JP2009134230A - Colored composition and color filter formed using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored composition having a minimum protrusion at an overlap portion on a black matrix, which is formed during the production of a color filter. <P>SOLUTION: The colored composition includes a photopolymerization initiator, an ethylenically unsaturated monomer, a resin, a coloring material and a solvent, wherein the proportion of nonvolatile portions to the entire colored composition is 10-15 wt.%. When films having a thickness of 3.0 and 1.8 μm formed by applying the colored composition on a substrate, drying it and removing the solvent are exposed to 100 mJ/cm<SP>2</SP>of ultraviolet rays from an ultrahigh-pressure mercury lamp of 20 mW/cm<SP>2</SP>via a photomask and patterned by alkali development, the films have a thickness t1 and t2 satisfying 0.10≤t1/t2≤0.40. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a coloring composition for a color filter used for manufacturing a color filter used for a transmissive / semi-transmissive color liquid crystal display device, a color imaging tube element, and the like, and a color filter formed using the same.

  A color filter has two or more kinds of fine band (striped) filter segments with different hues arranged on the surface of a transparent substrate such as glass (stripe arrangement), or the fine filter segments are arranged vertically and horizontally. It consists of arranged (delta array) etc.

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher.

For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.
In the case of the pigment dispersion method, a colored composition in which a pigment is dispersed in a photosensitive transparent resin solution is applied to a transparent substrate such as glass, and after removing the solvent by drying, pattern exposure of one filter color is performed, A color filter can be manufactured by removing the exposed portion in the development process to form a first color pattern and, if necessary, applying a process such as heating, and then repeating the same operation for all the filter colors.

  In filter segment formation using a coloring composition containing a pigment, in recent years, a demand for a color filter having a higher color density is increasing, and the coloring material concentration in the coloring composition tends to increase. However, as the colorant concentration increases, the flow characteristics of the colored composition deteriorate, and the horn step (FIG. 1) at the overlapping portion of the pixels on the black matrix (BM: resin black matrix) increases. This causes the display quality of the liquid crystal panel, such as Nation, to deteriorate. Usually, if the horn step is larger than 0.70 μm, it is considered that the display quality of the liquid crystal panel such as disclination is remarkably lowered. As a method for reducing this horn step, there is a method disclosed in Patent Documents 1 to 4 as an approach from the black matrix side (a method by improving the shape of the black matrix or a method of reducing the thickness thereof), As an approach from the coloring composition side, Patent Document 5 discloses a method of setting the molecular weight and glass transition temperature (Tg) of a resin contained in the coloring composition within a certain range.

JP H06-331815 A JP H10-153703 JP H10-288707 Japanese Patent No. 3573311 JP 2006-284660

  However, there has been a demand for a method of making the horn step as small as possible by simple adjustment without greatly changing the material and characteristics.

An object of the present invention is to provide a coloring composition in which a horn step at an overlapping portion on a black matrix, which occurs when a color filter is produced, is minimized.

The subject is a colored composition comprising a photopolymerization initiator, an ethylenically unsaturated monomer, a resin, a pigment, and a solvent, and the ratio of the non-volatile content in the total amount of the colored composition is 10 wt% or more and 15 wt% or less, and when the coating film having a thickness of 3.0 μm by the following treatment 1 of the colored composition is treated by the following treatment 2, the film thickness is t1, and the following treatment of the colored composition is performed. A colored composition characterized in that (t2 / t1) is not less than 0.10 and not more than 0.40, where t2 is a film thickness when a coating film having a thickness of 1.8 μm by 1 is treated by the following treatment 2. Solved by things.
Process 1: After coating a coloring composition on a board | substrate, it dries and removes a solvent.
Process 2: It exposes with 100 mJ / cm < ² > of ultraviolet-rays using a 20 mW / cm < ² > ultrahigh pressure mercury lamp through a photomask, Then, an unexposed part is developed and patterning is performed.

  One preferred form of the colored composition according to the present invention is a red colored composition mainly containing a red dye as a dye, wherein the weight (I) of the photopolymerization initiator is changed to the weight of the ethylenically unsaturated monomer ( The value (I / M) divided by M) is 0.05 or more and 0.20 or less, and the value obtained by dividing the weight of the ethylenically unsaturated monomer (M) by the weight (P) of the resin (M / P) is 0.20 or more and 0.90 or less.

  One preferred form of the colored composition according to the present invention is a green colored composition mainly containing a green dye as a dye and further containing a photosensitive resin as a resin, wherein the weight (I) of the photopolymerization initiator is adjusted to ethylene. The value (I / M) divided by the weight (M) of the ethylenically unsaturated monomer is 0.30 or more and 0.50 or less, and the weight (M) of the ethylenically unsaturated monomer is the weight of the resin. The value (M / P) divided by (P) is 0.30 or more and 0.50 or less, and the ratio (R / P) of the weight (R) of the photosensitive resin to the weight (P) of the resin is It is 0.10 or more and 0.40 or less.

  One of the preferred forms of the colored composition according to the present invention is a blue colored composition mainly containing a blue dye as a dye, wherein the weight (I) of the photopolymerization initiator is changed to the weight of the ethylenically unsaturated monomer ( The value (I / M) divided by M) is 0.10 or more and 0.20 or less, and the value obtained by dividing the weight (M) of the ethylenically unsaturated monomer by the weight (P) of the resin (M / P) is 0.30 or more and 0.50 or less.

