JPH09291239A - Red ink composition for color filter and production of color filter with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition high in the solubility of a dye, excellent in stability with time and not causing the clogging of ink jet printer heads by dissolving the specific red dye in an amide organic solvent aqueous solution. SOLUTION: This red ink composition is produced by dissolving (B) a chromium-containing azo anionic red dye in (A) an amide solvent aqueous solution. The component A is an active hydrogen-free compound such as N- methylpyrrolidone and is contained in an amount of 5-30wt.%. The component B is preferably contained in a concentration of 1-10%, and is preferably a chromium-containing phenylazopyrazolone anionic red dye of the formula [R1 -R4 are each H, a halogen, a 1-5C alkyl, an alkoxy; R5 , R6 are H, a 1-5C alkyl, a halogen, etc.; M<+> is a cation].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a red ink composition for a color filter used for producing a color filter having excellent optical properties used in liquid crystal display devices, color separation devices, sensors, etc. And a method for manufacturing a color filter manufactured by an inkjet method.

[0002]

2. Description of the Related Art Conventionally, a method of combining three primary color filters of red, green, blue, or yellow, magenta, and cyan has been used for colorizing liquid crystal display elements and solid-state image pickup elements. Although there are several methods for forming these color filters, the most basic method is the so-called dyeing method. The method of producing a color filter by the dyeing method is a film of a synthetic resin having a transparent cationic group in the form of a thin film such as a stripe or mosaic (called a pattern) on the surface of a substrate such as glass or a silicon wafer. The basic principle is to provide a film of a protein-based natural high molecular substance such as gelatin, casein, and glue to form a film to be colored, and dye (color) this with a dye. Dyeing method color
The following three methods are known as specific filter manufacturing processes.

(1) After a film to be colored is provided on the surface of the substrate, the pattern obtained by exposing and developing through a mask is dyed to form a colored layer. Then a non-coloring protective coat
A coating film is provided on the entire surface, and a second coating film to be colored is provided thereon by the same operation as above. Hereinafter, if necessary, colored layers are sequentially laminated.

(2) After a film to be colored is provided on the surface of the substrate, the pattern obtained by exposing and developing through a mask is dyed to form a colored layer, and then a dye is fixed with tannic acid or the like. Combined with dye-proof treatment. A second coating to be colored is provided by the same operation. Thereafter, if necessary, a colored layer is formed on the same substrate surface.

(3) A film to be colored (coloring film) is provided on the surface of the substrate. After providing a positive resist layer thereon, the film to be colored is exposed and developed through a mask to dye the exposed film to be colored, and then the positive resist layer is peeled off to form a colored portion. By repeating the operation after providing the positive resist layer, the same colored film is dyed into a desired pattern in a plurality of colors.

Color produced by the above process
Except for special ones, the filters are normally three primary colors R (red), G (green), B (blue) or three complementary primary colors Y (yellow), M (magenta), C (cyan). , (M may be omitted). The most important characteristic required for the color filter is the optical characteristic, and the spectral characteristic of each colored layer greatly controls the value of the final product.

Further, for heat treatment encountered in the process of manufacturing a liquid crystal display device having a color filter, for example, for a sputtering process for providing a transparent electrode layer, and for light applied during use as a final product. It has a high degree of tolerance and must not impair certain optical properties. Of course, the applied dye must also have good solubility in water (rate of dissolution and solubility) and be stable for a long time in an acidic dyebath.

Further, in the case of involving a step requiring fixing treatment, it is required that the fixing treatment effect is excellent. By the way, since protein type polymer substances such as gelatin, casein, and glue have a cationic group, they are dyed (colored) with a water-soluble anionic dye. When a photo-curable synthetic resin substrate is used instead of these, by retaining a cationic group in the resin component, it is dyed with a water-soluble anionic dye like a protein-based natural polymer substance. Become so.

As described above, the dyeing method has a feature that an extremely fine color pattern can be freely formed.
Since many manufacturing processes such as a photolithography process, a dyeing process, and a cleaning / fixing process are performed depending on the number of colors to be dyed, there is a high risk that yield may be reduced due to dust adhesion during manufacturing. Further, since the coloring density is almost proportional to the film thickness of the dyed resin film, the fluctuation of the film thickness causes unevenness of color and deteriorates the quality of the product. Depending on the order of dyeing, color unevenness may occur due to contamination or desorption of other colors. Further, a liquid crystal display element manufacturer has strongly demanded a method of reducing the number of steps for manufacturing a color filter to improve the yield and make the cost lower.

