JPH0841202A - Curable composition - Google Patents

Abstract

(57) [Summary] [Structure] An organosilane obtained by hydrolyzing an alkoxysilane having an amino group and / or a component obtained by reacting a condensate of the organosilane with a polyvalent carboxylic anhydride is mainly used. Curable composition as a component. [Effect] It is possible to obtain a curable composition which is free from coating unevenness and cracks, can form a protective film having a sufficiently high pencil hardness, is easy to manufacture, and has excellent storage stability.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition, and more particularly, to a curable composition which is preferably used for producing a protective film for a color filter, a flattening film and the like.

[0002]

2. Description of the Related Art In recent years, a color liquid crystal display device which can be applied to a personal computer, a word processor, a measuring instrument, a color television, etc. has been receiving attention. As an example of a general basic configuration of a color liquid crystal display element, there is known one in which a color filter, a transparent electrode made of ITO or the like, an alignment film, and a liquid crystal are sequentially arranged on a substrate.

In this basic structure, some problems that deteriorate the function as a color liquid crystal display element can be pointed out. First, there is a risk that metal ions such as sodium contained in the pigments and dyes used in the color filter will seep into the liquid crystal. The same phenomenon occurs when glass containing metal ions is used for the substrate. Further, when pattern processing is required for a transparent electrode made of ITO or the like, the film is etched by using photolithography after forming a vapor deposition film or a sputtered film of ITO or the like on the color filter. At this time, the color filter of the lower layer is used. Due to the difference in level, good patterning becomes impossible. Further, the step of the color filter causes unevenness in the distance between the upper and lower electrodes. Further, it is possible that the color filter may be damaged during the formation of the deposited film or the sputtered film.

Therefore, as a countermeasure against these problems, a method of forming a protective film on a color filter or a glass substrate has been taken. Conventionally, as a protective film, a siloxane polymer film (for example, JP-A-63-241076 and JP-A-3-12).
6612, JP-A-3-188179) and silicon-containing polyimide (for example, JP-A-61-1392).
7, JP-A-63-291922). Further, a curable composition comprising a siloxane-based polymer and a silicon-containing polyimide, which are obtained by improving these protective films, is proposed in JP-A-63-291924. However, this curable composition has a problem in storage stability as a coating liquid for forming a protective film such as a color filter, and a large increase in viscosity occurs during storage. Also,
This curable composition uses a mixed solution of a silicon-containing amic acid solution and an organosilane solution, and two types of the amic acid solution and the organosilane solution must be synthesized, and the manufacturing method is complicated. It has the drawback of
Here, it is possible to use only the silicon-containing amic acid solution or the organosilane solution as the protective film, but in the case of using only the silicon-containing amic acid solution obtained here, sufficient hardness cannot be obtained, and coating unevenness occurs. It cannot be used because of problems such as occurrence. On the other hand, when only the organosilane solution is used, there is a problem that the film is very brittle and cracks easily occur.

[0005]

The present invention was devised in view of the above-mentioned drawbacks of the prior art. The object of the present invention is to form a protective film free from coating unevenness and cracks and to provide a manufacturing method. An object is to provide a curable composition that is easy and has excellent storage stability.

[0006]

The object of the present invention is as follows.
Achieved by a curable composition containing an organosilane obtained by hydrolyzing an alkoxysilane having an amino group and / or a condensate of the organosilane and a polyvalent carboxylic acid anhydride as a main component To be done.

Examples of the alkoxysilane having an amino group include alkoxysilanes having an amino group represented by the general formula R _n Si (OR ') _4-n .

In the formula, R and R'represent hydrogen or an organic group. Examples of the organic group include an alkyl group, an allyl group, an aryl group, an alkenyl group, an alkynyl group, and a fluoroalkyl group. More specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, neohexyl group, vinyl group, allyl group, isopropenyl group , Ethynyl group, 2-propynyl group, 3,3,3-trifluoropropyl group, γ-glycidoxypropyl group, methacryl group,
Examples thereof include γ-methacryloxypropyl group, phenyl group and tolyl group.

However, at least one of R is a group containing a primary amino group and / or a secondary amino group. The group containing a primary amino group, a γ-aminopropyl group,
Examples thereof include aminoethyl group, p-aminophenyl group, m-aminophenyl group and o-aminophenyl group. Examples of the group containing a secondary amino group include N-phenyl-γ-aminopropyl group, N-methyl-γ-aminopropyl group, N
-Ethyl-γ-aminopropyl group and the like. Among these groups containing a primary amino group and / or a secondary amino group, preferred are γ-aminopropyl group and p-aminopropyl group.
An aminophenyl group and the like.

