JP2003003118A - Gas barrier coating composition and gas barrier coating film - Google Patents

Abstract

(57) [Summary] (Problem corrected) [Problem] A coating composition containing no isocyanate compound having an isocyanate group, melamine, formaldehyde and the like which are harmful to the human body, and harmless to the human body, and gas barrier properties Provide excellent coating film. SOLUTION: (a) (R ¹ ) _n Si (OR ² ) _4-n (wherein, R ¹ represents a monovalent organic group having 1 to 10 carbon atoms;
² represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, wherein n is an integer of 0 to 3), a hydrolyzate of the organosilane and an organosilane represented by the following formula: At least one selected from the group of condensates,
And (b) an organosiloxane oligomer having an SiO bond and having a weight average molecular weight in terms of polystyrene of 3,000 to 50,000, and a gas barrier coating composition on a synthetic resin film. A gas barrier coating film on which a coating film to be formed is laminated.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In recent years, packaging materials used for packaging applications such as pharmaceuticals, foods, cosmetics, cigarettes, and toiletries, for example, for foods, prevent alteration of contents such as protein and oxidation of fats and oils, In order to maintain quality such as taste, a material having a gas barrier property that does not allow permeation of oxygen, water vapor, and other gases that change the contents is used. In response to such a conventional problem, for example, Japanese Patent Laid-Open No. 7-2
Japanese Patent No. 66485 discloses a mixed solution of one or more kinds of metal alkoxide or a hydrolyzate thereof and an isocyanate compound having at least two or more isocyanate groups in a molecule on a base material made of a polymer resin composition. A gas barrier material having a gas barrier coating layer formed by applying a coating agent as a main ingredient and heating and drying has been proposed. However, this gas barrier material contains an isocyanate compound having an isocyanate group, melamine, formaldehyde, tin chloride, etc. and may be orally indirectly administered to the human body particularly in medical products and food applications, and is harmful to the human body. It has a problem that

[0003]

The present invention has been made against the background of the above-mentioned conventional technical problems, and is an isocyanate compound having an isocyanate group without lowering the barrier property against gases such as oxygen and water vapor. An object of the present invention is to provide a coating composition which does not contain a compound such as melamine, formaldehyde and tin chloride, which may be harmful to the human body, and is harmless to the human body, and a coating film using the same which has excellent gas barrier properties. .

[0004]

The present invention includes (a) the following general formula (1) (R ¹ ) _n Si (OR ² ) _4-n (1) (wherein R ¹ is When a plurality of R ² are present, they are the same or different and represent a monovalent organic group having 1 to 10 carbon atoms, and R ² is the same or different when a plurality of R ² are present, and is an alkyl group having 1 to 5 carbon atoms or a carbon number. 1 to 6 represents an acyl group, and n =
An integer of 0 to 3), at least one selected from the group consisting of an organosilane represented by the formula (3), a hydrolyzate of the organosilane, and a condensate of the organosilane (hereinafter also referred to as "component (a)"), And (b) having a SiO bond and having a polystyrene-equivalent weight average molecular weight of 3,000 to 50,
000 organosiloxane oligomers (hereinafter referred to as “(b)
(Also referred to as "component"). The gas barrier coating composition of the present invention may include (d) colloidal silica and / or colloidal alumina. In addition, the gas barrier coating composition of the present invention may include (e) a nitrogen-containing organic compound. Further, the gas barrier coating composition of the present invention may include (f) a condensation catalyst. Next, the present invention provides a gas barrier coating film in which a coating film formed from the above gas barrier coating composition is laminated on a synthetic resin film.
Further, the present invention provides a metal and / or metal on a synthetic resin film.
Alternatively, the invention provides a gas barrier coating film in which a vapor deposition film of an inorganic compound and a coating film formed from the gas barrier coating composition are laminated.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Gas Barrier Coating Composition Hereinafter, the gas barrier coating composition of the present invention will be described by constituent elements. Component (a): The component (a) is composed of the organosilane represented by the general formula (1) (hereinafter referred to as “organosilane (1)”), a hydrolyzate of the organosilane (1), and the organosilane (1). ) At least one selected from the condensation products of
It is a seed and functions as a binder in the composition of the present invention. That is, the component (a) may be only one of these three types, or may be a mixture containing all three types. Here, the hydrolyzate of the organosilane (1) has 1 to 1 parts of the organosilane (1).
It is not necessary that all four OR ² groups contained are hydrolyzed, for example, only one is hydrolyzed,
It may be one in which two or more are hydrolyzed, or a mixture thereof. Further, the hydrolyzate may be a part of which is condensed. When the organosilane (1) is used as the hydrolyzate as the component (a) as described above, it can be hydrolyzed in advance and used as the component (a), but it is mixed with the remaining components to form a composition. When the product is prepared, the organosilane (1) is hydrolyzed by adding an appropriate amount of water (c) described below,
The component (a) is preferable. In the present invention,
The component (a) can be used alone or in combination of two or more.

In the general formula (1), R ¹ has 1 to ¹⁰ carbon atoms.
Examples of the monovalent organic group 10 include, 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
-Alkyl group such as ethylhexyl group; Acyl group such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, caproyl group; vinyl group, allyl group, cyclohexyl group, phenyl group, epoxy group, glycidyl group , (Meth) acryloxy group, ureido group, amide group, fluoroacetamido group, isocyanate group and the like, and substituted derivatives of these groups.

The substituent in the substituted derivative of R ¹ is, for example, 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, (meth). An acryloxy group, a ureido group, an ammonium base etc. can be mentioned. However, the carbon number of R ¹ composed of these substituted derivatives is 10 or less including the carbon atoms in the substituent. When a plurality of R ¹ 's are present in the general formula (1), they may be the same or different.

Examples of the alkyl group having 1 to 5 carbon atoms for R ² include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group. Group, n-pentyl group and the like, and examples of the acyl group having 1 to 6 carbon atoms include acetyl group, propionyl group, butyryl group, valeryl group and caproyl group. When a plurality of R ² 's are present in the general formula (1), they may be the same or different.