Recently, the inventors of the present invention formed a photosensitive resin thin film having a very high dyeability with an anionic dye on a transparent substrate and irradiating it with an energy ray to cure the thin film to form a cured film layer. Japanese Unexamined Patent Publication No. 7-77607 discloses a method for producing a color filter in which a dye solution is ejected at a predetermined position by an inkjet method to form a desired colored pattern with high density and accuracy.

[0011]

DISCLOSURE OF THE INVENTION According to the present invention, a highly dyeable photosensitive resin thin film is formed on a transparent substrate, and a dye solution is selectively jetted onto the thin film layer by an inkjet method to form a desired colored pattern. It is to provide a red ink composition for a color filter, which is suitable for forming and wet-treating to obtain a color filter and which has extremely high dyeability and excellent stability, and a method for producing a color filter using the same. .

[0012]

The present inventors have completed the present invention as a result of various investigations for solving the above problems. That is, the present invention provides (1) a red ink composition for a color filter, wherein a chromium-containing azo anionic red dye is dissolved in an amide-based organic solvent aqueous solution,
(2) The red ink composition for a color filter according to (1), wherein the amide-based organic solvent is a compound having no active hydrogen.
(3) Compounds having no active hydrogen include N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N, N
-Dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone,
(2) Red ink composition for a color filter, which is N, N, N ', N'-tetramethylurea, (4) For a color filter (2), wherein the compound having no active hydrogen is N-methylpyrrolidone Red ink composition,

(5) The content of the amide-based organic solvent is 5-3
0% by weight of (1) to (4) the red ink composition for a color filter, (6) the ink composition contains substantially no organic solvent other than the amide organic solvent (1) to (5) The red ink composition for a color filter according to any one of (1) to (7), wherein the concentration of the chromium-containing azo anionic red dye in the ink composition is 1 to 10%. Red ink composition for filters,
(8) The red ink composition for a color filter according to (7), wherein the chromium-containing azo anionic red dye is a chromium-containing phenylazopyrazolone anionic red dye, and (9) the chromium-containing phenylazopyrazolone anionic red dye. General formula (1)

[0014]

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(In the formula (1), R ₁ , R ₂ , R ₃ and R ₄
Are each independently a hydrogen atom, a halogen atom, or a carbon number of 1-5.
Represents an alkyl group, a C 1-5 alkoxy group, a nitro group, a sulfonamide group or a sulfonic acid group, R ₅ ,
R ₆ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a sulfonic acid group or a sulfonamide group, and M ⁺ represents a cation. (8) a red ink composition for a color filter, which is an anionic red dye represented by the formula (8), and (10) an inkjet method on a transparent substrate having a crosslinked layer of an anionic dye dyeable polymer,
The red ink composition for a color filter of (1) to (9) is jetted to a predetermined position to form a desired colored pattern,
A method for producing a color filter, which comprises water treatment after drying, (11) a method for producing a color filter according to (10), wherein the anionic dye-dyeable polymer is a resin having a tertiary amino group, and (12) transparent. The crosslinked layer of the anionic dye-dyeable polymer formed on the substrate is patterned in a shape corresponding to the shape of the pixel of the liquid crystal display element (10).
Alternatively, the manufacturing method of the color filter according to (11), (13)
The crosslinked layer of the anionic dye-dyeable polymer formed on the transparent substrate is patterned into a shape corresponding to the shape of the pixel of the liquid crystal display element, and a black matrix is formed between the patterns (10 ) Or (11) the method for producing a color filter, (14) the water treatment is 30 to 100
The present invention relates to the method for producing a color filter according to (10) to (13), which is a treatment with hot water having a temperature of 3 to 7 ° C.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The color filter ink composition of the present invention is one in which a chromium-containing azo anionic red dye is dissolved in an aqueous amide organic solvent solution. Examples of the amide-based organic solvent include N-methylpyrrolidone, N,
N-dimethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone, N,
A compound having no active hydrogen such as N, N ′, N′-tetramethylurea is preferable from the viewpoint of dyeing property, and N-methylpyrrolidone is particularly preferable. The content of the amide-based organic solvent in the ink composition is preferably 3 to 40% by weight, more preferably about 5 to 30% by weight, and the water content is 96.5 to 40% by weight, More preferably, it is about 92 to 60% by weight.

