JP2006215160A - Colored composition, color filter obtained by using the same and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored composition which hardly produces thickness difference in a film at a peripheral portion of a substrate and forms a film excellent in surface smoothness even when used for film formation by a die coating method, and also to provide a method for manufacturing a color filter with filter segments and/or a black matrix having small thickness difference between central and peripheral portions and excellent in surface smoothness. <P>SOLUTION: The colored composition contains a dye carrier comprising: a transparent resin; its precursor or a mixture of those; a dye; an organic solvent; and a leveling agent, and dynamic surface tension (I) of the colored composition at 100 ms and dynamic surface tension (II) at 1,000 ms satisfy an expression (1) of [ä(I)-(II)}/(I)]×100≤7.0. The method for manufacturing the color filter includes coating on a substrate the colored composition by a die coating system coater to form the filter segments and/or the black matrix. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a colored composition used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, a color filter using the same, and a method for producing the same.

In the manufacture of color filters that make up liquid crystal displays (LCDs), color imaging tube elements (CCDs), etc., a coating solution is applied onto a transparent substrate, and a uniform coating film with a thickness of about 1 to 3 μm when dried is applied. Need to form. As a coating method, a spin coating method is generally used.
In the spin coating method, the coating liquid is dropped on the transparent substrate while rotating the transparent substrate at a constant rotation speed, and the coating liquid is thinly extended by centrifugal force, and the coating film has a film thickness determined by the coating liquid viscosity, the rotation speed, etc. Is a coating method of forming on the surface of the transparent substrate. The spin coating method includes an open air type and a closed cup type, but both methods have a drawback that the coating film thickness of the rotation center portion and the peripheral portion of the transparent substrate is too thick compared to the intermediate portion.

As a composition that eliminates this drawback and can form a coating film having a small surface difference between the central portion and the peripheral portion when coated by a spin coating method and having excellent surface smoothness, pigments, binder polymers, and radiation sensitive materials. A compound in which a compound is dissolved or dispersed in a specific organic solvent is known (for example, see Patent Document 1).
The difference in film thickness of the coating film is reduced by using the composition, but in the spin coating method, only a few percent of the coating solution dropped on the transparent substrate is applied to the surface of the transparent substrate, Since the remaining 90% of the coating solution is discharged from the transparent substrate, there is a disadvantage that there is a lot of waste, and this disadvantage has become a big problem with the recent increase in substrate size.
In order to eliminate such drawbacks of the spin coating method, a die coating method has recently been studied (for example, see Patent Documents 2 to 4). The die coating method has the advantage that the coating solution supply circuit is all sealed up to the tip of the coating head, in addition to less waste of the coating solution than the spin coating method.
JP-A-6-3521 JP-A-7-168015 JP 2000-193818 A JP 2001-195004 A

However, the die coating method has a drawback in that the coating film on the outer periphery of the substrate rises and becomes thicker than the coating film on the central part of the substrate, so-called horns occur. In order to use as a large panel up to the edge of the substrate with the recent increase in size of the panel, it is not preferable that a difference in film thickness occurs in the outer peripheral portion of the substrate. This problem is that the difference in film thickness between the central part and the peripheral part is small, and the use of a spin coating composition developed so as to form a coating film with excellent surface smoothness has the required characteristics. Difficult to solve because of differences.
Accordingly, an object of the present invention is to provide a colored composition that can form a coating film having excellent surface smoothness with little difference in the film thickness of the coating film on the outer periphery of the substrate even when used for coating formation by a die coating method. .
Another object of the present invention is to provide a method for producing a color filter having a filter segment and / or a black matrix having a small difference in film thickness between the central portion and the outer peripheral portion and excellent surface smoothness.

The coloring composition of the present invention is a coloring composition comprising a dye carrier comprising a transparent resin, a precursor thereof or a mixture thereof, a dye, an organic solvent, and a leveling agent, which is 100 ms of the coloring composition. The dynamic surface tension (I) at 1000 and the dynamic surface tension (II) at 1000 ms satisfy the following relational expression (1).
[{(I)-(II)} / (I)] × 100 ≦ 7.0 (1)
The color filter of the present invention is characterized by comprising a filter segment and / or a black matrix formed from the colored composition of the present invention.
The method for producing a color filter of the present invention is a method for producing a color filter comprising a black matrix and a filter segment, wherein the coloring composition of the present invention is applied onto a substrate by a die coating method, and the filter segment and / or Or forming a black matrix

Since the change rate of the dynamic surface tension at 100 ms and the dynamic surface tension at 1000 ms is 7.0% or less, the colored composition of the present invention has no horn at the outer periphery of the substrate and the outer periphery of the substrate. It is possible to form a uniform coating film with a small difference in film thickness between the substrate and the center of the substrate and no coating unevenness.
Therefore, by forming a filter segment and / or a black matrix using the colored composition of the present invention, it is possible to produce a color filter with a high yield.

