JP5550800B2 - Gas barrier coating composition, method for producing the same, and gas barrier coating film - Google Patents

Description

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

In recent years, packaging materials used for packaging applications such as pharmaceuticals, foods, cosmetics, tobacco, toiletries, etc., for example, for foods, prevent deterioration of contents such as oxidation of proteins and fats and oils, quality such as taste For holding, a material having a gas barrier property that does not allow permeation of oxygen, water vapor, or other gas that alters the contents is used.
In response to such a conventional problem, for example, Japanese Patent Application Laid-Open No. 7-266485 discloses that one or more metal alkoxides or hydrolysates thereof and a molecule are formed on a substrate made of a polymer resin composition. A gas barrier material in which a gas barrier coating layer formed by applying a coating agent mainly composed of a mixed solution with an isocyanate compound having at least two isocyanate groups and drying by heating has been proposed. However, this gas barrier material contains an isocyanate compound having an isocyanate group, melamine, formaldehyde, tin chloride, etc., and may be orally administered to the human body, especially for medical products and foods, and is harmful to the human body. It has the problem that it is.
On the other hand, Japanese Patent No. 1,476,209 proposes a coating material made of polyvinyl alcohol that does not contain isocyanate and has low toxicity. However, when used for food retort packaging, etc., the retort treatment is performed under high-temperature and high-humidity conditions of 120 ° C. or higher, so that oxygen barrier properties under high-humidity subcutaneous conditions are required. The gas barrier property of a coating material made of polyvinyl alcohol is remarkably influenced by humidity, and there is a problem that the gas barrier property is greatly lowered under high humidity.

Problems to be solved by the invention

  The present invention has been made against the background of the above-mentioned conventional technical problems, and does not deteriorate the barrier property against gases such as oxygen and water vapor even under humid conditions, and also has an isocyanate compound having an isocyanate group, melamine, formaldehyde, organic It is an object of the present invention to provide a coating composition that does not contain a compound such as tin that is harmful to the human body and is harmless to the human body, and a coating film having excellent gas barrier properties using the same.

Means for solving the problem

The present invention includes (a) a polyvinyl alcohol-based resin (hereinafter also referred to as “component (a)”), and (b) a general formula (1).
R ¹ _m M (OR ² ) _n (1)
(In the formula, M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, or A metal alcoholate, a hydrolyzate of the metal alcoholate, and a condensation of the metal alcoholate, each of which represents a phenyl group, and m and n are each an integer of 0 or more and m + n is a valence of M) And the metal alcoholate chelate compound, hydrolyzate of the metal chelate compound, condensate of the metal chelate compound, metal acylate, hydrolyzate of the metal acylate, and condensate of the metal acylate. At least one (hereinafter also referred to as “component (b)”)
It is related with the gas barrier coating composition (henceforth a "coating composition") characterized by the heating gelation rate of this coating composition being 1-90%.
Here, as said (a) polyvinyl alcohol-type resin, at least 1 sort (s) chosen from the group of polyvinyl alcohol and an ethylene-vinyl alcohol copolymer is mentioned.
Moreover, the coating composition of this invention may improve gas-barrier property further, if it contains (c) nitrogen-containing organic compound (henceforth "(c) component") as needed.
Further, if the coating composition of the present invention further contains (d) inorganic fine particles (hereinafter also referred to as “component (d)”) as required, the gas barrier property may be further improved.
Next, the present invention provides the gas barrier coating composition, wherein the component (b) is hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent, and then mixed with the component (a). It relates to the manufacturing method.
The present invention also relates to a gas barrier coating film, wherein a coating film formed from the gas barrier coating composition is laminated on a base resin film.
Furthermore, the present invention is characterized in that a deposited film of a metal and / or an inorganic compound is provided on a base resin film, and a cured coating film formed from the gas barrier coating composition is further laminated. The present invention relates to a gas barrier coating film.
The vapor deposition film is preferably an inorganic oxide vapor deposition film formed by chemical vapor deposition and / or physical vapor deposition.

Coating composition (a) component;
Examples of the polyvinyl alcohol resin as the component (a) used in the present invention include at least one selected from the group of polyvinyl alcohol and ethylene / vinyl alcohol copolymers.
Among the components (a), polyvinyl alcohol is generally obtained by saponifying polyvinyl acetate. The polyvinyl alcohol may be partially saponified polyvinyl alcohol in which several tens of percent of acetic acid groups remain, or completely saponified polyvinyl alcohol in which no acetic acid groups remain, or modified polyvinyl alcohol in which OH groups have been modified. It is not limited. Specific examples of the polyvinyl alcohol include RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (degree of saponification) manufactured by the same company. = 40%, polymerization degree = 2,000), Gohsenol NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, polymerization degree = 1,400), and the like.
Among the components (a), the ethylene / vinyl alcohol copolymer is obtained by saponifying a copolymer of ethylene and vinyl acetate, that is, an ethylene-vinyl acetate random copolymer. , Including a partially saponified product in which several tens mol% of acetic acid groups remain to a complete saponified product in which acetic acid groups remain only several mol% or no acetic acid groups remain, but is not particularly limited. From the viewpoint of gas barrier properties, the preferable degree of saponification is 80 mol% or more, more preferably 90 mol% or more, and still more 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 Kuraray Co., Ltd., Eval EP-F101 (ethylene content; 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908, D2935 (ethylene content; 29 mol%), D2630 (ethylene amount; 26%), A4412 (ethylene amount 44%), and the like.

The melt flow index of the above (a) polyvinyl alcohol-based resin is 1 to 50 g / 10 minutes, preferably 5 to 45 g / 10 minutes under the conditions of 210 ° C. and a load of 21.168 N. If the melt flow index is less than 1 g / 10 minutes, the gas barrier properties may deteriorate. On the other hand, if it exceeds 50 g / 10 minutes, the water resistance and the solvent resistance may decrease, which is not preferable.
These (a) polyvinyl alcohol resins can be used singly or in combination of two or more.

The polyvinyl alcohol resin constituting the component (a) itself is excellent in gas barrier properties, weather resistance, organic solvent resistance, transparency, gas barrier properties after heat treatment, and the like.
In addition, when (a) the polyvinyl alcohol-based resin is used to cure the coating film obtained from the composition of the present invention, the hydroxyl group present in the repeating unit derived from the polyvinyl alcohol has a component (b), (d) ) Co-condensation with at least one selected from vapor-deposited films of components, metals and / or inorganic compounds provides a coating film with excellent coating performance, particularly gas barrier properties under high humidity and / or after heat treatment be able to.

  The proportion of the component (a) in the coating composition of the present invention is 10 to 10,000 parts by weight, preferably 20 to 5,000 parts by weight, based on 100 parts by weight of the component (b) before hydrolysis and / or condensation. Parts, more preferably 100 to 1,000 parts by weight. If it is less than 10 parts by weight, the resulting coating film is likely to crack, and the gas barrier property is lowered. On the other hand, if it exceeds 10,000 parts by weight, the resulting coating film has a gas barrier property under high humidity and / or after heat treatment. May decrease.

(B) component;
Component (b) used in the present invention is a metal alcoholate, a hydrolyzate of the metal alcoholate, a condensate of the metal alcoholate, or a chelate compound of the metal alcoholate represented by the general formula (1). (Hereinafter also referred to as “metal chelate compound”), hydrolyzate of the metal chelate compound, condensate of the metal chelate compound, metal acylate, hydrolyzate of the metal acylate, and condensate of the metal acylate At least one of them. That is, (b) component may be only 1 type in these 9 types, and arbitrary 2 or more types of mixtures may be sufficient as it.
Furthermore, 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, ketoalcohols, and aminoalcohols. (Hereinafter also referred to as “chelating agent”). Among these chelating agents, β-diketones or β-ketoesters are preferably used. 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-methyl-hexane-dione and the like.
Here, the hydrolyzate of the metal alcoholate, the hydrolyzate of the metal chelate compound, and the hydrolyzate of the metal acylate do not need to have all the OR ² groups contained in the metal alcoholate hydrolyzed. For example, only one may be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof.
In addition, the metal alcoholate condensate, the metal chelate compound condensate, and the metal acylate condensate are condensed with the metal alcoholate, metal chelate compound, and metal acylate hydrolyzate M-OH group. However, in the present invention, it is not necessary that all M-OH groups are condensed, and only a small part of M-OH groups are condensed, the degree of condensation. Are different, or a mixture of condensates in which M-OR groups and M-OH groups are mixed.
When a condensate is used as the component (b), a product obtained by previously hydrolyzing and condensing the metal alcoholate, the metal chelate compound, and the metal acylate may be used, or a commercially available condensate. May be used. In addition, the metal alcoholate condensate may be used as it is, or may be used as a metal chelate compound condensate by reacting with the chelating agent.
Examples of the commercial product of the metal alcoholate condensate include A-10, B-2, B-4, B-7, and B-10 manufactured by Nippon Soda Co., Ltd.
The component (b) is considered to act to form a cocondensate with at least one selected from the component (a), the component (d), and a vapor deposition film component composed of a metal and / or an inorganic compound.

In the general formula (1), examples of the metal atom represented by M include zirconium, titanium, and aluminum, and titanium is particularly preferable.
The monovalent organic group having 1 to 8 carbon atoms of R ¹ is different depending on whether the compound represented by the general formula (1) is a metal alcoholate or a metal acylate.
In the case of a metal alcoholate, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group , N-heptyl group, n-octyl group, 2-ethylhexyl group and other alkyl groups; acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group and other acyl groups; vinyl group, allyl group, cyclohexyl group In addition to phenyl group, glycidyl group, (meth) acryloxy group, ureido group, amide group, fluoroacetamide group, isocyanate group and the like, substituted derivatives of these groups and the like can be mentioned. Examples of the substituent in the substituted derivative of R ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) acryloxy group, Examples thereof include a ureido group and an ammonium base. However, the carbon number of R ¹ composed of these substituted derivatives is 8 or less including the carbon atom in the substituent.
In the case of a metal acylate, the monovalent organic group having 1 to 8 carbon atoms of R ¹ includes an acetoxyl group, a propionyloxyl group, a butyryloxyl group, a valeryloxyl group, a benzoyloxyl group, and a trioyloxyl group. And acyloxyl groups such as
In the general formula (1), when two R ^{1 s} are present, they may be the same as or different from each other.

Examples of the alkyl group having 1 to 5 carbon atoms of R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n- A pentyl group etc. can be mentioned, As a C1-C6 acyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a caproyl group etc. can be mentioned, for example.
A plurality of R ² present in the general formula (1) may be the same as or different from each other.

Among these (b) components, as specific examples of metal alcoholates and metal alcoholate chelate compounds,
(I) Tetra-n-butoxyzirconium, tri-n-butoxyethylacetoacetatezirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n -Zirconium compounds such as propyl acetoacetate) zirconium, tetrakis (acetyl acetoacetate) zirconium, tetrakis (ethyl acetoacetate) zirconium;

  (B) Tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetra-t-butoxy titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (acetylacetate) titanium Di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (triethanolaminato) titanium, dihydroxy bislactatetitanium, dihydroxytitanium lactate, tetrakis (2-ethylhexyloxy) titanium, etc. Titanium compounds of

(C) Tri-i-propoxyaluminum, di-i-propoxyethyl acetoacetate aluminum, di-i-propoxy acetylacetonate aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy bis ( Aluminum compounds such as acetylacetonato) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis (ethylacetoacetate) aluminum;
And so on.
Among these metal alcoholates and metal alcoholate chelate compounds, preferred are tri-n-butoxy ethylacetoacetate zirconium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy Bis (triethanolaminato) titanium, dihydroxy bislactatetotitanium, di-i-propoxy-ethyl acetoacetate aluminum and tris (ethyl acetoacetate) aluminum can be mentioned, and particularly preferred compounds are di-i-propoxy. Titanium compounds such as bis (acetylacetonato) titanium, di-n-butoxy bis (triethanolaminato) titanium, dihydroxy bislactatetotitanium.