  The present invention also relates to a color filter comprising a filter segment formed from the colored composition.

  By forming a color filter using the colored composition of the present invention, it is possible to reduce the horn level difference at the overlapping portion of the pixels as compared with the conventional colored composition. Therefore, a color filter for a color liquid crystal display device having excellent display quality can be produced by forming a filter segment using the colored composition of the present invention.

  First, the coloring composition of the present invention will be described. The colored composition of the present invention is a colored composition comprising a photopolymerization initiator, an ethylenically unsaturated monomer, a transparent resin, a pigment, and a solvent, and the total amount of the colored composition The proportion of the non-volatile content is from 10% by weight to 15% by weight. When the ratio of the non-volatile content in the total amount of the coloring composition is less than 10% by weight, drying of the coloring composition becomes very slow, and the coloring composition remarkably wraps around the back surface of the substrate, which is not preferable. In addition, it takes a long time to dry, and the productivity is also deteriorated. Moreover, when the ratio of the non-volatile part which occupies for the whole quantity of a coloring composition is larger than 15 weight%, since the fluidity | liquidity of a coloring composition will worsen and a horn step will become large, it is not preferable.

<< Photopolymerization initiator >>
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane Acetophenone photopolymerization initiators such as -1-one and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone;
Benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal;
Benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, and 4-benzoyl-4′-methyldiphenyl sulfide;
Thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone;
2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloro) Methyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, and 2,4-trichloromethyl (4'-methoxystyryl) -6 -Triazine photoinitiators such as triazine;
Borate photopolymerization initiator; carbazole photopolymerization initiator; and
An imidazole photopolymerization initiator or the like is used.

The above photopolymerization initiators can be used alone or in admixture 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, and 4,4'-diethylamino A compound such as benzophenone 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 total weight of the photopolymerization initiator and the sensitizer can be used in an amount of 1 to 100 parts by weight, preferably 5 to 60 parts by weight, with respect to 100 parts by weight of the dye in the colored composition.

<< ethylenically unsaturated monomer >>
As an ethylenically unsaturated monomer contained in the coloring composition,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri Various (meth) acrylic esters such as cyclodecanyl (meth) acrylate, melamine (meth) acrylate, and epoxy (meth) acrylate;
(Meth) acrylic acid;
(Meth) acrylamide;
N-hydroxymethyl (meth) acrylamide;
Styrene; vinyl acetate; and
Examples include acrylonitrile.
The total weight of the ethylenically unsaturated monomer can be used in an amount of 10 to 500 parts by weight, preferably 30 to 300 parts by weight, with respect to 100 parts by weight of the dye in the colored composition.

"resin"
Since the resin contained in the coloring composition does not impair the color characteristics of the pigment, the transmittance is preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region, Furthermore, a solvent-soluble resin, an alkali-soluble resin, or a photosensitive resin is more preferable.

  A solvent-soluble resin is a resin having high solubility in a solvent used as a developer because patterning is performed by solvent development, and an alkali-soluble resin is a resin having an acid value because patterning is performed by alkali development. The photosensitive resin is a resin having a photosensitive group because it is patterned by photocuring by ultraviolet light irradiation.

  As the resin, since a high-temperature heating process is performed in the manufacturing process of the color filter, it is preferable to use a resin having good resistance even in the heating process. Furthermore, in the manufacturing process of the color filter, since the coating of the colored composition is thermally cured and then treated with various solvents and chemicals, a resin having excellent solvent resistance and chemical resistance when used as a cured coating is used. Is preferred.

  Examples of the alkali-soluble resin include a (meth) acrylic acid copolymer, a styrene-maleic acid copolymer, and a polyester resin having a carboxyl group.

  Photosensitive resins include (meth) acrylic compounds having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups on linear polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups. A resin in which photocrosslinkable groups such as a (meth) acryloyl group and a styryl group are introduced into the linear polymer by reacting with cinnamic acid 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. Moreover, the photosensitive resin may have alkali solubility.

In addition to the solvent-soluble resin, alkali-soluble resin, or photosensitive resin, the colored composition of the present invention is insoluble in a solvent developer or an alkali developer for the purpose of imparting characteristics such as heat resistance and adhesion, and is photosensitive. It is also possible to contain a resin that does not have any.
Examples of the resin that is insoluble in a solvent developer or an alkali developer and does not have photosensitivity include thermoplastic resins and thermosetting resins.

  Examples of the thermoplastic transparent resin include butyral resin, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic resin, and alkyd resin. Styrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polybutadiene, and polyimide resin.

Moreover, as a thermosetting resin, an epoxy resin, a phenol resin, a benzoguanamine resin, a melamine resin, a urea resin etc. are mentioned, for example.
The content of these resins is usually preferably 10 to 1000 parts by weight, more preferably 50 to 800 parts by weight with respect to 100 parts by weight of the colorant.

<Dye>
The colored composition of the present invention contains at least one colorant among a red colorant, a green colorant, and a blue colorant as a coloring matter, and appropriately other colors such as yellow according to the use of the obtained color filter. -Toning may be performed using colorants such as orange, purple, brown, and black. The colorant may be an organic colorant or an inorganic colorant. The organic colorant specifically means a dye, an organic pigment, a natural colorant, and the like, and the inorganic colorant specifically means an inorganic salt other than an inorganic pigment, an inorganic salt called an extender pigment, etc. Since the filter is required to have high-definition color development and heat resistance, the colorant is preferably a colorant having high color developability and high heat resistance, particularly a colorant having high heat resistance decomposability, and usually an organic colorant. Particularly preferably, organic pigments are used.

