JPH0820565B2 - Method for manufacturing color filter - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention uses a heat-resistant aromatic polyamide having a photosensitive group as an image forming material for fine color separation of a color image sensor, a color sensor, a color display, or the like. The present invention relates to a method for manufacturing a color filter of the above.

[Conventional technology]

Conventionally, as a method for producing a color filter, there is a method in which a dyed organic dye filter is formed on a transparent substrate such as glass using gelatin or the like, and the filter is attached to the solid-state image sensor with an adhesive.

The outline of the manufacturing method of this conventional color filter will be described below.
Explaining with reference to the drawings, first, a glass substrate 1 is coated with a gelatin or the like having photosensitivity, dried, exposed through a desired mask pattern, and developed to dye the layer to be dyed. To form a filter component 2'of the first color, for example, red [Fig. 2 (A)], and then to cover the entire surface with a transparent intermediate protective layer 3 [Fig. 2 (B)]. )]. Next, similarly, a layer to be dyed is formed and dyed to form a second color, for example, green filter component 4 [FIG. 2 (C)], and this step is repeated to form the intermediate protective layer 3
(FIG. 2 (D)), a third color, for example, blue filter component 5 is formed (FIG. 2 (E)), and finally a surface protective layer 6 is deposited to color the glass substrate. A filter is formed [Fig. 2 (F)].

The simplest means for producing a multicolor surface coloring material such as a color filter is a printing method.

Further, JP-A-60-237403 discloses a method for producing a color filter using a polyimide resin known as a heat-resistant film forming material having photosensitivity.

[Problems to be solved by the invention]

The conventional method for producing a color filter using gelatin or the like has the following problems (1) and (2).

(1) Since gelatin, which has poor heat resistance, is used as an image forming material, there is a restriction on the selection of an adhesive in the color filter bonding process and the heat treatment in the assembly process after the color filter formation or bonding. There is a problem of fading.

(2) Each color requires complicated and troublesome steps such as application of photosensitive gelatin, pattern exposure, pattern formation by development, dyeing, and application of an intermediate protective layer, which must be repeated several times in a multicolor filter. Therefore, it is difficult to achieve a high yield and a low cost in forming a color filter.

In addition, the above-mentioned printing method has difficulty in positioning during multicolor printing, has limited positional accuracy and dimensional accuracy, and cannot manufacture a highly accurate and fine color filter.

Further, the method disclosed in the above-mentioned JP-A-60-237403 has the following problems. That is, the polyimide resin is generally in the visible region, especially because of poor light transmission in 400 ~ 450 nm, turbidity occurs for blue, and the polyimide resin is provided as a polyimide precursor,
200-300 for a polyimide with good film properties
High temperature treatment of ℃ or higher is required, which causes a problem that the organic pigment is deteriorated by heat. Further, there is a problem that the polyimide resin is colored yellow.

Therefore, the object of the present invention is excellent in heat resistance and transparency,
Another object of the present invention is to provide a method capable of easily producing a highly accurate color filter at a low temperature.

[Means for solving problems]

As a result of various studies, the present inventors have found that the above object can be achieved by using a specific aromatic polyamide as an image forming material.

The present invention has been made based on the above findings, and a heat-resistant aromatic polyamide having a photosensitive group having a structural unit represented by the following general color (I) on a support, and a first
A pigment-dispersed polyamide solution containing an organic pigment exhibiting a hue of color is applied, dried to form a photosensitive polyamide film on the support, and the photosensitive polyamide film is pattern-exposed and developed to develop a first photosensitive polyamide film. A colored image of the first color is formed, and then the above-mentioned aromatic polyamide and the hue of the second color are applied to a portion of the support on which the first colored image is formed, on which the first colored image is not formed. Using a pigment-dispersed polyamide solution containing an organic pigment to be presented, a second colored image is formed in the same manner as the above-described first colored image is formed, and thereafter, the first and second colored images are formed. A colored image of the third color is formed on the portion on which the colored images of the first and second colors are not formed on the support on which the colored image is formed, in the same manner as the formation of the colored image of the second color. Characterized by It is intended to provide a process for the production of that color filter.

