JP2000081508A - Color filter, its production and photosensitive coloring composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to reduce a development residue on a light shielding layer or on a transparent part of a substrate, after developing. SOLUTION: A color filter is constituted of a transparent substrate, a patterned light shielding layer formed on the transparent substrate and a patterned color pixel colored with plural colors and formed on the substrate except a part where the light shielding film is formed. Then, at least one color of the color pixel is a photosensitive coloring composition containing (A) a pigment, (B) a copolymer with (meth)acrylic acid as one of a monomer, (C) a photo-polymerizable monomer, (D) a photoinitiator and (F) a solvent and which is formed from the compound having an acid value of its nonvolatile components of 25-60 mg.KOH/g. After forming the color pixel, the reflectivity at a wave length of 380-780 nm of the light shielding part is not less than 95% of the reflectivity of the light shielding layer before coating the composition, and the transmissivity at the wave length of 380-780 nm of the transparent substrate part in a colored image is not less than 95% of the transmissivity of the transparent substrate before coating the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a color filter used for a color liquid crystal display device, an image pickup device, and the like, and a method of manufacturing the same. The present invention is also directed to a photosensitive coloring composition used for producing the color filter.

[0002]

2. Description of the Related Art A color filter in a color liquid crystal display device or an image pickup device is usually manufactured by forming three primary color pixels of red, green and blue on a transparent substrate such as glass. In addition, a light-shielding layer called a black matrix is usually provided to shield light between these pixels. To form a colored pixel using the photosensitive colored composition, on a transparent substrate on which a light-shielding layer is patterned, after uniformly applying a photosensitive colored composition containing a pigment corresponding to each color by a spin coater or the like, Heat drying (pre-bake)
Then, a method of exposing and developing the coating film and further post-curing (post-baking) is adopted. By repeating these operations for each color required for the color filter, pixels of each color are obtained.

The light-shielding layer generally has a single-layer structure of chromium or a multilayer structure having a chromium layer and a chromium oxide layer on the surface, which includes a chromium layer and a chromium oxide layer. Pixels of each color required for the color filter are formed on the substrate as described above. On the light-shielding layer after development and on the transparent substrate, development residues mainly derived from pigments are formed. Occurs and is a problem. The development residue on the light-shielding layer causes a decrease in adhesion between the ITO (transparent electrode) or overcoat (smoothing layer of the color filter) and the substrate, which are laminated after the formation of the colored pixels, and separation at the interface. The development residue on the transparent substrate leads to deterioration of color reproducibility since the color filter is manufactured by a method of sequentially forming pixels for each color.

Various methods have been conventionally studied to remove such development residues. In particular,
From the process side, a method of treating with a hydrofluoric acid-containing solution as described in JP-A-5-224014 is known, while from the viewpoint of the developer, JP-A-8-286387
As described in JP-A-8-292487, a method using a specific nonionic surfactant is used, or an alkaline aqueous solution containing a specific amine and a nonionic surfactant is used as described in JP-A-8-292487. Methods are known.

However, there is a problem that the removal of the development residue is not sufficient only by the improvement of the process surface or the improvement of the developing solution as described above, and the improvement from the process surface leads to an increase in cost.

Japanese Patent Application Laid-Open No. 7-306530 discloses that an acid value of 20 to 300 is used in order to improve the dispersion stability of a pigment.
Using a dispersion resin in the range of mg KOH / g, and a photosensitive solution in which an organic solvent and a dispersion resin are combined so that the viscosity of a solution obtained by dissolving the dispersion resin in an organic solvent is in a specific range, is further described. JP-A-7-319161 discloses that an acid value of 20 is used in order to improve photosensitivity and dispersion stability of a pigment.
It describes a photosensitive solution which uses a dispersion resin having an unsaturated equivalent in the range of 600 to 300,000 KOH / g and a specific range of thixotropic property. In these publications, the development residue after development is not regarded as a problem, and according to the study of the present inventors, the conditions specified there alone were not always effective in reducing the development residue.

