c),
20 parts of n-propyl alcohol and 6 parts of water were mixed and cohydrolyzed (condensed) for 30 minutes at room temperature to mix the cohydrolyzed condensate at room temperature to obtain the coating composition (A) of the present invention. .. The heating gelation rate of the coating composition (A) was 45%.

Example 2 As component (a), an ethylene / vinyl alcohol copolymer [Soarnol D2935X manufactured by Nippon Synthetic Chemical Industry Co., Ltd.,
Degree of saponification: 98% or more, ethylene content: 29 mol%, melt flow index: 35 g / 10 minutes] 5% water /
100 parts of n-propyl alcohol solution (water / n-propyl alcohol weight ratio 40/60) was prepared. Then
2 parts of the titanium chelate compound (b-1) prepared in Reference Example 1 as the component (b), 0.8 part of 1,3,5-tris (trimethoxysilylpropyl) isocyanurate as the component (c), n- 16.8 parts of propyl alcohol and 11.2 parts of water were mixed and cohydrolyzed (condensed) at 25 ° C. for 4 hours to obtain a cohydrolyzed condensate. Then, this cohydrolysis condensate was mixed with the component (a) heated to 50 ° C., stirred for 2 hours, and then cooled to room temperature to obtain the coating composition (B) of the present invention. The heating gelation rate of the coating composition (B) was 30%.

Example 3 Example 1 was repeated except that N-β- (aminoethyl) γ-aminopropyltrimethoxysilane was used instead of γ-glycyloxypropyltrimethoxysilane.
According to the gas barrier coating composition (C) of the present invention,
Got The heating gelation rate of this coating composition (C) was 40%.

Example 4 A coating composition (D) of the present invention was obtained except that 0.5 part of γ-glycyloxypropyltrimethoxysilane was used in Example 1. The heating gelation rate of the coating composition (D) was 25%.

Example 5 A gas barrier coating composition (E) of the present invention was obtained according to Example 1 except that (b-2) was used in place of (b-1). The heating gelation rate of this coating composition (E) was 60%.

Example 6 In Example 2, as component (a), polyvinyl alcohol [RS polymer RS-110 manufactured by Kuraray Co., Ltd.
(Saponification degree = 99%, polymerization degree = 1,000)] was used in the same manner as in Example 2 to obtain a gas barrier coating composition (F). The heating gelation rate of this coating composition (F) was 35%.

Comparative Example 1 A 15% water / n-propyl alcohol solution of the ethylene-vinyl alcohol copolymer used in Example 1 (water / n-propyl alcohol weight ratio = 6/4) was used as a coating composition for comparison. The product (α). Coating composition (α)
The heat gelation rate of was 0%.

Evaluation Examples 1 to 6 and Comparative Evaluation Example 1 The compositions obtained in Examples 1 to 6 and Comparative Example 1 were applied by a bar coater onto a polyethylene terephthalate (PET) film having a thickness of 12 μm which was subjected to corona discharge treatment. Then
Dry for 1 minute at 120 ° C with a hot-air dryer to obtain a film thickness of 1μ
m coating film was formed to obtain a gas barrier coating material (coating film). The gas barrier property of the obtained gas barrier property coating material was measured at room temperature and a humidity of 90% using an oxygen permeability measuring device (MOCON OXTRAN2 / 20, manufactured by Modern Control Co., Ltd.). In addition, the transparency of the coating film was evaluated by visual observation. Further, the coating film was immersed in hot water of 90 ° C. for 30 minutes and then hand-rubbed to evaluate the water-resistant adhesion. The results are shown in Table 1.

[0073]

[Table 1]