General color (I) (However, in the above formula (I), R ₁ and R ₂ each represent a hydrogen atom or a residue of a reactive organic compound, Ar ₁ represents an aromatic residue, and Ar ₂ has a photosensitive group. An aromatic residue is shown.) The method for producing the color filter of the present invention is described in detail below.

As a preferable example of the heat-resistant aromatic polyamide having a photosensitive group used in the present invention, the constitutional unit represented by the following general formula (I) is 10 mol% or more, preferably 20 mol% or more, more preferably 40 mol% % Or more and the following general formula (II)
An aromatic polyamide having a structural unit represented by the following formula in an amount of 90 mol% or less, preferably 80 mol% or less, more preferably 60 mol% or less, or a structural unit represented by the following general formula (I) Aromatic polyamide is 10 mol% or more, preferably 20 mol% or more, more preferably 40 mol% or more and aromatic polyamide having a structural unit represented by the following general formula (II) is 90 mol% or less, preferably 80 A mixture of aromatic polyamides mixed in a proportion of not more than mol%, more preferably not more than 60 mol% can be mentioned.

General formula (I) General formula (II) (However, in the above formulas (I) and (II), R ₁ , R ₂ , R ₃ and R ₄ are
Each represents a hydrogen atom or a residue of a reactive organic compound, Ar,
₁ , Ar ₃ and Ar ₄ each represent an aromatic residue, and Ar ₂ represents an aromatic residue having a photosensitive group. ) Examples of the aromatic residue represented by Ar ₁ and Ar ₃ in the general formulas (I) and (II) include an aromatic residue of an aromatic dicarboxylic acid, and examples of the aromatic dicarboxylic acid include: Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4,4'-dicarboxy-biphenyl, 4,4'-dicarboxy-diphenylmethane and 4,4'-dicarboxy-diphenyl ether, and their acid halides. You can Among these aromatic dicarboxylic acid components, acid halides of the above aromatic dicarboxylic acids, particularly acid chlorides, are preferable.

In the general formula (I), examples of the aromatic residue having a photosensitive group represented by Ar ₂ include an aromatic residue of an aromatic diamine having a photosensitive group. Examples of the aromatic diamine include: 3,5-diaminobenzoic acid ethyl acrylate, 2,4-diaminobenzoic acid ethyl acrylate, 3,5-diaminobenzoic acid ethyl methacrylic acid ester, 2,4-diaminobenzoic acid ethyl methacrylic acid ester, 3 5,5-diaminobenzoic acid glycidyl acrylate ester, 2,4-diaminobenzoic acid glycidyl acrylate ester, 3,5-diaminobenzoic acid glycidyl methacrylate ester, 2,4-diaminobenzoic acid glycidyl methacrylate ester, 3,5-diaminobenzoic acid Benzoic acid esters such as cinnamic ester and 2,4-diaminobenzoic acid cinnamic ester; 3,5-dia Benzyl acrylates such as nobenzyl acrylate, 3,5-diaminobenzyl methacrylate, 2,4-diaminobenzyl acrylate, and 2,4-diaminobenzyl methacrylate; 4-acrylamido-3,4'-diaminodiphenyl ether, 2-acrylamido-3 4,4'-diaminodiphenyl ether, 4-cinnamamide-3,4'-diaminodiphenyl ether, 3,4'-diacrylamide-3 ',
4-diaminodiphenyl ether, 3,4'-dicinnamamide-3 ', 4-diaminodiphenyl ether, 4-methyl-2'-(2-methacryloyloxyethoxycarbonyl) -3,4'-diaminodiphenyl ether, 4-methyl-2 ' Diphenyl ethers such as-(2-acryloyloxyethoxycarbonyl) -3,4'-diaminodiphenyl ether; and 4,4'-diaminochalcone, 3,
3'-diaminochalcone, 3,4'-diaminochalcone,
Chalcones such as 3 ', 4-diaminochalcone, 4'-methyl-3', 4-diaminochalcone, 4'-methoxy-3 ', 4-diaminochalcone, 3'-methyl-3,5-diaminochalcone Can be mentioned.