[0007]

SUMMARY OF THE INVENTION The present inventors have made intensive studies to solve the above-mentioned problems of the prior art and to reduce the development residue when producing a color filter. The acid value of the non-volatile component in the photosensitive coloring composition of Example 1 affects the amount of development residue, and the use of the composition having the controlled acid value allows the development of the light-shielding layer and the transparent portion of the substrate after development. The inventors have found that the residue is significantly reduced, and have completed the present invention.

[0008] Accordingly, an object of the present invention is to produce a color filter having a light-shielding layer on a substrate after development and a development residue of a transparent portion with a small amount from a specific photosensitive coloring composition.
Another object of the present invention is to provide a photosensitive coloring composition capable of reducing the development residue on a light-shielding layer or a transparent portion of a substrate after development.

[0009]

According to the present invention, there is provided a transparent substrate, a light-shielding layer patterned on the transparent substrate, and a plurality of colors formed on the substrate other than the light-shielding layer. At least one of the colored pixels is composed of (A) a pigment, (B) a copolymer containing (meth) acrylic acid as one monomer, (C) a photopolymerizable monomer, and (D) light. A photosensitive coloring composition containing a polymerization initiator and (F) a solvent, wherein the acid value of the nonvolatile component is 25 to
Formed from those in the range of 60 mg KOH / g,
The reflectance at 380 to 780 nm of the light-shielding layer portion after forming the colored pixel is 95% or more of the reflectance of the light-shielding layer before applying the photosensitive coloring composition, and 380 of the transparent substrate portion after forming the colored pixel. The transmittance at 〜780 nm is 99.5% of the transmittance of the transparent substrate before applying the photosensitive coloring composition.
The above color filter is provided.

This color filter is obtained by applying the above-mentioned photosensitive coloring composition on a transparent substrate having a light-shielding layer, drying the composition,
It is manufactured by a method in which the obtained coating film is irradiated with light through a mask, and then developed to form a colored pixel. Further, according to the present invention, (A) a pigment, (B) a copolymer containing (meth) acrylic acid as one monomer, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, and (F) Containing solvent,
A composition having an acid value of the non-volatile component in the range of 25 to 60 mg KOH / g. The composition is applied on a transparent substrate having a light-shielding layer, dried, subjected to patterning exposure and alkali development to be colored. After forming the pixel, 3
The reflectance at 80 to 780 nm gives a value of 95% or more of the reflectance of the light-shielding layer before the composition is applied, and the transmittance at 380 to 780 nm of the transparent substrate portion before the application of the composition. And a photosensitive coloring composition which gives a value of 99.5% or more of the transmittance of the transparent substrate.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
At least one color pixel constituting the color filter of the present invention includes (A) a pigment, (B) a copolymer containing (meth) acrylic acid as one monomer, (C) a photopolymerizable monomer,
It is formed from a photosensitive coloring composition containing (D) a photopolymerization initiator and (F) a solvent and having an acid value of a non-volatile component in the range of 25 to 60 mg KOH / g. This photosensitive coloring composition is generally called a pigment-dispersed resist, in which a pigment (A) is dispersed in a solvent (F), a copolymer (B) called a binder resin, and a photopolymerizable monomer (C). And the photoinitiator (D), and optionally other additives, are dissolved or dispersed.

The pigment (A) can be an organic pigment or an inorganic pigment usually used for a pigment-dispersed resist.
Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts.Specifically, iron, cobalt, nickel, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and the like Oxides of metals or composite metal oxides are mentioned. Specifically, as an organic pigment, a color index (Colour Index)
(Pigment) in The Society of Dyers and Colorists (published by The Society of Dyers and Colorists). These pigments can be used alone or in combination of two or more. More specifically, compounds having the following color index (C.I.) numbers are included, but are not limited thereto.

