JP2003301109A - Film forming composition and gas barrier film using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sol-gel process that forms a film having uniform film quality and excellence in strength and that is capable of forming the film having high barrier properties. <P>SOLUTION: The sol-gel process is conducted using a sol solution comprising a hydrolized partial condensation product of a metal alkoxide and an amine compound having a particular structure. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a sol-gel method in which gelation proceeds in a short time and forms a dry gel having an improved film quality, and more particularly to an additive used in the sol-gel method. It also relates to a gas barrier film in which the gas barrier property is remarkably improved by using this sol-gel method. INDUSTRIAL APPLICABILITY The present invention is suitably used for applications such as organic EL materials and packaging materials that require high gas barrier properties.

[0002]

2. Description of the Related Art In recent years, the sol-gel method has attracted attention as a basic reaction of organic / inorganic hybrid technology. In this method, the metal alkoxide is hydrolyzed and polycondensed to form a polymer. However, when these reactions are performed, an extremely long reaction time of 24 to 700 hours is required, and when used in a film form, a sintering process at a high temperature of 400 ° C. or higher is required, which is extremely severe. The reaction must be carried out under the conditions.

In order to avoid the reaction under such severe conditions, JP-A-60-27611 and JP-A-60-
Japanese Patent Laid-Open No. 215532 and Japanese Patent Laid-Open No. 63-229146 disclose a technique in which a catalyst or the like is used in combination. According to these methods, a certain effect is recognized, but the uniformity of the prepared dry gel is not sufficient, and there is a problem in the film quality (cracks,
Cracks, etc.), and further improvements have been desired.

On the other hand, in recent years, electroluminescence (E
The L) element has come to be widely used for pixels of a display, a back light source of a liquid crystal display, and the like, taking advantage of high visibility due to self-coloring. However, in all of these devices, deterioration of durability due to moisture and oxygen has been a serious problem in practical use. As a means for coping with this problem, a technique for producing a gas barrier layer by using the sol-gel method is disclosed in JP-A-2000-32327.
It is disclosed in Japanese Patent No. 3 and 2001-148287. However, even if these techniques are used, the gas barrier property cannot be said to be sufficient, and there are also problems with the uniformity and film quality associated with the sol-gel method described above, and further improvement in performance is desired. It was

[0005]

In view of these circumstances of the prior art, the present invention provides a sol-gel method capable of forming a film having uniform film quality, excellent strength, and high gas barrier property. Aimed at. In particular, it was an object to provide an additive for the sol-gel method that enables the formation of such an excellent film.

[0006]

As a result of intensive studies, the present inventor has found that the object can be achieved by the present invention described below. [1] A sol liquid containing a hydrolyzed partial condensate of a metal alkoxide and a compound represented by the following general formula (1).

[Chemical 3] [R ¹ and R ² each independently represent a hydrogen atom, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic sulfonyl group or an aromatic sulfonyl group, and R ³ is an aliphatic group. Group, aliphatic oxy group, aromatic group,
It represents an aromatic oxy group, an aliphatic thio group, an aromatic thio group, an acyloxy group, an aliphatic oxycarbonyloxy group, an aromatic oxycarbonyloxy group, a substituted amino group, a heterocyclic group or a hydroxy group. However, when R ³ is not an aromatic group, at least one of R ¹ and R ² is a hydrogen atom. ]

[1a] The sol liquid according to [1], wherein the compound represented by the general formula (1) is represented by the following general formula (2).

[Chemical 4] [R ^{1 ′} and R ^{2 ′} each independently represent a hydrogen atom, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic sulfonyl group or an aromatic sulfonyl group, and R ⁴ is Aliphatic group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, acyloxy group,
It represents an aliphatic oxycarbonyloxy group, an aromatic oxycarbonyloxy group, a substituted amino group, a heterocyclic group or a hydroxy group. Moreover, n represents the integer of 1-5. ]

[2] A film-forming composition containing a metal alkoxide, an acid, and a compound represented by the above general formula (1). [2a] The film forming composition as described in [2], wherein the compound represented by the general formula (1) is represented by the following general formula (2). [3] A method of forming a film by a sol-gel method using the sol solution according to [1] or the film-forming composition according to [2]. [3a] The method according to [3], wherein the compound represented by the general formula (1) is represented by the general formula (2). [3b] A film produced by the method described in [3] or [3a]. [3c] A gas barrier film produced by the method described in [3] or [3a]. [4] A gas barrier film formed by coating the composition for film formation according to [2] on a support. [5] Organic E having the gas barrier film according to [4]
L material. [5a] An organic EL panel having the gas barrier film according to [4]. [6] In a method of forming a film by a sol-gel method using a sol solution containing a hydrolyzed partial condensate of a metal alkoxide, the gas barrier property improvement added to the sol solution in order to enhance the gas barrier property of the film. An agent for improving gas barrier properties, which comprises a compound represented by the above general formula (1). [6a] The gas barrier property improving agent according to [6], wherein the compound represented by the general formula (1) is represented by the general formula (2).

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below. In addition, in this specification, "-" is used by the meaning including the numerical value described before and after that as a lower limit and an upper limit.