  Below, the color index (CI) number of the organic pigment classified as Pigment in the color index (CI; issued by The Society of Dyers and Colorists) is shown for each hue.

  Examples of the red pigment used in the coloring composition of the present invention include CI pigment red 1, CI pigment red 2, CI pigment red 3, CI pigment red 4, and CI pigment red 1. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 8, C.I. Pigment Red 9, C.I. Pigment Red 10, C.I. Pigment Red 11, C.I. Pigment Red 12, C.I. Pigment Red 14, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 17, C.I. Pigment Red 18, CI Pigment Red 19, C.I. Pigment Red 21, C.I. Pigment Red 22, C.I. Pigment Red 23, C.I. Pigment Red 30, C.I. Pigment Red 31, C.I. I. Pi Mment Red 32, C.I. Pigment Red 37, C.I. Pigment Red 38, C.I. Pigment Red 40, C.I. Pigment Red 41, C.I. Pigment Red 42, C.I. Pigment Red 48: 1, CI Pigment Red 48: 2, C.I. Pigment Red 48: 3, C.I. Pigment Red 48: 4, C.I. Pigment Red 49: 1, C.I. Pigment Red 49: 2, C.I. Pigment Red 50: 1, C.I. Pigment Red 52: 1, C.I. Pigment Red 53: 1, C.I. Pigment Red 57, C.I. Pigment Red 57: CI Pigment Red 58: 2, CI Pigment Red 58: 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 63: 2. CI Pigment Tread 64: 1, C.I. Pigment Red 81: 1, C.I. Pigment Red 83, C.I. Pigment Red 88, C.I. Pigment Red 90: 1, C.I. Pigment Red 97, C CI Pigment Red 101, C.I. Pigment Red 102, C.I. Pigment Red 104, C.I. Pigment Red 105, C.I. Pigment Red 106, C.I. Pigment Red 108, C.I. Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment C.I. Pigment Red 149, C.I. Pigment Red 150, C.I. Pigment Red 151, C.I. Pigment Red 166, C.I. CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 180, C.I. Pigment Red 185, C.I. Pigment Red 187, CI Pigment Red 188, C.I. Pigment Red 190, C.I. Pigment Red 193, C.I. Pigment Red 194, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. CI Pigment Red 207, C.I. Pigment Red 208, C.I. Pigment Red 209, C.I. Pigment Red 21 CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, C CI pigment red 245, CI pigment red 254, CI pigment red 255, CI pigment red 264, CI pigment red 265, and the like.

  Examples of the green pigment used in the coloring composition of the present invention include CI Pigment Green 7, CI Pigment Green 10, CI Pigment Green 36, CI Pigment Green 37, and CI Pigment Green 7. Pigment Green 58 and the like.

  Examples of the blue pigment used in the coloring composition of the present invention include CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, and CI Pigment Blue 15: 6 and CI Pigment Blue 60 and the like.

  Examples of yellow pigments used in the toning of the coloring composition of the present invention include CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, and C.I. CI Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. Pigment Yellow 16, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 55, C.I. Pigment Yellow 60, C.I. Pigment Yellow 61, C.I. Pigment Yellow 65, C.I. Pigment Yellow 71, C.I. Pigment Yellow 73, C.I. Pigment Yellow 74, C.I. Pigment Yellow 81, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, C.I. Pigment Yellow 108, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 113, C.I. Pigment Yellow 114, C.I. Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128 C.I. Pigment Yellow 129, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155 CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 175, CI Pigment Yellow 185, and the like.

  Examples of the orange pigment used for toning the coloring composition of the present invention include CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, and C.I. Pigment Orange 16, C.I. Pigment Orange 17, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43, C.I. Pigment Orange 46, C.I. Pigment Orange 49, C.I. Pigment Orange 51, C.I. Pigment Orange 61, C.I. Pigment Examples include orange 63, CI pigment orange 64, CI pigment orange 71, CI pigment orange 73, and the like.

  As the purple pigment used for toning the coloring composition of the present invention, CI pigment violet 1, CI pigment violet 19, CI pigment violet 23, CI pigment violet 29, C CI pigment violet 32, CI pigment violet 36, CI pigment violet 38, and the like.

  Examples of the brown pigment used for the toning of the coloring composition of the present invention include CI Pigment Brown 23 and CI Pigment Brown 25.

  Examples of the black pigment used for the toning of the coloring composition of the present invention include CI Pigment Black 1 and Pigment Black 7.

  Specific examples of the inorganic colorant or extender include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue. , Bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black. These inorganic colorants or extender pigments can be used alone or in admixture of two or more.

  The content of the colorant is usually preferably 1 to 80% by weight, more preferably 2 to 70% by weight, based on the solid content of the photosensitive coloring composition. If the content of the colorant is less than 1% by weight, the film thickness of the color filter becomes excessively thick, which is not preferable, and if it exceeds 70% by weight, a good dispersion state cannot be obtained.

  Moreover, the coloring composition of this invention can be made to contain a dye within the range which does not reduce heat resistance for color matching.