R and R'may be the same or different. The n Rs may be the same or different. The (4-n) OR 'groups may be the same or different. n is a number from 1 to 3.

Such a general formula R _n Si (OR ') _4-n
Specific examples of the alkoxysilane having an amino group represented by: γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-
Aminopropyldimethylethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropyldiethylethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-
Aminopropylethyldimethoxysilane, γ-aminopropyldiethylmethoxysilane, γ-aminopropylethylmethoxyethoxysilane, γ-aminopropylethylmethylethoxysilane, γ-aminopropylethylmethylmethoxysilane, N-β (aminoethyl) γ- Aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N
-Β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenylγ-amino Propyltrimethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-
Aminophenylmethyldiethoxysilane, p-aminophenylethyldimethoxysilane, p-aminophenylethyldiethoxysilane, γ- (p-aminophenyl) propyltrimethoxysilane, γ- (p-aminophenyl) ethyltrimethoxysilane, γ- (p-aminophenyl) methyltrimethoxysilane, γ- (p-aminophenyl) propyltriethoxysilane, γ- (p-aminophenyl) ethyltriethoxysilane, γ- (p-aminophenyl) methyltriethoxysilane Silane etc. can be mentioned. Among these, preferred are γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane,
γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane and the like. Particularly preferred are γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane and the like, and one of R is a γ-aminopropyl group. It is a thing. These alkoxysilanes having an amino group can be used alone or in combination of two or more.

The organosilane obtained by hydrolyzing the alkoxysilane in the present invention means that an alkoxy group is substantially added by adding water to the above-mentioned alkoxysilane or a solution of the alkoxysilane dissolved in a solvent. Refers to an organosilane obtained by completely hydrolyzing. Further, the organosilane condensate means a product obtained by dehydration condensation reaction of a plurality of organosilanes. Here, an alkoxysilane other than the alkoxysilane represented by the general formula can be mixed with the alkoxysilane.

Solvents for dissolving the alkoxysilane include alcohols such as ethanol, methanol, isopropanol, butanol, 3-methoxy-3-methylbutanol, butylcellosolve, methylcellosolve, ethylcellosolve, N-methyl-2-pyrrolidone and dimethyl. Examples include, but are not limited to, aprotic polar solvents such as formamide, dimethylacetamide, γ-butyrolactone, and mixtures thereof.

Examples of the polycarboxylic acid anhydride in the present invention include tetracarboxylic acid dianhydride, tricarboxylic acid monoanhydride and tetracarboxylic acid monoanhydride.
Tetracarboxylic acid dianhydride is common. Examples of the tetracarboxylic dianhydride may include all known tetracarboxylic dianhydrides. Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone Tetracarboxylic acid dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4
′ -Biphenyltetracarboxylic dianhydride, 2,2 ′,
3,3'-biphenyltetracarboxylic dianhydride, 2,
3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylether tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, pyridinetetracarboxylic dianhydride, 3,3 ′, 4,4′-Diphenyldimethylmethanetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyldi (trifluoromethyl) methanetetracarboxylic dianhydride, 3,3 ′, 4,4 -Diphenylsulfone tetracarboxylic acid dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, 1,2,4,5-tetracarboxylic acid dianhydride, 3,3 ', 4,4' -Diphenylmethane tetracarboxylic dianhydride, 2,3,4,5-thiophene tetracarboxylic tetracarboxylic dianhydride, 1,
Examples thereof include, but are not limited to, 8,9,10-phenanthrene tetracarboxylic acid dianhydride.
Among these, preferred are 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4
These are ′ -biphenyltetracarboxylic dianhydride and pyromellitic dianhydride, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride is particularly preferable. It is also possible to use an acid anhydride terminated polyamic acid. Examples of the polyamic acid used herein include compounds produced by the reaction of diamine and tetracarboxylic dianhydride. Examples of the tetracarboxylic acid dianhydride include the above-mentioned tetracarboxylic acid dianhydride, and examples of the diamine include known diamines. For example, 4,4'-diaminodiphenyl ether, 3,3 '
(Or 4,4 ′)-diaminodiphenyl sulfone,
4,4'-diaminodiphenyl sulfide, paraphenylenediamine, 4,4'-diaminodiphenylmethane,
Bis (3-aminopropyl) tetramethyldisiloxane, metaphenylenediamine, 4,4'-diaminodiphenylethane, 1,5-diaminonaphthalene, 3,3 '
-Dimethyl-4,4'-diaminobiphenyl, 3,3 '
-Diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,3
-Propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, 1,4
Examples thereof include, but are not limited to, -bis (4-aminophenoxy) benzene.