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

Example 7 (1) As a base material, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used. A vapor-deposited film of 012 μm silicon oxide was formed on one surface of the biaxially stretched polyethylene terephthalate film. (Deposition conditions) Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1:10:10 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 x 10 ^-6 mbar Degree of vacuum in deposition chamber : 6.5 × 10 ^-2 mbar Cooling / electrode drum power supply: 18 kW Film transport speed: 80 m / min Deposition surface: Corona treated surface (2) Next, biaxial stretching in which a vapor deposition film of silicon oxide is formed as above. The surface of the polyethylene terephthalate film on which silicon oxide was deposited was subjected to corona treatment under the following conditions. As a result, the surface tension of the surface of the deposited film of silicon oxide was 35 dyn.
To 62 dyn. Output: 10 kW Treatment speed: 100 m / min (3) Next, using the biaxially stretched polyethylene terephthalate film on which the corona-treated vapor-deposited film of silicon oxide is formed, the corona-treated surface of the vapor-deposited film of silicon oxide is Using a gravure printing machine, arranging a roll for gravure coating on the first color, and using the gas barrier coating composition (A) obtained in Example 1, this was coated by the gravure roll coating method to give a thick film. 0.
A coating film of 5 g / m ² (dry state) was formed.
Then, the gas barrier coating film of the present invention was manufactured by performing a heat treatment at 120 ° C. for 2 minutes to form a cured coating film. Then, on the coating cured film of the gas barrier coating film, using the gravure printing machine, using the gravure ink composition,
The desired multicolor printed picture layer was formed. (4) Next, the biaxially stretched polyethylene terephthalate film on which the printed pattern surface was formed as described above was mounted on the first delivery roll of the dry laminating machine, and the printed pattern layer surface was coated with a two-component curing type by a gravure roll coating method. A polyurethane-based laminating adhesive was applied at a rate of 4.5 g / m ² (dry state) to form a laminating adhesive layer. Then, a thickness of 7 is applied to the adhesive layer surface for lamination.
A 0 μm low-density polyethylene film 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. In addition, the water resistant adhesion was good.

Example 8 (1) As a base material, a biaxially stretched polypropylene film having a thickness of 20 μm (manufactured by Nimura Chemical Co., Ltd., trade name, GH)
-I, single-sided corona-treated product) was mounted on a delivery roll of a plasma chemical vapor deposition apparatus, and a vapor-deposited film of silicon oxide having a thickness of 0.015 μm was formed on the biaxially oriented polypropylene film under the following conditions. It was formed on one surface. (Deposition conditions) Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1:11:10 (unit: slm) Degree of vacuum in vacuum chamber: 5.2 x 10 ^-6 mbar Degree of vacuum in deposition chamber : 5.1 × 10 ^-2 mbar Cooling / electrode drum power supply: 18 kW Film transport speed: 70 m / min Deposition surface: Corona treated surface (2) Next, biaxial stretching in which a vapor deposition film of silicon oxide is formed above The surface of the polypropylene film on which silicon oxide was deposited was subjected to corona treatment under the following conditions. As a result, the surface tension of the deposited film of silicon oxide was 42 dyn to 65 d.
improved to yn. Output: 10 kW Treatment speed: 100 m / min (3) Next, using a biaxially stretched polypropylene film having a corona-treated vapor-deposited film of silicon oxide formed thereon,
On the corona-treated surface of the vapor-deposited film of silicon oxide, a gravure printing machine is used, a roll for gravure coating is arranged in the first color, and the gas barrier coating composition (B) obtained in Example 2 is used, 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 gas barrier coating film of the present invention was manufactured by forming a cured coating film by heating at 3 ° C. for 3 minutes. Next, a desired multicolor printed picture layer was formed on the cured coating film of the gas barrier coating film by using the gravure printing machine and using the gravure ink composition. (4) Next, the biaxially stretched polypropylene film having the printed pattern surface formed thereon is mounted on the first delivery roll of the dry laminating machine, and the printed pattern layer surface is a two-component curing type polyurethane using the gravure roll coating method. A system laminating adhesive was applied at a rate of 4.5 g / m ² (dry state) to form a laminating adhesive layer. Then
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 permeability of this laminated material is 0.2 cm.
^{It was 3} / m ² · atm · 24 hr. In addition, the water resistant adhesion was good.