Specific examples of the metal acylate include dihydroxy titanium dibutyrate, di-i-propoxy titanium diacetate, di-i-propoxy titanium dipropionate, di-i-propoxy titanium dimalonate, di- i-propoxy-titanium dibenzoylate, di-n-butoxy-zirconium diacetate, di-i-propylaluminum monomalonate, and the like. Particularly preferred compounds are dihydroxy-titanium dibutyrate, di-i-propoxy. -Titanium compounds such as titanium diacetate.
These components (b) are used singly or in combination of two or more.

As the component (b), since the viscosity of the coating liquid does not change with time and it is easy to handle, hydrolysis treatment is performed in water or a mixed solvent containing water and a hydrophilic organic solvent described in a hydrophilic solvent described later. It is preferable to use what has been applied. Before mixing with the component (a), by performing such a hydrolysis treatment, the component (b) not hydrolyzed, the component (b) partially hydrolyzed, the component (b) partially condensed It becomes a mixture, and an abrupt increase in viscosity due to a shock or the like generated when the composition is mixed with the component (a) or a viscosity increase with time is suppressed.
In this case, the amount of water _{^{used, R 1 m M (OR 2}} ) n 1 mole of 0.1 to 1,000 mol, preferably 0.5 to 500 moles.
In the case of a 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, more preferably. 30-70 / 70-30.
As the component (b), titanium compounds such as di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (triethanolaminato) titanium, and dihydroxy bislactatetotitanium are particularly preferable. Is hydrolyzed with the above mixed solvent.

(C) component;
It is preferable that the coating composition of this invention contains the nitrogen-containing compound which is (c) component as needed.
Examples of the nitrogen-containing compound (c) include hydrophilic nitrogen-containing organic solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, γ-butyrolactone, N-methylpyrrolidone, and pyridine; thymine, glycine, Examples thereof include nucleobases such as cytosine and guanine; hydrophilic nitrogen-containing polymers such as polyvinylpyrrolidone, polyacrylamide and polymethacrylamide, and copolymers obtained by copolymerizing these components.
Of these, N, N-dimethylacetamide, N, N-dimethylformamide and polyvinylpyrrolidone are preferred.
By mixing the component (c), a coating with a thin film can be obtained with a more transparent appearance and a catalytic effect when condensed with inorganic particles and / or inorganic laminates is exhibited. The ratio 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.

(D) component;
The coating composition of the present invention preferably contains inorganic fine particles as component (d) as necessary. The inorganic fine particles are particulate inorganic substances having an average particle diameter of 0.2 μm or less and substantially free of carbon atoms, and examples thereof include metals or silicon oxides, metals or silicon nitrides, and metal borides. For example, in order to obtain silicon oxide, a vapor phase method in which silicon tetrachloride is obtained by hydrolysis in a flame of oxygen and hydrogen, a liquid phase method in which sodium silicate is ion-exchanged, a silica gel mill, etc. However, it is not limited to these methods.

Specific compound examples include SiO ₂ , Al ₂ O ₃ , TiO ₂ , WO ₃ , Fe ₂ O ₃ , ZnO, NiO, RuO ₂ , CdO, SnO ₂ , Bi ₂ O ₃ , 3Al ₂ O ₃ .2SiO. ₂ , oxides such as Sn—In ₂ O ₃ , Sb—In ₂ O ₃ and CoFeO _x , nitrides such as Si ₃ N ₄ , Fe ₄ N, AlN, TiN, ZrN and TaN, Ti ₂ B and ZrB ₂ , Borides such as TaB ₂ and W ₂ B. Examples of the form of the inorganic fine particles include powder, water, or a colloid or sol dispersed in an organic solvent, but these are not limited. Of these, colloidal silica, colloidal alumina, alumina sol, tin sol, zirconium sol, pentoxide are preferable in order to obtain excellent coating performance by co-condensing with component (a) and / or component (b). Colloidal oxides having a hydroxyl group on the particle surface, such as antimony sol, cerium oxide sol, zinc oxide sol, and titanium oxide sol, are used.
The average particle diameter of the inorganic fine particles is 0.2 μm or less, preferably 0.1 μm or less. If the average particle diameter exceeds 0.2 μm, the gas barrier property may be inferior from the viewpoint of the denseness of the film.

  The proportion of the component (d) in the composition of the present invention is preferably 900 parts by weight or less, particularly preferably 400 parts by weight or less, with respect to 100 parts by weight of the total amount of the components (a) and (b). . When it exceeds 900 weight part, the gas barrier property of the coating film obtained may fall.

Optional ingredients;
In order to cure the composition of the present invention more quickly and to facilitate the formation of a cocondensate of the component (a) and the component (b), (e) a curing accelerator may be used, It is more effective to use this (e) curing accelerator together in order to obtain curing at a low temperature and a denser coating film.

As this (e) curing accelerator, inorganic acids such as hydrochloric acid; alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate and carbonic acid; alkaline compounds such as sodium hydroxide and potassium hydroxide; alkyl Acidic compounds such as titanic acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, phthalic acid, succinic acid, glutaric acid, oxalic acid, 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 Aminoethyl) - aminopropyl methyl dimethoxy silane, and amine compounds such as γ- anilino trimethoxysilane is used.
The proportion of these (e) curing accelerators in the composition is usually 50 parts by weight or less, preferably 30 parts by weight or less with respect to 100 parts by weight of the solid content of the composition of the present invention.

  Furthermore, the β-diketones and / or β-ketoestils listed above can be added to the composition of the present invention as a stability improver. That is, by coordinating with the metal atom in the metal alcoholate present in the composition as the component (b), it acts to control the condensation reaction between the component (a) and the component (b). It is considered that it acts to improve the storage stability of the resulting composition. The amount of the β-diketone and / or β-ketoester to be used is preferably 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal atom in the component (b).

The coating composition of the present invention is usually obtained by dissolving and dispersing the above components (a) to (b) and optionally the above optional components in water and / or a hydrophilic organic solvent.
Here, specific examples of the hydrophilic organic solvent include methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, diacetone alcohol, ethylene glycol, diethylene glycol, triglyceride. C1-C8 saturated aliphatic monohydric alcohol or dihydric alcohol such as ethylene glycol; C1-C8 saturated aliphatic ether compound such as ethylene glycol monobutyl ether or ethylene glycol monoethyl ether; ethylene glycol Ester compounds of saturated aliphatic dihydric alcohols having 1 to 8 carbon atoms such as monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; Sulfur-containing compounds such as Rusuruhokishido; lactate, methyl lactate, ethyl lactate, salicylate, hydroxycarboxylic acids or hydroxycarboxylic acid esters such as methyl salicylate and the like. Of these, preferred are saturated aliphatic monohydric alcohols having 1 to 8 carbon atoms such as methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and the like. Can be mentioned. Moreover, you may use the hydrophilic nitrogen-containing organic solvent illustrated as (c) component as a part or all of a hydrophilic organic solvent.

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

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

  As the organic solvent, the above water and / or hydrophilic organic solvent is preferable, but in addition to the hydrophilic organic solvent, for example, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as tetrahydrofuran and dioxane, Ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate can also be used.

  Thus, the coating composition of the present invention is obtained by mixing the components (a) to (b) and optionally the optional components (c) to (e) in water and / or a hydrophilic organic solvent. Preferably, the above components (a) and (b) are added, and if necessary, components (c) to (e) are added to hydrolyze component (b) in water and / or a hydrophilic organic solvent. And / or by (co) condensation. In this case, the reaction conditions are a temperature of 5 to 100 ° C., preferably 20 to 90 ° C., and a time of 0.005 to 20 hours, preferably 0.1 to 10 hours.

In addition, the coating composition of the present invention is separately provided with a filler in order to develop various characteristics such as coloring of the obtained coating film, thickening of the coating film, prevention of UV transmission to the base, provision of corrosion resistance, and heat resistance. It is also possible to add and disperse. However, the filler excludes the components (c) to (d).
Examples of fillers include water-insoluble pigments such as organic pigments and inorganic pigments, and particles, fibers or scale-like metals and alloys, and oxides, hydroxides, carbides, nitrides thereof, and the like. Examples thereof include sulfides. Specific examples of the filler include particulate, fibrous or scale-like iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, chromium oxide. , Manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, Magnesium carbonate, barium sulfate, bentonite, mica, zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, chellet green, green earth, manganese green, pigment green, ultramarine, bituminous, pigment green, rock ultramarine, Cobalt blue, cerulean blue, copper borate, molyb Blue, copper sulfide, cobalt purple, mars purple, manganese purple, pigment violet, lead oxide, calcium leadate, zinc yellow, lead sulfide, chromium yellow, ocher, cadmium yellow, strontium yellow, titanium yellow, resurge, pigment yellow, Cuprous oxide, cadmium red, selenium red, chromium vermilion, bengara, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead zinc white, bunchison white, phthalate Lead acid, manganese white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide, and the like.

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

  The coating composition of the present invention includes other known dehydrating agents such as methyl orthoformate, methyl orthoacetate, and tetraethoxysilane, various surfactants, silane coupling agents, titanium coupling agents, and dyes other than those described above. Additives such as dispersants, thickeners and leveling agents can also be blended.

  In preparing the coating composition of the present invention, the components (a) to (b), the components (a) to (c), the components (a) to (b) and the component (d), or (a) A composition containing the component (d) may be prepared. Preferably, the component (b) is hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent, and then (a) ) Mix with ingredients. If it does in this way, the coating composition which does not have the viscosity change of a coating composition with time, and was excellent in the handleability will be obtained.

Specific examples of the method for preparing the coating composition of the present invention when the component (d) is used include the following (1) to (4). In these preparation methods, as the component (b), one that has been subjected to hydrolysis treatment in advance in water or a mixed solvent containing water and a hydrophilic organic solvent may be used.
(1) A method of adding the component (b) after adding the component (d) to the component (a) dissolved in water and / or a hydrophilic organic solvent.
(2) A method in which the component (d) is added to the component (a) dissolved in water and / or a hydrophilic organic solvent, and then the component (b) is added for hydrolysis and / or condensation.
(3) A method in which the component (d) is added to the component (b) dissolved in water and / or a hydrophilic organic solvent, followed by hydrolysis and / or condensation, and then the component (a).
(4) A method in which the components (a) to (b) and (d) are added all at once to water and / or a hydrophilic organic solvent and dissolved and dispersed. Or the method of performing hydrolysis and / or condensation after that.

  In addition, as a specific example of the method for preparing the coating composition of the present invention when the component (c) is used, the component (c) dispersed (dissolved) in a mixed solvent containing water and / or a hydrophilic organic solvent in advance. Is added to the component (a) dissolved in a mixed solvent containing water and / or a hydrophilic organic solvent, or the components (a) to (b) or (a) to (b) and (d) A method of adding the component (c) dissolved in a mixed solvent containing water and / or a hydrophilic organic solvent after preparing the coating composition is common, but is not limited thereto.

