JPH08259895A - Thermosetting composition, its production and color filter - Google Patents

Abstract

PURPOSE: To obtain a thermosetting composition which contains an organosilsesquioxane oligomer, a polybasic carboxylic acid and an amino group- containing silicon compound and is suitable for electric material such as a buffer coat for semiconductors, an interlayer insulation membrane or a passivation membrane. CONSTITUTION: This thermosetting composition comprises (A) an organosilsesquioxane oligomer, a (hydrolytic) condensate of the compound of the formula: RSi(OR')3 (R, R' are each H, an alkyl, aryl, allyl, fluoroalkyl), (B) a polybasic carboxylic acid selected from the group consisting of aromatic tetracarboxyic acids, aromatic tricarboxylic acid, aliphatic tetracarboxylic acid, maleic acid and fumaric acid and (C) a silicon compound of the formula: [Rn1 Si(OR<2> )]4-n (at least one of R<1> is an (N-alkyl)aminoalkyl, an (N-alkyl) aminoaryl and the others are each an alkyl or an aryl; R<2> is H, an alkyl, an aryl; n is 1-3] or its hydrolyzate (condensate).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a semiconductor buffer buffer.
The present invention relates to a thermosetting composition suitable for electronic materials such as an insulating film, an interlayer insulating film, and a passivation film, and is particularly suitable for forming a protective film such as a transparent substrate or a color filter in a liquid crystal element. Thermosetting composition.

[0002]

2. Description of the Related Art In recent years, many color liquid crystal display devices have been proposed in which a color separation color filter is combined with a liquid crystal device. As a general color filter structure, pixels are 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 an adhesive property with respect to pixels constituting the lower layer, glass and further with chromium used as a black matrix component, adhesive property with ITO constituting the upper layer, an epoxy sealant for constituting a liquid crystal cell. Adhesiveness with, blocking from pixel impurity components, smoothness, light resistance, moist-heat resistance, solvent resistance, chemical resistance, toughness and transparency, heat treatment required in the post-process when forming a liquid crystal cell A wide range of properties such as heat resistance are required. Similar characteristics are required as a protective film on a glass substrate, and as a thermosetting composition for forming such a protective film, a siloxane polymer precursor or a silicone polyimide precursor is proposed from the viewpoint of heat resistance. Is being carried out. Examples of the polyalkylsilsesquioxane precursor which is one of the siloxane polymer precursors include, for example, JP-A-63-241076 and JP-A-3-1266.
No. 12, JP-A-3-188179, etc., and are widely known, and JP-A-61-1103927.
Japanese Patent Laid-Open No. 63-291922 and Japanese Patent Laid-Open No. 63-291922 disclose a method for producing a silicone polyimide precursor.
Further, Japanese Patent Application Laid-Open No. 63-291924 discloses a color
A curable composition consisting of a siloxane polymer precursor and a silicone polyimide precursor has been proposed mainly for the purpose of forming a protective film for a filter. JP-A-63-29
The curable composition proposed in Japanese Patent No. 1924 provides an overall excellent color filter-protective film, but it has applicability as a coating liquid composition, adhesiveness with upper and lower layer constituents, and color. Problems remain in the storability and the like as a coating liquid composition for forming a filter-protective film, and its improvement has been desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermosetting composition suitable for forming a protective film such as a transparent substrate or a color filter in a liquid crystal device, which is particularly suitable for coating. The present invention provides a thermosetting composition which provides a good protective film with improved adhesion and has excellent storage stability.

[0004]

The object of the present invention is as follows.
It is achieved by a thermosetting composition characterized by containing at least the following components A, B and C.

A: organosilsesquioxane oligomer B: polyvalent carboxylic acid C: silicon compound having at least one or more primary amino group or secondary amino group in the molecule

The present inventors have focused on siloxane polymer precursors, particularly organosilsesquioxane oligomers, which give coatings having both heat resistance and transparency, and to improve toughness and adhesiveness which are problems of the coatings. As a result of intensive studies aimed at introducing a heat-resistant organic structure into the coating, the inventors have found that these problems can be easily avoided with the above-mentioned constitution, and arrived at the present invention.

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

The organosilsesquioxane oligomer used as the component A in the present invention is not particularly limited and widely known organosilsesquioxane oligomers can be widely used. However, the organotrialkoxysilane represented by the following general formula can be used. [RSi (OR ′) ₃ ] (1) (wherein R and R ′ may be the same or different and each is hydrogen, an alkyl group, an aryl group, an allyl group or a fluoroalkyl group). An oligomer obtained by decomposition / condensation or condensation is preferably used. Specific examples of the raw material component organotrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and phenyltrimethoxysilane.
Examples thereof include, but are not limited to, trifluoromethylmethoxysilane, trifluoroethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropyltriethoxysilane. Further, tetraalkoxysilane or dialkoxysilane such as tetramethoxysilane, tetraethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane and diphenyldimethoxysilane can be used in combination.

Here, especially as at least a part of the organotrialkoxysilane compound, phenyltrialkoxysilane such as phenyltriethoxysilane and phenyltrimethoxysilane and methyltrialkoxysilane such as methyltriethoxysilane and methyltrimethoxysilane. It is useful to use together to obtain a thermosetting composition solution having good adhesiveness and storage stability, and improve the toughness of the coating film obtained from the composition.

As the polyvalent carboxylic acid used as the component B in the present invention, known polyvalent carboxylic acids can be widely used. Specifically, pyromellitic acid, 3,3 ', 4
4'-benzophenone tetracarboxylic acid, 3,3 ',
4,4'-biphenyltetracarboxylic acid, 3,3 ',
4,4'-diphenylethertetracarboxylic acid, 1,
2,3,4-cyclobutanetetracarboxylic acid, 1,2,
Examples thereof include 3,4-butanetetracarboxylic acid, trimellitic acid, fumaric acid, maleic acid, or a mixture thereof. Particularly, aromatic tetracarboxylic acid, aliphatic tetracarboxylic acid, aromatic tricarboxylic acid, maleic acid. Alternatively, it is preferably at least one selected from fumaric acid. These polyvalent carboxylic acids may be used in the state of an acid anhydride and may be hydrolyzed or partially esterified in the process of preparing the thermosetting composition.

These polyvalent carboxylic acids may be mixed and added as a thermosetting composition component, but they are used as a catalyst for the hydrolysis or hydrolysis / condensation of the starting organotrialkoxysilane in the synthesis of the organosilsesquioxane oligomer. It is preferable to employ such a method of use, in order to obtain a thermosetting composition solution having excellent coatability and storage stability.

The silicon compound having at least one primary amino group or secondary amino group in the molecule used as the component C in the present invention is an aminoalkylalkoxysilane represented by the following general formula (2):
Aminoarylalkoxysilanes (both of which are collectively referred to as "aminoorganoalkoxysilanes") and their hydrolyzates and / or hydrolyzed condensates are preferably used, and [R ¹ _n Si (OR ² )] _4-n ] ( 2) (However, R ¹ represents an organic group, which may be the same or different, and at least one organic group is an aminoalkyl group, an N-alkyl-aminoalkyl group, an aminoaryl group or an N-alkyl-aminoaryl group. And other groups are organic groups selected from an alkyl group, an aryl group, an allyl group, and a fluoroalkyl group, R ^{2 s} may be the same or different and each is hydrogen, an alkyl group,
It is a group selected from an aryl group, an allyl group and a fluoroalkyl group. N is an integer of 1 to 3).

Specifically, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyl Trimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, 2-aminoethylaminomethyltrimethylsilane, 2-aminoethylaminomethyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 2-
(2-Aminoethylthioethyl) triethoxysilane or the like, or a hydrolyzate and / or a hydrolytic condensate thereof can be used, but the compound is not limited to these compounds.

At least one or more 1 in the molecule of component C
The silicon compound having a primary amino group or a secondary amino group is added to and mixed with a solution comprising an organosilsesquioxane oligomer of component A and a polycarboxylic acid of component B,
A thermosetting composition is preferably prepared by adding, mixing and reacting. The structure of the silicon compound having at least one primary amino group or secondary amino group in the molecule is preferably a co-condensation product with a part of the organosilsesquioxane oligomer component.

The amount of the silicon compound having at least one primary amino group or secondary amino group in the molecule is such that the amino group of the compound is equivalent to the carboxy group of the polycarboxylic acid or the polycarboxylic acid. When the carboxy groups are adjacent to each other as in the ortho position, it is preferably 1/2 equivalent.

The method for producing the thermosetting composition of the present invention is not particularly limited, but preferably, the organotrialkoxysilane is hydrolyzed or hydrolyzed in an organic solvent using a polycarboxylic acid as a catalyst. -After condensation, it is obtained by adding and mixing aminoorganoalkoxysilane, or adding, mixing, and heating to react. Here, the addition timing of the aminoorganoalkoxysilane may be before hydrolysis of the organotrialkoxysilanes, during hydrolysis, or during hydrolysis / condensation, and in any method, the thermosetting composition of the present invention Is what you get.

The hydrolysis / condensation conditions of the organotrialkoxysilane compound are as follows: in the presence of a hydrolyzate of a polyvalent carboxylic acid or a polyvalent carboxylic anhydride, a necessary amount of water is added and the condition is 0 to 130 ° C. It can be easily performed by stirring. The amount of water used for hydrolysis is 1 with respect to the alkoxy groups of the organotrialkoxysilane and the organoaminoalkoxysilane of the raw material components.
/ 2 equivalents or more is preferable, but the amount used is not particularly limited, and a polyorganosiloxane having an alkoxy group remaining can be obtained when water of less than 1/2 equivalent is used. Is. If necessary, the alcohol or water formed may be distilled off under normal pressure or reduced pressure.

As the structure of the thermosetting composition obtained by such a method, a mixture of a siloxane oligomer having an amino group at a side chain or a terminal and an organosilsesquioxane oligomer and / or a cocondensation product thereof is used. Although it has a salt structure of a carboxylic acid, it is not limited to such a structure.

The thermosetting composition of the present invention is preferably composed of an organotrialkoxysilane such as an alkyltrialkoxysilane or an aryltrialkoxysilane, a polycarboxylic acid or an anhydride thereof, and one or more first compounds in the molecule. Primary amino group or secondary amino group and 1
A composition obtained by hydrolyzing and condensing a silicon compound having one or more alkoxy groups in an organic solvent.

The organic solvent used in the preparation of the thermosetting composition of the present invention is not particularly limited, but it is preferably a solvent mainly used for obtaining a coating composition having good coatability. The component has a boiling point of 10 having at least one hydroxyl group and at least one ether bond in the molecule.
The liquid of 0-300 degreeC is mentioned. Examples of such organic solvent components include 3-methyl-3-methoxybutanol, propylene glycol-mono-methyl ether,
Dipropylene glycol-mono-methyl ether, tripropylene glycol-mono-methyl ether, propylene glycol-mono-tertiary-butyl ether, ethyl cellosolve, butyl cellosolve, methyl carbitol,
Examples thereof include, but are not limited to, ethyl carbitol and the like. Further, particularly in the preparation of the thermosetting composition of the present invention, a polar solvent such as N-methylpyrrolidone, γ-butyrolactone or N, N-dimethylacetamide may be used together.

Known surfactants and other additives can be used to further improve the coating properties of the thermosetting composition of the present invention.

The thermosetting composition of the present invention has excellent coatability and storage stability, and is usually cured by heating after coating on a substrate. The cured film has both heat resistance and transparency, adhesiveness and toughness. Its excellent electrical properties and good electrical properties make it useful as a protective film forming material for transparent substrates and color filters used in liquid crystal display devices, but it is also useful as an insulating film, passivation film, buffer film, semiconductor integrated device for semiconductor solid-state devices. It can also be used as an interlayer insulating film of a circuit or a multilayer printed wiring board, a material for forming an optical waveguide, a material for a phase shifter, and a protective film for various electronic components.

For example, when it is used as a protective film for a color filter, the heat-sensitive layer 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. A curable composition is applied and cured to form a transparent protective film.

[0024]

Next, the present invention will be described in more detail with reference to examples.

Example 1 40.8 g (0.3 mol) of methyltrimethoxysilane,
Phenyltrimethoxysilane (59.4 g, 0.3 mol) and 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (4.83 g, 0.015 mol) were added to 3-methyl-3-methoxybutanol. Dissolved in 200 g, 30
While stirring at 3 ° C, 34.2 g of distilled water was added, and the mixture was heated and stirred for 1 hour to carry out hydrolysis / condensation.

This solution was gradually heated and heated under stirring, and after heating for 2 hours, the bath temperature was set to 135 ° C. and heating and stirring were continued for 2 hours to distill off the formed alcohol and 61.5 g of water.
An organosilsesquioxane oligomer solution containing 3,3 ′, 4,4′-benzophenone tetracarboxylic acid was prepared. This solution was cooled to 80 ° C., and 5.76 g (0.03 mol) of γ-aminopropylmethyldiethoxysilane and 57.3 g of 3-methyl-3-methoxybutanol.
The mixture solution was added, heated at the same temperature for 2 hours, stirred, and cooled to room temperature to obtain an organic structure-modified organosilsesquioxane oligomer solution. The solution thus obtained had a solid content concentration of 21.5 wt% as measured by a solvent removal method of heating at 300 ° C. for 30 minutes, and a viscosity of 21 centipoise (25 ° C.).

This organic structure-modified organosilsesquioxane oligomer solution was filtered through a filter having a pore size of 0.2 μm to prepare a coating solution. 1 mm of this coating liquid
Apply with a spin coater on a thick alkali-free glass plate,
290 after pre-curing for 5 minutes in a hot air dryer at 100 ° C
Curing was carried out at 1 ° C. for 1 hour to form a coating film of 1.5 μm. This coating has no coating unevenness or defects and is 400-80
It showed a light transmittance of 98% or more in the visible region of 0 nm, and had a pencil scratch hardness of 3H. Adhesiveness to a glass plate is checked by tape peeling (JIS K-5400)
However, peeling was not observed at all. These characteristics do not deteriorate even after heat treatment for 200 hours in a gear oven at 220 ° C, and at 120 ° C, 2 atmospheres, 10 atmospheres.
It did not decrease even after performing moist heat treatment at 0% 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 to show a practical strength of 2 Kg / cm or more. 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.

Instead of a 1 mm-thick non-alkali glass plate, a color filter having a black matrix of vapor-deposited chrome and a pigment-dispersed RGB pixel having polyimide as a binder component is formed on the glass plate. When the same coating and pre-cure / cure were performed on this color filter, the characteristics were almost the same as the coating on the alkali-free glass plate.

Comparative Example 1 A similar experiment was conducted without using 4.83 g (0.015 mol) of 4,4'-benzophenonetetracarboxylic dianhydride in Example 1, but the obtained solution was It contained a gel-like material and could not be filtered with a filter having a pore size of 0.2 μm. In addition, when this organic structure-modified organosilsesquioxane oligomer solution was allowed to stand at room temperature for 1 week, it was gelled and solidified.

Comparative Example 2 The same experiment was carried out as in Example 1 except that 5.76 g (0.03 mol) of γ-aminopropylmethyldiethoxysilane was not used. When the same coating and evaluation were performed on a non-alkali glass substrate using the obtained solution,
100% in a goose-eye test (JIS K-5400) after 120 ° C., 2 atm, 100% RH, moist heat treatment for 24 hours.
Peeled off.

Example 2 136 g (1.0 mol) of methyltrimethoxysilane, 198 g (1.0 mol) of phenyltrimethoxysilane,
32.2 g (0.1 mol) of 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride was added to 140 g of γ-butyrolactone and 3-methyl-3-methoxybutanol 42.
It was dissolved in 1 g, 118 g of distilled water was added with stirring at 30 ° C., and the mixture was heated and stirred for 1 hour to carry out hydrolysis / condensation.

This solution was gradually heated and stirred, and the temperature was raised under stirring for 2 hours, and the bath temperature was kept at 135 ° C. for 2 hours under heating and stirring to distill off the generated alcohol and 215 g of water.
An organosilsesquioxane oligomer solution containing 3 ', 4,4'-benzophenone tetracarboxylic acid was prepared. The solution was cooled to 80 ° C., and 38.3 g (0.2 mol) of γ-aminopropylmethyldiethoxysilane was added to a mixed solution of 133 g of γ-butyrolactone and 355 g of 3-methyl-3-methoxybutanol. , At the same temperature, 2
After heating for 3 hours, stirring and cooling to room temperature, 3-methyl-3
It was diluted with 60 g of -methoxybutanol to obtain an organic structure-modified organosilsesquioxane oligomer solution.
The solid content concentration of the solution thus obtained was adjusted to 300 ° C. and 30
It was 19.1% by weight and the viscosity was 18 centipoise (25 ° C.) as measured by the solvent removal method of partial heating.

This organic structure-modified organosilsesquioxane oligomer solution was filtered through a filter having a pore size of 0.2 μm to prepare a coating solution. 1 mm of this coating liquid
Apply with a spin coater on a thick alkali-free glass plate,
290 after pre-curing for 5 minutes in a hot air dryer at 100 ° C
Curing was carried out at 1 ° C. for 1 hour to form a coating film of 1.5 μm. This coating has no defects and has good flatness (± 0.05
μm or less), and 9 in the visible region of 400 to 800 nm.
It exhibited a light transmittance of 7% or more and a pencil scratch hardness of 3H. The adhesiveness to the glass plate was evaluated by a goose-eye test (JISK-5400) by tape peeling, but no peeling was observed. These characteristics are geared at 220 ° C.
It did not decrease even after the heat treatment in the oven for 200 hours, and did not decrease even after the wet heat treatment at 120 ° C., 2 atmospheres, 100% RH for 96 hours.

Further, the epoxy resin for encapsulating a liquid crystal cell was applied to the coating film on the glass plate and cured 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, and the adhesiveness was 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.

Instead of the 1 mm-thick non-alkali glass plate, a black filter of vapor-deposited chrome and a color filter in which pigment-dispersed RGB pixels having polyimide as a binder component are formed on the glass plate are used. Then, the same coating, pre-cure and cure were performed on this color filter. 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 properties were almost the same as the coating on the alkali-free glass plate.

Example 3 In Example 2, 20.0 g (0.1 mol) of trimellitic acid was used instead of 32.2 g (0.1 mol) of 4,4'-benzophenonetetracarboxylic dianhydride. , And almost the same result was obtained.

Example 4 In Example 2, 9.8 g (0.1 mol) of maleic anhydride was used instead of 32.2 g (0.1 mol) of 4,4'-benzophenone tetracarboxylic acid dianhydride. , And almost the same result was obtained.

Example 5 Instead of 38.3 g (0.2 mol) of γ-aminopropylmethyldiethoxysilane in Example 2, 46.9 g (0 of N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane was used. .2 mol) was used with almost similar results.

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Claims (14)

[Claims] 1. A thermosetting composition comprising at least the following components A, B and C: A: Organosilsesquioxane oligomer B: Polycarboxylic acid C: Silicon compound having at least one or more primary amino group or secondary amino group in the molecule 2. The thermosetting composition according to claim 1, wherein the organosilsesquioxane oligomer as the component A is a hydrolysis / condensation product or a condensation product of a compound represented by the following general formula (1). Stuff. [RSi (OR ') ₃ ] (1) (However, R and R'may be the same or different and each is hydrogen, an alkyl group, an aryl group, an allyl group or a fluoroalkyl group.) 3. The thermosetting composition according to claim 1, wherein the organosilsesquioxane oligomer as the component A is a hydrolysis / condensation product or a condensation product of methyltrialkoxysilane and phenyltrialkoxysilane. . 4. The organosilsesquioxane oligomer as the component A is an organosilsesquioxane oligomer obtained by hydrolyzing and condensing an organotrialkoxysilane using a polycarboxylic acid as a catalyst. The thermosetting composition according to 1. 5. The polyvalent carboxylic acid as the component B is a compound selected from the group consisting of aromatic tetracarboxylic acid, aromatic tricarboxylic acid, aliphatic tetracarboxylic acid, maleic acid and fumaric acid. The thermosetting composition according to claim 1. 6. A silicon compound having at least one primary amino group or secondary amino group in the molecule of component C is an aminoalkylalkoxysilane, an aminoarylalkoxysilane represented by the following general formula (2): The thermosetting composition according to claim 1, which is a hydrolyzed product or a hydrolyzed condensate thereof. [R ¹ _n Si (OR ² )] _4-n ] (2) (wherein R ¹ represents an organic group and may be the same or different, and at least one organic group is an aminoalkyl group or an N-alkyl group. An aminoalkyl group, an aminoaryl group or an N-alkyl-aminoaryl group,
The other is an organic group selected from an alkyl group, an aryl group, an allyl group and a fluoroalkyl group. R ^{2 s} 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. N is an integer of 1 to 3). 7. A thermosetting composition comprising at least 1 in the molecule.
A thermosetting composition according to claim 1, which contains a liquid having a boiling point of 100 to 300 ° C having one hydroxyl group and at least one ether bond as a solvent component. 8. A thermosetting composition for a color filter protective film, comprising the thermosetting composition according to claim 1. 9. A thermosetting composition for an insulating film, a passivation film or a buffer film of a semiconductor solid element, which comprises the thermosetting composition according to claim 1. 10. A thermosetting composition for an interlayer insulating film of a semiconductor integrated circuit or a multilayer printed wiring board, which comprises the thermosetting composition according to claim 1. 11. A thermosetting composition for forming an optical waveguide, which comprises the thermosetting composition according to claim 1. 12. At least an organotrialkoxysilane is hydrolyzed or hydrolyzed / condensed in the presence of a polyvalent carboxylic acid and / or a polycarboxylic acid anhydride in an organic solvent, and then an aminoalkylalkoxysilane and / or Or add aminoarylaualkoxysilane
The method for producing a thermosetting composition according to claim 1, wherein the thermosetting composition is reacted. 13. An organic solvent containing at least an organotrialkoxysilane, a polycarboxylic acid and / or a polycarboxylic anhydride, and one or more primary amino groups and / or secondary amino groups in the molecule. The method for producing a thermosetting composition according to claim 1, wherein a silicon compound having a group and one or more alkoxy groups is hydrolyzed and condensed. 14. A color filter comprising a transparent substrate and at least a colored layer and a protective film provided in this order on the transparent substrate, wherein the protective film is formed by curing the thermosetting composition for a color filter protective film according to claim 8. Characteristic color filter.