Example 9 (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 plasma chemical vapor deposition apparatus, and the thickness was 0.015 μm under the following conditions.
A vapor-deposited film of silicon oxide of m was formed on one surface of the biaxially stretched nylon film. (Deposition conditions) Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1:11:10 (unit: slm) Degree of vacuum in vacuum chamber: 5.2 x 10 ^-6 mbar Degree of vacuum in deposition chamber : 5.1 × 10 ^-2 mbar Cooling / electrode drum power supply: 18 kW Film transport speed: 70 m / min Deposition surface: Corona treated surface (2) Next, biaxial stretching in which a silicon oxide deposition film is formed as described above Corona treatment was applied to the silicon oxide vapor-deposited film surface of the nylon film under the following conditions. As a result, the surface tension of the vapor-deposited film of silicon oxide was improved from 42 dyn to 65 dyn. Output: 10 kW Treatment speed: 100 m / min (3) Next, using a biaxially stretched nylon film having a corona-treated silicon oxide vapor-deposited film formed thereon, the corona-treated surface of the silicon oxide vapor-deposited film was gravure-coated. A printing machine is used, a roll for gravure coating is arranged in the first color, the gas barrier coating composition (C) obtained in Example 3 is used, and this is coated by a gravure roll coating method to give a thickness. A 0.5 g / m ² (dry state) coating film was formed. Then, the gas barrier coating film of the present invention was manufactured by performing a heat treatment at 120 ° C. for 1 minute to form a coating cured film. 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 on which the printed pattern surface is formed is mounted on the first delivery roll of the dry laminating machine, and the printed pattern layer surface is a two-component curing type polyurethane using the gravure roll coating method. A system laminating adhesive was applied at a rate of 4.5 g / m ² (dry state) to form a laminating adhesive layer. Then, a 70 μm-thick unstretched polypropylene film was dry-laminated on the adhesive layer surface for lamination to produce a laminated material. The oxygen permeability of this laminated material is 0.4 cm ³ / m ²
・ Atm was 24 hours. In addition, the water resistant adhesion was good.

Example 10 In (4) of Example 7 above, the biaxially stretched polyethylene terephthalate film having a print pattern layer formed thereon had a thickness of 70 μm on the print pattern layer side via an adhesive layer for laminating.
Instead of producing a laminated material by dry laminating a low-density polyethylene film of m, a printed pattern layer was formed.
The axially stretched polyethylene terephthalate film was mounted on the first delivery roll of the extrusion laminating machine, and low-density polyethylene for melt extrusion was used for the printed pattern layer surface, while melt-extruding it to a thickness of 20 μm, while the thickness was 70 μm. A polyethylene film was extrusion laminated, and otherwise the same as in Example 7 above,
A laminated material was manufactured. The oxygen permeability of this laminated material is 0.4.
It was cm ³ / m ² · atm · 24 hr. In addition, the water resistant adhesion was good.

Example 11 In (4) of Example 8 above, a 70 μm-thick unstretched polypropylene film was formed on the printed pattern layer side of the biaxially stretched polypropylene film having a printed pattern layer formed thereon, with an adhesive layer for lamination interposed therebetween. Instead of dry laminating to produce a laminated material, a biaxially oriented polypropylene film having a printed pattern layer formed thereon is mounted on the first delivery roll of an extrusion laminating machine, and the low density polyethylene for melt extrusion is attached to the printed pattern layer surface. A 70 μm-thick low density polyethylene film was extruded and laminated while being melt extruded to a thickness of 20 μm, and a laminated material was manufactured in the same manner as in Example 8 except for the above. The oxygen permeability of this laminated material is 0.6 cm ³ / m ² · atm · 2
It was 4 hours. In addition, the water resistant adhesion was good.

Example 12 In (4) of Example 9 above, a 70 μm-thick unstretched polypropylene film was formed on the printed pattern layer surface of the biaxially stretched nylon film having the printed pattern layer, with an adhesive layer for lamination interposed therebetween. Instead of dry laminating to produce a laminated material, a biaxially stretched nylon film having a printed pattern layer is mounted on the first delivery roll of an extrusion laminating machine, and a low density polyethylene for melt extrusion is attached to the printed pattern layer surface. A 70 μm-thick low density polyethylene film was extruded and laminated while being melt extruded to a thickness of 20 μm, and otherwise the same as in Example 9 above, to produce a laminated material. The oxygen transmission rate of this laminated material was 0.4 cm ³ / m ² · atm · 24 hr. In addition, the water resistant adhesion was good.