Examples of the chromium-containing azo anionic red dye used in the present invention include chromium-containing phenylazopyrazolone anionic red dye. Examples of the chromium-containing phenylazopyrazolone-based anionic red dye include the anionic red dye represented by the above general formula (1). In the general formula (1),
R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms.
Is an alkoxy group, a nitro group, a sulfonamide group or a sulfonic acid group, and R ₅ and R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a sulfonic acid group or a sulfonamide group. , M ⁺ is a cation.
Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, isoamyl group, sec-amyl group, t-
Examples include amyl groups. Examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n-pentyloxy group and the like. As a halogen atom,
Examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of M ⁺ cations include Na, K,
Examples thereof include alkali metal cations such as Li and quaternary ammonium groups. Examples of the quaternary ammonium group include NH
₄ , NH ₃ C ₂ H ₄ OH, NH ₂ (C ₂ H ₄ OH) ₂ ,
Examples thereof include ethanolamine-based quaternary ammonium groups such as NH (C ₂ H ₄ OH) ₃ and N (CH ₃ ) ₄ .

As a compound of a preferable combination of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ , for example, R ₁ is a nitro group, R ₂ is a methyl group, R ₃ is a hydrogen atom, and R ₄ is N-ethylsulfonamide group, R ₅ is a sulfonamide group, R ₆
Wherein R is a hydrogen atom or R ₁ is a sulfonic acid group, R
₂ is a nitro group, R ₃ is a hydrogen atom, R ₄ is a nitro group, R ₅
Is a hydrogen atom, R ₆ is a hydrogen atom, or a compound or R in which R ₁ is a nitro group, R ₂ is a methyl group, R ₃ nitro group, R ₄ is a methyl group, and R ₅ and R ₆ are sulfonamide groups. _A compound in which ₁ is a chlorine atom R ₂ R ₃ R ₄ R ₅ and R ₆ are hydrogen atoms, or R ₁ is a sulfonic acid group, R ₂ is a nitro group, R ₃ is a sulfonic acid group, R ₄ is a nitro group, R ₅ And a compound in which R ₆ is a hydrogen atom, or R ₁ is a hydrogen atom, R
₂ is an N-ethylsulfonamide group, R ₃ is a hydrogen atom, R
Compounds in which ₄ is a sulfonamide group, R ₅ and R ₆ are hydrogen atoms, or R ₁ is a sulfonic acid group, R ₂ is a nitro group, R
₃ is a hydrogen atom, R ₄ is a nitro group, R ₅ is a hydrogen atom, R ₆
And a compound in which is a chlorine atom. Preferable substitution positions of these groups include, for example, R ₁ in 3-position and R ₂
Is 5-position, R ₃ is 3-position, R ₄ is 4-position or 5-position, R
₅ is 3-position and R ₆ is 3- or 4-position.

As the chromium-containing azo anionic red dye used in the present invention, for example, the following compound No. 1
~ Compound No. Compounds such as 9 are mentioned. The chromium-containing azo anionic red dye is, for example, the compound represented by the general formula (1) above.
It is prepared by mixing the dyes represented by

[0020]

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[0021]

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[0022]

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[0023]

[Chemical 6]

[0024]

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The dye concentration in the color filter ink composition of the present invention is preferably 0.5 to 20% by weight, and particularly preferably 3 to 10% by weight. Inorganic salts such as sodium chloride and sodium sulfate are generally mixed in the anionic dye during the dye synthesis. Further, calcium ions, magnesium ions, etc. contained in general water are mixed in in a trace amount. These inorganic components not only significantly deteriorate the solubility and storage stability of the dye, but also cause corrosion and wear of the printer head, so it is desirable to remove them as much as possible, but in practice set standards and manage them. Must. Its content must be at least 1% by weight or less based on the anionic green dye,
It is preferably 0.5% by weight or less, more preferably 0.1% by weight or less. Further, in the color filter ink composition of the present invention, an organic solvent other than an amide organic solvent such as an alcohol solvent from the viewpoint of dyeability, particularly an organic solvent other than an amide organic solvent having no active hydrogen. It is preferably substantially free. Here, “not substantially containing” means that an organic solvent other than the amide-based organic solvent, particularly an organic solvent other than the amide-based organic solvent having no active hydrogen, is not contained in an amount such that the dyeing property is deteriorated.

The color filter ink composition of the present invention can be produced, for example, as follows. That is, a chromium-containing azo anionic red dye is dissolved in an amide organic solvent aqueous solution, and after removing inorganic salts by a method such as ultrafiltration, reverse osmosis, or ion exchange, the desired dye is diluted or concentrated. By adjusting the concentration, the color filter ink composition of the present invention can be obtained. The ink composition of the present invention may contain a dye content of 0.5 to 20% by weight, and 2 to 10% by weight is preferable in practice. After adjusting the dye concentration, liquid filtration is performed using a cellulose-based filter aid to remove dust, foreign matter, and other impurities, and then microfiltration is performed using a membrane filter (for example, pore size 1 μm). It is preferable to perform microfiltration with a membrane filter having a pore size of 0.45 μm or less.

