JP2011063717A - Coloring composition, color filter and color liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring composition formable of a smooth coating film without causing unevenness formed from fine projection and recess parts even when a slit die coating method is applied as a coating method and formable of a pixel excellent in flatness even when the pixel having high color purity is formed. <P>SOLUTION: The coloring composition contains (A) a colorant, (B) a binder resin, (C) a polyfunctional monomer and (D) a specific fluorine-based surfactant and the content of the colorant (A) is 20-70 mass% in a non-volatile portion. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a coloring composition, a color filter, and a color liquid crystal display element, and more specifically, a color used for a transmissive or reflective color liquid crystal display element, a color imaging tube element, an organic EL display element, electronic paper, and the like. The present invention relates to a colored composition used for forming a colored layer useful for a filter, a color filter including a colored layer formed using the colored composition, and a color liquid crystal display element including the color filter.

  As a method for forming a color filter using a colored radiation-sensitive composition, a coating film of a colored radiation-sensitive composition is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed. A method of obtaining pixels of each color by irradiating radiation through a photomask having a pattern (hereinafter referred to as “exposure”), developing to dissolve and remove unexposed portions, and then post-baking (for example, patents) Document 1 and Patent Document 2) are known. In addition, a method of obtaining pixels of each color by an ink jet method using a colored resin composition (for example, see Patent Document 3) is also known.

  Conventionally, a spin coater or a slit spin coater has been used to form a coating film of a colored radiation-sensitive composition. However, in recent years, it has become the mainstream to use a slit die coater without a spin mechanism in order to save liquid in the colored radiation-sensitive composition and cope with an increase in substrate size.

  As a colored photosensitive resin composition suitable for a liquid-saving coater having no spin mechanism, for example, Patent Document 4 proposes a colored photosensitive resin composition containing a silicone-based surfactant, a fluorosurfactant, and the like. Yes. However, when forming a coating film using a slit die coater, there is a problem that unevenness consisting of minute irregularities occurs in the coating film around the pins supporting the substrate, and the conventional colored photosensitive resin composition is The problem has not been solved.

On the other hand, the content ratio of the colorant in the coloring composition tends to be higher in order to meet the recent demand for higher color purity for color liquid crystal display devices. When it is going to form a coating film on a large-sized board | substrate with a level | step difference using this coloring composition, the problem that the film thickness of a coating film becomes non-uniform | heterogenous has become obvious.

JP-A-2-144502 JP-A-3-53201 JP 2000-310706 A JP 2004-126549 A

An object of the present invention is to provide a coloring composition capable of forming a flat coating film without causing unevenness including minute irregularities even when a slit die coating method is employed as a coating method. There is. Another object of the present invention is to provide a coloring composition capable of forming a pixel having excellent flatness even when a pixel with high color purity is formed.
Furthermore, the objective of this invention is providing the color liquid crystal display element which comprises the color filter provided with the colored layer formed from the said coloring composition, and the said color filter.

  In view of such circumstances, the present inventors have conducted extensive research and found that the above-mentioned problems can be solved by incorporating a specific fluorosurfactant in the coloring composition, and the present invention has been completed. did.

  That is, the present invention comprises (A) a colorant, (B) a binder resin, (C) a polyfunctional monomer, and (D) a compound represented by the following formula (1) (hereinafter referred to as “surfactant ( D) ”), and (A) the coloring agent content is 20 to 70% by mass in the non-volatile content.

In (Equation ^(1), R 1 ~R ⁴ are independently of each _{other, C 6 F 11 -, C} 9 F 17 -, represents _{C 9 F 17 -O-C 6} H 4 -CO- or a hydrogen atom , provided that at least one of which _{C 6 F 11 -, C 9} F 17 - or _{C 9 F 17 -O-C 6} H 4 is -CO-, a are independently of each other, an ethylene group or Represents a propylene group, and a to d each independently represent an integer of 0 to 30, provided that the total of a to d is 2 to 50, and n is 0 or 1.