CI Pigment Yellow 20, 24, 31, 5
3, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 13
9, 147, 148, 150, 152, 153, 154, 155, 166, 173,180
And 185; CI Pigment Orange 13, 31, 36, 3
8, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;
I. Pigment Red 9, 97, 105, 122, 123, 144, 14
9, 166, 168, 176,177, 180, 192, 215, 216, 224, 242
And 254; CI Pigment Violet 14, 19, 2
3, 29, 32, 33, 36, 37 and 38; CI Pigment Blue 15 (15: 3, 15: 4, 15: 6 etc.), 21, 22, 28, 60
And 64; CI Pigment Green 7, 10, 15, 25, 3
6 and 47; CI Pigment Brown 28; CI Pigment Black 1 and 7, and the like.

The pigment (A) is used in an amount of preferably 5 to 60% by weight, more preferably 10 to 50% by weight, based on the total solid content in the photosensitive coloring composition.

The binder resin imparts alkali developability to the unexposed coating film and acts as a dispersion medium for the pigment. In the present invention, (meth) acrylic acid is used as one monomer as the binder resin. Copolymer (B)
Is used. The (meth) acrylic acid referred to in the present specification means acrylic acid or methacrylic acid. In addition, for example, (meth) acrylate also means acrylate or methacrylate. This copolymer (B) is usually obtained by copolymerizing (meth) acrylic acid with another monomer copolymerizable therewith, and contains a carboxyl group derived from (meth) acrylic acid.

The monomer copolymerizable with (meth) acrylic acid is a compound having a polymerizable carbon-carbon unsaturated bond. Specifically, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl Of unsaturated carboxylic acid alkyl esters such as (meth) acrylate, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate, vinyl acetate and vinyl propionate; Carboxylic acid vinyl esters,
Examples include vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile, and unsaturated carboxylic acids other than (meth) acrylic acid such as crotonic acid, itaconic acid, maleic acid, and fumaric acid. These monomers can be copolymerized with (meth) acrylic acid alone or in combination of two or more.

Examples of suitable copolymers using (meth) acrylic acid as one monomer include (meth) acrylic acid / benzyl (meth) acrylate copolymer and (meth) acrylic acid / benzyl (meth) acrylate / Styrene copolymer, (meth) acrylic acid / methyl methacrylate copolymer, (meth) acrylic acid / methyl methacrylate / styrene copolymer and the like can be mentioned. Further, such a copolymer having (meth) acrylic acid as one monomer, in which the side chain is modified with a compound having a photosensitive group, is also referred to in the present invention as (meth) acrylic acid as one monomer. (B).

The copolymer (B) preferably has a weight average molecular weight in the range of 5,000 to 400,000 in terms of polystyrene, and more preferably has a weight average molecular weight in the range of 10,000 to 300,000. This copolymer (B) is generally used in an amount of 5 to 5 based on the total solid content in the photosensitive coloring composition.
90% by weight, preferably in the range of 20 to 70% by weight.

The photopolymerizable monomer (C) is a compound that undergoes polymerization by the action of light and a photopolymerization initiator, and generally corresponds to a compound having a polymerizable carbon-carbon unsaturated bond. The photopolymerizable monomer (C) can be a monofunctional monomer, a difunctional or other polyfunctional monomer. Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. Further, specific examples of the bifunctional monomer include 1,6
-Hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methyl Examples of other polyfunctional monomers include pentanediol di (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentane Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (methacryloyloxyethyl) isocyan Rate and the like. The photopolymerizable monomers (C) can also be used alone or in combination of two or more. The photopolymerizable monomer (C) is generally in the range of 5 to 90% by weight, preferably 2 to 90% by weight, based on the total solid content in the photosensitive coloring composition.
It is contained in the range of 0 to 70% by weight.

The photopolymerizable monomer (C) particularly has an acrylic group (CH ₂ ＣＨCHCO—) and has a large number of acrylic groups per unit weight of the compound, in other words,
Those having a small acrylic group equivalent expressed by the number of grams of the compound per equivalent of the acrylic group are preferred, and among them, compounds having an acrylic group equivalent of 100 or less are preferably used. In some cases, such a monomer having a small acrylic group equivalent can be used in combination with another monomer. When the acrylic equivalent is large, when a dried coating film obtained therefrom is exposed and developed, sensitivity is likely to be insufficient, which may lead to a reduction in the productivity of the color filter. In order to be a compound having a small acrylic group equivalent, a polyfunctional monomer having two or more functional groups is preferable. For monomers having an acrylic group equivalent of 100 or less,
Ethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like are included. It is preferably used.