Among the various properties, the ink composition of the present invention prepared as described above is particularly excellent in stability and long-term storability, and is characterized in that it does not clog the ejection orifice. In addition, the stabilizer of the ink composition (sodium polyacrylate, for example, Kayachelator C-produced by Nippon Kayaku Co., Ltd.)
1000 etc.) and antibacterial / antifungal agents (eg Takeda Pharmaceutical Co., Ltd.)
In the case of adding a product such as Dell Top), it is advisable to add it before the microfiltration.

To carry out the method for manufacturing a color filter of the present invention, for example, the following may be carried out. That is, by an inkjet method on a transparent substrate having a crosslinked layer of an anionic dye dyeable polymer, a desired color pattern is formed by spraying the ink composition for a color filter at a predetermined position, and after drying, water is used. Just process it. Dyeing (coloring) by the inkjet method may be performed for each color or for multiple colors simultaneously.
After dyeing, heat drying treatment is performed for 3 to 15 minutes on a hot plate or oven at 70 to 180 ° C. After that, water treatment is carried out in order to remove the ink adhering to a place other than a predetermined place and to sufficiently develop the dye printed on the dyed thin film.
Examples of the water treatment include a fixing treatment using water containing a fixing treatment agent and a hot water treatment containing no fixing treatment agent. The hot water treatment is 30 to 100 ° C., more preferably 60 to 80 ° C. and pH 3
Use ~ 7 water. For adjusting the pH of this water, organic acids, particularly lower carboxylic acids such as acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, tartaric acid and malic acid are preferably used. However, since it is not a fixing treatment, this hot water does not contain a fixing treatment agent such as tannin and tartarite. Examples of the water treatment method include dipping or shower washing, but it is preferable to wash with hot water, that is, to wash the dyed product with warm water from the viewpoint of simplicity of treatment. The ink composition of the present invention is characterized in that the desorption of the dye is very little even after such a washing treatment, and the fixing treatment for preventing the elution of the dye is not required. The manufacturing method is advantageous. There is no problem even if the fixing treatment is carried out in an aqueous solution containing tannic acid and tartarite. Further, if necessary, a transparent protective layer is coated on the entire surface of the dyed thin film for the purpose of protecting the color filter layer.

The transparent substrate having the crosslinked layer of the anionic dye dyeable polymer used in the present invention is produced as follows. That is, an anionic dye dyeable polymer and an anionic dye dyeable photosensitive resin containing a photosensitive compound as an essential component are dissolved in a solvent such as methyl cellosolve acetate and the photosensitive resin liquid is prepared by a method such as spin coating. Is coated on a transparent substrate, dried and then exposed to light to cure the photosensitive resin to obtain a photosensitive resin thin film (crosslinked layer of anionic dye dyeable polymer). The film thickness of the photosensitive resin thin film is 0.2 to
5 μm is preferable, and 0.5 to 1.5 μm is particularly preferable. The photosensitive resin thin film may be exposed with a predetermined pattern through a mask, or may be exposed by the whole surface without a pattern and cured. When the pattern is provided, partition walls may be formed as a black matrix in the gap between the patterns.
The dyed thin film may be exposed through a mask to form a predetermined pattern, or may be exposed over the entire surface without a pattern.

The substrate used in the present invention is not particularly limited as long as it is a colorless transparent plate, and examples thereof include plates made of glass, polyester, polycarbonate, polyacrylate, polyether sulfone and the like. Its thickness is 0.5
About 1.5 mm is preferable.

The crosslinked product of the anionic dye-dyeable polymer used in the present invention is a cured product of an anionic dye-dyeable photosensitive resin containing an anionic dye-dyeable polymer and a photosensitive compound as essential components. is there. The anionic dye dyeable polymer contains a hydrophilic monomer other than the anionic dye dyeable monomer and the anionic dye dyeable monomer (hereinafter simply referred to as “hydrophilic monomer”) as an essential component. This anionic dye dyeable polymer can be prepared by using a conventionally known solution polymerization method.