《Other dispersion aids》
In the coloring composition of the present invention, when a pigment is used as the dye, in order to improve the dispersibility of the pigment in the dye carrier, a dispersion aid such as a surfactant, a resin-type pigment dispersant, and a dye derivative is appropriately used. An agent can be included. Since the dispersion aid is excellent in pigment dispersion 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.

<Surfactant>
As surfactant,
Polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, lauryl Anionic surfactants such as ammonium sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate;
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate;
Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts;
Alkylbetaines such as alkyldimethylaminoacetic acid betaines, and amphoteric surfactants such as alkylimidazolines;
A fluorosurfactant; and
Examples include silicone-based surfactants.

<Resin type dispersant>
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. Specifically, as a resin-type pigment dispersant,
Polycarboxylic acid ester such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamidophosphoric acid Oil-based dispersants such as salts, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, and amides formed by the reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group and salts thereof;
Water-soluble polymer systems such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, polyester Examples thereof include aqueous dispersants such as a system, a modified polyacrylate system, an ethylene oxide / propylene oxide addition compound system, and a phosphate ester system, and these can be used alone or in admixture of two or more.

<Dye derivative>
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 singly or in combination of two or more.

"solvent"
Specific examples of the solvent contained in the colored composition of the present invention include ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 1-methoxy-2-propanol, ethyl cellosolve , Ethylbenzene, dipropyl ether, diisopropyl ether, dioxane, trioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, acetal, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone , Cyclohexanone, 2-heptanone, 4-heptanone, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, Ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl acetate, sec-hexyl acetate, methyl propionate, ethyl propionate, butyl propionate, ethyl 3-ethoxypropionate, Propylene glycol diacetate, diethylene glycol dimethyl ether, 3,3,5-trimethylcyclohexanone, cyclohexanol acetate, γ-butyrolactone, tripropylene glycol monomethyl ether (TPM), 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 diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether dipropylene glycol monoethyl ether, dipropylene glycol monopropyl Ether, dipropylene glycol dimethyl ether, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, N, N-dimethylacetamide, N-methylpyrrolidone, p-chlorotoluene, o-diethylbenzene, m-diethylbenzene, p- Diethylbenzene, o-dichlorobenzene , M-dichlorobenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, cyclohexanol, methylcyclohexanol, dipropylene glycol monobutyl ether, propylene glycol phenyl ether, dipropylene glycol methyl ether acetate, 1,3- Butylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, 3-methoxybutanol, 1,3-butylene glycol, 3,3,5-trimethyl-2-cyclohexen-1-one, diacetone Alcohol, isophorone, dibasic acid ester, benzyl alcohol, and propylene glycol monomethyl ether propio Mention may be made of the over door or the like. These can be used alone or in combination. Among them, at least one solvent selected from the group consisting of cyclohexanone, propylene glycol monomethyl ether acetate, 1-methoxy-2-propanol, and isopentyl acetate, ethyl 3-ethoxypropionate, propylene glycol diacetate, diethylene glycol Combining at least one solvent selected from the group consisting of diethyl ether and cyclohexanol acetate is preferable because it exhibits excellent properties in the dispersibility of the dye and the drying properties of the coating film.

《Other additives》
<Storage stabilizer>
In addition, the colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition.
Examples of storage stabilizers include:
Hydroquinone compounds such as hydroquinone, methyl hydroquinone, 2,5 di-tert-butyl hydroquinone, tert-butyl hydroquinone, tert-butyl-β benzoquinone, and tert-butyl hydroquinone 2,5 diphenyl-p-benzoquinone, benzyltrimethyl chloride, And organic acids such as quaternary ammonium chlorides such as diethylhydroxyamine, lactic acid, and oxalic acid;
Methyl ester of the organic acid;
Phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine;
Phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide;
Phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite; and
Examples thereof include t-butyl pyrocatechol.

  The storage stabilizer can be used in an amount of 0.001 to 10 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

<Adhesion improver>
In addition, the coloring composition of the present invention may contain an adhesion improving agent such as a silane coupling agent in order to enhance the adhesion between the composition and the transparent substrate. As a silane coupling agent,
Vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane;
(meth) acryl silanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- ( Epoxy such as 3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane Silanes;
N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-amino Aminosilanes such as propyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltriethoxysilane; and
and 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.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, the coloring composition of the present invention may contain a surface conditioner. As the surface conditioner, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include, but are not limited to, FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie, but are not limited thereto. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. The content of the surface conditioning agent is usually 0.003 to 0.5% by weight based on the total weight (100% by weight) of the green coloring composition.

<Pigment dispersion>
The coloring composition of the present invention comprises one or two or more dyes, if necessary, in the three-roll mill, two-roll mill, and sand mill in the dye carrier and the organic solvent together with the dispersion aid and the photopolymerization initiator. It can be produced by finely dispersing using various dispersing means such as a kneader and an attritor. Moreover, the coloring composition containing 2 or more types of pigment | dyes can also mix and manufacture what disperse | distributed each pigment | dye separately in the pigment | dye carrier and the organic solvent separately. The leveling agent is added when the dye is dispersed in the dye carrier or after the dye is dispersed in the dye carrier.

  The colored 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.

  The colored composition of the present invention can be prepared as a 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.

