JPH07225314A - Color filter and its production - Google Patents

Abstract

PURPOSE:To obtain a color filter having satisfactory adhesion to all over the surfaces of the transparent substrate and transparent protective layer and to obtain a color filter having satisfactory adhesion and high reliability. CONSTITUTION:When a colored layer, a light shielding layer and a transparent protective layer are disposed on a transparent substrate to produce a color filter, an adhesive layer of polyimide resin is interposed between the protective layer and the light shielding layer so that the adhesive layer exists in a region in which at least one of the light shielding layer and the colored layer in the color filter exists and the objective color filter is obtd. Since the adhesive layer is chiefly formed on the colored layer and on the light shielding layer, the adhesion of the protective layer to the light shielding layer is improved. Since the protective layer adheres directly to the part of the substrate on which the colored layer and light shielding layer are not disposed, the adhesion of the protective layer to the part of the substrate is improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter used for a liquid crystal display device, a solid-state image pickup device and the like and a method for manufacturing the same.

[0002]

2. Description of the Related Art A color filter comprises a transparent substrate and three colored layers of red (R), green (G) and blue (B). However, it is difficult to obtain the flatness required for the liquid crystal display device only with the colored layer, and it is considered that the operation of the liquid crystal display device is hindered when the ionic impurities of the transparent substrate are mixed in the liquid crystal. Therefore, a transparent protective layer is placed on the colored layer for the purpose of improving flatness and protecting the surface. As such a transparent protective layer, currently, acrylic resin (JP-A-3-251819), epoxy resin (JP-A-2-228630), polyimide resin (JP-A-61-254905), silicone resin ( JP 63-2
41076), imide-modified silicone (JP-A-63-291)
924) is used. Further, the conventional transparent protective layer has a sufficient function as flatness, a barrier effect against ionic impurities, and adhesion to a transparent substrate such as glass, but the adhesion to the light shielding layer may be poor. ,
An adhesion layer is also formed between the colored layer and the transparent protective layer. A polyimide resin, for example, is known as such an adhesive layer (Japanese Patent Laid-Open No. 1-196926).

[0003]

However, the adhesion layer made of a polyimide resin provided for improving the adhesion between the transparent protective layer and the light-shielding layer is not so good that the adhesion between the adhesion layer and the transparent substrate is high. There was a problem such as peeling in a reliability test such as high humidity.

[0004]

In order to solve the above-mentioned problems, the inventors of the present invention have made extensive studies and, as a result, arrived at the present invention.

That is, according to the present invention, in a color filter in which a light shielding layer, a coloring layer and a transparent protective layer are provided on a transparent substrate, an adhesion layer made of a polyimide resin is provided between the light shielding layer and the transparent protective layer. Further, the adhesion layer is
In the method for producing a color filter characterized by being in a region where at least one of the light-shielding layer and the colored layer exists, and a light-shielding layer, a colored layer and a transparent protective layer provided on a transparent substrate, light-shielding In the method for producing a color filter, an adhesion layer is formed on a transparent substrate on which a layer and a coloring layer are formed, in a region where at least one of the light shielding layer and the coloring layer exists.

With this arrangement, the adhesion between the transparent protective layer and the light-shielding layer is improved by the adhesion layer in the pixel portion and the light-shielding layer portion, and the transparent substrate portion does not have the adhesion layer. And the transparent protective layer firmly adhere to each other. In this way, the color filter of the present invention which can provide a highly reliable color filter having good adhesion is a colored layer, a patterned adhesion layer and a transparent protective layer provided in this order on a transparent substrate. A transparent electrode layer of indium tin oxide or the like is formed on this.

The transparent substrate is not particularly limited, but a glass plate such as alkali glass or non-alkali glass or a resin substrate such as polycarbonate or polymethacrylate can be used. Among these, "705
Alkali-free glass such as 9 "(Corning Co.)," OA2 "(Nippon Electric Glass Co., Ltd.), and" NA45 "(HOYA) are suitable from the viewpoint of alkali elution, heat resistance, chemical resistance, cleanliness and the like.

Although the colored layer is not particularly limited,
Acrylic resin, polyester resin, polyvinyl alcohol resin, polyimide resin and the like, or a mixture of two or more kinds thereof, and a colorant such as a dye or a pigment are dispersed and mixed in these photosensitive resins to form red, blue and green pixels. The formed one is used. As a method for forming this colored layer, a dyeing method, a pigment dispersion method, a transfer method, a printing method, an electrodeposition method or the like can be appropriately used.