The present invention also provides a color filter comprising a colored layer formed using the colored composition, and a color liquid crystal display device comprising the color filter. Here, the “colored layer” means each color pixel, black matrix, etc. used in the color filter.

The colored layer formed using the colored composition of the present invention is extremely excellent in flatness.
Therefore, the colored composition of the present invention is used for various color filters including color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be used very suitably for production.

Hereinafter, the present invention will be described in detail.
Coloring composition will be described components of the colored composition of the present invention.

-(A) Colorant-
The (A) colorant in the present invention is not particularly limited as long as it has colorability, and the color and material can be appropriately selected according to the use such as a color filter. Specifically, any of pigments, dyes, and natural pigments can be used as the colorant, but organic pigments and inorganic pigments are preferred because color filters are required to have heat resistance.

Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyer and Colorists). Specific examples include those with the following color index (CI) names.

C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211;

C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment Orange 74

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

In the present invention, the organic pigment may be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.

  Examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide green. , Cobalt green, amber, titanium black, synthetic iron black, carbon black and the like.

These colorants may be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the particle surface of the pigment include the polymers described in JP-A-8-259876, and various commercially available pigment-dispersing polymers or oligomers. As a polymer coating method on the surface of carbon black, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed.
In the present invention, (A) the colorant can be used alone or in admixture of two or more.

When the colored composition of the present invention is used for forming a pixel, since the pixel is required to have high-definition color development, the colorant (A) is preferably a colorant having high color developability, specifically an organic pigment. Is preferably used.
On the other hand, when the colored composition of the present invention is used for forming a black matrix, the black matrix is required to have a light-shielding property. Therefore, an organic pigment or carbon black is preferably used as the colorant (A).

In this invention, the content rate of (A) coloring agent is 20-70 mass% in non volatile matter. The non-volatile component is a component excluding a volatile component containing a solvent described later as a main component, and the total mass thereof can be measured, for example, by heating and drying the colored composition. The heating temperature for drying the colored composition by heating can be appropriately set in consideration of the boiling point of the solvent, the decomposition temperature of the components (B) to (E) described later, and the like.
In general, when forming each color pixel, the NTSC standard (red: x = 0.670, y = 0.330 / green: x = 0.210, y = 0.710) which is a standard color reproduction region of CRT. / Blue: x = 0.140, y = 0.080) and sRGB standards (red: x = 0.640, y = 0.330 / green: x = 0.300, y = 0.600 / blue: x = 0.150, y = 0.060), it is preferable to achieve a chromaticity of 1.0 μm to 3.0 μm after post-baking. In this case, the content ratio of the (A) colorant is preferably 25% by mass or more, and particularly preferably 30% by mass or more in the nonvolatile content. In forming a black-black matrix, it is preferable to achieve an OD value (optical density) of 3.5 to 4.0 / μm with a film thickness of about 1.0 μm after post-baking. In this case, in the black colored composition, the content ratio of (A) the colorant is preferably 40% by mass or more in the nonvolatile content. (A) If the content ratio of the colorant is too small, it is necessary to increase the film thickness when trying to form a pixel or a black matrix as described above. Therefore, a colored layer having excellent flatness on a large substrate is required. It may be difficult to form. According to the coloring composition of this invention, even if it is a case where the content rate of (A) coloring agent becomes high as mentioned above, the colored layer excellent in flatness on a large sized board | substrate can be formed. On the other hand, if the content ratio of (A) the colorant is too large, it may be difficult to ensure developability. In the sense of making the developability better, the content ratio of the (A) colorant is preferably 60% by mass or less based on the solid content.

  The colorant in the present invention can be used together with a dispersant and a dispersion aid as desired. As the dispersing agent, for example, an appropriate dispersing agent such as a cationic type, an anionic type, or a nonionic type can be used, and a polymer dispersing agent is preferable. Specifically, an acrylic copolymer, polyurethane, polyester, polyethyleneimine, polyallylamine, and the like can be given.