<Adjusting the thickness of the colored composition>
The colored composition of the present invention is a colored composition comprising a photopolymerization initiator, an ethylenically unsaturated monomer, a resin, a dye, and a solvent, and is a non-volatile component that accounts for the total amount of the colored composition. The thickness of the colored composition is 10% by weight or more and 15% by weight or less, and when the coating film having a thickness of 3.0 μm by the following treatment 1 of the colored composition is treated by the following treatment 2, the film thickness is t1. Adjust the thickness so that (t2 / t1) is not less than 0.10 and not more than 0.40, where t2 is the film thickness when the coating film with a thickness of 1.8 μm by treatment 1 is treated by treatment 2. Thus, the horn step can be reduced to 0.70 μm or less. That is, the present invention relates to a coloring composition characterized in that the reduction rate of the film thickness after treatment 2 is larger when the film thickness after treatment 1 is thicker (t2) than when the film thickness after treatment 1 is thick (t1). It is.
Process 1: After coating a coloring composition on a board | substrate, it dries and removes a solvent.
Process 2: It exposes with 100 mJ / cm < ² > of ultraviolet-rays using a 20 mW / cm < ² > ultrahigh pressure mercury lamp through a photomask, Then, an unexposed part is developed and patterning is performed.

  When the treatment 1 is performed on the colored composition of the present invention on the substrate on which the resin BM having a film thickness of 1 to 3 μm is disposed, the coating film thickness in the flat portion where the resin BM is not disposed is (A), When the coating film thickness in the BM part is (B), (B / A) varies depending on the viscosity of the colored composition and the coating conditions, but is approximately 0.5 to 0.6. For example, when the coating film thickness in the flat part where the resin BM is not disposed is 3.0 μm, the coating film thickness in the resin BM part is 1.5 to 1.8 μm. Moreover, when processing 2 is performed on the colored composition of the present invention, when the film thickness in the flat portion where the resin BM is not disposed is 2.0 μm (t1), (t2 / t1) is 0.1 Therefore, the film thickness on the resin BM is 0.20 to 0.80 μm (t2). That is, the reduction rate of the film thickness due to the processing 2 is higher in the film on the thin BM than in the film of the flat portion where the resin BM is not disposed.

  Thereafter, the substrate is baked (post-baked) at a high temperature of 230 ° C. or higher in the color filter forming step, the pattern thickness of the colored composition is shrunk to 75 to 80%, and the flat where the resin BM is not disposed. The film thickness at the portion is 1.5 to 1.6 μm, and the film thickness (horn step) on the resin BM is 0.20 to 0.64 μm. Usually, if the horn step is larger than 0.70 μm, it can be considered that the display quality of the liquid crystal panel such as disclination is remarkably lowered. However, by using the coloring composition of the present invention, a color with a small horn step is provided. A filter can be formed.

  A colored composition having (t2 / t1) of less than 0.10 is not preferable because the sensitivity to ultraviolet rays is low and the pattern is easily peeled off in the development process. A colored composition having (t2 / t1) larger than 0.40 is not preferable because the surface of the coating film is cured and the film thickness on the resin BM becomes thick (the horn step is large).

When a colored composition that does not suppress the curing of the coating film surface as described in JP-A-11-038613 is used, the coating film thickness in the flat portion where the resin BM is not disposed after the treatment 2 is 2. When the thickness is 0 μm, the coating film thickness in the resin BM portion is 1.0 to 1.2 μm. The substrate is exposed to 100 mJ / cm ² of ultraviolet light using a 20 mW / cm ² ultrahigh pressure mercury lamp through a photomask, and then the unexposed portion is developed, and then the film on the flat portion where the resin BM is not disposed The thickness is very close to 2.0 μm, and the thickness on the resin BM is 1.0 to 1.2 μm. When such a substrate is post-baked, the film thickness in the flat portion where the resin BM is not disposed is 1.5 to 1.6 μm, the film thickness (horn step) on the resin BM is 0.75 to 0.96 μm, This is not preferable because the step height becomes large.

<< Composition of coloring composition >>
When the coloring composition of the present invention is a red coloring composition mainly containing a red pigment, a value obtained by dividing the weight (I) of the photopolymerization initiator by the weight (M) of the ethylenically unsaturated monomer ( I / M) is 0.05 or more and 0.20 or less, and a value (M / P) obtained by dividing the weight (M) of the ethylenically unsaturated monomer by the weight (P) of the resin is 0.20 or more and 0. By setting it to .90 or less, it is possible to suppress the ultraviolet curing of the coating film surface and reduce the horn step by utilizing oxygen inhibition during ultraviolet irradiation.

  When the (I / M) of the red coloring composition is less than 0.05, when the dried coating film of the red coloring composition is irradiated with ultraviolet rays, it is not sufficiently cured, and pattern peeling occurs in the development process. It is not preferable. When (I / M) is larger than 0.20, the vicinity of the coating film is hard to be affected by oxygen inhibition, and the above (t2 / t1) is larger than 0.40 and the horn step is preferably increased. Absent. When (M / P) is less than 0.20, the dried coating film of the colored composition is not sufficiently cured when irradiated with ultraviolet rays, and pattern peeling or the like occurs in the development step, which is not preferable. When (M / P) is greater than 0.90, it is not preferred because it is not easily affected by oxygen inhibition, the vicinity of the coating surface is cured, and (t2 / t1) is greater than 0.40, resulting in an increased horn step. .

