JPH07331074A - Curable composition - Google Patents

Abstract

PURPOSE:To provide a curable composition containing a specific amic acid, a slloxane polymer and a metal chelate compound, having excellent applicability, adhesion and storage stability, useful for forming a color filter protection film of a liquid crystal element, etc., and giving a flat surface even by applying to a stepped part. CONSTITUTION:This composition contains (A) an amic acid having silanol group or alkoxysilyl group on the molecular terminals or side chains, (B) a hydrolysis condensation product of an alkoxysilane and (C) a metal chelate compound (e.g. an aluminum chelate compound). The coating film of the composition has high adhesiveness to glass, pixel, chromium and epoxy resin and is resistant to deterioration with time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition used for forming a buffer coat for semiconductors, an interlayer insulating film, a passivation film, etc., and particularly for protecting a transparent substrate or a color filter in a liquid crystal element. The present invention relates to a curable composition suitable for forming a film.

[0002]

2. Description of the Related Art In recent years, many color liquid crystal display elements have been proposed in which a color filter for color separation is combined with a liquid crystal element. As a general color filter structure, a pixel is formed on a transparent substrate such as glass, a protective film layer is provided, and then an ITO transparent electrode is arranged.
This protective film layer has adhesiveness with pixels forming the lower layer, glass, and chromium used as a black matrix component provided in the gap between the pixels, and I forming the upper layer.
Adhesiveness with TO, adhesiveness with epoxy sealant for forming liquid crystal cell, blocking property with pixel impurity component, smoothness,
A wide range of properties such as light resistance, resistance to humidity and heat, solvent resistance, chemical resistance, toughness and transparency, and heat resistance to heat treatment required in a later step of forming a liquid crystal cell are required. Similar characteristics are required for a protective film on a glass substrate.

As a thermosetting composition for forming such a protective film, a siloxane polymer precursor, a silicone polyimide precursor, etc. have been proposed from the viewpoint of heat resistance. Examples of the polyalkylsilsesquioxane precursor which is one of the siloxane polymer precursors include, for example, JP-A-63-241076 and JP-A-3-126612.
As disclosed in JP-A-3-188179 and JP-A-3-188179, the methods for producing a silicone polyimide precursor are disclosed in JP-A-61-103927 and JP-A-63-291922. ing. Further, Japanese Patent Application Laid-Open No. 63-291924 proposes a curable composition composed of a siloxane polymer precursor and a silicone polyimide precursor mainly for the purpose of forming a protective film for a color filter.

However, JP-A-63-291924
The curable composition proposed in Japanese Patent Publication gives an overall excellent color filter protective film, but the coating property as a coating composition, the adhesiveness with upper and lower layer constituents, and the formation of a color filter protective film. Problems remain in the preservability and the like of the coating liquid composition for use, and its improvement has been desired.

[0005]

The object of the present invention is suitable for forming a protective film such as a transparent substrate or a color filter in a liquid crystal element, and particularly, a protective film having good coatability and improved adhesiveness. It is intended to provide a thermosetting composition which gives a film and has excellent storage stability.

[0006]

The object of the present invention is as follows.
This is achieved by a curable composition containing the following components A, B and C.

A: Amic acid having a silanol group or an alkoxysilyl group at the molecular end or side chain B: Compound obtained by hydrolyzing and condensing an alkoxysilane C: Metal chelate compound

That is, a metal chelate compound is added to a curable composition comprising a siloxane polymer precursor and a silicone polyimide precursor, which has good heat resistance and is suitable for forming a protective film such as a transparent substrate or a color filter in a liquid crystal device. By doing so, it was found that the adhesiveness with the components constituting the upper and lower layers of the color filter protective film is greatly improved, and the present invention has been achieved.

The structure of the present invention will be described below in order.

The amic acid having a silanol group or an alkoxysilyl group at the molecular end or side chain of the component A of the present invention is not particularly limited as long as it has such a structure, but an alkoxysilane having an amino group. A tetracarboxylic dianhydride is added to a hydrolyzate of the alkoxysilane, a hydrolyzed condensate of the alkoxysilane, or a compound obtained by hydrolyzing and co-condensing the alkoxysilane and an alkoxysilane having no amino group. Amic acid obtained by reaction is typical.