The photopolymerization initiator (D) is commonly used in this field and includes, for example, acetophenone, benzoin, benzophenone, thioxanthone and other initiators. Specific examples of the acetophenone-based initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1-
[4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-
Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, etc. And specific examples of the benzoin-based initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Specific examples of the benzophenone-based initiator include benzophenone and o- Methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-
4'-methyldiphenyl sulfide, 3,3 ', 4
Examples thereof include 4'-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone. Specific examples of the thioxanthone-based initiator include 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 2,4. -Diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4
-Propoxythioxanthone; and specific examples of other initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5 '-Tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone,
Examples include benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like. These photopolymerization initiators can also be used alone or in combination of two or more.

Further, a photopolymerization initiator may be used in combination with a photoinitiator. Examples of the photoinitiating aid include amine-based and alkoxyanthracene-based ones, and specific examples thereof include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, and 4-dimethylamine. Ethyl aminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (Commonly known as Michler's ketone), 4,
4'-bis (diethylamino) benzophenone, 9.1
0-dimethoxyanthracene, 2-ethyl-9,10-
Dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and the like are included. These photoinitiating assistants can be used alone or in combination of two or more.

The photopolymerization initiator (D) and the optional photoinitiator are generally used in a total amount of 100 parts by weight of the copolymer (B) and the photopolymerizable monomer (C) in total. It is contained in the range of 3 to 50 parts by weight, preferably in the range of 5 to 40 parts by weight.

The solvent (F) can be any of those used in this field. Specific examples include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, ethyl pyruvate, methyl 3-methoxypropionate, Esters such as ethyl 3-ethoxypropionate; ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone and cyclohexanone; glycol ethers such as 3-methoxybutyl acetate and propylene glycol monomethyl ether acetate Esters; aromatic hydrocarbons such as benzene, toluene, o-, m- or p-xylene. These solvents are
Each can be used alone or in combination of two or more. The amount of the solvent used is preferably 60 to 90% by weight, more preferably 70 to 85% by weight, based on the total amount of the photosensitive coloring composition containing the solvent.

The photosensitive coloring composition according to the present invention may also contain, if necessary, a filler, another polymer compound, a surfactant (pigment dispersant), an adhesion promoter, an antioxidant, an ultraviolet absorber, An additive such as an anti-agglomeration material may be contained.
Specific examples of the filler include glass, silica, and alumina, and specific examples of other polymer compounds include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. As the (pigment dispersant), various types such as nonionic, cationic, and anionic are used. Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy) silane. , N- (2-aminoethyl)-
3-aminopropylmethyldimethoxysilane, N- (2
-Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-
Epoxycyclohexyl) ethyltrimethoxysilane,
3-Chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like, specifically, 2,2'- Thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol and the like are specifically exemplified as 2- (3-tert-butyl-2-butyl) as an ultraviolet absorber. (Hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like, and specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

In producing the color filter of the present invention, a photosensitive coloring composition containing each of the above components is used. The acid value of the nonvolatile component is 25 to 60 mg KOH /
Adjust to the range of g. The acid value as used herein refers to 1 g of the nonvolatile component in the photosensitive coloring composition, that is, the amount of the component 1 excluding the solvent.
The amount (mg) of potassium hydroxide required to neutralize the acidic groups contained in g can be defined. This acid value is
Although it is greatly affected by the carboxyl group in the copolymer (B), it is also affected by other components, particularly when a pigment dispersant is used, and thus is usually determined by titration. If this acid number becomes too low,
The solubility of the dried coating film formed therefrom in the developing solution is reduced, and poor dissolution results in increased development residues. on the other hand,
If the acid value is too large, the dissolved components will be excessively dissolved in the developing solution during development, and the remaining insoluble components will appear as development residues. In any case, a development residue is generated in the light-shielding layer portion and the transparent glass portion, leading to a decrease in adhesion and a decrease in color reproducibility.