First, the coloring composition in this invention is demonstrated concretely.
The coloring composition of the present invention is a coloring composition comprising a dye carrier comprising a transparent resin, a precursor thereof or a mixture thereof, a dye, an organic solvent, and a leveling agent, which is 100 ms of the coloring composition. The dynamic surface tension (I) at 1000 and the dynamic surface tension (II) at 1000 ms satisfy the following relational expression (1).
[{(I)-(II)} / (I)] × 100 ≦ 7.0 (1)
When a coating film is formed using a colored composition having a value on the left side of greater than 7.0, the coating film on the outer peripheral portion of the substrate rises thicker than the coating film on the central portion of the substrate, causing horns.

式中、ｍは５〜３０、好ましくは１０〜２０の整数であり、ｎは５０〜１００、好ましくは６０〜９０の整数であり、ｘは１〜２０、好ましくは５〜１５の整数である。 As the leveling agent contained in the coloring composition of the present invention, a silicon-based leveling agent, particularly a compound represented by the following general formula (2) is preferably used.

In the formula, m is an integer of 5 to 30, preferably 10 to 20, n is an integer of 50 to 100, preferably 60 to 90, and x is an integer of 1 to 20, preferably 5 to 15. .

As a commercially available silicon leveling agent composed of the compound represented by the general formula (2), “BYK-330” (by formula (2), m is 14, n is 77, and x is 10). ). Other commercially available silicon leveling agents include “BYK-320”, “BYK-323”, and “BYK-333” manufactured by BYK Chemie. A leveling agent can be used individually by 1 type or in mixture of 2 or more types.
The leveling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the dye in the coloring composition.

The dye carrier contained in the coloring composition of the present invention is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Examples of the transparent resin include thermoplastic resins, thermosetting resins, and photosensitive resins, and precursors thereof include monomers or oligomers that are cured by irradiation with radiation to form transparent resins. Or a mixture of two or more.
The dye carrier can be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight, with respect to 100 parts by weight of the dye in the coloring composition. Moreover, when using the mixture of transparent resin and its precursor as a pigment | dye carrier, transparent resin is 20-400 weight part with respect to 100 weight part of pigment | dyes in a coloring composition, Preferably it is 50-250 weight part. Can be used. The precursor of the transparent resin can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the pigment in the colored composition.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  Monomers and oligomers that are precursors of transparent resins include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β -Carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (me Acrylate), neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy ( Various acrylic and methacrylic esters such as (meth) acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxy Examples include methyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

As the dye contained in the colored composition of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance, particularly pigments having high heat decomposition resistance are preferred, and organic pigments are usually used.
Below, the specific example of the organic pigment which can be preferably used for the coloring composition of this invention is shown by a color index number.
Red pigmented compositions for forming red filter segments include, for example, CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2. 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224 Red pigments such as 226, 227, 228, 240, 246, 254, 255, 264, and 272 can be used. A yellow pigment and an orange pigment can be used in combination with the red coloring composition.

  Examples of the yellow coloring composition for forming the yellow filter segment include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20. 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 It can be used yellow pigments such 168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199.

For example, an orange pigment such as CI Pigment orange 36, 43, 51, 55, 59, 61 can be used as the orange coloring composition for forming the orange filter segment.
As the green coloring composition for forming the green filter segment, for example, a green pigment such as CI Pigment Green 7, 10, 36, 37 can be used. A yellow pigment can be used in combination with the green coloring composition.
Examples of blue coloring compositions for forming blue filter segments include CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. Blue pigments can be used. Purple pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination with the blue coloring composition.
For example, CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 or the like is used as a cyan coloring composition for forming a cyan filter segment. Can do.

For the magenta coloring composition for forming the magenta color filter segment, for example, purple pigments and red pigments such as CI Pigment Violet 1, 19, CI Pigment Red 144, 146, 177, 169, 81 can be used. A yellow pigment can be used in combination with the magenta colored composition.
Examples of the black coloring composition for forming the black matrix include carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically CI pigment black 1, 6, 7, 12, 20, 31 and the like. Can be used. A mixture of a red pigment, a blue pigment, and a green pigment can also be used for the black coloring composition. As the black pigment, carbon black is preferable from the viewpoint of price and light shielding properties, and the carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, a blue pigment and a purple pigment can be used together in a black coloring composition.

