JP2011180169A - Coloring composition for color filter, color filter, and color liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring composition for a color filter, achieving high luminance and high color purity exceeding those of a pigment-dispersed coloring composition. <P>SOLUTION: The coloring composition for the color filter contains (A) a colorant, (B) a binder resin and (C) a multifunctional monomer, wherein a compound represented by formula (I) is contained as (A) the colorant. In formula (I), R<SP>1</SP>to R<SP>3</SP>each independently denotes a hydrogen atom, a substituted or non-substituted alkyl group or a substituted or non-substituted cycloalkyl group. <P>COPYRIGHT: (C)2011,JPO&INPIT

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 used for forming a colored layer useful for a color filter to be used, a color filter provided with a colored layer formed using the colored composition, and a color liquid crystal display element including the color filter.

  In producing a color filter using a colored radiation-sensitive composition, a colored radiation-sensitive composition in which an organic pigment is dispersed is applied on a substrate or a substrate on which a light-shielding layer having a desired pattern is formed in advance. There is known a method (Patent Documents 1 and 2) of obtaining a pixel of each color by irradiating a dry coating film with a desired pattern shape after drying (hereinafter referred to as “exposure”) and developing. . A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an ink jet method using a colored resin composition in which an organic pigment is dispersed (Patent Document 4) is also known.

  By the way, color liquid crystal display elements such as televisions and monitors are required to have high brightness and an expanded color reproduction area. Therefore, the color filters constituting the color liquid crystal display elements have recently been increasing in light transmittance. What has high color purity is required. In response to this demand, use of a new pigment such as polyhalogenated zinc phthalocyanine has been proposed (Patent Document 5). However, the conventional pigment-dispersed coloring composition has a limit in increasing luminance and color purity.

  Against the background as described above, there is a strong demand for the development of a color filter coloring composition that can achieve higher brightness and higher color purity than conventional pigment-dispersed coloring compositions.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2007-284589 A

The subject of this invention is providing the coloring composition for color filters which can implement | achieve the high brightness and high color purity exceeding a pigment dispersion type coloring composition.
Furthermore, the subject 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 this situation, the present inventors have conducted intensive research and found that the above-mentioned problems can be solved by using a specific yellow dye as a colorant, thereby completing the present invention.

  That is, the present invention is a color filter coloring composition containing (A) a colorant, (B) a binder resin, and (C) a polyfunctional monomer, and (A) the following formula ( The present invention provides a coloring composition for a color filter comprising a compound represented by I) (hereinafter referred to as “yellow dye (I)”).

(In Formula (I), R ^{1 to} R ³ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group.)

  The present invention provides a color filter comprising a colored layer containing a yellow dye (I) and a red pigment or a green pigment, 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.

If the coloring composition of this invention is used, the color filter which has each color pixel with very high brightness | luminance and color purity can be obtained.
Therefore, the colored composition of the present invention has various colors 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 producing a filter.

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

-(A) Colorant-
The colored composition of the present invention is characterized by containing a yellow dye (I) as a colorant (A). By using the yellow dye (I), a pixel with extremely high luminance and color purity can be formed.

In R ^{1 to} R ³ of the above formula (I), the alkyl group is, for example, an alkyl group having 1 to 12 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and pentyl. Group, hexyl group, octyl group, nonyl group, dodecyl group and the like.

In R ^{1 to} R ³ of the above formula (I), the cycloalkyl group is, for example, a cycloalkyl group having 5 to 7 carbon atoms, and specific examples thereof include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Etc.

The alkyl group and cycloalkyl group may have a substituent, and examples of the substituent include an alkoxy group, a halogen, a cyano group, an alkylsulfanyl group, an aryl group, and an arylsulfanyl group. .

In the present invention, R ¹ is preferably a cycloalkyl group having 5 to 7 carbon atoms, and particularly preferably a cyclohexyl group. R ² is preferably a hydrogen atom. Moreover, as R < ³ >, a C1-C12 alkyl group is preferable, a C1-C6 alkyl group is more preferable, and an ethyl group is especially preferable. Preferable specific examples of the yellow dye (I) include compounds represented by the following formula.

  The compound represented by the above formula (Ib) is C.I. I. Solvent Yellow 179, which is commercially available from LANXESS, for example, under the trade name MACROLEX (registered trademark) Yellow 6G Gran.

