JP5636675B2 - Coloring composition for color filter, color filter, and color liquid crystal display element - Google Patents

Description

  The present invention relates to a coloring composition for a color filter, a color filter, and a color liquid crystal display element. More specifically, the present invention relates to 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 for a color filter used for forming a colored layer useful for the color filter used, a color filter provided with a colored layer formed using the colored composition, and a color liquid crystal display device including the color filter. .

  In producing a color filter using a photocurable coloring composition, the photocurable coloring composition is applied on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed in advance, and then dried. There are known methods (Patent Documents 1 and 2) for obtaining pixels of each color by irradiating a film in a desired pattern shape (hereinafter referred to as “exposure”) and developing the film. In addition, a method of forming a black matrix using a photopolymerizable composition containing a black material (Patent Document 3), and a method of obtaining pixels of each color by an inkjet method using a resin composition for a color filter (Patent Document 4) ) Is also known.

  On the other hand, Patent Document 5 discloses a vinyl having a repeating unit derived from 2- (2-vinyloxyethoxy) ethyl acrylate in order to provide a curable resin composition that gives a cured product having a high coating film hardness after curing. It has been proposed to use a polymer. However, Patent Document 5 does not specifically describe the copolymer having the above repeating unit, and a pixel constituting a color filter is formed using the curable resin composition containing the vinyl polymer. It is not described to do.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2008-63400 A

The subject of this invention is providing the coloring composition for color filters excellent in alkali developability and sclerosis | hardenability.
Furthermore, the subject of this invention is providing the color liquid crystal display element which comprises the color filter which has the colored layer formed using the said coloring composition for color filters, and the said color filter.

  In view of this situation, the present inventors have conducted intensive research and found that a vinyl ether monomer having a (meth) acryloyl group and an ethylenically unsaturated monomer having an acidic group capable of cationic polymerization with the monomer. It has been found that the above-mentioned problems can be solved by including a copolymer having a repeating unit derived from the body, and the present invention has been completed.

That is, the present invention includes the following components (A) to (B):
(A) a colorant,
(B) (b1) a repeating unit represented by the following formula (1), and (b2) a polymer having a repeating unit derived from an ethylenically unsaturated monomer having an acidic group (hereinafter referred to as “polymer (B ) ")
It is intended to provide a coloring composition for a color filter, which contains

(In Formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a substituted or unsubstituted divalent hydrocarbon group, and n is a positive integer. )

  Moreover, this invention provides the color liquid crystal display element which comprises the color filter which has a colored layer formed using this coloring composition for color filters, and this color filter. Here, in the present invention, the “colored layer” means pixels of each color used in the color filter, a black matrix, or the like.

  The coloring composition for a color filter of the present invention is excellent in alkali developability and curability. Accordingly, the color composition for color filters of the present invention is a color filter for color liquid crystal display elements, a color filter for color separation of solid-state image sensors, a color filter for organic EL display elements, and a color filter for electronic paper. It can be used very suitably for the production of a color filter.

It is explanatory drawing of the taper angle in the pixel pattern formed on the board | substrate.

Hereinafter, the present invention will be described in detail.
Color Filter Coloring Composition Hereinafter, the components of the color filter coloring composition of the present invention (hereinafter also simply referred to as “coloring composition”) will be described.

-(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 resin, if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. As a resin coating method on the carbon black surface, 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. Preferably used.
On the other hand, when the colored composition of the present invention is used for forming a black matrix, since the black matrix is required to have light shielding properties, an organic pigment or carbon black is preferably used as the colorant (A).

  (A) Content of a coloring agent is 5-70 mass% in the total solid of the coloring composition of this invention from the point which forms the pixel which is excellent in transparency and color purity, or the black matrix which is excellent in light-shielding property. It is preferably 5 to 60% by mass. The “solid content” here is a component other than the solvent described later. The coloring composition of the present invention is excellent in alkali developability even when the content of the coloring agent is 30% by mass or more in the total solid content of the coloring composition.

  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 can be obtained commercially. 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) polymer-
The colored composition of the present invention comprises a polymer (B), that is, (b1) a repeating unit represented by the above formula (1) (hereinafter also referred to as “repeating unit (b1)”), and (b2) an acidic group. And a polymer having a repeating unit derived from the ethylenically unsaturated monomer (hereinafter, also referred to as “repeating unit (b2)”). By containing such a polymer (B), the colored composition of the present invention has excellent alkali developability and curability.