The coating composition of the present invention has a gel content after coating.
Specifically, after coating the coating composition of the present invention on a PET film so as to have a film thickness of 1 μm, the film was dried at 140 ° C. for 2 minutes to form 0.25 g of n-propanol / water ( (Weight ratio) = 1. The insoluble fraction calculated from the insoluble matter obtained by dissolving and dissolving the insoluble matter after being dissolved in 1/183 ml at 60 ° C. for 1 hour (hereinafter referred to as “heated gelation rate”) is preferably 1-90. %, More preferably 5 to 70%. When the heating gelation rate is less than 1%, the water resistance is remarkably lowered and the gas barrier property is lowered. On the other hand, if it exceeds 90%, the water absorption rate is improved and the gas barrier property is lowered.

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

  Examples of the base film constituting 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 resins, and polystyrene resins. , Polyvinyl alcohol, polyvinyl alcohol resin such as saponification part of ethylene-vinyl acetate copolymer, polyacrylonitrile resin, polyvinyl chloride resin, polyvinyl acetal resin, polyvinyl butyral resin, fluorine resin, and other various types Resin films and sheets can be used. In the present invention, as the method for forming the resin film and sheet, for example, one or more of the above resins are used, and the above resin is used alone by an inflation method, a T-die method, or other film forming methods. The method of forming a film by the method, or the method of forming a multi-layer coextrusion film using two or more different resins, and further using two or more resins and mixing them before forming a film. A resin film or sheet is manufactured by a method of forming a film, and further, for example, a resin film or sheet is formed by stretching in a uniaxial or biaxial direction using a tenter method or a tubular method. Can be formed. In this invention, as a film thickness of a base film, Preferably it is about 5-200 micrometers, More preferably, it is about 10-50 micrometers. In the above, when forming the resin into a film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slip properties, mold release properties, flame retardancy, antifungal properties, etc. Various plastic compounding agents and additives can be added for the purpose of improving and modifying properties, electrical characteristics, and the like. The addition amount can be arbitrarily added from a very small amount to several tens of percent depending on the purpose. In the above, as general additives, for example, lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, fillers, reinforcing agents, reinforcing agents, antistatic agents, flame retardants, flameproofing agents, foaming agents, An antifungal agent, a pigment, etc. can be used, and further, a modifying resin or the like can also be used.

  In the present invention, the base film is treated with, for example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, chemicals, etc. Oxidation treatment and other pretreatment can be optionally performed. The surface pretreatment may be performed in a separate step before forming the inorganic oxide vapor-deposited film. For example, in the case of surface treatment such as low-temperature plasma treatment or glow discharge treatment, the above-described inorganic oxidation treatment may be performed. As a pretreatment for forming a vapor-deposited film of an object, it can be performed by a pretreatment by an inline treatment. 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 base film and the inorganic oxide vapor-deposited film. As a method for improving the adhesion, other methods such as a base A primer coat agent layer, an undercoat agent layer, a vapor deposition anchor coat agent layer, or the like can be arbitrarily formed on the surface of the material film in advance. As the pretreatment coating agent layer, 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. 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. The coating time can be applied as a post-process after the biaxial stretching treatment of the base film or in-line treatment of the biaxial stretching treatment. In the present invention, specifically, as the base film, it is preferable to use a biaxially stretched polypropylene film, a biaxially stretched polyethylene terephthalate film, or a biaxially stretched nylon film.

At this time, it is also possible to laminate a deposited film of metal and / or inorganic compound (hereinafter also referred to as “deposited film”) on the substrate or the coating film of the present invention. By providing this deposited film, the gas barrier property is further improved.
When a deposited film is present, the deposited film and the component (b) form a chemical bond, hydrogen bond, or coordination bond by hydrolysis / cocondensation reaction, and the adhesion between the deposited film and the gas barrier coating layer is improved. improves.
The vapor deposition film is preferably an inorganic oxide vapor deposition film formed by chemical vapor deposition and / or physical vapor deposition.

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

Specifically, an example of the method for forming a deposited film of an inorganic oxide by the low temperature plasma chemical vapor deposition method will be described. FIG. 1 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of a method for forming a deposited film of an inorganic oxide by the plasma chemical vapor deposition method.
As shown in FIG. 1 above, in the present invention, the base film 2 is unwound from an unwinding roll 13 disposed in the vacuum chamber 12 of the plasma chemical vapor deposition apparatus 11, and the base film 2 is further removed. Then, it is conveyed to the circumferential surface of the cooling / electrode drum 15 through the auxiliary roll 14 at a predetermined speed.
Thus, in the present invention, vapor supply monomer gas such as oxygen gas, inert gas, organosilicon compound, and the like are supplied from the gas supply devices 16, 17 and the raw material volatilization supply device 18, etc. While preparing the mixed gas composition, the vapor deposition mixed gas composition is introduced into the chamber 12 through the raw material supply nozzle 19. Then, a plasma is generated by the glow discharge plasma 20 on the substrate film 2 conveyed on the peripheral surface of the cooling / electrode drum 15 and irradiated with this to form a continuous film of an inorganic oxide such as silicon oxide. To form a film.
In the present invention, a predetermined power is applied to the cooling / electrode drum 15 from the power source 21 disposed outside the chamber, and a magnet 22 is provided in the vicinity of the cooling / electrode drum 15. It is arranged to promote the generation of plasma. Next, the base film 2 on which a continuous film of an inorganic oxide such as silicon oxide is formed is wound on a take-up roll 24 via an auxiliary roll 23, whereby the inorganic film obtained by the chemical vapor deposition method of the present invention is used. An oxide deposition film can be formed. In the figure, reference numeral 25 denotes a vacuum pump.
The above illustrations exemplify one example, and it goes without saying that the present invention is not limited thereby.
Although not illustrated, in the present invention, the inorganic oxide vapor deposition film may be not only one layer of a continuous inorganic oxide film but also a composite vapor deposition film in which two or more layers are laminated, The materials to be used can also be used in one kind or a mixture of two or more kinds, and an inorganic oxide vapor deposition film in which different kinds of materials are mixed can also be constituted.

In the above, the inside of the vacuum chamber 12 is decompressed by the vacuum pump 25 and adjusted to a degree of vacuum of about 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a degree of vacuum of about 1 × 10 ⁻³ to 10 ⁻⁷ Torr. It is desirable.
In the raw material volatilization supply device 18, the organic silicon compound as the raw material is volatilized and mixed with oxygen gas, inert gas, etc. supplied from the gas supply devices 16, 17. Through the chamber 12.
In this case, the content of the organosilicon compound in the mixed gas is about 1 to 40 mol%, the content of oxygen gas is about 10 to 70 mol%, and the content of the inert gas is about 10 to 60 mol%. In addition, the mixing ratio of the organosilicon compound, oxygen gas, and inert gas can be about 1: 6: 5 to 1:17:14 in molar ratio.
On the other hand, since a predetermined voltage is applied to the cooling / electrode drum 15 from the power source 21, glow discharge plasma 20 is generated in the vicinity of the opening of the raw material supply nozzle 19 in the chamber 12 and the cooling / electrode drum 15. The glow discharge plasma 20 is derived from one or more gas components in the mixed gas. In this state, the base film 2 is conveyed at a constant speed, and an inorganic oxide vapor deposition film such as silicon oxide is formed on the base film 2 on the peripheral surface of the cooling / electrode drum 15 by glow discharge plasma 20. can do.
At this time, the degree of vacuum in the vacuum chamber 12 is desirably adjusted to about 1 × 10 ⁻¹ to 10 ⁻⁴ Torr, preferably about 1 × 10 ⁻¹ to 10 ⁻² Torr. The conveying speed of the base film 2 is desirably adjusted to about 10 to 300 m / min, preferably about 50 to 150 m / min.

Further, in a plasma chemical vapor deposition apparatus 11 described above, formation of a continuous film of an inorganic oxide such as silicon oxide, on the substrate film 2, the SiO _x while the plasma raw material gas is oxidized with oxygen gas Therefore, the formed deposited film of an inorganic oxide such as silicon oxide is a dense, flexible continuous layer with few gaps. 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. With this, a sufficient gas barrier property can be obtained.
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. This has the advantage that the adhesion between the oxide vapor deposition film and the substrate film is high.
Furthermore, as described above, the degree of vacuum at the time of forming a vapor deposition 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 ×. Adjust to about 10 ^-2 Torr. For this reason, it is a low vacuum degree compared with the vacuum degree at the time of forming the vapor deposition film | membrane of inorganic oxides, such as a silicon oxide, by the conventional vacuum vapor deposition method, 1 * 10 < ^-4 > -1 * 10 < ^-5 > Torr, It is possible to shorten the vacuum state setting time at the time of replacing the original film of the base film 2, to easily stabilize the degree of vacuum, and to stabilize the film forming process.

In the present invention, a vapor deposition film of silicon oxide formed using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organosilicon compound and oxygen gas, and the reaction product is It is in close contact with one surface of a base film to form a dense and flexible thin film, and is usually an oxidation represented by the general formula SiO _x (where X represents a number from 0 to 2). It is a continuous thin film mainly composed of silicon.
The above silicon oxide vapor-deposited film is a continuous film of silicon oxide represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) in terms of transparency and gas barrier properties. A thin film mainly composed of is preferable.
In the above, the value of X varies depending on the molar ratio of the vapor deposition monomer gas and oxygen gas, the plasma energy, etc. Generally, the gas permeability decreases as the value of X decreases, but the film itself is yellow. It becomes sexual and becomes less transparent.

In addition, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and at least one compound of carbon, hydrogen, silicon or oxygen, or a compound comprising two or more elements thereof is chemically bonded. It consists of the continuous film | membrane contained by these.
For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by chemical bonds.
Specific examples include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol.
In addition to the above, by changing the conditions of the vapor deposition process, the type and amount of the compound contained in the silicon oxide vapor deposition film can be changed.
The content of the above compound contained in the deposited film of silicon oxide is about 0.1 to 50 mol%, preferably about 5 to 20 mol%. If it is less than 0.1 mol%, the impact resistance, spreadability, flexibility, etc. of the deposited silicon oxide film will be inadequate, and scratches and cracks are likely to occur due to bending, etc., and high gas barrier properties are stably maintained. Difficult to do. On the other hand, if it exceeds 50 mol%, the gas barrier property is lowered, which is not preferable.
In the present invention, it is preferable that the content of the above-mentioned compound in the silicon oxide vapor-deposited film decreases from the surface of the silicon oxide vapor-deposited film in the depth direction. Thereby, on the surface of the deposited film of silicon oxide, the impact resistance is enhanced by the above-described compound, and on the other hand, since the content of the above-mentioned compound is small at the interface with the base film, There is an advantage that the adhesion with the deposited film of silicon oxide becomes strong.

In the present invention, for the deposited film of silicon oxide, for example, a surface analyzer such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS) or a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS) is used. The physical properties as described above can be confirmed by performing elemental analysis of the deposited film of silicon oxide using a method of analyzing by ion etching in the depth direction.
In the present invention, the thickness of the silicon oxide vapor deposition film is preferably about 5 to 400 nm, more preferably about 10 to 100 nm. If the film thickness is 10 nm or less than 5 nm, it is difficult to achieve the gas barrier effect, which is not preferable. On the other hand, it is not preferable that the film thickness is 100 nm, or more than 400 nm, because cracks or the like are likely to occur in the film.
In the above, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name: RIX2000 type) manufactured by Rigaku Corporation.
In the above, as means for changing the film thickness of the silicon oxide vapor deposition film, the volume velocity of the vapor deposition film is increased, that is, the method of increasing the amount of monomer gas and oxygen gas, or the vapor deposition rate is slowed. This can be done by a method or the like.