  It is preferable that the coloring composition of this invention contains a red pigment or a green pigment with a yellow dye (I) as a coloring agent. The red pigment is not particularly limited. And pyrantrone. More specifically, compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), that is, the color index (CI) name as shown below is attached. You can list what you have.

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.

Among these red pigments, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment red 242 and C.I. I. It is preferable to contain at least one selected from the group consisting of CI Pigment Red 254. I. Pigment red 177 and C.I. I. It is preferable to contain at least one selected from the group consisting of CI Pigment Red 254.
In this invention, a red pigment can be used individually or in mixture of 2 or more types.

The green pigment is not particularly limited, and examples thereof include halogenated zinc phthalocyanine, halogenated copper phthalocyanine, halogenated magnesium phthalocyanine, halogenated aluminum phthalocyanine, halogenated magnesium phthalocyanine, halogenated titanium phthalocyanine, and halogen. Examples thereof include halogenated metal phthalocyanines such as vanadium halide phthalocyanine, halogenated manganese phthalocyanine, halogenated iron phthalocyanine, halogenated cobalt phthalocyanine, halogenated nickel phthalocyanine, halogenated tin phthalocyanine, and halogenated germanium phthalocyanine. In these halogenated metal phthalocyanines, the substituent halogen is preferably chlorine, bromine or both.

Among these green pigments, when forming a green pixel, it is preferable to contain at least one selected from the group consisting of a halogenated zinc phthalocyanine and a halogenated copper phthalocyanine. As the halogenated zinc phthalocyanine, brominated zinc phthalocyanine and brominated chlorinated zinc phthalocyanine are preferable. Brominated chlorinated zinc phthalocyanine is C.I. in the color index (CI) name. I. It is a pigment classified as Pigment Green 58, and preferably has a structure represented by the following formula (1).

(In Formula (1), X shows a hydrogen atom, a chlorine atom, or a bromine atom mutually independently, 10-15 pieces of all X are a bromine atom, and 1-6 are a chlorine atom. )

  Moreover, as a halogenated copper phthalocyanine, chlorinated copper phthalocyanine, brominated chlorinated copper phthalocyanine, and brominated copper phthalocyanine are preferable. Chlorinated copper phthalocyanine is C.I. in the color index (CI) name. I. Pigment Green 7 is a pigment, and brominated chlorinated copper phthalocyanine is C.I. in the color index (CI) name. I. Pigments classified as Pigment Green 36.

In the present invention, it is particularly preferable to contain brominated chlorinated zinc phthalocyanine as a green pigment.
In this invention, a green pigment can be used individually or in mixture of 2 or more types.

  The coloring composition of the present invention can further contain a colorant other than the yellow dye (I), the red pigment, and the green pigment. Other colorants are not particularly limited as long as they have colorability, and any of pigments, dyes and natural pigments can be used, but in the sense of obtaining pixels with high luminance and color purity. Are preferably organic pigments and organic dyes. Examples of the organic pigment include compounds having 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 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 brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

  Examples of the organic dye include compounds having the following color index (CI) names.

C. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Azo dyes such as Moldant Black 7;

C. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Anthraquinone dyes such as Disperse Blue 60;

C. I. Phthalocyanine dyes such as Pad Blue 5;
C. I. Basic Blue 3, C.I. I. Quinone imine dyes such as Basic Blue 9;
C. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Quinoline dyes such as Disperse Yellow 64;
C. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Nitro dyes such as Disperse Yellow 42.
In the present invention, other colorants can be used alone or in admixture of two or more.

In the present invention, in the coloring composition for forming a red pixel, the content of the yellow dye (I) is preferably 1 to 50% by mass, particularly preferably 5 to 40% by mass in the total colorant. The content ratio of the red pigment is preferably 50 to 99% by mass, particularly preferably 60 to 95% by mass.
Moreover, in the coloring composition for forming a green pixel, the content ratio of the yellow dye (I) is preferably 1 to 90% by mass, and particularly preferably 5 to 70% by mass in all the colorants. The green pigment content is preferably 10 to 99% by mass, particularly preferably 30 to 95% by mass.
By using each colorant in such a manner, a pixel having high luminance and color purity can be obtained.

In the present invention, the pigment can 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. Moreover, it is preferable to use a pigment by refining primary particles by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

  Moreover, the pigment surface 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.

  (A) The content of the colorant is usually 5 to 70% by mass in the solid content of the colored composition, preferably from the point of forming a pixel having excellent transparency and color purity, or a black matrix having excellent light shielding properties. 5 to 60% by mass. Here, solid content is components other than the solvent mentioned later.