Further, in the general formula (II), examples of the aromatic residue represented by Ar ₄ include an aromatic residue of an aromatic diamine having no photosensitive group, and examples of the aromatic diamine include: , 5-diaminobenzoic acid, paraphenylenediamine, metaphenylenediamine, 2,4-diaminotoluene, 4,4'-diaminophenyl ether, 4,4'-diaminodiphenylmethane, O-tolidine, 1,4-bis (4 −
Aminophenoxy) benzene, 2,2'-bis (4-aminophenoxyphenyl) propane, diamines such as O-toluidine sulfone, and 9,9-bis (4-aminophenyl) -10-anthrone, 1,5-diamino Anthraquinone, 1,4-diaminoanthraquinone, 3,3'-diaminobenzophenone, 4'-N, N-dimethylamino-3,5-diaminobenzophenone, 1-dimethylamino-4- (3,5
Mention may be made of diamines containing ketone groups such as -diaminobenzoyl) -naphthalene. Of these, diamines containing a ketone group are particularly preferable because they can further improve the sensitivity and resolution of the polyamide.

In the general formulas (I) and (II), R ₁ , R ₂ ,
In the residue of the reactive organic compound represented by R ₃ and R ₄ , the organic compound (reactive organic compound) having reactivity with the hydrogen atom of the amide bond of polyamide is substituted with the hydrogen atom of the amide bond of polyamide. The organic group formed as a result, examples thereof include an acetyl group, an acryloyl group, a methacryloyl group, a cinnamoyl group, a para azidobenzoyl group, and the like, in particular, an acryloyl group, a methacryloyl group, a cinnamoyl group, etc. An organic group containing a group is preferable because it can further improve the sensitivity and resolution of the polyamide. Examples of the reactive organic compound having these residues include methacrylic acid chloride, acrylic acid chloride, cinnamic acid chloride, acetic acid chloride, benzyl chloride, and para-azido benzoyl chloride.

The aromatic polyamide, for example, the aromatic dicarboxylic acid component, the aromatic diamine component comprising an aromatic diamine having a photosensitive group and an aromatic diamine having no photosensitive group described above, approximately equimolar Used in an organic solvent at a reaction temperature of 100 ° C or lower, preferably 80 ° C or lower,
It is produced by carrying out a polymerization reaction for 48 hours. Also,
In the aromatic polyamide, at least one of R ₁ , R ₂ , R ₃ and R ₄ is a residue of a reactive organic compound, R ₁ , R ₂ , R ₃ and R synthesized as described above. _The aromatic polyamide in which ₄ is a hydrogen atom is added to the above-mentioned synthesis reaction solution.
It is produced by adding a reactive organic compound having an organic group corresponding to R ₁ , R ₂ , R ₃ and R ₄ and reacting at a reaction temperature of −5 to 100 ° C. for 0.1 to 48 hours.

In the aromatic polyamide, the presence of the structural unit represented by the general formula (II) has the effect of improving the thermal properties of the polyamide, but if it is too large, the concentration of the photosensitive group decreases and the photosensitivity decreases. Therefore, it may be adjusted appropriately within the above range.

The aromatic polyamide is polyamide 0.5 g / N-
Methyl-2-pyrrolidone 30 ℃ as a solution with a concentration of 100ml
Those having a logarithmic viscosity of 0.1 to 3.5, particularly 0.2 to 2.0, are preferable.

Further, the aromatic polyamide has a visible region (400 to 700
It is preferable to use one having a light transmittance of 90% or more in (nm).

The aromatic polyamide used in the present invention is, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, hexamethylenephosphoramide, in organic solvents such as diglyme. It is soluble and can be uniformly dissolved in the organic solvent at a concentration of about 1 to 40% by weight.

Further, as the organic pigment used in the present invention, those having good transparency and excellent heat resistance, light resistance and solvent resistance are preferable, and examples thereof include azo chelate type, condensed azo type, phthalocyanine type and benzo. Imidazolones, quinacridones, isoindolinones, pyranthrone, dibrom anzanthrone, indanthrone, anthrapyrimidine, flavanthrone, perylenes, perinone, quinophthalone, thioindigo, dioxazine, anthraquinone Examples thereof include organic pigments such as pigments, and one or two or more thereof are appropriately selected and used.