In the above, as a vapor deposition monomer gas such as an organosilicon compound for forming a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethyl Silane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, Methyltriethoxysilane, octamethylcyclotetrasiloxane and the like can be used.
In the present invention, among the above organosilicon compounds, the use of 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is easy to handle, It is a particularly preferable raw material because of its characteristics.
Moreover, in the above, as an inert gas, argon gas, helium gas, etc. can be used, for example.

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

  One example of a method of forming a vapor-deposited 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 take-up vacuum deposition apparatus. As shown in FIG. 2, in the vacuum chamber 52 of the take-up type vacuum vapor deposition apparatus 51, the base film 2 having the inorganic oxide vapor deposition film 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 through 54 and 55. A vapor deposition source 58 ripened in a crucible 57 on the inorganic oxide vapor deposition film of the base film 2 having a vapor deposition film of inorganic oxide by chemical vapor deposition guided on the cooled coating drum 56; For example, metal aluminum, aluminum oxide or the like is evaporated, oxygen gas or the like is ejected from an oxygen gas outlet 59 as necessary, and an inorganic oxide such as aluminum oxide is supplied through the masks 60 and 60 while supplying this. Then, a base film 2 formed by depositing an inorganic oxide vapor deposition film such as aluminum oxide on the inorganic oxide vapor deposition film by the chemical vapor deposition method is used as a guide roll 55 ′, An inorganic oxide vapor deposition film can be formed by the physical vapor deposition method of the present invention by feeding it through 54 'and winding it on a winding roll 61.

The inorganic oxide vapor-deposited film may be any thin film obtained by vapor-depositing a metal oxide. For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium Use vapor-deposited films of metal oxides such as (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) Can do. Examples of suitable materials for packaging include metal oxides such as silicon (Si) and aluminum (Al). The deposited metal oxide film can be called 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 , MgO _{x. X} (where M represents a metal element, and the value of X varies depending on the metal element). In addition, the range of the value of X is 0 to 2 for silicon (Si), 0 to 1.5 for aluminum (Al), 0 to 1 for magnesium (Mg), 0 to 1 for calcium (Ca), potassium. (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1.5, titanium (Ti) is 0 to 2, Lead (Pb) can take values ranging from 0 to 1, zirconium (Zr) from 0 to 2, and yttrium (Y) from 0 to 1.5. In the above, when X = 1, it is a complete metal and is not transparent and cannot be used at all. In addition, the upper limit of the range of X is a completely oxidized value. In the present invention, examples other than silicon (Si) and aluminum (Al) are generally poor as packaging materials. Silicon (Si) having a range of 1.0 to 2.0 and aluminum (Al) having a range of 0.5 to 1.5 can be preferably used. In the present invention, the film thickness of the inorganic oxide thin film varies depending on the metal to be used, the type of the metal oxide, etc., but is arbitrarily selected within the range of, for example, 5 to 200 nm, preferably 10 to 100 nm. It is desirable to form. Further, the inorganic oxide vapor deposition film of the present invention may be not only one layer of the inorganic oxide vapor deposition film but also a laminated body in which two or more layers are laminated. Moreover, the metal and metal oxide to be used can be used by 1 type, or 2 or more types of mixtures, and can comprise the thin film of the inorganic oxide mixed by the dissimilar material.

The following method is mentioned as a specific example of the method of forming the coating film of this invention using the coating composition of this invention.
(1) A method for forming a coating film of the present invention on a substrate surface. In addition, as needed, a primer may be previously apply | coated on the base-material surface as needed, and the coating film of this invention may be formed.
(2) A method of forming an inorganic oxide vapor-deposited film by chemical vapor deposition and / or physical vapor deposition on the surface of the substrate and forming the coating film of the present invention on the vapor-deposited film surface. In addition, when forming a vapor deposition film on the base-material surface, you may apply | coat a primer beforehand on a base-material surface as needed.
(3) A method for forming a deposited film on the surface of the coating film of the present invention as described in (1) above by chemical vapor deposition and / or physical vapor deposition.
(4) A method for forming a deposited film on the surface of the coating film of the present invention according to (2) above by chemical vapor deposition and / or physical vapor deposition.
(5) A method for further forming the coating film of the present invention on the surface of the vapor deposition film of (3).
(6) A method for further forming the coating film of the present invention on the surface of the deposited film of (4).
(7) The method of (1) to (6), wherein the surface of the base material of the above (1) to (6) is one side or both sides.

A cured coating film (hereinafter also 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 deposited film is laminated). To laminate, dry film can be applied to the surface of the substrate by one or more coatings such as roll coating such as gravure coater, spray coating, spin coating, dipping, brush, bar code, applicator, etc. A coating film of the present invention having a thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm, can be formed, and is at a temperature of 50 to 300 ° C., preferably 70 to 200 ° C. in a normal environment. Condensation is performed by heating and drying for 005 to 60 minutes, preferably 0.01 to 10 minutes, and the coating film of the present invention can be formed.
Further, if necessary, a printed 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 printed pattern layer.

  As the above-mentioned printed picture layer, for example, on the above-mentioned coating cured film, using a normal gravure ink composition, offset ink composition, letterpress ink composition, screen ink composition, other ink composition, For example, by using gravure printing method, offset printing method, letterpress printing method, silk screen printing method, and other printing methods, for example, it is configured by forming a desired printing pattern consisting of characters, figures, patterns, symbols, etc. can do. Regarding the ink composition, examples of the vehicle constituting the ink composition include polyolefin resins such as polyethylene resins and chlorinated polypropylene resins, poly (meth) acrylic resins, polyvinyl chloride resins, and polyvinyl acetate. Resin, vinyl chloride-vinyl acetate copolymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polybutadiene resin, polyester resin Resins, polyamide resins, alkyd resins, epoxy resins, unsaturated polyester resins, thermosetting poly (meth) acrylic resins, melamine resins, urea resins, polyurethane resins, phenol resins, xylene resins , Maleic resin, Fiber resins such as rocellulose, ethylcellulose, acetylbutylcellulose, ethyloxyethylcellulose, rubber resins such as chlorinated rubber and cyclized rubber, natural resins such as petroleum resins, rosin and casein, linseed oil, soybean oil, etc. A mixture of one or more of fats and oils and other resins can be used. In the present invention, one or more of the above-mentioned vehicles are used as a main component, and one or more of coloring agents such as dyes and pigments are added to this, and if necessary, a filler, Light stabilizers such as additives, plasticizers, antioxidants, UV absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, cross-linking agents, and other additives are optionally added, solvent, dilution Ink compositions having various forms obtained by sufficiently kneading with an agent or the like can be used.

  Next, the heat-sealable resin for forming the heat-sealable resin layer may be any resin that can be melted by heat and fused to each other. For example, low-density polyethylene, medium-density polyethylene, and 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, Acid modification by modifying polyolefin resins such as ethylene-propylene copolymer, methylpentene polymer, polyethylene and polypropylene with acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and other unsaturated carboxylic acids Polyolefin resin, polyvinyl acetate resin, polyester Ether-based resin, polystyrene resin, one or resin comprising more other resins. In the present invention, as the heat-sealable resin layer, one or more of the above-described resins are used, and for example, a resin film or sheet formed into a film by an inflation method, a T-die method, or other methods. Alternatively, it can be used in the form of a coating film made of a resin composition containing one or more of the above-described resins as a main component of the vehicle. The film thickness is about 5 to 100 μm, preferably about 10 to 50 μm.

  In the present invention, among the above resins, it is particularly preferable to use linear (linear) low density polyethylene. The linear low density polyethylene has the advantage of improving impact resistance with less propagation of breakage because it has adhesiveness, and since the inner layer is always in contact with the contents, it is environmentally resistant. It is also effective for preventing deterioration of stress cracking properties. In the present invention, other resins can be blended with the linear low density polyethylene. For example, by blending an ethylene-butene copolymer or the like, the resin is slightly inferior in heat resistance and sealed in a high temperature environment. Although the stability tends to deteriorate, there is an advantage that the tearability is improved and it contributes to easy opening. Specifically, as the linear low density polyethylene as the heat-sealable resin as described above, an ethylene-α / olefin copolymer polymerized using a metallocene catalyst can be used. Specifically, the product name “Kernel” manufactured by Mitsubishi Chemical Corporation, the product name “Evolue” manufactured by Mitsui Petrochemical Co., Ltd., and the product name “EXACT” manufactured by EXXON CHEMICAL, USA ”, An ethylene-α-olefin copolymer polymerized using a metallocene catalyst such as“ AFFINITY ”or“ engage ”manufactured by Dow Chemical Co., USA can do. 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 a bag is produced.

  In the laminated material using the gas barrier coating film of the present invention, since the packaging container is usually subjected to severe physical and chemical conditions, the laminated material constituting the packaging container is severe. The packaging suitability, that is, deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing performance, quality maintenance, workability, hygiene, and other various conditions are required. For this reason, in this invention, the material which satisfies the above various conditions can be selected arbitrarily, and in addition to the material which comprises a laminated material, a desired laminated material can be comprised. 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) acryl Resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin , Polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, and other known resin films or sheets. Can be used. In addition, for example, a film such as cellophane or a synthetic paper can be used. In the present invention, the film or sheet may be any of unstretched, uniaxially or biaxially stretched. The thickness is arbitrary, but can be selected from a range of several μm to 300 μm. The film or sheet may be any film having properties such as extrusion film formation, inflation film formation, and coating film.

In the present invention, as a method for producing the laminated material according to the present invention using the barrier film according to the present invention, the printed pattern layer, the heat-sealable resin layer, and other materials, for example, an adhesive for laminating is used. Can be performed by a dry lamination method in which lamination is performed through an adhesive layer for laminating, or an extrusion lamination method in which lamination is performed through a melt extrusion resin layer using a melt extrusion adhesive resin. In the above, as the laminating adhesive, for example, one-part or two-part curable or non-cured vinyl type, (meth) acrylic type, polyamide type, polyester type, polyether type, polyurethane type, epoxy type, etc. It is possible to use an adhesive for laminating such as a solvent type such as rubber, others, an aqueous type, or an emulsion type. As a coating method of the laminating adhesive, for example, direct gravure roll coating method, gravure roll coating method, kiss coating method, reverse roll coating method, fountain method, transfer roll coating method, and other methods can be used. The coating amount is preferably about 0.1 to 10 g / m ² (dry state), more preferably about 1 to 5 g / m ² (dry state). For example, an adhesion promoter such as a silane coupling agent can be arbitrarily added to the laminating adhesive. In the above, as the melt-extrusion adhesive resin, the heat-sealable resin that forms the heat-sealable resin layer can be used in the same manner, and low-density polyethylene, particularly linear low-density polyethylene and acid-modified polyethylene are used. It is preferable to use it. The film thickness of the melt-extruded resin layer by the melt-extruded adhesive resin is preferably about 5 to 100 μm, and more preferably about 10 to 50 μm. In the present invention, when it is necessary to obtain a stronger adhesive strength when performing the above-mentioned lamination, an adhesion improving agent such as an anchor coating agent can be coated. Examples of the anchor coating agent include organic titanium anchor coating agents such as alkyl titanates, isocyanate anchor coating agents, polyethyleneimine anchor coating agents, polybutadiene anchor coating agents, and other various aqueous or oil-based anchor coating agents. Can be used. In the present invention, the anchor coating agent is coated by roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating method, and the solvent, diluent, etc. are dried to form the anchor coating agent layer. can do. The coating amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

  Of the chemical vapor deposition method and physical vapor deposition method described above, when vapor deposition is performed by chemical vapor deposition, more functional groups such as organic components and hydroxyl groups are used than when vapor deposition is performed by physical vapor deposition. It contains more and the adhesiveness of a gas barrier coating layer and a 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 · 24 hr or less at a temperature of 23 ° C. and a relative humidity of 90% RH. The oxygen permeability is measured using, for example, an oxygen permeability measuring machine [model name, OX-TRAN 2/20] manufactured by MOCON, USA, under the conditions of 23 ° C. and 90% RH. Can be measured.

