JP2003246964A - Coating composition and film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition for producing films having high moistureproofness and good gas-barrier property, and to provide such films formed using the same. <P>SOLUTION: The coating composition comprises a metal-containing product and a solvent. The metal-containing product is selected from the compounds [A1] and [A2]. The compound [A1] is a reaction product from a component (a1) and a component (a2). The component (a1) is at least one compound selected from (1) a metal alkoxide and (2) a reaction product from the metal alkoxide and at least one compound selected from the group consisting of β- diketone, β-ketoester, β-dicarboxylic ester, lactic acid, ethyl lactate and 1,5- cyclooctadiene, and the component (a2) is at least one compound selected from an amino alcohol and a compound having in the molecule two or more hydroxy groups (except the amino alcohol). The component [A2] is the hydrolyzate of the compound [A1]. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coating composition which is used in the fields of electronic materials, pharmaceuticals, foods, cosmetics, cigarettes, toiletries and the like, and is particularly suitable for preventing permeation of water vapor and / or oxygen, and It relates to a film using this.

[0002]

2. Description of the Related Art In the fields of electronic materials, pharmaceuticals, foods, cosmetics, cigarettes, toiletries and the like, high-quality moisture-proof films and gas barrier films are required.

[0003] For example, as a packaging material for foods, oxygen, water vapor, and other gases that modify the contents are transmitted to prevent deterioration of the contents such as oxidation of proteins and fats and oils and to maintain quality such as taste. There is a demand for a material having a gas barrier property that does not prevent the gas.

In response to such a request, for example, Japanese Patent Laid-Open No. 7-
Japanese Patent No. 266485 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 composed of a polymer resin composition. A gas barrier material has been proposed in which a gas barrier film layer formed by applying a main coating composition and heating and drying is formed. However, this gas barrier material contains, in addition to the isocyanate compound having an isocyanate group, melamine, formaldehyde, tin chloride, etc., and when used for medical or food applications, it may be indirectly orally administered to the human body. There is a problem that it is harmful to the human body.

Further, Japanese Patent No. 1,476,209 proposes a coating material made of polyvinyl alcohol which does not contain isocyanate and has low toxicity. However, such a material is used as a material for retort packaging for foods under retort processing conditions (120
The gas barrier properties are not sufficient under high temperature and high humidity conditions (° C or higher) and are not sufficient.

On the other hand, in an organic EL device, a transparent electrode such as indium tin oxide (ITO) is usually used as an anode, and magnesium, aluminum, calcium, silver are used as a cathode in order to efficiently inject electrons. A metal electrode having a low work function such as an alloy or a lithium alloy is used. However, these cathode materials are easily oxidized by moisture and oxygen in the atmosphere, and as a result, the cathode is peeled from the organic layer, and defects generally called dark spots (portions that do not emit light on the light emitting surface of the device) occur. The number and size of dark spots in the organic EL element increase when the element is stored or driven for a long period of time. For this reason,
It brings about the shortcoming of durability, which is the biggest problem of the organic EL element. If the deterioration of the organic EL device due to dark spots is not improved and the light emission characteristics are unstable, it is a major problem as a light source for facsimiles, copiers, backlights of liquid crystal displays, etc., and as a display device for flat panel displays etc. Is also not desirable.

As described above, in order to improve the stability and the reliability of the organic EL element, the sealing for protecting the element from moisture and oxygen in the atmosphere is indispensable. Usually, polychlorotrifluoroethylene (hereinafter PCTF
Abbreviated as E. ) Is mainly used, and a transparent plastic film having a silicon-based or aluminum-based transparent oxide thin film provided on a transparent plastic film is sealed and used as a transparent film having excellent moisture-proof properties. However, since the former laminated film mainly composed of PCTFE is extremely expensive, not only the manufacturing cost of the final backlight becomes high, but also when heat-sealing the light emitting layer, the step portion of the edge is sealed by the sealing pressure. There is a problem that the brightness of the EL is reduced from the peripheral portion due to thinning and moisture absorption therefrom. Further, a transparent film obtained by laminating a transparent oxide thin film of silicon or aluminum based on a vapor deposition method has also been proposed, but neither of them has sufficient moisture proof performance, and the blackening resistance, moisture proofness and There is no sealing method or sealing material that can sufficiently satisfy the gas barrier property, and its development is desired.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a coating composition for producing a film having excellent moisture resistance and gas barrier properties, and a film formed by using the coating composition. It is in.

Other objects and advantages of the present invention will be apparent from the following description.

[0010]

According to the present invention, the above object of the present invention is, firstly, a coating composition containing a metal-containing product and a solvent, wherein the metal-containing product is: It is achieved by a coating composition, which is at least one selected from the group consisting of [A1] and [A2].

[A1]; a reaction product of the following components (a1) and (a2); (a1); at least one compound selected from the following, metal alkoxides, β-diketones, β-ketoesters, β -Reaction of at least one compound selected from the group consisting of dicarboxylic acid ester, lactic acid, ethyl lactate and 1,5-cyclooctadiene (hereinafter sometimes referred to as "(a1) -II component") with a metal alkoxide Product, (a2);
At least one compound selected from amino alcohols and compounds having two or more hydroxyl groups in the molecule (excluding amino alcohols), [A2];
1] The hydrolyzate of the reaction product.

The above object of the present invention is secondly, on a substrate,
It is achieved by a film having a coating film formed from the above composition.

Each component of the coating composition of the present invention will be described below.

The metal-containing product used in the present invention is at least one selected from the group consisting of the above [A1] and [A2], and the above [A1] comprises the above components (a1) and (a2). It is a reaction product. In addition, the above (a
1) The component is at least 1 selected from the above and
It is a compound of species.

(A1 ) Metal Alkoxide Examples of the metal alkoxide used in the present invention include the following formula (1) R _mm (OR ′) _nm (1) (where M is tantalum, titanium, aluminum,
Zirconium or silicon, R is a monovalent organic group having 1 to 8 carbon atoms, R'is an alkyl group having 1 to 6 carbon atoms, n is a valence of M, and m is 0 to n. It is an integer of -1, and when there are a plurality of R or R ', they may be the same or different. The compound represented by) is preferably used.

Here, as the monovalent organic group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group,
i-propyl group, n-butyl group, i-butyl group, sec
-Butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and other alkyl groups; acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group Acyloxy group such as acetoxyl group, propionyloxyl group, butyryloxyl group, valeryloxyl group, benzoyloxyl group, trioyloxyl group; vinyl group, allyl group, cyclohexyl group, phenyl group, glycidyl group, ( (Meth) acryloxy group, ureido group,
Amido group, fluoroacetamido group, isocyanate group, etc., and some or all of hydrogen atoms contained in these groups are halogen atoms, substituted or unsubstituted amino groups, hydroxyl groups, mercapto groups, isocyanate groups, glycidoxy groups, 3 , 4-epoxycyclohexyl group, (meth) acryloxy group, ureido group, group substituted with ammonium base and the like.

The alkyl group having 1 to 6 carbon atoms represented by R'is, 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 and the like can be mentioned.

Specific examples of such metal alkoxides include titanium alkoxides such as titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide and titanium tetrabutoxide; tantalum pentamethoxide and tantalum pentaethoxide. , Tantalum pentaisopropoxide, tantalum pentoxide and the like tantalum alkoxides; aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum tributoxide and the like aluminum alkoxides; zirconium tetrabutoxide, zirconimute Trisopropoxide, zirconium tetraethoxide,
Zirconium alkoxides such as zirconium tetramethoxide;

Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetraacetyloxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane. , Ethyltrimethoxysilane, ethyltriethoxysilane,
n-propyltrimethoxysilane, 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, allyltrimethoxysilane, 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-isocyanatopropyltriethoxysilane, 3 -Ureidopropyltrimethoxysilane, 3
-Ureidopropyltriethoxysilane, methyltriacetyloxysilane, methyltriphenoxysilane, 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 methyldi Ethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-
n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane,
Examples thereof include silane alkoxides such as dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dimethyldiacetyloxysilane, and dimethyldiphenoxysilane.