In the above general formula (1), n is 0.
Is an integer of ˜3. Specific examples of the organosilane (1) with n = 0 include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane and tetra-i-.
Tetraalkoxysilanes such as propoxysilane and tetra-n-butoxysilane; and specific examples of the organosilane (1) with n = 1 include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyltrimethoxysilane. Ethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-
Propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyl Trimethoxysilane,
Vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane,
Phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-amino Propyltrimethoxysilane, 3-
Aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3
-Hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2
-(3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl)
Trialkoxysilanes such as ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane. Kind;

Further, specific examples of the organosilane (1) with n = 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane and di-n-propyl. Diethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n- Pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n -Octyldiethoxysilane, di-n-
Cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane,
Dialkoxysilanes such as diphenyldiethoxysilane;

Further, specific examples of the organosilane (1) with n = 3 include trimethylmonomethoxysilane, trimethylmonoethoxysilane, triethylmonoethoxysilane, tri-n-propylmonomethoxysilane and tri-.
n-propyl monoethoxysilane, tri-i-propyl monomethoxysilane, tri-i-propyl monoethoxysilane, tri-n-butyl monomethoxysilane, tri-
Examples thereof include monoalkoxysilanes such as n-butylmonoethoxysilane, di-methyl-phenylmonomethoxysilane, and di-ethyl-phenylmonoethoxysilane.

Among these, tetramethoxysilane and tetraethoxysilane are preferable as tetraalkoxysilanes, methyltrimethoxysilane and methyltriethoxysilane are preferable as trialkoxysilanes, and dialkoxysilanes are further preferable. Are preferably dimethyldimethoxysilane and dimethyldiethoxysilane, and the monoalkoxysilanes are preferably trimethylmonoalkoxysilane and triethylmonomethoxysilane. These organosilanes can be used alone or
A mixture of two or more species can be used. Of the organosilane (1) that constitutes the component (a), it is preferably 50% by weight in terms of solid content (in terms of complete hydrolysis-condensation product).
As described above, more preferably 70% by weight or more, it is desirable that n = 1 and / or n = 2. When the organosilane (1) with n = 1 and / or n = 2 is 50% by weight or more, the obtained gas barrier coating composition has an excellent balance between storage stability and curability, which is preferable. In addition, in the above organosilane (1), n
= 3 is the solid content conversion (complete hydrolysis condensate conversion)
It is desirable that the amount is preferably 20% by weight or less, more preferably 5% by weight or less. When it is desired to ensure long-term storage stability of the composition, it is effective to add an organosilane of n = 3 in an amount of 5% by weight or less. In the organosilane (1) that constitutes the component (a), if the organosilane of n = 3 exceeds 20% by weight, the curability may be poor and sufficient hardness may not be obtained. In particular, trialkoxysilane alone, or 40 to 95% by weight of trialkoxysilane and 60 to 60% of dialkoxysilane in terms of solid content.
A combination with 5% by weight is preferred. By using dialkoxysilane in combination with trialkoxysilane, it is possible to soften the obtained coating film and improve the alkali resistance. The completely hydrolyzed condensate of organosilane (1) means that the R ² O-group of organosilane (1) is 100.
% Hydrolyzed to form a SiOH group and further completely condensed to form a siloxane structure.

Component (b): The component (b) has a SiO bond and has a polystyrene-equivalent weight average molecular weight of 3,000.
A siloxane oligomer in the range of
They may be used alone or as a mixture of two or more.
The component (b) has a SiO bond and a siloxane oligomer having a polystyrene-equivalent weight average molecular weight in the range of 3,000 to 50,000 is synthesized in advance, and the siloxane oligomer is blended as the component (b) to reduce the volume shrinkage. Can be relaxed and the crack resistance of the coating film can be improved. The method for producing the component (b) is not particularly limited, but a condensate of chlorosilane or a condensate of alkoxysilane is mainly preferable. In the siloxane oligomer, the terminal functional group of siloxane is a hydroxyl group, a halogen atom, an organic group having 1 to 15 carbon atoms [for example, an alkyl group, an acyl group, an alkoxyl group, an alkoxysilyl group, a vinyl group, an allyl group, an acetoxyl group, Acetoxysilyl group, cycloalkyl group, phenyl group, glycidyl group, (meth) acryloxy group, ureido group, amide group, fluoroacetamide group, isocyanato group], as well as-(RO) _p- (R'O) _q -R "(wherein R and R'are the same or different and have 1 to 5 carbon atoms)
Represents an alkyl group of R ″ is a hydrogen atom or a carbon number of 1 to
5 represents an alkyl group of 5 and p and q have a value of p + q of 2
Is a number of ˜30). These groups may be partially hydrolyzed and condensed,
It may be a substituted derivative.

Examples of the halogen atom include fluorine and chlorine. Moreover, as a C1-C15 alkyl group, a methyl group, an 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, n-nonyl group, n-decyl group, undecyl group , Dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, heptadecyl group, octadecyl group, 2-ethylhexyl group, and the like. As the acyl group, acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group. Examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group and a butoxy group, and examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group. To be The group represented by — (RO) _p — (R′O) _q —R ″ is a polyoxyalkylene group such as a polyoxyethylene group, a polyoxypropylene group, and a poly (oxyethylene / oxypropylene) group.

The substituent in the above substituted derivative is
For example, halogen atom, substituted or unsubstituted amino group, hydroxyl group, mercapto group, isocyanate group, glycidoxy group, 3,4-epoxycyclohexyl group, (meth) acryloxy group, ureido group, ammonium group, ketoester group, etc. Can be mentioned.

The weight average molecular weight of the component (b) (hereinafter referred to as "M
w)) is a molecular weight distribution curve diagram obtained by gel permeation chromatography (GPC) and has a polystyrene-equivalent molecular weight of 3,000 to 50,000, preferably 3,000 to 30,000, and particularly preferably 3,
3,000 to 20,000, 3,000
If the amount is less than the above range, the flexibility of the obtained coating film may be insufficient, so that the coating film strength may decrease. On the other hand, if it exceeds 50,000, the resulting composition may have poor storage stability and may gel, which is not preferable. In addition, as the component (b), 2 having different Mw ranges from 3,000 to 50,000.
A mixture of one or more oligomers may be used.

Commercially available products of the component (b) include silicon resin manufactured by Toray Dow Corning, silicon resin manufactured by Toshiba Silicone Co., Ltd., silicon resin manufactured by Shin-Etsu Chemical Co., Ltd., and Dow Corning Asia Co., Ltd. ), A hydroxyl group-containing polydimethylsiloxane, and a silicon oligomer manufactured by Nippon Yunika Co., Ltd., which may be used as they are or after being condensed. In the present invention,
The component (b) can be used alone or in combination of two or more.

The ratio of the components (a) and (b) used is
(A) component 5 to 95% by weight, preferably 10 to 90% by weight, and component (b) component 5 to 95 in terms of complete hydrolysis condensate
% By weight, preferably 10 to 90% by weight (however, (a)
+ (B) = 100% by weight]. If the content of the component (a) is less than 5% by weight, the resulting coating composition may have poor curability, whereas if it exceeds 95% by weight, crack resistance may decrease.