  The gas barrier coating film and the laminated material thereof of the present invention can be used to produce a packaging container suitable for filling and packaging various forms of articles by bag making and box making. The packaging container obtained by using the gas barrier coating film of the present invention is excellent in gas barrier properties against oxygen, water vapor, transparency, heat resistance, impact resistance, etc., laminating, printing, bag making, box making It is suitable for post-processing, such as foods and drinks, pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives, adhesives, and other chemicals, cosmetics, and other various articles. It is what. The bag making and box making method will be described. For example, in the case of a flexible packaging bag, the laminated material of the gas barrier coating film is used, and the inner surface of the heat-sealable resin layer is faced and folded. Alternatively, the two sheets can be overlapped, and the peripheral end portion can be further heat sealed to provide a seal portion to form a bag body. As the bag making method, the laminated material is folded with its inner layer faces facing each other, or two of them are overlapped, and the peripheral end of the outer periphery is a side seal type, two-side seal type, three-side seal type , Four-side seal type, envelope sticker seal type, palm seal sticker type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, and other heat seal forms, and various packaging containers Manufacturing. In addition, the laminated material can also produce a self-supporting packaging bag (stand-up pouch), a tube container, and the like. As the heat sealing method, known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing, and ultrasonic sealing can be used. Furthermore, for example, a one-piece type, a two-piece type, other spouts, an opening / closing zipper, and the like can be arbitrarily attached to the packaging container.

Moreover, when manufacturing the packaging container containing a paper base material, the laminated material which laminated | stacked the paper base material is manufactured, the blank board which manufactures a desired paper container from this laminated material is manufactured, The said blank board is manufactured. It is possible to manufacture a liquid paper container such as a brick type, a flat type, and a gobel top type by making a box, a bottom, a head, and the like. Also, any shape such as a rectangular container or a cylindrical paper can such as a round shape can be manufactured. The packaging container manufactured as described above can be used for filling and packaging various foods, chemicals such as adhesives and pressure-sensitive adhesives, cosmetics, pharmaceuticals, miscellaneous goods, and other various articles.
The gas barrier coating film of the present invention thus obtained is excellent in gas barrier properties even under humid conditions, so that it is useful not only for packaging materials for food, tobacco, toiletries, etc., but also for solar cells, protective films, moisture-proof films, etc. Used for

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example.
In the examples, parts and% are based on weight unless otherwise specified.
Moreover, each evaluation item in an Example was measured according to the following.

The heated gelation rate coating composition was applied onto a PET film using a 40 / 10,000 inch applicator and dried at 140 ° C. for 2 minutes in a Tabai dryer. After the obtained film is isolated with tweezers, it is collected in a 0.25 g sample bottle, adjusted to a concentration of 0.3% with n-propanol / water = 1/1, and at 60 ° C. for 1 hour with a magnetic stirrer. Stir. The obtained dispersion was filtered through paper filter paper (No. 2), and the filtrate was vacuum dried at 120 ° C. for 1 hour. From the obtained residue, the insoluble fraction (heated gelation ratio) was calculated.

The appearance of the coating film was evaluated by visual observation of the appearance of the coating film.
Viscosity of coating liquid The viscosity at a liquid temperature of 25 ° C. was measured with a B-type viscometer. Viscosity measurements were taken immediately after the coating composition was prepared and 24 hours later.
The oxygen permeability was measured using MOCON OXTRAN 2/20 manufactured by Modern Control Co., Ltd. under a temperature of 25 ° C. and a humidity of 90 RH%.

Reference Example 1 (Preparation of titanium chelate compound)
To a reactor equipped with a reflux condenser and a stirrer, 100 parts of tetra-i-propoxytitanium and 70 parts of acetylacetone were added and stirred at 60 ° C. for 30 minutes to obtain a titanium chelate compound (b-1). 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 stirred at 60 ° C. for 30 minutes to obtain a zirconium chelate compound (b-2). Got. The purity of this reaction product was 77%.

Example 1
(A) 15 ethylene / vinyl alcohol copolymer (manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol D2630, degree of saponification; 98% or more, ethylene content; 26 mol%, melt flow index; 30 g / 10 min) 100 parts of a% water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio = 6/4) and 10 parts of the titanium chelate compound (b-1) prepared in Reference Example 1 as the component (b) were mixed. A coating composition (A) was obtained. The heating gelation rate of the coating composition of the present invention was 60%.

Example 2
(A) 15 ethylene / vinyl alcohol copolymer (manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol D2630, degree of saponification; 98% or more, ethylene content; 26 mol%, melt flow index; 30 g / 10 min) % Water / n-propyl alcohol / N, N-dimethylformamide solution (water / n-propyl alcohol / N, N-dimethylformamide weight ratio = 6/3/1) 100 parts, and (b) Reference Example 1 as component 10 parts of the titanium chelate compound (b-1) prepared in Step 1 was mixed to obtain the coating composition (B) of the present invention. The heating gelation rate of the coating composition (B) was 55%.

Example 3
(A) 15 ethylene / vinyl alcohol copolymer (manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol D2630, degree of saponification; 98% or more, ethylene content; 26 mol%, melt flow index; 30 g / 10 min) % Water / n-propyl alcohol / N, N-dimethylformamide solution (water / n-propyl alcohol / N, N-dimethylformamide weight ratio = 6/3/1) 100 parts in advance as a reference example as component (b) 10 parts of the titanium chelate compound (b-1) prepared in 1 and 10 parts of water were mixed and stirred for 1 hour at room temperature to obtain a coating composition (C) of the present invention. The heating gelation rate of the coating composition (C) was 70%.

Example 4
In Example 1, 50 parts of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex IPA-ST, dispersion medium: isopropyl alcohol, average particle size: 10 nm, solid content concentration: 30%) is further added as component (d). Except for the addition, a coating composition (D) of the present invention was obtained in the same manner as in Example 1. The heating gelation rate of the coating composition (D) was 60%.

Example 5
In Example 1, the coating composition (E) of the present invention was prepared in the same manner as in Example 1 except that 10 parts of the zirconium chelate compound (b-2) prepared in Reference Example 2 was used as the component (b). Obtained. The heating gelation rate of the coating composition (E) was 40%.

Example 6
(A) 15 ethylene / vinyl alcohol copolymer (manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol A3245, degree of saponification; 98% or more, ethylene content; 32 mol%, melt flow index; 45 g / 10 min) % Water / n-propyl alcohol (water / n-propyl alcohol weight ratio = 3/7) 100 parts, and (b) component 10 parts titanium chelate compound (b-1) prepared in Reference Example 1, A coating composition (F) of the present invention was obtained. The heating gelation rate of the coating composition (F) was 30%.

Example 7
(A) 5 of ethylene / vinyl alcohol copolymer [manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol D2935, saponification degree: 98% or more, ethylene content: 29 mol%, melt flow index: 35 g / 10 min] % Water / n-propyl alcohol / i-propyl alcohol solution (water / n-propyl alcohol / i-propyl alcohol weight ratio = 38/41/21) 100 parts, and the titanium chelate compound prepared in Reference Example 1 (b- 1) 2 parts, 6.6 parts of n-propyl alcohol, 3.3 parts of i-propyl alcohol, 6 parts of water, and 12.1 parts of N, N-dimethylformamide were mixed and hydrolyzed at room temperature for 30 minutes ( The coating composition (G) of the present invention was obtained by mixing the components b) and (c) at room temperature. The heating gelation rate of the coating composition (G) was 70%.

Example 8
(A) 5 of ethylene / vinyl alcohol copolymer [manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol D2935X, degree of saponification; 98% or more, ethylene content; 29 mol%, melt flow index; 35 g / 10 min] % Water / n-propyl alcohol / i-propyl alcohol solution (water / n-propyl alcohol / i-propyl alcohol weight ratio = 38/41/21) 100 parts, and the titanium chelate compound prepared in Reference Example 1 (b- 1) 2 parts, 18.7 parts of n-propyl alcohol, 3.3 parts of i-propyl alcohol, and 6 parts of water were mixed and hydrolyzed at room temperature for 30 minutes. An inventive coating composition (H) was obtained. The heating gelation rate of the coating composition (H) was 65%.

Example 9
(A) 5 of ethylene / vinyl alcohol copolymer [manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol D2935, saponification degree: 98% or more, ethylene content: 29 mol%, melt flow index: 35 g / 10 min] % Water / n-propyl alcohol / i-propyl alcohol solution (water / n-propyl alcohol / i-propyl alcohol weight ratio = 38/41/21) 100 parts, and the titanium chelate compound prepared in Reference Example 1 (b- 1) 2 parts, 12.5 parts of n-propyl alcohol, 1.3 parts of i-propyl alcohol and 4 parts of water were mixed and hydrolyzed at room temperature for 30 minutes, and (b) was mixed at room temperature. A coating composition (I) was obtained. The heating gelation rate of the coating composition (I) was 40%.

Example 10
(A) 5 of ethylene / vinyl alcohol copolymer [manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol D2935, saponification degree: 98% or more, ethylene content: 29 mol%, melt flow index: 35 g / 10 min] % Water / n-propyl alcohol / i-propyl alcohol solution (water / n-propyl alcohol / i-propyl alcohol weight ratio = 38/41/21) 100 parts, and the titanium chelate compound prepared in Reference Example 1 (b- 1) 0.7 part, 6.4 parts of n-propyl alcohol, 1.1 part of i-propyl alcohol, and 2 parts of water were mixed and hydrolyzed at room temperature for 30 minutes. An inventive coating composition (J) was obtained. The heating gelation rate of the coating composition (J) was 20%.

Example 11
(A) an ethylene-vinyl alcohol copolymer (manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol D2935X, degree of saponification; 98% or more, ethylene content; 29 mol%, melt flow index; 35 g / 10 min), and (C) Water / n-propyl alcohol / i-propyl alcohol solution (water / n-propyl alcohol / i-propyl) containing 5% each of polyvinyl pyrrolidone [manufactured by Wako Pure Chemical Industries, Ltd., Mw = 25,000] as component (c) Alcohol weight ratio = 38/41/21) 100 parts, titanium chelate compound (b-1) 2 parts prepared in Reference Example 1, n-propyl alcohol 18.7 parts, i-propyl alcohol 3.3 parts, and The coating composition (K) of the present invention was mixed with 6 parts of water and mixed at room temperature with component (b) hydrolyzed at room temperature for 30 minutes. Obtained. The heating gelation rate of the coating composition (K) was 50%.

