JP3463412B2 - Pigment-dispersed thermosetting resin solution composition, method for producing the same, and color filter - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigment-dispersed thermosetting resin solution composition comprising a polyimide siloxane precursor solution as a main component and pigments dispersed therein, and further manufactured by using the composition. The present invention also relates to a light-shielding film for an optical element, a coating film for an optical fiber, a color filter used for a liquid crystal display, an image pickup device, and the like.

[0002]

2. Description of the Related Art A composition prepared by dispersing a pigment in a polyimide precursor solution and its use include light resistance and heat resistance used in liquid crystal displays and image pickup devices.
A composition comprising a polyimide precursor for a color filter having excellent chemical resistance and a pigment, and a color filter formed using the composition are known (Japanese Patent Laid-Open No. 60-18).
No. 4202, No. 60-184203, No. 61-180203).

A composition in which a pigment is dispersed in a polyimide precursor solution is particularly useful for producing a color filter by a photolithography method, and, for example, JP-A-60-247603.
As disclosed in Japanese Patent Publication No. Sho 61-77804 and Japanese Laid-Open Patent Publication No. 61-77804, a pattern processing technique using a positive photoresist is known, and it has good pattern accuracy, light resistance and heat resistance.
It is possible to obtain a color filter having excellent chemical resistance and the like.

With the photolithography method, the printing method and other known methods, a colored coating film is formed on the glass substrate with the pigment-dispersed polyimide precursor composition. In this case, the finely pulverized pigment is uniformly dispersed in the polyimide precursor solution. It is especially important for the performance of the color filter such as the flatness of the coating film and the pixel contrast.

Conventionally known polyimide precursor solution compositions using an amide-based polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide have a dispersibility of fine pigments. Insufficient, aggregation of the pigment in the pigment-dispersed polyimide precursor solution composition is likely to occur, and the solution of the polyamic acid that is the polyimide precursor itself is susceptible to hydrolysis and gelation, and storage stability However, it had a problem that it was poor and needed to be stored in a freezer.

Further, the color filter composed of polyimide and pigment has an absorption due to the imide structure, and there is a problem that the blue purity of the color filter is lowered depending on the structure of the carrier resin.

[0007]

The object of the present invention is to provide a patterning property such as a pigment-dispersed polyimide precursor solution particularly in the production of a color filter, and a light resistance, heat resistance and chemical resistance of the resulting color filter. Another object is to obtain a novel pigment-dispersed thermosetting resin composition having excellent pigment dispersibility and storage stability, and to provide a color filter having a high contrast ratio and a high color purity from this composition.

[0008]

The object of the present invention is as follows.
Pigment and imide bond and siloxane bond by heat curing
And a pigment-dispersed thermosetting resin solution composition containing a polyimide siloxane precursor.

The present inventors have paid attention to a polyimidesiloxane precursor which gives a coating having both heat resistance and transparency and has good developability with an organic alkali or an inorganic alkali, and prepares various polyimidesiloxane precursor solutions. Then, a pigment-dispersed thermosetting resin composition was prepared, and its application as a color filter was examined. As a result, the present invention has been achieved. Here, the polyimide siloxane precursor means a precursor that forms a polymer by generating an imide bond and a siloxane bond by heat curing.

The polyimide siloxane precursor used in the present invention is, for example, JP-A-63-291922.
The production method disclosed in Japanese Patent Application Laid-Open No. 2004-242242 is known, and this polyimidesiloxane precursor is a tetrasiloxane containing a silicon compound having at least one or more primary amino group or secondary amino group and one or more alkoxy group in the molecule, and a tetra compound. It is a compound obtained by reacting a carboxylic acid dianhydride in an organic solvent, or a hydrolysis / condensation product of the compound.

As the improvement method, in addition to the hydrolysis / condensation product of the polyimidesiloxane precursor, the following (1) to (6)
The method of can be considered.