In the above formula (1), R ² is, for example, a linear or cyclic alkylene group having 2 to 18 carbon atoms (preferably 2 to 6 carbon atoms), a phenylene group, or a 1,4-phenylenebis (methylene) group. Etc. These groups may have a substituent such as a linear or cyclic alkyl group having 1 to 6 carbon atoms, a linear or cyclic alkoxy group having 1 to 6 carbon atoms, or halogen.
In the above formula (1), n is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.

As a monomer which gives a repeating unit (b1), the following compound is mentioned, for example.
(Meth) acrylic acid 2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxypropyl, (meth) acrylic acid 2-vinyloxypropyl, (meth) acrylic acid 1-vinyloxypropyl, (meth) acrylic acid 1-methyl 2-vinyloxyethyl, 1-methyl-3-vinyloxypropyl (meth) acrylate, 2-methyl-3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxypropyl (meth) acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, 2-vinyloxybutyl (meth) acrylate,
(Meth) acrylic acid 4-vinyloxycyclohexyl, (meth) acrylic acid 6-vinyloxyhexyl,
(Meth) acrylic acid 4-vinyloxymethylcyclohexylmethyl, (meth) acrylic acid 3-vinyloxymethylcyclohexylmethyl, (meth) acrylic acid 2-vinyloxymethylcyclohexylmethyl, (meth) acrylic acid p-vinyloxymethylphenyl Methyl, (meth) acrylic acid m-vinyloxymethylphenylmethyl, (meth) acrylic acid o-vinyloxymethylphenylmethyl, (meth) acrylic acid 4-vinyloxymethylphenylmethyl, (meth) acrylic acid 3-vinyloxy Methylphenylmethyl, 2-vinyloxymethylphenylmethyl (meth) acrylate,

2- (2-vinyloxyethoxy) ethyl (meth) acrylate, 2- (2-vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (2-vinyloxyethoxy) propyl (meth) acrylate, ( 2- (2-vinyloxyisopropoxy) propyl (meth) acrylate, 2- (2-vinyloxyethoxy) isopropyl (meth) acrylate, 2- (2-vinyloxyisopropoxy) isopropyl (meth) acrylate,
2- (2- (2- (2-vinyloxyethoxy) ethoxy) ethyl (meth) acrylate, 2- {2- (2-vinyloxyisopropoxy) ethoxy} ethyl (meth) acrylate, 2- (meth) acrylic acid 2- {2- (2-vinyloxyisopropoxy) isopropoxy} ethyl, (meth) acrylic acid 2- {2- (2-vinyloxyethoxy) ethoxy} propyl, (meth) acrylic acid 2- {2- (2- Vinyloxyethoxy) isopropoxy} propyl, (meth) acrylic acid 2- {2- (2-vinyloxyisopropoxy) ethoxy} propyl, (meth) acrylic acid 2- {2- (2-vinyloxyisopropoxy) iso Propoxy} propyl, (meth) acrylic acid 2- {2- (2-vinyloxyethoxy) ethoxy} isopropyl, (meth) acrylic acid 2- {2- (2- Nyloxyethoxy) isopropoxy} isopropyl, (meth) acrylic acid 2- {2- (2-vinyloxyisopropoxy) ethoxy} isopropyl, (meth) acrylic acid 2- {2- (2-vinyloxyisopropoxy) iso Propoxy} isopropyl, (meth) acrylic acid 2- [2- {2- (2-vinyloxyethoxy) ethoxy} ethoxy] ethyl, (meth) acrylic acid 2- [2- {2- (2-vinyloxyisopropoxy) ) Ethoxy} ethoxy] ethyl, 2- (2- [2- {2- (2-vinyloxyethoxy) ethoxy} ethoxy] ethoxy) ethyl (meth) acrylate 2- (isopropenoxyethoxy) (meth) acrylate Ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropene Ethoxy ethoxy) ethyl, ethyl (meth) acrylic acid 2- (isopropenoxysilane ethoxy ethoxy ethoxy ethoxy), (meth) Polyethylene glycol monovinyl ether acrylate, (meth) acrylic acid polypropylene glycol monovinyl ether.