Example 13 (1) As a base material, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and this film was mounted on a delivery roll of a winding-type vacuum vapor deposition apparatus, and then the film was coated on a coating drum. A film of 0.02 μm was formed on the above biaxially stretched polyethylene terephthalate film by an oxidation reaction vacuum deposition method using an electron beam (EB) heating method while feeding aluminum and using oxygen as a deposition source and supplying oxygen gas. A deposited film of aluminum oxide was formed. (Deposition conditions) Deposition source: Degree of vacuum in aluminum vacuum chamber: 5.2 × 10 ⁻⁶ mbar Degree of vacuum in deposition chamber: 1.1 × 10 ⁻⁶ mbar EB output: 40 kW Film transfer speed: 600 m / min Vapor-deposited surface: Corona-treated surface (2) Next, the aluminum-oxide-vapor-deposited film surface of the biaxially stretched polyethylene terephthalate film on which the aluminum oxide vapor-deposited film was formed was subjected to corona treatment under the following conditions. As a result, the surface tension of the aluminum oxide vapor deposition film surface improved from 45 dyn to 60 dyn. Output: 10 kW Treatment speed: 100 m / min (3) Next, using the biaxially stretched polyethylene terephthalate film on which the vapor deposition film of corona-treated aluminum oxide was formed, the corona-treated surface of the vapor deposition film of aluminum oxide was Using a gravure printing machine, arranging a roll for gravure coating on its first color, and using the gas barrier coating composition (D) obtained in Example 4,
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, the gas barrier coating film of the present invention was manufactured by performing a heat treatment at 120 ° C. for 1 minute to form a coating cured film. Next, a desired multicolor printed picture layer was formed on the cured coating film of the gas barrier coating film by using the gravure printing machine and using the gravure ink composition. (4) Next, the biaxially stretched polyethylene terephthalate film on which the printed pattern layer was formed as described above was mounted on the first delivery roll of the dry laminating machine, and the printed pattern layer surface was coated with a two-component curing type by a gravure roll coating method. A polyurethane-based laminating adhesive was applied at a rate of 4.5 g / m ² (dry state) to form a laminating adhesive layer. Then, a thickness of 7 is applied to the adhesive layer surface for lamination.
A 0 μm low-density polyethylene film was dry-laminated to produce a laminated material. The oxygen transmission rate of this laminated material was 0.3 cm ³ / m ² · atm · 24 hr. In addition, the water resistant adhesion was good.

Example 14 (1) As a base material, a biaxially stretched polypropylene film having a thickness of 20 μm (manufactured by Nimura Chemical Co., Ltd., trade name, GH)
-I, single-sided corona treated product), this was mounted on a delivery roll of a winding type vacuum vapor deposition device, and then the above film was unrolled onto a coating drum, and aluminum was used as a vapor deposition source, and oxygen gas was used. While being supplied, a vapor-deposited film of aluminum oxide having a thickness of 0.02 μm was formed on the biaxially oriented polypropylene film by an oxidation reaction vacuum vapor deposition method using an electron beam (EB) heating system. (Deposition conditions) Deposition source: Degree of vacuum in aluminum vacuum chamber: 8.2 × 10 ⁻⁶ mbar Degree of vacuum in deposition chamber: 1.0 × 10 ⁻⁶ mbar EB output: 40 kW Film transport speed: 500 m / min (2) Next, a corona treatment was applied to the aluminum oxide vapor-deposited film surface of the biaxially stretched polypropylene film having the aluminum oxide vapor-deposited film formed thereon under the following conditions. As a result, the surface tension of the aluminum oxide film surface was 47
It improved from dyn to 62 dyn. Output: 10 kW Treatment speed: 100 m / min (3) Next, using the biaxially stretched polypropylene film on which the vapor-deposited film of aluminum oxide corona-treated above was formed, the corona-treated surface of the vapor-deposited film of aluminum oxide was gravure-coated. A gravure coat roll is placed on the first color of the ink using a printing machine, and the gas barrier coating composition (E) obtained in Example 5 is used. This is coated by the gravure roll coating method to give a thickness of 0.
A coating film of 5 g / m ² (dry state) was formed.
Then, the gas barrier coating film of the present invention was manufactured by heating at 100 ° C. for 3 minutes to form a cured coating film. Then, on the coating cured film of the gas barrier coating film, using the gravure printing machine, using the gravure ink composition,
The desired multicolor printed picture layer was formed. (4) Next, the biaxially stretched polypropylene film having the print pattern layer formed thereon was mounted on the first delivery roll of the dry laminating machine, and the print pattern layer surface was coated with a gravure roll coating method to prepare a two-component curing type polyurethane. A system laminating adhesive was applied at a rate of 4.5 g / m ² (dry state) to form a laminating adhesive layer. Then
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 permeability of this laminated material is 0.3 cm.
^{It was 3} / m ² · atm · 24 hr. In addition, the water resistant adhesion was good.