Among these, in particular, a primary amino group and a secondary amino group in a molecule obtained by hydrolyzing and condensing an alkoxysilane mixture having no amino group and an alkoxysilane mixture containing an alkoxysilane having an amino group. A reaction product of a polyorganosiloxane (siloxane type polymer precursor) having at least one group selected from a primary amino group, a silanol group and a tetracarboxylic acid dianhydride,
It is preferable from the viewpoint of providing a thermosetting coating film having good smoothness and a curable composition having good storage stability.

Examples of the alkoxysilane having no amino group include compounds represented by the following general formula (1). [R _X Si (OR ') _4-X ] (1) (However, R and R'may be the same or different and each is a group selected from hydrogen, an alkyl group, an aryl group, an allyl group and a fluoroalkyl group. And x
Is an integer of 0 to 3. )

Specifically, tetrahydroxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trifluoromethylmethoxysilane, trifluoroethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane However, the present invention is not limited to these.

Examples of the alkoxysilane having an amino group include compounds represented by the following general formula (2). [R ¹ _n Si (OR ² ) _4-n ] (2) (wherein R ¹ represents an organic group, at least one of R ¹ is an organic group having a ^primary to tertiary amino group, and the others are It is a group selected from an alkyl group, an aryl group, an allyl group, and a fluoroalkyl group, and R ^{2 s} may be the same or different and each is hydrogen, an alkyl group, an aryl group,
It is a group selected from an allyl group and a fluoroalkyl group.
Further, n is an integer of 1 to 3. )

Specifically, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-amino Propyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, 2-aminoethylaminomethyltrimethylsilane, 2-aminoethylaminomethyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 2-
Examples thereof include (2-aminoethylthioethyl) triethoxysilane, but are not limited thereto.

The use ratio of the alkoxysilane having no amino group represented by the general formula (1) and the alkoxysilane having an amino group represented by the general formula (2) is not particularly limited and is as described above. It is also possible to use only the alkoxysilane having an amino group alone. However, the preferable usage ratio is such that the ratio of alkoxysilanes having an amino group in all alkoxysilanes is 5 to 95% by weight, and more preferably 30 to 80% by weight.

In order to obtain a polyorganosiloxane by hydrolyzing / condensing such an alkoxysilane or a mixture thereof, a catalyst for hydrolysis / condensation of an acid or amine component is optionally used in the presence of no solvent or an organic solvent. Can be easily performed by adding a necessary amount of water and stirring the mixture at a temperature of 0 to 130 ° C. The water used for the hydrolytic condensation reaction of these components is preferably ion-exchanged water, and the amount thereof is preferably in the range of 1 to 4 times mol per mol of the alkoxysilane. The catalyst used for the hydrolysis condensation reaction is preferably an acid catalyst, and hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, phosphoric acid, boric acid, paratoluenesulfonic acid, etc. are preferably used.

The organic solvent used for preparing the component A is not particularly limited, but the solvent main component preferably used to obtain a coating composition having good coatability is at least in the molecule. A liquid having one hydroxyl group and a boiling point of 100 to 300 ° C. and / or a boiling point of 100 containing at least one ether bond in the molecule.
Liquids at ˜300 ° C. may be mentioned. Examples of such organic solvent components include 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, propylene glycol-mono-methyl ether, propylene glycol-mono-methyl ether acetate, dipropylene glycol- Mono-methyl ether, tripropylene glycol-mono-methyl ether, propylene glycol-mono-tertiary-butyl ether, isobutyl alcohol, isoamyl alcohol, ethyl cellosolve,
Examples thereof include, but are not limited to, ethyl cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, methyl carbitol, methyl carbitol acetate, ethyl carbitol, ethyl carbitol acetate, and the like. Further, particularly in the preparation of the component A, it is desirable to use a polar solvent such as N-methylpyrrolidone, γ-butyrolactone, N, N-dimethylacetamide in combination, because an amide acid bond is generated.

The conditions for the hydrolysis and condensation of the alkoxysilane or the mixture thereof are determined according to the constitution of the reaction system and are not particularly limited, but the hydrolysis is 0 to 7
0 ° C, 0.1-5 hours, condensation 30-150 ° C, 1-1
It is desirable to proceed for 0 hours, and in order to obtain a siloxane polymer having a particularly high storage stability and a high molecular weight, the condensation while distilling the generated water under normal pressure or reduced pressure is performed at 40 to 150 ° C. It is preferable to proceed.