Here, the anionic dye dyeable monomer is
For example, it is a monomer having a tertiary nitrogen or a quaternary nitrogen in its molecule and has a property of imparting the dyeing ability of an anionic dye to the polymer. Specifically, for example, (N, N-dimethylamino) ethyl acrylate,
(N, N-dimethylamino) ethyl methacrylate,
(N, N-diethylamino) ethyl acrylate,
(N, N-diethylamino) ethyl methacrylate, 3
-(N, N-dimethylamino) propyl acrylate,
(N, N-di (C ₁ -C ₄ ) alkylamino) such as 3- (N, N-dimethylamino) propyl methacrylate
(C ₁ -C ₄ ) alkyl (meth) acrylate, 3-
(N, N-dimethylamino) propylacrylamide,
(N, N-di (C ₁ -C ₄ ) alkylamino) such as 3- (N, N-dimethylamino) propylmethacrylamide
(C ₁ -C ₄ ) alkyl (meth) acrylamide,
(N, N-diethylaminoethyl vinyl ether, 4-
Vinyl pyridine, diarylamine, 2-hydroxy-
3-methacryloyloxypropyltrimethylammonium chloride and methacryloyloxyethyltrimethylammonium chloride are mentioned, but (meth) acrylamide-based monomers are preferable from the viewpoint of stability and the like, and in consideration of the dyeing property of anionic dyes, tertiary Most preferred are nitrogen-containing monomers, such as 3- (N, N-dimethylamino) propylacrylamide and 3- (N, N-dimethylamino) propylmethacrylamide-containing (meth) acrylamide-based monomers having a tertiary nitrogen. These anionic dye dyeable monomers are independent,
Alternatively, two or more kinds are mixed and used.

Examples of the hydrophilic monomer include hydroxy (C ₁ -C ₄ ) alkyl (meth), such as hydroxyethyl acrylate and hydroxyethyl methacrylate.
Examples thereof include acrylate, acrylamide, methacrylamide, dimethylaminoacrylamide, and methylaminoacrylamide, and (meth) acrylamide to which one or two (C ₁ -C ₄ ) alkyl groups may be bonded, vinylpyrrolidone, and the like. These hydrophilic monomers alone
Alternatively, two or more kinds are mixed and used.

The blending ratio of these anionic dye dyeable monomer and hydrophilic monomer is such that the anionic dye dyeable monomer is 25 to 85% by weight, preferably 30 to 80% by weight, and the hydrophilic monomer is 15 to 75% by weight. , Preferably 20
~ 70% by weight is preferred.

Examples of the photosensitive compound include diazidochalcone, 4,4'-diazidostilbene-2,2'-disulfonic acid and 4,4'-diazidostilbene-2,2 '.
-Sodium disulfonate, 4,4'-diazidostilbene-2,2'-disulfonic acid (bis (methoxyethyl)) amide, 4,4'-diazidostilbene-2,
4,4′-diazidostilbene-2,2′-disulfonic acid (mono or bis ((C ₁ -C ₄ ) alkoxy (C) such as 2′-disulfonic acid (bis (ethoxyethyl)) amide)
₁ -C ₄₎ alkyl)) azide compounds such as amides, acrylic compound such as a known functional groups having two or more thereof. These photosensitive compounds may be used alone or in admixture of two or more. When an azide compound is used as the photosensitive compound, it is preferably used in an amount of about 2 to 15% by weight, more preferably 3 to 15% by weight based on the anionic dye-dyeable polymer.
It is preferable to use about 8% by weight.

In addition, 0.1 to 10 parts by weight of a compound having a (meth) acryloyl group other than the above-mentioned anionic dye dyeable monomer and hydrophilic monomer is added to 100 parts by weight of anionic dye dyeable polymer. In particular, the addition of about 0.5 to 6 parts by weight is preferable because the curing rate is increased. (Meta)
Examples of the compound having an acryloyl group include spiroglycol diacrylate [3,9-bis (2-acryloyloxy-1,1-dimethyl) 2,4,8,10-
Tetraoxaspiro [5,5] undecane] cyclohexane dimethylol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, butylene glycol diacrylate, neopentyl glycol di Acrylate, 1,4-
Butanediol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, bisphenol A epoxy acrylate, alkylene glycol diepoxy acrylate, glycidyl ester acrylate. , Polyester diacrylate, bisphenol A diacrylate,
Urethane-based diacrylate, methylenebisacrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, pentylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,4- Examples thereof include butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate and the like.

When a conventionally known acrylic compound having two or more functional groups is used as the photosensitive compound, it is preferably used in an amount of about 10 to 40% by weight, more preferably 15 to 40% by weight based on the anionic dye-dyeable polymer. It is preferable to use about 35% by weight. In this case, a photosensitizer may be used together.