Example 15 (1) As a base material, a biaxially stretched nylon film having a thickness of 15 μm was used, and this was mounted on a delivery roll of a winding type vacuum vapor deposition device, and then the above film was placed on a coating drum. And aluminum gas as a vapor deposition source, while supplying oxygen gas, by an oxidation reaction vacuum vapor deposition method by an electron beam (EB) heating system, a film thickness of 0.02 μm was formed on the biaxially stretched nylon film.
A deposited film of aluminum oxide was formed. (Deposition conditions) Deposition source: Degree of vacuum in aluminum vacuum chamber: 7.2 × 10 ⁻⁶ mbar Degree of vacuum in deposition chamber: 1.0 × 10 ⁻⁶ mbar EB output: 40 kW Film transfer speed: 500 m / min Vapor-deposited 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 film surface was 45 dyn.
Improved to 60 dyn. Output: 10 kW Treatment speed: 100 m / min (3) Next, using a biaxially stretched nylon film having a corona-treated aluminum oxide vapor deposition film formed thereon,
On the corona-treated surface of the vapor-deposited film of aluminum oxide, a gravure printing machine was used, a roll for gravure coating was placed in the first color, and the gas barrier coating composition (F) obtained in Example 6 was used, This is coated by the gravure roll coating method to a thickness of 0.5 g / m
^{A 2} (dry state) coating film was formed. Then
A gas-cured coating film of the present invention was manufactured by forming a cured coating film by heat treatment at 120 ° C. for 2 minutes. Next, a desired multicolor printed picture layer was formed on the cured coating film of the gas barrier coating film by using the gravure printing machine and using the gravure ink composition. (4) Next, the biaxially stretched nylon film on which the printed pattern layer is formed is mounted on the first delivery roll of the dry laminating machine, and the printed pattern layer surface is a two-component curing type polyurethane using the gravure roll coating method. A system laminating adhesive was applied at a rate of 4.5 g / m ² (dry state) to form a laminating adhesive layer. Then, a 70 μm-thick unstretched polypropylene film was dry-laminated on the adhesive layer surface for lamination to produce a laminated material. The oxygen permeability of this laminated material is 0.4 cm ³ / m ²
・ Atm was 24 hours. In addition, the water resistant adhesion was good.

Example 16 In (4) of Example 13 above, the biaxially stretched polyethylene terephthalate film having a print pattern layer formed thereon had a thickness of 70 on the print pattern layer side with an adhesive layer for laminating interposed.
Instead of dry laminating a low-density polyethylene film having a thickness of μm to produce a laminated material, a biaxially stretched polyethylene terephthalate film having a print pattern layer formed thereon was mounted on a first feeding roll of an extrusion laminating machine, and the print pattern layer surface was provided with A low-density polyethylene for melt extrusion was used, and a low-density polyethylene film having a thickness of 70 μm was extrusion-laminated while melt-extruding the low-density polyethylene to a thickness of 20 μm, and otherwise the same as in Example 13 above, to obtain a laminated material. Manufactured. The oxygen permeability of this laminated material is
It was 0.4 cm ³ / m ² · atm · 24 hr. Also,
The water resistant adhesion was good.

Example 17 In the above (14) of Example 14, on the printed pattern layer side of the biaxially oriented polypropylene film having the printed pattern layer formed thereon,
Instead of dry laminating an unstretched polypropylene film having a thickness of 70 μm through a laminating adhesive layer to produce a laminated material, a biaxially stretched polypropylene film having a printed pattern layer is extruded and the first delivery roll of a laminating machine. Mounted on the printed pattern layer, using a low-density polyethylene for melt extrusion, and extruding and laminating a low-density polyethylene film having a thickness of 70 μm while melt-extruding this to a thickness of 20 μm.
A laminated material was produced in exactly the same manner as in Example 14 above.
The oxygen permeability of this laminated material is 0.5 cm ³ / m ² · atm
-It was 24 hours. In addition, the water resistant adhesion was good.

Example 18 In (4) of Example 15 above, a printed pattern layer was formed.
On the printed pattern layer of the biaxially stretched nylon film.
70 μm thick unstretched polyp via adhesive layer for coating
Manufacture laminated materials by dry laminating ropylene film
Instead of forming, biaxially stretched nylon with a printed pattern layer formed
The first feeding roll of the laminating machine that extrudes the film
Mounted on the printed pattern layer surface, low density for melt extrusion
Use polyethylene and press it to a thickness of 20μm
70 μm thick low density polyethylene fill
Extruded and laminated, otherwise the above Example 1
A laminated material was manufactured in exactly the same manner as in No. 5. Of this laminated material
Oxygen permeability is 0.4 cm ³/ M²・ Atm ・ 24hr
there were.