Also, inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black. And metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.
The coloring composition of the present invention can contain a dye within a range that does not decrease heat resistance for color matching.

  Examples of the organic solvent contained in the colored composition of the present invention include 2-heptanone, 4-heptanone, cyclohexanone, n-butyl acetate, isobutyl acetate, isoamyl acetate, n-amyl acetate, methyl isobutyl ketone, n-butyl alcohol (, Ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl Ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate Propylene glycol monoethyl ether acetate, N, N-dimethylformamide, 1,2,3-trichloropropane, o-chlorotoluene, o-xylene, m-xylene, 3-methoxy-3-methyl-1-butanol, 1,3-butanediol, 3-methyl-1,3-butanediol, 2-methyl-1,3-propanediol, diisobutyl ketone, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monobutyl ether acetate, ethylene Glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol Monobutyl ether, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethyl 3-ethoxypropionate, 3-methoxy Butyl acetate, 3-methoxy-3-methylbutyl acetate, γ-butyrolactone, N, N-dimethylacetamide, N-methylpyrrolidone, p-chlorotoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, o-dichlorobenzene M-dichlorobenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, cyclohexanol, Le cyclohexanol, and the like. These may be used alone or in combination of two or more. The organic solvent can be used in an amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

When the composition is cured by irradiation with light such as ultraviolet rays, a photopolymerization initiator is added to the colored composition of the present invention.
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone photopolymerization initiators such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin photopolymerization initiators such as ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzene Benzophenone photopolymerization initiators such as zoyl-4′-methyldiphenyl sulfide, thioxanthone light such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Polymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4 -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (to Chloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine , 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine and other triazine photopolymerization initiators, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazole photopolymerization initiators and the like are used. It is done. A photoinitiator can be used in the amount of 5-200 weight part with respect to 100 weight part of pigment | dyes in a coloring composition, Preferably it is 10-150 weight part.

  The above photopolymerization initiators can be used alone or in combination of two or more. As the sensitizer, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10- Phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone These compounds can also be used in combination. The sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the colored composition.

  The coloring composition of the present invention comprises one or more dyes in a three-roll mill, two-roll mill, sand mill in a dye carrier and an organic solvent together with a leveling agent and, if necessary, the photopolymerization initiator. It can be produced by finely dispersing using various dispersing means such as a kneader and an attritor. The leveling agent may be added after the dye is dispersed in the dye carrier and the organic solvent. Moreover, the coloring composition containing 2 or more types of pigment | dyes can also mix and manufacture what each disperse | distributed finely in the pigment | dye carrier and the organic solvent separately. When the dye is dispersed in the dye carrier and the organic solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a dye derivative can be appropriately contained. Since the dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion, a coloring composition obtained by dispersing the pigment in a dye carrier and an organic solvent using the dispersion aid is used. If so, a color filter excellent in transparency can be obtained. The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

  Resin-type pigment dispersant is a resin that has a pigment-affinity part that adsorbs to the pigment and a part that is compatible with the dye carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the dye carrier. It works to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkylene imines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more.

  A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Such organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.
Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the dye in the coloring composition.

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the dye in the coloring composition.

The coloring composition of the present invention can be prepared as gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type colored resist material. The solvent development type or alkali development type colored resist material is a pigment in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin as a dye carrier, a monomer, a photopolymerization initiator, and an organic solvent. Are dispersed.
The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.
Further, the colored composition of the present invention has a viscosity at 25 ° C. of 6 mPa · s or less measured at a rotation speed of 20 rpm using an E-type viscometer in order to obtain a uniform coating without causing uneven coating. It is preferable to adjust so that it may become, and it is more preferable to adjust so that it may become 2 mPa * s or more and 6 mPa * s or less.