The organic pigment preferably has a particle size of 1 μm or less from the viewpoints of light transmittance, film surface uniformity, and the like.

Next, a preferred embodiment of the method for manufacturing a color filter of the present invention will be described with reference to FIG.

First, a pigment-dispersed polyamide solution containing the heat-resistant aromatic polyamide having a photosensitive group and the organic pigment exhibiting a hue of the first color, for example, red is prepared, and this solution is
It is applied on a support such as a glass substrate and dried to form a red photosensitive polyamide film 2 on the support 1, as shown in FIG.

Preparation of a polyamide solution in which the pigment is dispersed, for example, by adding the organic pigment in advance to the organic solvent capable of dissolving the aromatic polyamide, after dispersing by stirring or ultrasonic waves,
This is filtered with a 1 μm filter to adjust the particle size of the organic pigment to obtain a pigment-dispersed organic solvent solution, the aromatic polyamide is added to the solution, and the polyamide solution is further filtered with a 1 μm filter as necessary. Or do
After dissolving the aromatic polyamide in the organic solvent, the organic pigment may be added to the polyamide solution, which may be sufficiently kneaded with a three-roll mill or the like, and filtered with a 1 μm filter.

The mixing ratio of the aromatic polyamide and the organic pigment is
10 to 3 organic pigments per 100 parts by weight of aromatic polyamide
It is preferably 00 parts by weight, especially 20 to 150 parts by weight.

Further, it is preferable that the pigment-dispersed polyamide solution has a rotational viscosity (25 ° C.) of about 0.5 to 1000 poises, particularly about 1 to 500 poises.

If necessary, a dispersion aid such as a surfactant may be added to the pigment-dispersed polyamide solution to enhance the dispersibility of the organic pigment, and a silane coupler or the like may be added to enhance the adhesion to the support. A binding promoter may be added.

Further, the pigment-dispersed polyamide solution, for example, Michler's ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, 4, A photopolymerization initiator and a sensitizer such as 4'-bis (diethylamino) benzophenone, acetophenone, benzophenone, 1,5-acenaphthene, thioxanthone or a derivative thereof (for example, chlorothioxanthone, methylthioxanthone), anthranilate dimethylaminobenzoate, etc. are added. Further, a thermal polymerization inhibitor such as hydroquinone, 2,6-t-butyl-4-methylphenol (BHT), methyl ether hydroquinone or benzoquinone may be blended.

The pigment-dispersed polyamide solution can be applied to the support by a method such as a spin coating method, a roll coating method, a dipping method, or a spray method. The coating film is dried
150 ℃ or less by hot air dryer, hot plate, etc., especially 1
It is preferably carried out at 00 ° C. or lower for 1 to 60 minutes, particularly 10 to 30 minutes. At this time, the pressure may or may not be reduced.

The thickness of the photosensitive polyamide film is usually about
It is preferably 0.2 to 3.0 μm.

Then, a mask having a predetermined shape such as a dot pattern or a stripe pattern is adhered to the photosensitive polyamide film formed as described above, and a parallel light beam of an ultra-high pressure mercury lamp (250 W) is irradiated through the mask to form a pattern. After exposure, development is performed to form a red image 2a (first colored image) on the support 1 as shown in FIG. 1 (b).

Development of the pattern-exposed photosensitive polyamide film
The non-light-cured portion of the coating is eluted by immersing the coating in a suitable developing solution at a temperature of about 0 to 100 ° C. or by a commonly used method such as a spray developing method or a paddle developing method. It is done by removing.

The developer, N, N- dimethylformamide,
N, N-dimethylacetamide, dimethyl sulfoxide,
Organic solvents such as N-methyl-2-pyrrolidone, hexamethylenephosphoramide and diglyme, and mixed systems of these organic solvents with methanol and ethanol can be used.

In the immersion development, it is appropriate to apply ultrasonic waves to the developing solution.