  Such a dispersant is commercially available. For example, as an acrylic copolymer, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK Corporation (BYK)), As polyurethane, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (manufactured by Lubrizol Corp.), polyethylene As imine, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.) and as polyester, Ajisper PB821, Ajisper PB822, Ajisper PB880 ( Mention may be made of the Moto Fine-Techno Co., Ltd.), and the like.

These dispersants can be used alone or in admixture of two or more. Content of a dispersing agent is 100 mass parts or less normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 1-70 mass parts, More preferably, it is 10-50 mass parts. When there is too much content of a dispersing agent, there exists a possibility that developability etc. may be impaired.

Examples of the dispersion aid include pigment derivatives, and specific examples include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

-(B) Binder resin-
Although it does not specifically limit as (B) binder resin in this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as “unsaturated monomer (b2)”).

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate and the like. These unsaturated monomers (b1) can be used alone or in admixture of two or more.
In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) is preferably 5 to 50% by mass, more preferably 10 to 10%. 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

Moreover, as said unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxy-α-methylstyrene;
Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide of paracumylphenol Unsaturated carboxylic esters such as modified (meth) acrylates;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (b2) can be used alone or in admixture of two or more.

  Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. Copolymers disclosed in Japanese Patent Application Laid-Open No. 10-300902, Japanese Patent Application Laid-Open No. 11-174224, Japanese Patent Application Laid-Open No. 11-258415, Japanese Patent Application Laid-Open No. 2000-56118, Japanese Patent Application Laid-Open No. 2004-101728, and the like. Can be mentioned.

In the present invention, for example, in JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-11-140144, JP-A-2008-181095, etc. As disclosed, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

The weight average molecular weight in terms of polystyrene (hereinafter sometimes referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the binder resin in the present invention is usually 1,000 to 50,000. , Preferably 3,000 to 30,000. If Mw is too small, the remaining film rate of the resulting film may be reduced, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, resolution may be reduced. In addition, the pattern shape may be damaged, and dry foreign matter may be easily generated during application by the slit nozzle method.

  Further, the ratio (Mw / Mn) of the Mw of the binder resin in the present invention and the polystyrene-equivalent number average molecular weight (hereinafter sometimes referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran). ) Is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

In this invention, binder resin can be used individually or in mixture of 2 or more types.
In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. If the content of the binder resin is too small, for example, the alkali developability may be decreased, or the storage stability of the resulting colored composition may be decreased. On the other hand, if the content is too large, the colorant concentration is relatively high. Therefore, it may be difficult to achieve the target color density as a thin film.

-(C) polyfunctional monomer-
The (C) polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.
As such a polyfunctional monomer, for example,
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and their dicarboxylic acid modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of both end hydroxyl polymers such as both end hydroxypoly-1,3-butadiene, both end hydroxypolyisoprene;
Examples include tris [2- (meth) acryloyloxyethyl] phosphate, isocyanuric acid ethylene oxide-modified triacrylate, poly (meth) acrylate having a urethane structure, poly (meth) acrylate having a caprolactone structure, and the like.

Among these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid-modified products, poly (meth) acrylates having a urethane structure, and poly (meth) acrylates having a caprolactone structure (Meth) acrylate is preferred. Examples of poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate. , Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, monoesterified product of pentaerythritol triacrylate and succinic acid, pentaerythritol trimethacrylate and succinic acid Monoesterified product with dipentaerythritol Monoesterified products of acrylate and succinic acid, and monoesterified products of dipentaerythritol pentamethacrylate and succinic acid are preferred, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Monoesterified products of hexaacrylate, pentaerythritol triacrylate and succinic acid and monoesterified products of dipentaerythritol pentaacrylate and succinic acid have high strength of the colored layer, excellent surface smoothness of the colored layer, and unexposed This is preferable in that ground stains, film residues, and the like are hardly generated on the substrate and the light shielding layer.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  In the present invention, the content of the (C) polyfunctional monomer is preferably 5 to 500 parts by mass, particularly preferably 20 to 300 parts by mass with respect to 100 parts by mass of the (B) binder resin. In this case, if the content of the polyfunctional monomer is too small, sufficient curability may not be obtained. On the other hand, if the content of the polyfunctional monomer is too large, when the color composition of the present invention is imparted with alkali developability, the alkali developability is lowered, and on the unexposed portion of the substrate or the light shielding layer. There is a tendency that dirt, film residue, etc. are likely to occur.