Below, the manufacturing method of the color filter using the coloring composition of this invention is demonstrated.
The color filter of the present invention comprises a filter segment and a black matrix on a substrate, and can comprise, for example, a black matrix and red, green, and blue filter segments. The filter segment and / or the black matrix is formed on the substrate by applying the coloring composition of the present invention by a die coating method.
Application of the coloring composition by the die coating method can be performed using a known die coater, and the application conditions at that time may be appropriately selected depending on the composition of the coloring composition, the type of the color filter to be manufactured, and the like. For example, the lip width at the nozzle tip is preferably 50 to 500 μm, and the distance between the nozzle tip and the substrate surface is preferably 30 to 300 μm. In order to adjust the coating film thickness, the lip running speed and the amount of coating from the lip may be adjusted.
Color filter substrates include glass plates such as soda-lime glass, low alkali borosilicate glass, and non-alkali aluminoborosilicate glass that have a high transmittance for visible light, and resins such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate. A plate is used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

Formation of each color filter segment and black matrix by photolithography is performed by the following method. That is, the coloring composition of the present invention prepared as a solvent developing type or alkali developing type colored resist material is applied on a substrate using a die coating type coating apparatus so that the dry film thickness is 0.2 to 10 μm. To do. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for the necessary colors to repeat each color filter segment and A black matrix can be formed. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.
The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
In the examples and comparative examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.
First, preparation of acrylic resin solutions used in Examples and Comparative Examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

(Preparation of acrylic resin solution)
370 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Methacrylic acid 20.0 parts
Methyl methacrylate 10.0 parts
Butyl methacrylate 55.0 parts
2-Hydroxyethyl methacrylate 15.0 parts
Azobisisobutyronitrile 4.0 parts After the addition, the mixture was further reacted at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and further at 100 ° C. The reaction was continued for 1 hour to obtain an acrylic resin solution. The weight average molecular weight of the acrylic resin was about 40,000.
After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. An acrylic resin solution was prepared.

[Example 1]
A mixture having the following composition was stirred and mixed uniformly, then dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a copper phthalocyanine dispersion.
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) 12.0 parts (“Heliogen Blue L-6700F” manufactured by BASF)
Dispersant (“Solsperse 20000” manufactured by Zeneca) 2.4 parts Acrylic resin solution 28.1 parts Cyclohexanone 57.5 parts Next, the mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter. Thus, a colored composition prepared as a blue resist material was obtained. Table 1 shows the composition of the coloring composition (weight ratio with the total amount of the coloring composition being 100, and the amount in parentheses is the weight with respect to 100 parts by weight of the pigment).
Copper phthalocyanine dispersion 45.0 parts Acrylic resin solution 12.5 parts Trimethylolpropane triacrylate 4.8 parts (“NK Ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba-Geigy Co., Ltd.) 2.5 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts Silicone leveling agent ("BYK-330" manufactured by BYK Chemie)
2% ethylene glycol monoethyl ether acetate diluted solution) 1.0 part cyclohexanone 34.0 parts

[Examples 2 to 7 and Comparative Example 1]
The ratio of the pigment, dispersant, acrylic resin, monomer, photopolymerization initiator, sensitizer, solvent, and leveling agent shown in Table 1 (weight ratio with the total amount of the colored composition being 100). A colored composition prepared as each color resist material was obtained in the same manner as in Example 1 except that the weight was changed to (weight relative to).

Blue pigment: ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) 5.40 parts ("Heliogen Blue L-6700F" manufactured by BASF)
Red pigment: 5.08 parts of diketopyrrolopyrrole pigment (CI Pigment Red 254) ("Irga Four Red B-CF" manufactured by Ciba Geigy)
0.82 part of anthraquinone pigment (CI Pigment Red 177) (“Chromophthal Red A2B” manufactured by Ciba Geigy)
Anthraquinone pigment (CI Pigment Yellow 199) 0.20 part (Ciba Geigy's "Chromophthal Yellow GT-AD")
6.10 parts in total Green pigment: 3.25 parts of copper halide phthalocyanine pigment (CI Pigment Green 36) (“Rionol Green 6YK” manufactured by Toyo Ink Co., Ltd.)
Monoazo pigment (CI Pigment Yellow 150) 2.35 parts ("Funchon First Yellow Y-5688" manufactured by Bayer)
Total 5.60 parts Black pigment: Carbon black
(Tegusa “Printex75”) 5.50 parts