Among these monomers, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, ( (Meth) acrylic acid 4-vinyloxybutyl, (meth) acrylic acid 6-vinyloxyhexyl, (meth) acrylic acid 4-vinyloxycyclohexyl, (meth) acrylic acid 4-vinyloxymethylcyclohexylmethyl, (meth) acrylic acid 2- (2-vinyloxyethoxy) ethyl, 2- (2-vinyloxyisopropoxy) propyl (meth) acrylate, and 2- {2- (2-vinyloxyethoxy) ethoxy} ethyl (meth) acrylate are preferred.
The monomer which gives a repeating unit (b1) can be used individually or in mixture of 2 or more types.

  Moreover, as a monomer which gives a repeating unit (b2), as long as it is copolymerizable with the vinyloxy group of the monomer which gives a repeating unit (b1), and is an ethylenically unsaturated monomer which has an acidic group Although not particularly limited, an ethylenically unsaturated monomer capable of cationic polymerization and having an acidic group is preferable. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. Among these, a carboxyl group is preferable from the viewpoint of alkali developability.

  Examples of the monomer that gives the repeating unit (b2) include a vinyl ether having a carboxyl group, an aromatic vinyl compound having a carboxyl group, an aromatic vinyl compound having a phenolic hydroxyl group, a vinyl compound having a sulfonic acid group, and a sulfonic acid. And aromatic vinyl compounds having a group.

Examples of the vinyl ether having a carboxyl group include compounds obtained by reacting a vinyl ether having a hydroxyl group with an acid anhydride. Specific examples of the vinyl ether having a hydroxyl group include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, cyclohexane dimethanol monovinyl ether and the like. These compounds include Maruzen Petrochemical Co., Ltd. and BASF. It is commercially available from the company. Specific examples of the acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride.
Specific examples of the aromatic vinyl compound having a carboxyl group include p-vinylbenzoic acid and p-isopropenylbenzoic acid.
Specific examples of the aromatic vinyl compound having a phenolic hydroxyl group include o-vinylphenol, m-vinylphenol, p-vinylphenol, p-isopropenylphenol and the like.
Specific examples of the vinyl compound having a sulfonic acid group include vinyl sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-3- (meth) allyloxypropane sulfonic acid, (meth) acrylic acid-2-sulfoethyl, ( Examples include 2-methacrylic acid-2-sulfopropyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, and the like.
Specific examples of the aromatic vinyl compound having a sulfonic acid group include styrene sulfonic acid.

Among these monomers, a vinyl ether having a carboxyl group and an aromatic vinyl compound having a carboxyl group are preferable, and a vinyl ether having a carboxyl group is particularly preferable.
The monomer which gives a repeating unit (b2) can be used individually or in mixture of 2 or more types.

  A polymer (B) can have another repeating unit with a repeating unit (b1) and a repeating unit (b2). As the monomer that gives other repeating units, a monomer capable of cationic polymerization is preferable. For example, a vinyl ether having a chain or cyclic alkyl group, a vinyl ether having an epoxy group, a vinyl ether having a hydroxyl group, an aromatic vinyl compound (However, the monomer which gives the said repeating unit (b2) is remove | excluded.), An N-vinyl compound, an aliphatic conjugated diene, carboxylic acid vinyl ester, etc. can be mentioned.

Specific examples of the vinyl ether having a chain or cyclic alkyl group include methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, isobornyl vinyl ether, and tricyclo [5.2. 1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, and the like.
Specific examples of the vinyl ether having an epoxy group include 3- (vinyloxymethyl) -3-methyloxetane and 3- (vinyloxymethyl) -3-ethyloxetane.

Specific examples of the vinyl ether having a hydroxyl group include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, cyclohexane dimethanol monovinyl ether, and the like.
Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-methoxystyrene, acenaphthylene, p-vinylbenzylglycidyl ether and the like.
Specific examples of the N-vinyl compound include N-vinyl carbazole and N-vinyl pyrrolidone.

Specific examples of the aliphatic conjugated diene include 1,3-butadiene, isoprene, chloroprene and the like.
Specific examples of the carboxylic acid vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and the like.
The monomer which gives another repeating unit can be used individually or in mixture of 2 or more types.