In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable unsaturated bond.
Examples of the monofunctional monomers include divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl]. Mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, such as mono [(meth) acryloyloxyalkyl] ester of acid, ω-carboxypolycaprolactone mono (meth) acrylate, and N- (meth) In addition to acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, commercially available products include M-5600 (trade name, manufactured by Toagosei Co., Ltd.).
These monofunctional monomers can be used alone or in admixture of two or more.

  The content ratio of the monofunctional monomer in the present invention is preferably 90% by mass or less, more preferably 50% by mass or less, with respect to the total of the polyfunctional monomer and the monofunctional monomer. In this case, when there is too much usage-amount of a monofunctional monomer, there exists a tendency for sclerosis | hardenability to fall.

-Surfactant (D)-
The compound represented by the above formula (1), that is, the surfactant (D) is a component that functions as a surfactant in the colored composition of the present invention. By containing the specific surfactant, the colored composition of the present invention can form a colored layer having excellent flatness. Specific examples of the surfactant (D) include compounds represented by the following formula.

(In formula ^{(1-1) ~ (1-4),} R 1 ~R 4 and a~d have the same meanings as ^R 1 to R ⁴ and a~d in Formula (1).)
In the above formula (1), at least two of R ^{1 to} R ⁴ are preferably C ₆ F ₁₁ —, C ₉ F ₁₇ — or C ₉ F ₁₇ O—C ₆ H ₄ —CO—, particularly R ¹ to R all _C 6 _F 11 of ⁴ _-, C _{9 F 17 -} or _{C 9 F 17 O-C 6} H is preferably 4 -CO-. Examples of C ₆ F ₁₁ — and C ₉ F ₁₇ — include residues derived from hexafluoropropene dimers or trimers, for example, structures represented by the following formulae.

(In the above formula, “*” indicates a bond.)
In the present ^invention, the _{^{R 1 ~R 4, C 9 F}} 17 - are preferred.

In the above formula (1), A represents an ethylene group or a propylene group, and when any of ad is 2 or more, that is, any of (AO) a to (AO) d is a polyoxyalkylene. When forming a chain, the polyoxyalkylene chain may contain both an ethylene group and a propylene group.
Moreover, in said formula (1), it is preferable that the sum total of ad is 5-30, and it is especially preferable that it is 8-18.

There is no restriction | limiting in particular regarding the manufacturing method of surfactant (D), For example, it can manufacture by the method of Unexamined-Japanese-Patent No. 4-145041.

Content of surfactant (D) in the coloring composition of this invention becomes like this. Preferably it is 0.01-5 mass parts with respect to 100 mass parts of (B) binder resin, More preferably, it is 0.05-3. Part by mass. By incorporating the surfactant (D) in such a range, even when the slit die coating method is adopted as the coating method, the flatness of the colored layer becomes extremely good.

In the present invention, as the surfactant, a known fluorosurfactant other than the surfactant (D), a silicon surfactant and the like can be used together with the surfactant (D).

-(E) Photopolymerization initiator-
The coloring composition of the present invention can be provided with radiation sensitivity by incorporating a photopolymerization initiator. The term “radiation” as used herein means a substance including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.
The (E) photopolymerization initiator used in the present invention is the above-mentioned (C) polyfunctional monomer and the single monomer used in some cases by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates an active species capable of initiating polymerization of a functional monomer.
Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound etc. can be mentioned.

  In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

  Among preferred photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

  Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′. -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

  In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) polyfunctional monomers, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

-Solvent-
The colored composition of the present invention is usually prepared as a liquid composition by blending a solvent. As said solvent, it disperse | distributes or melt | dissolves other components, such as (A)-(D) component and (E) component which comprise a coloring composition, does not react with these components, and has moderate volatility. As long as it is a thing, it can select and use suitably.