  In the present invention, the pigment 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 pigments, 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”). (B1) ") and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as" unsaturated monomer (b2) ") are preferred.

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, p-vinylbenzoic acid and the like.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

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-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

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, G Serol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meta ) (Meth) acrylic acid esters such as acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
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.

  In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 1 to 60% by mass. More preferably, it is 20-50 mass%. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

  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 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, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, 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 binder resin in the present invention has a polystyrene-equivalent Mw measured by GPC (elution solvent: tetrahydrofuran) of usually 1,000 to 100,000, preferably 3,000 to 50,000. 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.

  In addition, the ratio (Mw / Mn) between the Mw of the binder resin in the present invention and the number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) measured by GPC (elution solvent: tetrahydrofuran) is preferably 1.0. It is -5.0, More preferably, it is 1.0-3.0.

  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-
In the present invention, the (C) polyfunctional monomer means a compound 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, 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. A 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 residue 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.

  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.

-(D) Photopolymerization initiator-
The coloring composition of the present invention can contain (D) a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator (D) used in the present invention has an activity capable of initiating polymerization of the polyfunctional monomer (C) by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. A compound that generates seeds.

  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.

-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 acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: 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-propanediol, 4-amino-1,2-butanedio It can be mentioned the residue improving agents such as Le.

-Solvent-
The colored composition of the present invention contains the above components (A) to (C) and other components that are optionally added, but is usually prepared as a liquid composition by blending a solvent.
As said solvent, (A)-(C) component which comprises a coloring composition, and another component are disperse | distributed or melt | dissolved, and it does not react with these components, but suitably has appropriate volatility. You can choose to use.

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, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl 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, dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, lactic acid Ethyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl lopionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate N-butyl butyrate, ethyl pyruvate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone 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 high boiling point solvents may be used alone or in combination of two or more.

  Although content of a solvent is not specifically limited, From viewpoints of the applicability | paintability of a coloring composition obtained, stability, etc., the total density | concentration of each component except the solvent of the said coloring composition is 5-50. An amount of mass% is preferred, and an amount of 10 to 40 mass% is particularly preferred.

Color filter and production method thereof The color filter of the present invention comprises a yellow dye (I) and a colored layer containing a red pigment or a green pigment, and is 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 the red radiation-sensitive composition of the present invention on this 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, each colored radiation-sensitive composition of green or blue is used, and each colored radiation-sensitive composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above, so that the green pixel array and blue 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.

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 colored radiation-sensitive composition is applied to the substrate, an appropriate coating 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 may be employed. In particular, it is 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 0.6 to 8.0 μm, preferably 1.2 to 5.0 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.

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.

The post-baking conditions are usually 120 to 280 ° C. and about 10 to 60 minutes. The post-baking temperature is preferably 120 to 240 ° C, particularly preferably 120 to 180 ° C, from the viewpoint of heat resistance of the yellow dye (I).
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, for example, after the red composition of the present invention is discharged by an ink jet apparatus into the formed partition wall, 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, using each colored composition of green or blue, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate 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 the 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 radiation sensitive 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.

  Since the color filter of the present invention thus obtained has extremely high luminance and color purity, it is extremely useful for color liquid crystal surface elements, color imaging tube elements, color sensors, organic EL display elements, 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.

The color liquid crystal display element of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light using a red LED, a green LED, and a blue LED having independent spectra, a white LED that obtains white light by mixing colors by combining the red LED, the green LED, and the blue LED, White LED that obtains white light by color mixing by combining blue LED, red LED and green phosphor, White LED that obtains white light by color mixing by combining blue LED, red light emitting phosphor and green light emitting phosphor, Blue LED and YAG system White LED that obtains white light by mixing phosphors, white LED that obtains white light by mixing blue LED, orange light emitting phosphor and green light emitting phosphor, UV LED, red light emitting phosphor, green light emitting phosphor and blue A white LED that obtains white light by mixing colors by combining light emitting phosphors can be exemplified.

The color liquid crystal display element of the present invention includes a TN (twisted nematic) type, a STN (super twisted nematic) type, an IPS (in-plane switching) type, a VA (vertical aligned type) type, and an OCB (optically conjugated type). An appropriate liquid crystal mode can be applied.