  In a polymer (B), the content rate of a repeating unit (b1) becomes like this. Preferably it is 10-99 mass%, More preferably, it is 30-95 mass%. Moreover, the content rate of a repeating unit (b2) becomes like this. Preferably it is 1-80 mass%, More preferably, it is 5-70 mass%. In such a range, a colored composition excellent in alkali developability and curability can be obtained by copolymerizing the repeating unit (b1) and the repeating unit (b2).

The weight average molecular weight in terms of polystyrene (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the polymer (B) is usually 1,000 to 100,000, preferably It is 3,000 to 50,000, more preferably 5,000 to 30,000. If Mw is too small, the curability may be impaired, while if it is too large, the resolution may be reduced, or alkali developability and pattern shape may be impaired.
Further, the ratio (Mw / Mn) of Mw of the polymer (B) and polystyrene-equivalent number average molecular weight (hereinafter also referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) is: Preferably it is 1.0-5.0, More preferably, it is 1.0-3.0, Most preferably, it is 1.0-1.9.

  The polymer (B) can be produced, for example, by cationic polymerization of the above monomer. The cationic polymerization method is preferably a living cationic polymerization method, Macromolecules, Vol. 17, 265-268 (1984), Polymer Bretan, Vol. 15, 417 (1986), Macro Molecule, Vol. 26, 744 (1993). ), Macromol. Symp. 85, 33-43 (1994), Macromolecule, 25, 2587 (1992), J. MoI. Polym. Sci. Part A Polym, Chem. 46, 1913-1918 (2008), Japanese Patent Application Laid-Open No. 2006-241189, and the like.

In this invention, a polymer (B) can be used individually or in mixture of 2 or more types.
In the present invention, the content of the polymer (B) is usually 0.5 to 1,000 parts by weight, preferably 1.5 to 500 parts by weight, more preferably 100 parts by weight of the colorant (A). Is 3 to 300 parts by mass. If the content of the polymer (B) is too low, the desired effect may not be obtained. On the other hand, if the content is too high, the pigment concentration is relatively lowered, so that the target color density as a thin film is achieved. May become difficult.

-(C) polyfunctional monomer-
In the present invention, the curability of the colored composition can be enhanced by further containing (C) a polyfunctional monomer. The (C) polyfunctional monomer in the present invention is not particularly limited as long as it is a monomer having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the (C) polyfunctional monomer is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a caprolactone-modified polyfunctional ( (Meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, hydroxyl-functional (meth) acrylate and polyfunctional isocyanate obtained by reacting with polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid The polyfunctional (meth) acrylate which has a carboxyl group obtained by making an anhydride react can be mentioned.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include ethylene oxide of bisphenol A and / or propylene oxide modified di (meth) acrylate, ethylene oxide of isocyanuric acid and / or propylene oxide modified tri (meth) acrylate, tri Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of methylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modified tetra (meth) acrylate of pentaerythritol Dipentaerythritol ethylene oxide and / or propylene oxide modified penta (meth) acrylate, di It can be mentioned pointer ethylene oxide erythritol and / or propylene oxide-modified hexa (meth) acrylate.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, a melamine structure and a benzoguanamine structure are the concept also including a melamine, a benzoguanamine, or those condensates. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N, N, N, N-hexa (alkoxymethyl) melamine, N, N, N, N-tetra (alkoxymethyl). ) Benzoguanamine, N, N, N, N-tetra (alkoxymethyl) glycoluril and the like.

  Of these polyfunctional monomers, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, Polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N, N, N, N-hexa (alkoxymethyl) melamine, N, N, N, N-tetra (alkoxymethyl) ) Benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Among polyfunctional (meth) acrylates having a carboxyl group, erythritol hexaacrylate is obtained by reacting pentaerythritol triacrylate and succinic anhydride, and reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.

In the present invention, the polyfunctional monomer (C) can be used alone or in admixture of two or more.
The content of the polyfunctional monomer (C) in the present invention is preferably 10 to 700 parts by mass, more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the polymer (B). By containing the polyfunctional monomer (C) at such a ratio, a colored composition having further excellent curability can be obtained.