The present invention is characterized by using a compound represented by the general formula (1). In formula (1), R ¹ and R ² are each independently a hydrogen atom, an aliphatic group (eg, methyl group, ethyl group, tert-butyl group, octyl group, methoxyethoxy group), acyl group (eg, acetyl group, Pivaloyl group, methacryloyl group), aliphatic oxycarbonyl group (eg methoxycarbonyl group, hexadecyloxycarbonyl group), aromatic oxycarbonyl group (eg phenoxycarbonyl group), aliphatic sulfonyl group (eg methanesulfonyl group, butanesulfonyl group) ), Or an aromatic sulfonyl group (for example, a benzenesulfonyl group)
And R ³ is an aliphatic group (eg, methyl group, ethyl group,
tert-butyl group, octyl group), aliphatic oxy group (eg methoxy group, methoxyethoxy group, octyloxy group), aromatic group (eg phenyl group, substituted phenyl group), aromatic oxy group (eg phenoxy group, p -Methoxyphenoxy group), aliphatic thio group (for example, methylthio group, octylthio group), aromatic thio group (for example, phenylthio group, p-methoxyphenylthio group), acyloxy group (for example, acetoxy group, pivaloyloxy group), aliphatic oxy Carbonyloxy group (for example, methoxycarbonyloxy group, octyloxycarbonyloxy group), aromatic oxycarbonyloxy group (for example, phenoxycarbonyloxy group), substituted amino group (as long as the substituent is substitutable, for example, aliphatic group, Aromatic group, acyl group, aliphatic sulfonyl , Amino group substituted with an aromatic sulfonyl group, etc.), a Hajime Tamaki (e.g. piperidine ring represents a thiomorpholine ring), or hydroxy group. If possible, R ¹ and R ² , R ¹ and R ³ , R ² and R ³ are bonded to each other,
A 5- to 7-membered ring (eg piperidine ring, pyrazolidine ring) may be formed. However, never both of R ^1, R ² is a hydrogen atom, the total number of carbon atoms of R ¹ and R ² is 5 or more. When R ³ does not contain an aromatic group, at least one of R ¹ and R ² is a hydrogen atom.

Among the compounds represented by the general formula (1), the compound represented by the general formula (2) is particularly preferable. In the general formula (2), R ^{1 ′} and R ^{2 ′} have the same ^{meanings as} in the general formula (1), and R ⁴ is an aliphatic group (eg, methyl group, ethyl group, tert-butyl group, octyl group), fat Group oxy groups (eg methoxy group, methoxyethoxy group, octyloxy group), aromatic oxy groups (eg phenoxy group,
p-methoxyphenoxy group), aliphatic thio group (eg methylthio group, octylthio group), aromatic thio group (eg phenylthio group, p-methoxyphenylthio group), acyloxy group (eg acetoxy group, pivaloyloxy group), aliphatic Oxycarbonyloxy group (eg, methoxycarbonyloxy group, octyloxycarbonyloxy group), aromatic oxycarbonyloxy group (eg, phenoxycarbonyloxy group), substituted amino group (substituent may be any substituent, for example, aliphatic group , An aromatic group, an acyl group, an aliphatic sulfonyl group, a substituted amino group such as an aromatic sulfonyl group), a heterocyclic group (for example, a piperidine ring, a thiomorpholine ring), or a hydroxy group.

In the present invention, only one compound represented by the general formula (1) may be used, or two or more compounds represented by the general formula (1) may be used in combination. The total amount of the compound represented by the general formula (1) used is 0.1 to 20 mol%, preferably 0.1 to 2 mol% per mol of the metal alkoxide.

Specific examples of the compound represented by the general formula (1) are shown below, but the compound of the general formula (1) usable in the present invention is not limited to these.

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

(A) Metal Alkoxide Next, the metal alkoxide used in the present invention will be described. The metal alkoxide that can be used in the present invention is
It can be selected from a wide range of metal alkoxides that can be used in the sol-gel method. An organosilane compound can be mentioned as a typical metal alkoxide.

Examples of the organosilane compound that can be used in the present invention include compounds represented by the following general formula. Si (OR ¹⁴ ) _x (R ¹⁵ ) _{4-X In the} above formula, R ¹⁴ is preferably an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, n- Propyl group, i-propyl group, n-
Examples thereof include a butyl group, a sec-butyl group, a tert-butyl group and an acetyl group. Further, R ¹⁵ is a carbon number of 1 to
10 organic groups are preferred, such as methyl, ethyl,
n-propyl group, i-propyl group, n-butyl group, te
rt-butyl group, n-hexyl group, cyclohexyl group,
Unsubstituted hydrocarbon groups such as n-octyl group, tert-octyl group, n-decyl group, phenyl, vinyl group, allyl group, etc., γ-chloropropyl group, CF ₃ CH ₂ —, CF
_{3 CH 2 CH 2 -, C} 2 F 5 CH 2 CH 2 -, C 3 F 7 CH 2 CH
_{2 CH 2 -, CF 3 OCH} 2 CH 2 CH 2 -, C 2 F 5 OCH 2
_{CH 2 CH 2 -, C 3} F 7 OCH 2 CH 2 CH 2 -, (CF 3)
₂ CHOCH ₂ CH ₂ CH ₂ —, C ₄ F ₉ CH ₂ OCH ₂ CH ₂
CH ₂ -, 3- (perfluoro-cyclohexyloxy)
_{Propyl, H (CF 2) 4 CH} 2 OCH 2 CH 2 CH 2 -,
H (CF ₂ ) ₄ CH ₂ CH ₂ CH ₂ —, a substituted hydrocarbon group such as γ-glycidoxypropyl group, γ-mercaptopropyl group, 3,4-epoxycyclohexylethyl group, γ-methacryloyloxypropyl group Can be mentioned. x is 2
It is preferably an integer from 4 to 4.

Specific examples of these organosilane compounds are shown below. Examples of x = 4 (hereinafter referred to as a tetrafunctional organosilane compound) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane and tetra-acetoxysilane. And so on.