  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 pigment dispersion>
Preparation Example 1
As a coloring agent, C.I. I. 15 parts by mass of Pigment Green 58, 12.5 parts by mass of BYK-LPN21116 (produced by BYK) as a dispersant (solid content concentration = 40% by mass), and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent The pigment dispersion (A-1) was prepared by using a bead mill.

Preparation Example 2
As a coloring agent, C.I. I. In place of Pigment Green 58, C.I. I. A pigment dispersion (A-2) was prepared in the same manner as in Preparation Example 1, except that CI Pigment Green 36 was used.

Preparation Example 3
As a coloring agent, C.I. I. In place of Pigment Green 58, C.I. I. A pigment dispersion (A-3) was prepared in the same manner as in Preparation Example 1, except that CI Pigment Red 254 was used.

Preparation Example 4
As a coloring agent, C.I. I. In place of Pigment Green 58, C.I. I. A pigment dispersion (A-4) was prepared in the same manner as in Preparation Example 1, except that CI Pigment Red 177 was used.

Preparation Example 5
As a coloring agent, C.I. I. In place of Pigment Green 58, C.I. I. A pigment dispersion (A-5) was prepared in the same manner as in Preparation Example 1, except that CI Pigment Yellow 150 was used.

<Preparation of dye solution>
Preparation Example 6
As a coloring agent, C.I. I. 5 parts by mass of Solvent Yellow 179 (trade name MACROLEX (registered trademark) Yellow 6G Gran, manufactured by LANXESS) and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a dye solution (A-6).

<Synthesis of binder resin>
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate A mixed solution of 38 parts, 12 parts by mass of N-phenylmaleimide and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added dropwise over 1 hour, and this temperature was maintained and polymerization was conducted for 2 hours. . Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33%). The obtained binder resin was Mw = 12,200 and Mn = 6,500. This binder resin is referred to as “binder resin (D1)”.

<Preparation of coloring composition>
Preparation Example 7
84 parts by mass of pigment dispersion (A-1), 48 parts by mass of dye solution (A-6), 11.8 parts by mass of binder resin (D1) solution as binder resin, dipentaerythritol hexaacrylate as multifunctional monomer 12.2 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name: IRGACURE 369, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator 2 parts by mass and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a colored composition (CR1) having a solid content concentration of 20% by mass.

Preparation Example 8
80 parts by mass of pigment dispersion (A-2), 60 parts by mass of dye solution (A-6), 12.4 parts by mass of binder resin (D1) solution as binder resin, dipentaerythritol hexaacrylate as multifunctional monomer 12.2 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name: IRGACURE 369, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator 2 parts by mass and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a colored composition (CR2) having a solid content concentration of 20% by mass.

Preparation Example 9
31 parts by mass of pigment dispersion (A-3), 46 parts by mass of pigment dispersion (A-4), 69 parts by mass of dye solution (A-6), 26.7 parts by mass of binder resin (D1) solution as binder resin, 18.9 parts by mass of dipentaerythritol hexaacrylate as a polyfunctional monomer, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Ciba Special) as a photopolymerization initiator A colored composition (CR3) having a solid content concentration of 20 mass% was prepared by mixing 3.5 parts by mass of trade name IRGACURE 369) manufactured by Tea Chemicals Co., Ltd. and propylene glycol monomethyl ether acetate as a solvent.

Comparative Preparation Example 1
72 parts by mass of pigment dispersion (A-1), 28 parts by mass of pigment dispersion (A-5), 9.4 parts by mass of binder resin (D1) solution as binder resin, dipentaerythritol hexa as a polyfunctional monomer 12.2 parts by mass of acrylate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, trade name: IRGACURE 369) 2 as a photopolymerization initiator .2 parts by mass and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a colored composition (CR4) having a solid content concentration of 20% by mass.

Comparative Preparation Example 2
68 parts by mass of pigment dispersion (A-2), 32 parts by mass of pigment dispersion (A-5), 9.4 parts by mass of binder resin (D1) solution as binder resin, dipentaerythritol hexa as multifunctional monomer 12.2 parts by mass of acrylate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, trade name: IRGACURE 369) 2 as a photopolymerization initiator .2 parts by mass and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a colored composition (CR5) having a solid content concentration of 20% by mass.