-(D) Binder resin-
In the present invention, by further including (D) a binder resin (excluding the above component (B)), the alkali developability and storage stability of the resulting colored composition can be enhanced. The (D) binder resin in the present invention is not particularly limited, but is a (meth) acrylic monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (d1)”). ) And an ethylenically unsaturated monomer (hereinafter referred to as “unsaturated monomer (d2)”) capable of radical copolymerization with the monomer.

  Examples of the unsaturated monomer (d1) 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 (c1) can be used alone or in admixture of two or more.

Examples of the unsaturated monomer (d2) include:
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, polyethylene glycol (n = 2 -10) methyl ether (meth) acrylate, polypropylene glycol (n = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) ) Mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, Glyce Rumono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, such as unsaturated carboxylic acid ester of ethylene oxide-modified (meth) acrylate of p-cumylphenol;
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 (d2) can be used alone or in admixture of two or more.

  In the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2), the copolymerization ratio of the unsaturated monomer (d1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (d1) in such a range, a colored composition having excellent storage stability and alkali developability can be obtained.

  Specific examples of the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. Copolymers disclosed in JP-A-10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-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 Mw of the binder resin in the present invention is usually 1,000 to 300,000, preferably 3,000 to 100,000. If Mw is too small, the remaining film ratio of the resulting coating may decrease, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, the pattern shape will be impaired. In addition, there is a risk that dry foreign matter is likely to occur during application by the slit nozzle method.
The Mw / Mn of the binder resin is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.
In this invention, binder resin can be used individually or in mixture of 2 or more types.

  In the present invention, the content of the binder resin is preferably 10 to 1,000 parts by mass, more preferably 15 to 500 parts by mass, and still more preferably 20 to 300 parts by mass with respect to 100 parts by mass of the (A) colorant. It is. By including the binder resin in such a ratio, a colored composition having further excellent alkali developability and storage stability can be obtained.

-(E) Photopolymerization initiator-
The coloring composition of the present invention may contain a photopolymerization initiator.
The photopolymerization initiator (E) used in the present invention is obtained by exposing the polymer (B) and (C) polyfunctional monomer by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates active species capable of initiating polymerization.
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, 0.01-500 mass parts is preferable with respect to 100 mass parts of polymers (B), and, as for content of a photoinitiator, 1-300 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.

-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 improvers such as propanediol and 4-amino-1,2-butanediol; succinic acid mono [2- (meth) acryloyl Kishiechiru], phthalic acid mono- [2- (meth) acryloyloxyethyl], .omega. carboxypolycaprolactone mono (meth) may be mentioned acrylate developability improving agents such like.

-Solvent-
The coloring composition of the present invention contains the above components (A) to (B) and other components that are optionally added, and is usually prepared as a liquid composition by blending a solvent.
As said solvent, (A)-(B) component which comprises the coloring composition of this invention, and another component are disperse | distributed or melt | dissolved, and it does not react with these components, but has moderate volatility. As long as it can be appropriately selected and used.

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.

Furthermore, 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 high boiling point solvents may be used alone or in combination of two or more.

  The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the colored composition is usually 5 to 5 from the viewpoint of the coating property and stability of the colored composition to be obtained. An amount of 50% by mass is preferable, and an amount of 10 to 40% by mass is particularly desirable.

  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 (B) together with a solvent and other components optionally added. Can do. As a preferred method for preparing the coloring composition, for example, a bead mill, a roll mill, or the like is used, with (A) the coloring agent in the solvent in the presence of the dispersing agent, optionally with a part of the component (B) and / or (D). Mix and disperse while pulverizing to obtain a colorant dispersion, and then add (B) component and, if necessary, additional solvent and other components to the colorant dispersion and mix. The method of preparing by 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 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 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 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 composition, it can be formed in the same manner as in the case of forming the pixel.

Examples of the substrate used when forming the color filter 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 the liquid composition of the colored composition of the present invention is applied to a 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 be employed, it is particularly preferable to employ a spin coating method or a slit die coating method.
Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.
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.