Example 19 (1) A 12 μm-thick biaxially stretched polyethylene terephthalate film was used as a substrate, and this was mounted on a delivery roll of a plasma chemical vapor deposition apparatus, and the thickness was adjusted to 0. A vapor-deposited film of 012 μm silicon oxide was formed on one surface of the biaxially stretched polyethylene terephthalate film. (Deposition conditions) Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1:10:10 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 x 10 ^-6 mbar Degree of vacuum in deposition chamber : 6.5 × 10 ^-2 mbar Cooling power supply to electrode drum: 18 kW Film transport speed: 80 m / min Deposition surface: Corona treated surface (2) Next, the biaxially formed silicon oxide deposition film A stretched polyethylene terephthalate film was used, which was attached to a delivery roll of a winding type vacuum vapor deposition device, which was fed onto a coating drum, and aluminum was used as a vapor deposition source, while supplying oxygen gas while supplying an electron beam ( EB) Biaxially stretched polyethylene terephthalate film on which the above-mentioned vapor-deposited film of silicon oxide is formed by a reaction vacuum vapor deposition method using a heating method. On the deposited film of silicon oxide of Lum, to form a deposited film of aluminum oxide having a thickness of 0.02 [mu] m. Further, a corona treatment was applied to the surface of the vapor-deposited aluminum oxide film under the following conditions. As a result, the surface tension of the aluminum oxide film surface was 40 dyn.
Improved to 65 dyn. Output: 10 kW Treatment speed: 100 m / min (3) Next, using the biaxially stretched polyethylene terephthalate film on which the vapor deposition film of aluminum oxide and the vapor deposition film of silicon oxide are formed, the surface of the vapor deposition film of aluminum oxide is used. The gas barrier coating composition (F) obtained by Example 6 using a gravure printing machine, arranging a roll for gravure coating on the first color of the roll,
Was coated by a gravure roll coating method to form a coating film having a thickness of 1.0 g / m ² (dry state). Then, the gas barrier coating film of the present invention was manufactured by performing a heat treatment at 120 ° C. for 1 minute to form a coating cured film. Next, a desired multicolor printed picture layer was formed on the cured coating film of the gas barrier coating film by using the gravure printing machine and using the gravure ink composition. (4) Next, the biaxially stretched polyethylene terephthalate film on which the printed pattern layer was formed as described above was mounted on the first delivery roll of the dry laminating machine, and the printed pattern layer surface was coated with a two-component curing type by a gravure roll coating method. A polyurethane-based laminating adhesive was applied at a rate of 4.5 g / m ² (dry state) to form a laminating adhesive layer. Then, a thickness of 7 is applied to the adhesive layer surface for lamination.
A 0 μm low-density polyethylene film was dry-laminated to produce a laminated material. The oxygen transmission rate of this laminated material was 0.3 cm ³ / m ² · atm · 24 hr. In addition, the water resistant adhesion was good.