X = 3 (hereinafter trifunctional organosilane
(Referred to as a compound), methyltrimethoxysilane,
Methyltriethoxysilane, ethyltrimethoxysila
, Ethyltriethoxysilane, n-propyltrimetho
Xysilane, n-propyltriethoxysilane, i-type
Ropyltrimethoxysilane, i-propyltriethoxy
Silane, γ-chloropropyltrimethoxysilane, γ-
Chloropropyltriethoxysilane, γ-glycidoxy
Propyltrimethoxysilane, γ-glycidoxypropyi
Lutriethoxysilane, γ-methacryloyloxypro
Pyrtrimethoxysilane, γ-mercaptopropyltri
Ethoxysilane, phenyltrimethoxysilane, vinyl
Triethoxysilane, 3,4-epoxycyclohexyl
Ethyltrimethoxysilane, 3,4-epoxycyclohexyl
Xylethyltriethoxysilane, CF₃CH₂CH₂S
i (OCH₃)₃, C₂F_FiveCH₂CH₂Si (OCH₃)₃,
C₂F _FiveOCH₂CH₂CH₂Si (OCH₃)₃, C₃F₇O
CH₂CH₂CH₂Si (OC₂H _Five)₃, (CF₃)₂CHO
CH₂CH₂CH₂Si (OCH₃)₃, C_FourF₉CH₂OCH
₂CH₂CH₂Si (OCH₃)₃, H (CF₂)_FourCH₂OC
H₂CH₂CH₂Si (OCH₃)₃, 3- (perfluoro
Cyclohexyloxy) propyltrimethoxysilane, etc.
Can be mentioned.

X = 2 (hereinafter bifunctional organosilane
), Dimethyldimethoxysilane,
Dimethyldiethoxysilane, methylphenyldimethoxy
Silane, diethyldimethoxysilane, diethyldioxy
Sisilane, di-n-propyldimethoxysilane, di-n
-Propyldiethoxysilane, di-i-propyldimeth
Xysilane, di-i-propyldiethoxysilane, dif
Phenyldimethoxysilane, divinyldiethoxysilane,
(CF₃CH₂CH₂)₂Si (OCH₃)₂, (C ₃F₇OC
H₂CH₂CH₂)₂Si (OCH₃)₂, [H (CF₂)₆C
H₂OCH₂CH ₂CH₂]₂Si (OCH₃)₂, (C₂F_Five
CH₂CH₂)₂Si (OCH₃)₂Etc.
Wear.

When the above-mentioned bifunctional or trifunctional organosilane compound is used, an organosilane compound having a fluorine atom in R ¹⁵ is preferable from the viewpoint of refractive index. Also, R
^{When an} organosilane compound having no fluorine atom is used as ¹⁵ , methyltrimethoxysilane or methyltriethoxysilane is preferably used.

The above organosilane compounds may be used alone or in combination of two or more.
When two or more kinds of the above-mentioned organosilane compounds are used in combination, the proportion of the bifunctional organosilane compound in the composition is 0 to 150% by mass, preferably 5 to 5 mass% with respect to the tetrafunctional organosilane compound and the trifunctional organosilane compound. -100% by mass, more preferably 10-60% by mass
Is.

The sol solution of the present invention contains a hydrolyzed partial condensate of a metal alkoxide and a compound represented by the general formula (1). The hydrolyzed partial condensate of metal alkoxide can be produced by a known method described later. The sol liquid of the present invention can be obtained, for example, by adding the compound represented by the general formula (1) to a dispersion liquid of a hydrolyzed partial condensate of a metal alkoxide.

In the sol-gel method using the sol liquid of the present invention, various materials can be used as additives. For example, a silyl group-containing polymer, a sol-gel catalyst (hydrolysis / condensation catalyst), a solvent, a chelate ligand compound, water, a filler and the like can be appropriately used according to the purpose. These materials may be added to the gel of the present invention or may be added during the step of the sol-gel method. Further, it may be added to the gas barrier property improving agent of the present invention containing the compound of the general formula (1). Hereinafter, these additives will be described in order. In the following description, the case where an alkoxysilane compound is used as the metal alkoxide as the component (a) will be described as an example.

(B) Silyl Group-Containing Polymer The silyl group-containing polymer comprises a main chain polymer, and one molecule of a polymer having a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at the terminal or side chain. At least one, preferably two or more are contained therein, and a preferable structure of the silyl group is represented by the following general formula. —Si (R ¹⁶ ) _3-a (X) _a (In the formula, X is a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group,
A hydrolyzable group such as an amino group and / or a hydroxyl group, R ¹⁶ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and a is 1 to 3
Is an integer).

Particularly preferred as the silyl group-containing polymer is a silyl group-containing vinyl polymer whose main chain is a vinyl polymer. Generally, these can be easily synthesized by the following method. The manufacturing method is not limited to these methods. (A) A hydrosilane compound is reacted with a vinyl polymer having a carbon-carbon double bond. (B) The following general formula: R ¹⁸ —Si (R ¹⁷ ) _3-a (X) a (In the formula, X is a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group,
A hydrolyzable group such as an amino group and / or a hydroxyl group, R ¹⁷ has the same meaning as R ¹⁶ , R ¹⁷ is an organic group having a polymerizable double bond, and a is an integer of 1 to 3. )
The silane compound represented by and various vinyl compounds are polymerized.