Examples of radiation light sources used in forming pixels and / or black matrices include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, and low pressure mercury lamps. Examples of the light source include a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. Radiation having a wavelength in the range of 190 to 450 nm is preferable.
Exposure of the radiation is generally preferred 10~10,000J / 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.
The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

Further, as a second method for producing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723 and JP-A-2000-310706 can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, after the liquid composition of the colored composition of the present invention in which, for example, a red colorant is dispersed in the formed partition wall is discharged by an ink jet apparatus, pre-baking is performed to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a red pixel pattern.
Next, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate using a liquid composition of each coloring composition in which a green or blue colorant is dispersed in the same manner as described above. Thereby, a color filter in which pixel patterns 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.
In addition, the partition has not only a light shielding function but also a function for preventing the color composition of each color discharged in the section from being mixed, so that the film is a film compared to the black matrix used in the first method described above. Thick. Therefore, a partition is normally formed using a black coloring composition.

The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. Thus, the film thickness of the pixel formed by the ink jet method is approximately the same as the thickness of the black matrix.
The color filter of the present invention thus obtained is excellent in various characteristics, and thus is extremely useful for a color liquid crystal surface element, a color imaging 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.

Preparation of colorant dispersion Preparation Example 1
(A) 20 parts by mass of carbon black as a colorant, 8 parts by mass of Disperbyk-167 (manufactured by BYK Corporation) as a dispersant (solid content concentration 52% by mass), and 72 parts by mass of propylene glycol monomethyl ether acetate as a solvent The mixture was mixed and dispersed for 12 hours using a bead mill to prepare a colorant dispersion (A-1).

Preparation Example 2
(A) C.I. I. Pigment red 254 / C.I. I. 15 parts by weight of a mixture of CI Pigment Red 177 (manufactured by Ciba Specialty Chemicals) = 80/20 (mass ratio), 4 parts by weight of Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a dispersant, and solvent Using 81 parts by mass of propylene glycol monomethyl ether acetate and mixing and dispersing for 12 hours by a bead mill, a colorant dispersion (A-2) was prepared.

Preparation Example 3
(A) C.I. I. Pigment Green 58 (above, Dainippon Ink & Chemicals, Inc.) / C.I. I. 15 parts by weight of a pigment yellow 150 = 60/40 (mass ratio) mixture, 6.5 parts by weight of BYK-LPN6919 (manufactured by BYK Co., Ltd., hereinafter the same) as a dispersant (solid content concentration 60% by weight), Using 78.5 parts by mass of a propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 90/10 (mass ratio) mixture as a solvent, mixing and dispersing by a bead mill for 12 hours to prepare a colorant dispersion (A-3) did.

Preparation Example 4
(A) C.I. I. Pigment green 36 / C.I. I. 15 parts by weight of a mixture of CI Pigment Yellow 150 = 60/40 (mass ratio), 6.5 parts by weight of BYK-LPN6919 as a dispersant (solid content concentration 60% by weight), and propylene glycol monomethyl ether acetate / propylene glycol monomethyl as a solvent A colorant dispersion (A-4) was prepared by using 78.5 parts by mass of a mixture of ether = 90/10 (mass ratio) and mixing and dispersing with a bead mill for 12 hours.

Synthesis of polymer (B) Synthesis example 1
In a three-necked flask sufficiently dried with a drier, under a dry nitrogen atmosphere, 1.0 g of 2- (2-vinyloxyethoxy) ethyl succinate, 10.2 g of 2- (2-vinyloxyethoxy) ethyl acrylate and Diethyl ether (100 mL) was charged, and the internal temperature was cooled to 0 ° C. with an ice-water bath. Next, 4.5 mL of 1M-HCl in diethyl ether was added, and the temperature was maintained for 3 hours for cationic polymerization. Then, 2.3 mL of 2M-NH ₃ in diethyl ether was added. The reaction solution was washed twice with 50 g of ion-exchanged water once, and then concentrated under reduced pressure to replace the solvent with propylene glycol monoethyl ether acetate, and the polymer [B-1] was 40% by mass. A solution containing was obtained. Polymer [B-1] was Mw = 8,000 and Mw / Mn = 1.5.

Synthesis Examples 2-4
Polymers [B-2], [B-3] and Polymers [B-2] and [B-3] were prepared in the same manner as in Synthesis Example 1 except that the types and amounts used of monomers and polymerization initiators were as shown in Table 1. A solution containing 40% by mass of [b-1] was obtained. The analysis results for each polymer are shown in Table 1.