As such a solvent, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxy (Poly) alkylene glycol monoalkyl ether acetates such as butyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl 3-methylbutanoate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-acetate -Amyl, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2 -Other esters such as ethyl oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Pioneto acetate n- butyl acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Further, together with the above solvents, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination.
The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the composition is usually 5 to 5 from the viewpoints of applicability and stability of the resulting colored composition. An amount of 50% by mass is preferable, and an amount of 10 to 40% by mass is particularly desirable.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy) silane. N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyl bird Adhesion promoters such as toxisilane, 3-mercaptopropyltrimethoxysilane; antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol; UV absorbers such as 3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; anti-aggregating agents such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, Citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3- Residue improving agents such as propanediol and 4-amino-1,2-butanediol can be exemplified.

In the present invention, the coloring composition can be prepared by an appropriate method. For example, the coloring composition is prepared by mixing the components (A) to (D) together with a solvent and other components optionally added. Can do. As a preferred method for preparing a coloring composition, (A) a coloring agent is mixed in a solvent in the presence of a dispersing agent, optionally together with a part of component (B), for example, using a bead mill, a roll mill or the like. -Disperse to give a colorant dispersion, and then add (B) to (D) components and, if necessary, additional solvents and other components to the colorant dispersion, and mix. The method of doing can be mentioned.

Color filter and production method thereof The color filter of the present invention comprises a colored layer formed from the colored composition of the present invention.
As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, after applying a liquid composition of the colored radiation-sensitive composition of the present invention in which a red colorant is dispersed on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement.
Next, using the liquid composition of each colored radiation-sensitive composition in which a green or blue colorant is dispersed, the liquid composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above. A green pixel array and a blue pixel array are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method. Using the radiation-sensitive composition, it can be formed in the same manner as in the case of forming the pixel. The step between the black matrix made of a metal thin film and the substrate is usually 0.1 to 0.2 μm, but the step between the resin black matrix formed using the black radiation-sensitive composition and the substrate is around 1 μm. Become. According to the colored radiation-sensitive composition of the present invention, a pixel having excellent flatness can be formed even on a substrate having a resin black matrix and having a large level difference.

Examples of the substrate used when forming the pixel and / or the black matrix include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
When applying the liquid composition of the colored radiation-sensitive composition to the substrate, an appropriate application method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method is used. Although it can employ | adopt, it is preferable to employ | adopt especially the slit-die coating method.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm as the film thickness after drying.

As the radiation used when forming the pixel and / or the black matrix, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, but the wavelength is in the range of 190 to 450 nm. Some radiation is preferred.
In general, the exposure dose of radiation is preferably 10 to 10,000 J / m ² .
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
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 development conditions are preferably 5 to 300 seconds at room temperature.

As a second method for producing a color filter, a method for obtaining pixels of each color by an ink jet method, which is disclosed in JP-A-7-318723, JP-A-2000-310706, and the like, is also known.
Since the color filter of the present invention thus obtained is excellent in the flatness of the colored layer, it is extremely useful for a color liquid crystal surface element, a color image pickup tube element, a color sensor, an organic EL display element, electronic paper and the like.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
The color liquid crystal display element of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. In addition, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Synthesis of Surfactant (D) The following compounds were synthesized by the method described in JP-A-4-145041.
Surfactant (D-1): In the above formula (1-3), all of R ^{1 to} R ⁴ are C ₉ F ₁₇ —, and the total of a to d is 5 (D— 2): Compound surfactant (D-3) in which all of R ^{1 to} R ⁴ are C ₉ F ₁₇ — and the sum of a to d is 8 in the above formula (1-3): 1-3) Compound surfactant (D-4) in which all of R ^{1 to} R ⁴ are C ₉ F ₁₇ — and the sum of a to d is 12: In the above formula (1-3), Compound surfactant (D-5) in which all of R ^{1 to} R ⁴ are C ₉ F ₁₇ — and the sum of a to d is 18: In the above formula (1-1), R ^{1 to} R ³ all _C 9 _{F 17} - a and compound total a~c is 24 surfactant (D-6): in the above formula ^(1-3), all of R 1 to R ⁴ C ₉ F ₁₇ - a and compound total a~d is 30