(1) Compound A obtained by reacting the following components A and B: a silicon compound having at least one or more primary amino group or secondary amino group and one or more alkoxy group in the molecule. Hydrolysis / condensation product B: Tetracarboxylic acid dianhydride (2) Compound A obtained by reacting the following components A and B: at least one or more primary amino group or secondary amino group and 1 in the molecule Hydrolysis / cocondensation product of a silicon compound having one or more alkoxy groups and a silicon compound having at least one alkoxy group in the molecule and not having an amino group B: tetracarboxylic acid dianhydride (3) organosyl A compound obtained by reacting a sesquioxane oligomer with the following components A and B or a hydrolysis / condensation product A of the compound: at least one or more primary amino groups in the molecule Alternatively, a silicon compound B having a secondary amino group and one or more alkoxy groups B: tetracarboxylic dianhydride (4) Compound A obtained by reacting an organosilsesquioxane oligomer with the following components A and B: molecule Hydrolyzed / condensed product of a silicon compound having at least one or more primary amino group or secondary amino group and one or more alkoxy group therein: tetracarboxylic acid dianhydride (5) organosilsesquioxane oligomer And a compound A obtained by reacting the following components A and B: a silicon compound having at least one or more primary amino groups or secondary amino groups and one or more alkoxy groups in the molecule, and at least one in the molecule Hydrolysis / cocondensation product of silicon compound having at least one alkoxy group and having no amino group B: tetracarboxylic acid dianhydride (6 Hydrolyzate of the following components A, B, and C or its hydrolysis / condensation product A: Silicon compound B having at least one or more primary amino group or secondary amino group and one or more alkoxy group in the molecule : Silicon compound having at least one alkoxy group in the molecule and having no amino group C: Polyvalent carboxylic acid having at least one set of adjacent carboxyl groups in the molecule or an anhydride thereof. However, as one of the polyimide siloxane precursors having good pigment dispersibility and stability for the purpose of the present invention, at least one or more primary amino group or secondary amino group in the molecule is particularly preferable. A silicon compound having an amino group and at least one alkoxy group, and optionally a silico compound having at least one alkoxy group in the molecule and not having an amino group. A polyimide siloxane precursor solution composed of a reaction product solution of a hydrolysis / condensation product of an elementary compound in an organic solvent and tetracarboxylic dianhydride can be mentioned. Alternatively, it may be a polyimidesiloxane precursor solution in which the prepared silsesquioxane oligomer solution is added separately to this solution.

Further, a polyimide siloxane precursor composed of a hydrolyzate of the following components A, B and C in an organic solvent or a hydrolyzate / condensate thereof can be preferably used.

A: Silicon compound having at least one primary amino group or secondary amino group and at least one alkoxy group in the molecule B: Amino group having at least one alkoxy group in the molecule No-containing silicon compound C: a polyvalent carboxylic acid having at least one set of adjacent carboxyl groups in the molecule or an anhydride thereof, as a raw material component used in the production of these polyimidesiloxane precursor solutions, at least in the molecule As the silicon compound having one or more primary amino groups or secondary amino groups and one or more alkoxy groups, an aminoalkylalkoxysilane represented by the following general formula (1),
Aminoarylalkoxysilanes are preferably used. [R ¹ _n Si (OR ² )] _4-n ] (1) (wherein R ¹ represents an organic group, and at least one of n organic groups is an aminoalkyl group, N-alkyl-aminoalkyl group, amino An aryl group or an N-alkyl-aminoaryl group, and the other is an organic 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, an allyl group, and a fluoroalkyl group, and 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 and the like can be used, but not limited to these compounds.

As the silicon compound having at least one alkoxy group in the molecule and having no amino group, an organotrialkoxysilane represented by the following general formula is preferably used, and [RSi (OR ') ₃ ] ( 2) (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.) Specific examples of these organotrialkoxysilanes , Methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, trifluoromethylmethoxysilane, trifluoroethyltrimethoxysilane, γ -Methacrylic oxyp Examples include, but are not limited to, ropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, and tetramethoxysilane, tetraethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diphenyl. It is also possible to use tetraalkoxysilane or dialkoxysilane such as dimethoxysilane together.

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 in combination to obtain a thermosetting resin solution composition having good dispersibility and storage stability in the thermosetting resin solution composition of the present invention, and of the coating film obtained from the composition. The toughness can be improved.

As the organosilsesquioxane oligomer used in the present invention, those obtained by hydrolyzing and condensing the above organotrialkoxysilane compound in an organic solvent are preferably used. In particular, a silsesquioxane oligomer solution obtained by hydrolyzing and condensing the produced alcohol and water in a high temperature range of 80 to 150 ° C. is preferably used. In addition, adding metal chelates such as zirconium chelate and titanium chelate to the generated silsesquioxane oligomer solution is effective for pigment dispersibility and storage stability of the polyimidesiloxane precursor solution using this silsesquioxane oligomer solution as a raw material component. It is effective for improving the sex.

As the tetracarboxylic dianhydride used in the present invention, widely known tetracarboxylic dianhydrides can be widely used. Specifically, pyromellitic dianhydride, 3,3 ', 4 , 4'-Benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-Diphenylethertetracarboxylic dianhydride , 1, 2, 3, 4-
Cyclobutanetetracarboxylic dianhydride, 1,2,3
4-butanetetracarboxylic dianhydride, 3,3 ', 4,
Examples thereof include 4′-diphenylsulfone tetracarboxylic acid dianhydride or a mixture thereof, but are not limited thereto.

Examples of the polycarboxylic acid having at least one set of adjacent carboxyl groups in the molecule or its anhydride include the above-mentioned tetracarboxylic dianhydride or its hydrolyzate, and further trimellitic acid, Examples thereof include fumaric acid, maleic acid, anhydrides thereof, and mixtures thereof. Particularly, aromatic tetracarboxylic acid, aliphatic tetracarboxylic acid, aromatic tricarboxylic acid,
It is preferably at least one selected from maleic acid, fumaric acid and their anhydrides. The organic solvent used for preparing the polyimidesiloxane precursor solution of the present invention or for preparing the silsesquioxane oligomer solution as a raw material component is not particularly limited, but γ-butyrolactone, N-methyl-2-pyrrolidone , N, N-dimethylacetamide, N, N-dimethylformamide and other polar solvents, preferably γ-butyrolactone, N-methyl-2-pyrrolidone and at least one hydroxyl group and at least one ether bond in the molecule. A liquid mixed solvent having a boiling point of 100 to 300 ° C. is preferably used, and particularly, a boiling point of 100 to 3 containing at least one hydroxyl group and at least one ether bond in the molecule.
The use of a solvent at 00 ° C. is preferable in order to obtain a composition having good coatability, and improves the dispersibility of the pigment in the resulting polyimidesiloxane precursor solution. Examples of such organic solvent components include 3-methyl-3-methoxybutanol, propylene glycol-mono-methyl ether, dipropylene glycol-mono-methyl ether.
And tripropylene glycol-mono-methyl ether, propylene glycol-mono-tertiary-butyl ether, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol and the like, but are not limited thereto. Not a thing.

A pigment-dispersed thermosetting resin solution composition comprising the pigment-dispersed polyimidesiloxane precursor solution of the present invention is
Since it is mainly used for forming a colored coating film for a color filter, as the pigment used in the present invention,
Those having high transparency and excellent light resistance, heat resistance, and chemical resistance are preferable. Specific examples of typical pigments are shown by color index (CI) numbers. Examples of yellow pigments are Pigment Yellow 20, 24, 83, 86, 93, 9
4, 109, 110, 117, 125, 137, 13
8, 139, 147, 148, 153, 154, 16
6,173, etc. are mentioned, but it is not limited to these. Pigment Orange 13 and 3 are examples of orange pigments.
1, 36, 38, 40, 42, 43, 51, 55, 5
Examples include, but are not limited to, 9, 61, 64, and 65. Pigment Red 9 and 9 are examples of red pigments.
7, 122, 123, 144, 149, 166, 16
8, 177, 180, 192, 215, 216, 224
However, the present invention is not limited to these. Examples of purple pigments include pigment violet 19, 23, 29, 3
2, 33, 36, 37, 38 and the like, but are not limited to these. Examples of blue pigments include Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21,
22, 60, 64, and the like, but are not limited to these. Pigment Green 7 and 1 are examples of green pigments.
Examples thereof include, but are not limited to, 0, 36, 47 and the like. Examples of black pigments include, but are not limited to, Pigment Black 7.

The above-mentioned pigments are practically used by being toned by combining several colors.

These raw materials may be treated with rosin, if necessary,
Surface treatment such as acidic group treatment and basic basic treatment is performed.

To prepare the pigment-dispersed polyimidesiloxane precursor solution, the pigment and the polyimidesiloxane precursor solution may be directly mixed and dispersed.
-Butyrolactone, N-methylpyrrolidone, 3-methyl-3-methoxybutanol and the like are dispersed in an organic solvent compatible with the polyimidesiloxane precursor solution,
A polyimide siloxane precursor solution may be mixed with this. Lactones such as γ-butyrolactone have particularly good pigment dispersibility. In dispersing the pigment, a surfactant containing no alkali metal or a polymeric dispersant is preferably used, and particularly a polyamic acid oligomer can be effectively used. The use of these dispersants is usually pigment 10
It is selected from the range of 1 to 20 parts by weight with respect to 0 part, but is not limited thereto.

The good pigment dispersibility of the polyimidesiloxane precursor solution of the present invention is that the polyimidesiloxane precursor is composed of an oligomer and has many polar groups such as hydroxyl groups in the molecule, and has a wide range of chemical structure and solvent selection. This is because it is large and various modifications are possible.

The amount of the pigment added in the pigment-dispersed thermosetting resin solution composition containing the pigment-dispersed polyimide siloxane precursor solution as a main component is preferably in the range of 1 to 300 parts by weight with respect to 100 parts by weight of the polyimide siloxane precursor. Further, it is preferably 25 to 200 parts by weight, and particularly preferably 50 to 150 parts by weight from the viewpoint of the balance of coloring degree and physical properties of the coating film to be formed.

The pigment-dispersed polyimide siloxane precursor solution of the present invention is added to benzoin tosylate, tri (nitrobenzyl) phosphate, trianisoinfosphate,
Known photoacid generators such as diaryliodonium salts and triarylsulfonium salts, known photobase generators such as nitrobenzylcyclohexylcarbamate and di (methoxybenzyl) hexamethylenedicarbamate, or acrylic monomers and known photopolymerization initiators. A sensitizer and the like can be added to obtain a photosensitive pigment-dispersed polyimide siloxane precursor solution.

A metal chelate is added to the pigment-dispersed polyimidesiloxane precursor solution of the present invention to improve the stability and storability of the pigment-dispersed solution, and further, the substrate or overcoat layer of the pigment-dispersed polyimidesiloxane film produced. , The adhesion to the ITO layer can be improved.
As such a metal chelate component, at least one metal chelate compound selected from an aluminum chelate compound, a titanium chelate compound or a zirconium chelate compound is used, and it is not particularly limited, but aluminum A metal chelate compound obtained by reacting trialcooxide, titanium tetraalcooxide, zirconium tetraalcooxide with a β-diketone compound or a β-ketoester is preferably used. Specifically, aluminum tris (ethylacetoacetate) is used. ), Dipropoxytitanium bis (ethylacetoacetate), dibutoxyzirconium bis (ethylacetoacetate), zirconium tetra (ethylacetoacetate), titanium tetra (ethylacetoacetate).
G), aluminum tris (acetylacetona-
G), dipropoxytitanium bis (acetylacetona-
G), dibutoxyzirconium bis (acetylacetonate), zirconium tetra (acetylacetonate)
G), titanium tetra (acetylacetonate) 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. The organic solvent is not particularly limited, but the pigment-dispersed polyimidesiloxane precursor of the present invention is used. A solvent component similar to the solvent component of the solution can be used.

The amount of such a metal chelate component used is preferably in the range of 0.01 to 10% by weight based on the resin component of the pigment-dispersed polyimidesiloxane precursor solution.

The pigment-dispersed thermosetting resin solution composition containing the pigment-dispersed polyimidesiloxane precursor solution of the present invention as a main component is used for a light-shielding film of an optical element, a coating film of an optical fiber, a color filter of a liquid crystal display element, and the like. .

An example of a method of using a color filter, which is a typical application of the pigment-dispersed thermosetting resin solution composition containing the pigment-dispersed polyimidesiloxane precursor solution of the present invention as a main component, will be described.

A colored coating film of, for example, G (green) is formed on the transparent substrate with the pigment-dispersed polyimide siloxane precursor solution. For the coating, spinner, spray coating, dip coating, roll coating, die coating and the like are applied. Drying is performed using an oven, a hot plate or infrared rays within a range of 50 to 180 ° C for several hours.
It is preferably within a range in which curing is carried out for several seconds and curing does not proceed so much. A photoresist for forming a pattern is applied on this to form a photoresist layer. Subsequently, a mask is placed on the photoresist layer coating using an exposure device, and exposed to actinic rays. When a positive photoresist is used, the photoresist layer is developed with a developer for the positive photoresist and the polyimide siloxane precursor colored coating film is simultaneously etched. After etching, the photoresist layer that is no longer needed is peeled and removed, usually with a solvent of acetone, cellosolve, or propylene glycol alkyl ether acetate. The polyimide siloxane precursor colored coating film is heat-treated to complete the patterning of the G (green) colored coating film. Final heat treatment temperature is 180-400
C, preferably 180-350 C, depending on the temperature 5 hours to 5 minutes are applied.

The above steps are R (red), B (blue)
By repeating the process for the pixels of No. 1 and BK (black) (black mask) as necessary, a color filter can be manufactured.

[0034]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these.

Preparation Example 1 40.8 g (0.3 mol) of methyltrimethoxysilane,
Phenyltrimethoxysilane 59.4 g (0.3 mol), γ-aminopropylmethyldiethoxysilane 28
8.0 g (1.5 mol) was dissolved in 1284 g of 3-methyl-3-methoxybutanol and 1000 g of γ-butyrolactone, and 86.4 g of distilled water was added while stirring at 30 ° C., and then gradually. The temperature was raised under heating and stirring and 1 hour later, the bath temperature was set to 55 ° C., and hydrolysis and condensation were carried out at this temperature for 3 hours with stirring. 241.7 g of 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride was added to this solution.
(0.75 mol) was added, and the mixture was further heated and stirred at 55 ° C. for 3 hours to obtain a polyimidesiloxane precursor solution.
The solid content concentration of the solution thus obtained was adjusted to 300 ° C. and 30
It was 15.3% as measured by the solvent-removal method with partial heating, and the solution viscosity was 23 centipoise (25 ° C.).

Preparation Example 2 272.0 g (2.0 mol) of methyltrimethoxysilane and 395.0 g (2.
0 mol) to 3-methyl-3-methoxybutanol 78
It was dissolved in 5.6 g and stirred at 30 ° C. for 216.0
g of distilled water and 0.34 g of acetic acid were added, and the mixture was heated and stirred for 0.5 hours to carry out hydrolysis / condensation.

This solution was gradually heated and stirred, and the temperature was raised under stirring for 1 hour, then the temperature of the bath was kept at 105 ° C. for 2 hours under heating and stirring to distill off the formed alcohol and 302.4 g of water.
Next, the bath temperature was set to 130 ° C. and the mixture was heated and stirred for 2 hours, and the produced water and 146.7 g of alcohol were distilled off. After cooling the resulting silsesquioxane oligomer solution, 3
-Methyl-3-methoxybutanol 85.7 g was added and diluted.

The solid content concentration of the solution thus obtained was 3
30.2 when measured by the solvent removal method of heating at 00 ° C for 30 minutes
%, And the solution viscosity was 40 centipoise (25 ° C.).

Preparation Example 3 1306.7 g of the solution obtained in Preparation Example 2 was used to prepare a solution of zirconium acetoacetic acid ethyl ester divalent chelate in 3-methyl-3-methoxybutanol (concentration in terms of zirconia:
10% by weight) (196 g) and 3-methyl-3-methoxybutanol (143.7 g) were added, and the mixture was stirred and mixed at 30 ° C. for 1 hour.

The solid content of the solution thus obtained was adjusted to 3
25.3 when measured by the solvent removal method of heating at 00 ° C for 30 minutes
%, And the solution viscosity was 20 centipoise (25 ° C.). Preparation Example 4 393.48 g of γ-butyrolactone and 573.48 g of 3-methyl-3-methoxybutanol were added to 3,3 ′, 4,4 ′.
-Benzophenone tetracarboxylic acid dianhydride 180.0
g (0.5586 mol) and stirred at 20 ° C. for 10 minutes, then γ-aminopropylmethyldiethoxysilane (213.72 g, 1.1172 mol) was added, and the mixture was stirred at 40 ° C. for 3 hours to prepare polyimide. A siloxane precursor solution was obtained. The solid concentration of the solution thus obtained was 300 ° C.,
It was 20.1% as measured by the solvent removal method by heating for 30 minutes, and the solution viscosity was 32 centipoise (25 ° C.).

Preparation Example 5 27.2 g (0.2 mol) of methyltrimethoxysilane,
39.6 g (0.2 mol) of phenyltrimethoxysilane and 32.2 g (0.10 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic acid dianhydride were added to 3-methyl-3-methoxybutanol. 61.7 g and 61.7 g of γ-butyrolactone were added and stirred at 30 ° C.
Add 25.2 g of distilled water, stir for 1 hour, and
Condensation was performed. This solution was gradually heated and heated under stirring for 1 hour, and after heating for 1 hour at a bath temperature of 90 ° C., the solution was heated and stirred for 1 hour to obtain γ-aminopropylmethyldiethoxysilane 38.
A mixed solution of 3 g (0.2 mol), 76.6 g of 3-methyl-3-methoxybutanol, and 76.6 g of γ-butyrolactone was added, and the mixture was heated at the same temperature as a bath temperature of 125 ° C. for 2 hours with stirring to generate. After distilling off the alcohol and 38.3 g of water, the mixture was cooled to 30 ° C. and diluted with a mixed solution of 35.9 g of 3-methyl-3-methoxybutanol and 35.9 g of γ-butyrolactone to dilute the polyimidesiloxane. A precursor solution was obtained. The solid concentration of the solution thus obtained was 300 ° C.,
It was 20.4% as measured by the solvent removal method of heating for 30 minutes, and the solution viscosity was 122 centipoise (25 ° C.).

Preparation Example 6 27.2 g (0.2 mol) of methyltrimethoxysilane,
39.6 g (0.2 mol) of phenyltrimethoxysilane and 19.6 g (0.20 mol) of maleic anhydride were used.
-Methyl-3-methoxybutanol 50.4 g and γ
-In addition to 50.4 g of butyrolactone, 28.8 g of distilled water was added with stirring at 30 ° C, and the mixture was stirred for 1 hour to carry out hydrolysis / condensation. This solution was gradually heated and heated under stirring for 1 hour, and after heating for 1 hour at a bath temperature of 90 ° C., the solution was heated and stirred for 7 hours, and 76.6 g (0.4 mol) of γ-aminopropylmethyldiethoxysilane and 3- Methyl-3-methoxybutanol 76.6 g, γ-butyrolactone 76.6 g
Add the mixed solution of and set the bath temperature to 125 ° C and
After heating and stirring for 5 hours to distill off the alcohol and 54.2 g of water produced, the mixture is cooled to 30 ° C. and 64.2 g of 3-methyl-3-methoxybutanol and γ-butyrolactone 64.
The mixture was diluted with 2 g of a mixed solution to obtain a polyimidesiloxane precursor solution. The solid content of the solution thus obtained was adjusted to 30
20.2% when measured by the solvent removal method of heating at 0 ° C for 30 minutes
And the solution viscosity was 50 centipoise (25 ° C.).

Preparation Example 7 6.3 g of Pigment Red 177 (Chromoftal Red A3B manufactured by Ciba-Geigy Co., Ltd.) and 83.7 g of γ-butyrolactone were dispersed together with 90 g of glass beads at 7,000 rpm for 30 minutes, and then the glass beads were dispersed. Was removed by filtration to obtain a pigment dispersion.

Example 1 1000 g of the solution obtained in Preparation Example 1 and 600 g of the solution obtained in Preparation Example 3 were mixed to prepare a new polyimidesiloxane precursor solution.

6 g of this polyimidesiloxane precursor solution
Was added to and mixed with 14 g of the pigment dispersion liquid obtained in Preparation Example 7 to obtain a colored pigment-dispersed polyimidesiloxane precursor solution of the present invention. This dispersion was applied onto a glass substrate with a spinner so that the film thickness when it became polyimidesiloxane after heating was 1.0 μm, dried at 90 ° C. for 10 minutes, and after cooling,
On top of this, a positive photoresist (OF, manufactured by Tokyo Ohka Co., Ltd.)
PR-800) was applied by a spinner so that the film thickness after drying was 1.0 μm, and dried at 80 ° C. for 20 minutes. Using a UV exposure machine PLA-501F manufactured by Canon Inc., 150 mJ / cm through a photomask made of chromium.
2 (UV intensity of 365 nm). 2.38% of tetramethylammonium hydroxide after exposure
The photoresist was developed and the polyimide siloxane precursor colored coating film was etched at the same time. After etching, the unnecessary photoresist layer was removed with acetone. The pattern-formed polyimide siloxane precursor colored coating film thus obtained was heat-treated at 300 ° C. for 30 minutes to be converted into polyimide siloxane.

The contrast of the colored coating film thus obtained was 820, and when the coating film was observed under a microscope at 1000 times, no pigment agglomeration was observed and the pigment was uniformly dispersed.

Here, as a method for measuring the contrast, a parallel nicols state of the sample is obtained in a field of view twice with a color luminance meter (Topcon BM-5A) on a backlight (Meitaku system), that is, at a position where the sample is sandwiched. The luminance (I _parallel ) when the polarization axes of the polarizing plates are parallel to each other and the luminance (I _orthogonal ) in the orthogonal Nicol state are measured, and the ratio (I) between the luminance in the parallel Nicol state and the luminance in the orthogonal Nicol state (I _Parallel / I _orthogonal ) was taken as the contrast.

The same applies to the following embodiments.

Example 2 1000 g of the solution obtained in Preparation Example 1 and 600 g of the solution obtained in Preparation Example 3 were mixed to prepare a polyimidesiloxane precursor solution.

This polyimide siloxane precursor solution 45
90 g of 3-methyl-3-methoxybutanol, 2.9 g of Pigment Red 177, and Pigment Yellow 8
0.7 g of 3 was dispersed with 90 g of glass beads using a homogenizer at 7,000 rpm for 30 minutes, and then the glass beads were filtered and removed to obtain a pigment dispersion.

A colored coating film of polyimidesiloxane was obtained from this dispersion in exactly the same manner as in Example 1. The contrast of the thus-obtained colored coating film was 390, and when the coating film was observed under a microscope at 1000 times, no pigment aggregation was observed and the pigment was uniformly dispersed.

After the pigment-dispersed polyimidesiloxane precursor solution obtained in this example was allowed to stand at 25 ° C. for 1 month, a similar colored coating film of polyimidesiloxane could be obtained.

Example 3 1000 g of the solution obtained in Preparation Example 4, 2000 g of the solution obtained in Preparation Example 2 and 1000 g of 3-methyl-3-methoxybutanol were mixed to prepare a polyimidesiloxane precursor solution.

This polyimide siloxane precursor solution 45
g, 3-methyl-3-methoxybutanol 90 g, Pigment Red 177 (Ciba Geigy Co., Ltd. Chromophtal Red A3B) 3.6 g were dispersed for 30 minutes at 7,000 rpm using a homogenizer together with 90 g of glass beads, and then glass beads. Was removed by filtration to obtain a pigment dispersion.

A colored coating film of polyimidesiloxane was obtained from this dispersion in exactly the same manner as in Example 1. The contrast of the colored coating film thus obtained was 430, and when the coating film was observed under a microscope at 1000 times, no aggregation of the pigment was observed and the pigment was uniformly dispersed.

Example 4 Polyimide siloxane precursor solution 4 obtained in Preparation Example 5
Using 5 g, 45 g of 3-methyl-3-methoxybutanol, and 3.6 g of Pigment Green 7 together with 90 g of glass beads, using a homogenizer, 30 at 7,000 rpm.
After dispersing for a minute, the glass beads were filtered and removed to obtain a pigment dispersion liquid.

A colored coating film of polyimidesiloxane was obtained from this dispersion in exactly the same manner as in Example 1 except that a developing solution containing a 5.5% aqueous solution of tetramethylammonium hydroxide was used.

The thus-obtained colored coating film had a contrast of 925, and when the coating film was observed under a microscope at 1000 ×, no pigment aggregation was observed and the pigment was uniformly dispersed.

Example 5 Polyimide siloxane precursor solution 4 obtained in Preparation Example 6
Using 5 g, 45 g of 3-methyl-3-methoxybutanol, and 3.6 g of Pigment Blue 15 together with 90 g of glass beads, 30 at 7,000 rpm using a homogenizer.
After dispersing for a minute, the glass beads were filtered and removed to obtain a pigment dispersion liquid.

A colored coating film of polyimidesiloxane was obtained from this dispersion in exactly the same manner as in Example 1 except that a developer containing a 5.5% aqueous solution of tetramethylammonium hydroxide was used.

The thus-obtained colored coating film had a contrast of 980, and when the coating film was observed under a microscope at 1000 ×, no pigment aggregation was observed and the pigment was uniformly dispersed.

Comparative Example 1 147 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was charged together with 775 g of N-methyl-2-pyrrolidone, and 95.1 g of 4,4'-diaminodiphenyl ether and bis (3 -Aminopropyl) tetramethyldisiloxane (6.2 g) was added and reacted at 60 ° C. for 3 hours to obtain a polyimide precursor solution (A having a viscosity of 730 poise).
1) was obtained.

Pigment Red 177 (Chromoftal Red A3B manufactured by Ciba-Geigy Co., Ltd.) 6.3 g, N-
Glass beads 90 containing 83.7 g of methyl-2-pyrrolidone
Using a homogenizer with g, the mixture was dispersed at 7,000 rpm for 30 minutes, and then the glass beads were filtered and removed to obtain a pigment dispersion liquid (B1).

A solution obtained by diluting 25 g of the polyimide precursor solution (A1) with 25 g of N-methyl-2-pyrrolidone was added to 47 g of the pigment dispersion (B1) and mixed to obtain a pigment-dispersed polyimide precursor composition.

A colored coating film of polyimidesiloxane was obtained from this dispersion in exactly the same manner as in Example 1. The contrast of the colored coating film thus obtained was 250, and when this coating film was observed under a microscope at 1000 ×, aggregation of the pigment was recognized.

When this pigment-dispersed polyimide precursor composition was allowed to stand at 25 ° C. for 1 month, the composition was separated.

Preparation Example 8 Pigment Red 177 4.3 g, Pigment Yellow 83 1.2 g, γ-butyrolactone 70.0 g, 3
30 g of -methyl-3-methoxybutanol and 1 g of the polyimidesiloxane precursor solution obtained in Preparation Example 5 were used together with 90 g of glass beads using a homogenizer.
After dispersing at 000 rpm for 30 minutes, filter the glass beads.
After removal, a red (R) pigment dispersion was obtained.

Preparation Example 9 In Preparation Example 8, 4.3 g of Pigment Red 177,
Pigment Yellow 83 1.2 g instead of Pigment Green 7 5.2 g, Pigment Yellow 83
Using 0.7 g, a green (G) pigment dispersion liquid was obtained by the same operation.

Preparation Example 10 In Preparation Example 8, 4.3 g of Pigment Red 177,
Pigment Blue 15 (7.2 g) was used in place of Pigment Yellow 83 (1.2 g), and a blue (B) pigment dispersion liquid was obtained by the same operation.

Preparation Example 11 In Preparation Example 8, 4.3 g of Pigment Red 177,
Pigment Yellow 83 (1.2 g) was used in place of carbon black (5.2 g), and a light-shielding agent (BL) dispersion was obtained by the same operation.

Example 6 As shown in the conceptual diagram of the manufacturing process of the color filter shown in FIG. 1, a cleaned glass substrate having a thickness of 1 mm was patterned by chrome plating, photolithography and etching by a known technique to form a black mask. A chrome pattern having a thickness of 1 μm was formed. A red (R) pigment-dispersed polyimidesiloxane precursor solution obtained by adding 6 g of the solution obtained in Preparation Example 1 to 14 g of the pigment dispersion obtained in Preparation Example 8 and mixing the solution on the chrome-patterned glass substrate was added. By coating, the pixel shown by R in FIG. 1 was formed by the method shown in Example 1.

Similarly, the solution obtained in Preparation Example 1 was prepared as Preparation Example 9
The green (G) pigment-dispersed polyimide siloxane precursor solution obtained by adding and mixing to the pigment dispersion obtained in 1. was applied thereon to form pixels shown by G in FIG.
Further, the solution obtained in Preparation Example 1 was added to and mixed with the pigment dispersion obtained in Preparation Example 10, and a blue (B) pigment-dispersed polyimide siloxane precursor solution obtained was coated thereon,
The pixel indicated by B in FIG. 1 was formed. On top of this, the solution obtained in Preparation Example 6 was applied, dried, and cured to form 1 μm.
After forming an overcoat layer having a thickness, an ITO layer was formed by a known technique to obtain a color filter.

Example 7 6 g of the solution obtained in Preparation Example 1 was added to and mixed with 14 g of the light-shielding agent dispersion liquid obtained in Preparation Example 11 (B
L) The dispersion polyimide siloxane precursor solution was applied onto a glass substrate by a spinner so that the film thickness when it became polyimide siloxane after heating was 1.0 μm, and it was applied at 90 ° C. for 1 hour.
After drying for 0 minutes and cooling, a positive photoresist (OFPR-800 manufactured by Tokyo Ohka Co., Ltd.) was applied on this with a spinner so that the film thickness after drying was 1.0 μm, and 90 ° C.
And dried for 20 minutes. Canon Inc. UV exposure machine P
Using LA-501F, it was exposed to 150 mJ / cm 2 (ultraviolet intensity of 365 nm) through a photomask made of chromium. After the exposure, it was immersed in a developing solution composed of a 2.38% tetramethylammonium hydroxide aqueous solution, and the photoresist was developed and the polyimide siloxane precursor colored coating film was simultaneously etched. After etching, the unnecessary photoresist layer was removed with acetone. Thus, the polyimide siloxane precursor light-shielding agent coating film etched in a black mask pattern corresponding to the chromium pattern shown in FIG.
It was heat-treated for a minute and converted into polyimide siloxane. RGB pixels were formed on the glass substrate having the black mask pattern in the same manner as in Example 6 to obtain a color filter.

[0074]

The pigment-dispersed thermosetting resin solution composition of the present invention has excellent pigment dispersibility and stability, and a color filter having excellent heat resistance, light resistance, chemical resistance and contrast ratio can be obtained from this composition. Obtainable.

[Brief description of drawings]

FIG. 1 shows a conceptual diagram of a color filter manufacturing process.

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Claims (17)

(57) [Claims] 1. A pigment and a imide bond formed by heat curing
A pigment-dispersed thermosetting resin solution composition containing a polyimidesiloxane precursor that forms a roxane bond . 2. The polyimide siloxane precursor has the following A,
A compound obtained by reacting the component B or a hydrolysis / condensation product of the compound, which is characterized in that
The pigment-dispersed thermosetting resin solution composition described. A: Silicon compound having at least one or more primary amino group or secondary amino group and one or more alkoxy group in the molecule B: Tetracarboxylic acid dianhydride 3. A polyimide siloxane precursor having the following A,
The pigment-dispersed thermosetting resin solution composition according to claim 1, comprising a compound obtained by reacting the component B. A: Hydrolysis / condensation product of silicon compound having at least one or more primary amino group or secondary amino group and one or more alkoxy group in the molecule B: tetracarboxylic acid dianhydride 4. The polyimide siloxane precursor has the following A,
The pigment-dispersed thermosetting resin solution composition according to claim 1, comprising a compound obtained by reacting the component B. A: Silicon compound having at least one or more primary amino group or secondary amino group and at least one alkoxy group in the molecule, and silicon having at least one alkoxy group in the molecule and having no amino group. Hydrolysis / cocondensation compound B: tetracarboxylic acid dianhydride 5. The polyimide siloxane precursor comprises a compound obtained by reacting an organosilsesquioxane oligomer with the following components A and B, or a hydrolyzed / condensed product of the compound. Pigment dispersion thermosetting resin solution composition. A: Silicon compound having at least one or more primary amino group or secondary amino group and one or more alkoxy group in the molecule B: Tetracarboxylic acid dianhydride 6. A pigment-dispersed thermosetting resin solution composition according to claim 1, wherein the polyimidesiloxane precursor comprises a compound obtained by reacting an organosilsesquioxane oligomer with the following components A and B. object. A: Hydrolysis / condensation product of silicon compound having at least one or more primary amino group or secondary amino group and one or more alkoxy group in the molecule B: tetracarboxylic acid dianhydride 7. A pigment-dispersed thermosetting resin solution composition according to claim 1, wherein the polyimidesiloxane precursor comprises a compound obtained by reacting an organosilsesquioxane oligomer with the following components A and B. object. A: Silicon compound having at least one or more primary amino group or secondary amino group and at least one alkoxy group in the molecule, and silicon having at least one alkoxy group in the molecule and having no amino group. Hydrolysis / cocondensation compound B: tetracarboxylic acid dianhydride 8. A polyimide siloxane precursor having the following A,
The pigment-dispersed thermosetting resin solution composition according to claim 1, which comprises a hydrolyzate of components B and C or a hydrolyzate / condensate thereof. A: Silicon compound having at least one primary amino group or secondary amino group and one or more alkoxy groups in the molecule B: At least one alkoxy group having no amino group in the molecule Silicon compound C: polyvalent carboxylic acid having at least one set of adjacent carboxyl groups in the molecule or its anhydride 9. The pigment-dispersed thermosetting resin solution composition according to claim 1, which contains a metal chelate compound. 10. A compound having a boiling point of 100 to 300 ° C., in which the organic solvent component of the pigment-dispersed thermosetting resin solution composition contains at least one ether bond and a hydroxyl group in the molecule, N
A pigment-dispersed thermosetting resin solution composition according to claim 1, which contains a polar solvent selected from the group of -methyl-2-pyrrolidone and γ-butyrolactone. 11. The pigment-dispersed thermosetting resin solution composition according to claim 1, which contains a photo-acid generator or a photo-base generator. 12. The pigment-dispersed thermosetting resin solution composition according to claim 1, which contains an acrylic monomer and a photopolymerization initiator or a sensitizer. 13. The pigment-dispersed thermosetting resin solution composition according to claim 1, which is colored R (red), G (green), B (blue) or BL (black). 14. The method for producing a pigment-dispersed thermosetting resin solution composition according to claim 1, further comprising a step of dispersing the pigment in the polyimidesiloxane precursor solution. 15. A step of adding a polyimidesiloxane precursor solution to a pigment dispersion liquid containing a lactone as a main solvent and a dispersed pigment as a main component.
A method for producing the pigment-dispersed thermosetting resin solution composition described. 16. The method according to claim 15, further comprising the step of adding a polyimidesiloxane precursor solution to a pigment dispersion liquid having a pigment as a main component, which is dispersed by using a lactone as a main solvent and a polyamic acid oligomer as a dispersant. A method for producing the pigment-dispersed thermosetting resin solution composition described. 17. A color filter having a cured film of the pigment-dispersed thermosetting resin solution composition according to claim 1 on a transparent substrate.