Of these, tantalum pentaethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, aluminum triisopropoxide,
And zirconium tetrabutoxide are preferred.

These metal alkoxides can be used alone or in combination of two or more kinds. (A1) Metal alkoxide, β-diketone, β-ke
Ester, β-dicarboxylic acid ester, lactic acid, lactic acid ester
From the group consisting of tyl and 1,5-cyclooctadiene
At least one compound ((a1) -II compound selected
Reaction product with the same as the above-mentioned (a1) metal alkoxide can be used as the above-mentioned metal alkoxide.

Examples of the β-diketone include acetylacetone, propionylacetone, methyldiacetylmethane, dipropionylmethane, n-butyrylacetone, isobutyrylacetone, 3-methyl-2,4-hexanedione, diacetylethylmethane, n-valerylacetone, propionyl-n-butyrylmethane, 3-methyl-2,4-hexanedione, diacetylethylmethane, n-valerylacetone, propionyl-n-butyrylmethane, 3-methyl-2,4-heptanedione, Isovalerylacetone, pivaloylacetone, isopropyldiacetylmethane, caproylacetone, di-n-butyrylmethane, 2,2,6,6-tetramethyl-3,5-
Heptanedione, benzoylacetone, 3-phenyl-
2,4-pentanedione, dibenzoylmethane, ethoxycarbonyldiacetylmethane, 1,1,1,5,5,5
And compounds such as 5-hexafluoro-2,4-pentanedione. Of these, acetylacetone and propionylacetone are particularly preferably used.

Examples of the β-keto ester include compounds such as methyl acetoacetate, ethyl acetoacetate and methyl-α-methyl acetoacetate. Of these, methyl acetoacetate and ethyl acetoacetate are particularly preferable.

The above β-dicarboxylic acid ester includes
For example, dimethyl malonate, diethyl malonate, dibutyl malonate, dihexyl malonate, dioctyl malonate,
Examples include compounds such as diundecyl malonate, dihexadecyl malonate, di-9-octadecyl malonate, di-9,12-octadecadienyl malonate and di-9,11,13-octadecatrienyl malonate. Of these, dimethyl malonate and diethyl malonate are particularly preferably used.

The above compounds can be used alone or in admixture of two or more.

The above metal alkoxide and (a1) -I
The reaction with the component I is as follows:
The component (a1) -II is preferably 0.1 to 1,000.
Mol, more preferably 0.5 to 100 mol, particularly preferably 1 to 10 mol.

The reaction temperature is preferably -30 to 150.
° C, more preferably 0 to 100 ° C, even more preferably 0
~ 70 ° C. The reaction pressure may be normal pressure, but if necessary, it can be carried out under pressure or under reduced pressure.

The above reaction can be carried out in the presence of a solvent, if necessary. When using a solvent, it is preferable to use a solvent that does not react with the metal alkoxide and the component (a1) -II, and the reaction products thereof.

Examples of such a solvent will be described later (a
As the solvent that can be used in the reaction between the component (1) and the component (a2), the same solvents as those exemplified can be used.

The above reaction products are presumed to be, for example, the following.

I) When the component (a1) -II contains lactic acid or ethyl lactate, an alkoxyl group of a metal alkoxide (when the metal alkoxide has an acyl group, an alkoxyl group and / or an acyl group). (A1) -I
A reaction product in which at least one hydroxyl group in component I has lost its hydrogen atom, and the oxygen atom in the hydroxyl group that has lost the hydrogen atom forms a bond with a metal atom. Where (a1)
When a plurality of hydroxyl groups in one molecule of the -II component participate in the reaction, the metal atoms bonded to them may be the same or different.

Ii) When the component (a1) -II contains a β-diketone, β-ketoester or β-dicarboxylic acid ester, an alkoxyl group of the metal alkoxide (when the metal alkoxide has an acyl group) A part or all of an alkoxyl group and / or an acyl group) is eliminated, and the CH ₂ group sandwiched between the two carbonyl groups in the component (a1) -II loses its hydrogen atom. The reaction product in which the β-diketone structure which has lost the structure takes a resonance structure to form a chelate bond on one metal atom.

Iii) In the case where the component (a1) -II contains lactic acid, the alkoxyl group of the metal alkoxide (when the metal alkoxide has an acyl group, the alkoxyl group and / or the acyl group) Part or all is eliminated, and at least one carboxyl group in the component (a1) -II loses its hydrogen atom, and the oxygen atom in the carboxyl group that has lost the hydrogen atom forms a bond with the metal atom. Reaction product. At this time, the carboxyl group which has lost the hydrogen atom may have a resonance structure and may be chelated to one metal atom.

Iv) A reaction product in which two oxygen atoms of the ester group form a bond with a metal atom when the component (a1) -II contains ethyl lactate.

V) In the above i) to iv), the oxygen atom or the nitrogen atom in the component (a1) -II which has formed a bond with the metal atom is replaced with another reaction product or the metal atom in the unreacted metal alkoxide. The reaction product that caused further binding.

Vi) When the component (a1) -II contains 1,5-cyclooctadiene, an alkoxyl group of a metal alkoxide (when the metal alkoxide has an acyl group, an alkoxyl group and (Or an acyl group) is partially or entirely eliminated to give 1,5
A product in which at least one double bond in cyclooctadiene forms a coordinate bond with at least one metal atom.

Vii) A reaction product in which an oxygen atom or a nitrogen atom in the component (a1) -II forms a bond with a metal atom in the reaction product according to any one of the above i) to vi).

Viii) The metal atom in the reaction product described in any one of the above i) to vii) is bonded to the metal atom in another reaction product or the unreacted metal alkoxide via an oxygen atom. The resulting reaction product.

Ix) Any one of i) to viii) above
The metal atom in the reaction product according to one of the metal atoms in the other reaction product or the metal atom in the unreacted metal alkoxide, the alkoxyl group remaining in the reaction product or in the unreacted metal alkoxide A reaction product obtained by bridging via an oxygen atom of an alkoxyl group (when the metal alkoxide has an acyl group, an alkoxyl group and / or an acyl group).

X) A mixture of any two or more of the above reaction products.

Here, the newly formed bond can be, for example, a covalent bond, an ionic bond, a coordinate bond, a hydrogen bond or an intermediate bond between these bonds.

Of the reaction products presumed to have the above structures, compounds having a chelate structure are preferable.

Specific examples of such a compound include tri-n-butoxy ethyl acetoacetate zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate). Zirconium compounds such as zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; di-i-propoxy bis (ethylacetoacetate) titanium, di-i- Propoxy bis (acetylacetate) titanium, di-i-propoxy bis (acetylacetonato) titanium, dihydroxy bislactetotitanium, dihydroxytitanium lactate, Tetrakis (2-ethylhexyl oxy) titanium such as titanium compounds;

Di-i-propoxy ethyl acetoacetate aluminum, di-i-propoxy acetyl acetonate aluminum, i-propoxy bis (ethyl acetoacetate) aluminum, i-propoxy bis (acetyl acetonate) aluminum, Tris Aluminum compounds such as (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonatobis (ethylacetoacetate) aluminum; tetraethoxy. (Acetylacetonato) tantalum, triethoxybis (acetylacetonate). Tantalum, diethoxy tris (acetylacetonate) tantalum, ethoxy tetrakis (acetylacetonate) tantalum, penta (acetylacetonate) tantalum It can be exemplified tantalum compounds such as Le.