Comparative Preparation Example 3
32 parts by mass of pigment dispersion (A-3), 47 parts by mass of pigment dispersion (A-4), 21 parts by mass of pigment dispersion (A-5), 23.0 parts by mass of binder resin (D1) solution as binder resin , 18.9 parts by mass of dipentaerythritol hexaacrylate as a polyfunctional monomer, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Ciba A colored composition (CR6) having a solid content of 20% by mass was prepared by mixing 3.5 parts by mass of trade name IRGACURE 369) manufactured by Specialty Chemicals and propylene glycol monomethyl ether acetate as a solvent.

Example 1
The coloring composition (CR1) was applied on a glass substrate using a spin coater, and then pre-baked on an 80 ° C. hot plate for 10 minutes to form a coating film. Three coating films having different film thicknesses were formed by the same operation while changing the rotation speed of the spin coater.
Next, after cooling these substrates to room temperature, a high-pressure mercury lamp is used and a radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without using a photomask at an exposure dose of 2,000 J / m ² . And exposed. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 180 ° C. for 30 minutes to form a cured film for evaluation.

  The three cured films obtained were measured for chromaticity coordinate values (x, y) in the CIE color system using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) with a C light source and a 2-degree field of view. . Moreover, the film thickness of the obtained cured film was measured using the alpha step IQ made from KLA-Tencor. From the measurement results, the chromaticity coordinate value x, the stimulus value (Y), and the film thickness at the chromaticity coordinate value y = 0.600 were obtained. The evaluation results are shown in Table 1. The larger the stimulus value (Y), the higher the light transmittance (brightness), and the thinner the film thickness, the higher the coloring power.

  Further, the substrate on which the cured film is formed is sandwiched between two deflecting plates, and the front side deflecting plate is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and the luminance meter LS-100 (Minolta) The maximum value and the minimum value of the transmitted light intensity were measured. And about each cured film, the value which remove | divided the maximum value by the minimum value was made into the contrast ratio. From the measurement result, the contrast ratio at the chromaticity coordinate value y = 0.600 was obtained. The evaluation results are shown in Table 1.

Examples 2-3 and Comparative Examples 1-3
Evaluation was performed in the same manner as in Example 1 except that the colored compositions (CR2) to (CR6) were used instead of the colored composition (CR1). The evaluation results are shown in Table 1. For the red colored compositions (CR3) and (CR6), the stimulation value (Y), film thickness and contrast ratio at the chromaticity coordinate value x = 0.650 are set to the green colored composition (CR2) and For (CR4) to (CR5), the stimulation value (Y), film thickness, and contrast ratio at the chromaticity coordinate value y = 0.600 were determined. The evaluation results are shown in Table 1.

In Table 1, “G58” means C.I. I. Pigment Green 58, “Y179” is C.I. I. Solvent Yellow 179, “G36” is C.I. I. Pigment Green 36, “R254” means C.I. I. Pigment Red 254, “R177” is C.I. I. Pigment Red 177, “Y150” is C.I. I. Each means CI Pigment Yellow 150.

Claims (11)

(A) Colorant, (B) Binder resin, and (C) Color composition for color filter containing polyfunctional monomer, (A) As a colorant, it represents with following formula (I) A coloring composition for a color filter comprising a compound.

(In Formula (I), R ^{1 to} R ³ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group.)   (A) The coloring composition for color filters of Claim 1 which contains a red pigment or a green pigment further as a coloring agent. The coloring composition for a color filter according to claim 1 or 2, wherein R ² in the formula (I) is a hydrogen atom. The coloring composition for a color filter according to claim 3, wherein R ¹ is a cyclohexyl group, R ² is a hydrogen atom, and R ³ is an ethyl group in the formula (I).   The coloring composition for color filters according to any one of claims 2 to 4, wherein the green pigment contains at least one selected from the group consisting of a halogenated zinc phthalocyanine and a halogenated copper phthalocyanine.   The coloring composition for color filters according to any one of claims 2 to 4, wherein the green pigment contains brominated chlorinated zinc phthalocyanine.   The green pigment is C.I. I. The coloring composition for a color filter according to any one of claims 2 to 4, which contains Pigment Green 58.   The red pigment is C.I. I. Pigment red 177 and C.I. I. The coloring composition for color filters according to any one of claims 2 to 4, comprising at least one selected from the group consisting of CI Pigment Red 254.   (D) The coloring composition for color filters of any one of Claims 1-8 which further contains a photoinitiator. A color filter comprising a colored layer containing a compound represented by the following formula (I) and a red pigment or a green pigment.

(In Formula (I), R ^{1 to} R ³ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group.)   A color liquid crystal display device comprising the color filter according to claim 10.