Example 12
(A) 5 of ethylene / vinyl alcohol copolymer [manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol D2935, saponification degree: 98% or more, ethylene content: 29 mol%, melt flow index: 35 g / 10 min] 100 parts of a% water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio 40/60), 2 parts of the titanium chelate compound (b-1) prepared in Reference Example 1 and 16.8 parts of n-propyl alcohol, And 11.2 parts of water was mixed and hydrolyzed at 55 ° C. for 4 hours, and (b) was mixed at 80 ° C. and stirred for 2 hours to obtain a coating composition (L) of the present invention. The heating gelation rate of the coating composition (L) was 5%.

Example 13
(A) ethylene vinyl alcohol copolymer (manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol D2935, saponification degree: 98% or more, ethylene content: 29 mol%, melt flow index; 35 g / 10 min) and (a) component c) 100 parts of a water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio 40/60) containing 5% each of polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., Mw = 25,000) as a component, and 2 parts of the titanium chelate compound (b-1) prepared in Reference Example 1, 16.8 parts of n-propyl alcohol, and 11.2 parts of water were mixed and hydrolyzed at 55 ° C. for 4 hours. And mixed for 2 hours to obtain a coating composition (M) of the present invention. The heating gelation rate of the coating composition (M) was 10%.

Example 14
In Example 12, the above Example was used except that polyvinyl alcohol [manufactured by Kuraray Co., Ltd., RS polymer RS-110 (degree of saponification = 99%, degree of polymerization = 1,000)] was used as the component (a). In the same manner as in No. 12, a gas barrier coating composition (N) was obtained. The heating gelation rate of this coating composition (N) was 30%.

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

Comparative Example 2
In Example 1, instead of the component (a), the procedure was carried out except that 100 parts of a 15% aqueous solution of a polyvinyl alcohol polymer not copolymerized with ethylene (manufactured by Nippon Synthetic Chemical Co., Ltd., Gohsenol NL-05) was used. In the same manner as in Example 1, a comparative coating composition (β) was obtained. The heating gelation rate of the coating composition (β) was 0%.

Comparative Example 3
(B) A comparative coating composition (γ) was obtained in the same manner as in Example 1 except that 40 parts of the titanium chelate compound (b-1) prepared in Reference Example 1 were mixed and used. . The heating gelation rate of the coating composition (γ) was 97%.

Evaluation Examples 1 to 13 and Comparative Evaluation Examples 1 to 3
The composition obtained in Examples 1 to 13 and Comparative Examples 1 to 3 was coated with a bar coater on a 12 μm-thick polyethylene terephthalate (PET) film subjected to measurement of the initial viscosity and 24 hours after the corona discharge treatment. Then, it was dried at 120 ° C. for 1 minute by a hot air dryer to form a coating film having a thickness of 1 μm to obtain a gas barrier coating material (coating film). The gas barrier property of the obtained gas barrier coating material was measured using an oxygen permeability measuring device (MOCON OXTRAN 2/20, manufactured by Modern Control Co., Ltd.) at room temperature and humidity of 90%. Further, the transparency of the coating film was evaluated by visual observation. These results are shown in Tables 1-2.

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

Example 15
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as a base material, which is mounted on a feeding roll of a plasma chemical vapor deposition apparatus, and a silicon oxide film having a thickness of 0.012 μm is deposited under the following conditions. A membrane was formed on one side of the biaxially stretched polyethylene terephthalate film.
(Deposition conditions)
Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 (unit: slm)
Degree of vacuum in the vacuum chamber: 5.5 × 10 ⁻⁶ mbar
Degree of vacuum in the deposition chamber: 6.5 × 10 ⁻² mbar
Cooling / electrode drum power supply: 18kW
Film conveyance speed: 80 m / min Deposition surface: Corona treatment surface (2) Next, the silicon oxide deposition film surface of the biaxially stretched polyethylene terephthalate film on which the silicon oxide deposition film is formed as described above is subjected to corona treatment under the following conditions. Was given. As a result, the surface tension of the deposited silicon oxide film surface was improved from 35 dyn to 62 dyn.
Output: 10kW
Processing speed: 100m / min
(3) Next, the biaxially stretched polyethylene terephthalate film in which the silicon oxide deposited film subjected to the corona treatment is used, and a gravure printing machine is used on the corona-treated surface of the silicon oxide deposited film. A roll for gravure coating is arranged for the first color, and the gas barrier coating composition (L) obtained in Example 12 is used, and this is coated by the gravure roll coating method to have a thickness of 0.5 g / m ² (dried). State) was formed. Subsequently, it heat-processed at 120 degreeC for 2 minutes, the coating cured film was formed, and the gas barrier coating film of this invention was manufactured. Next, a desired multicolor printing pattern layer was formed on the coating cured film of the gas barrier coating film using the gravure printing machine and using the gravure ink composition.
(4) Next, the biaxially stretched polyethylene terephthalate film on which the printed pattern surface is formed is attached to the first delivery roll of the dry laminating machine, and the printed pattern layer surface is a two-component curable type using a gravure roll coating method. The polyurethane-based laminating adhesive was applied at a rate of 4.5 g / m ² (dry state) to form a laminating adhesive layer. Next, a low-density polyethylene film having a thickness of 70 μm was dry-laminated on the surface of the laminating adhesive layer to produce a laminated material. This laminated material had an oxygen permeability of 0.2 cm ³ / m ² · atm · 24 hr.

Example 16
(1) A biaxially stretched polypropylene film having a thickness of 20 μm (trade name, GH-I, single-sided corona-treated product, manufactured by Futamura Chemical Co., Ltd.) is used as a substrate, and this is sent out by a plasma chemical vapor deposition apparatus. The film was mounted on a roll, and a silicon oxide deposited film having a thickness of 0.015 μm was formed on one surface of the biaxially oriented polypropylene film under the following conditions.
(Deposition conditions)
Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: slm)
Degree of vacuum in the vacuum chamber: 5.2 × 10 ⁻⁶ mbar
Degree of vacuum in the deposition chamber: 5.1 × 10 ⁻² mbar
Cooling / electrode drum power supply: 18kW
Film conveyance speed: 70 m / min Deposition surface: Corona-treated surface (2) Next, corona treatment is performed on the silicon oxide-deposited film surface of the biaxially stretched polypropylene film on which the silicon oxide-deposited film is formed as described above under the following conditions. gave. As a result, the surface tension of the deposited silicon oxide film surface was improved from 42 dyn to 65 dyn.
Output: 10kW
Processing speed: 100m / min
(3) Next, the biaxially stretched polypropylene film on which the corona-treated silicon oxide vapor-deposited film is formed is used, and a gravure printing machine is used on the corona-treated surface of the silicon oxide vapor-deposited film. A gravure coating roll was placed in the color, and the gas barrier coating composition (H) obtained in Example 8 was used, and this was coated by the gravure roll coating method to a thickness of 0.9 g / m ² (dry state) ) Coating film was formed. Subsequently, it heat-processed at 100 degreeC for 3 minute (s), the coating cured film was formed, and the gas barrier coating film of this invention was manufactured. Next, a desired multicolor printing pattern layer was formed on the coating cured film of the gas barrier coating film using the gravure printing machine and using the gravure ink composition.
(4) Next, the biaxially stretched polypropylene film on which the printed pattern surface is formed is mounted on the first delivery roll of the dry laminating machine, and the two-part curable polyurethane is applied to the printed pattern layer surface using the gravure roll coating method. An adhesive for laminating was applied at a rate of 4.5 g / m ² (dry state) to form an adhesive layer for laminating. Next, an unstretched polypropylene film having a thickness of 70 μm was dry-laminated on the surface of the laminating adhesive layer to produce a laminated material. This laminated material had an oxygen permeability of 0.6 cm ³ / m ² · atm · 24 hr.

Example 17
(1) A biaxially stretched nylon film having a thickness of 15 μm is used as a base material, and this is attached to a delivery roll of a plasma chemical vapor deposition apparatus, and a deposited film of silicon oxide having a thickness of 0.015 μm under the following conditions: Was formed on one side of the biaxially stretched nylon film.
(Deposition conditions)
Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: slm)
Degree of vacuum in the vacuum chamber: 5.2 × 10 ⁻⁶ mbar
Degree of vacuum in the deposition chamber: 5.1 × 10 ⁻² mbar
Cooling / electrode drum power supply: 18kW
Film conveyance speed: 70 m / min Deposition surface: Corona treatment surface (2) Next, the silicon oxide deposition film surface of the biaxially stretched nylon film on which the silicon oxide deposition film is formed as described above is subjected to corona treatment under the following conditions. gave. As a result, the surface tension of the deposited silicon oxide film surface was improved from 42 dyn to 65 dyn.
Output: 10kW
Processing speed: 100m / min
(3) Next, using the biaxially stretched nylon film on which the corona-treated silicon oxide vapor-deposited film was formed, a gravure printing machine was used on the corona-treated surface of the silicon oxide vapor-deposited film. A gravure coating roll was placed in the color, and the gas barrier coating composition (M) obtained in Example 13 was used, and this was coated by the gravure roll coating method to a thickness of 0.5 g / m ² (dry state) ) Coating film was formed. Subsequently, it heat-processed at 120 degreeC for 1 minute, the coating cured film was formed, and the gas barrier coating film of this invention was manufactured. Next, a desired multicolor printing pattern layer was formed on the coating cured film of the gas barrier coating film using the gravure printing machine and using the gravure ink composition.
(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 two-part curable polyurethane is applied to the printed pattern layer surface using the gravure roll coating method. An adhesive for laminating was applied at a rate of 4.5 g / m ² (dry state) to form an adhesive layer for laminating. Next, an unstretched polypropylene film having a thickness of 70 μm was dry-laminated on the surface of the laminating adhesive layer to produce a laminated material. This laminated material had an oxygen permeability of 0.5 cm ³ / m ² · atm · 24 hr.

Example 18
In Example 15 (4), a low-density polyethylene film having a thickness of 70 μm was dry-laminated on the printed pattern layer surface of the biaxially stretched polyethylene terephthalate film on which the printed pattern layer was formed via a laminating adhesive layer. Instead of producing a laminated material, a biaxially stretched polyethylene terephthalate film on which a printed pattern layer is formed is attached to the first feeding roll of an extrusion laminating machine, and low density polyethylene for melt extrusion is used on the surface of the printed pattern layer. A 70 μm-thick low-density polyethylene film was extruded and laminated while being melt-extruded to a thickness of 20 μm, and a laminate was produced in exactly the same manner as in Example 15 above. This laminated material had an oxygen permeability of 0.3 cm ³ / m ² · atm · 24 hr.

Example 19
In Example 16 (4) above, a 70 μm-thick unstretched polypropylene film is dry-laminated and laminated on the printed pattern layer surface of the biaxially stretched polypropylene film on which the printed pattern layer is formed via a laminating adhesive layer. Instead of manufacturing the material, the biaxially stretched polypropylene film on which the printed pattern layer is formed is mounted on the first feeding roll of the extrusion laminating machine, and the printed pattern layer surface is made of low-density polyethylene for melt extrusion and has a thickness of 20 μm. While this was melt-extruded, a 70 μm-thick low-density polyethylene film was extruded and laminated, and a laminate was produced in exactly the same manner as in Example 16 above. The oxygen permeability of this laminated material was 0.8 cm ³ / m ² · atm · 24 hr.