Preparation of colorant dispersion Preparation Example 1
(A) C.I. I. Pigment red 254 and C.I. I. 12 parts by weight of an 80/20 (mass ratio) mixture with Pigment Red 177, 4 parts by weight of Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a dispersant, and a solid content concentration of 16% by weight of propylene glycol monomethyl ether acetate as a solvent The mixture was mixed and dispersed with a bead mill for 12 hours to prepare a colorant dispersion (A-1).

Preparation Example 2
(A) C.I. I. Pigment Green 36 and C.I. I. 11 parts by weight of a 60/40 (mass ratio) mixture with Pigment Yellow 150, 2 parts by weight of BYK-LPN21116 (produced by BYK) as a dispersant (solid content conversion) and Azisper PB880 (produced by Ajinomoto Fine Techno Co., Ltd.) Using 2 parts by mass of propylene glycol monomethyl ether acetate as a solvent at a solid content concentration of 15% by mass, the mixture was mixed and dispersed for 12 hours by a bead mill to prepare a colorant dispersion (A-2).

Preparation Example 3
(A) C.I. I. Pigment blue 15: 6 and C.I. I. 10 parts by mass of a 95/5 (mass ratio) mixture with Pigment Violet 23, 2 parts by mass of Disperbyk-2000 (by Big Chemy (BYK)) as a dispersant (in terms of solid content) and BYK-LPN21324 (by Big Chemy (BYK)) ) 2 parts by mass (in terms of solid content), propylene glycol monomethyl ether acetate as a solvent to a solid content concentration of 14% by mass, mixed and dispersed for 12 hours by a bead mill, and the colorant dispersion (A-3) Prepared.

Preparation Example 4
(A) C.I. I. Pigment red 254 / C.I. I. Pigment red 177 / C.I. I. Pigment Yellow 139 = 13.5 parts by weight of a 50/35/15 (mass ratio) mixture, Adisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a dispersant, 6.0 parts by weight, and 1,3-butylene glycol diacetate as a solvent Using it so that it might become 19.5 mass% of solid content concentration, it mixed and disperse | distributed for 12 hours with the bead mill, and prepared the colorant dispersion liquid (A-4).

Preparation Example 5
(A) C.I. I. Pigment Green 36 and C.I. I. 15 parts by weight of a 50/50 (mass ratio) mixture with Pigment Yellow 150, 3 parts by weight of BYK-LPN21116 (produced by BYK Corporation) as a dispersant (in terms of solid content) and Ajisper PB880 (produced by Ajinomoto Fine Techno Co., Ltd.) Using 3 parts by mass and 1,3-butylene glycol diacetate as a solvent so as to have a solid content concentration of 21% by mass, the mixture was mixed and dispersed for 12 hours by a bead mill to prepare a colorant dispersion (A-5).

Preparation Example 6
(A) C.I. I. Blue 15: 6 and C.I. I. 12/10 parts by weight of 90/10 (mass ratio) mixture with Pigment Violet, 3 parts by weight of Disperbyk-2000 (produced by BYK (BYK)) as a dispersant (in terms of solid content) and BYK-LPN21324 (made by BYK-Chemie (BYK)) 3 parts by mass (in terms of solid content), 1,3-butylene glycol diacetate as a solvent was used so as to have a solid content concentration of 18% by mass, mixed and dispersed by a bead mill for 12 hours, and a colorant dispersion (A-6 ) Was prepared.

(B) Synthesis of binder resin Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 2 parts by mass of 2,2′-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate, followed by 15 parts by mass of methacrylic acid and 20 parts by mass of N-phenylmaleimide. , 55 parts by mass of benzyl methacrylate, 10 parts by mass of styrene and 3 parts by mass of 2,4-diphenyl-4-methyl-1-pentene (trade name: NOFMER MSD, manufactured by NOF Corporation) as a molecular weight regulator, Replaced. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a binder resin solution (solid content concentration = 32.3% by weight). The obtained binder resin was Mw = 16,000 and Mn = 7,000. This binder resin is referred to as “binder resin (B-1)”.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 136 parts by mass of propylene glycol monomethyl ether acetate and heated to 80 ° C. while injecting nitrogen gas. At the same temperature, 20 parts by mass of methacrylic acid, 12 parts by mass of N-phenylmaleimide, 5 parts by mass of benzyl methacrylate, 10 parts by mass of styrene, 15 parts by mass of 2-hydroxyethyl methacrylate and 38 parts by mass of 2-ethylhexyl methacrylate were mixed with propylene glycol monomethyl ether. A solution prepared by dissolving 40 parts by mass of acetate and a solution prepared by dissolving 6 parts by mass of 2,2′-azobisisobutyronitrile in 24 parts by mass of propylene glycol monomethyl ether acetate were simultaneously added dropwise over 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and this temperature was maintained for 1 hour for polymerization to obtain a binder resin solution (solid content concentration = 33.0 wt%). The obtained binder resin was Mw = 11,000 and Mn = 6,000. This binder resin is referred to as “binder resin (B-2)”.

Example 1
Preparation of colored radiation-sensitive composition (A) 100 parts by mass of colorant dispersion (A-1), (B) 10 parts by mass of binder resin (B-1) (solid content conversion) as binder resin, (C) many 15 parts by mass of dipentaerythritol hexaacrylate as a functional monomer, 0.05 parts by mass of a surfactant (D-1), (E) 2-benzyl-2-dimethylamino-1- (4 as a photopolymerization initiator -Morpholinophenyl) butan-1-one 4 parts by weight, 4,4'-bis (diethylamino) benzophenone 1 part by weight, and propylene glycol monomethyl ether acetate as a solvent were mixed so that the solid content concentration would be 15% by weight. Thus, a liquid composition (S-1) was prepared. The liquid composition (S-1) was weighed in an aluminum dish, heated on a hot plate at 180 ° C. for 1 hour, and measured for the weight before and after heating to measure the nonvolatile content concentration. It was 8 mass%. In a liquid composition (S-1), the content rate of the coloring agent in a non volatile matter is 26 mass%.
The liquid composition (S-1) was evaluated according to the following procedure. The evaluation results are shown in Table 1.

Appearance evaluation of coating film The liquid composition (S-1) prepared above was applied to a slit die coater (manufactured by Tokyo Ohka Kogyo Co., Ltd., model “TR6321055-CL” on a 550 × 650 mm chromium film-forming glass. ”), The ultimate pressure was set to 100 Pa, the solvent was removed by vacuum drying, and the film was further pre-baked at 80 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm.
About this coating film, the generation | occurrence | production state of the nonuniformity originating in the proxy pin of a prebaking furnace was evaluated visually under a sodium lamp. The coating film appearance was “excellent” when almost no unevenness was seen, the appearance “good” when the unevenness was slightly seen, and the appearance “bad” when the unevenness was clearly visible.

Evaluation of film thickness uniformity of coating film In the above "appearance evaluation of coating film", a 550x650 mm resin black matrix having a film thickness of 1 m was formed instead of a 550x650 mm chromium film-forming glass. A coating film was formed on the substrate in the same manner as in the above “appearance evaluation of coating film” except that non-alkali glass was used. About this coating film, the film thickness was measured at 20 measurement points, and the film thickness uniformity was calculated by the following formula.
Film thickness uniformity (%) = (maximum value of coating film thickness−minimum value) × 100 / ((average of coating film thickness of 20 points) × 2)
When the uniformity of the coating film thickness calculated in this way is 1% or less, it can be said that the film thickness uniformity is good.
The 20 measurement points were determined as follows. That is, an inner region (450 × 550 mm) excluding a range of 50 mm from each end of the long side and the short side of the substrate (550 × 650 mm) is set as a measurement region, and the long side direction and the short side direction in the region Ten points (20 points in total) were determined every 40 mm on a straight line, and these were used as measurement points.