In the composition of the present invention, the component (b) is usually co-hydrolyzed and condensed with the component (a). In this case, the amount of water (c) described below used for hydrolysis / condensation of the organosilane (1) and the component (b) is the same as that of the alkoxy groups (-OR ² etc.) in the organosilane (1) and the component (b). The amount is usually 0.1 mol or more, preferably about 0.2 to 2 mol, based on 1 mol in total. When an aqueous dispersion is used as the component (c), water present in the aqueous dispersion can be used for hydrolysis of the organosilane (1) and the component (b).

The hydrolysis / condensation reaction at this time, that is, the reaction when preparing the composition of the present invention, is carried out at a temperature of 30-80.
C., preferably 40 to 70.degree. C., reaction time 0.5 to 10 hours, preferably 1 to 7 hours. In the composition of the present invention, the weight average molecular weight of the cohydrolysis condensate (hydrolyzate and / or its condensate) when the components (a) and (b) are cohydrolyzed and condensed, Usually 5
00-100,000, preferably 600-80,0
It is about 00.

Component (c): Component (c) is water and / or an organic solvent. The composition of the present invention comprises the above (a),
The component (b) is essential and will be described later (d) if necessary.
To (h) component and the like. Then, when these compositions are prepared, water is usually added in order to cause the hydrolysis / condensation reaction of the organosilane (1) or to disperse the particulate components described later. The amount of water used in the present invention is such that the organosilane (1) constituting the component (a) or the alkoxy group (—O) contained in the component (b).
R ² or the like): usually 0.1 or more, and preferably about 0.2 to 2 mol per 1 mol.

The organic solvent is mainly composed of
The components (a) and (b) and the optional components (d) to (h) are uniformly mixed to adjust the total solid content concentration of the composition, and at the same time, to be applicable to various coating methods,
It is also used to further improve the dispersion stability and storage stability of the composition. The organic solvent is not particularly limited as long as it can uniformly mix the above components, and examples thereof include alcohols, aromatic hydrocarbons, ethers, ketones, and esters. . Among these organic solvents, specific examples of alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n. -Octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, diacetone alcohol and the like.

Specific examples of aromatic hydrocarbons are benzene, toluene, xylene, etc., specific examples of ethers are tetrahydrofuran, dioxane, etc. Specific examples of ketones are acetone, methyl ethyl ketone, Methyl isobutyl ketone, diisobutyl ketone and the like can be mentioned, and specific examples of the esters include ethyl acetate, propyl acetate, butyl acetate and propylene carbonate. These organic solvents may be used alone or in admixture of two or more.

The amount of the organic solvent (c) used is such that the total solid content concentration of the composition is preferably 50% by weight or less. For example, when it is used for the purpose of forming a thin film, it is usually 1 to 30% by weight, and when it is used for the purpose of forming a thick film, it is usually 10 to 50% by weight, preferably 2%.
It is 0 to 45% by weight. When the total solid content concentration of the composition exceeds 50% by weight, the storage stability of the composition tends to decrease.

When the coating composition of the present invention is prepared, a composition containing the above-mentioned components (a) to (b) may be prepared. For example, the following preparation methods are preferable. In the presence of the component (a), the component (b), and the organic solvent (c),
Hydrolysis / condensation reaction is performed by adding a predetermined amount of (c) water,
Then, a method of adding (d) component, (c) organic solvent for concentration adjustment, and (e) to (h) described later, if necessary.

In the presence of the component (a), the component (b), the organic solvent (c), and the component (f) described later, a predetermined amount of water (c) is added to carry out the hydrolysis / condensation reaction, and then the necessary A method of adding the component (d), the organic solvent for adjusting the concentration (c), the component (e), the component (g), and the component (h) described below. In the presence of the component (a), the organic solvent (c) and the component (d),
A predetermined amount of (c) water is added to carry out the hydrolysis / condensation reaction, then the component (b) is mixed, and the condensation reaction is further carried out. Further, a method of adding (c) an organic solvent for adjusting the concentration and components (e) to (h) described later, if necessary. In the presence of the component (a), the organic solvent (c), the component (d) and the component (f) described later, a predetermined amount of water (c) is added to carry out a hydrolysis / condensation reaction, and then the component (b). And (c) for concentration adjustment, if necessary, for further condensation reaction.
An organic solvent, and a component (e) and a component (g) described later,
A method of adding the component (h).

Component (d): The composition of the present invention contains the component (d), colloidal silica and / or colloidal alumina, for the purpose of enhancing the adhesion to the substrate and the crack resistance. Those that do are preferred. Here, colloidal silica, colloidal alumina, for example, is a dispersion liquid dispersed in water or an organic solvent, usually,
The average particle size is 1 μm or less, preferably 0.5 μm or less, and the solid content concentration is about 10 to 40% by weight. Examples of such colloidal silica include Nissan Chemical Industry Co., Ltd., methanol silica sol and isopropanol silica sol; Catalyst Kasei Kogyo Co., Ltd., Oscar, and the like. As the colloidal alumina, for example, alumina sol 520, manufactured by Nissan Chemical Industries, Ltd.
00, the same 200; alumina clear sol, alumina sol 10, the same 132 manufactured by Kawaken Fine Chemicals Co., Ltd. and the like. The above (d) colloidal silica and / or colloidal alumina may be used alone or in combination of two or more. Further, as the component (d) in the composition of the present invention, colloidal silica is particularly preferable.

The amount of the component (d) used in the composition of the present invention is usually 1 to 5 in terms of solid content based on 100 parts by weight of the completely hydrolyzed condensate of the components (a) and (b).
00 parts by weight, preferably 3 to 300 parts by weight, and more preferably 5 to 100 parts by weight. In this case, (d)
If the amount of the component used is less than 1 part by weight, the adhesion to the base material and the crack resistance may not be sufficiently exhibited. On the other hand, when it exceeds 500 parts by weight, the film forming property of the obtained coating agent is poor, and cracking or peeling may occur. If necessary, the composition of the present invention will be described later (e).
~ (H) component can be used.

Component (e): The coating composition of the present invention may optionally contain a nitrogen-containing organic compound which is the component (e). Examples of the nitrogen-containing organic compound as the component (e) include N, N-dimethylacetamide, N, N
-Hydrophilic nitrogen-containing organic solvents such as dimethylformamide, γ-butyrolactone, N-methylpyrrolidone and pyridine; nucleobases such as thymine, glycine, cytosine and guanine; hydrophilic nitrogen-containing solvents such as polyvinylpyrrolidone and poly (meth) acrylamide Examples thereof include polymers and copolymers obtained by copolymerizing these components. Of these, N, N-dimethylacetamide, N, N-dimethylformamide and polyvinylpyrrolidone are preferred.
By mixing the component (e), a coating having a more transparent appearance and a good coating film can be obtained in coating with a thin film, and a catalytic effect at the time of condensation with the inorganic particles and / or the inorganic laminate is exhibited. The use ratio of the nitrogen-containing organic compound (e) is usually 70% by weight or less, preferably 50% by weight or less in the composition of the present invention.