Example 20 (1) As a base material, a biaxially oriented polypropylene film having a thickness of 20 μm (manufactured by Nimura Chemical Co., Ltd., trade name, GH)
-I, single-sided corona-treated product) was mounted on a delivery roll of a plasma chemical vapor deposition apparatus, and a vapor-deposited film of silicon oxide having a thickness of 0.015 μm was formed on the biaxially oriented polypropylene film under the following conditions. It was formed on one surface. (Deposition conditions) Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1:11:10 (unit: slm) Degree of vacuum in vacuum chamber: 5.2 x 10 ^-6 mbar Degree of vacuum in deposition chamber : 5.1 × 10 ^-2 mbar Cooling / electrode drum power supply: 18 kW Film transport speed: 70 m / min Deposition surface: Corona treated surface (2) Next, biaxial stretching in which a silicon oxide deposition film is formed as described above A polypropylene film is used, which is attached to a roll-out of a roll-up type vacuum vapor deposition device, which is unrolled onto a coating drum, and aluminum is used as a vapor deposition source, while supplying oxygen gas and electron beam (EB). Silicon oxide vapor-deposited film of biaxially stretched polypropylene film on which the above-mentioned silicon oxide vapor-deposited film is formed by a reaction vacuum vapor deposition method using a heating method. Above, the film thickness 0.02μ
m vapor-deposited film of aluminum oxide was formed. Further, a corona treatment was applied to the surface of the vapor-deposited aluminum oxide film under the following conditions. As a result, the surface tension of the aluminum oxide vapor deposition film surface was improved from 42 dyn to 65 dyn. Output: 10 kW Processing speed: 100 m / min (3) Next, using the biaxially oriented polypropylene film on which the vapor deposition film of aluminum oxide and the vapor deposition film of silicon oxide are formed, the surface of the vapor deposition film of aluminum oxide is Using a gravure printing machine, arranging a roll for gravure coating on the first color, and using the gas barrier coating composition (A) obtained in Example 1, this was coated by the gravure roll coating method to give a thick film. 0.8 g /
A coating film of m ² (dry state) was formed. Then, the gas barrier coating film of the present invention was manufactured by performing a heat treatment at 120 ° C. for 1 minute to form a coating cured film. Next, a desired multicolor printed picture layer was formed on the cured coating film of the gas barrier coating film by using the gravure printing machine using the gravure ink composition. (4) Next, the biaxially stretched polypropylene film having the print pattern layer formed thereon was mounted on the first delivery roll of the dry laminating machine, and the print pattern layer surface was coated with a gravure roll coating method to prepare a two-component curing type polyurethane. A system laminating adhesive was applied at a rate of 4.5 g / m ² (dry state) to form a laminating adhesive layer. Then
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 permeability of this laminated material is 0.4 cm.
^{It was 3} / m ² · atm · 24 hr. In addition, the water resistant adhesion was good.

Example 21 (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 plasma chemical vapor deposition apparatus, and the thickness was 0.015 μm under the following conditions.
A vapor-deposited film of silicon oxide of m was formed on one surface of the biaxially stretched nylon film. (Deposition conditions) Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1:11:10 (unit: slm) Degree of vacuum in vacuum chamber: 5.2 x 10 ^-6 mbar Degree of vacuum in deposition chamber : 5.1 × 10 ^-2 mbar Cooling / Electric drum power supply: 18 kW Film transport speed: 70 m / min Deposition surface: Corona treated surface (2) Next, biaxially stretched to form a silicon oxide deposition film A nylon film is used, which is attached to a delivery roll of a roll-up type vacuum vapor deposition device, which is unrolled onto a coating drum, and aluminum is used as a vapor deposition source to supply an oxygen gas and an electron beam (E
B) A vapor-deposited film of aluminum oxide having a thickness of 0.02 μm was formed on the vapor-deposited film of silicon oxide of the biaxially stretched nylon film on which the vapor-deposited film of silicon oxide was formed, by a reaction vacuum vapor deposition method using a heating system. Further, a corona treatment was applied to the surface of the vapor-deposited aluminum oxide film under the following conditions.
As a result, the surface tension of the aluminum oxide vapor deposition film surface improved from 45 dyn to 65 dyn. Output: 10 kW Processing speed: 100 m / min (3) Next, using the biaxially stretched nylon film on which the vapor deposition film of aluminum oxide and the vapor deposition film of silicon oxide are formed, the surface of the vapor deposition film of aluminum oxide is Using a gravure printing machine, arranging a roll for gravure coating on the first color, and using the gas barrier coating composition (B) obtained in Example 2, this was coated by a gravure roll coating method to obtain a thick film. 1.2 g / m
^{A 2} (dry state) coating film was formed. Then
A gas-cured coating film of the present invention was manufactured by forming a cured coating film by heat treatment at 120 ° C. for 2 minutes. Next, a desired multicolor printing pattern layer was formed on the cured coating film of the gas barrier coating film by using the gravure printing machine and using the gravure ink composition. (4) Next, the biaxially stretched nylon film on which the printed pattern layer is formed is mounted on the first delivery roll of the dry laminating machine, and the printed pattern layer surface is a two-component curing type polyurethane using the gravure roll coating method. A system laminating adhesive was applied at a rate of 4.5 g / m ² (dry state) to form a laminating adhesive layer. Then, a 70 μm-thick unstretched polypropylene film was dry-laminated on the adhesive layer surface for lamination to produce a laminated material. The oxygen permeability of this laminated material is 0.3 cm ³ / m ²
・ Atm was 24 hours. In addition, the water resistant adhesion was good.