Synthesis example 5
In a three-necked flask sufficiently dried with a dryer, 750 g of diethylene glycol dimethyl ether was charged in a dry nitrogen atmosphere, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C.
On the other hand, as a monomer dropping tank, 250 g of benzyl methacrylate, 65 g of methyl methacrylate, 185 g of methacrylic acid, 10 g of t-butylperoxy-2-ethylhexanoate (PBO; manufactured by NOF Corporation, trade name “Perbutyl O”) A well-stirred and mixed one was prepared, and a chain transfer agent dropping tank containing 22.5 g of n-dodecanethiol was prepared.
After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel, and polymerization was started. While maintaining the temperature at 90 ° C., the dropwise addition was performed over 180 minutes, and the temperature increase was started 30 minutes after the completion of the dropwise addition to bring the reaction vessel to 110 ° C. After maintaining at 110 ° C. for 90 minutes, it was cooled to room temperature. Add 1.2 g of 2,2′-methylenebis (4-methyl-6-tert-butylphenol) as an inhibitor, attach a gas introduction tube to the flask, and bubble oxygen / nitrogen = 5/95 (v / v) mixed gas. Started. While the reaction vessel was cooled in a water bath, 267 g of 2- (2-vinyloxyethoxy) ethyl methacrylate was added dropwise over 3 hours. The water bath was removed, the temperature of the reaction vessel was raised to 40 ° C. with an oil bath, and stirring was continued at 40 ° C. for 3 hours. After cooling to room temperature, the mixture was diluted with 400 g of diethylene glycol dimethyl ether, and polymer [b-2] Was obtained. The polymer [b-2] had Mw = 12,000 and Mw / Mn = 1.2.

(D) Synthesis of binder resin Synthesis Example 5
In a flask equipped with a condenser and a stirrer, 44.0 g of p-vinylbenzylglycidyl ether, 40.0 g of N-phenylmaleimide and 16.0 g of benzyl methacrylate were dissolved in 300 g of propylene glycol monomethyl ether acetate, and 2,2′- Azobisisobutyronitrile (8.0 g) and α-methylstyrene dimer (8.0 g) were added, and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling and polymerized for 5 hours.
Subsequently, 17.0 g of methacrylic acid, 0.5 g of p-methoxyphenol and 4.4 g of tetrabutylammonium bromide were added to this reaction solution, and the mixture was reacted at a temperature of 120 ° C. for 9 hours. Further, 18.5 g of succinic anhydride was added and reacted at a temperature of 100 ° C. for 6 hours, then washed twice with the liquid temperature kept at 85 ° C., and concentrated under reduced pressure to obtain a binder resin [D- 1] was obtained. This binder resin [D-1] was Mw = 7,800 and Mw / Mn = 2.8.

Synthesis Example 6
In a flask equipped with a condenser and a stirrer, 30.0 g of benzyl methacrylate, 20.0 g of butyl methacrylate, 15.0 g of hydroxyethyl methacrylate, 20.0 g of styrene and 15.0 g of methacrylic acid were dissolved in 200 g of propylene glycol monomethyl ether acetate. Further, 3.0 g of 2,2′-azobisisobutyronitrile and 5.0 g of α-methylstyrene dimer were added, and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling, and polymerized for 5 hours to obtain a solution containing 33% by weight of binder resin [D-2]. This binder resin [D-2] was Mw = 10,000 and Mw / Mn = 2.5.

Example 1
Preparation of Coloring Composition for Color Filter 100 parts by weight of colorant dispersion (A-1), 20.6 parts by weight of polymer [B-1] solution as polymer (B), (C) polyfunctional monomer M-402 manufactured by Toagosei Co., Ltd. (mainly dipentaerythritol hexaacrylate) and 1.9 parts by mass M-450 manufactured by Toagosei Co., Ltd. (mainly pentaerythritol tetraacrylate), (E ) 2.6 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, In addition, 71.2 parts by mass of ethyl 3-ethoxypropionate was mixed as a solvent to prepare a liquid colored composition for a color filter.
About the obtained coloring composition for color filters, it evaluated according to the following procedure. The evaluation results are shown in Table 2.