Component (f): The component (f) is a catalyst that accelerates the hydrolysis / condensation reaction of the components (a) and (b). By using the component (f), the curing speed of the resulting coating film is increased, and the molecular weight of the polysiloxane resin produced by the polycondensation reaction of the organosilane component used is increased, resulting in strength, long-term durability, etc. An excellent coating film can be obtained, and the coating film can be thickened and the coating operation can be facilitated.

Examples of the component (f) include acidic compounds, alkaline compounds, metal salts, amine compounds, organometallic compounds and / or their partial hydrolysates (hereinafter organometallic compounds and / or their partial hydrolysates). Are collectively referred to as “organic metal compound and the like”). Examples of the acidic compound include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkyltitanic acid, p-toluenesulfonic acid, phthalic acid, and the like, and acetic acid is preferable. Examples of the alkaline compound include sodium hydroxide and potassium hydroxide, and sodium hydroxide is preferable. Examples of the metal salt include alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminic acid and carbonic acid.

Examples of the above amine compounds include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, m-phenylenediamine, p-phenylenediamine, ethanolamine, triethylamine, 3 -Aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3- (2-aminoethyl) -aminopropyl trimethoxysilane, 3- (2-aminoethyl) -aminopropyl triethoxysilane, 3 -(2-aminoethyl) -aminopropyl methyl dimethoxysilane, 3
In addition to anilinopropyl trimethoxysilane, alkylamine salts and quaternary ammonium salts, various modified amines used as a curing agent for epoxy resins can be mentioned, and preferably 3-aminopropyltrimethoxysilane. , 3-aminopropyl triethoxysilane, and 3- (2-aminoethyl) -aminopropyl trimethoxysilane.

Examples of the organic metal compound and the like include compounds represented by the following general formula (2) (hereinafter referred to as "organic metal compound (2)"), having 1 to 1 carbon atoms bonded to the same tin atom. Examples thereof include tetravalent tin organometallic compounds having 1 to 2 alkyl groups of 10 (hereinafter referred to as “organotin compound”), and partial hydrolyzates of these compounds.

M (OR ³ ) _r (R ⁴ COCHCOR ⁵ ) _s (2) [wherein M represents zirconium, titanium or aluminum, and R ³ and R ⁴ are the same or different and each represents an ethyl group. , N-propyl group, i-propyl group, n-butyl group,
sec-butyl group, t-butyl group, n-pentyl group, n
A monovalent hydrocarbon group having 1 to 6 carbon atoms such as a hexyl group, a cyclohexyl group, and a phenyl group, and R ⁵ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms similar to R ³ and R ⁴ ; In addition to, methoxy group, ethoxy group, n-propoxy group, i-
Propoxy group, n-butoxy group, sec-butoxy group,
t-butoxy group, lauryloxy group, stearyloxy group, and other alkoxyl groups having 1 to 16 carbon atoms are shown, r and s are integers from 0 to 4, and (r + s) = (valence of M)
Is. ]

Specific examples of the organometallic compound (2) include (a) tetra-n-butoxyzirconium and tri-n-
Butoxy / ethylacetoacetate zirconium, di-
n-butoxy bis (ethylacetoacetate) zirconium, n-butoxy tris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, etc. An organic zirconium compound of

(B) Tetra-i-propoxytitanium, di-i-propoxybis (ethylacetoacetate) titanium, di-i-propoxybis (acetylacetate) titanium, di-i-propoxybis (acetylacetone) Organic titanium compounds such as titanium; (C) tri-i-propoxyaluminum, di-i-propoxyethylacetoacetate aluminum, di-
i-propoxy acetylacetonate aluminum,
i-Propoxy bis (ethyl acetoacetate) aluminum, i-propoxy bis (acetyl acetonate) aluminum, tris (ethyl acetoacetate)
Examples thereof include organic aluminum compounds such as aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate / bis (ethylacetoacetate) aluminum, and the like.

Among these organometallic compounds (2) and partial hydrolysates thereof, tri-n-butoxyethylacetoacetate zirconium, di-i-propoxy bis (acetylacetonato) titanium, di-i-propoxy. -Aluminum ethyl acetoacetate, tris (ethyl acetoacetate) aluminum, or
Partial hydrolysates of these compounds are preferred.

Specific examples of the organic tin compound include (C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ and (C ₄ H _{9) 2 Sn (OCOCH = CHCOOC} 4 H 9) 2, (C 8 H 17) 2 Sn (OCOC 8 H 17) 2, (C 8 H 17) 2 Sn (OCOC 11 H 23) 2, (C 8 H ₁₇ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC
₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC
_{8 H 17) 2, (C} 8 H 17) 2 Sn (OCOCH = CHCOOC 16 H 33)
_{2, (C 8 H 17)} 2 Sn (OCOCH = CHCOOC 17 H 35)
_{2, (C 8 H 17)} 2 Sn (OCOCH = CHCOOC 18 H 37)
_{2, (C 8 H 17)} 2 Sn (OCOCH = CHCOOC 20 H 41)
₂ ,

[0039] Carboxylic acid type organic tin compounds such as (C ₄ H ₉ ) Sn (OCOC ₁₁ H ₂₃ ) ₃ and (C ₄ H ₉ ) Sn (OCONa) ₃ ;

(C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC
_{8 H 17) 2, (C} 4 H 9) 2 Sn (SCH 2 CH 2 COOC 8 H 17) 2, (C 8 H 17) 2 Sn (SCH 2 COOC 8 H 17) 2, (C 8 H 17) _{2 Sn (SCH 2 CH 2 COOC} 8 H 17) 2, (C 8 H 17) 2 Sn (SCH 2 COOC 12 H 25) 2, (C 8 H 17) 2 Sn (SCH 2 CH 2 COOC 12 H 25) _{2, (C 4 H 9)} Sn (SCOCH = CHCOOC 8 H 17) 3, (C 8 H 17) Sn (SCOCH = CHCOOC
₈ H ₁₇ ) ₃ ,

[0041] Mercaptide type organotin compounds such as;

(C ₄ H ₉ ) ₂ Sn = S, (C ₈ H ₁₇ ) ₂ Sn
= S, Sulfide type organotin compounds such as;

(C ₄ H ₉ ) SnCl ₃ , (C ₄ H ₉ ) ₂ Sn
Cl ₂ , (C ₈ H ₁₇ ) ₂ SnCl ₂ , Chloride type organotin compounds such as; (C ₄ H ₉ ) ₂ Sn
O, organotin oxides such as (C ₈ H ₁₇ ) ₂ SnO,
Reaction products of these organic tin oxides with ester compounds such as silicate, dimethyl maleate, diethyl maleate and dioctyl phthalate;

The component (f) can be used alone or in admixture of two or more, and can also be used in admixture with a zinc compound or another reaction retarder.