After the hydrolysis of the alkoxysilane or the mixture thereof, it is preferable to carry out the condensation while distilling the alcohol and water as by-products under normal pressure or reduced pressure.
By distilling alcohol and water in this manner, it is possible to obtain a curable composition having particularly excellent coatability and storage stability.

The reaction of the polyorganosiloxane thus obtained with the tetracarboxylic dianhydride is usually carried out by adding an equivalent amount of tetracarboxylic dianhydride to the amino group of the compound having an amino group in the presence of an organic solvent. In addition, the reaction can be easily carried out at a concentration of 5 to 40% by weight under the condition of 0 to 130 ° C., and the amic acid can be obtained.

As the tetracarboxylic acid dianhydride used in this amic acid synthesis, all known tetracarboxylic acid dianhydrides can be used, but pyromellitic acid dianhydride, 3,3 ', 4,4 is preferable. 4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4
′ -Diphenyl ether tetracarboxylic acid dianhydride,
Examples thereof include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride or a mixture thereof.

The component B of the present invention is a compound obtained by hydrolyzing and condensing an alkoxysilane. The alkoxysilane as a raw material component is an alkoxysilane having no amino group, which is used as a raw material for the component A. Can be used.

The constitution of the component B used in the present invention is not particularly limited, but 30 to 70 mol% of methyltrimethoxysilane and 3 of phenyltrimethoxysilane are used.
A composition comprising 0 to 70 mol% or γ-methacryloxypropyltrialkoxysilane of 0 to 100 mol% is preferably used from the viewpoint of the properties and coating properties of the coating film obtained.

The hydrolysis and condensation of these alkoxysilanes may be carried out in the same manner as the hydrolysis and condensation of the polyorganosiloxane as the raw material of the component A, and the same organic solvent may be used for the adjustment.

As the metal chelate compound of component C of the present invention, at least one metal chelate compound selected from aluminum chelate compounds, titanium chelate compounds and zirconium chelate compounds is used. A metal chelate compound obtained by reacting oxide or zirconium tetraalcooxide with a β-diketone compound or a β-ketoester is preferably used. Specifically, aluminum tris (ethyl acetoacetate), dipropoxy titanium bis (ethyl acetoacetate), dibutoxy zirconium bis (ethyl acetoacetate), zirconium tetra (ethyl acetoacetate), titanium tetra (ethyl acetoacetate), aluminum tris ( Acetyl luacetonate), dipropoxy titanium bis (acetyl acetonate), dibutoxy zirconium bis (acetyl acetonate), zirconium tetra (acetyl acetonate), titanium tetra (acetyl acetonate) and the like.

These metal chelate compounds are preferably used as an organic solvent solution having a metal oxide concentration of 1 to 30% by weight, and the organic solvent is not particularly limited, but the components A and B of the present invention can be used. The same solvent component as the component can be used.

The curable composition of the present invention comprises the above components A and B.
It can be obtained by mixing the component and the component C, and is usually carried out at room temperature to 50 ° C. with stirring. The mixing ratio is A component: 1 to 80% by weight, B component: 1 to 90% by weight, C component: 0.1 to 20% by weight, preferably A component: 10 to 50% by solid content ratio upon curing. % By weight, B component: 5
0 to 80% by weight, C component: 0.5 to 10% by weight.
When the concentration of the component A is less than 1% by weight, the toughness of the obtained coating film is insufficient, and when it is more than 80% by weight, a problem occurs in the wet heat resistance of the coating film. If the concentration of the component B is less than 1% by weight, the smoothness of the obtained coating film is insufficient, and if it is more than 90% by weight, the toughness of the coating film becomes problematic.
If the concentration of the component is less than 0.1% by weight, the adhesiveness of the obtained coating film is insufficient, and if it exceeds 20% by weight, the coating film is apt to crack.

The curable composition of the present invention is usually used as a coating composition in a solution system. As a solvent composition, γ-butyrolactone or N-methylpyrrolidone is contained in an amount of 5 to 50% by weight, 3- Methyl-3-methoxybutanol or its acetate or propylene glycol monomethyl ether is preferably 30 to 90% by weight from the viewpoint of coating properties.

When the curable composition of the present invention is used as a coating composition, it may be usually cured by heating after coating a substrate, and heat for forming a protective film or a flattening film of a color filter of a liquid crystal display device. Although it is useful as a curable composition, it can also be used as a protective film for semiconductor elements, an interlayer insulating film, a material for forming a waveguide, a material for phase shifters, and a protective film for various electronic parts.