  When the colored composition of the present invention is a green colored composition mainly containing a green pigment, a value obtained by dividing the weight (I) of the photopolymerization initiator by the weight (M) of the ethylenically unsaturated monomer ( I / M) is 0.30 or more and 0.50 or less, and the value (M / P) obtained by dividing the weight (M) of the ethylenically unsaturated monomer by the weight (P) of the resin is 0.30 or more and 0. .50 or less, and the ratio (R / P) of the weight (R) of the photosensitive resin to the weight (P) of the resin is 0.10 or more and 0.40 or less, thereby inhibiting oxygen inhibition during ultraviolet irradiation. By utilizing this, it is possible to suppress UV curing on the surface of the coating film and reduce the horn step.

  When the (I / M) of the green coloring composition is less than 0.30, when the dried coating film of the green coloring composition is irradiated with ultraviolet rays, it is not sufficiently cured, and pattern peeling occurs in the development process. It is not preferable. When (I / M) is larger than 0.50, the vicinity of the coating film is hard to be affected by oxygen inhibition, and the above (t2 / t1) is larger than 0.40 and the horn step is preferably increased. Absent.

  When the value obtained by dividing the weight of the ethylenically unsaturated monomer by the weight of the resin (M / P) is less than 0.30, the cured coating film of the green coloring composition is not sufficiently cured when irradiated with ultraviolet rays. In the development process, pattern peeling or the like occurs, which is not preferable. When (M / P) is greater than 0.50, it is difficult to be affected by oxygen inhibition, and the vicinity of the coating surface is cured, and (t2 / t1) is greater than 0.40, resulting in an increased horn step. .

  When the colored composition of the present invention is a blue colored composition mainly containing a blue pigment, a value obtained by dividing the weight (I) of the photopolymerization initiator by the weight (M) of the ethylenically unsaturated monomer ( I / M) is 0.10 or more and 0.20 or less, and the value (M / P) obtained by dividing the weight (M) of the ethylenically unsaturated monomer by the weight (P) of the resin is 0.30 or more and 0 By setting it to .50 or less, oxygen inhibition at the time of ultraviolet irradiation can be utilized to suppress ultraviolet curing of the coating film surface and to reduce the horn step.

  When the (I / M) of the blue colored composition is less than 0.10, the dried coating film of the blue colored composition is not sufficiently cured when irradiated with ultraviolet rays, and pattern peeling occurs in the development process. It is not preferable. When (I / M) is greater than 0.20, it is difficult to be affected by oxygen inhibition, so the vicinity of the coating surface is cured, and the above (t2 / t1) is greater than 0.40, resulting in an increased horn step. It is not preferable. When (M / P) is less than 0.30, it is not preferable because the dry coating film of the blue colored composition is not sufficiently cured when irradiated with ultraviolet rays, and pattern peeling occurs in the development process. When (M / P) is greater than 0.50, it is difficult to be affected by oxygen inhibition, and the vicinity of the coating surface is cured, and (t2 / t1) is greater than 0.40, resulting in an increased horn step. .

《Color filter》
Next, the color filter of the present invention will be described.

  The color filter of the present invention is provided with a filter segment and a black matrix formed from the colored composition of the present invention on a substrate, and includes, for example, a black matrix and red, green, and blue filter segments. be able to. The filter segment is formed on the substrate by applying the coloring composition of the present invention by a spin coat method or a die coat method.

  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.

  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.

  The present invention will be specifically described with reference to examples. In the examples and comparative examples, “part” means “part by weight”. Table 1 shows the chemical structures of the dye derivatives used in the examples.

(Preparation of acrylic resin solution)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., purged with nitrogen in the reaction vessel, and then dropped. N-Butyl methacrylate 13.3 parts, 2-hydroxyethyl methacrylate 4.6 parts, methacrylic acid 4.3 parts, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 7.4 A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a solid content of 30% by weight and a weight average molecular weight of 26000.

  After cooling to room temperature, about 2 g of the resin solution was sampled, 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% by weight. To prepare an acrylic resin solution.

(Adjustment of photosensitive resin solution)
560 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 34.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 45.0 parts of n-butyl methacrylate, glycerol monomethacrylate 47.0 parts and 2,2'-azobisisobutyronitrile 4.0 parts were dripped over 1 hour, and the polymerization reaction was performed.
After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 55 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A polymer solution was obtained.

  Next, a mixture of 32.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate and 120.0 parts of cyclohexanone was added to 338 parts of the obtained copolymer solution at 70 ° C. over 3 hours. And dripped.

  After cooling to room temperature, about 2 g of the resin solution was sampled, 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% by weight. Thus, a photosensitive resin solution was prepared.

(Preparation of red treated pigment 1)
Red pigment C.I. I. Pigment Red 254 (Cirba Japan “IRGAZIN R”
ED 2030 ”), 160 parts of sodium chloride, and 190 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, It dried at 80 degreeC for 24 hours, and obtained 156 parts of red pigment 1 (R1).

(Preparation of green treated pigment 1)
Preparation of 500 parts of phthalocyanine-based green pigment CI Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol into a 1 gallon kneader (manufactured by Inoue Seisakusho) And kneading at 120 ° C. for 4 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of green-treated pigment 1 (G1) were obtained.