The component (f) may be added at the time of preparing the composition, or may be added to the composition at the stage of forming the coating film, and further, the preparation of the composition and the coating film. May be added at both stages of forming The amount of component (f) used is
In the case of other than the organometallic compound, it is usually 0 based on 100 parts by weight in total of the organosilane (1) and the component (b) in the component (a) in terms of complete hydrolysis condensate.
To 100 parts by weight, preferably 0.01 to 80 parts by weight,
More preferably, it is from 0.1 to 50 parts by weight, and in the case of an organometallic compound or the like, the total amount of the organosilane (1) in the component (a) and the component (b) is 100 parts by weight (completely hydrolyzed condensate equivalent). ), Usually 0-10
The amount is 0 parts by weight, preferably 0.1 to 80 parts by weight, and more preferably 0.5 to 50 parts by weight. in this case,
When the amount of the component (f) used exceeds 100 parts by weight, the storage stability of the composition tends to deteriorate, and cracks are likely to occur in the coating film.

Component (g): The component (g) is represented by the following general formula (3) R ⁴ COCH ₂ COR ⁵ (3) [wherein R ⁴ and R ⁵ are in the organometallic compound (2). Each of the above general formulas has the same meaning as R ⁴ and R ⁵ ] and is selected from the group consisting of β-diketones and β-ketoesters, carboxylic acid compounds, dihydroxy compounds, amine compounds, and oxyaldehyde compounds. It is at least one kind. Such a component (g) is particularly preferably used together when an organometallic compound or the like is used as the component (f).

The component (g) acts as a stability improver for the composition. That is, the action of the component (g) coordinating with the metal atom of the organometallic compound or the like to promote the co-condensation reaction of the organometallic compound or the like with the components (a) and (b) is appropriately controlled. Therefore, it is presumed that the composition has an effect of further improving the storage stability of the obtained composition.

Specific examples of the component (g) include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate-sec-butyl. , Tert-butyl acetoacetate, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione,
Octane-2,4-dione, Nonane-2,4-dione,
5-methylhexane-2,4-dione, malonic acid, oxalic acid, phthalic acid, glycolic acid, salicylic acid, aminoacetic acid, iminoacetic acid, ethylenediaminetetraacetic acid, glycol, catechol, ethylenediamine, 2,2-bipyridine, 1,10 -Phenanthroline, diethylenetriamine, 2-ethanolamine, dimethylglyoxime, dithizone, methionine, salicylaldehyde and the like. Of these, acetylacetone and ethyl acetoacetate are preferable. The component (g) can be used alone or in combination of two or more.

The amount of the component (g) used is usually 1 with respect to 1 mol of the organometallic compound in the above organometallic compound.
It is at least mol, preferably 2 to 20 mol. in this case,
If the amount of component (g) used is less than 1 mol, the effect of improving the storage stability of the resulting composition tends to be insufficient.

Component (h): The component (h) comprises a powder and / or sol or colloid of an inorganic compound other than the component (c), and is blended according to the desired characteristics of the coating film.
When the component (h) is in the form of a sol or colloid, the average particle size thereof is usually about 0.005 to 100 μm.

Specific examples of the compound constituting the component (h)
Is TiO₂, ZnO₂, CeO₂, AlGaAs, Al
(OH)₃, Sb₂O_Five, Si₃N_Four, Sn-In₂O
₃, Sb-In₂O₃, MgF, CeF₃, BeO, S
iC, AlN, Fe, Co, Co-FeOx, Cr
O₂, Fe_FourN, BaTiO₃, BaO-Al₂O₃−
SiO₂, Ba ferrite, SmCO_Five, YCO_Five, C
eCO_Five, PrCO_Five, Sm ₂CO₁₇, Nd₂Fe
₁₄B, Al_FourO₃, Α-Si, SiN_Four, CoO, Sb
-SnO₂, Sb₂O_Five, MnO₂, MnB, Co₃O
_Four, Co₃B, LiTaO ₃, MgO, MgAl
₂O_Four, BeAl₂O_Four, ZrSiO_Four, ZnSb, P
bTe, GeSi, FeSi₂, CrSi₂, CoSi
₂, MnSi_1.73, Mg₂Si, β-B, BaC, B
P, TiB₂, ZrB₂, HfB₂, Ru₂Si₃, T
iO₃, PbTiO₃, Al₂TiO_Five, Zn₂SiO
_Four, Zr₂SiO_Four2MgO₂-Al₂O₃-5Si
O₂, Nb₂O_Five, Li₂O-Al₂O₃-4Si
O₂, Mg ferrite, Ni ferrite, Ni-Zn ferrite
Elite, Li ferrite, Sr ferrite, etc.
You can These (h) components may be used alone or in 2
A mixture of two or more species can be used.

The component (h) is present in the form of powder, an aqueous sol or colloid dispersed in water, a polar solvent such as isopropyl alcohol, or a solvent sol or colloid dispersed in a nonpolar solvent such as toluene. There is. In the case of a solvent-based sol or colloid, depending on the dispersibility of the semiconductor, it may be diluted with water or a solvent and used, or may be surface-treated to improve the dispersibility.

When the component (h) is an aqueous sol or colloid, or a solvent sol or colloid, the solid content concentration is preferably 40% by weight or less.

As a method of incorporating the component (h) into the composition, the component (h) may be added after the composition is prepared, or the component (h) may be added after the composition is prepared. Co-hydrolyzed with component, (b) component or the above condensate
It may be condensed.

The amount of the component (h) used is generally 0 to 500 parts by weight, preferably, 0 to 500 parts by weight, based on 100 parts by weight of the completely hydrolyzed condensate of the components (a) and (b).
It is 0.1 to 400 parts by weight.

Other additives; In addition, the composition used in the present invention may be added to the obtained coating film for coloring, thickening, etc.
A filler can be added and dispersed separately. Examples of such fillers include water-insoluble organic pigments and inorganic pigments, particulate, fibrous or scale-like ceramics other than pigments, metals or alloys, and oxides and hydroxides of these metals. , Carbides, nitrides, sulfides and the like.