When the strength of the photo-cured product of the anionic dye-dyeable polymer comprising a copolymer of an anionic dye-dyeable monomer and a hydrophilic monomer is insufficient, a hydrophobic monomer is used as a monomer constituting the polymer. When used together, its strength can be increased. Examples of the hydrophobic monomer include alkyl acrylates of (meth) acrylic acid such as methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate, styrene and p-methylstyrene. Can be mentioned. The anionic dye dyeable monomer, the hydrophilic monomer, and the hydrophobic monomer are mixed in proportions of 20 to 70% by weight, preferably 25 to 60% by weight, and 10 to 60% by weight of the hydrophilic monomer. Preferably 2
It is preferable that the content is 0 to 50% by weight, the hydrophobic monomer is 10 to 50% by weight, and preferably 20 to 40% by weight. The molecular weight of the anionic dye-dyeable polymer thus prepared is preferably 5,000 to 200,000,
More preferably, it is about 10,000 to 100,000.

The photosensitive resin composition having the above composition is
Usually, it is diluted with an organic solvent or the like before use. Examples of the organic solvent include methyl cellosolve, ethyl cellosolve,
Tosopropyl cellosolve, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methyl ethyl ketone, methoxyisopropyl glycol and the like can be mentioned, but isopropyl cellosolve and diethylene glycol dimethyl ether are preferable from the viewpoint of coating property and the like. These may be used alone or in combination of two or more. The proportion of the organic solvent in the photosensitive resin liquid varies depending on the composition in the resin liquid and cannot be unconditionally specified, but it is preferable that the resin liquid has a viscosity that can be applied to the surface of the substrate. When an azide compound is used as the photosensitive compound, the water content in the photosensitive resin liquid is preferably 1% by weight or less in order to avoid its decomposition and side reactions.

As a specific example of the photosensitive resin composition, the photosensitive resin composition disclosed in JP-A-62-194203 is preferable. As the photosensitive resin liquid, for example, CFR6
33DHP, CFR633L1 (all manufactured by Nippon Kayaku Co., Ltd.) and the like. As the anionic dye dyeable polymer, a resin having a tertiary amino group is preferable in terms of dyeing property and heat resistance.

[0041]

EXAMPLES The present invention will be described in more detail below with reference to reference examples and examples. Reference example Preparation of anionic dye dyeable photosensitive resin liquid 3- (N, N-dimethylamino) propylacrylamide 38 parts 2-hydroxyethyl methacrylate 15 parts Dimethylaminoacrylamide 10 parts Vinylpyrrolidone 7 parts Methyl methacrylate 8 parts Methyl acrylate 22 parts The monomer of the above formulation was polymerized by a known solution polymerization method, and the polymer was precipitated by pouring it into a large amount of isopropyl ether, and then the polymer (average molecular weight 90,000) was taken out and the water content was 1% by weight or less. Dry until
To 100 parts of this dried polymer, 2 parts of 4,4'-diazidochalcone, 6 parts of 4,4'-diazidostilbene-2,2'-disulfonic acid (bis (ethoxyethyl)) amide, and silane coupler KBM603 (Shin-Etsu Chemical) Industry Co., Ltd. 2
Parts, isopropyl cellosolve 450 parts, and diethylene glycol dimethyl ether 450 parts are mixed and dissolved to obtain a photosensitive resin liquid having a water content of 1% by weight or less.

The present invention will be described in detail below with reference to Reference Examples and Examples.

Example 1 Anionic dye dyeable polymer obtained by copolymerizing an anionic dye dyeable monomer, a hydrophilic monomer and a hydrophobic monomer and an azide compound dissolved in a solvent. CFR633DHP which is a light-sensitive resin liquid
100 parts (manufactured by Nippon Kayaku Co., Ltd.) and 0.05 parts of a silane coupling agent KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed. This is coated on a glass substrate by spin coating and dried at 110 ° C for 3 minutes, and then a belt conveyor type U
The entire surface is exposed through a V irradiator at an exposure amount of 150 mJ / cm ² and cured. The glass substrate having the thin film to be dyed thus formed is accurately positioned by an optical treatment method and set in an inkjet printer.

Then, the compound No. A mixture of 15 parts, 23.8 parts of N-methylpyrrolidone and 71.2 parts of water is heated and dissolved, and the red ink of the present invention is prepared through a 0.2 μm membrane filter. Separately, the following N
o. 11 parts of the green pigment compound (4 parts), N-methylpyrrolidone (19 parts) and water (77 parts) were dissolved by heating,
Condition the green ink through a 0.2 μm membrane filter. Further, the following No. 10 blue pigment compounds 5
Part, 20 parts of N-methylpyrrolidone, and 75 parts of water are dissolved by heating, and a blue ink is prepared through a 0.2 μm membrane filter.