Among these chelate compounds, preferred are tri-n-butoxyethylacetoacetate zirconium, di-i-propoxy bis (acetylacetonato) titanium and tri-i-propoxy.
(Acetylacetonate) Titanium, dihydroxy
Examples thereof include bislactetotitanium, di-i-propoxy.ethylacetoacetate aluminum, tris (ethylacetoacetate) aluminum, penta (acetylacetonato) tantalum, and the like.

(A2) Amino alcohol and intramolecular
A compound having two or more hydroxyl groups in the
Excluding calls. At least one selected from the above ) Examples of the amino alcohol include compounds such as triethanolamine, diethanolamine, triisopropanolamine, diisopropanolamine, methyldiethanolamine, and ethyldiethanolamine. Of these, triethanolamine and diethanolamine are particularly preferably used.

Examples of the compound having two or more hydroxyl groups in the molecule (excluding aminoalcohol) include alcohols having two or more hydroxyl groups in the molecule (excluding aminoalcohol) and intramolecular. To 2
Examples thereof include phenols having one or more hydroxyl groups.

Examples of alcohols having two or more hydroxyl groups in the molecule (excluding amino alcohols) are, for example, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol and nonanediol. , Dialcohols such as decanediol, diethylene glycol, bistrimethylene glycol, glycerol monomethyl ether, glycerol monoethyl ether and hydroquinone; and polyhydric alcohols such as glycerol. Of these, diethylene glycol, butanediol and pentanediol can be particularly preferably used.

Examples of the phenols having two or more hydroxyl groups in the molecule include catechol, resorcin,
Examples include polyphenols such as hydroquinone and phloroglucin. Of these, hydroquinone is particularly preferably used.

In the reaction of the above-mentioned component (a1) with the component (a2), the component (a2) is preferably added in an amount of 0.01 to 1,000 moles to 1 mole of the metal atom contained in the component (a1). , More preferably 0.1 to 100 mol, particularly preferably 1 to 10 mol.

The reaction temperature is preferably -30 to 150.
° C, more preferably 0 to 100 ° C, even more preferably 0
~ 70 ° C. The reaction pressure may be normal pressure, but if necessary, it can be carried out under pressure or under reduced pressure.

The above reaction can also be carried out in the presence of monoalcohols (except amino alcohols) and / or monophenols.

Examples of the monoalcohols (excluding aminoalcohols) include methanol, ethanol, propanol, isopropanol, butanol, and t.
ert-butanol, hexanol, cyclohexanol, octanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, glycerol dimethyl ether , Glycerol diethyl ether and the like.

Examples of monophenols include phenol, methylphenol, dimethylphenol,
Examples include trimethylphenol, ethylphenol, diethylphenol, triethylphenol and the like.

Of these, phenol, methylphenol and ethylphenol can be preferably used.

When the above reaction is carried out in the presence of monoalcohols (excluding amino alcohols) and / or monophenols, the amount of these compounds used is
It is preferably 10 mol or less, more preferably 5 mol or less, still more preferably 3 mol or less, relative to 1 mol of the component (a2). Here, if the amount used exceeds 10 moles,
The reaction between the component (a1) and the component (a2) may be hindered.

The above reaction can be carried out in the presence of a solvent, if necessary. When using a solvent, (a1)
Component, component (a2) and their reaction products ([A
It is preferable to use a solvent that does not react with component 1).

Examples of such a solvent include n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, n-octane, cyclooctane, decane, cyclodecane, dicyclopentadiene hydride and benzene. , Hydrocarbon solvents such as toluene, xylene, durene, indene, tetrahydronaphthalene, decahydronaphthalene, squalane; diethyl ether, dipropyl ether, dibutyl ether,
Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol diethyl ether,
Ether-based solvents such as diethylene glycol methyl ethyl ether, tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, p-dioxane; propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone, Examples include polar solvents such as dimethylformamide, acetonitrile, dimethylsulfoxide, methylene chloride and chloroform.

Of these, diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dimethylformamide, acetonitrile, dimethylsulfoxide, methylene chloride and chloroform can be particularly preferably used.

These solvents may be used alone or in admixture of two or more.

When the reaction between the component (a1) and the component (a2) is carried out in the presence of a solvent, the amount of the solvent used is usually (a1).
With respect to 1 g of the component, preferably 1 to 100 mL, more preferably 5 to 50 mL, further preferably 5 to 30 mL
Is.

The reaction product ([A] component) produced by the reaction of the (a1) component and the (a2) component comprises a bond between the metal atom in the (a1) component and an alkoxyl group and / or other group. Part or all of which is dissociated, and at least one hydroxyl group in the component (a2) loses its hydrogen atom,
It is considered that the oxygen atom in the hydroxyl group that has lost the hydrogen atom is a reaction product in which a bond is formed with the metal atom. here,
When a plurality of hydroxyl groups in one molecule of the component (a2) participate in the reaction, the metal atoms to which they are bound may be the same atom or different atoms.

Here, the newly formed bond can be, for example, a covalent bond, an ionic bond, a coordinate bond, a hydrogen bond, or an intermediate bond between these bonds.

The reaction product as described above may contain an unreacted alkoxyl group or an alkoxyl group in which an alkoxyl group in a metal alkoxide has undergone an exchange reaction with an optionally added monoalcohol.

The reaction product as described above may contain an unreacted alkoxyl group or an alkoxyl group in which an alkoxyl group in a metal alkoxide has undergone an exchange reaction with an optionally added monoalcohol (subsequently). ,
These may be collectively referred to simply as "unreacted alkoxyl group". ).

The component [A1] of the present invention has a reaction conversion rate defined by the following formula (1) of preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 85 mol%. % Or more.

Reaction conversion rate = {1- (total number of unreacted alkoxyl groups in reaction product / total number of alkoxyl groups in raw material metal alkoxide)} × 100 (mol%) (1) This value is less than 50 mol%. If so, the moisture resistance and gas barrier properties of the formed film may be insufficient. [A2] Component The [A2] component of the present invention is a hydrolyzate of the above-mentioned [A1] component.

The component [A2] is, for example, the component [A1] described above, preferably 0.01 to 1.0 with respect to 1 equivalent of the metal atom.
It can be synthesized by treating in the presence of 00 mol of water at a temperature of room temperature to 100 ° C with stirring.

The hydrolyzate of the above reaction product includes a compound in which all of the hydrolyzable moieties are hydrolyzed and a partial hydrolyzate in which some of them are hydrolyzed and some of which are not hydrolyzed. Included.

In the present invention, the above reaction product and its hydrolyzate may be used alone or in combination of two or more kinds.

Other Components The moisture-proof coating composition of the present invention contains at least one selected from the above-mentioned [A1] component and [A2] component as an essential component, but may contain other components as necessary. You may have.

Examples of such components include orthocarboxylic acid esters, acids, other metal compounds, surface tension adjusting agents, inorganic particles and the like.

These will be described below.

Orthocarboxylic Acid Ester The composition of the present invention may further contain an orthocarboxylic acid ester.

The orthocarboxylic acid ester is particularly suitable for the moisture-proof coating composition of the present invention as the component (a1) and the component (a2).
When it contains a reaction product of components, it reacts with moisture existing in the environment in the step of forming a coating using the same, and the adverse effect of humidity in the atmosphere can be reduced. Therefore, a film having a film formed from the composition of the present invention containing an orthocarboxylic acid ester has high quality.