Specific examples of the filler include iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, chromium oxide, manganese oxide, iron oxide, synthetic mullite, aluminum hydroxide. , Iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, mica, zinc green, chrome green, cobalt green, Viridian, Guinea green, cobalt chrome green,
Shale green, green soil, manganese green, pigment green,
Ultramarine, Navy Blue, Pigment Green, Rock Ultramarine, Cobalt Blue, Cerulean Blue, Copper Borate, Molybdenum Blue, Copper Sulfide, Cobalt Purple, Mars Purple, Manganese Purple, Pigment Violet, Lead Suboxide, Calcium Lead, Zinc Yellow, Lead Sulfide , Chrome yellow, ocher, cadmium yellow, strontium yellow, titanium yellow, litharge, pigment yellow, cuprous oxide, cadmium red, selenium red, chrome vermillion, red iron oxide, zinc white, antimony white, basic lead sulfate,
Titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead, zinc white, bunchson white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, titanium Examples thereof include potassium acid whiskers and molybdenum disulfide. These fillers can be used alone or in admixture of two or more. The amount of the filler used is usually 300 parts by weight or less based on 100 parts by weight of the total solid content of the composition.

Further, in the composition of the present invention, if desired, known dehydrating agents such as methyl orthoformate, methyl orthoacetate and tetraethoxysilane; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene. Fatty acid ester, polycarboxylic acid type polymer surfactant, polycarboxylic acid salt, polyphosphoric acid salt, polyacrylic acid salt, polyamide ester salt,
Dispersants such as polyethylene glycol; methyl cellulose, ethyl cellulose, hydroxyethyl cellulose,
Cellulose such as hydroxypropylcellulose and hydroxypropylmethylcellulose, and thickeners such as castor oil derivative and ferrosilicate; ammonium carbonate,
Inorganic foaming agents such as ammonium hydrogen carbonate, ammonium nitrite, sodium borohydride, calcium azide, azo compounds such as azobisisobutyronitrile, hydrazine compounds such as diphenylsulfone-3,3'-disulfohydrazine, and semicarbazide compounds In addition to organic blowing agents such as triazole compounds and N-nitroso compounds, other additives such as surfactants, silane coupling agents, titanium coupling agents and dyes can also be added.

Further, the gas barrier coating composition of the present invention may contain a leveling agent in order to further improve the coating property of the composition. Among such leveling agents, examples of fluorine-based leveling agents (trade name; hereinafter the same) include BM Chemie (B
M-CHEMIE) BM1000, BM1100;
Examples include Fuka 772 and Fuka 777 manufactured by Fuka Chemicals; Floren series manufactured by Kyoeisha Chemical Co., Ltd .; FC series manufactured by Sumitomo 3M Limited; Fluoronal TF series manufactured by Toho Chemical Co., Ltd., and silicone leveling. Examples of the agent include B manufactured by Big Chemie.
YK series; Shmegmann
Shmego series of the company; Efka 30, Efka 31, Efka 34, Efka 35, Efka 36, Efka 39, Efka 83, Efka 86, Efka 88, etc. of Efka Chemicals can be mentioned, ether-based or ester-based leveling Examples of the agent include Carfinol manufactured by Nissin Chemical Industry Co., Ltd .; Emulgen and Homogenol manufactured by Kao Corporation.

By blending such a leveling agent, the finished appearance of the coating film is improved, and a thin film can be applied uniformly. The amount of leveling agent used is
Preferably 0.01 to 5% by weight, based on the total composition,
More preferably, it is 0.02 to 3% by weight.

The leveling agent may be added at the time of preparing the composition, or may be added to the composition at the stage of forming a coating film, and further, preparation and coating of the composition. You may mix | blend at both the steps of film formation.

The composition used in the present invention may be blended with other resins. Other resins include acrylic-urethane resin, epoxy resin, polyester, acrylic resin, fluororesin, acrylic resin emulsion,
Examples thereof include epoxy resin emulsion, polyurethane emulsion, polyester emulsion and the like.

In preparing the composition of the present invention,
When the component (f) and the component (g) are not used, the mixing method of each component is not particularly limited, but the component (f) and the component (g) are not limited.
When used with components, preferably (a) to (h)
A method is used in which after the mixture (g) is removed from the components, a mixture (g) is added to the mixture.

The total solid concentration of the gas barrier coating composition of the present invention is preferably 50% by weight or less,
It is appropriately adjusted according to the purpose of use. For example, when it is used for the purpose of forming a thin film, it is usually 1 to 30% by weight, and when it is used for the purpose of forming a thick film, it is usually 10 to 50% by weight.
%, Preferably 20 to 45% by weight. When the total solid content concentration of the composition exceeds 50% by weight, the storage stability tends to decrease. In particular, the gas barrier coating composition of the present invention preferably has a total solid content concentration of 1 to 30% by weight, but is appropriately adjusted depending on the type of substrate, coating method, coating film thickness and the like.

Gas Barrier Coating Film The coating composition of the present invention is particularly useful for gas barrier applications. That is, a coating layer comprising the coating composition of the present invention on the synthetic resin film, or
By laminating a vapor-deposited layer of a metal and / or an inorganic compound and a coating layer made of the coating composition of the present invention,
A coating film having excellent gas barrier properties can be obtained.

Here, the synthetic resin film is in the form of a sheet or film, and is made of polyethylene,
Polyolefins such as polypropylene; polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate; nylon 6, nylon 6,6, nylon 4,6, nylon 1
2, such as polyamide, polyvinyl chloride, polyvinyl alcohol, aromatic polyamide, polyamideimide, polyetherimide, polysulfone, polyethersulfone, polyetherketone, polyarylate, polyphenylene sulfide, polyphenylene oxide, tetrafluoroethylene, trimonochloride. Sheets or films used as packaging materials such as ethylene fluoride, ethylene fluoride-propylene copolymer, and polyimide can be used. These synthetic resin films, if necessary,
A biaxially stretched film can also be used. In addition, additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, and a coloring agent can be added to the synthetic resin film.

Further, the surface of the synthetic resin film on which the coating film is formed is subjected to known surface activation treatment such as corona discharge treatment, plasma activation treatment, glow discharge treatment, reverse sputtering treatment, roughening treatment, or ethylene treatment. It is also possible to perform a primer treatment with a primer agent such as an imine type, amine type, epoxy type, urethane type or polyester type. The thickness of the synthetic resin film is not particularly limited, but usually 5 to
The thickness is 100 μm, preferably 10 to 50 μm.