A light-shielding layer made of metal, resin, or the like is provided between the pixels as needed to improve the contrast. Specifically, metallic chromium, chromium oxide,
Resins in which molybdenum, tantalum, aluminum and oxides thereof, carbon, and black pigment are dispersed are used. Among these, metallic chromium and chromium oxide are preferable in terms of light-shielding properties and film forming properties.

For the transparent protective layer, known resins such as acrylic resin, epoxy resin, polyimide resin and silicone resin can be appropriately used, but imide excellent in heat resistance, surface flatness, hardness and transparency is preferable. It is a modified silicone. The imide-modified silicones, for example, the following general formula ₍₁₎ in ^{_{H 2 N- (CH 2) m}} -SiR 1 n (OR 2) 3-n ...... (1) ( Formula (1), m is 1 or more , N is an integer of 0 to 2, R ¹ is an alkyl group or an aryl group, and R ² is an alkyl group or an acyl group.) And a tetracarboxylic acid dianhydride. And the general formula (2) R ³ _p Si (OR ⁴ ) _4-p (2) (in the formula (2), p is an integer of 1 to ³ , R ³ is an organic compound) The group, R ⁴ represents an alkyl group or an acyl group.) Is a curable composition containing a partial condensate (B) obtained by hydrolysis of a compound represented by formula (B) or a concentrated compound (B ′).

Examples of the tetracarboxylic dianhydride used in the present invention include aliphatic and aromatic tetracarboxylic dianhydrides, such as pyromellitic dianhydride, 3,3 ′, 4, 4'-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-Diphenylsulfone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,5
-Tricarboxycyclopentyl acetic acid dianhydride, 1,2,3,
4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4
-Cyclopentanetetracarboxylic dianhydride and the like. These can be used alone or in combination.

Examples of the amino compound represented by the above formula (1) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxysilane and 3-aminopropylmethyldimethoxy. Silane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldipropoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, 3-
Examples thereof include aminopropylethyldipropoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldimethylpropoxysilane and the like. These amino compounds can also be used in combination.

Examples of the silicone component represented by the above formula (2) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane and phenyl. Trimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane, vinylmethyl Diethoxysilane, vinylmethyldipropoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxy B pills tripropoxysilane,
3-glycidoxypropylmethyldimethoxysilane, 3
-Glycidoxypropylmethyldiethoxysilane, 3-
Glycidoxypropylmethyldipropoxysilane, 3-
Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyl Dipropoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3, 4-epoxycyclohexylethyltriethoxysilane, 3,4-epoxycyclohexylethylmethyldimethoxysilane, 3,4-epoxycyclohexylethylmethyldiethoxysilane Sisilane etc. are mentioned. These alkoxysilane compounds can also be used in combination. Particularly preferably, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane and these. Polymers of are preferable.

It is more preferable to add a silicone type surfactant to the compounds (A) and (B). The surfactant may be added at the time of preparing the components (A) and (B) or after the preparation, but it is preferable to disperse the surfactant in advance in a solvent added at the time of preparation in order to mix the components uniformly. Here, as the silicone-based surfactant, "Floren" WS (manufactured by Kyoeisha Yushi) and "Disparon"# 161
0, # 1721, # 1761 (made by Kusumoto Kasei), "Aditol" SL121, 122 (made by Hoechst), Byk
-300 (manufactured by Bibb Chemie) and the like.

The transparent protective layer can be applied by any method such as a spinner method, a roll coater method, a printing method and a dipping method.

In the present invention, the adhesion layer is made of polyimide resin.

Examples of the polyimide resin used in the present invention include those represented by the general formula (3):

[Chemical 2] (In the formula, R ⁵ represents a tetravalent organic group having at least 2 carbon atoms, and R ⁶ represents a divalent organic group having at least 2 carbon atoms.) Polymers containing as a main constituent unit are mentioned. In the above formula, R ⁵ preferably has a structure in which the carbonyl group of the polymer main chain is directly bonded to the aromatic ring or the aromatic heterocycle in view of the heat resistance of the polyimide. Further, in the above formula, R ⁶ preferably has a structure in which the amide group of the polymer main chain is directly bonded to the aromatic ring.