Examples of the hydrosilane compound used in the production method (a) above include halogenated silanes such as methyldichlorosilane, trichlorosilane and phenyldichlorosilane; methyldiethoxysilane and methyldiethoxysilane. Alkoxysilanes such as dimethoxysilane, phenyldimethoxysilane, trimethoxysilane and triethoxysilane; Acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane and triacetoxysilane; Methyldiaminoxysilane, triaminoxysilane, Examples thereof include aminosilanes such as dimethylaminoxysilane and triaminosilane.

The vinyl polymer used in the production method (a) is not particularly limited except for the vinyl polymer having a hydroxyl group, and examples thereof include methyl (meth) acrylate and ethyl (meth) acrylate. , Butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth)
(Meth) acrylic acid ester such as acrylate and cyclohexyl (meth) acrylate; carboxylic acid such as (meth) acrylic acid, itaconic acid, fumaric acid and acid anhydride such as maleic anhydride; epoxy compound such as glycidyl (meth) acrylate Amino compounds such as diethylaminoethyl (meth) acrylate and aminoethyl vinyl ether; (meth) acrylamide, N-te
Amide compounds such as rt-butyl (meth) acrylamide, itaconic acid diamide, α-ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl (meth) acrylamide; acrylonitrile, styrene, vinyltoluene, α- A vinyl polymer obtained by copolymerizing a vinyl compound selected from methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate, N-vinylpyrrolidone, etc. with a monomer having a double bond in the side chain such as allyl methacrylate is preferable. It is particularly preferable to use at least one fluorine-containing monomer as the polymerization monomer. On the other hand, examples of the silane compound used in the production method shown in (B) include [Chemical Formula 5] described in JP 2001-42102 A.

Further, as the vinyl compound used in the production method shown in (b), it is possible to use the vinyl compound used in the polymerization of the vinyl polymer in the production method of (a) above. In addition to the method described in (a), vinyl compounds containing hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyvinyl ether, and N-methylolacrylamide. You can also mention Further, one using one type of fluorine-containing monomer is particularly preferable.

Specific preferred examples of the vinyl polymer containing a silyl group as described above include acrylic polymers containing a trialkoxysilyl group represented by the following general formula.

[0032]

[Chemical 8]

In the formula, R ⁵ and R ⁷ are each independently a hydrogen atom, a fluorine atom or a methyl group, R ⁶ is a hydrogen atom and has 1 to 1 carbon atoms.
12 alkyl groups (eg, methyl group, ethyl group, n-
Propyl group, allyl group, n-butyl group, i-butyl group,
n-pentyl group, n-hexyl group, benzyl group, (CF
_{3) 2 CH-, CF 3 CH} 2 -, C 7 F 15 CH 2 -, C 2 F 5 C
H ₂ CH ₂ — and the like (an alkyl group containing a fluorine atom described in the component (a)), R ⁸ is a methylene group, an ethylene group,
It represents an alkylene group having 1 to 4 carbon atoms such as a propylene group and a butylene group, R ⁹ has the same meaning as R ¹ described above, and n / (m
+ N) = 0.01 to 0.4, preferably 0.02 to 0.
It is 2. The number average molecular weight of this silyl group-containing vinyl polymer is preferably 2,000 to 100,000, more preferably 4,000 to 50,000.

Specific examples of the silyl group-containing vinyl polymer preferably used in the present invention include Kanefuchi Chemical Industry Co., Ltd.
Examples include Kaneka Zemulac manufactured and the following polymers, but the silyl group-containing vinyl polymer that can be used in the present invention is not limited thereto.

P-1 Methylmethacrylate / γ-acryloxypropyltrimethoxysilane (80/20: mass ratio) P-2 Methylmethacrylate / γ-methacryloxypropyltrimethoxysilane (85/15: mass ratio) P-3 Methyl methacrylate / ethyl acrylate /
γ-methacryloxypropyltrimethoxysilane (50
/ 40/10: mass ratio) P-4 FM-4 / γ-methacryloxypropyltrimethoxysilane (90/10: mass ratio) P-5 FM-1 / γ-methacryloxypropyltrimethoxysilane (80/20 : Mass ratio) P-6 FM-4 / FM-7 / γ-methacryloxypropyltrimethoxysilane (50/40/10: mass ratio) P-7 methyl methacrylate / methyl acrylate /
γ-acryloxypropyltrimethoxysilane (60 /
25/15: mass ratio) P-8 FM-4 / methyl methacrylate / γ-methacryloxypropyltrimethoxysilane (70/25 /
5: mass ratio) P-9 FM-5 / methyl methacrylate / γ-acryloxypropyltrimethoxysilane (70/20/1
0: mass ratio)

[0036]

[Chemical 9]

The proportion of the silyl group-containing polymer in the composition is preferably 1 to 200% by mass, more preferably 3 to 100% by mass, based on the total organosilane compound used.
More preferably, it is 5 to 50 mass%.

Preferred combinations of the above-mentioned components (a) and (b) in the present invention are exemplified below. The mixing ratio indicates the mass (g) of each compound used. In the present invention, in the following description, the coating composition of the hydrolyzed partial condensate of the organosilane compound is referred to as "sol solution", and the hydrolyzed partial condensation reaction of the organosilane compound for preparing the sol solution is referred to as "sol-gelation". ". In sol-gel formation (a)
The component is an essential component, and the component (b) may be used together in the sol-gel formation, or may be added to the prepared sol solution.