After development, the formed colored image is rinsed with 1,1,1-trichloroethane, isopropyl alcohol, etc., and then dried with a hot air dryer, hot plate, etc. for about 15 minutes.
It is preferable to perform heat treatment at 0 to 200 ° C. for 10 to 120 minutes.

Next, in the portion where the red image 2a is not formed on the support 1 on which the red image 2a (first colored image) is formed, the aromatic polyamide and the second hue, for example, green Using the pigment-dispersed polyamide solution containing the pigment, the green image adjacent to the red image 2a is formed as shown in FIG. 1 (C) in the same manner as the above-mentioned formation of the red image.
2b (second colored image) is formed.

After that, the support 1 on which the red image and the green image are formed
As shown in FIG. 1 (d), a blue image adjacent to the red image 2a and the green image 2b is formed on the portion where the red image 2a and the green image 2b are not formed, similarly to the formation of the green image described above. 2c (colored image of the third color) is formed.

Thus, as shown in FIG.
A color filter having a primary colored image is obtained.

Although FIG. 1 (d) shows an example in which the colored images of the three primary colors are closely formed, part or all of the colored images may be provided with a part where the colored image is not formed. it can.

〔Example〕

The present invention will be described in more detail below with reference to production examples of heat-resistant aromatic polyamides having a photosensitive group used in the present invention and examples of the present invention.

Production Example 1 After a dry nitrogen gas was passed through a three-necked flask to replace the gas in the flask, 3 g of lithium chloride and 31.714 g of 3,5-diaminobenzoic acid ethyl methacrylate ester were placed, and N-methyl-2 was added thereto. -Pyrrolidone (NMP) 240 ml was added and dissolved. After dissolution, 24.364 g of terephthalic acid dichloride was added with cooling to 3 ° C. and stirring. At this time, heat was generated and the temperature of the solution rose to 34 ° C. This was stirred for 30 minutes in ice water, and then stirred at room temperature for 1 hour to cause a polymerization reaction.

Next, after adding 300 ml of NMP to the reaction solution to dilute it, this was added to a mixed solution of methanol 6 and water 6 to precipitate an aromatic polyamide.

The precipitate was collected by filtration and dried to obtain 42.01 g of white aromatic polyamide powder.

Logarithmic viscosity of this aromatic polyamide powder (concentration; 0.5g / 10
0 ml solvent, solvent; NMP, measurement temperature; 30 ° C) was 1.73.

Example 1-Preparation of Pigment-dispersed Polyamide Solution Perylene red (4.25 g) was added as a red pigment to 86.0 g of N-methyl-2-pyrrolidone (NMP), and after mixing and stirring, ultrasonic waves of 50 W were applied for about 1 hour in a water tank. The above pigment was dispersed therein, and this was filtered under pressure using a 1 μm Teflon filter to obtain a pigment-dispersed NMP solution.

Next, 0.26 g of hydroquinone monoethyl ether as a thermal polymerization inhibitor and 8.5 g of the aromatic polyamide powder obtained in the above Production Example 1 were added to this pigment-dispersed NMP solution, and the mixture was sufficiently stirred to form a uniform viscous liquid. Then, 0.34 g of Michler's ketone as a photopolymerization initiator was added to this viscous liquid and stirred.
This solution was kneaded with a triple roll and pressure filtered using a 1 μm Teflon filter to prepare a red pigment-dispersed polyamide solution.

A green pigment-dispersed polyamide solution was prepared in the same manner as the above-described red pigment-dispersed polyamide solution, except that phthalocyanine green was used as the green pigment instead of the red pigment perylene red.

Further, a blue pigment-dispersed polyamide solution was prepared in the same manner as the above red pigment-dispersed polyamide solution, except that phthalocyanine blue was used as the blue pigment instead of the red pigment perylene red.

・ Production of color filter The red pigment-dispersed polyamide solution was spin-coated on a glass substrate to a dry film thickness of 1.5 μm,
After drying at 0 ° C. for 20 minutes, a photosensitive polyamide film was formed on the glass substrate, and the photosensitive polyamide film was contact-exposed with an ultrahigh pressure mercury lamp through a mask having a predetermined shape.