Example 20
In Example 17 (4) above, a 70 μm-thick unstretched polypropylene film is dry-laminated and laminated on the printed pattern layer surface of the biaxially stretched nylon film on which the printed pattern layer is formed via a laminating adhesive layer. Instead of manufacturing the material, a biaxially stretched nylon film with a printed pattern layer is attached to the first feeding roll of an extrusion laminating machine, and the printed pattern layer surface is made of low-density polyethylene for melt extrusion and has a thickness of 20 μm. While this was melt-extruded, a 70 μm-thick low-density polyethylene film was extruded and laminated, and a laminate was produced in the same manner as in Example 17 except that. This laminated material had an oxygen permeability of 0.6 cm ³ / m ² · atm · 24 hr.

Example 21
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as a base material, which is mounted on a feed roll of a take-up vacuum deposition apparatus, and then the film is fed onto a coating drum to obtain aluminum. Is used as a vapor deposition source, and an oxygen gas is deposited on the biaxially stretched polyethylene terephthalate film by an oxidation reaction vacuum vapor deposition method using an electron beam (EB) heating method while supplying oxygen gas. Formed.
(Deposition conditions)
Deposition source: Aluminum Vacuum degree in vacuum chamber: 5.2 × 10 ⁻⁶ mbar
Degree of vacuum in the deposition chamber: 1.1 × 10 ⁻⁶ mbar
EB output: 40kW
Film transport speed: 600 m / min Deposition surface: Corona-treated surface (2) Next, the aluminum oxide deposition film surface of the biaxially stretched polyethylene terephthalate film on which the aluminum oxide deposition film is formed as described above is subjected to corona treatment under the following conditions. Was given. As a result, the surface tension of the deposited aluminum oxide film surface was improved from 45 dyn to 60 dyn.
Output: 10kW
Processing speed: 100m / min
(3) Next, the biaxially stretched polyethylene terephthalate film in which the corona-treated aluminum oxide vapor deposition film is formed is used, and a gravure printing machine is used on the corona-treated surface of the aluminum oxide vapor deposition film. A roll for gravure coating is arranged for the first color, and the gas barrier coating composition (L) obtained in Example 12 is used, and this is coated by a gravure roll coating method to a thickness of 0.9 g / m ² (dry State) was formed. Subsequently, it heat-processed at 120 degreeC for 1 minute, the coating cured film was formed, and the gas barrier coating film of this invention was manufactured. Next, a desired multicolor printing pattern layer was formed on the coating cured film of the gas barrier coating film using the gravure printing machine and using the gravure ink composition.
(4) Next, the biaxially stretched polyethylene terephthalate film having the printed pattern layer formed thereon is mounted on the first delivery roll of a dry laminating machine, and the printed pattern layer surface is a two-component curable type using a gravure roll coating method. The polyurethane-based laminating adhesive was applied at a rate of 4.5 g / m ² (dry state) to form a laminating adhesive layer. Next, a low-density polyethylene film having a thickness of 70 μm was dry-laminated on the surface of the laminating adhesive layer to produce a laminated material. This laminated material had an oxygen permeability of 0.2 cm ³ / m ² · atm · 24 hr.

Example 22
(1) A biaxially stretched polypropylene film (trade name, GH-I, single-sided corona-treated product, manufactured by Futamura Chemical Co., Ltd.) having a thickness of 20 μm is used as a substrate, and this is sent out by a take-up vacuum deposition apparatus. The film is mounted on a roll, and then the film is drawn out on a coating drum, aluminum is used as a vapor deposition source, oxygen gas is supplied, and an oxidation reaction vacuum vapor deposition method using an electron beam (EB) heating method is used to form the two axes. A vapor deposition film of aluminum oxide having a thickness of 0.02 μm was formed on the stretched polypropylene film.
(Deposition conditions)
Deposition source: Aluminum Vacuum degree in vacuum chamber: 8.2 × 10 ⁻⁶ mbar
Degree of vacuum in the deposition chamber: 1.0 × 10 ⁻⁶ mbar
EB output: 40kW
Film conveyance speed: 500 m / min (2) Next, the aluminum oxide vapor deposition film surface of the biaxially stretched polypropylene film on which the aluminum oxide vapor deposition film was formed was subjected to corona treatment under the following conditions. As a result, the surface tension of the aluminum oxide deposition film surface was improved from 47 dyn to 62 dyn.
Output: 10kW
Processing speed: 100m / min
(3) Next, using the biaxially stretched polypropylene film on which the corona-treated aluminum oxide vapor-deposited film is formed, a gravure printing machine is used on the corona-treated surface of the aluminum oxide vapor-deposited film. A gravure coat roll was placed in the color, and the gas barrier coating composition (M) obtained in Example 13 was used, which was coded by the gravure roll coat method, and had a thickness of 0.5 g / m ² (dry state) ) Coating film was formed. Subsequently, it heat-processed at 100 degreeC for 3 minute (s), the coating cured film was formed, and the gas barrier coating film of this invention was manufactured. Next, a desired multicolor printing pattern layer was formed on the coating cured film of the gas barrier coating film using the gravure printing machine and using the gravure ink composition.
(4) Next, the biaxially stretched polypropylene film having the printed pattern layer formed thereon is mounted on the first delivery roll of the dry laminating machine, and the printed pattern layer surface is coated with a two-part curable polyurethane using a gravure roll coating method. An adhesive for laminating was applied at a rate of 4.5 g / m ² (dry state) to form an adhesive layer for laminating. Next, an unstretched polypropylene film having a thickness of 70 μm was dry-laminated on the surface of the laminating adhesive layer to produce a laminated material. This laminated material had an oxygen permeability of 0.6 cm ³ / m ² · atm · 24 hr.

Example 23
(1) A biaxially stretched nylon film having a thickness of 15 μm is used as a base material, and this is mounted on a feed roll of a take-up vacuum deposition apparatus, and then the film is fed onto a coating drum to obtain aluminum. Used as a vapor deposition source, an oxygen oxide vapor deposition film having a film thickness of 0.02 μm is formed on the biaxially stretched nylon film by an electron beam (EB) heating method using an electron beam (EB) heating method while supplying oxygen gas. did.
(Deposition conditions)
Deposition source: Aluminum Vacuum degree in vacuum chamber: 7.2 × 10 ⁻⁶ mbar
Degree of vacuum in the deposition chamber: 1.0 × 10 ⁻⁶ mbar
EB output: 40kW
Film transport speed: 500 m / min Deposition surface: Corona-treated surface (2) Next, the corona treatment was performed on the aluminum oxide-deposited film surface of the biaxially stretched nylon film formed with the aluminum oxide-deposited film as described above under the following conditions. gave. As a result, the surface tension of the deposited aluminum oxide film surface was improved from 45 dyn to 60 dyn.
Output: 10kW
Processing speed: 100m / min
(3) Next, using the biaxially stretched nylon film on which the corona-treated aluminum oxide vapor-deposited film is formed, a gravure printing machine is used on the corona-treated surface of the aluminum oxide vapor-deposited film. color a gravure coating roll arranged, using a gas barrier coating composition obtained in example 8 (H), which was coated by a gravure roll coating method, the thickness of 0.5 g / m ² (dry state ) Coating film was formed. Subsequently, it heat-processed at 120 degreeC for 2 minutes, the coating cured film was formed, and the gas barrier coating film of this invention was manufactured. Next, a desired multicolor printing pattern layer was formed on the coating cured film of the gas barrier coating film using the gravure printing machine and using the gravure ink composition.
(4) Next, the biaxially stretched nylon film having the printed pattern layer formed thereon is attached to the first delivery roll of the dry laminating machine, and the printed pattern layer surface is coated with a two-component curable polyurethane using a gravure roll coating method. An adhesive for laminating was applied at a rate of 4.5 g / m ² (dry state) to form an adhesive layer for laminating. Next, an unstretched polypropylene film having a thickness of 70 μm was dry-laminated on the surface of the laminating adhesive layer to produce a laminated material. This laminated material had an oxygen permeability of 0.5 cm ³ / m ² · atm · 24 hr.

Example 24
In Example 21 (4), a 70 μm-thick low-density polyethylene film was dry-laminated on the printed pattern layer surface of the biaxially stretched polyethylene terephthalate film on which the printed pattern layer was formed, via an adhesive layer for laminating. Instead of producing a laminated material, a biaxially stretched polyethylene terephthalate film on which a printed pattern layer is formed is attached to the first feeding roll of an extrusion laminating machine, and low density polyethylene for melt extrusion is used on the surface of the printed pattern layer. A laminated material was produced in the same manner as in Example 21 except that a 70 μm-thick low density polyethylene film was extruded and laminated while being melt extruded to a thickness of 20 μm. This laminated material had an oxygen permeability of 0.3 cm ³ / m ² · atm · 24 hr.

Example 25
In Example 22, (4), a 70 μm-thick unstretched polypropylene film is dry-laminated on the printed pattern layer surface of the biaxially stretched polypropylene film on which the printed pattern layer is formed, via a laminating adhesive layer. Instead of manufacturing the material, the biaxially stretched polypropylene film on which the printed pattern layer is formed is mounted on the first feeding roll of the extrusion laminating machine, and the printed pattern layer surface is made of low-density polyethylene for melt extrusion and has a thickness of 20 μm. While this was melt-extruded, a 70 μm-thick low-density polyethylene film was extruded and laminated, and a laminate was produced in the same manner as in Example 22 above. The oxygen permeability of this laminated material was 0.8 cm ³ / m ² · atm · 24 hr.

Example 26
In Example 23 (4), a non-stretched polypropylene film having a thickness of 70 μm is dry-laminated and laminated on the printed pattern layer surface of the biaxially stretched nylon film on which the printed pattern layer is formed, via an adhesive layer for laminating. Instead of manufacturing the material, a biaxially stretched nylon film with a printed pattern layer is attached to the first feeding roll of an extrusion laminating machine, and the printed pattern layer surface is made of low-density polyethylene for melt extrusion and has a thickness of 20 μm. While this was melt extruded, a low-density polyethylene film having a thickness of 70 μm was extruded and laminated, and a laminate was produced in the same manner as in Example 23 except that. This laminated material had an oxygen permeability of 0.6 cm ³ / m ² · atm · 24 hr.

Example 27
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as a base material, which is mounted on a feeding roll of a plasma chemical vapor deposition apparatus, and a silicon oxide film having a thickness of 0.012 μm is deposited under the following conditions. A membrane was formed on one side of the biaxially stretched polyethylene terephthalate film.
(Deposition conditions)
Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 (unit: slm)
Degree of vacuum in the vacuum chamber: 5.5 × 10 ⁻⁶ mbar
Degree of vacuum in the 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, using the biaxially stretched polyethylene terephthalate film on which the silicon oxide deposition film is formed as described above, this is sent out to a take-up vacuum deposition apparatus. It is mounted on a roll, and this is drawn out onto a coating drum, while aluminum is used as a vapor deposition source and oxygen gas is supplied, the above-mentioned vapor deposited film of silicon oxide is formed by a reactive vacuum vapor deposition method using an electron beam (EB) heating method. On the formed biaxially stretched polyethylene terephthalate film, a deposited silicon oxide film having a thickness of 0.02 μm was formed. Furthermore, the corona treatment was performed on the vapor deposition film surface of the aluminum oxide under the following conditions. As a result, the surface tension of the aluminum oxide deposition film surface was improved from 40 dyn to 65 dyn.
Output: 10kW
Processing speed: 100m / min
(3) Next, the biaxially stretched polyethylene terephthalate film in which the aluminum oxide vapor deposition film and the silicon oxide vapor deposition film are formed as described above is used, and a gravure printing machine is used on the aluminum oxide vapor deposition film surface. A gravure coating roll is arranged for the first color, and the gas barrier coating composition (L) obtained in Example 12 is used for the first color, and this is coated by a gravure roll coating method to obtain a thickness of 1. A coating film of 0 g / m ² (dry state) was formed. Subsequently, it heat-processed at 120 degreeC for 1 minute, the coating cured film was formed, and the gas barrier coating film of this invention was manufactured. Next, a desired multicolor printing pattern layer was formed on the coating cured film of the gas barrier coating film using the gravure printing machine and using the gravure ink composition.
(4) Next, the biaxially stretched polyethylene terephthalate film having the printed pattern layer formed thereon is mounted on the first delivery roll of a dry laminating machine, and the printed pattern layer surface is a two-component curable type using a gravure roll coating method. The polyurethane-based laminating adhesive was applied at a rate of 4.5 g / m ² (dry state) to form a laminating adhesive layer. Next, a low-density polyethylene film having a thickness of 70 μm was dry-laminated on the surface of the laminating adhesive layer to produce a laminated material. This laminated material had an oxygen permeability of 0.2 cm ³ / m ² · atm · 24 hr.