(Preparation of yellow treated pigment 1)
Except for changing the phthalocyanine-based green pigment CI Pigment Green 36 to an azo-based yellow pigment CI Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), in the same manner as the preparation of the green-treated pigment 1, 490 parts of yellow-treated pigment 1 (Y1) were obtained.

(Preparation of blue-treated pigment 1)
Blue pigment CI Pigment Blue 15: 6 (“Rionol Blue ES” manufactured by Toyo Ink Mfg. Co., Ltd.) 200 parts, sodium chloride 1600 parts, and diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) 100 parts 1 gallon kneader (Inoue Seisakusho) And kneaded at 70 ° C. for 12 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, It dried at 80 degreeC for 24 hours, and obtained 198 parts of blue pigment 1 (B1).

  The mixture of pigment, pigment derivative, acrylic resin solution, and organic solvent shown in Tables 2 to 4 was uniformly stirred and mixed, and then, using a zirconia bead having a diameter of 1 mm, an Eiger mill (“Mini Model M-250 manufactured by Eiger Japan Co., Ltd.) was used. MKII ") for 6 hours. Thereafter, 30.0 parts of an organic solvent was added, followed by filtration with a 5 μm filter to prepare a pigment dispersion. Here, propylene glycol monomethyl ether acetate was used as the organic solvent in the pigment dispersion RP-1, and cyclohexanone was used as the organic solvent in the pigment dispersions GP-1 and BP-1.

  Subsequently, the mixtures shown in Tables 5 to 7 were stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain colored compositions (alkali development resist materials). As the ethylenically unsaturated monomer in Tables 5 to 7, "DPHA" manufactured by Nippon Kayaku Co., Ltd. was used. Further, as the surface conditioner, a solution obtained by diluting 1 part of dimethylpolysiloxane having a polyether structure in the main chain (“FZ-2122” (non-volatile content: 100% by weight) manufactured by Toray Dow Corning) with 99 parts of cyclohexanone. Using. (Examples R1-R3, Comparative Examples R1-R6, Examples G1-G5, Comparative Examples G1-G8, Examples B1-B3, Comparative Examples B1-B6)

In Table 5, I is the weight of the photopolymerization initiator in the colored composition, M is the weight of the ethylenically unsaturated monomer in the colored composition, and P is the weight of the resin in the colored composition. . The resin is the total of the acrylic resin (nonvolatile content of the acrylic resin solution) in the pigment dispersion and the nonvolatile content in the acrylic resin solution contained in the coloring composition.

  In Table 6, I is the weight of the photopolymerization initiator in the colored composition, M is the weight of the ethylenically unsaturated monomer in the colored composition, and P is the weight of the resin in the colored composition. . The resin is the total of the acrylic resin (nonvolatile content of the acrylic resin solution) in the pigment dispersion, the nonvolatile content of the photosensitive resin solution, and the nonvolatile content in the acrylic resin solution contained in the coloring composition.

In Table 7, I is the weight of the photopolymerization initiator in the colored composition, M is the weight of the ethylenically unsaturated monomer in the colored composition, and P is the weight of the resin in the colored composition. . The resin is the total of the acrylic resin (nonvolatile content of the acrylic resin solution) in the pigment dispersion and the nonvolatile content in the acrylic resin solution contained in the coloring composition.

  About the coloring composition obtained by the Example and the comparative example, the following steps (t2 / t1) evaluated the horn step and the back surface color residue.

((T2 / t1) evaluation)
Each of the colored compositions obtained in Examples and Comparative Examples was applied on a 100 mm × 100 mm, 0.7 mm thick glass substrate, rotated with a spin coater, and then vacuum dried at a final vacuum of 1.0 Torr. A dry coating film having a thickness of 3.0 μm was formed. Stripe-shaped filter segments are exposed to 100 mJ / cm ² ultraviolet rays using a super high pressure mercury lamp with an illuminance of 20 mW / cm ² at 365 nm through a photomask, and after exposure, the unexposed portions are developed with an alkaline developer. Formed. Thereafter, heat treatment was performed at 230 ° C. for 60 minutes. In addition, as an alkaline developer, sodium carbonate 0.15% by weight sodium hydrogen carbonate 0.05% by weight anionic surfactant (“PERIEX NBL” manufactured by Kao Corporation) 8.0% by weight and water 90% by weight What was used. Then, the film thickness (t1) of the stripe pattern formed on the glass substrate was measured with a stylus type film thickness measuring instrument. In the same manner, after a dry coating film having a thickness of 1.8 μm was exposed and developed, the thickness (t2) of the stripe pattern was measured. The values of (t2 / t1) are shown in Table 8 to Table 10.