For example, when used as a protective film for a color filter, the curability of the present invention is applied on a colored layer on a transparent substrate such as glass and, if necessary, on a light-shielding layer provided in a gap between the colored layers. The composition is applied and cured to form a transparent protective film.

[0032]

EXAMPLES Next, the present invention will be described in more detail by way of examples.

Preparation Example 1 4.08 g (0.03 mol) of methyltrimethoxysilane and 9.9 g (0.05 of phenyltrimethoxysilane)
Mol), γ-aminopropylmethyldiethoxysilane 2
8.8 g (0.15 mol) of γ-butyrolactone 15
6.3 g, 3-methyl-3-methoxybutanol 150
g, and while stirring at 30 ° C., 9.12 g of distilled water was added, followed by heating and stirring at 50 ° C. for 2 hours for hydrolysis /
After carrying out the condensation, the temperature was raised to 130 ° C., and the alcohol and water produced were distilled off while the condensation was further advanced. After cooling this solution to 50 ° C., stirring it with 3,3 ′, 4,4
′ -Benzophenone tetracarboxylic acid dianhydride 24.1
7 g (0.075 mol) was added and reacted to obtain an amic acid-based polyorganosiloxane solution. The solid content concentration of the thus obtained solution was measured to be 13.5% by weight, and the viscosity was 25 centipoise (25 ° C.).

Preparation Example 2 4.08 g (0.03 mol) of methyltrimethoxysilane and 5.94 g (0.0
3 mol), 28.8 g (0.15 mol) of γ-aminopropylmethyldiethoxysilane was added to γ-butyrolactone 15
6.3 g, 3-methyl-3-methoxybutanol 150
g, dissolve in 30 g, add 8.64 g of distilled water with stirring at 30 ° C., then heat and stir at 80 ° C. for 2 hours to hydrolyze
Condensation was performed. After cooling this solution to 50 ° C., 24.17 g (0.075 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was added with stirring to give an amic acid-based polyorganosiloxane solution. Obtained. When the concentration of the solution thus obtained was measured, it was 12.2% by weight.
And the viscosity was 15 centipoise (25 ° C.). Preparation Example 3 Methyltrimethoxysilane 4.08 g (0.03 mol), Phenyltrimethoxysilane 5.94 g (0.0
3 mol), 28.8 g (0.15 mol) of γ-aminopropylmethyldiethoxysilane, and γ-butyrolactone 10
0.0 g, 3-methyl-3-methoxybutanol 169
g, and after adding 8.64 g of distilled water while stirring at 30 ° C., the mixture was heated and stirred at 50 ° C. for 2 hours to hydrolyze.
After the condensation, the alcohol and water produced by stirring under reduced pressure of 20 mmHg were distilled.

This solution was stirred at 50 ° C. for 3,3
24.17 g (0.075 mol) of ', 4,4'-benzophenone tetracarboxylic acid dianhydride was added to obtain an amic acid-based polyorganosiloxane solution. The concentration of the thus obtained solution was measured to be 15.5% by weight and the viscosity was 22.1 centipoise (25 ° C).

Preparation Example 4 5.44 g (0.04 mol) of methyltrimethoxysilane, 1-γ-aminopropylmethyldiethoxysilane 1
9.2 g (0.1 mol) of γ-butyrolactone 90 g,
It was dissolved in a mixed solution of 90 g of 3-methyl-3-methoxybutanol, and 5.7 g of distilled water was added while stirring at 30 ° C, followed by heating and stirring at 80 ° C for 2 hours to carry out hydrolysis / condensation. . After cooling this solution to 50 ° C., 14.72 g (0.05 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added with stirring to give an amic acid-based polyorganosiloxane solution. Obtained. When the concentration of the thus obtained solution was measured, it was 12.1% by weight, and the viscosity was 18 centipoise (25 ° C.).

Preparation Example 5 180.0 g (0.56 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride was added to 393.4 g of γ-butyrolactone, and 3-methyl-3-methoxybutanol 573. After dissolving in 5 g of the mixed solution and stirring at 30 ° C. for 10 minutes, 213.7 g (1.12 mol) of γ-aminopropylmethyldiethoxysilane was added. afterwards,
Stirring and heating at 40 ° C., at a concentration of 27.2% by weight, 32.5
A centipoise (25 ° C.) amic acid solution was obtained.

Preparation Example 6 272.0 g (2.0 mo of methyltrimethoxysilane)
l), 396.0 g of phenyltrimethoxysilane (2.
0 mol) to 3-methyl-3-methoxybutanol 78
After dissolving in 5.6g, phosphoric acid 3.34g and water 216g
Was added with stirring. The obtained solution was heated at a bath temperature of 105 ° C. for 1 hour to distill off 302 g of a component mainly composed of by-product methanol. Then bath temperature 1
The mixture was heated at 30 ° C. for 2.0 hours, the internal temperature was raised to 118 ° C., 147 g of a component mainly composed of water and alcohol was distilled off, and then the mixture was cooled to room temperature and 86 g of 3-methyl-3-methoxybutanol was added. In addition, a polyorganosiloxane-based solution having a concentration of 30.1% by weight and a concentration of 50.5 centipoise (25 ° C.) was obtained.

Preparation Example 7 272.0 g (2.0 mo of methyltrimethoxysilane)
l), 396.0 g of phenyltrimethoxysilane (2.
0 mol) to 3-methyl-3-methoxybutanol 78
After dissolving in 5.6 g, acetic acid 0.34 g and water 216 g
Was added with stirring. The obtained solution was heated at a bath temperature of 105 ° C. for 1 hour to distill off 302 g of a component mainly composed of by-product methanol. Then bath temperature 1
The mixture was heated at 30 ° C. for 2.0 hours, the internal temperature was raised to 118 ° C., 147 g of a component mainly composed of water and alcohol was distilled off, and then the mixture was cooled to room temperature and 86 g of 3-methyl-3-methoxybutanol was added. In addition, a 48.5 centipoise (25 ° C.) polyorganosiloxane-based solution was obtained at a concentration of 30.5% by weight.

Preparation Example 8 γ Methacryloxypropyltrimethoxysilane 46.4
After dissolving g (0.2 mol) in 97.2 g of 3-methyl-3-methoxybutanol, 0.23 g of acetic acid and 1 part of water were dissolved.
0.8 g of the mixture was added with stirring. The obtained solution was heated at a bath temperature of 50 ° C. for 2 hours and then stirred under reduced pressure of 20 mmHg to distill the produced alcohol and water, and
A 5.5 centipoise (25 ° C.) polyorganosiloxane-based solution was obtained at a concentration of 5.5% by weight.

Preparation Example 9 95.2 g (0.7 mo) of methyltrimethoxysilane
l), 36 g of dimethyldimethoxysilane (0.3 mo
l), 39.6 g of phenyltrimethoxysilane (0.2
mol) to propylene glycol monomethyl ether 1
Dissolve in 93.4g, 60g of water, 1.7g of phosphoric acid
Was added with stirring. The obtained solution was heated at a bath temperature of 105 ° C. for 2.5 hours, the internal temperature was raised to 90 ° C., and 113 g of a component mainly consisting of by-product methanol
Was distilled off. Next, the bath temperature was heated at 125 ° C for 3.5 hours, the internal temperature was raised to 112 ° C, and 78 g of a component mainly composed of water and propylene glycol monomethyl ether
Was distilled off, then cooled to room temperature and diluted with 82.1 g of propylene glycol monomethyl ether. Thus, a 25.5 centipoise (25 ° C.) polyorganosiloxane-based solution was obtained at a concentration of 30.5% by weight.

Preparation Example 10 650 g of acetoacetic acid ethyl ester and 3-methyl-3-
383 g of tetrabutoxy zirconium was added to a mixed solution of 1567 g of methoxybutanol, and the mixture was stirred at 30 ° C. for 1 hour and left standing for 24 hours to obtain a 5 wt% zirconium chelate solution in terms of zirconia.

Preparation Example 11 520 g of acetoacetic acid ethyl ester and 3-methyl-3-
After adding 340 g of tetrabutoxytitanium to a mixed solution of 818 g of methoxybutanol and stirring at 30 ° C. for 1 hour, 2
After standing for 4 hours, a titanium chelate solution having a titanium oxide equivalent concentration of 5% by weight was obtained.

Preparation Example 12 To 520 g of acetoacetic acid ethyl ester was added 1 kg of an isopropanol solution containing 1 mol / Kg of tri (2-ethoxyethoxy) aluminum, and the mixture was stirred at 30 ° C. for 1 hour and then allowed to stand for 24 hours to have an alumina concentration of 3 A 0.4 wt% aluminum chelate solution was obtained.

Example 1 7.5 g of the amic acid-based polyorganosiloxane solution obtained in Preparation Example 1, 10.0 g of the polyorganosiloxane solution obtained in Preparation Example 6 and the chelate solution obtained in Preparation Example 1. 5 g was mixed and filtered with a filter having a pore size of 0.2 μ to prepare a coating liquid. 1m of this coating liquid
After coating with a spin coater on a non-alkali glass plate having a thickness of m and pre-curing for 10 minutes in a hot air dryer at 80 ° C., 2
Curing was carried out at 80 ° C. for 1 hour to form a 1.5 μm coating film. This coating film has no defects and has good flatness (± 0.
1 μm or less), shows 95% or more of light transmittance in the visible region of 400 to 650 nm, and has a pencil scratch hardness of 4H.
showed that. Adhesiveness to the glass plate was evaluated by a goose-eye test (JIS K-5400) by peeling the tape, but no peeling was observed. These characteristics did not decrease even after heat treatment in a gear oven at 220 ° C. for 200 hours, and did not decrease even after performing wet heat treatment at 120 ° C., 2 atmospheres, 100% RH for 96 hours.

Further, the coating film on the glass plate was coated with an epoxy resin for encapsulating a liquid crystal cell in a width of 1 mm and a thickness of 8 μm, and the peeling force was measured. As a result, a practical strength of 2 Kg / cm or more was obtained. 120 ° C, 2 atm, 100%
It did not decrease even after performing the RH and wet heat treatment for 24 hours.

Further, this coating liquid was applied at room temperature (25
After leaving it for 30 days at the same temperature, the same application and evaluation are performed.
It was confirmed that a coating film having similar characteristics was obtained.

Comparative Example 1 A coating solution was prepared in the same manner as in Example 1 except that 1.5 g of the chelate solution obtained in Preparation Example 10 was not used, and the same coating and evaluation were carried out.
About 20% of the coating film peeling occurred in the goose-eye test (JIS K-5400) after the moist heat treatment under atmospheric pressure, 100% RH, and 96 hours.

Comparative Example 2 A coating solution was prepared in the same manner as in Example 1 without using 7.5 g of the amic acid-based polyorganosiloxane solution obtained in Preparation Example 1, and the same coating and evaluation were carried out. A crack was generated in a part of the coating film.

Example 2 Instead of the 1 mm-thick non-alkali glass plate in Example 1, a color filter in which a black matrix of vapor-deposited chromium and a pigment dispersion type RGB pixel using polyimide as a binder component were formed on the glass plate. The same coating and pre-cure / cure were performed on this color filter by using. Initially, the step between the black matrix and the pixel was 1.5 μm, but the step after forming the coating film was 0.3 μm. Other characteristics are shown in Example 1.
Was almost the same as, but at 120 ° C, 2 atm, 100% R
H, Goose-eye test after heat treatment for 96 hours (JIS K
In the case of -5400), the peeling of the coating film on the black matrix of vapor-deposited chrome was only about 30%, which was sufficient as a practical level.

Comparative Example 3 A coating solution was prepared in the same manner as in Example 1 without using 1.5 g of the chelate solution obtained in Preparation Example 10. The same coating and evaluation as in Example 2 were carried out.
In a goose-eye test (JIS K-5400) after moist heat treatment at 20 ° C., 2 atmospheres, 100% RH for 96 hours, 100% film peeling occurred on a black matrix of vapor-deposited chromium.

Comparative Example 4 A coating composition was prepared in the same manner as in Example 1 except that 10.0 g of the polyorganosiloxane solution obtained in Preparation Example 6 was not used, and the same coating and evaluation as in Example 2 were carried out. Initially, the step between the black matrix and the pixel is 1.5μ
However, the step difference after forming the coating film was 0.5 μm
Therefore, the flattening characteristic was deteriorated as compared with the case of Example 2. Also, in the visible region of 400 to 650 nm, about 5
% Loss of light transmission occurred.

Example 3 7.5 g of the amic acid-based polyorganosiloxane solution obtained in Preparation Example 2, 10.0 g of the polyorganosiloxane solution obtained in Preparation Example 7 and the chelate solution obtained in Preparation Example 11 0 g was mixed and filtered with a filter having a pore size of 0.2 μ to prepare a coating liquid. 1m of this coating liquid
After coating with a spin coater on a non-alkali glass plate having a thickness of m and pre-curing for 10 minutes in a hot air dryer at 80 ° C., 2
Curing was carried out at 80 ° C. for 1 hour to form a 2.0 μ film. This coating has no defects and has good flatness.
It had a light transmittance of 95% or more in the visible region of 00 to 650 nm, and had a pencil scratch hardness of 4H.

Adhesiveness to the glass plate was evaluated by a scoring test by tape peeling (JIS K-5400), but no peeling was observed. These characteristics did not decrease even after heat treatment in a gear oven at 220 ° C. for 200 hours, and did not decrease even after performing wet heat treatment at 120 ° C., 2 atmospheres, 100% RH for 96 hours.

Further, this coating liquid was applied at room temperature (25
After leaving it for 30 days at the same temperature, the same application and evaluation are performed.
It was confirmed that a coating film having similar characteristics was obtained.

Example 4 In Example 3, instead of 7.5 g of the amic acid-based polyorganosiloxane solution obtained in Preparation Example 2, Preparation Example 3 was used.
The same coating properties were prepared and evaluated using 7.5 g of the amic acid-based polyorganosiloxane solution obtained in 1., and the same excellent properties (flatness, light transmission, pencil scratch hardness, adhesiveness) were obtained. It was possible to obtain a coating film having a peeling force, storability).

Example 5 In Example 3, instead of 7.5 g of the amic acid-based polyorganosiloxane solution obtained in Preparation Example 2, Preparation Example 4 was used.
Amic acid-based polyorganosiloxane solution 5 obtained in
When the same coating solution was prepared and evaluated using g, a coating film having the same excellent properties (flatness, light transmission, pencil scratch hardness, adhesion, peeling force, storability) was obtained. I was able to.

Example 6 11.5 g of the amic acid solution obtained in Preparation Example 5, 10.0 g of the polyorganosiloxane solution obtained in Preparation Example 7 and 1.5 g of the chelate solution obtained in Preparation Example 10 were mixed. A coating solution was prepared by filtering with a filter having a pore size of 0.2 μm. This coating solution was applied onto a 1 mm-thick non-alkali glass plate by a spin coater, pre-cured in a hot air dryer at 80 ° C. for 10 minutes, and then cured at 280 ° C. for 1 hour to form a coating film of 1.5 μm. This coating film had no defects, had good flatness, had a light transmittance of 97% or more in the visible region of 400 to 650 nm, and had a pencil scratch hardness of 4H.

Adhesiveness to the glass plate was evaluated by a scoring test by tape peeling (JIS K-5400), but no peeling was observed at all. These characteristics did not decrease even after heat treatment in a gear oven at 220 ° C. for 200 hours, and did not decrease even after performing wet heat treatment at 120 ° C., 2 atmospheres, 100% RH for 96 hours.

Instead of a 1 mm-thick non-alkali glass plate as a substrate, a color filter in which a black matrix of vapor-deposited chrome and a pigment dispersion type RGB pixel having polyimide as a binder component were formed on the glass plate was used. The same application and pre-cure / cure were performed on this color filter. The characteristics of the coating film were almost the same as those on the glass plate, but at 120 ° C, 2 atmospheric pressure, 100%
RH, goose eye test after heat treatment for 24 hours (JIS
In K-5400), the film peeling of vapor-deposited chromium on the black matrix was only about 20%, which was sufficient as a practical level.

Comparative Example 5 A coating solution was prepared in the same manner as in Example 6, except that 1.5 g of the chelate solution obtained in Preparation Example 10 was not used, and the same coating and evaluation were conducted.
100% film peeling occurred on a black matrix of vapor-deposited chrome in a goose-eye test (JIS K-5400) after moist heat treatment at atmospheric pressure, 100% RH, and 96 hours.

Example 7 A coating solution was prepared in the same manner as in Example 3 except that 5 g of the polyorganosiloxane solution obtained in Preparation Example 8 was used instead of 10 g of the polyorganosiloxane solution obtained in Preparation Example 7. did. This coating solution was applied onto a 1 mm-thick non-alkali glass plate by a spin coater, pre-cured in a hot air dryer at 80 ° C. for 10 minutes, and then cured at 280 ° C. for 1 hour to form a coating film of 1.5 μm. This coating film has no defects and has good flatness, and 400 to 650 nm.
Had a light transmittance of 97% or more in the visible region and had a pencil scratch hardness of 5H.