The curable composition of the present invention contains as a main component a component obtained by reacting the above-mentioned organosilane and / or a condensate of the organosilane with a polyvalent carboxylic acid anhydride. The organosilane, the condensate of the organosilane, and the polycarboxylic acid anhydride can be used alone or in combination of two or more kinds.

As a reaction operation, first, an alkoxysilane is hydrolyzed and / or hydrolyzed and condensed to obtain an organosilane and / or a condensate of the organosilane,
Next, a polycarboxylic acid anhydride and, if necessary, a suitable solvent may be added. As such a solvent, a solvent containing an aprotic polar solvent such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, or γ-butyrolactone is preferable.

The reaction ratio of the organosilane and / or the condensate of the organosilane and the polyvalent carboxylic acid anhydride is not particularly limited, but the reaction ratio of the amino group contained in the organosilane and / or the condensate of the organosilane is The ratio is preferably such that the acid anhydride group of the carboxylic acid anhydride is about equimolar. In addition, a carboxyl group is generally formed by the reaction of a polyvalent carboxylic acid anhydride and an amino group, and the carboxyl group may be modified into a carboxylic acid ester.

If necessary, a metal chelate compound may be added to the curable composition of the present invention in order to enhance the adhesiveness to a substrate such as glass after heat curing.

The curable composition of the present invention is applied onto a substrate and then subjected to a curing treatment to form a coating film. As a method of applying the composition onto the substrate, for example, a spinner method, a dipping method, a spray method, or the like can be used, and preferably a spinner method
The dip method is preferable, and the spinner method is more preferable. A heat treatment is preferable as the curing treatment method, and for example, a ventilation oven, a hot plate, a vacuum oven, a furnace or the like can be used as the heat treatment method. A ventilation oven or a hot plate is preferable. The heat treatment temperature is preferably 50 to 400 ° C, more preferably 15
0 to 350 ° C, more preferably 200 to 300
° C. The temperature may be raised rapidly to this heat treatment temperature or may be raised stepwise. The method of raising the temperature stepwise is preferred. The heat treatment time at the maximum heat treatment temperature is preferably 10 minutes to 10 hours, more preferably 30 minutes to 4 hours in the case of a ventilation oven. In the case of a hot plate, the time is shorter than this, preferably 2 minutes to 2 hours, more preferably 6 minutes to 1 hour. Further, if a photosensitive component is added to the curable composition, it can be photocured.

The coating film thus obtained is used in addition to the protective film and the flattening film provided on the color filter, the protective film of the semiconductor element, the interlayer insulating film, the flattening film, the material for forming the waveguide, and the phase. It can be used as a shifter material, a protective film for various electronic components, and the like.

For example, when used as a protective film for a color filter, the curable composition of the present invention is formed 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.

[0022]

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited thereto.

Example 1 28.8 g (0.15 mol) of γ-aminopropylmethyldiethoxysilane in a 500 ml four-necked flask,
100.0 g of γ-butyrolactone and 128.0 g of 3-methoxy-3-methylbutanol were added, and the mixture was stirred for about 10 minutes. Next, after raising the temperature inside the flask to 50 ° C., water 6.0
g (0.33 mol) was added dropwise over 1 minute. Then, the mixture was stirred for 2 hours to complete the hydrolysis of γ-aminopropylmethyldiethoxysilane. Continued 3,3 ', 4,4'
-Benzophenone tetracarboxylic dianhydride 24.1 g
(0.075 mol) was added and stirring was continued for about 2 hours to obtain a curable composition solution. The solution thus obtained was applied onto a glass substrate with a spinner and heat-treated at 280 ° C. for 3 hours. As a result, there is no unevenness or cracks and the pencil hardness is 4
It was possible to form a favorable film having a high H. Further, this curable composition solution was composed of one kind of solution, and the manufacturing method was very easy. This solution was allowed to stand at 40 ° C. for 24 hours, the viscosity of the solution was measured (Tokyo Keiki rotational viscometer VISCONIC-ELD, the same applies hereinafter), and the storage stability was examined. As a result, the viscosity was about 27 cp and hardly changed, and the storage stability was excellent.