The mechanism of the reaction of the orthocarboxylic acid ester with water is presumed to be as shown in the following formula (2). R ¹ C (OR ² ) ₃ + 3H ₂ O → R ¹ COOH + 3R ² OH + H ₂ O (2) (wherein R ¹ and R ² are alkyl groups or aryl groups) Used in the present invention [B] Examples of the orthocarboxylic acid ester include trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, tripentyl orthoformate, diethylpropyl orthoformate, triphenyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, orthoacetate. Tripropyl,
Tributyl orthoacetate, tripentyl orthoacetate, diethylpropyl orthoacetate, triphenyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, tripropyl orthopropionate, tributyl orthopropionate, tripentyl orthopropionate, diethylpropylpropionate, Triphenyl orthopropionate, trimethyl orthobutyrate, triethyl orthobutyrate, tripropyl orthobutyrate, tributyl orthobutyrate, tripentyl orthobutyrate, diethylpropyl orthobutyrate, triphenyl orthobutyrate, trimethyl ortholaurate, triethyl ortholaurate, ortholauric acid Tripropyl, tributyl ortholaurate, tripentyl ortholaurate, diethylpropyl ortholaurate, o Toraurin acid triphenyl, orthobenzoate trimethyl orthobenzoate triethyl,
Tripropyl orthobenzoate, tributyl orthobenzoate, tripentyl orthobenzoate, diethylpropyl orthobenzoate, triphenyl orthobenzoate, trimethyl ortho-lactate, triethyl ortho-lactate, tripropyl ortho-lactate, tributyl ortho-lactate, tripentyl ortho-lactate, ortho- Diethyl propyl lactate, triphenyl ortho lactate and the like can be mentioned.

Of these orthocarboxylic acid esters,
Aliphatic esters are preferred because of their reactivity with water, and methyl esters and ethyl esters are particularly preferred. Specifically, trimethyl orthoformate, triethyl orthoformate and trimethyl orthobenzoate are particularly suitable.

These orthocarboxylic acid esters can be used alone or as a mixture of two or more kinds.

The amount of the orthocarboxylic acid ester used in the composition of the present invention can be appropriately set depending on the water content of the composition, the humidity of the atmosphere during the metal oxide film forming step, and the like. It is generally preferably 50% by weight or less, more preferably 30% by weight or less, and further preferably 20% by weight or less, based on the whole product.

The carboxylic acids and alcohols formed by the reaction of water with the orthocarboxylic acid ester and the hydroxyl groups of the ortholactic acid ester may react with the film-forming composition, which diminishes the effect of the present invention. Not a thing.

Acid The composition of the present invention may further contain an acid. The acid catalyzes the reaction between the above-mentioned orthocamponic acid ester and water, can efficiently remove water, and contributes to the quality of the formed film and the long-term storage stability of the composition.

Examples of the acid include aliphatic monocarboxylic acid, aromatic carboxylic acid, halogenated aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, acid anhydride and sulfonic acid.

Examples of such an acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid,
Aromatic carboxylic acids such as benzoic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, halogenated aliphatics such as trichloroacetic acid, dichloroacetic acid, monochloroacetic acid, trifluoroacetic acid, difluoroacetic acid, monofluoroacetic acid Aliphatic dicarboxylic acids such as monocarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, acid anhydrides such as acetic anhydride, propionic anhydride, phthalic anhydride, maleic anhydride, Examples thereof include sulfonic acid such as methanesulfonic acid, ethanesulfonic acid, and trifluoromethanesulfonic acid.

Among these acids, aliphatic carboxylic acids having 1 to 5 carbon atoms (including formic acid), halogenated aliphatic monocarboxylic acids and aliphatic dicarboxylic acids are preferable, and specific examples are formic acid, acetic acid and trichloroacetic acid. , Trifluoroacetic acid, oxalic acid and maleic acid are particularly preferred.

These acids can be used alone or in admixture of two or more.

The amount of the acid used is preferably 50% by weight or less, and 30% by weight based on the whole composition.
The content is more preferably below, and even more preferably 20% by weight or less.

Other Metal Compounds The composition of the present invention is used for increasing the metal concentration in the composition.
If necessary, a metal compound other than the above may be contained.

Surface tension adjusting agent In the composition of the present invention, a surface tension adjusting agent such as a fluorine type, silicone type or nonionic type may be added, if necessary, within a range that does not impair the intended function. You can

Inorganic Particles The moisture-proof coating composition of the present invention may optionally preferably contain inorganic particles. The inorganic fine particles are particulate inorganic substances having an average particle diameter of 0.2 μm or less and substantially not containing carbon atoms, and examples thereof include metal oxides, metal nitrides, and metal borides. The method for producing the inorganic fine particles is, for example, when a method for producing silicon oxide is taken as an example, a gas phase method for producing silicon tetrachloride by hydrolysis in a flame of oxygen and hydrogen, a liquid produced by ion exchange of sodium silicate. Examples of the manufacturing method include a phase method and a solid phase method in which silica gel is pulverized by a mill or the like.
The inorganic fine particles are not limited by the manufacturing method thereof.

Specific examples of such inorganic fine particles include:
SiO₂, Al₂O₃, TiO₂, WO ₃, Fe₂O₃, Zn
O, NiO, RuO₂, CdO, SnO₂, Bi₂O₃, Z
rO₂3 Al₂O₃・ 2SiO₂, Sn-In₂O₃, Sb
-In₂O₃, Oxides such as CoFeOx, Si₃N_Four, F
e_FourNitriding of N, AlN, TiN, ZrN, TaN, etc.
Thing, Ti₂B, ZrB₂, TaB₂, W₂Borides such as B
Is mentioned.

The inorganic particles may be in the form of powder or suspension dispersed in a suitable dispersion medium. It is not limited to these. For example, preferably, a dispersion such as colloidal silica, colloidal alumina, alumina sol, tin sol, zirconium sol, antimony pentoxide sol, cerium oxide sol, zinc oxide sol, titanium oxide sol is used.

The average particle size of the inorganic fine particles is preferably 0.2 μm or less, more preferably 0.1 μm or less. If the average particle diameter exceeds 0.2 μm, the moisture resistance and the gas barrier property may be deteriorated from the viewpoint of the denseness of the film.

The amount of these inorganic fine particles used is preferably 300 parts by weight or less, more preferably 200 parts by weight or less, relative to 100 parts by weight of the components other than the inorganic compound.

Coating Composition The coating composition of the present invention is prepared by dissolving at least one component selected from the above-mentioned [A1] component and [A2] component and optionally other components dissolved in a solvent or Used as a liquid composition in a dispersed state.

The solvent that can be used in the present invention is not particularly limited as long as it dissolves or disperses the above-mentioned components and does not react with them. As such a solvent,
What was illustrated as a solvent which can be used at the time of a reaction of a component (a1) and a component (a2) can be used, and also others, for example, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, octanol, decanol, ethylene glycol, ethylene. Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, glycerol, glycerol monomethyl ether , Glycerol dimethyl ether, glycerol Alcohol solvents such as ethyl ether and glycerol diethyl ether; ester solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl lactate and ethyl lactate are used. can do.

These solvents can be used alone or as a mixture of two or more kinds.

Of these, alcohol-based solvents and mixed solvents of alcohol-based solvents and other polar solvents are preferable from the viewpoint of solubility of each component and stability of the composition.

Preferred alcohol solvents are, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monopropyl ether. Further, as the mixed solvent of the alcohol solvent and the other polar solvent, a mixed solvent of an alcohol solvent / ether solvent and a mixed solvent of an alcohol solvent / ester solvent are preferable.

Preferred specific examples of the above mixed solvent of alcohol solvent / ether solvent include at least one alcohol solvent selected from propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monopropyl ether,
And a mixed solvent with at least one ether solvent selected from bis (2-methoxyethyl) ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether.

Preferable specific examples of the above mixed solvent of alcohol solvent / ester solvent include at least one alcohol solvent selected from propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monopropyl ether,
And a mixed solvent with at least one ester solvent selected from propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate.