A coating layer (hereinafter also referred to as "coating of the present invention") formed from the coating composition of the present invention is laminated on a substrate such as synthetic resin film (hereinafter also referred to as "substrate"). Can be applied to the surface of the substrate by coating means such as roll coating such as micro gravure coater, spray coating, spin coating, dipping, brush, bar code, applicator, etc., once or multiple times.
Dry film thickness is 0.01 to 30 μm, preferably 0.1 to 1
It is possible to form a coating film of the present invention having a thickness of 0 μm, and heat it in a normal environment at a temperature of 50 to 300 ° C., preferably 70 to 200 ° C. for 0.5 to 60 minutes, preferably 1 to 10 minutes. By drying, condensation is performed and the coating film of the present invention can be formed.

At this time, it is also possible to laminate a vapor deposition layer of a metal and / or an inorganic compound (hereinafter also referred to as "vapor deposition layer") on the substrate or the coating film of the present invention. By providing this vapor deposition layer, the gas barrier property is further improved. Here, the vapor deposition layer includes aluminum,
Metals and composite metals such as antimony, silicon, titanium, zinc, zirconium, magnesium, tin, copper, iron and indium, oxides, nitrides, sulfides and fluorides thereof, such as aluminum oxide, antimony oxide and silicon dioxide. , Titanium oxide, zirconium oxide, magnesium oxide, tin oxide, indium oxide, zinc sulfide, magnesium fluoride and the like are used.

The vapor deposition layer is formed by a chemical vapor deposition method such as plasma chemical vapor deposition method, thermochemical vapor deposition method, photochemical vapor deposition method and / or physical vapor deposition method such as vacuum vapor deposition, ion plating and sputtering. A vapor deposited film of an inorganic oxide is preferred. The thickness of the vapor deposition layer is 10 to
5,000 angstroms, preferably 30-3,0
If the thickness is 00 angstroms and less than 10 angstroms, the gas barrier property may not be sufficient.
If it exceeds 5,000 angstroms, the flexibility of the vapor-deposited layer is impaired, cracks and pinholes are likely to occur, and the gas barrier properties are poor. The vapor deposition layer may use a plurality of vapor deposition materials in combination, or may be a multilayer having two or more layers.

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

Since the coating film of the present invention thus obtained has excellent gas barrier properties, it is useful not only as a packaging material for foods, pharmaceuticals, cosmetics, cigarettes, toiletries, etc., but also as a solar cell and a protective film. Used for applications such as moisture-proof films.

[0073]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. In the examples, parts and% are based on weight unless otherwise specified. The weight average molecular weight and oxygen permeability in the examples were measured according to the following.

Weight average molecular weight It was measured by gel permeation chromatography. That is, under the following conditions, tetrahydrofuran was used as a solvent, and 1 g of the obtained cocondensate was added to 100 c.
It was dissolved in tetrahydrofuran of c to prepare a sample. Also,
The standard polystyrene used was standard polystyrene manufactured by Pressure Chemicals, Inc., USA. Device: US Waters Co., high temperature high speed gel permeation chromatogram (Model 150-C, ALC / GPC) Column: Showa Denko K.K., SHODEX KF-80
M (2 pieces), KF-802 (1 piece), length of each 30 cm Measurement temperature; 40 ° C. Flow rate; 1 cc / min

Oxygen Barrier Property Using a MOCON OXTRAN manufactured by Modern Control Co., a temperature was 23 ° C. and a humidity was 90 RH%. Water vapor barrier property Using MOCON OXTRAN manufactured by Modern Control Co., Ltd., the temperature was measured at 37.8 ° C. and humidity of 100 RH%. Bending resistance of the film The gas barrier coating film was bent 180 °, and the state of crack generation at the bent portion was evaluated by the following. ◯: No crack under 50 × microscope Δ: Crack under 50 × microscope X: Visually cracked

Example 1 In a reactor equipped with a reflux condenser and a stirrer, 165 parts of methyltrimethoxysilane as the component (a), 210 parts of isobutanol as the component (c), and a silicone resin [Toshiba as the component (b)] were used. Silicone resin, silicone resin, Mw: 4,000] 90 parts dissolved, (f)
As a component, 5 parts of di-i-propoxyethylacetoacetate aluminum was added and mixed, and the temperature was raised to 50 ° C. with stirring. Then, 40 parts of water as the component (c) was added dropwise over 30 minutes, and then a cocondensation reaction was carried out at 60 ° C. for 4 hours.
Then, the mixture was cooled to room temperature, and 347 parts of isopropanol was added as the component (c) to obtain the gas barrier coating composition (I) of the present invention having a solid content concentration of about 20%.

Example 2 A reactor equipped with a reflux condenser and a stirrer was charged with 165 parts of methyltrimethoxysilane as the component (a) and silica sol dispersed in methanol as the component (d) [manufactured by Nissan Chemical Industries, Ltd.,
95 parts of average particle diameter 10 nm, solid content concentration 30%], and 40 parts of water as the component (c) were added, heated to 60 ° C. and reacted for 4 hours, and then cooled to 25 ° C. Next, a solution prepared by dissolving 90 parts of silicone resin [Silicone resin, Mw: 4,000] manufactured by Toshiba Silicone Co., Ltd. as component (b) in 210 parts of isobutanol as component (c) was added, and (c) 400 parts of isopropanol was added as a component to obtain a gas barrier coating composition (II) of the present invention having a solid content concentration of about 20%.

Example 3 In a reactor equipped with a reflux condenser and a stirrer, 198 parts of tetramethoxysilane as component (a) and silica sol dispersed in methanol as component (d) [manufactured by Nissan Chemical Industries, Ltd., average particle size] 10 nm, solid content concentration 30%] 95 parts, and 40 parts of water as the component (c) were added, heated to 60 ° C. and reacted for 4 hours, and then cooled to 25 ° C. Then, 210 parts of isobutanol as the component (c) and silicone resin as the component (b) [silicone resin manufactured by Toshiba Silicone Co., Ltd.,
Mw: 4,000] 90 parts dissolved therein was added, and further, 367 parts isopropanol as a component (c) was added to obtain a gas barrier coating composition (III) of the present invention having a solid content concentration of about 20%. .

Comparative Example 1 As component (a), 1 part was added to 100 parts of tetraethoxysilane.
20 parts of / 1,000 N hydrochloric acid was added, and the mixture was heated to 60 ° C. and reacted for 6 hours to obtain a composition (x). The weight average molecular weight of this composition (x) was 4,000.