Example 2 28.8 g (0.15 mol) of γ-aminopropylmethyldiethoxysilane in a 500 ml four-necked flask,
100.0 g of γ-butyrolactone and 128.0 g of 3-methoxy-3-methylbutanol were added, and the mixture was stirred for about 10 minutes. Next, after raising the temperature inside the flask to 50 ° C., water 8.0
g (0.44 mol) was added dropwise over 1 minute. Then 10
Stirring was performed to complete hydrolysis of γ-aminopropylmethyldiethoxysilane. Continued 3,3 ', 4,4
′ -Benzophenone tetracarboxylic acid dianhydride 24.1
g (0.075 mol) was added and stirring was continued for about 2 hours to obtain a curable composition solution. The solution thus obtained was applied onto a glass substrate with a spinner and heat-treated at 280 ° C. for 3 hours. As a result, there was no unevenness or cracks and the pencil hardness was as high as 4H, and a good film could be formed. Further, this curable composition solution was composed of one kind of solution, and the manufacturing method was very easy. This solution was allowed to stand at 40 ° C. for 24 hours, the viscosity of the solution was measured, and the storage stability was examined. As a result, the viscosity was about 27 cp and hardly changed, and the storage stability was excellent.

Example 3 In a 500 ml four-necked flask, 24.6 g (0.15 mol) of γ-aminopropylmethyldimethoxysilane,
100.0 g of γ-butyrolactone and 128.0 g of 3-methoxy-3-methylbutanol were added, and the mixture was stirred for about 10 minutes. Next, after raising the temperature inside the flask to 80 ° C., water 8.0
g (0.44 mol) was added dropwise over 1 minute. Then 10
Stirring was performed to complete hydrolysis of γ-aminopropylmethyldimethoxysilane. Continued 3,3 ', 4,4
′ -Benzophenone tetracarboxylic acid dianhydride 24.1
g (0.075 mol) was added and stirring was continued for about 2 hours to obtain a curable composition solution. The solution thus obtained was applied onto a glass substrate with a spinner and heat-treated at 280 ° C. for 3 hours. As a result, there was no unevenness or cracks and the pencil hardness was as high as 4H, and a good film could be formed. Further, this curable composition solution was composed of one kind of solution, and the manufacturing method was very easy. This solution was allowed to stand at 40 ° C. for 24 hours, the viscosity of the solution was measured, and the storage stability was examined. As a result, the viscosity was about 27 cp and hardly changed, and the storage stability was excellent.

Comparative Example 1 γ-butyrolactone 1 was placed in a 500 ml four-necked flask.
00.0 g, 3-methoxy-3-methylbutanol 12
8.0 g, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride 24.1 g (0.075 mol) were stirred for about 10 minutes at a flask internal temperature of 50 ° C.
Then γ-aminopropylmethyldiethoxysilane 2
8.8 g (0.15 mol) was added and stirring was continued for about 2 hours to obtain a curable composition solution (solution A). This solution at 40 ℃
The solution was allowed to stand for 24 hours and the storage stability of the solution was examined. As a result, the viscosity was about 13 cp and hardly changed, and the storage stability was excellent. However, when the solution thus obtained was applied onto a glass substrate with a spinner and heat-treated at 280 ° C. for 3 hours, the obtained film had a large unevenness on the entire substrate surface, and the pencil hardness was as low as 2H. A good film could not be formed.

Comparative Example 2 100.0 g of methyltrimethoxysilane was placed in a 500 ml four-necked flask, and a 4% solution of 0.1% acetic acid in water was added.
g was added dropwise at 20 ° C., and the mixture was stirred for about 2 hours. Subsequently, 30.0 g of butyl cellosolve was added, the internal temperature was adjusted to 35 ° C., and vacuum distillation was performed until the total amount became 120 g to obtain a curable composition solution (solution B). The solution B thus obtained was coated on a glass substrate with a spinner and heat-treated at 280 ° C. for 3 hours. As a result, although the film obtained was about 1 μm thick, cracks were generated on the entire surface. The solution was allowed to stand at 40 ° C. for 24 hours, and the viscosity stability of the solution was examined. As a result, the viscosity increased to about 2.5 times the initial viscosity (about 20 cp) and the storage stability was poor.