Of the above, propylene glycol monoalkyl ethers have isomers, but any of them can be used, and a mixture of isomers can also be used.

Here, the synthesis of the above-mentioned component (a1),
And / or when a solvent is used in the reaction step of the component (a1) and the component (a2), the solvent may be directly used as the solvent of the composition of the present invention without removing the solvent,
After the reaction, the solvent may be removed once, and the reaction product of the components (a1) and (a2) may be purified, if necessary, and then the solvent may be added again. Further, the solvent used in the reaction step may not be removed, and a solvent may be further added to obtain the composition of the present invention.

If the solvent used contains a hydroxyl group, it may react with the unreacted alkoxyl group of the reaction product of the components (a1) and (a2).
This does not diminish the effect of the present invention.

When the composition of the present invention contains a solvent, the amount of the solvent used can be appropriately set according to the desired thickness of the coating film. The total concentration is preferably 0.1 to 50% by weight,
It is more preferably 0.5 to 50% by weight, further preferably 1 to 30% by weight, particularly preferably 1 to 20%.
% By weight.

Film Manufacturing Method Next, the film manufacturing method of the present invention will be described.

In the present invention, a film is produced by forming a coating film of the above composition on a substrate and then subjecting it to heat treatment and / or light treatment.

As the substrate used here, a resin film is preferable. Examples of the resin include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, nylon 6, nylon 6, and nylon 6.
Polyamide resin such as 6, nylon 4, 6, and nylon 12, polyamide imide, polyimide, polyether imide, polysulfone, polyether sulfone, polyether ketone, polycarbonate resin, polystyrene resin, polyvinyl alcohol, ethylene-vinyl acetate Polyvinyl alcohol-based resin such as saponified polymer,
Polyacrylonitrile resin, polyvinyl chloride resin,
Polyvinyl acetal resin, polyvinyl butyral resin, polyarylate, polyphenylene sulfide,
Polyphenylene oxide, tetrafluoroethylene,
Fluorine-based resins such as ethylene monofluoride trifluoride and fluorinated ethylene-propylene copolymer can be used.

The resin film is formed by, for example, an inflation method, a T-die method, or another appropriate film forming method.
A method of forming a film by using the above resin alone, a method of forming a multilayer co-extrusion film by using two or more different resins, and a method of forming a film by using two or more kinds of resins. It can be produced as an unstretched film by a method such as mixing with the above to form a film. Furthermore, for example, a tenter system or a tubular system can be used to form a stretched film obtained by stretching the unstretched film in the uniaxial or biaxial direction.

It is particularly preferable to use a biaxially oriented polypropylene film, a biaxially oriented polyethylene terephthalate film or a biaxially oriented nylon film as the resin film used as the substrate in the present invention.

In the present invention, the thickness of the resin film as the substrate is preferably about 5 to 200 μm, more preferably about 10 to 100 μm.

In the above, when the resin is formed into a film, for example, the processability of the film, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidation, slipperiness, releasability, flame retardancy, etc. , For the purpose of improving or modifying antifungal properties, electrical properties, etc., for example, lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, plasticizers, fillers, reinforcing agents, reinforcing agents, antistatic agents,
A resin containing a flame retardant, a flame retardant, a foaming agent, an antifungal agent, a paint, a coloring agent such as a pigment, other compounding agents and additives, and a modifying resin can be used.

The resin film as the base material used in the present invention may be subjected to, for example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, and the like, if necessary. It may be optionally subjected to reverse sputtering treatment, oxidation treatment using chemicals, or other pretreatment.

The above-mentioned base material may have a vapor-deposited film of an inorganic oxide (hereinafter also referred to as a "vapor-deposited film") formed on the surface thereof.

By providing such a vapor deposition film,
Further, the moisture resistance is improved.

The vapor-deposited film may be any film as long as it is a film formed by vapor-depositing a metal oxide. For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca). , Potassium (K),
Tin (Sn), Indium (In), Sodium (N
a), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), antimony (Sb) and other oxides, indium-tin composite oxide (also referred to as ITO), Antimony-tin composite oxide (A
A composite oxide such as (also referred to as TO) can also be used.

Such a vapor deposition film can be formed by a chemical vapor deposition method, a physical vapor deposition method, or the like.

Examples of the chemical vapor deposition method include chemical vapor deposition methods such as plasma chemical vapor deposition method, thermochemical vapor deposition method, photochemical vapor deposition method and the like.
rDeposition method, CVD method) and the like.

As the physical vapor deposition method, for example, a physical vapor deposition method (Physical Vapor D) such as a vacuum vapor deposition method, a sputtering method or an ion plating method is used.
Eposition method, PVD method) and the like.

The film thickness of the above-mentioned inorganic oxide vapor deposition film varies depending on the kind of metal oxide used and the like.
It can be arbitrarily selected within the range of 00 nm, preferably 10 to 200 nm. Further, the vapor deposition film of the inorganic oxide of the present invention may be not only one layer of the vapor deposition film of the inorganic oxide but also a laminated body in which two or more layers are laminated. Further, the metal oxides used may be one kind or a mixture of two or more kinds to form a thin film of an inorganic oxide mixed with different materials.

The vapor deposition film as described above may be formed after the surface treatment of the resin film in order to improve the adhesion.

Examples of such surface treatment include low temperature plasma treatment, glow discharge treatment and the like. These treatments can be performed by an in-line treatment as a pretreatment for forming a vapor deposition film, and in such a case, the manufacturing cost can be reduced.

As another method of surface treatment, for example, a primer coating agent layer, an undercoating agent layer, a vapor deposition anchor coating agent layer, etc. may be previously formed on the surface of the resin film.

As the coating agent layer, for example, a resin composition (primer) containing an ethyleneimine resin, an amine resin, an epoxy resin, a polyester resin, a polyurethane resin or another appropriate resin as a main component of the vehicle. Can be used.

As the method for forming the above coating agent layer, for example,
A solvent type, an aqueous type, an emulsion type or the like may be used, and coating can be performed by a roll coating method, a gravure roll coating method, a kiss coating method, or any other suitable coating method. The coating period is 2 for the base film.
It can be carried out after the axial stretching treatment or in the in-line treatment step of the biaxial stretching treatment.

In the present invention, a coating film of the coating composition of the present invention is formed on the above-mentioned substrate.

The coating film is formed on the surface of the substrate once or plural times by an appropriate coating means such as gravure coater, roll coating, spray coating, spin coating, dipping, brush, bar code, applicator and the like. A coating film having an appropriate film thickness can be formed by coating. The film thickness can be appropriately set according to the desired thickness of the coating layer (metal oxide film). For example, 0.001 to 20
μm is preferable, and 0.005 to 2 μm is more preferable. When the composition contains a solvent, the above film thickness should be understood as the film thickness after removal of the solvent.

In the coating step in the present invention, the humidity (water vapor content in the atmosphere) is 5 g / m ³ or less, preferably ³ g / m ^3.
It is carried out in an atmosphere of m ³ . Humidity at this time is 5g /
If it exceeds m ³ , the moisture resistance and gas barrier properties of the produced film may be adversely affected.

However, when the composition of the present invention contains a predetermined amount of orthocarboxylic acid ester, the coating film forming step can be carried out without being affected by humidity (water vapor content in the atmosphere). For example, it is possible to obtain a high-quality moisture-proof film even when a coating film is formed in an atmosphere having a humidity of more than 5 g / m ³ , and further, in an atmosphere of a humidity of 7 g / m ³ or more, particularly 9 g / m ³ or more. A high-quality film can be obtained even when the coating film is formed under the atmosphere of humidity.