Examples 4, 6 and Comparative Example 2 100 parts of the gas barrier coating compositions obtained in Examples 1, 3, and Comparative Example 1 were added to a reaction product i consisting of dibutyltin diacetate as a component (f) and a silicate oligomer. -Propyl alcohol solution (solid content 15%) was added to 10 parts and well stirred, and then subjected to corona discharge treatment to obtain a thickness of 1
It is coated on a 2 μm polyethylene terephthalate (PET) film with a bar coater and dried with a hot air dryer to 10
It was dried at 0 ° C. for 10 minutes to form a coating film having a thickness of 8.0 μm, and a gas barrier coating film having a total thickness of 20 μm was obtained. The oxygen barrier property, water vapor barrier property, and bending resistance of the obtained gas barrier coating film were evaluated. The results are shown in Table 1.

Example 5 The gas barrier coating composition obtained in Example 2 was
A polyethylene terephthalate (PET) film having a thickness of 12 μm subjected to corona discharge treatment was coated with a bar coater and dried with a hot air dryer at 100 ° C. for 10 minutes to form a coating film having a thickness of 8.0 μm, totaling 20 μm. A gas barrier coating film of was obtained. The oxygen barrier property, water vapor barrier property, and bending resistance of the obtained gas barrier coating film were evaluated. The results are shown in Table 1.

[0082]

[Table 1]

Examples 7 to 9 and Comparative Example 3 Polyethylene terephthalate (PET) having a thickness of 12 μm
On the film, using the metal oxides shown in Table 2 as a vapor deposition source,
A gas barrier coating composition 1 obtained by forming an inorganic compound vapor-deposited layer having a film thickness of 400 angstroms by a vacuum vapor deposition method, and further obtaining it in Examples 1 to 3 or Comparative Example 1
To 100 parts, 10 parts of an i-propyl alcohol solution (15% solid content) of a reaction product composed of dibutyltin diacetate and a silicate oligomer as a component (f) was added and well stirred, and the resulting mixture was applied with a bar coater and dried with a hot air dryer. At 100 ° C. for 10 minutes to form a coating film having a thickness of 1.0 μm to obtain a gas barrier coating film. The oxygen barrier property of the obtained gas barrier coating film,
The water vapor barrier property and the bending resistance of the gas barrier coating film were evaluated. The results are shown in Table 2.

[0084]

[Table 2]

Examples 10 to 12 Polyethylene terephthalate (PET) having a thickness of 12 μm
On the film, using the metal oxides shown in Table 3 as a vapor deposition source,
An inorganic compound vapor deposition layer having a film thickness of 400 angstrom was formed by a vacuum vapor deposition method, and 100 parts of the gas barrier coating composition obtained in Examples 1 and 2 was further treated with di-i-propoxy bis (acetyl) as a component (f). (Acetate) Titanium i-propyl alcohol solution (solid content 15%) was added in 15 parts and well stirred, and the mixture was applied with a bar coater and dried at 100 ° C. for 10 minutes with a hot air drier to give a film thickness of 1.0 μm. A coating film was formed to obtain a gas barrier coating film. The oxygen barrier property, the water vapor barrier property, and the bending resistance of the gas barrier coating film of the obtained gas barrier coating film were evaluated. The results are shown in Table 3.

Example 13 Polyethylene terephthalate (PET) having a thickness of 12 μm
On the film, using the metal oxides shown in Table 3 as a vapor deposition source,
An inorganic compound vapor deposition layer having a film thickness of 400 angstrom was formed by a vacuum vapor deposition method, and 100 parts of the gas barrier coating composition obtained in Example 2 was further treated with di-i-propoxy bis (acetylacetate) as a component (f). Titanium i-propyl alcohol solution (solid content 15
%) And 15 parts of N, N-dimethylformamide as the component (e) and well stirred, and the mixture is coated with a bar coater at 100 ° C. for 10 hours with a hot air dryer.
After being dried for a minute, a coating film having a thickness of 1.0 μm was formed to obtain a gas barrier coating film. The oxygen barrier property, the water vapor barrier property, and the bending resistance of the gas barrier coating film of the obtained gas barrier coating film were evaluated. The results are shown in Table 3.

[0087]

[Table 3]

[0088]

EFFECTS OF THE INVENTION According to the present invention, a gas barrier coating composition having extremely low oxygen permeability and water vapor permeability even under high humidity and harmless to the human body can be obtained. By coating on a synthetic resin film provided with a vapor deposited film of an inorganic compound and / or an inorganic compound, a more excellent gas barrier coating film can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 5/00 C09D 5/00 Z 183/04 183/04 // C08L 101: 00 C08L 101: 00 (72 ) Inventor Yuichi Hashiguchi 2-11-21 Tsukiji, Chuo-ku, Tokyo F-term in JSR Corporation (reference) 4F006 AA12 AA16 AA17 AA18 AA19 AA31 AA35 AA38 AA39 AA40 AB39 AB62 AB64 AB65 AB72 AB74 AB76 BA05 CA07 CA08 DA04 EA01 4F100 AA01B AA20B AA20C AB01B AH02C AH03C AH06C AH08C AK42A AK52C AT00A BA03 BA07 BA10A BA10C CA30C EH66B GB15 GB23 JA07C JD01 JD02 JD03 JD04 YY00C 4J038 CG172 CK032 DL021 DL022 DL031 DL032 DL051 DL052 DL071 DL072 DL081 DL082 DL111 DL112 DL121 DL122 HA166 HA446 JB10 JB12 JB29 KA04 KA06 LA02 MA14 NA08 NA27 PB01 PB02 PC02 PC03 PC08

Claims (6)

[Claims] 1. (a) General formula (1) (R ¹ ) _n Si (OR ² ) _4-n ... (1) (wherein, when a plurality of R ^1's are present, they are the same or different, R 1 represents a monovalent organic group having 1 to 10 carbon atoms, R ² is the same or different when a plurality of R ^2's are present, represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n =
An integer of 0 to 3), at least one selected from the group consisting of organosilane, a hydrolyzate of the organosilane and a condensate of the organosilane, and (b)
A gas barrier coating composition comprising an organosiloxane oligomer having a SiO bond and having a polystyrene equivalent weight average molecular weight of 3,000 to 50,000. 2. The gas barrier coating composition according to claim 1, which comprises (d) colloidal silica and / or colloidal alumina. 3. The method according to claim 1, further comprising (e) a nitrogen-containing organic compound.
The gas barrier coating composition according to claim 1. 4. The gas barrier coating composition according to claim 1, which further comprises (f) a condensation catalyst. 5. A gas barrier coating film, comprising a synthetic resin film and a coating film formed from the gas barrier coating composition according to any one of claims 1 to 4 laminated thereon. 6. A synthetic resin film, on which a vapor deposited film of a metal and / or an inorganic compound and a coating film formed from the gas barrier coating composition according to any one of claims 1 to 4 are laminated. A gas barrier coating film characterized by: