JP2575572B2 - Alkali-developing photosensitive color filter ink and color filter using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink for a photosensitive color filter of an alkaline aqueous solution development type and a color filter produced using the same. More specifically, it can be used as an ink at the time of producing a color filter used for various multicolor displays such as a color liquid crystal display device, a color facsimile, an image sensor and an optical device, and a color filter formed by them. Can be used for displays such as televisions, video monitors and computers.

[0002]

2. Description of the Related Art In a color liquid crystal display device comprising a liquid crystal and a color filter for controlling the amount of transmission or reflection of light, red, green, and blue pixels are used as color filters by a dyeing method, a printing method, or the like. And a black matrix formed on a glass substrate. In particular, when high-definition images are required,
Color filters produced by the dyeing method are mainly used.

A color filter formed by this dyeing method is obtained by forming a black matrix on a glass substrate and then sensitizing a natural photosensitive resin such as gelatin or a photosensitive synthetic resin such as amine-modified polyvinyl alcohol with dichromic acid. The solution is coated, exposed and developed through a photomask, developed and patterned, or made using a masking material coat and dyed with a dye such as an acid dye. In order to prevent color mixing, a portion which does not need to be colored must be subjected to a dye-proofing treatment, which has a disadvantage in that the manufacturing process becomes complicated. In addition, the physical properties of the coating film have problems in reliability such as light resistance, heat resistance, and moisture resistance.
-52,738). In addition, the thing by the printing method,
It is manufactured using an ink in which a pigment is dispersed in a thermosetting resin or an ultraviolet curable resin. However, it is necessary to accurately align the three color filter patterns at the time of printing. A problem arises in the formation of a fine pattern and the surface smoothness (Japanese Patent Application Laid-Open Nos. Sho 62-54,774 and 63-129,303).

Further, Japanese Patent Application Laid-Open No. 1-152,449 discloses that a benzyl methacrylate / methacrylic acid copolymer is used as a photosensitive resin and a pigment is dispersed in the copolymer. When this photosensitive paint is used, the exposed portion of the coating film constitutes a color filter as it is. However, in the case of this photosensitive paint, the curing reaction becomes insufficient in the presence of oxygen, and the resolution and sensitivity are reduced. For this reason, a complicated process of forming an oxygen blocking film before exposure and peeling the oxygen blocking film before development becomes necessary,
Furthermore, the resulting product had problems in heat resistance and developability.

[0005]

As described above, the color filters manufactured by the conventional printing method, dyeing method or pigment dispersion method have problems such as low resolution and complicated manufacturing process. I have. Thus, the present inventors have conducted intensive studies to solve such a problem, and as a result, based on a photopolymerizable unsaturated compound having a carboxyl group and a photopolymerizable unsaturated bond, an epoxy compound and The present inventors have found that the above problem can be solved by using an ink obtained by mixing a photopolymerization initiator or a sensitizer and a pigment in a predetermined ratio, and completed the present invention.

Accordingly, an object of the present invention is to produce a color filter without using an oxygen barrier film.
In addition, the resolution is high and the heat resistance after light irradiation (25
0 ° C. or higher), transparency, adhesion, hardness, solvent resistance, alkali resistance, and the like, and an object of the present invention is to provide an alkali-developing photosensitive color filter ink that can be developed with a weak alkaline aqueous solution. Another object of the present invention is to provide a color filter produced using such an ink for an alkaline development type photosensitive color filter. Further, an object of the present invention is to provide an alkali-developable photosensitive color filter ink which can be developed with a weakly alkaline aqueous solution, which is particularly suitable for manufacturing a color filter used as a display of a television, a video monitor, a computer, or the like. The purpose of the present invention is to provide a suitable color filter.

[0007]

That is, the present invention provides:
(A) The following general formula (1)

Embedded image (However, in the formula, R ₁ and R ₂ represent a hydrogen atom, a carbon number of 1 to 5)
R ₃ represents a hydrogen atom or a methyl group, and X represents -CO-, -SO
_{2 -, - C (CF 3} ) 2 -, - Si (CH 3) 2 -, -
CH ₂ —, —C (CH ₃ ) ₂ —, —O—,

Embedded image

[0008] Y represents a residue of an acid anhydride, Z represents a residue of an acid dianhydride, and a structural unit m:
n is a molar ratio of 1/99 to 90/10), and 0.5 g of the compound is added to N-methylpyrrolidone 1
A photopolymerizable unsaturated compound having an inherent viscosity (η _inh ) of 0.1 dl / g or more as measured at 30 ° C. in a solution dissolved in 00 ml; (B) a compound having an epoxy group;
(C) a photopolymerization initiator or a sensitizer, and (D) a pigment, wherein the B component with respect to 100 parts by weight of the A component,
The proportion of each of the C component and the D component is 5 to 50 parts by weight,
0.1 to 30 parts by weight and 10 to 200 parts by weight of an alkali developing type photosensitive color filter ink.

Further, according to the present invention, such an ink for an alkaline development type photosensitive color filter is coated and cured on a transparent substrate to provide red, blue, and green pixels and a black matrix, and further, on the surface thereof. This is a color filter provided with a transparent electrode layer.

Hereinafter, the contents of the present invention will be described in detail. In the present invention, the photopolymerizable unsaturated compound (A) (hereinafter referred to as A
In the compound represented by the general formula (1) constituting the above-mentioned component, bis (4-hydroxyphenyl) is a specific example of the bisphenol component containing —CO— as X.
Ketones, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone and the like can be mentioned, and those containing —SO ₂ — as X include Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5
-Dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, etc., and those containing -C (CF ₃ ) ₂ — as X include bis (4-hydroxyphenyl) Hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane and the like can be mentioned, and X is -Si ( C
Examples of those containing H ₃ ) ₂ include bis (4-hydroxyphenyl) dimethylsilane and bis (4-hydroxy-3,5
- dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane and the like can be exemplified, also, bis (4-hydroxyphenyl) methane as including -CH ₂ as X, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, and those containing -C (CH ₃ ) ₂ as X include 2,2-bis (4- Hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-
3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,
2-bis (4-hydroxy-3chlorophenyl) propane and the like can be mentioned, and those containing -O as X include bis (4-hydroxyphenyl) ether,
Bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl ether) and the like can be mentioned.

Embedded image Include 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3
-Methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-
Bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3
-Methoxyphenyl) fluorene, 9,9-bis (4-
(Hydroxy-3,5-dimethylphenyl) fluorene,
9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-
(3,5-dibromophenyl) fluorene and the like, and when X is absent, 4,4'-biphenol, 3,3'biphenol and the like can be mentioned.

Further, as for Y and Z in the general formula (1), Y represents a residue of an acid anhydride, and Z represents a residue of an acid dianhydride. Examples of the acid anhydride compound capable of forming such a residue Y include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride. Acid, chlorendic anhydride,
Methyltetrahydrophthalic anhydride and the like, and
Examples of the acid dianhydride compound capable of forming the residue Z include, for example, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride,
Aromatic polycarboxylic anhydrides such as biphenyl ether tetracarboxylic dianhydride are exemplified.

The component A represented by the general formula (1) is not necessarily limited to the above-mentioned one.
These can be used alone or as a mixture of two or more.

The photopolymerizable unsaturated compound as the component A can be produced as follows. For example, first, a bisphenolfluorene-type epoxy compound represented by the following general formula (2) synthesized from bisphenolfluorene is reacted with (meth) acrylic acid represented by the following general formula (3) to react with the following general formula: (4) A bisphenolfluorene-type epoxy acrylate resin represented by the formula (4) is synthesized, and then this is an acid anhydride which is a mixture of an acid anhydride compound and an acid dianhydride compound capable of forming the above-mentioned residue Y and residue Z. It is produced by reacting a compound by heating in a solvent.

[0014]

Embedded image

In the general formula (1), Y represents a residue of an acid anhydride compound, and Z represents a residue of an acid dianhydride compound. Is reacted with the bisphenol fluorene type epoxy acrylate of the general formula (4). The molar ratio of the acid anhydride compound to the acid dianhydride compound used in this case is 1:99 to 9: 9 to 9: 9.
0:10, preferably 5:95 to 80:20. m
Is less than 1 mol%, the total amount of carboxyl groups (-COOH) increases, alkali resistance decreases, and the exposed portion also elutes in an aqueous alkali solution as a developing solution,
The desired patterning cannot be obtained. On the other hand, if m exceeds 90%, the alkali developability deteriorates, and patterning becomes difficult.

Regarding the molecular weight of the photopolymerizable unsaturated compound, 0.5 g of this compound was added to N-methylpyrrolidone 1
The inherent viscosity (η _inh ) measured at 30 ° C. of the solution dissolved in 00 ml is 0.1 dl / g or more, preferably 0.15 dl / g or more. If it is less than 0.1 dl / g, the molecular weight is too low, causing a problem in tackiness after pre-curing (drying of the coating film), making it impossible to carry out contact exposure and causing stains on the mask.

Next, the compound (B) having an epoxy group
Examples of the (B component) include, for example, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, alicyclic type Epoxy resin such as epoxy resin, phenylglycidyl ether,
Compounds having at least one epoxy group, such as p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, and glycidyl methacrylate are exemplified.

Further, the photopolymerization initiator or sensitizer (C) (hereinafter referred to as C component) used in the present invention is not only the A component but also a photopolymerizable (meth) compound which is optionally added. It is used as a photopolymerization initiator for acrylic monomers and (meth) acrylic oligomers. Examples of the C component used for such purposes include acetophenone, 2,2-diethoxyacetophenone, and p-dimethylacetophenone. Acetophenones such as p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone and p-tert-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone and p, p'-bisdimethylaminobenzophenone; and benzyl , Benzoin, benzoin methyl ether, Benzoin ethers such as benzoin isopropyl ether and benzoin isobutyl ether, and benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone Sulfur compounds, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-
Anthraquinones such as benzanthraquinone and 2,3-diphenylanthraquinone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide and cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercapto Thiol compounds such as benzothiazole can be exemplified. One of these compounds may be used alone, or two or more of them may be used in combination. In addition, a compound which does not act as a photopolymerization initiator by itself, but can be used in combination with the above compound, can increase the ability of the photopolymerization initiator. Such compounds include, for example, tertiary amines such as triethanolamine, which are effective when used in combination with benzophenone.

In the present invention, a pigment (hereinafter, referred to as D component) is used for coloring a coating film. The pigment used here includes an organic pigment and an inorganic pigment. Specific examples of the organic pigment include, for example, azo lake-based, insoluble azo-based, phthalocyanine-based, quinacdrine-based, dioxazine-based, isoindolinone-based, berynone-based, anthraquinone-based, perylene-based, and mixtures thereof. . Further, as specific examples of the inorganic pigment, for example, Miloli blue, iron oxide, cobalt-based, manganese-based, ultramarine, navy blue, cobalt blue, cerulean blue, pyridian,
Emerald green, cobalt green and mixtures thereof. These pigments are preferably dispersed in a particle diameter of 0.4 μm or less, which is the lower limit of the wavelength of visible light, in order to color the coating film while maintaining the transparency of the coating film, and is more practically preferable. Is 0.2 to 0.3 μm
Having an average particle size of

The ink for an alkali-developable photosensitive color filter of the present invention comprises the above components A, B, C and D
It consists of components. The mixing ratio of these components is such that the B component is 5 to 50 parts by weight, preferably 10 to 30 parts by weight, and the C component is 0.1 to 30 parts by weight with respect to 100 parts by weight of the A component. Preferably 1 to 20
Parts by weight, and the C component is 10 to 200 parts by weight. The mixing ratio of the component B to 100 parts by weight of the component A is 5
If the amount is less than 10 parts by weight, the properties after curing of the resin component in the ink of the present invention, particularly the alkali resistance becomes insufficient. On the other hand, if the amount exceeds 50 parts by weight, cracks occur at the time of curing, and the adhesion decreases. It will be easier. On the other hand, if the proportion of the component C is less than 0.1 part by weight with respect to 100 parts by weight of the component A, the photopolymerization rate is reduced, and the sensitivity is reduced.
When the amount is more than the weight part, light hardly reaches the substrate, so that the adhesion between the substrate and the resin deteriorates. Further, when the mixing ratio of the component D is less than 10 parts by weight with respect to 100 parts by weight of the component A,
If the desired spectral characteristics cannot be obtained, and if it exceeds 200 parts by weight, the adhesion of the coating film is undesirably reduced.

The ink for an alkaline development type photosensitive color filter of the present invention can be suitably used as a color filter for a color liquid crystal display and the like. By coating a protective film on this color filter, the heat resistance of the conventional color filter is poor and the color filter has a low heat resistance.
Although the limit was 0 ° C., even at a high temperature of 250 ° C., I
The sputtering of TO becomes possible. Examples of the developing solution suitable for alkali developing the ink for an alkali developing type photosensitive color filter of the present invention include an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal, an aqueous solution of an alkali metal hydroxide, and the like. Among them, particularly, carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, etc.
A fine image can be precisely developed even with a weak alkaline aqueous solution dissolved at a concentration of 3% by weight. Alkaline development of the ink of the present invention can be carried out at a temperature of usually 10 to 50 ° C, preferably 20 to 40 ° C, using a commercially available developing machine or ultrasonic cleaning machine. The ink for an alkali-developable photosensitive color filter of the present invention is also cured by light or heat, and the light suitable for the curing is preferably a lamp such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, or a metal halide lamp. Oscillated light.

The ink for an alkali-developable photosensitive color filter of the present invention can be used as a multicolor display such as a color liquid crystal display, a color facsimile, an image sensor, etc., in addition to the color filter of the color liquid crystal display as described above. Can be used. In this case, first, a film is formed by applying the ink of the present invention to the surface of the substrate, and then a negative film is applied on the film obtained in this manner, and the film is exposed to actinic rays and exposed. The unexposed areas are eluted using a weak alkaline aqueous solution. Next, after the alkali development, it is desirable to carry out an epoxy curing treatment by heating to improve the alkali resistance. By performing the heat treatment, the ink of the present invention is not only significantly improved in durability against strong alkaline water, but also required for solder resists such as glass, adhesion to metals such as copper, heat resistance, and surface hardness. Various properties are also improved. The heating temperature and heating time in this heat curing treatment are, for example, 80 to 200 ° C. and 10
A range of up to 120 minutes is preferred.

The ink of the present invention is used as an ink solution dissolved or dispersed in a suitable solvent. Examples of a solvent suitable for preparing this ink solution include ketones such as methyl ethyl ketone and methyl isobutyl ketone;
Cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve acetate and the like. In addition, as a method for applying the ink of the present invention to a substrate, any method such as using a roller coater machine or a spinner machine can be adopted other than the solution immersion method and the spray method.

Further, in addition to the component A, a photopolymerizable monomer or oligomer acting as a viscosity modifier or a photocrosslinking agent is added to the ink of the present invention in a predetermined range in accordance with the physical properties of the intended use. be able to. Examples of the photopolymerizable monomer or oligomer include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, and ethylene glycol di ( (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane Tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate of (meth)
Acrylic esters and the like can be mentioned. One of these compounds can be used alone, and 2
More than one species can be used in combination. The amount of the photopolymerizable monomer or oligomer used must be within a range that does not impair the properties of the ink of the present invention, and is based on 100 parts by weight of the photopolymerizable unsaturated compound of the general formula (1).
Usually, it is used in a range of 50 parts by weight or less. 50 used
If the amount is more than 10 parts by weight, a problem occurs in tackiness after pre-curing.

The ink of the present invention may contain additives such as an epoxy group curing accelerator, a thermal polymerization inhibitor, a plasticizer, a leveling agent, and an antifoaming agent, if necessary. Examples of the epoxy group curing accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, methylol group-containing compounds, and the like. ,
Various properties such as heat resistance, solvent resistance, acid resistance, plating resistance, adhesion, electrical properties, and hardness of the obtained resist film can be improved. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and phenothiazine. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl. Examples of the antifoaming agent and the leveling agent include a silicon-based, a fluorine-based, and an acrylic-based compound.

Next, the ink for an alkaline development type photosensitive color filter of the present invention and a method for producing a color filter using the same will be described. In producing the ink of the present invention, first, a photopolymerizable unsaturated compound represented by the general formula (1) (A component) and a compound having an epoxy group (B component) are blended as required. A photopolymerizable monomer or oligomer, a pigment (component (C)), a dispersant, and a solvent, if necessary, are mixed under stirring.
Next, a photopolymerization initiator or a sensitizer (D component) is added and mixed again with stirring to obtain a desired ink for an alkaline development type photosensitive color filter.

In the method of manufacturing a color filter using the ink of the present invention, first, any one of red, blue, and green inks is applied to a substrate as a medium on which the color filter is formed, such as a spinner or a roll coater. Is applied over the entire surface, precured, and the solvent is evaporated. Next, through a photomask on which a desired pattern is formed, contact exposure is performed using an ultra-high pressure mercury lamp, and the unexposed portion is developed with an alkali developing solution such as a 1% aqueous sodium carbonate solution, and further washed with water. Then, the film is post-cured at an appropriate temperature, for example, 200 ° C., and the film is completely dried to form pixels of the first color filter. Next, a pixel of the second color filter is formed adjacent to the pixel of the first color filter by using an ink having a pigment of any one of the remaining two colors and following the same steps as described above. Further, the pixels of the third color filter are formed in the same manner by using the ink having the remaining one color pigment to obtain the pixels of the color filter composed of the three primary colors. And the red thus prepared,
A black matrix is provided in addition to the blue and green pixels, and a transparent electrode layer made of, for example, ITO (indium-tin oxide) is provided on the surface of the black matrix to form a color filter. Thus, the desired heat resistance, transparency, adhesion, hardness,
A color filter excellent in solvent resistance, alkali resistance and the like can be obtained.

[0028]

The present invention will be specifically described below based on examples and comparative examples. In the following, “parts” indicates “parts by weight”.

Synthesis Example 1 231 g of bisphenol fluorene type epoxy resin (epoxy equivalent 231) was placed in a 500 ml four-necked flask.
Triethylbenzylammonium chloride 450mg
And 2,6-di-isobutylphenol 100 mg,
72.0 g of acrylic acid was charged and mixed, and heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Although this solution was cloudy, the temperature was gradually raised as it was and heated to 120 ° C. to completely dissolve the solution. Although the solution gradually became transparent and viscous, stirring was continued as it was. During this time, the acid value was measured and the heating and stirring were continued until the acid value was less than 2.0 mgKOH / g. It took 8 hours for the acid value to reach the target (acid value 0.8). Thereafter, the mixture was cooled to room temperature to obtain a colorless and transparent solid.

Next, 303 g of the thus obtained bisphenol fluorene type epoxy acrylate resin [compound of the general formula (4)] was added to cellosolve acetate 2k.
g, to give a solution. Then, 38 g of 1,2,3,6-tetrahydrophthalic anhydride, 73.5 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are added, and gradually added. Heat to 110-115 ° C
For 2 hours to obtain a photopolymerizable unsaturated compound (m / n = 5/5) of the general formula (1). Reaction of acid anhydride is IR
Confirmed by spectrum. The inherent viscosity of the obtained compound was 0.2 dl / g (η _inh = 0.
2).

Example 1 The photopolymerizable unsaturated compound thus obtained (m / n
= 5/5) was used as the component A, and the following components B, C, an organic solvent and the like were blended in the following proportions to prepare a photosensitive resin composition (resin composition). Ingredients Ratio (parts by weight) Photopolymerizable unsaturated compound (m / n = 5/5) 20.0 Dipentaerythritol hexaacrylate 8.6 Tetramethylbiphenyl epoxy resin 4.4 Michler's ketone 0.2 Irgacure 907 2 Ethyl cellosolve acetate 65.6 Total 100

Next, as a red, green, blue and black pigment, CF Color Red EX-27 manufactured by Mikuni Pigment Co., Ltd.
4. Using CF Color Green EX-276, CF Color Blue EX-275, and CF Color Black EX-277, disperse these in an organic solvent in advance, and then mix with the above resin composition and perform dispersion treatment. RED, GREEN, BLUE and BLACK having the composition shown in Table 1.
Were prepared. In addition,
At this time, the dispersion treatment was performed so that the pigment particle diameter was 0.3 μm for each color.

[0033]

[Table 1]

A glass substrate washed with a neutral detergent, water, isopropyl alcohol, and chlorofluorocarbon is used as a transparent substrate.
On this glass substrate, the above RED, GREEN, BLUE
And four types of black inks were used, and color filters were produced under the ink application conditions and exposure amounts shown in Table 2. Prebaking was performed at 80 ° C. for 5 minutes, and development was performed using a 0.4% by weight aqueous sodium carbonate solution. In the application sequence, first, a black matrix was formed, and then pixels were formed at predetermined positions in the order of red (R) -green (G) -blue (B). The thickness of each pixel at this time is R, G, B
Each of the black matrix and the black matrix was 2 ± 0.1 μm. Further, an ITO transparent electrode layer formed by a sputtering method was coated on the black matrix and each pixel. Thus, as shown in FIG.
Black matrix 2a laminated on glass substrate 1
And a color filter 2 including a pixel 2b including a red pixel R, a green pixel G, and a blue pixel B provided at a predetermined position of the black matrix 2a and a transparent electrode layer 2c coated on the surface of the pixel 2b. It is made.

[0035]

[Table 2]

Comparative Example 1 Polyvinyl alcohol (manufactured by Nippon Gohsei Co., Ltd .: EG-3)
0) 6 parts by weight, 0.5 parts by weight of ammonium bichromate,
Using a photosensitive dye base material consisting of 0.3 parts by weight of chrome alum and 93.2 parts by weight of water, dyeing was carried out under the conditions shown in Table 3 using 24P red, 1P green and 5C blue as dyes. The pre-baking was performed at 60 ° C. for 10 minutes, and the application sequence was R
-GB. At this time, the thickness of each pixel was 1.5 ± 0.2 μm for R, G and B.

[0037]

[Table 3]

The thus obtained color filters of Example 1 and Comparative Example 1 were subjected to a light fastness test using a xenon fade meter. L after 1,000 hours
Table 4 shows the results of ΔE (color difference) by _ab . As is clear from the results in Table 4, the value of ΔE in Example 1 was clearly higher.
Was found to be small and excellent in lightfastness reliability.

[0039]

[Table 4]

Comparative Example 2 A color filter was produced in the same manner as in Example 1 using a color mosaic [R, G, B; manufactured by Fuji Hunt Co., Ltd.]. Prebaking was performed at 90 ° C. for 5 minutes, and development was performed using a specified developer. The film thickness of each manufactured pixel is R, G,
B was 2 ± 0.1 μm. The color filter of Example 1 and the color filter of Comparative Example 2 thus obtained were subjected to a heat resistance test (280 ° C., 1 hour). At that time, the peak value of the spectral transmittance decreased and the film thickness decreased. Table 5 shows the reduction rates. As is clear from the results in Table 5, the product of the present invention was remarkably excellent in light resistance and heat resistance as compared with the conventional product.

[0041]

[Table 5]

[0042]

The alkali developing type photosensitive color filter ink of the present invention can be easily produced in a simple process because the crosslinking reaction proceeds even in the presence of oxygen. It becomes tack-free and enables contact exposure, high resolution, heat resistance, transparency, acid resistance, alkali resistance, solvent resistance,
It has excellent performance in surface hardness and the like. Also,
The color filter produced using the ink of the present invention is excellent in acid resistance, alkali resistance, solvent resistance, surface hardness and the like, a color liquid crystal display device, a color facsimile,
It is useful for various multi-color displays such as image sensors, TVs, video monitors and computer displays.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a pixel in a color filter.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Glass substrate, 2 ... Color filter, 2a ... Black matrix, 2b ... Pixel, R ... Red pixel, G ... Green pixel, B ... Blue pixel, 2c ... Transparent electrode layer.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location G03F 7/038 G03F 7/038 (72) Inventor Koki Inada 2-6-Otemachi, Chiyoda-ku, Tokyo No. 3, Nippon Steel Corporation (56) References JP-A-63-129303 (JP, A) JP-A-63-205650 (JP, A) JP-A-49-2601 (JP, A) JP-A-4-51202 (JP, A) JP-A-3-247678 (JP, A) JP-A-4-355450 (JP, A)

Claims (5)

(57) [Claims] (A) The following general formula (1): (However, in the formula, R ₁ and R ₂ represent a hydrogen atom, a carbon number of 1 to 5)
R ₃ represents a hydrogen atom or a methyl group, and X represents -CO-, -SO
_{2 -, - C (CF 3} ) 2 -, - Si (CH 3) 2 -, -
CH ₂ —, —C (CH ₃ ) ₂ —, —O—, embedded image Y represents an acid anhydride residue, Z represents
Represents a residue of an acid dianhydride, and the structural unit m: n is represented by a molar ratio of 1/99 to 90/10), and 0.5 g of the compound is dissolved in 100 ml of N-methylpyrrolidone. The inherent viscosity (η) measured at 30 ° C.
_inh ) is 0.1 dl / g or more, (B) a compound having an epoxy group, (C) a photopolymerization initiator or a sensitizer, and (D) a pigment. The proportions of the components B, C and D are each 5 to 100 parts by weight of the component A.
50 parts by weight, 0.1 to 30 parts by weight, and 10 to 200 parts by weight of an ink for an alkali development type photosensitive color filter. 2. The ink according to claim 1, wherein R _{1 to} R ₃ in the general formula (1) are hydrogen atoms. 3. X in the general formula (1) is The ink for an alkaline development type photosensitive color filter according to claim 1, wherein 4. In addition to the component A, component B, component C and component D, at least one selected from photopolymerizable monomers and oligomers is added in an amount of 5 parts by weight per 100 parts by weight of the component A.
The ink for an alkali-developable photosensitive color filter according to any one of claims 1 to 3, which is blended in a range of 0 part by weight or less. 5. A transparent substrate coated with the ink for an alkali-developable photosensitive color filter according to claim 1 and cured to provide red, blue, and green pixels and a black matrix. A color filter comprising a transparent electrode layer provided on a surface thereof.