JP2000063751A - Coating composition and coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating composition not containing a compound in which harmfulness to human body is worried without lowering barrier property to gas such as oxygen or steam and useful for packaging uses, etc. of medicines, etc. by including a specific organosilane, etc. as a main component. SOLUTION: This coating composition consists mainly of (A) at least one kind of compound among an organosilane of the formula, R1nSi(OR2)4-n [R1 is a 1-8C organic group; R2 is a 1-5C alkyl, a 1-6C acyl or the like; and (n) is 0-2], a hydrolysate of the above silane and silane condensate and (B) a silanol group-modified polyvinyl alcohol. Furthermore, the coating composition preferably further contains (C) an organopolysiloxane of the formula [R3 to R8 are each a 1-8C organic group; (m) is >=1; weight average molecular weight expressed in terms of polystyrene is 150-10,000; and SiO bond is straight-chain- like and/or branch-like bond].

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 are
For example, in the case of foods, oxygen, to prevent deterioration of contents such as oxidation of proteins and fats and oils and to maintain quality such as taste,
A material having a gas barrier property that does not allow water vapor and other gases that deteriorate the contents to pass through is used. In order to address such a conventional problem, for example, Japanese Patent Laid-Open No. 7-266
Japanese Patent No. 485 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.
In food use, there is a possibility that it may be indirectly orally administered to the human body and is harmful to the human body.

[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 having excellent gas barrier properties. To do.

[0004]

The present invention provides (a) a general formula
(1) R¹ _nSi (OR² )_4-n... (1) (In the formula, R¹ Are the same or different and are organic with 1 to 8 carbon atoms
Group, R² Are the same or different and are alkyl having 1 to 5 carbons.
A group or an acyl group having 1 to 6 carbon atoms or a phenyl group
, N is an integer of 0 to 2)
Orchid (hereinafter also referred to as “(a) ′ organosilane”),
Hydrolyzate of organosilane and the organosilane
At least one selected from the group of condensates, and
(B) Main component is silanol group-modified polyvinyl alcohol
The present invention provides a coating composition. This
Here, the coating composition of the present invention includes (c)
Formula (2) (In the formula, R³~ R⁸Are the same or different and have 1 to 8 carbon atoms
Represents an organic group of R and ³~ R⁸At least Arco
Containing a xy group or a hydroxyl group, m is 1 or more, and poly
Styrene equivalent weight average molecular weight of 150 to 10,000
And the -Si-O- bond is linear and / or
Is a branched) organopolysiloxane represented by
What is contained is preferable. Also, the coating of the present invention
The composition for use includes (d) metal alcoholate and metal alcohol
And β-diketones and / or β-ketoesters
Chelate compound obtained by reaction with a metal, and the metal
Reaction of alcoholates and / or chelate compounds with water
At least selected from the group of hydrolyzates obtained by
Those containing one kind are preferable. Furthermore, the code of the present invention
The coating composition also contains (e) a curing accelerator.
Is preferred. Furthermore, the coating composition of the present invention
(F) Silicic acid having an average particle size of 0.01 to 0.2 μm
Containing fine particles of oxides and / or metal oxides
Is preferred. Furthermore, the coating composition of the present invention
Is the above component (a) and component (b), or
(A) component, (b) component and (c) component, (g)
By hydrolysis and / or condensation in a hydrophilic organic solvent
Is preferred. Furthermore, for the coating of the present invention
The composition is useful for gas barriers. Next, the present invention
Is a composition for coating the above on a synthetic resin film
Coating film with a coating layer formed from
It is to provide the system. The present invention also relates to a synthetic resin film.
A vapor-deposited layer of metal and / or an inorganic compound is formed on the film.
A coating layer formed from the coating composition
It is intended to provide a layered coating film.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The coating composition of the present invention is selected from the group consisting of (a) an organosilane represented by the above general formula (1), a hydrolyzate of the organosilane and a condensate of the organosilane. At least one selected (b)
Silanol group-modified polyvinyl alcohol, and if necessary, these and (c) the organopolysiloxane represented by the general formula (2) as main components.

In the (a) 'organosilane represented by the general formula (1), R ¹ is the same or different and is an organic group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group,
Alkyl groups such as n-propyl group, i-propyl group, etc., γ-chloropropyl group, vinyl group, 3,3,3-
Trifluoropropyl group, γ-glycidoxypropyl group,
Examples thereof include γ-methacryloxypropyl group, γ-mercaptopropyl group, phenyl group, and 3,4-epoxycyclohexylethyl group. In addition, in the (a) ′ organosilane represented by the general formula (1), R ^{2 s} are the same or different and each is an alkyl group having 1 to 5 carbon atoms or 1 carbon atom.
~ 6 is an acyl group or a phenyl group. Examples of the alkyl group having 1 to 5 carbon atoms of R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group. Examples of the acyl group having 1 to 6 carbon atoms include an acetyl group, a propionyl group, a butyryl group, a valeryl group and a caproyl group.

In the above general formula (1), n is an integer of 0 to 2, and when n is 3 or more, it is not suitable as the (a) 'organosilane of the present invention because it cannot be made into a high molecular weight. is there. n is preferably 1 or 0, more preferably 0. Here, in the (a) ′ organosilane, specific examples of the organosilane in which n is 0 include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-. Examples thereof include butoxysilane, tetraacetyloxysilane, tetraphenoxysilane and the like. Of these (a) ′ organosilanes,
Tetraalkoxysilanes are preferable, and tetramethoxysilane and tetraethoxysilane are more preferable. These organosilanes may be used alone or in combination of two or more.

In the general formula (1), specific examples of the organosilane in which n is 1 include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane and n-propyltrimethoxy. Silane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n
-Butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N- (2-aminoethyl) -3 -Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 2-
(3,4-Epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxy Silane, vinyltriacetoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane,
3-trifluoropropyltrimethoxysilane, 3,3
3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2
-Hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane,
3-isocyanatopropyltrimethoxysilane, 3-
In addition to trialkoxysilanes such as isocyanatopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane, methyltriacetyloxysilane, methyltriphenoxysilane and the like can be mentioned. The organosilane in which n in the general formula (1) is 1 can be used alone or in combination of two or more.

Further, as specific examples of the organosilane in which n in the general formula (1) is 2, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, Di-n-propyldiethoxysilane,
Di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane,
Di-n-butyldiethoxysilane, n-pentyl-methyldimethoxysilane, n-pentyl-methyldiethoxysilane, cyclohexyl-methyldimethoxysilane, cyclohexyl-methyldiethoxysilane, phenyl-methyldimethoxysilane, phenyl-methyldiethoxysilane Silane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-
Heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n
In addition to dialkoxysilanes such as octyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane, dimethyldiacetyloxysilane, dimethyldiphenoxysilane and the like can be mentioned. These organosilanes of the general formula (1) in which n is 2 can be used alone or in admixture of two or more. Of the above (a) 'organosilane, preferably 40 mol% or more, more preferably 5
It is desirable that 0 mol% or more is Si (OR ² ) ₄ . Further, R ² is preferably an alkyl group,
An acyl group, more preferably an alkyl group,
As a result, the more excellent coating composition that is the object of the present invention can be obtained.

Next, the (b) silanol group-modified polyvinyl alcohol used in the present invention has a main chain of polyvinyl alcohol, and preferably has at least one silanol group at one end or side chain in one molecule of the polymer, Preferably, it contains three or more. Such a silanol group-modified polyvinyl alcohol (b) has a silanol group and / or a hydroxyl group in polyvinyl alcohol, which is a main chain, when the coating film obtained from the composition of the present invention is cured. And / or co-condensation with the component (c) described below can provide excellent coating performance. The content of the silanol group in the component (b) is usually 0.001 to 50% by weight in terms of silicon atom based on the silanol group-modified polyvinyl alcohol. The saponification degree of the vinyl acetate unit constituting the silanol group-modified polyvinyl alcohol is usually 30
-100%, preferably 80-100%.

Examples of the method (b) for preparing the silanol group-modified polyvinyl alcohol include, but are not limited to, the following methods. Vinyl acetate is subjected to ordinary bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization using an initiator such as peroxide, persulfate or azo compound to obtain polyvinyl acetate, and then acid or Saponification with an alkali such as sodium hydroxide or sodium methylate gives polyvinyl alcohol. A method for producing a silanol group-modified polyvinyl alcohol by hydrolyzing and condensing a hydroxyl group of the obtained polyvinyl alcohol and a chlorosilane compound and / or an alkoxysilane compound.

A vinyl acetate copolymer having a carbon-carbon double bond is subjected to an addition reaction with a SiH group-containing hydrosilane compound (hereinafter also referred to as "hydrosilane compound"), and then an acid or sodium hydroxide or sodium hydroxide is added. A method for producing a silanol group-modified polyvinyl alcohol by saponifying with an alkali such as a salt. Here, as the hydrosilane compound, for example, methyldichlorosilane, trichlorosilane,
Halogenated silanes such as phenyldichlorosilane; alkoxysilanes such as methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethoxysilane, triethoxysilane; methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxysilane And acylsilanes; aminosilanes such as methyldiaminoxysilane, triaminoxysilane, dimethylaminoxysilane, and triaminosilane.

With vinyl acetate (In the formula, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
Or an aralkyl group having 1 to 10 carbon atoms, R'is an organic group having a polymerizable double bond, X is a hydrolysis of a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group, an amino group, etc. With a silane compound represented by a functional group and / or a hydroxyl group, r is an integer of 1 to 3), and then saponified with an acid or an alkali such as sodium hydroxide or sodium methylate to obtain a silanol group-modified polyvinyl. A method of producing alcohol. Here, as the silane compound, for example,

[0015]

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4] And so on.

(B) Specific examples of silanol group-modified polyvinyl alcohol include R polymer manufactured by Kuraray Co., Ltd.
R-2105 (saponification degree = 100%, polymerization degree = 50
0), manufactured by the same company, ABD-111A (saponification degree = 30%,
Polymerization degree = 1,100) and the like. Above (b)
The weight average molecular weight of the silanol group-modified polyvinyl alcohol is preferably 2,000 to 500,000, more preferably 5,000 to 300,000. The above-mentioned (b) silanol group-modified polyvinyl alcohol may be used alone or in combination of two or more.

The proportion of the silanol group-modified polyvinyl alcohol (b) in the composition is the proportion of the component (a) [or (a)
Component + component (c) described below] 2 to 2, based on 100 parts by weight
000 parts by weight, preferably 5 to 900 parts by weight, more preferably 10 to 400 parts by weight. If it is less than 2 parts by weight, cracks are likely to be formed in the obtained coating film and the gas barrier property is deteriorated. On the other hand, if it exceeds 2,000 parts by weight, the gas coating property of the obtained coating film is deteriorated under high humidity, which is not preferable.

Next, in the coating composition of the present invention, the above components (a) and (b) may be further added, if necessary.
The organopolysiloxane (c) represented by the general formula (2) can be blended. In the organopolysiloxane (c) represented by the general formula (2), R ^{3 to} R
⁸ are the same or different and represent an organic group having 1 to 8 carbon atoms, R ^{3 to} R ⁸ include at least an alkoxy group or a hydroxyl group, m is 1 or more, and a polystyrene-equivalent weight average molecular weight of 150 to 10,000, and the -Si-O- bond is linear and / or branched.

Examples of the organic group having 1 to 8 carbon atoms include halogenated alkyl groups such as γ-chloropropyl group and 3,3,3-trifluoropropyl group, vinyl group, phenyl group, γ-methacryloxypropyl group. Groups such as (meta)
Acrylic ester group, epoxy-containing alkyl group such as γ-glycidoxypropyl group, mercapto-containing alkyl group such as γ-mercaptopropyl group, aminoalkyl group such as γ-aminopropyl group, and isocyanate such as γ-isocyanatopropyl group A linear or branched alkyl group such as an alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclohexyl group,
Alicyclic alkyl group such as cyclopentyl group, linear or branched alkoxy group such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, acetyl group, propionyl group, butyryl group, valeryl group, caproyl group, etc. An acyl group can be mentioned. In order to obtain a strong coating composition, a reaction by hydrolysis / condensation of the components (a) to (c) is preferable. From the viewpoint of reactivity, the component (c) has m of 1 or more and polystyrene. The weight average molecular weight is 150 to 10,000, preferably 2
It is from 00 to 8,000. If the polystyrene-reduced weight average molecular weight is less than 150, cracks are likely to occur in the resulting coating film and the gas barrier property is deteriorated, whereas if it exceeds 10,000, curing of the coating film tends to be insufficient, and thus the resulting coating film. Hardness is lowered and the gas barrier property is deteriorated.

Specific examples of the organopolysiloxane (c) include the following. In addition, these (c) organopolysiloxanes may be used as they are, or may be used after being hydrolyzed and / or condensed. Mitsubishi Chemical Co., Ltd., MS-51 (R ^{3 to} R ⁸ = methoxy group, weight average molecular weight = 600) Shin-Etsu Chemical Co., Ltd., X-40-9220 (R ^{3 to} R)
⁶ = methoxy group, R ^{7 to} R ⁸ = methyl group, weight average molecular weight = 4,000) Trial product (R ^{3 to} R ⁶ = methoxy group, R ^{7 to} R ⁸ = phenyl group, weight average molecular weight = 500) Trial Product (weight average molecular weight = 7,000) Here, the chemical structure of the prototype is shown below. In addition, commercially available products of (c) organopolysiloxane include MKC silicate manufactured by Mitsubishi Chemical Corporation, silicate manufactured by Tama Chemical Co., Ltd., silicon resin manufactured by Toray Dow Corning, and Silicon Silicone manufactured by Toshiba Silicone Co., Ltd. Examples include silicon resins and silicon oligomers manufactured by Nippon Unica Co., Ltd.

In the coating composition of the present invention,
The proportions of the component (a) (calculated as organosilane) and the organopolysiloxane (c) are 5 to 95% by weight, preferably 10 to 90% by weight, and 95 to 5% by weight, preferably 90 to 90%. 10% by weight (however, (a) + (c) = 1
00% by weight]. When the content of (a) is less than 5% by weight, the densification of the coating film is low and the gas barrier property is poor, while
If it exceeds 95% by weight, the flexibility of the coating film is impaired, film defects such as cracks appear, and the gas barrier property deteriorates.

In the coating composition of the present invention, in addition to the above-mentioned components (a) to (b) or components (a) to (c), (d) a metal alcoholate, a metal alcoholate and β-.
Chelate compound obtained by reaction with diketones and / or β-ketoesters, and at least one selected from the group of hydrolyzates obtained by reacting the metal alcoholate and / or chelate compound with water are added. Preferably. Among the components (d), the metal alcoholates are components (a) to (b) or (a) to (c).
It is considered to act to form a co-condensate with the components. Examples of the metal alcoholate include those represented by the general formula M
(OR ⁹ ) _p (R ¹⁰ COCH ₂ COR ¹¹ ) _q [wherein M
Is a metal atom, R ^{9 to} R ¹⁰ are the same or different, and have 1 carbon atom.
6 alkyl group, R ¹¹ represents an alkyl group or an alkoxy group having 1 to 16 carbon atoms having 1 to 6 carbon atoms, p, q is 0
Is an integer of 4 and (p + q) = valence of M].

R ⁹ and R ^{10 in} the metal alcoholate of the component (d) are the same or different and are alkyl groups having 1 to 6 carbon atoms, specifically ethyl group, n-propyl group, i-propyl group, n. -Butyl group, sec-butyl group, t-butyl group, n-pentyl group, phenyl group and the like. Also, R
¹¹ is an alkyl group having 1 to 6 carbon atoms similar to the above,
Alkoxy group having 1 to 16 carbon atoms, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-
Examples thereof include butoxy group, sec-butoxy group, t-butoxy group, lauryl group and stearyl group.

These metal alcoholates of component (d),
Metal alcoholates and β-diketones and / or β-
Specific examples of the chelate compound obtained by the reaction with ketoesters include tetrabutoxyzirconium and tri-n.
-Butoxyethyl acetoacetate zirconium, di-
n-Butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate)
Zirconium compounds such as zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium and tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis ( Acetyl acetate)
Titanium compounds such as titanium, diisopropoxy bis (acetylacetate) titanium, tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetra-t-butoxy titanium, tetrakis (2-ethylhexyloxy) titanium; diisopropoxy Ethyl acetoacetate aluminum, diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, mono Acetylacetonate
Aluminum compounds such as bis (ethylacetoacetate) aluminum may be used. Among these metal alcoholates, preferred are tri-n-butoxyethylacetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, diisopropoxyethylacetoacetate aluminum, and tris (ethylacetoacetate) aluminum. These metal alcoholates may be used alone or in combination of two or more. As the chelate compound obtained by the reaction of metal alcoholate or metal alcoholate with β-diketones and / or β-ketoesters, hydrolyzates of these compounds can also be used.

The proportion of the metal alcoholate in the component (d) in the composition is such that the component (a) (calculated as organosilane) [and the organopolysiloxane which is the component (c)] [(a)
Alternatively, with respect to (a) + (c)] 100 parts by weight, preferably 0.01 to 100 parts by weight, more preferably 0.5.
˜50 parts by weight. If it is less than 0.01 part by weight, (a)
-(C) component or the co-condensate with (a)-(c) component is insufficiently produced, the denseness of the coating film is insufficient, and as a result, the gas barrier property is deteriorated. On the other hand, 100
If the amount is more than parts by weight, the storage stability of the composition may be deteriorated and the resulting coating film may be cracked, which is not preferable.

In the component (d), the β-diketones and / or β-ketoesters have the general formula R
Examples include compounds represented by ¹⁰ COCH ₂ COR ¹¹ (wherein R ^{10 to} R ¹¹ are the same as above). The β-diketones and / or β-ketoesters constituting the component (d) act as a stability improver for the composition of the present invention. That is, the metal atom in the metal alcoholate (zirconium, titanium and / or aluminum compound) present in the composition containing the components (a) to (b) or the components (a) to (c) as a main component. By coordinating with, the metal chelate compound acts to control the condensation reaction of the components (a) to (b) or (a) to (c), and the resulting composition has stable storage stability. It is considered that it acts to improve the sex. R ¹⁰ and R ¹¹ constitute a β- diketone and / or β- ketoesters are the same as R ¹⁰ and R ¹¹ forming the metal alcoholate.

Specific examples of the β-diketones and / or β-ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetic acid-n-
Propyl, acetoacetic acid-i-propyl, acetoacetic acid-n
-Butyl, acetoacetic acid-sec-butyl, acetoacetic acid-
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- Zion etc. can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferable, and acetylacetone is particularly preferable. These β
-Diketones and / or β-ketoesters are 1
It is also possible to use one kind alone or a mixture of two or more kinds. The β-diketones and / or β-ketoesters are preferably 2 mol or more, and more preferably 3 to 20 mol, based on 1 mol of the metal alcoholate.
If it is less than 2 mol, the composition obtained will be inferior in storage stability.

In order to cure the composition of the present invention faster, (e) a curing accelerator may be used depending on the curing conditions, and in order to cure at a relatively low temperature,
It is more effective to use this (e) curing accelerator together.

As the curing accelerator (e), hydrochloric acid, etc.
Inorganic acids; naphthenic acid, octylic acid, nitrous acid, sulfurous acid,
Alkali metal salts such as aluminate and carbonic acid; sodium hydroxide
Alkaline compounds such as um and potassium hydroxide; Alky
Lutitanic acid, phosphoric acid, methanesulfonic acid, p-toluene
Acidic compounds such as sulfonic acid and phthalic acid; ethylenedia
Min, hexanediamine, diethylenetriamine, tri
Ethylene tetramine, tetraethylene pentamine, pipette
Lysine, piperazine, metaphenylenediamine, ethano
Hardener for epoxy resin, triethylamine, epoxy resin
Various modified amines used as γ-aminopropyl
Triethoxysilane, γ- (2-aminoethyl) -ami
Nopropyltrimethoxysilane, γ- (2-aminoethyl
) -Aminopropylmethyldimethoxysilane, γ-a
Amine compounds such as nilinopropyltrimethoxysilane
Thing, (C_Four H₉ )₂ Sn (OCOC₁₁H_{twenty three})₂ , (C_Four 
H ₉ )₂ Sn (OCOCH = CHCOOCH₃ )₂ ,
(C_Four H₉ )₂ Sn (OCOCH = CHCOOC_Four H
₉ )₂ , (C₈ H₁₇)₂ Sn (OCOC₁₁H_{twenty three})₂ ,
(C₈ H₁₇)₂ Sn (OCOCH = CHCOOCH₃ )
₂ , (C₈ H₁₇)₂ Sn (OCOCH = CHCOOC_Four 
H₉ )₂ , (C₈ H₁₇)₂ Sn (OCOCH = CHCO
OC₈ H₁₇)₂ , Sn (OCOCC₈ H₁₇)₂ Such as
Rubonic acid type organic tin compound; (C_Four H₉ )₂ Sn (SC
H₂ COOC₈ H₁₇)₂ , (C_Four H₉ )₂ Sn (SCH
₂ COOC₈ H₁₇)₂ , (C₈ H₁₇)₂ Sn (SCH₂ 
COOC₈ H ₁₇)₂ , (C₈ H₁₇)₂ Sn (SCH₂ C
H₂ COOC₈ H₁₇)₂ , (C₈ H₁₇)₂ Sn (SCH
₂ COOC₈ H₁₇)₂ , (C₈ H₁₇)₂ Sn (SCH₂ 
COOC₁₂H_{twenty five})₂ ,

[0030] Mercaptide type organotin compounds such as; Sulfide type organotin compounds such as;

(C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ S
nO, or (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ S
An organic tin compound such as a reaction product of an organic tin oxide such as nO and an ester compound such as ethyl silicate, dimethyl maleate, diethyl maleate and dioctyl phthalate is used. The proportion of these (e) curing accelerators in the composition is usually 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the solid content of the composition of the present invention. Used.

Further, in the composition of the present invention, in order to improve the hardness of the obtained coating film, (f) the average particle size is 0.01 to 0.2 μm, preferably 0.05 to 0, if necessary. ．
It is also possible to add 1 μm of silicon oxide and / or metal oxide. Here, the average particle size is 0.2 μm
If it exceeds, the gas barrier property is deteriorated from the viewpoint of the denseness of the film, which is not preferable. Examples of the component (f) include colloidal silica, colloidal alumina, alumina sol,
Tin sol, zirconium sol, antimony pentoxide sol,
Cerium oxide sol, zinc oxide sol, titanium oxide sol and the like can be mentioned. In the presence of the component (f), (a) to
The co-condensation reaction with the component (b) or the components (a) to (c) may be carried out, or the reaction may be followed by mixing.

The coating composition of the present invention usually comprises
It can be obtained by hydrolyzing and / or condensing the components (a) to (b) or the components (a) to (c) in the hydrophilic organic solvent (g). Here, examples of the hydrophilic organic solvent (g) include monohydric alcohols and dihydric alcohols, and among these, the monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms. Specific examples of these alcohols include methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol,
Examples thereof include ethylene glycol monobutyl ether and ethylene glycol monoethyl ether acetate.

The amount of the hydrophilic organic solvent (g) used is such that the total solid content concentration 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 5 to 40% by weight, preferably 10 to 30% by weight.
When it is used for the purpose of forming a thick film, it is usually 20 to 50% by weight, preferably 30 to 45% by weight. When the total solid content concentration of the composition exceeds 60% by weight, the storage stability of the composition tends to decrease. As the organic solvent, the above hydrophilic organic solvent is preferable, but in addition to the hydrophilic organic solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, tetrahydrofuran, ethers such as dioxane, acetone, methyl ethyl ketone, etc. The ketones, esters such as ethyl acetate and butyl acetate, etc. can also be used.

The composition of the present invention has the above (a) to
The component (b) or the components (a) to (c) are the main components, but usually the components (a) to (b) or (a) to
(G) ′ when preparing a composition containing the component (c)
Water is added to the organosilane which constitutes the component (a). The amount of (g) 'water used is usually 0.1 to 1 with respect to 1 mol of component (a) (calculated as organosilane) [and (c) alkoxy group contained in organopolysiloxane].
It is about mol, preferably about 0.3 to 0.7 mol.

As described above, the coating composition of the present invention comprises the above-mentioned component (a) and (b) silanol group-modified polyvinyl alcohol, or these and (c) organopolysiloxane, (g) a hydrophilic organic solvent. In, it is obtained by hydrolysis and / or condensation. At this time, the reaction condition is that the temperature is 20 to 100 ° C., preferably 3
0 to 80 ° C., time is 0.1 to 20 hours, preferably 1 to
10 hours. The weight average molecular weight of the resulting composition is
In terms of polystyrene converted by the general GPC method,
It is 500 to 1,000,000, preferably 1,000 to 100,000. Details of the method for measuring the weight average molecular weight are shown in Examples.

In the composition of the present invention, in order to exhibit various properties such as coloring of the obtained coating film, thickening of the film, prevention of ultraviolet ray transmission to the base, provision of corrosion resistance, heat resistance, etc.
(H) It is also possible to add / disperse the filler. However, the filler (h) does not include the above component (f). Examples of the (h) filler include water-insoluble pigments such as organic pigments and inorganic pigments, and particulate, fibrous or scale-like metals and alloys other than pigments, and oxides, hydroxides and carbides thereof. , Nitrides, sulfides, and the like. Specific examples of the filler (h) include iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, and aluminum oxide in the form of particles, fibers or scales. , Chromium oxide, manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride,
Clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, mica, zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, shale green, green soil , Manganese green, pigment green, ultramarine,
Navy Blue, Pigment Green, Rock Group Blue, Cobalt Blue, Cerulean Blue, Copper Borate, Molybdenum Blue, Copper Sulfide, Cobalt Purple, Mars Purple, Manganese Purple, Pigment Violet, Lead Oxide, Calcium Lead, Zincello, Lead Sulfide, Chromium Yellow, ocher, cadmium yellow, strontium yellow, titanium yellow, litharge, pigment yellow, cuprous oxide, cadmium red, selenium red, chrome vermillion, red iron oxide, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, Lead silicate, zircon oxide, tungsten white, lead zinc white, buntison white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black,
Thermatomic black, vegetable black, potassium titanate whiskers, molybdenum disulfide, etc. may be mentioned.

The average particle diameter or average length of these (h) fillers is usually 50 to 50,000 nm, preferably 100 to 5,000 nm. The proportion of the component (h) in the composition is (a) to (b) or (a) to
It is preferably 0.1 to 300 parts by weight, more preferably 1 to 200 parts by weight, based on 100 parts by weight of the total solid content of the component (c).

In the coating composition of the present invention, other known dehydrating agents such as methyl orthoformate, methyl orthoacetate, and tetraethoxysilane, various surfactants, silane coupling agents other than the above, titanium cups, etc. Additives such as ring agents, dyes, dispersants, thickeners and leveling agents can also be added.

In preparing the coating composition of the present invention, the above-mentioned components (a) to (b) or (a)
Although a composition containing the components (c) to (c) may be prepared, for example, the following preparation methods are preferable. (A) component, (b) silanol group-modified polyvinyl alcohol [and (c) organopolysiloxane], and (d) a solution of the metal alcoholate in the solution, and (a) component (calculated as organosilane) [and (C)
Alkoxy group of organopolysiloxane] 0.1 to 1 mol of water is added to 1 mol, and a composition comprising components (a) to (b) or (a) to (c) and a metal alcoholate. Of the component (d) after forming
A method of adding diketones and / or β-ketoesters.

To the component (a), 0.1 to 1 mol of water is added to 1 mol of the component (a) (calculated as organosilane) [and (c) the alkoxy group of the organopolysiloxane], and hydrolysis / condensation is carried out. The reaction is carried out, then (b) a silanol group-modified polyvinyl alcohol [and (c) an organopolysiloxane], and a metal alcoholate of the component (d) are added and mixed, and a condensation reaction is further carried out.
(B) component or (a) to (c) component and a composition comprising a metal alcoholate, and then adding β-diketones and / or β-ketoesters of component (d) .

In a solution containing a metal alcoholate which is the component (a) and the component (d), 0.1 mol is added to 1 mol of the component (a) (calculated as organosilane) [and (c) the alkoxy group of the organopolysiloxane]. ~ 1 mol of water is added to carry out hydrolysis / condensation reaction, then (b) silanol group-modified polyvinyl alcohol [and (c) organopolysiloxane] is added to carry out further condensation reaction, and further with (d) component. A method of adding certain β-diketones and / or β-ketoesters.

The coating composition of the present invention comprises, in particular:
Useful for gas barrier applications. That is, a coating layer made of the coating composition of the present invention, or a vapor deposition layer of a metal and / or an inorganic compound and a coating layer made of the coating composition of the present invention are laminated on a synthetic resin film. Thereby, a coating film having excellent gas barrier properties can be obtained.

Here, the synthetic resin film is in the form of a sheet or a 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 coating surface of the synthetic resin film is subjected to a 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 on a substrate (hereinafter also referred to as "substrate") such as a synthetic resin film.
In order to laminate, the surface of the substrate is coated once or plural times by a coating means such as roll coating such as micro gravure coater, spray coating, spin coating, dipping, brush, bar code and applicator.
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 (hereinafter also referred to as "vapor deposition layer") of a metal and / or an inorganic compound 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,
Silicon, titanium, zinc, zirconium, magnesium,
Metals such as tin, copper and iron, and oxides, nitrides, sulfides and fluorides of these metals such as aluminum oxide, silicon dioxide, titanium oxide, zirconium oxide, magnesium oxide, tin oxide, zinc sulfide and fluorine. Magnesium oxide or the like is used.

The vapor deposition layer is formed by vacuum vapor deposition or ion implantation.
Vapor deposition methods such as rating and sputtering are used.
However, vacuum evaporation and ion plating are the points of production efficiency.
Is preferred. The inside of the vapor deposition device is 2 × 10^-6~ 8x
10^-3Torr, preferably 8 × 10 ^-6~ 8 × 10^-FiveT
After evacuation to orr, a vapor deposition process is performed. This steam
The coating layer has a barrier property against oxygen and water vapor, but especially
Aluminum, silicon oxide, aluminum oxide, etc.
It has excellent barrier properties. The film thickness of the vapor deposition layer is 10 to 5,000.
0 angstrom, preferably 30-3,000 on
Is less than 10 angstroms,
The gas barrier property may not be sufficient, while 5,000
When it exceeds 0 angstrom, the flexibility of the vapor deposition layer is impaired.
Cracks and pinholes are more likely to occur
These also have poor gas barrier properties. The vapor deposition layer is a plurality of vapor deposition materials.
It may be used in combination with two or more layers.
Yes.

Using the coating composition of the present invention,
Specific examples of the method for forming the coating film of the present invention include the following methods. A method for forming the coating film of the present invention on the surface of a substrate. If necessary, a primer may be previously applied to the surface of the substrate to form the coating film of the present invention as described above. 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 substrate, a primer may be applied on the surface of the substrate in advance, 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.

[0051]

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 Measured by gel permeation chromatography. That is, under the following conditions, 1 g of the obtained composition (solid content) was added to 100 cc of tetrahydrofuran, sufficiently stirred, and then filtered with a 0.45 μm membrane filter to obtain a filtrate. 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 permeability Modern Control Co., MOCON OXTRAN, temperature 25 ° C., humidity 90 RH% atmosphere It was measured at.

Reference Example 1 (Preparation of zirconium chelate compound) 16 parts of tetrabutoxyzirconium and 4 parts of acetylacetone were added to a reactor equipped with a reflux condenser and a stirrer to prepare 6
After stirring at 0 ° C for 30 minutes, 80 parts of i-propyl alcohol was added to obtain a zirconium chelate compound (K-1 component).

Example 1 In a reactor equipped with a reflux condenser and a stirrer, a silanol group-modified polyvinyl alcohol [R210 manufactured by Kuraray Co., Ltd.] was used.
5, saponification degree = 100%] 340 parts of a 15% water / isopropyl alcohol mixed solution (water / isopropyl alcohol weight ratio = 7/3) and 60 parts of a 0.01 mol% hydrochloric acid aqueous solution were added, and the mixture was heated to 40 ° C. -Agitate and mix 60 parts of methyltrimethoxysilane and 140 parts of tetraethoxysilane with a mixture of 2
The mixture was added dropwise over a period of time, the reaction was continued for another 2 hours, and then cooled to room temperature to obtain a composition (A). This composition (A)
Had a weight average molecular weight of 83,000.

Example 2 A reactor equipped with a reflux condenser and a stirrer was charged with 140 parts of tetraethoxysilane, 60 parts of methyltrimethoxysilane, and silanol group-modified polyvinyl alcohol [Kuraray Co., Ltd.].
Manufactured by ABD-111A, prototype with saponification degree = 30%] 340 parts of 15% water / isopropyl alcohol mixed solution (water / isopropyl alcohol weight ratio = 4/6), tetramethoxysilane oligomer [Mitsubishi Chemical Corporation] Made, MS-
51] 100 parts, isopropyl alcohol dispersed colloidal silica [manufactured by Nissan Chemical Industries, Ltd., IPA-ST, solid content concentration 30%] 67 parts, isopropyl alcohol solution of ethyl acetate aluminum diisopropylate [manufactured by Kawaken Fine Chemical Co., Ltd.] , ALCH-75, solid content concentration 75%] 8.5 parts, water 21 parts, isopropyl alcohol 12.5 parts were added, and the mixture was heated to 40 ° C. and reacted for 4 hours, after which 7 parts of acetylacetone was added, and further 2 parts were added. After reacting for a time, a composition (B) was obtained. This composition (B)
The weight average molecular weight of the co-condensate was 131,000.

Comparative Example 1 20 parts of water was added to 100 parts of methyltrimethoxysilane,
It heated at 60 degreeC and made it react for 6 hours, and obtained the composition (C). The weight average molecular weight of this composition (C) was 40,000. Comparative Example 2 Tetramethoxysilane oligomer [manufactured by Mitsubishi Chemical Corporation,
MS-51] 20 parts of water was added to 100 parts, and it heated at 40 degreeC and was made to react for 4 hours, and the composition (D) was obtained. The weight average molecular weight of this composition (D) was 30,000.