Then, the coating film formed as described above is converted into a coating layer (metal oxide film) by heat and / or light treatment, whereby a film can be produced.

The temperature of the heat treatment is preferably 50 ° C. or higher, more preferably 80 to 400 ° C. or higher, further preferably 100 to 300 ° C. The heating time can be appropriately set depending on the film thickness and the like, but it is preferable to heat for 0.2 minutes or more to obtain a high-quality film,
It is more preferably 0.5 to 90 minutes, further preferably 1 to 60 minutes.

The atmosphere in the heating step is preferably such that the oxygen concentration is higher.

The heat treatment atmosphere is, for example, air, pure oxygen, ozone or N ₂ O, or a mixed gas thereof, and further, an oxidizing gas thereof and an inert gas such as nitrogen, helium or argon. Gas can be used.

As the light source used in the above light treatment,
In addition to low-pressure or high-pressure mercury lamp, deuterium lamp or discharge light of rare gas such as argon, krypton, xenon, YAG laser, argon laser, carbon dioxide laser, XeF, XeCl, XeBr, KrF, KrC.
1, excimer laser such as ArF, ArCl and the like can be used. The output of these light sources is preferably 10 to 5,000 W, more preferably 100 to
It is 1,000W. Irradiation time is preferably 0.1-6
It is 0 minutes, more preferably 1 to 30 minutes. The wavelength of these light sources is not particularly limited, but 170 nm to 600 nm
Those containing a wavelength of nm are preferred.

As the atmosphere during the light treatment, the same atmosphere as that during the above-mentioned heat treatment can be used. The temperature during these light treatments is not particularly limited, but is usually room temperature to 3
It is about 00 ° C. Further, when irradiating light, it may be irradiated through a mask in order to irradiate only a specific part.

In order to obtain a moisture-proof film having a higher moisture-proof property or a high gas-barrier film having a gas barrier property, it is preferable to carry out both the heat treatment and the light treatment. The processing order in that case can be set arbitrarily, and both may be performed simultaneously.

The film thickness of the coating layer (metal oxide film) formed as described above is preferably 0.001 to 10 μm, more preferably 0.005 to 1 μm.

A vapor-deposited film of the above-mentioned inorganic oxide film may be further formed on the upper surface of the coating layer (metal oxide film) formed as described above to obtain a higher quality moisture-proof film. Further, a coating layer (metal oxide film) may be formed on the vapor deposition film thus formed by further repeating the above-mentioned operation. Such lamination can be carried out a plurality of times if necessary.

Further, the coating layer (metal oxide film) as described above and the vapor deposition film provided as necessary may be formed not only on one surface of the substrate but also on both surfaces thereof.

The thus-obtained coating film of the present invention has excellent moisture resistance even under high humidity conditions and also has excellent gas barrier performance, so that it is used as an EL sealing material, solar cell, protective film, moisture resistant film and gas barrier film. Not only is it useful as a packaging material for foods, cigarettes, toiletries, etc.

[0140]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

In the examples, parts and% are based on weight unless otherwise specified. In addition, each evaluation item in the examples was measured according to the following.

Appearance of moisture-proof film The appearance of the moisture-proof film was visually evaluated. Water vapor transmission rate MOCON PERMATR made by Modern Control
The measurement was performed using AN under an atmosphere of a temperature of 40 ° C. and a humidity of 90 RH%. Oxygen permeability Modern Control Co., MOCON OXTRAN2
/ 20 at a temperature of 25 ° C. and a humidity of 90 RH%.

Synthesis Example 1 To a solution of 8.1 g of tantalum pentaethoxide in 67 mL of tetrahydrofuran (THF), a mixed solution of 10 g of triethanolamine and 67 mL of THF was added over 15 minutes while stirring at room temperature under a nitrogen atmosphere. After the addition was completed, the mixture was further stirred for 1 hour at room temperature. The reaction solution changed from colorless and transparent to slightly cloudy. Then, the mixture was concentrated under reduced pressure, the residue was washed with hexane, redissolved in a small amount of tetrahydrofuran, and reprecipitated with hexane. The obtained white solid was filtered off and dried under reduced pressure to obtain a metal-containing product (metal compound). ^When analyzed by ¹ H-NMR, the peak derived from ethoxy of tantalum pentaethoxide disappeared and the peak derived from triethanolamine appeared. The yield was 80%. The reaction conversion rate of the ethoxy group of the raw material tantalum pentaethoxide was 100 mol%. GP
When the number average molecular weight was measured by C analysis, the number average molecular weight was 1,500.

The GPC measurement was carried out under the following conditions (Synthesis examples 2 to 5, 7, 8 and 10 were the same). Solvent: Tetrahydrofuran (THF) Concentration: 0.1 g of metal-containing product (metal compound) dissolved in 10 mL of THF Standard sample: Standard polystyrene apparatus manufactured by Pressure Chemical Co .: High temperature high performance gel permeation chromatograph (Model 1)
500-C ALC / GPC, manufactured by Waters Co., Ltd.) Column: SHOWDEX A-80M manufactured by Showa Denko KK
(Length 50 cm) Measurement temperature: 40 ° C. Flow rate: 1 mL / min FIG. 1 shows a ¹ H-NMR chart.

Synthesis Example 2 In a 200 mL round-bottomed flask that had been sufficiently replaced with nitrogen, 8.12 g of tantalum pentaethoxide (2
0 mmol) and tetrahydrofuran (THF) 50 mL
Then, while stirring, 8.1 g of diethylene glycol (7
6 mmol) was added at room temperature over 15 minutes. Then, the mixture was further stirred at room temperature for 1 hour. The reaction liquid remained colorless and transparent, and the viscosity slightly increased. Then, the solvent was completely removed under reduced pressure to obtain 7.8 g of a white solid (metal-containing product).

As a result of ¹ H-NMR analysis, a peak derived from an unreacted ethoxyl group of tantalum pentaethoxide and a peak derived from a reactant of diethylene glycol were confirmed, and the integration ratio thereof was 1:20. The reaction conversion rate of the ethoxy group of tantalum pentaethoxide was calculated from this ratio, and it was 91 mol%. When the number average molecular weight was measured by GPC analysis, the number average molecular weight was 730. The tantalum content was calculated by elemental analysis and found to be 40.9% by weight. Fig. 2 shows the product ¹ H
-Shows an NMR chart.

Synthesis Example 3 The amount of diethylene glycol was 16.2 g (584 mmo).
The same procedure as in Synthesis Example 2 was carried out except that 1) to obtain 12.5 g of a white solid (metal-containing product). Generated solid
^{As a result of 1} H-NMR analysis, a peak derived from an unreacted ethoxyl group of tantalum pentaethoxide and a peak derived from a reactant with diethylene glycol were confirmed, and the integral ratio thereof was 1:36. The reaction conversion rate of the ethoxy group of tantalum pentaethoxide was calculated from this ratio, and it was 93 mol%. When the number average molecular weight was measured by GPC analysis, the number average molecular weight was 680.
In addition, when the tantalum content rate was calculated by elemental analysis,
It was 25.5% by weight.

Synthesis Example 4 In a 200 mL round-bottomed flask that had been sufficiently replaced with nitrogen, 8.12 g of tantalum pentaethoxide (2
0 mmol) and tetrahydrofuran (THF) 50 mL
Was charged and, under stirring, 5.5 g of hydroquinone (50 mmo
1) was added at room temperature over 15 minutes. At this time, a white solid was precipitated and became cloudy at the same time when the dropping of hydroquinone was started.
Then, the mixture was further stirred at room temperature for 1 hour.

After completion of the reaction, the produced solid was isolated by filtration and the solvent was completely removed under reduced pressure to obtain 8.6 g of a white solid (metal-containing product). The obtained solid is ¹ H-NM
When analyzed by R, a peak derived from an unreacted ethoxyl group of tantalum pentaethoxide and a peak derived from a reactant with hydroquinone were confirmed, and the integral ratio thereof was 1:21.
Met. The reaction conversion rate of the ethoxyl group of tantalum pentaethoxide was calculated from this ratio, and it was 94 mol%. The tantalum content was calculated by elemental analysis to be 39.8% by weight.

Synthesis Example 5 15 g (37 m) of tantalum pentaethoxide was placed in a 300 mL eggplant-shaped flask that had been sufficiently replaced with nitrogen under a nitrogen atmosphere.
mol) and tetrahydrofuran (THF) (150 mL) were charged, the mixture was cooled to 0 ° C., and a solution of 9.8 g (92 mmol) of diethylene glycol in 75 mL of THF was added at room temperature over 1 hour and 30 minutes. After that, 8 more at 0 ℃
Stir for hours. The reaction liquid remained colorless and transparent, and the viscosity slightly increased. Then, the solvent was completely removed under reduced pressure, and the solid was washed with 25 mL of hexane and vacuum dried to obtain 13 g of a white solid.
Got

As a result of ¹ H-NMR analysis, a peak derived from an unreacted ethoxyl group of tantalum pentaethoxide and a peak derived from a reactant of diethylene glycol were confirmed, and the integration ratio thereof was 1:16. When the reaction conversion rate of the ethoxyl group of tantalum pentaethoxide was calculated from this ratio, it was 86 mol%. It was 930 when the number average molecular weight was measured by GPC analysis. FIG. 3 shows the ¹ H-NMR chart of the product.

Synthesis Example 6 A solution of 8.1 g of tantalum pentaisopropoxide in 67 mL of tetrahydrofuran (THF) was added to 10 mL of triethanolamine and 67 mL of THF under a nitrogen atmosphere.
The mixed solution of was added over 15 minutes while stirring at room temperature. After the addition was completed, the mixture was further stirred for 1 hour at room temperature. The reaction solution changed from colorless and transparent to slightly cloudy. Then, the mixture was concentrated under reduced pressure, the residue was washed with hexane, redissolved in a small amount of tetrahydrofuran, and reprecipitated with hexane. The resulting precipitate was filtered off and dried under reduced pressure. ^{When the} product was analyzed by ¹ H-NMR, the peak derived from the isopropoxyl group of tantalum pentaisopropoxide disappeared and the peak derived from triethanolamine appeared. The yield was 85%. The reaction conversion rate of the isopropoxyl group of the raw material tantalum pentaisopropoxide was 100 mol%. When the number average molecular weight was measured by GPC analysis, the number average molecular weight was 1,800.

Synthesis Example 7 In a 200 mL round-bottomed flask that had been sufficiently replaced with nitrogen, under a nitrogen atmosphere, 11 g of tantalum pentab toxide (20 m
mol) and tetrahydrofuran (THF) (50 mL) were charged, and with stirring, hydroquinone (5.5 g, 50 mmol) was added.
Was added at room temperature over 15 minutes. At this time, a white solid was precipitated and became cloudy at the same time when the dropping of hydroquinone was started. Then, the mixture was further stirred at room temperature for 1 hour. After completion of the reaction, the produced solid was isolated by filtration and the solvent was completely removed under reduced pressure to obtain 12 g of a product.

When the obtained product was analyzed by ¹ H-NMR, a peak derived from an unreacted butoxyl group of tantalum pentab toxide and a peak derived from a reaction product of hydroquinone were confirmed, and the integration ratio thereof was 1:21. Met. When the reaction conversion rate of the butoxyl group of tantalum pentab toxide was calculated from this ratio, it was 94 mol%.

Synthesis Example 8 In a 200 mL round-bottomed flask that had been sufficiently replaced with nitrogen, 8.12 g (2% of tantalum pentaethoxide was placed in a nitrogen atmosphere.
0 mmol) and tetrahydrofuran (THF) 50 mL
Then, 5.3 g of diethylene glycol (5
0 mmol) and 50 mL of THF were added at room temperature over 15 minutes. Then, the mixture was further stirred at room temperature for 1 hour. The reaction liquid remained colorless and transparent, and the viscosity slightly increased. Then, the solvent was completely removed under reduced pressure, and a white solid (metal-containing product) 7.
8 g was obtained.

As a result of ¹ H-NMR analysis, a peak derived from an unreacted ethoxyl group of tantalum pentaethoxide and a peak derived from a reactant of diethylene glycol were confirmed, and the integration ratio thereof was 1:20. When the number average molecular weight was measured by GPC analysis, the number average molecular weight was 7
It was 30.

Synthesis Example 9 A white solid (titanium-containing product) was obtained in the same manner as in Synthesis Example 1 except that 8.12 g of tantalum pentaethoxide was replaced with 7.11 g (25.0 mmol) of titanium tetraisopropoxide. 8 g was obtained. Generated solid ¹ H
-When analyzed by NMR, a peak derived from an unreacted propoxyl group of titanium tetraisopropoxide,
A peak derived from the reaction product with diethylene glycol was confirmed, and its integral ratio was 1:36. When the number average molecular weight was measured by GPC analysis, the number average molecular weight was 680.
Met.

Synthesis Example 10 The procedure of Synthesis Example 1 was repeated except that tantalum pentaethoxide (8.12 g) was changed to zirconium butoxide (9.59 g, 25.0 mmol) to obtain 8.5 g of a white solid (zirconium-containing product). It was ¹ H-NMR of the produced solid
As a result of analysis, a peak derived from an unreacted butoxy group of zirconium butoxide and a peak derived from a reactant with diethylene glycol can be confirmed, and the integral ratio thereof is 1: 2.
It was 5. When the number average molecular weight was measured by GPC analysis, the number average molecular weight was 900.

Synthesis Example 11 The procedure of Synthesis Example 1 was repeated except that 8.12 g of tantalum pentaethoxide was changed to 6.74 g (33.3 mmol) of aluminum isopropoxide, and 6.5 g of a white solid (aluminum-containing product). Got ¹ H-
When analyzed by NMR, a peak derived from an unreacted isopropoxyl group of aluminum isopropoxide and a peak derived from a reactant with diethylene glycol were confirmed, and the integration ratio thereof was 1:30. When the number average molecular weight was measured by GPC analysis, the number average molecular weight was 750.
Met.

Synthesis Example 12 A white solid (silicon-containing product) was prepared in the same manner as in Synthesis Example 1 except that 8.12 g of tantalum pentaethoxide was replaced with 5.21 g (25.0 mmol) of tetraethoxysilane.
5.0 g was obtained. When the produced solid was analyzed by ¹ H-NMR, a peak derived from an unreacted ethoxyl group of tetraethoxysilane and a peak derived from a reactant with diethylene glycol were confirmed, and the integral ratio thereof was 1:25. When the number average molecular weight was measured by GPC analysis,
The number average molecular weight was 830.

Examples 1 to 4 5 g of the metal-containing products obtained in Synthetic Examples 1 to 4 were dissolved in 95 g of propylene glycol monomethyl ether, and then filtered with a 0.1 μm Teflon (registered trademark) filter to obtain coating. Compositions (A)-(D) were prepared.

Examples 5 to 7 After dissolving 5 g of the metal-containing product obtained in each of Synthesis examples 5 to 7 in 95 g of propylene glycol monopropyl ether, it was filtered with a Teflon (registered trademark) filter having a thickness of 0.1 μm. Coating compositions (E) to (G)
Was prepared.

Examples 8 to 14 Coating compositions (A) obtained in Examples 1 to 7
(G) is a polychlorotrifluoroethylene (PCTF) having a film thickness of 50 μm in an atmosphere of a humidity of 3 g / m ^3.
E) After coating on a film with a gravure coater and drying with a hot air dryer at 120 ° C. for 1 minute, a high pressure mercury lamp was irradiated for 1 minute to form a coating film with a thickness of 0.5 μm, and a film was obtained. . The water vapor transmission rate and oxygen transmission rate of the obtained film were measured. The transparency of the film was evaluated by visual observation. The results are shown in Table 1.

Comparative Example 1 Polychlorotrifluoroethylene (PC with a film thickness of 50 μm
The water vapor transmission rate and oxygen transmission rate of the TFE) film were measured. The transparency of this film was evaluated by visual observation. The results are shown in Table 1.

[0165]

[Table 1]

In Table 1, the units of water vapor transmission rate and oxygen transmission rate are both cc / m ² · atm · 24h. Further, the water vapor transmission rates of Examples 8 to 14 were below the measurement detection limit.

Examples 15 to 21 Coating compositions (A) obtained in Examples 1 to 7
Indium-tin complex oxide (IT) was formed on a polyethylene terephthalate (PET) film having a film thickness of 38 μm under the atmosphere of (G) and humidity of 3 g / m ^3.
O) was vacuum-deposited to a thickness of 100 nm on a vapor-deposited film, which was applied by a gravure coater and dried by a hot air dryer at 120 ° C. for 1 minute, and then a high pressure mercury lamp was turned on.
It was irradiated for minutes to form a coating film having a thickness of 0.5 μm to obtain a film. The water vapor transmission rate and oxygen transmission rate of the obtained film were measured. In addition, the transparency of the coating film was evaluated by visual observation. The results are shown in Table 2.

Comparative Example 2 Polyethylene terephthalate (PET) having a film thickness of 38 μm
On-Film The indium-tin composite oxide (ITO) was vacuum-deposited on the film to a thickness of 100 nm to measure the water vapor transmission rate and oxygen transmission rate of the vapor-deposited film. Also,
The transparency of the coating film was evaluated by visual observation. The results are shown in Table 2.

[0169]

[Table 2]

In Table 2, the units of water vapor transmission rate and oxygen transmission rate are both cc / m ² · atm · 24h. Further, the water vapor transmission rates of Examples 15 to 21 were below the measurement detection limit.

Examples 22 to 26 5 g of the metal-containing products obtained in Synthesis Examples 8 to 12 were dissolved in 95 g of propylene glycol monomethyl ether, and the mixture was filtered through a 0.1 μm Teflon (registered trademark) filter to obtain a coating. Compositions (H)-(L) were prepared.

Example 27 5 g of the metal-containing product obtained in Synthesis Example 8 and 3 g of methyl orthoformate were dissolved in 95 g of propylene glycol monomethyl ether, and then filtered through a 0.1 μm Teflon (registered trademark) filter, Coating composition (M)
Was prepared.

Examples 28 to 32 The coating compositions (H) to (L) obtained in Examples 22 to 26 were each subjected to a humidity of 3 g / m ^{3 in} an atmosphere of polychlorotrifluoroethylene having a film thickness of 50 μm. A (PCTFE) film was coated with a gravure coater and dried with a hot air drier at 120 ° C. for 1 minute, followed by irradiation with a high pressure mercury lamp for 1 minute to form a coating film having a thickness of 0.5 μm. It was The water vapor transmission rate and oxygen transmission rate of the obtained film were measured. The transparency of the film was evaluated by visual observation. The results are shown in Table 3.

Example 33 A film was formed in the same manner as in Example 28 except that the coating composition (M) obtained in Example 27 was used to form a film in an atmosphere having a humidity of 7 g / m ^3. ,evaluated. The results are shown in Table 3.

[0175]

[Table 3]

In Table 3, the units of water vapor transmission rate and oxygen transmission rate are both cc / m ² · atm · 24h. Further, the water vapor transmission rates of Examples 28 to 33 were below the measurement detection limit.

Examples 34 to 38 Examples 22 to 26 Coating compositions obtained (H)
To (L) in an atmosphere of a humidity of 3 g / m ³ on a polyethylene terephthalate (PET) film having a film thickness of 38 μm on the indium tin complex oxide (I).
(TO) was applied on a vapor-deposited film vacuum-deposited to a thickness of 100 nm with a gravure coater and dried with a hot air dryer at 120 ° C. for 1 minute, and then irradiated with a high pressure mercury lamp for 1 minute to form a film thickness of 0.5 μm. The coating film of was formed to obtain a film. The water vapor transmission rate and oxygen transmission rate of the obtained film were measured. In addition, the transparency of the coating film was evaluated by visual observation. The results are shown in Table 4.

Example 39 A film was formed in the same manner as in Example 34 except that the coating composition (M) obtained in Example 27 was used to form a film in an atmosphere having a humidity of 7 g / m ^3. ,evaluated. The results are shown in Table 4.

[0179]

[Table 4]

In Table 4, the units of water vapor transmission rate and oxygen transmission rate are both cc / m ² · atm · 24h. In addition, the water vapor transmission rates of Examples 34 to 39 were below the measurement detection limit.

[0181]

Industrial Applicability According to the present invention, there are provided a moisture-proof film having excellent moisture-proof property and a gas-barrier film having excellent gas-barrier property, and a coating composition for use therein.

[Brief description of drawings]

FIG. 1 ¹ H—N of a metal-containing product obtained in Synthesis Example 1
MR chart.

FIG. 2 ¹ H—N of the metal-containing product obtained in Synthesis Example 2
MR chart.

FIG. 3 ¹ H—N of the metal-containing product obtained in Synthesis Example 5
MR chart.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hitoshi Kato             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. (72) Inventor Isamu Yonekura             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. F-term (reference) 4F100 AA01A AA01C AA17C AH08A                       AK01B AK17 AT00B BA02                       BA03 BA07 BA10A BA10C                       DE01A EH46A EH66C JD02A                       JD04A                 4J038 CL011 DL021 DL031 DL071                       DL081 DM021 HA166 HA316                       HA446 HA476 JA12 JA39                       JA55 JA59 JB34 KA06 KA08                       KA20 MA06 NA04 NA08 PB01                       PB04 PB09

Claims (9)

[Claims] 1. A coating composition containing a metal-containing product and a solvent, wherein the metal-containing product has the following [A:
1] and at least one selected from the group consisting of [A2]. [A1]; Reaction product of the following component (a1) and component (a2), (a1): at least one compound selected from the following and, metal alkoxide, β-diketone, β-ketoester, β-dicarboxylic acid A reaction product of a metal alkoxide with at least one compound selected from the group consisting of ester, lactic acid, ethyl lactate and 1,5-cyclooctadiene, (a2); having an amino alcohol and two or more hydroxyl groups in the molecule At least one compound selected from compounds (excluding amino alcohols), [A2]; a hydrolyzate of the reaction product of the above [A1]. 2. The coating composition according to claim 1, wherein the metal alkoxide is at least one selected from the group consisting of tantalum alkoxide, titanium alkoxide, aluminum alkoxide, silane alkoxide and zirconium alkoxide. 3. The coating composition according to claim 1, further comprising inorganic particles. 4. A moisture-proof coating.
The coating composition according to any one of 1. 5. A moisture-proof film having a coating film formed from the composition according to claim 4 on a substrate. 6. The moisture-proof film according to claim 5, wherein the substrate is a resin film or a resin film on which a vapor deposition film of an inorganic oxide is formed. 7. The coating composition according to claim 1, which is used for gas barrier coating. 8. A gas barrier film having a coating film formed from the composition according to claim 7 on a substrate. 9. The gas barrier film according to claim 8, wherein the substrate is a resin film or a resin film on which a vapor deposition film of an inorganic oxide is formed.