Example 22 In (4) of Example 19 above, the biaxially stretched polyethylene terephthalate film having a print pattern layer formed thereon had a thickness of 70 on the print pattern layer surface via an adhesive layer for laminating.
Instead of dry laminating a low-density polyethylene film having a thickness of μm to produce a laminated material, a biaxially stretched polyethylene terephthalate film having a print pattern layer formed thereon was mounted on a first feeding roll of an extrusion laminating machine, and the print pattern layer surface was provided with A low-density polyethylene for melt extrusion was used, and a low-density polyethylene film having a thickness of 70 μm was extruded and laminated while melt-extruding the low-density polyethylene to a thickness of 20 μm. Manufactured. The oxygen permeability of this laminated material is
It was 0.4 cm ³ / m ² · atm · 24 hr. Also,
The water resistant adhesion was good.

Example 23 In (4) of Example 20 above, on the printed pattern layer side of the biaxially oriented polypropylene film having the printed pattern layer formed thereon,
Instead of dry laminating an unstretched polypropylene film having a thickness of 70 μm through a laminating adhesive layer to produce a laminated material, a biaxially stretched polypropylene film having a printed pattern layer is extruded and the first delivery roll of a laminating machine. Mounted on the printed pattern layer, using a low-density polyethylene for melt extrusion, and extruding and laminating a low-density polyethylene film having a thickness of 70 μm while melt-extruding this to a thickness of 20 μm.
A laminated material was produced in exactly the same manner as in Example 20 above.
The oxygen permeability of this laminated material is 0.3 cm ³ / m ² · atm
-It was 24 hours. In addition, the water resistant adhesion was good.

Example 24 In (4) of Example 21 above, a print pattern layer was formed.
On the printed pattern layer of the biaxially stretched nylon film.
70 μm thick unstretched polyp via adhesive layer for coating
Manufacture laminated materials by dry laminating ropylene film
Instead of forming, biaxially stretched nylon with a printed pattern layer formed
The first feeding roll of the laminating machine that extrudes the film
Mounted on the printed pattern layer surface, low density for melt extrusion
Use polyethylene and press it to a thickness of 20μm
70 μm thick low density polyethylene fill
Example 2 above except that the film was extruded and laminated.
A laminated material was manufactured in exactly the same manner as in 1. Of this laminated material
Oxygen permeability is 0.3 cm ³/ M²・ Atm ・ 24hr
there were. In addition, the water resistant adhesion was good.

Example 25 A laminated material was produced in the same manner as in Example 21 except that the gas barrier coating composition (C) was used in (3) of Example 21. The oxygen transmission rate of this laminated material was 0.3 cm ³ / m ² · atm · 24 hr.

[0094]

EFFECTS OF THE INVENTION According to the present invention, a gas barrier coating composition having extremely low oxygen permeability even under high humidity, good adhesion to a base material, and harmless to the human body can be obtained. . Further, using the gas barrier coating composition of the present invention, a synthetic resin film, a metal and / or
Alternatively, by coating on a synthetic resin film provided with a vapor deposition film of an inorganic compound, a coating material having further excellent gas barrier property can be obtained.

[Brief description of 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 roll-up type vacuum vapor deposition device.

[Explanation of symbols]

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

Continued front page    (72) Inventor Aki Nishikawa             2-11-24 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. F term (reference) 4F100 AK01B AK21A AK42 AL06A                       AL08A EH462 EJ552 GB15                       JD02                 4J038 CE021 CE022 DM021 DM022                       KA06 MA08 MA10 NA08 PB04                       PC08

Claims (2)

[Claims] 1. (a) Polyvinyl alcohol-based resin, and (b) General formula (1) R ¹ _m M (OR ² ) _n (1) (wherein M is titanium, zirconium, and A metal atom selected from aluminum, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, having 1 to 1 carbon atoms
A metal alcoholate represented by an alkyl group of 5 or an acyl group having 1 to 6 carbon atoms or a phenyl group, m and n are each an integer of 0 or more, and m + n is a valence of M; Metal alcoholate hydrolyzate, metal alcoholate condensate, metal alcoholate chelate compound, metal chelate compound hydrolyzate, metal chelate compound condensate, metal acylate, metal acylate hydrolyzate And a co-hydrolyzate and / or a co-condensate of (c) a silane coupling agent and at least one member selected from the group consisting of a product and a condensate of the metal acylate. 2. The component (b) and the component (c) are cohydrolyzed and / or cocondensed in water or a mixed solvent containing water and a hydrophilic organic solvent, and then mixed with the component (a). The method for producing the gas barrier coating composition according to claim 1.