[0045]

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The above-mentioned blue ink is jetted by an ink jet to adhere to the portion of the thin film to be dyed that is to be colored blue. Next, the green ink described above is jetted onto the dyed thin film by an ink jet so that the dyed thin film is attached to the portion to be colored green. Finally, the above red ink is jetted onto the dyed thin film by an ink jet so that the dyed thin film is attached to a portion to be colored red. This is dried by heating on a hot plate heated to 150 ° C. for 10 minutes. Next, the printed glass substrate is shower washed with warm water of 70 ° C. and pH 7 for 5 minutes, and then dried at 130 ° C. for 10 minutes, and then R, G, B having a substantially circular pattern of about 150 μm.
Three color filters were obtained.

Example 2 Anionic dye dyeable polymer, azide compound and anionic dye dyeable monomer and hydrophilic monomer obtained by copolymerizing anionic dye dyeable monomer, hydrophilic monomer and hydrophobic monomer Other than CFR633L1 (manufactured by Nippon Kayaku Co., Ltd.), which is an anionic dye-staining photosensitive resin liquid in which a compound having a (meth) acryloyl group is dissolved in a solvent, and a silane coupling agent KBM60
3 (manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed with 0.05 part. This was coated on a glass substrate having a black stripe made of a pigment-dispersed resist by spin coating,
After drying at ℃ for 3 minutes, the entire glass surface is exposed and cured. Subsequently, the film is immersed in a 2% aqueous solution of tetramethyl hydroxide for development, washed with water, and dried at 150 ° C. for 20 minutes to obtain a highly dyeable resin film having a black stripe on the substrate. This glass substrate is precisely positioned and set in an inkjet printer.

Then, No. A mixture of 6 parts of the compound No. 2 (6 parts), N-methylpyrrolidone (19 parts) and water (75 parts) is dissolved by heating and the red ink of the present invention is prepared through a 0.2 μm membrane filter. Separately, from the above No. 10
Blue pigment compound 5 parts, N-methylpyrrolidone 20
Part of water and 75 parts of water are dissolved by heating to give 0.2 μm.
A blue ink is prepared through a membrane filter of m. Further, the above No. 11 green pigment compounds, 5 parts, N
A mixture of 20 parts of methylpyrrolidone and 75 parts of water is dissolved by heating, and a green ink is prepared through a 0.2 μm membrane filter.

The above blue ink is jetted onto the above glass substrate with an ink jet printer to adhere to the portion of the thin film to be dyed that is to be colored blue. Next, the above-mentioned green ink is jetted onto this dyed thin film by an inkjet printer to adhere to the portion of the dyed thin film to be colored green. Finally, the above-mentioned red ink is jetted onto this dyed thin film by an ink jet printer to adhere to the portion of the dyed thin film to be colored red. This is dried by heating on a hot plate heated to 150 ° C. for 10 minutes. Next, a shower washing treatment is performed for 5 minutes with warm water containing 0.2% of acetic acid at 70 ° C. and pH 3, followed by washing with water and drying at 130 ° C. for 10 minutes.
A striped color filter of three colors G and B was obtained.

Example 3 100 parts of CFR633L1 (manufactured by Nippon Kayaku Co., Ltd.) and a silane coupling agent KBM603 (Shin-Etsu Chemical Co., Ltd.)
(Manufactured) 0.05 parts. This was spin-coated on a glass substrate with a spinner to a film thickness of 1.5 μm,
After drying at 0 ° C. for 20 minutes, exposure is performed using a mask and development is performed to form a stripe pattern having a line width of 20 μm and a line interval of 120 μm. The substrate having the stripe pattern thus obtained is precisely positioned and set in an inkjet printer.

Then, a mixture consisting of 6 parts of PC Black181P (a color filter dye manufactured by Nippon Kayaku Co., Ltd.), 20 parts of N-methylpyrrolidone and 74 parts of water was dissolved by heating and passed through a 0.2 μm membrane filter to give black. Prepare the ink. This black ink is jetted by an inkjet printer to dye the stripe pattern black. This is dried at 150 ° C. for 10 minutes, then immersed in a solution containing 3 g of tannin, 1 g of tartar, and 3 g of acetic acid in 1 liter of water to fix and dry it. Subsequently, CFR633L1 is applied onto the substrate having the black stripes, and the same operation as in Example 2 is performed to obtain a color filter.