Comparative Example 3 The curable composition was prepared by mixing 10 g of the solution (Solution A) obtained in Comparative Example 1 and 10 g of the solution (Solution B) obtained in Comparative Example 2 and stirring at room temperature for about 2 hours. A solution was obtained. The solution thus obtained was applied onto a glass substrate with a spinner and heat-treated at 280 ° C. for 3 hours. As a result, there is no unevenness and the pencil hardness is 4
It was possible to form a film having a high H. However, when synthesizing this curable composition solution, two kinds of solutions, solution A and solution B, had to be synthesized, which was complicated and very time-consuming. The solution was allowed to stand at 40 ° C. for 24 hours, and the storage stability of the solution was examined. As a result, the viscosity increased to about twice the initial viscosity (about 17 cp) and the storage stability was poor.

Example 4 In Example 1, 24.1 g (0.075 mo) of 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride was obtained.
Instead of using 1), 12.3 g (0.03) of 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride was used.
8 mol) and 8.3 g of pyromellitic dianhydride.
A curable composition solution was obtained in exactly the same manner as in Example 1 except that (0.038 mol) was used. The solution thus obtained was coated on a glass substrate with a spinner, and the temperature was 280 ° C.
And heat treated for 3 hours. As a result, there was no unevenness and the pencil hardness was as high as 4H, and a good film could be formed. Further, this curable composition solution was composed of one kind of solution and was very easy to manufacture. The solution was allowed to stand at 40 ° C. for 24 hours, and the storage stability of the solution was examined. As a result, the viscosity was about 25 cp and hardly changed, and the storage stability was excellent.

Example 5 In Example 2, 24.1 g (0.075 mo) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was obtained.
Instead of using 1), 12.3 g (0.03) of 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride was used.
8 mol) and 8.3 g of pyromellitic dianhydride.
A curable composition solution was obtained in exactly the same manner as in Example 2 except that (0.038 mol) was used. The solution thus obtained was coated on a glass substrate with a spinner, and the temperature was 280 ° C.
And heat treated for 3 hours. As a result, there was no unevenness and the pencil hardness was as high as 4H, and a good film could be formed. Further, this curable composition solution was composed of one kind of solution and was very easy to manufacture. The solution was allowed to stand at 40 ° C. for 24 hours, and the storage stability of the solution was examined. As a result, the viscosity was about 25 cp and hardly changed, and the storage stability was excellent.

Examples 6 to 10 Color filters having RGB pixels of pigment dispersion type having a black matrix of vapor deposited chromium and polyimide as a binder resin component were formed on a glass plate instead of the glass substrate in Examples 1 to 5. When used and applied and cured and evaluated in the same manner, the same evaluations as in Examples 1 to 5 were obtained.

[0032]

EFFECT OF THE INVENTION It is possible to obtain a curable composition which is free from coating unevenness and cracks, can form a protective film having a sufficiently high pencil hardness, is easy to manufacture, and has excellent storage stability.

Claims (7)

[Claims] 1. A curing method comprising an organosilane obtained by hydrolyzing an alkoxysilane having an amino group and / or a component obtained by reacting a condensate of the organosilane with a polycarboxylic acid anhydride as a main component. Sex composition. 2. An alkoxysilane having an amino group is represented by the general formula R _n Si (OR ') _{4- n} (R and R'represent hydrogen or an organic group. At least one of R is a primary amino group and / or The curable composition according to claim 1, wherein the curable composition is a group containing a secondary amino group, and n is a number of 1 to 3.). 3. The curable composition according to claim 1, wherein the polyvalent carboxylic acid anhydride is a tetracarboxylic acid dianhydride. 4. A tetracarboxylic dianhydride as 3,3
The curable composition according to claim 3, wherein ′, 4,4′-benzophenone tetracarboxylic acid dianhydride is used. 5. The curable composition according to claim 2, wherein one of R is a γ-aminopropyl group. 6. A curable composition for a color filter protective film, comprising the curable composition according to claim 1. 7. A color filter in which at least a colored layer and a protective film are provided in this order on a transparent substrate, wherein the protective film is formed by curing the curable composition for a color filter protective film according to claim 6. And color filter.