This photosensitive coloring composition can be prepared, for example, as follows. That is, the pigment (A) is mixed in advance with the solvent (F) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, a dispersant is used as needed, and a part or all of the copolymer (B) may be blended. In the obtained pigment dispersion, the remainder of the copolymer (B), the photopolymerizable monomer (C), the photopolymerization initiator (D), other components used as needed, and further additional Solvent
It is added so as to have a predetermined concentration to obtain a desired photosensitive coloring composition.

This photosensitive coloring composition has a viscosity at 25 ° C. in the range of 3 to 20 mPa · s in order to be applied on the substrate surface in a uniform thickness and to give a uniform dried coating film. Is preferred. It is also preferable that the thixotropic property is in an appropriate range. Specifically, using a R-type viscometer, the viscosity measured at a rotor rotation speed of 5 rpm is defined as X, and the viscosity measured at a rotor rotation speed of 20 rpm is defined as Y. Sometimes, the thixotropy represented by X / Y is between 0.9 and 1.0.
It is preferably in the range of 5. If the viscosity or thixotropy is out of the above range, the in-plane film thickness distribution at the time of coating tends to be large or unevenness tends to occur.

The photosensitive resin composition thus prepared is
For example, it is applied on a substrate as described below, and becomes a colored pixel through photo-curing and development. First, this composition is placed on a transparent substrate (usually glass) on which a light-shielding layer is patterned,
It is applied using a bar coater, a spin coater, a liquid-saving spin coater provided with a slit, or the like, and dried by heating (prebaking) to obtain a smooth dried coating film. The thickness of the coating film at this time is usually 3 μm or less, preferably 1-2 μm
It is about. The obtained coating film is irradiated with ultraviolet rays through a negative photomask for forming a target pixel.
At this time, it is also effective to use a device such as a mask aligner so that the entire exposed portion is uniformly irradiated with parallel light beams and accurate alignment between the mask and the substrate is performed. After that, the photo-cured coating film is brought into contact with an alkaline aqueous solution to dissolve and develop the unexposed portions, thereby obtaining target pixels. After development, if necessary,
Post-curing (post-baking) at about 230 ° C. for about 10 to 60 minutes can also be performed.

The developer used for the development after the patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be any of inorganic and organic alkaline compounds. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide,
Disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate , Potassium borate, ammonia and the like. Further, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine,
Triethylamine, monoisopropylamine, diisopropylamine, ethanolamine and the like. These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The preferred concentration of the alkaline compound in the alkaline developer is
0.01 to 10% by weight, more preferably 0.0 to 10% by weight.
5 to 5% by weight.

The surfactant may be any of a nonionic surfactant, a cationic surfactant and an anionic surfactant. Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene alkyl ether. Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like can be mentioned. Specific examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; sodium dodecylbenzene sulfonate; Alkyl aryl sulfonates such as sodium dodecylnaphthalene sulfonate, and the like. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants can be used alone or in combination of two or more. The concentration of the surfactant in the alkali developer is usually 0.0
1 to 10% by weight, preferably 0.05 to 8% by weight,
More preferably, the content is 0.1 to 5% by weight.

Through the above operations of coating and drying the photosensitive coloring composition, patterning exposure to the obtained dried coating film, and developing, the pixels corresponding to the color of the pigment in the photosensitive coloring composition are obtained. The color filter is obtained by repeating these operations by the number of colors required for the color filter.

An example of a process for manufacturing such a color filter will be described with reference to FIG. 1 which is a schematic sectional view. FIG. 1A shows a state in which light shielding layers 2, 2,... Are formed on a transparent substrate 1. FIG. A photosensitive coloring composition corresponding to the first color is applied thereon and dried to form a first dried coating film 11, as shown in FIG. Next, as shown in FIG. 1C, ultraviolet light is irradiated through the photomask 3 in the direction of the arrow. Photomask 3 of coating film 11
The part exposed to ultraviolet light through becomes hardened and becomes alkali-insoluble, and the unexposed part remains alkali-soluble,
The first pixel 12 is formed as shown in FIG. 2D by developing by contacting with an alkaline developer. Next, as shown in FIG. 3E, a photosensitive coloring composition corresponding to the second color is applied and dried to form a second dried coating film 13, and as shown in FIG. Ultraviolet light is irradiated in the direction of the arrow through the photomask 4 and then alkali development is performed to form a second pixel 14 as shown in FIG. Further, as shown in FIG. 3H, a photosensitive coloring composition corresponding to the third color is applied and dried to form a third dried coating film 15, and as shown in FIG. Photo mask 5
Then, ultraviolet light is irradiated in the direction of the arrow through the substrate, and then alkali development is performed to form a third pixel 16 as shown in FIG.

In the present invention, after pixels of each color are formed by development, 380 to 780 of the portions of the light shielding layers 2, 2,...
The reflectance at 380 nm is 95% or more of the reflectance of the portion before applying the photosensitive coloring composition, and the transmittance at 380 to 780 nm of the portion of the transparent substrate 1 is before applying the photosensitive coloring composition. Is 99.5% or more of the transmittance of the relevant portion. Here, the fact that the reflectance at 380 to 780 nm is 95% or more means that the value does not fall below 95% at the wavelength in this range even if the reflectance is the smallest, and similarly, 380 to 780 nm. That the transmittance is 99.5% or more means that the value does not fall below 99.5% even when the transmittance is the smallest at a wavelength in this range. As described above, it is, of course, necessary to select a developing solution so that the development residue on the light-shielding layer and the transparent substrate is reduced, but the photosensitive coloring such that the acid value of the nonvolatile component falls within the range specified in the present invention. By using the composition, when a normal alkaline developer is used, the development residue is small, and therefore, the reflectance of the light shielding layer portion and the reflectance of the transparent substrate portion can be adjusted as described above. The last color pixel, the third pixel 1 in FIG.
Even after forming 6, a transparent portion remains on the outermost side of the transparent substrate, and the transmittance of that portion may be measured.

The color filter usually has red, green, and blue pixels arranged on a substrate. As described above, the red, green, and blue pixels are formed on the substrate. Become. Then, by performing the above operation using the photosensitive coloring composition of the present invention containing a pigment corresponding to a certain color, a pixel of that color is obtained, and the other colors also include a pigment corresponding to a desired color. By performing the same operation using the photosensitive coloring composition of the present invention, pixels of three colors can be arranged on the substrate. Of course, the photosensitive coloring composition of the present invention can be applied to only one or two of the three colors, but it is advantageous to apply the requirements of the present invention to all three colors. In this way, a color filter having less development residue and excellent transparency can be obtained on both the light-shielding layer and the transparent substrate, and the liquid crystal display panel equipped with the same has excellent performance.

[0036]

The present invention will be described in more detail with reference to the following examples. As a typical example, an example in which a blue photosensitive coloring composition is prepared, applied on a substrate, and evaluated is shown, but the present invention is not limited to these examples. In the following examples, percentages and parts representing contents or amounts used are by weight unless otherwise specified.

Example 1 The compositions shown in Table 1 were prepared. The acid value, viscosity and thixotropy of the non-volatile components of this composition were measured as described below, and the results are shown in Table 1.

Acid value of nonvolatile content: The composition was diluted with 4 times by weight of acetone, and a 0.1 mol / liter ethanolic potassium hydroxide solution was added dropwise thereto, and titration was performed by potentiometric titration. Viscosity: Measured with an R-type viscometer at a rotor rotation speed of 20 rpm. Thixotropic property: The viscosity measured by a R-type viscometer at a rotor rotation speed of 5 rpm is X, and the rotor rotation speed is 20.
The viscosity measured at rpm was represented by Y and represented by X / Y.

[0039]

[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ (A) Pigment: CI element blue 15: 6 5.05 Part CI pigment violet 23 0.17 parts (B) binder resin: pentamethyl methacrylate / methacrylic acid copolymer 5.77 parts (weight composition ratio 80/20, weight average molecular weight 43,000) (C) photopolymerizable monomer: dipentaerythritol hexaacrylate 5.77 Department (“KAYARAD DPHA” sold by Nippon Kayaku Co., Ltd.) (D) Photopolymerization initiator: 2-methyl-1- (4-methylthiophenyl) -2-morpholinofurovan-1-one 0.77 part (Nippon Kayaku Ikki ( “IRGACURE 907” sold by K.K.) 0.38 parts of 2,4-diethylthioxanthone (“KAYACURE DETX-S” sold by Nippon Kayaku Co., Ltd.) (E) Additive: High molecular pigment dispersant 2.09 parts (F) Solvent: fluoropolycarbonate monomethyl 80.00 parts ル Acid value of non-volatile matter (mg KOH / g) 37.1 Viscosity (mPa · s) 7.42 Thixotropy 1.18 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

A glass substrate (Corning # 70) having a multilayer structure of chromium and chromium oxide and having a light-shielding layer of chromium on the surface.
59), the composition shown in Table 1 was applied by a spin coater, and then prebaked at 70 ° C. for 3 minutes to obtain a dried film having a thickness of 1.2 μm. Next, the dried coating film is exposed to 200 mJ / cm ² by an ultra-high pressure mercury lamp through a photomask, and then immersed in a 0.8% aqueous sodium carbonate solution containing an anionic surfactant for development. 20 at 230 ° C
After post-curing for minutes, a blue pixel was obtained.

The unexposed portion (the light-shielding layer portion and the transparent glass portion after the removal of the blue coating film) of the substrate on which the blue pixels are formed is subjected to the instant multi-photometry system “MCPD-1000” manufactured by Otsuka Electronics Co., Ltd. The reflectance of the light-shielding layer portion and the transmittance of the transparent glass portion were determined from 380 nm to 780, respectively, with the substrate before applying the above composition as a control (100%).
It was measured in the nm range. As a result, the reflectance of the light-shielding layer portion is at least 97.9%, and the transmittance of the transparent glass portion is at least 97.9%.
9.8%, and almost no development residue was observed.
Good results.

Examples 2-6 and Comparative Examples 1-2 Except that the type and amount of the binder resin and the amount of the photopolymerizable monomer in Example 1 were changed as shown in Table 2,
A composition similar to that of Example 1 was prepared and evaluated by the same method. Table 2 shows the results together with the variables and results of Example 1.
Shown in The photopolymerizable monomer used in these examples is the same dipentaerythritol hexaacrylate used in Example 1, and the following three types of binder resins are used and are indicated by the respective symbols.

(B) Binder resin BP1: benzyl methacrylate / methacrylic acid copolymer (weight composition ratio 80/20, weight average molecular weight 43,000) BP2: benzyl methacrylate / methacrylic acid copolymer (weight composition ratio 82.7 / 17.3, weight) Average molecular weight 40,000) BP3: benzyl methacrylate / methacrylic acid copolymer (weight composition ratio 85/15, weight average molecular weight 42,000)

[0044]

[Table 2] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example Comparative Example 1 2 3 4 5 612 (B) binder resin BP1 (part) 5.77 8.08 − ---9.81-BP2 (parts)--5.77 8.08----BP3 (parts)----5.77 8.08-4.62 (C) Photopolymerizable monomer (parts) 5.77 3.46 5.77 3.46 5.77 3.46 1.73 6.92 ───酸 Acid value (mg KOH / g) 37.1 52.9 33.0 44.9 28.3 39.9 65.1 22.2 Viscosity ( mPa ・ s) 7.42 8.97 7.08 7.54 6.97 7.31 10.61 6.32 Thixotropy 1.18 1.12 0.99 1.21 1.15 1.08 1.26 1.04 ────────────────────────────反射 Reflectivity of light shielding layer (%) 97.9 97.1 97.5 98.3 95.1 97.6 66.7 77.2 Transmittance of transparent part (%) 99.8 99.7 100.0 99.9 99.6 99.8 82.4 99.2 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━

[0045]

According to the present invention, the development residue after developing the color filter pixels can be reduced, so that good color reproducibility can be achieved for the pixels of each color constituting the color filter, and lamination after forming the color pixels. This can prevent a decrease in the adhesion between the transparent electrode or overcoat and the substrate. Therefore, a color filter and a liquid crystal display panel can be manufactured with a high yield.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing steps of manufacturing a color filter in order.