SP-1 Hydrofluoric / partial condensate of 25 g of trifluoropropyltrimethoxysilane and 25 g of tetraethoxysilane SP-2 5 g of tetraethoxysilane, 10 g of trifluoropropyltrimethoxysilane, 1H, 1H, 2H, 2H-per Hydrolysis / partial condensate SP-3 of fluorodecyltrimethoxysilane 3g 8g of trifluoropropyltrimethoxysilane, 5g of tetraethoxysilane, hydrolyzation / partial condensate of methylg of trimethoxysilane 2g SP-4 tetraethoxysilane 20g, tri Hydrolysis / partial condensate of fluoropropyltrimethoxysilane 200 g, bis (trifluoropropyl) dimethoxysilane 10 g SP-5 tetraethoxysilane 10 g, trifluoropropyltrimethoxysilane 8 g, bis (trifluoro) Propyl)
Dimethoxysilane 5g, Methyltrimethoxysilane 3
g, hydrolysis-partial condensate 2g of dimethyldimethoxysilane SP-6 22g of trifluoropropyltrimethoxysilane, 3g of divinyldimethoxysilane, 10g of the compound of P-6
Hydrolysis, partial condensate SP-7 trifluoropropyltrimethoxysilane 20 g, tetraethoxysilane 3 g, the above-mentioned P-6 compound 6 g hydrolysis / partial condensate SP-8 trifluoropropyltrimethoxysilane 10 g, vinyltri Hydrolysis and partial condensate of 5 g of methoxysilane and 1
H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane 3g, hydrolysis and partial condensate SP-9 tetraethoxysilane 15g, pentafluorobutyltrimethoxysilane 10g, compound P- Compound 3 of 5
g of hydrolysis / partial condensate SP-10 tetraethoxysilane 15 g, bis (trifluoropropyl) diethoxysilane 20 g, compound 3 of P-2 above
g hydrolysis / partial condensate

(C) Sol-Gel Catalyst Various catalyst compounds can be preferably used in the sol solution of the present invention for the purpose of promoting the hydrolysis / partial condensation reaction of the organosilane compound. The catalyst used is not particularly limited and may be used in an appropriate amount according to the constituent components of the sol liquid used. Generally effective are the following (c1) to (c
It is the compound of 5), and preferable compounds can be added in the required amount among these. Also, 2 of these groups
One or more kinds can be appropriately selected and used in combination within a range where the promoting effects of each other are not hindered.

(C1) Organic or inorganic acid As the inorganic acid, hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid,
Organic acid compounds such as sulfurous acid, nitric acid, nitrous acid, phosphoric acid, and phosphorous acid are carboxylic acids (formic acid, acetic acid, propionic acid,
Butyric acid, succinic acid, cyclohexanecarboxylic acid, octanoic acid, maleic acid, 2-chloropropionic acid, cyanoacetic acid, trifluoroacetic acid, perfluorooctanoic acid, benzoic acid, pentafluorobenzoic acid, phthalic acid, etc., sulfonic acids (methane Sulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid), p-toluenesulfonic acid, pentafluorobenzenesulfonic acid, etc.), phosphoric acid
Phosphonic acids (phosphoric acid dimethyl ester, phenylphosphonic acid, etc.), Lewis acids (boron trifluoride etherate, scandium triflate, alkyl titanic acid, aluminate, etc.), heteropoly acids (phosphomolybdic acid, phosphotungstic acid, etc.) You can

(C2) Organic or Inorganic Base As the inorganic base, sodium hydroxide, potassium hydroxide,
Examples of organic base compounds such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and ammonia include amines (ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, triethylamine, dibutylamine, tetramethylethylenediamine, piperidine, piperazine, morpholine. , Ethanolamine, diazabicycloundecene, quinuclidine, aniline, pyridine, etc.), phosphines (triphenylphosphine, trimethylphosphine, etc.), and metal alkoxides (sodium methylate, potassium ethylate, etc.).

(C3) Metal chelate compound General formula R^TenOH (in the formula, R^TenIs alkyl having 1 to 6 carbon atoms
Group), an alcohol represented by¹¹COCH₂C
OR¹²(In the formula, R¹¹Is an alkyl group having 1 to 6 carbon atoms, R¹²
Is an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 16 carbon atoms.
A diketone represented by the formula
In addition, if the metal is a central metal, there is no particular limitation.
It can be used appropriately. 2 or more in this category
You may use together the metal chelate compound of. The metal of the present invention
Especially preferred as the chelate compound is A as the central metal.
It has the general formula Zr (OR
^Ten) _p1(R¹¹COCHCOR¹²)_p2, Ti (OR^Ten)_q1
(R¹¹COCHCOR¹²)_q2And Al (OR^Ten)_r1
(R¹¹COCHCOR¹²)_r2Selected from the compound group represented by
Preferred are the above components (a) and (b)
Acts to accelerate the condensation reaction of.

R ¹⁰ and R in the metal chelate compound
¹¹ may be the same or different and may be an alkyl group having 1 to 6 carbon atoms, specifically, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-
Examples thereof include a butyl group, an n-pentyl group and a phenyl group. R ¹² is an alkyl group having 1 to 6 carbon atoms as described above, or an alkoxy group having 1 to 16 carbon atoms, for example, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group. Group, sec-butoxy group, tert-
Examples include butoxy group, lauryl group and stearyl group. In addition, p1, p2, q1, q in the metal chelate compound
2, r1 and r2 represent integers determined so as to have a 4- or 6-dentate coordination.

Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium and tetrakis (n). -Propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium chelate compounds such as diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium , Titanium chelate compounds such as diisopropoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum , Diisopropoxy acetylacetonate aluminum, diisopropoxy bis (ethylacetoacetate) aluminum, diisopropoxy bis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, mono-acetylacetonate ·
An aluminum chelate compound such as bis (ethylacetoacetate) aluminum may be used. Preferred among these metal chelate compounds are tri-n-
Butoxyethyl acetoacetate zirconium, diisopropoxy bis (acetylacetonato) titanium,
Diisopropoxyethyl acetoacetate aluminum and tris (ethylacetoacetate) aluminum. These metal chelate compounds can be used alone or in combination of two or more. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

(C4) Organometallic compound The preferred organometallic compound is not particularly limited, but
Organic transition metals are preferable because they have high activity. Above all
Tin compounds are particularly preferred due to their good stability and activity.
Yes. Specific examples of these compounds include (C_FourH₉)₂S
n (OCOC₁₁H_{2 3})₂, (C_FourH₉)₂Sn (OCOCH
= CHCOOC_FourH₉)₂, (C₈H₁₇)₂Sn (OCOC
₁₁H_{twenty three})₂, (C₈H₁₇)₂Sn (OCOCH = CHCO
OC_FourH₉)₂, Sn (OCOCC₈H₁₇)₂Such as carbo
Acid type organic tin compound; (C_FourH₉)₂Sn (SCH₂CO
OC₈H₁₇)₂, (C_FourH₉)₂Sn (SCH₂COOC₈H
₁₇)₂, (C₈H₁₇)₂Sn (SCH₂CH₂COOC
₈H₁₇)₂, (C₈H₁₇)₂Sn (SCH ₂COOC
₁₂H_{twenty five})₂,

[Chemical 10] Examples thereof include mercaptide type and sulfide type organotin compounds. In addition, (C ₄ H ₉ ) ₂ SnO,
(C ₈ H ₁₇ ) ₂ SnO, or (C ₄ H ₉ ) ₂ SnO, (C ₈
Examples thereof include organic tin compounds such as a reaction product of an organic tin oxide such as H ₁₇ ) ₂ SnO and an ester compound such as ethyl silicate maleate dimethyl, diethyl maleate and dioctyl phthalate.

(C5) Metal salts As the metal salts, alkali metal salts of organic acids (for example, sodium naphthenate, potassium naphthenate, sodium octanoate, sodium 2-ethylhexanoate, potassium laurate etc.) are preferably used.

The ratio of the sol-gel catalyst compound in the composition is based on the organosilane compound as the raw material of the sol liquid.
It is preferably 0.01 to 50% by mass, more preferably 0.
1 to 50% by mass, more preferably 0.5 to 10% by mass
Is.

(D) Solvent As a solvent, the respective components in the sol liquid are uniformly mixed to prepare a solid content of the composition of the present invention, and at the same time, it can be applied to various coating methods to improve the dispersion stability of the composition. And to improve storage stability. These solvents are not particularly limited as long as they can fulfill the above purpose. Preferable examples of these solvents include water, alcohols, aromatic hydrocarbons, ethers, ketones and esters.

Of these, examples of the alcohols 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-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

Specific examples of the aromatic hydrocarbons are benzene, toluene, xylene, etc., specific examples of the ethers are tetrahydrofuran, dioxane, etc., and specific examples of the ketones are acetone, methyl ethyl ketone, methyl. Isobutyl ketone, diisobutyl ketone, etc., specific examples of esters include ethyl acetate,
Examples thereof include propyl acetate, butyl acetate, propylene carbonate and the like. These organic solvents may be used alone or in combination of two or more. The ratio of the organic solvent in the composition is not particularly limited, and an amount that adjusts the total solid content concentration according to the purpose of use is used.

(E) When using a metal complex compound in the chelate ligand compound sol liquid, it is also preferable to use a compound having a chelate coordination ability from the viewpoint of controlling the curing reaction rate and improving the liquid stability. Preferably used are β-diketones and / or β-ketoesters represented by the general formula R ¹⁰ COCH ₂ COR ^11, which act as a stability improver for the composition of the present invention. That is, by coordinating with the metal atom in the metal chelate compound (preferably zirconium, titanium and / or aluminum compound) present in the accelerating liquid, the components (a) and (b) of these metal chelate compounds are coordinated. It is considered that the action of promoting the condensation reaction is suppressed and the curing rate of the obtained film is controlled. R ¹⁰ and R ¹¹ have the same meaning as R ¹⁰ and R ¹¹ constituting the metal chelate compound, but they do not have to have the same structure in use.

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-
tert-butyl, 2,4-hexane-dione, 2,4
-Heptane-dione, 3,5-heptane-dione, 2,
4-octane-dione, 2,4-nonane-dione, 5-
Methyl-hexane-dione etc. can be mentioned.
Of these, ethyl acetoacetate and acetylacetone are preferable, and acetylacetone is particularly preferable. These β-diketones and / or β-ketoesters may be used alone or in combination of two or more. The amount of such β-diketones and / or β-ketoesters is 2 mol or more, preferably 3 to 20 mol, per 1 mol of the metal chelate compound, and if less than 2 mol, the resulting composition is inferior in storage stability. Become.

(F) Water Preferred sol liquids of the present invention include the above (a) and (b).
Water is added for the hydrolysis / condensation reaction of the components. The amount of water used is usually 1.2 to 3.0 mol, preferably 1.3 to 2.0 mol, per 1 mol of the components (a) and (b). The sol liquid of the present invention has a total solid content concentration of preferably 0.1 to 50% by mass, more preferably 1 to 50% by mass.
It is 40 mass%. When the total solid content concentration exceeds 50% by mass, the storage stability of the composition tends to deteriorate.

(G) Filler Colloidal silica may be added to the sol solution of the present invention for the purpose of improving the hardness of the resulting coating film. Examples of the colloidal silica include water-dispersed colloidal silica and organic solvent-dispersed colloidal silica such as methanol or isopropyl alcohol.