Evaluation of development resistance The obtained color filter coloring composition was applied onto the surface of a glass substrate using a spin coater, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to obtain a film thickness of 2.0 μm. The coating film was formed. Then, after cooling the substrate to room temperature, the coating film on the substrate, using a high-pressure mercury lamp, through a photomask having a plurality of different slit size in the range of width 5 to 50 [mu] m, of 400 J / m ² It exposed with the exposure amount. Then, shower development was performed by discharging a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. to the coating film on the substrate at a development pressure of 1.5 kgf / cm ² (nozzle diameter 1 mm) for 60 seconds. Thereafter, it was washed with ultrapure water and air-dried. Further, post-baking was performed in a clean oven at 220 ° C. for 30 minutes to form a pixel array in which red stripe pixel patterns were arranged on the substrate. At this time, the substrate was observed with an optical microscope, and whether or not the edge of the pixel pattern was recognized was evaluated in the following three stages.

Evaluation criteria ○: No chipping is observed.
Δ: Some chipping is observed.
X: Many cracks are recognized.

  At this time, the minimum value of the width of the pixel pattern that remained without peeling off the entire pattern was evaluated as the width (μm) of the minimum pattern that can be formed.

Evaluation of pattern shape The obtained color filter coloring composition was applied on the surface of a glass substrate using a spin coater, and then pre-baked on a 90 ° C. hot plate for 4 minutes to obtain a film thickness of 2.0 μm. A coating film was formed. Subsequently, after cooling this board | substrate to room temperature, the coating film on a board | substrate was exposed by the exposure amount of 400 J / m < ² > through the photomask using the high pressure mercury lamp. Then, shower development was performed by discharging a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. to the coating film on the substrate at a development pressure of 1.5 kgf / cm ² (nozzle diameter 1 mm) for 60 seconds. Thereafter, it was washed with ultrapure water and air-dried. Further, post-baking was performed at 220 ° C. for 30 minutes to form a 90 μm stripe pixel pattern on the substrate. Subsequently, the cross-sectional shape of the obtained pixel pattern was observed with a scanning electron microscope, and the taper angle 1 shown in FIG. 1 was measured. If the taper angle is 80 degrees or more, the transparent electrode film may be disconnected. The ideal taper angle is 30 to 70 degrees.

Examples 2-6 and Comparative Examples 1-3
The types and amounts used of the colorant dispersion, (B) polymer, (C) polyfunctional monomer, (D) binder resin, (E) photopolymerization initiator and solvent are as shown in Table 2. Otherwise, a color filter coloring composition was prepared in the same manner as in Example 1, and the development resistance and pattern shape were evaluated. The evaluation results are shown in Table 2.

Each component described in Table 2 is as follows.
C-1: M-402 manufactured by Toagosei Co., Ltd. (mainly dipentaerythritol hexaacrylate)
C-2: M-450 manufactured by Toagosei Co., Ltd. (pentaerythritol tetraacrylate is the main component)
E-1: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals)
E-2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name IRGACURE OX02, Ciba Specialty・ Made by Chemicals
EEP: ethyl 3-ethoxypropionate MBA: 3-methoxybutyl acetate

1 taper angle 2 pixel pattern 3 substrate 10 pixels

Claims (7)

The following components (A) to (B);
(A) a colorant,
(B) (b1) and characterized in that it contains a copolymer having repeating units represented by the following formula (1), and (b2) repeating units derived from ethylenically unsaturated monomer having an acidic group A coloring composition for a color filter.

(In Formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a substituted or unsubstituted divalent hydrocarbon group, and n is a positive integer. )   The colored composition for a color filter according to claim 1, wherein (b2) is at least one selected from the group consisting of a vinyl ether having a carboxyl group and an aromatic vinyl compound having a carboxyl group.   The coloring composition for a color filter according to claim 1 or 2, further comprising (C) a polyfunctional monomer.   The coloring composition for a color filter according to any one of claims 1 to 3, further comprising (D) a binder resin (excluding the component (B)).   Furthermore, (E) The coloring composition for color filters of any one of Claims 1-4 containing a photoinitiator.   The color filter which has a colored layer formed using the coloring composition for color filters of any one of Claims 1-5.   A color liquid crystal display device comprising the color filter according to claim 6.