[Explanation of Signs] 1... Transparent substrate 2... Shielding layer 3 4 5 Photomask 11 First photosensitive coloring composition Dry film formed 12 First pixel 13 Dry film formed from second photosensitive coloring composition 14 Second pixel , 15... A dried coating film formed from the third photosensitive coloring composition, 16... A third pixel.

Claims (8)

[Claims] 1. A transparent substrate, a light-shielding layer patterned on the transparent substrate, and a plurality of colored pixels pattern-formed on the substrate other than the light-shielding layer, wherein at least one color of the colored pixels is ( A) pigment, (B)
A copolymer containing (meth) acrylic acid as one monomer,
A photosensitive coloring composition containing (C) a photopolymerizable monomer, (D) a photopolymerization initiator, and (F) a solvent, wherein the acid value of the nonvolatile component is in the range of 25 to 60 mg KOH / g. The reflectance at 380 to 780 nm of the light-shielding layer portion after forming the colored pixel is 95% or more of the reflectance of the light-shielding layer before applying the composition, and A color filter, wherein the transmittance of the subsequent transparent substrate portion at 380 to 780 nm is 99.5% or more of the transmittance of the transparent substrate before applying the composition. 2. The color filter according to claim 1, wherein the copolymer (B) is a copolymer of (meth) acrylic acid and benzyl (meth) acrylate. 3. The photopolymerizable monomer (C) is an acryl group 1
The color filter according to claim 1, wherein the color filter contains a compound having an acrylic group equivalent of 100 or less expressed in grams of the compound per equivalent. 4. A compound having an acrylic group equivalent of 100 or less,
The color filter according to claim 3, wherein the color filter is selected from trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate. 5. A method comprising the steps of: (A) pigment, (B) a copolymer containing (meth) acrylic acid as one monomer, (C) a photopolymerizable monomer,
A photosensitive coloring composition containing (D) a photopolymerization initiator and (F) a solvent, wherein the acid value of the nonvolatile component is 25 to 60.
mg KOH / g is applied and dried, and then the obtained dried coating film is irradiated with light through a mask, and then developed to form a colored pixel. The reflectance is 95% or more of the reflectance of the light shielding layer before applying the composition, and the reflectance of the transparent substrate portion is 380 to 7%.
A method for producing a color filter, comprising obtaining a pixel-forming substrate having a transmittance at 80 nm of 99.5% or more of the transmittance of the transparent substrate before applying the composition. 6. A composition comprising (A) a pigment, (B) a copolymer containing (meth) acrylic acid as one monomer, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, and (F) a solvent. A composition having a non-volatile acid value in the range of 25 to 60 mg KOH / g, which is coated on a transparent substrate having a light-shielding layer, dried, subjected to patterning exposure and alkali development. To form a colored pixel, the light shielding layer portion 38
The reflectance at 0 to 780 nm gives a value of 95% or more of the reflectance of the light-shielding layer before applying the composition, and the transmittance at 380 to 780 nm of the transparent substrate portion applies the composition. A photosensitive colored composition, which gives a value of 99.5% or more of the transmittance of the transparent substrate. 7. The composition according to claim 6, wherein the viscosity at 25 ° C. is in the range of 3 to 20 mPa · s. 8. Using an R-type viscometer, rotor speed 5 rpm
The thixotropy represented by X / Y is in the range of 0.9 to 1.5, where X is the viscosity measured at step S, and Y is the viscosity measured at a rotor rotation speed of 20 rpm.
A composition as described.