The composition of the present invention has the above-mentioned colloidal form in order to exhibit various properties such as coloring of the resulting coating film, imparting unevenness, preventing ultraviolet ray from passing through the substrate, imparting anticorrosion property, and heat resistance. It is also possible to add / disperse a filler in addition to silica.

Examples of the filler include water-insoluble pigments such as organic pigments and inorganic pigments, or particles other than pigments,
Examples thereof include fibrous or scale-like metals and alloys, and oxides, hydroxides, carbides, nitrides and sulfides thereof. Specific examples of this filler include particulate, fibrous or scaly iron, copper, aluminum, nickel,
Silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, manganese oxide, iron oxide, zirconium oxide,
Cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, mica, Zinc green, Chrome green, Cobalt green, Viridian, Guinea green, Cobalt chrome green, Shale green, Green top, 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. can be mentioned.

The average particle size or average length of these fillers is usually 5 to 500 nm, preferably 10 to 2 nm.
00 nm. When the filler is used, the proportion in the composition is 10 to 30 with respect to 100 parts by mass of the total solid content of the sol liquid.
It is about 0 parts by mass.

(H) Other Additives In addition to the sol liquid and accelerating liquid of the present invention, known dehydrating agents such as methyl orthoformate, methyl orthoacetate, and tetraethoxysilane, various surfactants, and silane cups other than the above Ring agent, titanium coupling agent, dye, dispersant,
Additives such as a thickener and a leveling agent can also be added.

Further, the sol liquid of the present invention may contain a solvent other than the above-mentioned solvent, and such a solvent does not cause precipitation when the components (a) to (c) are mixed. Any solvent may be used, and aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ketones, esters, ethers, ketone ethers used in general paints, coating agents, etc. Examples thereof include ketones, ketone esters and ester ethers, and specific examples thereof include benzene, toluene,
Examples include xylene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate and isoamyl acetate. These organic solvents are usually used in an amount of 10 parts by weight per 100 parts by weight of the composition of the present invention.
It is used in an amount of 0 parts by mass or less.

In preparing the sol solution of the present invention, any method may be used as long as it is a method of adding water to the composition containing the components (a) and (b) to cause hydrolysis.
At this time, if necessary, a catalyst may be used to accelerate the hydrolysis. The amount of the catalyst used is not particularly limited as long as it does not impair the stability of the liquid over time. For example
Is preferred.

The organosilane compound 1 is added to a solution containing the components (a) and (b), a solvent and a hydrolysis catalyst.
A method of performing hydrolysis / condensation reaction by adding 0.2 to 3 mol of water per mol. To a solution consisting of the component (a) and a solvent, 0.2 to 3 mol of water is added to 1 mol of the organosilane compound to carry out a hydrolysis / condensation reaction, and then a hydrolysis catalyst and optionally a component (b). How to add. Hydrolysis / condensation reaction is carried out by adding 0.2 to 3 mol of water to 1 mol of the organosilane compound to a solution consisting of component (a), solvent and hydrolysis catalyst, and then (b).
A method in which components are added and mixed, and then a condensation reaction is performed.

Curtain flow coating with the sol solution of the present invention,
It can be formed on a support such as a transparent film by a coating method such as dip coating, spin coating or roll coating. In this case, the timing of hydrolysis may be any time during the manufacturing process. For example, a method of preparing a desired sol liquid by hydrolyzing and partially condensing a liquid having a necessary composition in advance and coating and drying it, a liquid having a necessary composition is prepared and dried while being hydrolyzed and partially condensed simultaneously with coating. The method, coating-primary drying, and subsequent coating with a water-containing liquid necessary for hydrolysis and coating for hydrolysis can be suitably adopted. As the coating method, it is possible to take various forms. However, when productivity is emphasized, a lower layer coating liquid and an upper layer coating liquid are required on a slide giser having a multi-stage discharge port. A method (simultaneous layering method) in which the discharge flow rate is adjusted so that the coating amount is obtained, and the formed multi-layer flow is continuously placed on a support and dried is preferably used.

The above-mentioned hydrolysis temperature is applied from the start of the hydrolysis reaction to the end of coating. Therefore, the coating temperature in the present invention is 50 ° C or lower, more preferably 10 ° C.
C. to 50.degree. C., particularly preferably 20.degree. C. to 45.degree. The hydrolysis reaction time is determined to the effect that the partial condensation reaction does not proceed too much, but generally, if it is within 30 minutes, the object intended by the present invention can be achieved, preferably within 20 minutes, particularly preferably. Is in the range of 1 minute to 15 minutes. The drying temperature after coating is not particularly limited as long as it does not cause deformation of the support, but is preferably 150 ° C. or lower, more preferably 30 to 150 ° C., particularly preferably 5 ° C.
It is 0 ° C to 130 ° C. The hydrolysis temperature is 50 ° C
When it exceeds, the hydrolysis-condensation reaction of the organosilane compound proceeds and the formation of colloidal silica proceeds. The colloidal silica is hard particles, and even if the coating solution containing the particles is applied and dried and cured at a relatively low temperature of about a hundred and several tens of degrees, fusion of the particles does not occur and a uniform and strong film is formed. Can't get Within the above temperature range, the partial condensate which is easily fused can be cured to form a strong coating.