Dispersant: “Solsperse 20000” manufactured by Zeneca
Monomer: Trimethylolpropane triacrylate (Shin Nakamura Chemical "NK Ester ATMPT")
Photopolymerization initiator: “Irgacure 907” manufactured by Ciba Geigy
Sensitizer: “EAB-F” manufactured by Hodogaya Chemical Co., Ltd.
Silicone leveling agent A: 2% ethylene glycol monoethyl ether acetate diluted solution of BYK-330 manufactured by Big Chemie Silicone leveling agent B: 1% cyclohexanone diluted solution of BYK-323 manufactured by BYK Chemie Silicone leveling agent C : BYK-333 "BYK-333" 1% cyclohexanone diluted solution silicon leveling agent D: BYK-Chemie "BYK-320" 1% cyclohexanone diluted solution fluorine leveling agent E: Dainippon Ink & Chemicals "BL" -20 "5% ethylene glycol monoethyl ether acetate diluted solution

The dynamic surface tension (I) at 100 ms and the dynamic surface tension (II) at 1000 ms of each color resist material obtained in Examples 1 to 7 and Comparative Example 1 were measured with a dynamic surface tension meter (manufactured by Cruz). , [{(I)-(II)} / (I)] × 100 was calculated. Moreover, the viscosity at 25 degreeC of each obtained color resist material was measured at the rotation speed of 20 rpm using the E-type viscosity meter (made by Tokimec). Further, each color resist material obtained was applied on a 360 mm × 465 mm size glass substrate as shown in FIG. 2 using a die coating type coating apparatus shown in FIG. 1 so that the average film thickness was 2.0 μm. The obtained coated substrate was pre-baked at 70 ° C. for 20 minutes to obtain a dried coating film. The film thickness was measured every 5 mm from the center of the short side of the obtained dried coating film to 10 cm in the coating direction. The maximum film thickness at that time is T _max , the minimum film thickness is T _min , and the average film thickness is T _avg . Using the following formula (3), the film thickness uniformity U (Uniformity) is evaluated as 1% less than ◎, 1% to less than 2% ○, 2% to less than 5% △, 5% or more to × It was.
U [%] = (T _max −T _min ) / (T _avg × 2) (3)
Further, the coating substrate was evaluated for coating unevenness with white transmitted light. The case where there was no coating unevenness by visual observation was indicated by ◯, the case where slight coating unevenness was observed was indicated by Δ, and the case where coating unevenness was clearly observed was indicated by ×. Table 2 shows the results of film thickness uniformity and coating unevenness evaluation.

The coating film formed using the resist material of Examples 1-7, especially the coating film formed using the resist material of Examples 1-4 containing the silicon type leveling agent shown by the said Formula (2) is The film thickness difference between the substrate end face and the substrate center was small, and the film was uniform. On the other hand, the coating film formed using the resist material of Comparative Example 1 had a large film thickness difference between the substrate end face and the substrate center.
Moreover, although the coating nonuniformity was not seen in the coating film formed using the resist material of Examples 1-7, the coating nonuniformity was observed in the coating film formed using the resist material of Comparative Example 1. It was done.

  The resist material obtained in Examples 1 to 7 was applied on a glass substrate having a size of 360 mm × 465 mm by a die coating method, and a color filter was manufactured by the photolithography method described above. A color filter having no horns on the outer periphery of the substrate and no coating unevenness could be obtained.

Schematic of the die coat type coating apparatus used in the examples. The perspective view which shows the application state by the coating device (die coater) of FIG.

Explanation of symbols

1: coating head 2: front lip 3: rear lip 4: manifold 5: slit 6: pipe 7: valve 8: metering pump 9: filter 10: coating liquid tank 11: coating film 12: coated substrate 13: transport stage

Claims (6)

A colored composition comprising a transparent carrier, a precursor thereof or a dye carrier comprising the precursor or a mixture thereof, a dye, an organic solvent, and a leveling agent, the dynamic surface tension (I) of the colored composition at 100 ms And a dynamic surface tension (II) at 1000 ms satisfy the following relational expression (1).
[{(I)-(II)} / (I)] × 100 ≦ 7.0 (1)   The coloring composition according to claim 1, wherein the leveling agent is a silicon-based leveling agent. The coloring composition according to claim 2, wherein the silicon leveling agent is a compound represented by the following formula (2).

(In the formula, m is an integer of 5 to 30, n is an integer of 50 to 100, and x is an integer of 1 to 20.)   The colored composition according to any one of claims 1 to 3, wherein the viscosity at 25 ° C is 6 mPa · s or less.   A color filter comprising a filter segment and / or a black matrix formed from the colored composition according to claim 1. A method for producing a color filter comprising a black matrix and a filter segment, wherein the colored composition according to any one of claims 1 to 4 is applied on a substrate by a die coating method to form a filter segment and / or a black matrix. A method for producing a color filter characterized by the above.

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