Example 28
(1) A biaxially stretched polypropylene film having a thickness of 20 μm (trade name, GH-I, single-sided corona-treated product, manufactured by Futamura Chemical Co., Ltd.) is used as a substrate, and this is sent out by a plasma chemical vapor deposition apparatus. The film was mounted on a roll, and a silicon oxide deposited film having a thickness of 0.015 μm was formed on one surface of the biaxially oriented polypropylene film under the following conditions.
(Deposition conditions)
Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: slm)
Degree of vacuum in the vacuum chamber: 5.2 × 10 ⁻⁶ mbar
Degree of vacuum in the deposition chamber: 5.1 × 10 ⁻² mbar
Cooling / electrode drum power supply: 18kW
Film transport speed: 70 m / min Deposition surface: Corona-treated surface (2) Next, the biaxially stretched polypropylene film on which a silicon oxide deposition film is formed as described above is used, and this is fed into a roll-up vacuum deposition apparatus. The silicon oxide vapor deposition film is formed by a reaction vacuum vapor deposition method using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a vapor deposition source. An aluminum oxide vapor deposition film having a thickness of 0.02 μm was formed on the silicon oxide vapor deposition film of the biaxially stretched polypropylene film. Furthermore, the corona treatment was performed on the vapor deposition film surface of the aluminum oxide under the following conditions. As a result, the surface tension of the aluminum oxide deposition film surface was improved from 42 dyn to 65 dyn.
Output: 10kW
Processing speed: 100m / min
(3) Next, the biaxially stretched polypropylene film on which the aluminum oxide vapor deposition film and the silicon oxide vapor deposition film are formed is used, and a gravure printing machine is used on the surface of the aluminum oxide vapor deposition film. A roll for gravure coating is arranged in the first color, and the gas barrier coating composition (G) obtained in Example 7 is used, and this is coated by the gravure roll coating method to obtain a thickness of 0.8 g / m ² (dry) State) was formed. Subsequently, it heat-processed at 120 degreeC for 1 minute, the coating cured film was formed, and the gas barrier coating film of this invention was manufactured. Next, on the coating cured film of the gas barrier coating film, using the gravure printing machine, a gravure ink composition was used to form a desired multicolor printing picture layer.
(4) Next, the biaxially stretched polypropylene film having the printed pattern layer formed thereon is mounted on the first delivery roll of the dry laminating machine, and the printed pattern layer surface is coated with a two-part curable polyurethane using a gravure roll coating method. An adhesive for laminating was applied at a rate of 4.5 g / m ² (dry state) to form an adhesive layer for laminating. Next, an unstretched polypropylene film having a thickness of 70 μm was dry-laminated on the surface of the laminating adhesive layer to produce a laminated material. This laminated material had an oxygen permeability of 0.5 cm ³ / m ² · atm · 24 hr.

Example 29
(1) A biaxially stretched nylon film having a thickness of 15 μm is used as a base material, and this is attached to a delivery roll of a plasma chemical vapor deposition apparatus, and a deposited film of silicon oxide having a thickness of 0.015 μm under the following conditions: Was formed on one side of the biaxially stretched nylon film.
(Deposition conditions)
Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: slm)
Degree of vacuum in the vacuum chamber: 5.2 × 10 ⁻⁶ mbar
Degree of vacuum in the deposition chamber: 5.1 × 10 ⁻² mbar
Cooling / electrode drum power supply: 18kW
Film conveyance speed: 70 m / min Deposition surface: Corona-treated surface (2) Next, the biaxially stretched nylon film on which the silicon oxide deposition film is formed as described above is used, and this is fed into a roll-up vacuum deposition apparatus. The silicon oxide vapor deposition film is formed by a reaction vacuum vapor deposition method using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a vapor deposition source. An aluminum oxide vapor deposition film having a thickness of 0.02 μm was formed on the silicon oxide vapor deposition film of the biaxially stretched nylon film. Furthermore, the corona treatment was performed on the vapor deposition film surface of the aluminum oxide under the following conditions. As a result, the surface tension of the vapor deposition film surface of aluminum oxide was improved from 45 dyn to 65 dyn.
Output: 10kW
Processing speed: 100m / min
(3) Next, the biaxially stretched nylon film having the aluminum oxide vapor deposition film and the silicon oxide vapor deposition film formed thereon is used, and a gravure printing machine is used on the surface of the aluminum oxide vapor deposition film. A roll for gravure coating is arranged for the first color, and the gas barrier coating composition (L) obtained in Example 12 is used, and this is coated by a gravure roll coating method to a thickness of 1.2 g / m ² (dry State) was formed. Subsequently, it heat-processed at 120 degreeC for 2 minutes, the coating cured film was formed, and the gas barrier coating film of this invention was manufactured. Next, on the coating cured film of the gas barrier coating film, using the gravure printing machine, a desired multicolor printing picture layer was formed using the gravure ink composition.
(4) Next, the biaxially stretched nylon film having the printed pattern layer formed thereon is attached to the first delivery roll of the dry laminating machine, and the printed pattern layer surface is coated with a two-component curable polyurethane using a gravure roll coating method. An adhesive for laminating was applied at a rate of 4.5 g / m ² (dry state) to form an adhesive layer for laminating. Next, an unstretched polypropylene film having a thickness of 70 μm was dry-laminated on the surface of the laminating adhesive layer to produce a laminated material. The oxygen permeability of this laminated material was 0.4 cm ³ / m ² · atm · 24 hr.

Example 30
In Example 27 (4), a low-density polyethylene film having a thickness of 70 μm was dry-laminated on the printed pattern layer surface of the biaxially stretched polyethylene terephthalate film on which the printed pattern layer was formed via a laminating adhesive layer. Instead of producing a laminated material, a biaxially stretched polyethylene terephthalate film on which a printed pattern layer is formed is attached to the first feeding roll of an extrusion laminating machine, and low density polyethylene for melt extrusion is used on the surface of the printed pattern layer. A 70 μm-thick low-density polyethylene film was extruded and laminated while being melt-extruded to a thickness of 20 μm, and a laminate was produced in the same manner as in Example 27 except that. This laminated material had an oxygen permeability of 0.2 cm ³ / m ² · atm · 24 hr.

Example 31
In Example 28 (4), a non-stretched polypropylene film having a thickness of 70 μm is dry-laminated and laminated on the printed pattern layer surface of the biaxially stretched polypropylene film on which the printed pattern layer is formed via a laminating adhesive layer. Instead of manufacturing the material, the biaxially stretched polypropylene film on which the printed pattern layer is formed is mounted on the first feeding roll of the extrusion laminating machine, and the printed pattern layer surface is made of low-density polyethylene for melt extrusion and has a thickness of 20 μm. While this was melt-extruded, a 70 μm-thick low-density polyethylene film was extruded and laminated, and a laminate was produced in the same manner as in Example 28 except that. This laminated material had an oxygen permeability of 0.6 cm ³ / m ² · atm · 24 hr.

Example 32
In Example 29 (4) above, a 70 μm-thick unstretched polypropylene film is dry-laminated on the printed pattern layer surface of the biaxially stretched nylon film on which the printed pattern layer is formed, via a laminating adhesive layer. Instead of manufacturing the material, a biaxially stretched nylon film with a printed pattern layer is attached to the first feeding roll of an extrusion laminating machine, and the printed pattern layer surface is made of low-density polyethylene for melt extrusion and has a thickness of 20 μm. While this was melt-extruded, a 70 μm-thick low-density polyethylene film was extruded and laminated, and a laminate was produced in the same manner as in Example 29 except that. This laminated material had an oxygen permeability of 0.5 cm ³ / m ² · atm · 24 hr.

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

Effect of the invention

  According to the present invention, a gas barrier coating composition having an extremely low oxygen permeability even under high humidity and harmless to the human body can be obtained, and a synthetic resin provided with a synthetic resin film and a metal and / or inorganic compound vapor-deposited film By coating on a film, a coating material exhibiting further excellent gas barrier properties can be obtained.

  It is a schematic block diagram of a plasma chemical vapor deposition apparatus.   It is a schematic block diagram of a winding type vacuum evaporation system.

2: Base film 11: Plasma chemical vapor deposition apparatus 15: Cooling / electrode drum 20: Glow discharge plasma 51: Rewind-type vacuum deposition apparatus 56: Coating drum 58: Deposition source

Claims (7)

(A) a polyvinyl alcohol resin comprising an ethylene / vinyl alcohol copolymer , and (b) a general formula (1)
R ¹ _m M (OR ² ) _n (1)
(In the formula, M is zirconium, titanium or 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 represents an alkyl group or phenyl group having 1 to 5 carbon atoms. , M and n are each an integer of 0 or more, and m + n is a valence of M), a metal alcoholate chelate compound, a hydrolyzate of the metal chelate compound, and a condensation of the metal chelate compound at least a coating composition comprising a species, the gas barrier coating composition, wherein the heating gelation rate of the coating composition as defined below is 5% to 70% selected from the group of the object.
Heating gelation rate: After coating the coating composition on a PET film so as to have a film thickness of 1 μm, the film was dried at 140 ° C. for 2 minutes to form 0.25 g of n-propanol / water (weight ratio) ) = 1/1 Insoluble fraction calculated from insoluble matter obtained by dissolving in 83 ml at 60 ° C. for 1 hour and filtering and drying the insoluble matter.
The gas barrier coating composition according to claim 1 , further comprising N, N-dimethylacetamide, N, N-dimethylformamide or polyvinylpyrrolidone.
The gas barrier according to claim 1 or 2 , further comprising (d) inorganic fine particles selected from colloidal silica, colloidal alumina, alumina sol, tin sol, zirconium sol, antimony pentoxide sol, cerium oxide sol, zinc oxide sol, and titanium oxide sol. Coating composition.
According to claim 1, wherein, after hydrolysis of the component (b) in a mixed solvent comprising water or water and a hydrophilic organic solvent, characterized by mixing with the component (a), any one of claims 1 to 3 A method for producing the gas barrier coating composition according to claim 1.
A gas barrier coating film, wherein a cured coating film formed from the gas barrier coating composition according to any one of claims 1 to 3 is laminated on a base resin film.
A metal and / or inorganic compound vapor-deposited film is provided on the base resin film, and a cured coating film formed from the gas barrier coating composition according to any one of claims 1 to 3 is further laminated. A gas barrier coating film characterized by
The gas barrier coating film according to claim 6 , wherein the deposited film is an inorganic oxide deposited film formed by chemical vapor deposition and / or physical vapor deposition.

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