Specific examples of this polyimide include pyromellitic dianhydride, 3,3'- (or 4,4 '-) diaminodiphenyl sulfone, 3,3', 4,4'-benzophenone. Tetracarboxylic acid dianhydride and 3,3'- (or 4,4 '
-) Diaminodiphenyl sulfone, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 3,3'- (or 4,
4'-) diaminodiphenyl sulfone, pyromellitic dianhydride and 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, and 3,3'- (or 4,4'-) diaminodiphenyl Sulfone, 3,3 ', 4,4'-benzophenone tetracarboxylic anhydride, 3,3'- (or 4,4'-) diaminodiphenyl sulfone and bis (3-aminopropyl) tetramethyldisiloxane, 3,3 ', 4,4'-benzophenone tetracarboxylic anhydride and 3,3'- (or 4,
A polyamic acid synthesized from 4 ′-) diaminodiphenyl sulfone, 3,3′-diaminodiphenylmethane, bis (3-aminopropyl) tetramethyldisiloxane or the like to form a polyimide by heating is preferably used. More preferably, it is synthesized from 3,3 ', 4,4'-benzophenone tetracarboxylic acid anhydride, 3,3'- (or 4,4'-) diaminodiphenyl sulfone and 3,3'-diaminodiphenylmethane. The polyamic acid may be a polyimide.

The polyimide may be composed of only the one represented by the general formula (3) or may be a copolymer with another structural unit. Typical types of structural units used for copolymerization include structural units of polyether amic acid and polyester amic acid, but are not limited thereto.

These polyimide adhesion layers are effective when a known resin such as an acrylic resin, an epoxy resin or a silicone resin is used as the transparent protective layer, and are particularly suitable when an imide-modified silicone is used.

The adhesion layer may be applied by any method such as a spinner method, a roll coater method, a printing method or a dipping method, as in the case of the transparent protective film.

In the present invention, the adhesion layer is provided in the region where at least one of the light shielding layer and the coloring layer exists. Most ideally, it is preferable that the adhesion layer is formed so as to exactly overlap the region where at least one of the light shielding layer and the coloring layer is present. However, in the present invention, even when the adhesion layer is formed outside the region where at least one of the light-shielding layer and the coloring layer is present, the effect of the present invention can be achieved as long as it is in the vicinity of the outside, and thus the light-shielding The vicinity of the outside of the region where at least one of the layer and the coloring layer is present is also included in the range of the region where at least one of the light shielding layer and the coloring layer of the present invention is present.

The method for forming the adhesion layer inside the region where at least one of the light-shielding layer and the colored layer of the color filter is present is not particularly limited, but, for example, on the transparent substrate on which the light-shielding layer and the colored layer are formed. An adhesion layer is formed in a region where at least one of the light shielding layer and the colored layer is present. Specifically, for example, after applying the adhesion layer on the entire surface of the transparent substrate on which the light-shielding layer and the coloring layer are formed, the adhesion layer outside the region where at least one of the light-shielding layer and the coloring layer of the color filter is present is applied. Obtained by removing. Examples of the removing method include a photolithography method. After coating the entire surface, the solvent is removed in an oven, a resist is applied on the semi-cured polyimide, and prebaking is performed, and then exposure is performed using a mask on which a predetermined pattern is drawn. Next, since the polyimide is etched by the alkaline solution that develops the resist, development and etching can be performed simultaneously.
When the resist is soaked in an alkaline solution which is also a developing solution, that is, an etching solution, the solubility of the resist in alkali becomes extremely large, and the removed polyimide is etched. Add 25% of polyimide with an alkaline solution (for example, Shipley's "MP351" diluted with pure water to make the volume 5% to 50%).
Immerse at 15 ° C. for about 15 to 30 seconds. For development etching with an alkaline solution, a dipping method, a spray method, or the like can be used. The temperature of the developing solution can be used at a temperature at which over-etching or under-etching does not occur in consideration of the developing speed, but 10 ° C to 50 ° C is preferable. Next, methyl cellosolve acetate (MC
A), ethyl cellosolve acetate (ECA), propylene glycol monomethyl ether acetate (PGM
The resist is stripped with a suitable solvent such as EA) and butyl acetate. In this way, the polyimide adhesion layer is formed inside the region where at least one of the light shielding layer and the coloring layer of the color filter exists.

In order to form the adhesion layer inside the region where at least one of the light-shielding layer and the coloring layer of the color filter is present, a method of coating only a predetermined portion by a die coater method, a roll coater method or a printing method is used. It is also possible to use. In the die coater method, a slit die is used, and it can be applied to the inside of the region where at least one of the light-shielding layer and the coloring layer of the color filter is present by a method such as slot coating, curtain coating, and slide coating. The roll coater method can be applied using either a natural coater or a reverse coater. In the printing method, flexo printing (topographic printing), screen printing,
Although planographic printing, intaglio printing and the like can be used as appropriate, the flexographic printing method and the screen printing method are preferable because the material design of the coating film is easy.

As described above, according to the present invention, the adhesion layer is formed inside the region where at least one of the light-shielding layer and the coloring layer of the color filter is present, so that the adhesion between the glass and the transparent protective layer in the seal portion is also improved. It is possible to provide a color filter having good adhesion over the entire surface. .

[0026]

EXAMPLES Examples of the present invention will now be described.
The invention is not limited to the examples.

Reference Example 1 (Production of Polyimide Resin) 314 g of N-methyl-2-pyrrolidone was placed in a three-necked 2 liter flask, and 3,3'-diaminodiphenyl sulfone 4 was stirred under aeration of nitrogen with stirring.
9.65 g, 4,4-diaminodiphenylmethane 39.
66 g was added. After stirring for 20 minutes, 3,3 ', 4,4'
-Benzophenone tetracarboxylic acid anhydride 126.01
6 g was gradually added together with a little N-methyl-2-pyrrolidone, and when completely dissolved, the temperature was raised to 50 ° C. 50 ° C
The mixture was stirred for 3 hours while controlling the temperature. 1.6 for end preparation
6 g of maleic anhydride was added and stirred for another hour. After standing at room temperature for a whole day and night, it was diluted with a mixed solvent of N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether to a solid content concentration of 11% to obtain a polyamic acid varnish as a polyimide precursor.

Reference Example 2 (Production of imide-modified silicone) 131 g of N-methyl-2-pyrrolidone was placed in a round bottom flask, and benzophenonetetracarboxylic dianhydride 6 was added while stirring under a nitrogen atmosphere.
0g was charged. After the internal temperature was lowered to 6 ° C with an ice bath, 71 g of 3-aminopropyldiethoxysilane was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 3 hours to obtain a brown solution (d).

290 g of methyltrimethoxysilane was placed in another round-bottomed flask, and the internal temperature was adjusted to 6 ° C. by stirring and cooling with ice. 115 g of 0.1% acetic acid aqueous solution was added dropwise at an internal temperature of 30 ° C. or lower. After completion of dropping, remove the ice bath and stir for 3 hours,
The stirring was stopped to obtain a solution (e).

A flask was charged with 50 g of ethylene glycol monobutyl ether and 0.28 g of a silicone surfactant ("Disparlon"# 1610 manufactured by Kusumoto Kasei).
While N ₂ aeration was stirred for 1 hour. Next, solution (d) 1
5 g and solution (e) 37.5 g were added and stirred for 1 hour to obtain an imide-modified silicone.

Example 1 (Production of Color Filter) The color filter shown in FIG. 1 was produced as follows.

A patterned metallic chromium light-shielding layer (2) was provided on the transparent substrate OA-2 (1), and a colored polyimide layer containing a heat resistant pigment was patterned by photolithography (3). The polyamic acid varnish prepared in Reference Example 1 was applied thereon as a contact layer (4) by a spinner. Then, it was put into an oven at 100 ° C. for 10 minutes and dried. The film thickness was set to be about 0.1 μm after drying. Furthermore, a resist ("Microposit" RC-100 series manufactured by Shipley Co., Ltd.) on this semi-cured adhesion layer.
Was dried and then applied with a spinner to a film thickness of 1 to 2 μm, and prebaked in an oven at 90 ° C. for 10 minutes. The adhesion layer was formed only in the pixel portion and the frame chrome portion, and patterning was performed as follows to remove the adhesion layer on the glass portion. A mask having a pattern is placed on a substrate for exposure, and then pure water is added to alkali (“MP351” manufactured by Shipley Co., Ltd.) to make a capacity of 16.7.
% Developer was immersed at 25 ° C. for 30 seconds. Development and etching of the adhesion layer were performed in this developer. Next, the remaining resist was removed using a stripping agent (methyl cellosolve acetate), and the transparent protective layer (5) prepared in Reference Example 2 was dried to obtain an imide-modified silicone having a film thickness of about 1
It was applied with a spinner so as to have a thickness of μm. After semi-curing in an oven at 100 ° C. for 10 minutes, main curing was performed in an oven at 300 ° C. for 30 minutes to completely cure the adhesion layer and the protective layer at the same time to manufacture a color filter.

Example 2 After providing a patterned light-shielding layer and a colored layer on a transparent substrate (OA-2) in the same manner as in Example 1, Example 1 was performed.
An adhesion layer similar to the above was prepared and applied by a flexographic printing method to the inside of the region of the color filter where at least one of the light-shielding layer and the coloring layer was present. Next, a transparent protective layer was prepared with the same formulation as in Example 1, and this transparent protective layer was subjected to the same treatment to obtain a color filter.

Comparative Example 1 A color filter was prepared in the same manner as in Example 1 except that the polyimide adhesion layer was applied on the entire surface of the colored layer with a spinner and no patterning was performed.

Example 3 (Evaluation) The color filters produced in Example 1, Example 2 and Comparative Example 1 were treated under the conditions of 121 ° C. and 100% RH for 0 to 24 hours, and then subjected to JIS K-5400. A cross-cut tape peeling test was conducted in conformity with the above. The results are shown in Table 1. In Comparative Example 1, peeling began to be seen on the cross cut in 3 hours, and almost peeled off in 12 hours. As a result of microscopic observation,
This peeling occurred between the glass and the adhesion layer. on the other hand,
In Examples 1 and 2, peeling did not occur even after 24 hours, and the cross-cut remained as it was.

[0036]

[Table 1]

[0037]

According to the present invention, since the adhesion layer is mainly formed on the colored layer and the light shielding layer, the adhesion between the transparent protective layer and the light shielding layer is improved, and at the same time, the coloring layer and the light shielding layer are not provided. Since the transparent protective layer directly adheres to the transparent substrate portion, the adhesion between the transparent substrate portion and the transparent protective layer improves. That is, it is possible to provide a color filter having good adhesion over the entire surfaces of the transparent substrate and the transparent protective layer, and thus it is possible to provide a highly reliable color filter having good adhesion.

[Brief description of drawings]

FIG. 1 is an enlarged schematic cross-sectional view of a color filter manufactured according to an embodiment of the present invention.

[Explanation of symbols]

 1: transparent substrate 2: light-shielding layer 3: colored layer 4: adhesion layer 5: transparent protective layer 6: transparent electrode

Claims (10)

[Claims] 1. A color filter having a light-shielding layer, a colored layer and a transparent protective layer provided on a transparent substrate, wherein an adhesive layer made of a polyimide resin is provided between the light-shielding layer and the transparent protective layer, and the adhesive layer is further provided. Is in the region where at least one of the light-shielding layer and the colored layer is present. 2. The color filter according to claim 1, wherein the light shielding layer contains at least one of metallic chromium and chromium oxide. 3. The color filter according to claim 1, wherein the transparent protective film is made of imide-modified silicone. 4. The imide-modified silicone has the following general formula (1) H ₂ N— (CH ₂ ) _m —SiR ¹ _n (OR ₂ ) _3-n (1) (wherein, m is An integer of 1 or more, n is an integer of 0 to 2, R ¹ is an alkyl group or an aryl group, and R ² is an alkyl group or an acyl group.) And a tetracarboxylic acid dianhydride is reacted. The imide precursor compound (A) thus obtained and the general formula (2) R ³ _p Si (OR ⁴ ) _4-p (2) (In the formula (2), p is an integer of 1 to ³ , R ³ Is an organic group, and R ⁴ is an alkyl group or an acyl group.) Is a curable composition containing a partial condensate (B) or a concentrated compound (B ′) obtained by hydrolysis of the compound represented by The color filter according to claim 1, wherein 5. The polyimide resin is represented by the general formula (3): (In the formula, R ⁵ represents a tetravalent organic group having at least 2 carbon atoms, and R ⁶ represents a divalent organic group having at least 2 carbon atoms.) The color filter according to claim 1, which is a polymer containing as a main constituent unit. 6. The polyimide resin comprises 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride and 3,3′- (or 4,4′-
6. The color filter according to claim 5, wherein the polyimide is a polyamic acid synthesized from diaminodiphenyl sulfone, bis (3-aminopropyl) tetramethyldisiloxane and pyromellitic acid dimethyl ester. 7. In a method for producing a color filter in which a light shielding layer, a coloring layer and a transparent protective layer are provided on a transparent substrate, an adhesion layer is provided on the transparent substrate on which the light shielding layer and the coloring layer are formed,
A method for producing a color filter, which is formed in a region where at least one of the light shielding layer and the colored layer is present. 8. An adhesive layer is applied over the entire surface of a transparent substrate having a light-shielding layer and a colored layer, and then the adhesive layer outside the region where at least one of the light-shielding layer and the colored layer is present is removed. The method for producing a color filter according to claim 7, wherein 9. The method for manufacturing a color filter according to claim 8, wherein the adhesion layer is removed by a photolithography method. 10. The method for producing a color filter according to claim 7, wherein the adhesion layer is formed in a region where at least one of the light shielding layer and the colored layer is present, by a printing method or a partial coating method.