Then, the pattern-exposed photosensitive polyamide film was ultrasonically developed using a dicryme solution, rinsed with isopropyl alcohol, and then heat-treated at 200 ° C. for 30 minutes to give a red image as shown in FIG. 1 (b). Formed.

Next, the green pigment-dispersed polyamide solution was spin-coated on the entire surface of the glass substrate on which the red image had been formed so as to have a dry film thickness of 1.5 μm.
After drying at 0 ° C for 20 minutes, a photosensitive polyamide film is formed on the glass substrate, a mask having a predetermined shape is precisely aligned with the photosensitive polyamide film, and then contact exposure is performed in the same manner as in the formation of the red image. After development, rinsing, and heat treatment, a green image was formed at a position on the glass substrate where the red image was not formed and adjacent to the red image, as shown in FIG. 1 (c).

Further, the blue pigment-dispersed polyamide solution is spin-coated on the entire surface of the glass substrate on which the red and green images are formed so that the dry film thickness becomes 1.5 μm on the glass substrate,
The coating film is dried at 70 ° C. for 20 minutes to form a photosensitive polyamide film on the glass substrate, and a mask having a predetermined shape is precisely aligned with the photosensitive polyamide film, and then the same procedure as that for forming the green image is performed. By contact exposure, development, rinsing, and heat treatment, a blue image is formed on a portion of the glass substrate where the red and green images are not formed and at a position adjacent to the red and green images, as shown in FIG. 1 (d). Then, a color filter in which colored images of three primary colors were arranged on the same plane was obtained.

〔The invention's effect〕

According to the method for manufacturing a color filter of the present invention, the following effects are exhibited.

(1) When forming a color filter composed of two or more colors, it is not necessary to form a transparent dye-proof resin film for each color when a colored image is provided adjacently on a support, and the same plane Since a colored image can be formed on the top, the manufacturing process is simplified.

(2) A color filter having excellent heat resistance and transparency and high precision can be easily manufactured. In particular, by using an aromatic polyamide having a light transmittance of 90% or more in the visible region (400 to 700 nm), a color filter having an extremely high transmittance can be manufactured.

(3) Since a specific aromatic polyamide is used, it does not require high temperature treatment as in the case of using a conventional polyimide resin, and by the low temperature treatment of 150 to 200 ° C, it can be used under high heat during component assembly and during use. It is possible to produce a color filter having a film characteristic that can withstand.

[Brief description of drawings]

FIG. 1 is a schematic view showing a process sequence of a color filter manufacturing method of the present invention, and FIG. 2 is a schematic view showing a process sequence of a conventional color filter manufacturing method using gelatin. 1 ... Support, 2 ... Photosensitive polyamide film 2a, 2b, 2c ... Colored image

Continuation of the front page (56) References JP-A 61-45226 (JP, A) JP-A 60-129707 (JP, A) JP-A 60-78401 (JP, A)

Claims (1)

[Claims] 1. A pigment-dispersed polyamide solution containing, on a support, a heat-resistant aromatic polyamide having a photosensitive group having a structural unit represented by the following general formula (I) and an organic pigment exhibiting a hue of the first color. Is applied and dried to form a photosensitive polyamide film on the support, and the photosensitive polyamide film is subjected to pattern exposure and then developed to form a colored image of the first color. Using a pigment-dispersed polyamide solution containing the above aromatic polyamide and an organic pigment exhibiting a second-color hue on a portion where the first-color coloring image is not formed on the support on which the colored image is formed, A second color image is formed in the same manner as the first color image formation described above, and thereafter, the first color image and the second color image on the support having the first color image and the second color image are formed. Second color painting The portion not forming method of a color filter, which comprises forming a colored image of the third color in the same manner as in the formation of a colored image of the second color of the. General formula (I) (However, in the above formula (I), R ₁ and R ₂ each represent a hydrogen atom or a residue of a reactive organic compound, Ar ₁ represents an aromatic residue, and Ar ₂ represents a photosensitive group. The aromatic residues are shown.)