Comparative Example 1 The glass substrate having the thin film to be dyed formed in Example 1 was set in a printer and No. Compound of 1 5
Part, 25 parts of γ-butyrolactone, and 70 parts of water are heated and dissolved, and a red ink is prepared by passing through a 0.2 μm membrane filter. The red ink is jetted by an ink jet to adhere to the thin film to be dyed. This is dried by heating on a hot plate heated to 150 ° C. for 10 minutes. Next, print the glass substrate at 70 ℃, pH
After shower washing with hot water of No. 7 for 5 minutes, it was dried at 130 ° C. for 10 minutes to obtain a red color filter.

The spectroscopic spectra of this and the red portion filter obtained in Example 1 were analyzed by the microspectrophotometer MCPD100.
0 (manufactured by Otsuka Electronics Co., Ltd.).

The transmittances at 500 nm and 600 nm in Example 1 slightly decreased after print drying and hot water treatment, showing that desorption of dye due to hot water treatment was scarce and improvement in density due to color development was slight. It means that. On the other hand, 500 nm of Comparative Example 1
The large change in the transmittance of the sample after the print was dried and after the hot water treatment indicated that the dye was desorbed during the hot water treatment.

[0055]

EFFECT OF THE INVENTION The ink composition used in the present invention has a high solubility of the dye, is excellent in stability over time, and does not cause clogging of the inkjet printer head. This ink composition has the function of increasing the affinity of the dye for the highly dyeable photosensitive resin thin film used in the present invention and significantly reducing color bleeding. Therefore, a highly accurate colored pattern can be obtained. According to the present invention, it is not necessary to carry out the patterning and dye fixing treatment such as conventional dyeing three times, and the process is remarkably simplified. In addition, the decrease in yield due to dust adhesion in the conventional developing process and dyeing process is very small. Further, the control of the jetting position of the dye solution by the inkjet method is easy, and the accuracy can sufficiently meet the user's needs.

Claims (14)

[Claims] 1. A red ink composition for a color filter, wherein a chromium-containing azo anionic red dye is dissolved in an amide organic solvent aqueous solution. 2. The red ink composition for a color filter according to claim 1, wherein the amide-based organic solvent is a compound having no active hydrogen. 3. A compound having no active hydrogen is N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-diethylformamide,
N, N-dimethylpropionamide, N-methyl-ε-
The red ink composition for a color filter according to claim 2, which is caprolactam, 1,3-dimethyl-2-imidazolidinone, or N, N, N ', N'-tetramethylurea. 4. The red ink composition for a color filter according to claim 2, wherein the compound having no active hydrogen is N-methylpyrrolidone. 5. The red ink composition for a color filter according to claim 1, wherein the content of the amide-based organic solvent is 5 to 30% by weight. 6. The red ink composition for a color filter according to claim 1, wherein the ink composition contains substantially no organic solvent other than an amide-based organic solvent. 7. The red ink composition for a color filter according to claim 1, wherein the concentration of the chromium-containing azo anionic red dye in the ink composition is 1 to 10%. 8. The red ink composition for a color filter according to claim 1, wherein the chromium-containing azo anionic red dye is a chromium-containing phenylazopyrazolone anionic red dye. 9. A chromium-containing phenylazopyrazolone-based anionic red dye is represented by the general formula (1): (In the formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a nitro group, Represents a sulfonamide group or a sulfonic acid group, R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a sulfonic acid group or a sulfonamide group, and M ⁺ represents a cation. 9.) The red ink composition for a color filter according to claim 8, wherein the red ink composition is an anionic red dye. 10. The red ink composition for a color filter according to claim 1 is jetted to a predetermined position by an inkjet method on a transparent substrate having a crosslinked layer of an anionic dye dyeable polymer. A desired colored pattern is formed by using the above method, and after drying, water treatment is carried out. 11. The method for producing a color filter according to claim 10, wherein the anionic dye-dyeable polymer is a resin having a tertiary amino group. 12. The color filter according to claim 10, wherein the crosslinked layer of the anionic dye-dyeable polymer formed on the transparent substrate is patterned in a shape corresponding to the shape of the pixel of the liquid crystal display element. Manufacturing method. 13. A crosslinked layer of an anionic dye-dyeable polymer formed on a transparent substrate is patterned into a shape corresponding to the shape of a pixel of a liquid crystal display element, and a black matrix is formed between the patterns. The method for producing a color filter according to claim 10 or 11, which is provided. 14. The method for producing a color filter according to claim 10, wherein the water treatment is treatment with hot water having a temperature of 30 to 100 ° C. and a pH of 3 to 7.