(Tsuno step evaluation)
The colored compositions obtained in Examples and Comparative Examples were respectively applied on a glass substrate for test as shown in FIG. 2 on which a resin black matrix (BM) having a thickness of 3.0 μm was formed, and rotated by a spin coater. Then, after vacuum-drying at an ultimate vacuum of 1.0 Torr, 100 mJ / cm ² of ultraviolet light was exposed using a super high pressure mercury lamp with an illuminance of 20 mW / cm ² at 365 nm through a photomask. The unexposed portion was developed to form a stripe-shaped filter segment on the resin BM. Thereafter, heat treatment was performed at 230 ° C. for 60 minutes. At this time, the conditions of the spin coater were selected when the coloring composition was applied so that the film thickness was 1.8 μm on a flat portion without the resin BM. In addition, as an alkaline developer, sodium carbonate 0.15% by weight sodium hydrogen carbonate 0.05% by weight anionic surfactant (“PERIEX NBL” manufactured by Kao Corporation) 8.0% by weight and water 90% by weight What was used.
The film thickness of the stripe pattern formed on the resin BM substrate was measured with a stylus type film thickness measuring instrument. As shown in FIG. 1, the film thickness of the horn step was calculated from the film thickness of the pattern on the resin BM and the film thickness of the horn step portion. The results are shown in Tables 8-10. The case where the horn step was 0.70 μm or less was rated as ◯, and the case where the horn step was larger than 0.70 μm was marked as x.

(Back side color remaining evaluation)
The case where the coating liquid did not wrap around 5 mm or more from the edge of the substrate on the back surface of the coated substrate was rated as ◯, and the case where the coating liquid wrapped around 5 mm or more was marked as x.
In the colored compositions of Examples R1 to R3, Examples G1 to G5, and Examples B1 to B3, the horn step was 0.70 μm or less, and the back surface color residue was not observed. In the colored compositions of Comparative Examples R1, G1, and B1, in which the weight of the non-volatile content in the total amount of the colored composition was less than 10% by weight, drying was slow, and the back color residue was x. In the colored compositions of Comparative Examples R2, G2, and B2 in which the weight of the non-volatile component in the total amount of the colored composition is greater than 15% by weight, the coating film that has run on the BM at the time of coating is dried before being leveled. The horn step was large and x.

The red colored composition of Comparative Example R3 with (I / M) greater than 0.20 and (M / P) of 0.90
The red colored composition of Comparative Example R6 greater than, the green colored composition of Comparative Example G4 with (I / M) greater than 0.50 and the Comparative Example G6 with (M / P) greater than 0.50. A green colored composition of Comparative Example G8 having a ratio of the green colored composition to the photosensitive resin of greater than 0.40, a blue colored composition of Comparative Example B3 having a (I / M) greater than 0.20, and (M / In the case of the blue colored composition of Comparative Example B6 where P) is greater than 0.50, the vicinity of the coating surface was cured when irradiated with ultraviolet rays, and the horn step was large and x.

The red coloring composition of Comparative Example R4 with (I / M) less than 0.05 and (M / P) of 0.20
Red colored composition of Comparative Example R5 smaller than, Comparative Example G with (I / M) smaller than 0.30
The green coloring composition of No. 3 and the green coloring composition of Comparative Example G7 whose M / P ratio is less than 0.30 and the photosensitive resin ratio (R / P) is less than 0.10. In the blue colored composition of Comparative Example 4 in which (I / M) is smaller than 0.10 and Comparative Example 5 in which (M / P) is smaller than 0.30, pattern peeling is observed in the development process. The color filter could not be formed.

It is the figure which showed the horn level | step difference when forming the color filter of a coloring composition in the transparent substrate in which resin BM is arrange | positioned. It is the figure which showed the glass substrate in which the resin black matrix (BM) for a test with a film thickness of 3.0 micrometers was formed.

Claims (5)

A colored composition comprising a photopolymerization initiator, an ethylenically unsaturated monomer, a resin, a dye, and a solvent, wherein the ratio of the nonvolatile content in the total amount of the colored composition is 10% by weight or more The film thickness of 15% by weight or less, and the thickness of the colored composition treated by the following treatment 1 by 3.0 μm when treated by the following treatment 2 is defined as t1, and the thickness 1 by the treatment 1 of the colored composition is 1 A colored composition, wherein (t2 / t1) is 0.10 or more and 0.40 or less, when a film thickness when a coating film of 8 μm is treated by treatment 2 is defined as t2.
Process 1: After coating a coloring composition on a board | substrate, it dries and removes a solvent.
Process 2: It exposes with 100 mJ / cm < ² > of ultraviolet-rays using a 20 mW / cm < ² > ultrahigh pressure mercury lamp through a photomask, Then, an unexposed part is developed and patterning is performed. A value (I / M) obtained by dividing the weight (I) of the photopolymerization initiator by the weight (M) of the ethylenically unsaturated monomer is from 0.05 to 0.20. The value (M / P) obtained by dividing the weight (M) of the ethylenically unsaturated monomer by the weight (P) of the resin is 0.20 or more and 0.90 or less. Coloring composition. The value (I / M) obtained by dividing the weight (I) of the photopolymerization initiator by the weight (M) of the ethylenically unsaturated monomer is 0.00. The value (M / P) of 30 to 0.50 and the weight (M) of the ethylenically unsaturated monomer divided by the weight (P) of the resin was 0.30 to 0.50. 2. The coloring composition according to claim 1, wherein a ratio (R / P) of a weight (R) of the photosensitive resin to a weight (P) of the resin is 0.10 or more and 0.40 or less. . A value (I / M) obtained by dividing the weight (I) of the photopolymerization initiator by the weight (M) of the ethylenically unsaturated monomer is 0.10 or more and 0.20 or less. The value (M / P) obtained by dividing the weight (M) of the ethylenically unsaturated monomer by the weight (P) of the resin is 0.30 or more and 0.50 or less. Coloring composition. A color filter comprising a filter segment formed from the colored composition according to claim 1.