In the present invention, irradiation with energy rays may be performed. The type of irradiation ray is not particularly limited, but irradiation with ultraviolet rays, electron beams or microwaves can be particularly preferably used in consideration of the influence on the deformation and modification of the support. Irradiation intensity is preferably 30 mJ / cm ^{2 to} 500 m
J / cm ² and particularly preferably 50 mJ / cm ² to 4
It is 00 mJ / cm ² . The irradiation temperature can be adopted from room temperature to the deformation temperature of the support without limitation, preferably 30 ° C to 150 ° C, particularly preferably 50 ° C to 1 ° C.
It is 30 ° C.

When the film produced by the present invention is used for EL or the like, JP-A-11-335661 and JP-A-11-335661 disclose the same.
-335368, JP 2001-192651 A, 2001-192652 A, 2001-2001
192653, 2001-335776, 2001-247859, 2001-1.
No. 81616, No. 2001-181617,
Japanese Patent Application No. 2001-58834, 2001-58
It is preferable to use it together with the contents described in the specification of No. 835, the specification of No. 2001-89663, and the specification of No. 2001-334858. The present invention is particularly preferably used for manufacturing an organic EL panel having a gas barrier property.

[0067]

EXAMPLES The features of the present invention will be described more specifically below with reference to examples and comparative examples. Materials shown in the following examples,
The usage amount, ratio, processing content, processing procedure, etc. can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following specific examples.

Tetraethoxysilane 41.7 g (0.2
mol) was added with 12.5 ml of 0.01 mol / L hydrochloric acid, and the mixture was stirred for 90 minutes at 25 ° C., and then 1.2 mmol of the compound (1-1) was added over 30 minutes, and further 30 minutes were added. After stirring for a minute, a coating liquid was prepared. Then, this coating solution was applied onto a PET film having a thickness of 12.5 μm by a bar coater so as to have a volume of 12.2 ml / m ² , and then dried at 120 ° C. for 20 minutes to give a film thickness of 0.
A coating film having a thickness of 5 μm was formed to prepare Sample A. Further, samples B to J were prepared by using the compounds shown in Table 1 instead of the compound (1-1).

Using these samples, the film strength, oxygen permeation amount, and water vapor permeation amount were measured. The film strength was evaluated by its hardness using a pencil hardness meter. The oxygen permeation amount is measured by an oxygen gas permeation measuring device (M
OCON OX-TRAN 2/20), temperature 2
It was measured under the conditions of 5 ° C. and 80% humidity. The results are shown in Table 1.

[0070]

[Table 1]

As is clear from Table 1, when the compound represented by the formula (1) was added according to the present invention, it was confirmed that the film quality and the gas barrier ability were remarkably improved as compared with the comparative example. It was Gas barrier film thickness is 1
If it is from 00 nm to 2 μm, a sufficient gas barrier property was obtained, and the gas barrier property could be further enhanced by increasing the thickness of the film.

[0072]

The film formed by the sol-gel method using the sol liquid of the present invention has high uniformity and excellent film quality. Therefore, it has an advantage that cracks and cracks are less likely to occur as compared with the film formed by the conventional sol-gel method. Also, since it has a high gas barrier property, it is possible to manufacture a gas barrier material by forming it on a gas permeable support. The sol liquid of the present invention can be effectively used for forming a film of an organic EL material.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/00 C08K 5/00 H05B 33/02 H05B 33/02 33/04 33/04 33/14 33 / 14 AF terms (reference) 3K007 AB11 AB12 AB13 BA07 BB01 CA06 DB03 4F071 AA66 AA67 AC12 AC13 AF08 AH04 AH12 BA08 BB02 BC01 BC02 4F100 AH03B AH06B AH08B AK42 AK52 AK52 AK52 AK52 BB52 EE026 EE066 EN126 EP016 EQ026 ES006 ET006 EU136 EU236 EV266 EV306 FD010 FD150 GG02 GQ00 HA06 HA08 4J035 AA01 AB02 AB03 BA02 BA03 BA12 BA13 CA112 CA132 CA142 CA162 CA172 CA282 EA01 EB02 EB04 EB10 LA07 LB20

Claims (5)

[Claims] 1. A sol solution containing a hydrolyzed partial condensate of a metal alkoxide and a compound represented by the following general formula (1). [Chemical 1] [R ¹ and R ² each independently represent a hydrogen atom, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic sulfonyl group or an aromatic sulfonyl group, and R ³ is an aliphatic group. Group, aliphatic oxy group, aromatic group,
It represents an aromatic oxy group, an aliphatic thio group, an aromatic thio group, an acyloxy group, an aliphatic oxycarbonyloxy group, an aromatic oxycarbonyloxy group, a substituted amino group, a heterocyclic group or a hydroxy group. However, when R ³ is not an aromatic group, at least one of R ¹ and R ² is a hydrogen atom. ] 2. A film-forming composition containing a metal alkoxide, an acid, and a compound represented by the following general formula (1). [Chemical 2] [R ¹ and R ² each independently represent a hydrogen atom, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic sulfonyl group or an aromatic sulfonyl group, and R ³ is an aliphatic group. Group, aliphatic oxy group, aromatic group,
It represents an aromatic oxy group, an aliphatic thio group, an aromatic thio group, an acyloxy group, an aliphatic oxycarbonyloxy group, an aromatic oxycarbonyloxy group, a substituted amino group, a heterocyclic group or a hydroxy group. However, when R ³ is not an aromatic group, at least one of R ¹ and R ² is a hydrogen atom. ] 3. The sol liquid according to claim 1 or claim 2.
A method for forming a film by the sol-gel method using the film forming composition described in 1. 4. A gas barrier film formed by applying the film-forming composition according to claim 2 on a support. 5. An organic EL material having the gas barrier film according to claim 4.