Examples 2-11, Comparative Examples 1-7
In Example 1, except that the types and amounts of the colorant dispersion, the binder resin, the polyfunctional monomer, and the surfactant were changed as shown in Table 1, the liquid composition ( S-2) to (S-18) were prepared.
Next, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (S-2) to (S-18) were used instead of the liquid composition (S-1). The results are shown in Table 1. In Comparative Example 5, the same color as that of the coating film formed in Example 7 is used in Comparative Example 6 so that the film thickness becomes the same chromaticity x as that of the coating film formed in Example 1. In Comparative Example 7, a coating film was formed and evaluated so as to have a film thickness with a chromaticity y equivalent to that of the coating film formed in Example 8, so that the film thickness would be a degree y.

In Table 1, each component is as follows.
d-1: Commercially available fluorosurfactant (manufactured by Dainippon Ink & Chemicals, Inc., trade name: Megafac R08)
d-2: Commercially available silicone surfactant (trade name: SH8400 manufactured by Toray Dow Corning Co., Ltd.)
In Table 1, the “colorant concentration” is the content ratio (% by mass) in the non-volatile content of the colorant.

Example 12
Preparation of inkjet ink (A) 545 parts by weight of colorant dispersion (A-4), (B) 19 parts by weight of binder resin (B-2) as a binder resin (in terms of solid content), (C) polyfunctional monomer 78 parts by mass of dipentaerythritol hexaacrylate as a body, 0.15 parts by mass of surfactant (D-3), and 310 parts by mass of 1,3-butylene glycol diacetate as a solvent (E) Prepared.

Evaluation of pixel flatness Using a inkjet printer Nanoprinter-1500S (manufactured by Microjet Co., Ltd.), near the center of the pixel after drying in a pixel partitioned by a partition wall having a height of 2.0 μm, a length of 500 μm and a width of 150 μm The inkjet ink prepared above was discharged so that the film thickness of the film became 2.0 μm. Using α-step IQ (manufactured by KLA Tencor), the film thickness at the center of the pixel was measured in the width direction. As a result, it was confirmed that the flatness of the pixel was good.

Examples 13-14
In Example 12, except that the colorant dispersion (A-4) was changed to the colorant dispersion (A-5) or the colorant dispersion (A-6), an inkjet ink was prepared. Prepared and evaluated pixel flatness. It was confirmed that the flatness of the pixels was good when any of the inkjet inks was used. It turns out that the coloring composition of this invention is excellent in leveling property.

Claims (7)

(A) a colorant, (B) a binder resin, (C) a polyfunctional monomer, and (D) a compound represented by the following formula (1), and (A) the content ratio of the colorant is The coloring composition characterized by being 20-70 mass% in non volatile matter.

In (Equation ^(1), R 1 ~R ⁴ are independently of each _{other, C 6 F 11 -, C} 9 F 17 -, represents _{C 9 F 17 -O-C 6} H 4 -CO- or a hydrogen atom , provided that at least one of which _{C 6 F 11 -, C 9} F 17 - or _{C 9 F 17 -O-C 6} H 4 is -CO-, a are independently of each other, an ethylene group or Represents a propylene group, and a to d each independently represent an integer of 0 to 30, provided that the total of a to d is 2 to 50, and n is 0 or 1. The coloring composition according to claim 1, wherein the total of a to d is 5 to 30 in the formula (1). Wherein at least one of ^R 1 ^{~R 4} _C 9 _{F 17} In the equation (1) - a coloring composition according to claim 1 or 2. Furthermore, (E) The coloring composition of any one of Claims 1-3 containing a photoinitiator.   The coloring composition according to claim 4, which is used in a slit die coating method.   The color filter provided with the colored layer formed using the coloring composition of any one of Claims 1-5.   A color liquid crystal display device comprising the color filter according to claim 6.