The adhesiveness to the glass plate was evaluated by a tape-shaped peeling test (JIS K-5400), but no peeling was observed. These characteristics did not decrease even after heat treatment in a gear oven at 220 ° C. for 200 hours, and did not decrease even after performing wet heat treatment at 120 ° C., 2 atmospheres, 100% RH for 96 hours.

Example 8 A coating liquid was prepared in the same manner as in Example 3 except that 10 g of the polyorganosiloxane solution obtained in Preparation Example 7 was replaced with 10 g of the polyorganosiloxane solution obtained in Preparation Example 9. did. This coating solution was applied onto a 1 mm-thick non-alkali glass plate by a spin coater, pre-cured in a hot air dryer at 80 ° C. for 10 minutes, and then cured at 280 ° C. for 1 hour to form a coating film of 1.5 μm. This coating film has no defects and has good flatness, and is 400 to 650n.
It had a light transmittance of 97% or more in the visible region of m, and had a pencil scratch hardness of 3H.

Adhesiveness to the glass plate was evaluated by a scoring test by tape peeling (JIS K-5400), but no peeling was observed. These characteristics did not decrease even after heat treatment in a gear oven at 220 ° C. for 200 hours, and did not decrease even after performing wet heat treatment at 120 ° C., 2 atmospheres, 100% RH for 96 hours.

Example 9 In Example 3, using 3 g of the chelate solution obtained in Preparation Example 12 instead of 3.0 g of the chelate solution obtained in Preparation Example 11, the same coating solution preparation and evaluation were carried out. When carried out, a coating film having the same excellent properties (flatness, light transmission, pencil scratch hardness, adhesion, peeling force, storability) could be obtained.

[0067]

INDUSTRIAL APPLICABILITY The curable composition of the present invention has excellent coatability, adhesiveness and storage stability, and is particularly suitable for use as a color filter protective film in liquid crystal devices. Adhesion to chromium, chrome, and epoxy resin is good, and deterioration over time is unlikely to occur. Further, since it contains the component B (siloxane polymer), it has excellent flatness even when applied on a substrate having a step such as a color filter,
In addition, the light transmittance is also excellent.

Claims (6)

[Claims] 1. A curable composition comprising the following components A, B and C: A: Amic acid having a silanol group or an alkoxysilyl group at the molecular end or side chain B: Compound obtained by hydrolyzing and condensing an alkoxysilane C: Metal chelate compound 2. A polyorganosiloxane obtained by hydrolyzing and condensing an alkoxy silane mixture having an amino group-free alkoxy silane and an amino group-containing alkoxy silane as the component A, and tetracarboxylic dianhydride. A reaction product of a product.
The curable composition described. 3. The curable composition according to claim 2, wherein the alkoxysilane having no amino group is a compound represented by the following general formula (1). [R _X Si (OR ') _4-X ] (1) (However, R and R'may be the same or different and each is a group selected from hydrogen, an alkyl group, an aryl group, an allyl group and a fluoroalkyl group. And x
Is an integer of 0 to 3. ) 4. The alkoxysilane having an amino group is
The curable composition according to claim 2, which is a compound represented by the following general formula (2). [R ¹ _n Si (OR ² ) _4-n ] (wherein R ¹ represents an organic group, at least one of R ¹ is an organic group having a ^primary to tertiary amino group, and the other is an alkyl group, A group selected from an aryl group, an allyl group and a fluoroalkyl group, R ² may be the same or different and each is hydrogen, an alkyl group, an aryl group,
It is a group selected from an allyl group and a fluoroalkyl group.
Further, n is an integer of 1 to 3. ) 5. The curable composition according to claim 1, wherein the alkoxysilane which is a raw material of the component B is a compound represented by the following general formula (1). [R _X Si (OR ') _4-X ] (1) (However, R and R'may be the same or different and each is a group selected from hydrogen, an alkyl group, an aryl group, an allyl group and a fluoroalkyl group. And x
Is an integer of 0 to 3. ) 6. The curable composition according to claim 1, wherein the component C metal chelate compound is at least one selected from the group consisting of an aluminum chelate compound, a titanium chelate compound and a zirconium chelate compound.