10 parts of the zirconium chelate compound (K-1 component), which is one of the curing agents prepared in Reference Example 1, was added to the compositions obtained in Examples 1-2 and Comparative Examples 1-2.
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 gas barrier property of the obtained gas barrier coating film was measured by an oxygen permeability measuring device (MOCON O manufactured by Modern Control Co., Ltd.).
XTRAN). The results are shown in Table 1.

[0057]

[Table 1]

As is clear from Examples 1 and 2 in Table 1,
It can be seen that the coating composition of the present invention has excellent gas barrier properties. On the other hand, Comparative Example 1 is a product obtained by condensing only organosilane, and Comparative Example 2 is a product using only organopolysiloxane, and it can be seen that both have poor gas barrier properties.

Examples 3 to 4, Comparative Examples 3 to 4 Polyethylene terephthalate (PET) having a thickness of 12 μm
An inorganic compound vapor deposition layer having a film thickness of 400 Å was formed on the film by a vacuum vapor deposition method using silicon dioxide as a vapor deposition source, and further, Examples 1 and 2 or Comparative Example 1
Compositions (A) to (D) obtained in No. 2 to 10 parts of a zirconium chelate compound (K-1 component), which is one of the curing agents prepared in Reference Example 1, is added to the composition for gas barrier coating. 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 film thickness of 1.0 μm to obtain a gas barrier coating film.
The gas barrier property of the obtained gas barrier coating film was measured in the same manner as in Example 1 to measure the oxygen permeability.
The results are shown in Table 2.

[0060]

[Table 2]

As is clear from Examples 3 to 4 in Table 2,
It can be seen that the gas barrier property is further excellent by previously providing the PET film with the vapor deposition layer of the inorganic compound. On the other hand, Comparative Example 3 uses the one obtained by condensing only organosilane, and Comparative Example 4 uses only the organopolysiloxane.
It can be seen that even if the vapor deposition layer is provided on the film, the gas barrier property is inferior to that of Examples 1 and 2.

[0062]

According to the present invention, it is possible to obtain a coating composition which has extremely low oxygen permeability and is harmless to the human body, and a coating film which is excellent in gas barrier property.

Continued front page    (72) Inventor Satoshi Ishikawa             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. F-term (reference) 4F006 AA12 AA16 AA17 AA19 AA32                       AA35 AA38 AA39 AA40 AB20                       AB24 AB39 AB64 AB65 AB67                       AB68 AB73 AB74 BA05 CA07                       DA04 EA03                 4F100 AA01C AA17B AA17H AA20B                       AA20H AB01C AH02B AH08B                       AK01A AK21B AK42 AK52B                       AL05B AL08B BA02 BA03                       BA07 BA10A BA10B CA02B                       CA23B DE01B DE01H EH66C                       GB16 GB23 JA07B JD02                       JD03 JL00 YY00B YY00H                 4J038 CE022 DL031 DL052 GA02                       GA03 GA15 HA446 JA23                       JA34 JC32 JC38 KA04 KA20                       MA14 PA07 PB04 PC08

Claims (9)

[Claims] 1. (a) General formula (1) R ¹ _n Si (OR ² ) _4-n (1) (wherein R ¹ is the same or different, and is an organic group having 1 to 8 carbon atoms, R ² are the same or different and each represents an alkyl group having 1 to 5 carbon atoms, an acyl group having 1 to 6 carbon atoms or a phenyl group, and n is an integer of 0 to 2), and the organosilane. The coating composition containing at least one selected from the group consisting of the hydrolyzate and the organosilane condensate, and (b) a silanol group-modified polyvinyl alcohol as a main component. 2. (c) General formula (2) (In the formula, R³~ R⁸Are the same or different and have 1 to 8 carbon atoms
Represents an organic group of R and ³~ R⁸At least Arco
Containing a xy group or a hydroxyl group, m is 1 or more, and poly
Styrene equivalent weight average molecular weight of 150 to 10,000
And the -Si-O- bond is linear and / or
Is a branched) organopolysiloxane represented by
The coating composition according to claim 1, which contains. 3. (d) A metal alcoholate, a chelate compound obtained by the reaction of a metal alcoholate with β-diketones and / or β-ketoesters, and a reaction of the metal alcoholate and / or chelate compound with water. The coating composition according to claim 1 or 2, containing at least one selected from the group of hydrolyzates obtained by the above. 4. The method according to claim 1, which further comprises (e) a curing accelerator.
3. The coating composition according to claim 1. 5. The coating composition according to claim 1, which further comprises (f) fine particles of silicon oxide and / or metal oxide having an average particle diameter of 0.01 to 0.2 μm. 6. The component (a) and the component (b), or the component (a), the component (b) and the component (c),
(G) The coating composition according to any one of claims 1 to 5, which is formed by hydrolysis and / or condensation in a hydrophilic organic solvent. 7. The coating composition according to claim 1, which is used for a gas barrier. 8. A coating film in which a coating film layer formed from the coating composition according to any one of claims 1 to 7 is laminated on a synthetic resin film. 9. A coating film in which a vapor deposition layer of a metal and / or an inorganic compound and a coating layer formed from the coating composition according to any one of claims 1 to 7 are laminated on a synthetic resin film. .