JP2014240935A - Colored composition for color filter, color filter and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored composition for a color filter, from which a green colored layer having good chromaticity characteristics can be formed.SOLUTION: The colored composition for a color filter comprises (A) a colorant comprising a specific compound, (B) a binder resin, and (C) a polymerizable compound. The specific compound is Si-rhodamine, Ge-rhodamine or a compound having a cation expressed by formula (1) shown below. In formula (1), Z represents a silicon atom or a germanium atom; R1 and Reach independently represent a hydrogen atom or an organic group, where Rand Rmay be bonded to each other to form a cyclic structure together with a silicon atom or a germanium atom bonded to these groups, and the cyclic structure may have a substituent; Rrepresents a hydrogen atom or an organic group; and Ar each independently represents a substituted or unsubstituted arylene group.

Description

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

  In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. A method of obtaining pixels of each color by irradiation (hereinafter referred to as “exposure”) and development is known (for example, see Patent Documents 1 and 2). In addition, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (for example, see Patent Document 4).

  In recent years, there has been a strong demand for higher contrast of liquid crystal display elements and higher definition of solid-state imaging elements. In order to realize these, application of dyes as colorants has been studied, and triarylmethane dyes, xanthene dyes, and the like have been studied as dyes.

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

  However, at present, sufficient studies have not been made on a coloring composition that can be used to form a green colored layer having excellent chromaticity characteristics. Therefore, there is a strong demand for the development of a green coloring composition suitable for producing a color filter having good chromaticity characteristics.

  Therefore, the subject of this invention is providing the coloring composition for color filters which can form the green coloring layer which has a favorable chromaticity characteristic. Another object of the present invention is to provide a color filter provided with a colored layer containing a specific colorant, and a display element including the 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 colorant, and have completed the present invention.

  That is, the present invention includes (A) a colorant containing at least one selected from Si-rhodamine and Ge-rhodamine, (B) a binder resin, and (C) a polymerizable compound. A coloring composition is provided.

  The present invention also includes (A) a colorant containing a compound having a cation represented by the following formula (1), (B) a binder resin, and (C) a polymerizable compound. A coloring composition is provided.

[In Formula (1),
Z represents a silicon atom or a germanium atom.
R ¹ and R ² each independently represent a hydrogen atom or an organic group. However, R ¹ and R ² may be bonded to each other to form a ring structure together with the silicon atom or germanium atom to which they are bonded, and the ring structure may have a substituent.
R ³ represents a hydrogen atom or an organic group.
Ar independently represents a substituted or unsubstituted arylene group. ]

  In addition, the present invention includes a color filter including a colored layer including at least one selected from Si-rhodamine and Ge-rhodamine, and a colored layer including a compound having a cation represented by the above formula (1). And a display element having the color filter. Here, the “colored layer” means each color pixel, black matrix, black spacer, etc. used in the color filter.

  If the coloring composition for color filters of this invention is used, the green colored layer which is excellent in chromaticity characteristic can be formed. Therefore, the color composition for color filter of the present invention includes various color filters including a color filter for display elements, a color filter for color separation of solid-state imaging elements, a color filter for organic EL display elements, and a color filter for electronic paper. Can be used very suitably.

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

-(A) Colorant-
The coloring composition of this invention contains the compound which has a cation represented by (A) at least 1 sort (s) chosen from Si-rhodamine and Ge-rhodamine as a coloring agent, or following formula (1). In the present invention, “Si-rhodamine” and “Ge-rhodamine” mean a compound having a structure in which an oxygen atom constituting rhodamine is substituted with a silicon atom or a germanium atom. Hereinafter, Si-rhodamine, Ge-rhodamine and compounds having a cation represented by the formula (1) are collectively referred to as “present colorant”.

[In Formula (1),
Z represents a silicon atom or a germanium atom.
R ¹ and R ² each independently represent a hydrogen atom or an organic group. However, R ¹ and R ² may be bonded to each other to form a ring structure together with the silicon atom or germanium atom to which they are bonded, and the ring structure may have a substituent.
R ³ represents a hydrogen atom or an organic group.
Ar independently represents a substituted or unsubstituted arylene group. ]

Examples of the organic group for R ¹ and R ² include a substituted or unsubstituted alkyl group.
Examples of the organic group for R ³ include a substituted or unsubstituted aryl group.
Examples of the arylene group in Ar include a phenylene group.

  Typical examples of the cation represented by the formula (1) include a cation represented by the following formula.

Next, the anion part of the compound having a cation represented by the formula (1) will be described.
Although it does not specifically limit as this anion, For example, a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, a metide anion etc. can be mentioned. As the anion, either a monovalent anion or a divalent or higher anion can be suitably used.

  Examples of the halogen ion include fluoride ion, chloride ion, bromide ion, and iodide ion.

As the boron anion, for example, BF ₄ ^-, etc. of the inorganic boron anion;
(CF ₃ ) ₄ B ⁻ , (CF ₃ ) ₃ BF ⁻ , (CF ₃ ) ₂ BF ₂ ⁻ , (CF ₃ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₄ B ⁻ , (C ₂ F ₅ ) ₃ BF ⁻ , (C ₂ F ₅ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₂ BF ₂ ⁻ , (CF ₃ ) (C ₂ F ₅ ) ₂ BF ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , [( CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ , (CF ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ F ₅ ) ₂ BF ₂ ⁻ , (C ₆ F ₅ ) BF ₃ ⁻ , (C ₆ H ₃ F ₂ ) ₄ B ⁻ , B (CN) ₄ ⁻ , B (CN) F ₃ ⁻ , B (CN) ₂ F ₂ ⁻ , B (CN) ₃ F ⁻ , (CF ₃ ) ₃ B (CN) ⁻ , (CF ₃ ) ₂ B (CN) ₂ ⁻ , (C ₂ F ₅ ) ₃ B (CN) ⁻ , (C ₂ F ₅ ) ₂ B (CN) ₂ ⁻ , (nC ₃ F ₇ ) ₃ B ^{(CN) -, (n-} C 4 F 9) 3 B (CN) -, (n-C 4 F 9) 2 B (CN) 2 -, (n-C 6 F 13) 3 B (CN) - , (CHF ₂ ) ₃ B (CN) ⁻ , (CHF ₂ ) ₂ B (CN) ₂ ⁻ , (CH ₂ CF ₃ ) ₃ B (CN) ⁻ , (CH ₂ CF ₃ ) ₂ B (CN) ₂ ⁻ , (CH ₂ C ₂ F ₅ ) ₃ B (CN) ⁻ , (CH ₂ C ₂ F ₅ ) ₂ B (CN) ₂ ⁻ , (CH ₂ CH ₂ C ₃ F ₇ ) ₂ B (CN) ₂ ⁻ , (n-C _{3 F 7 CH 2) 2 B (} CN) 2 -, (C 6 H 5) 3 B (CN) -, tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl ) Borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ In addition to organic boron anions such as lith (pentafluorophenyl), phenyl] borate and tridecahydride-7,8-dicarboundeborate, JP-A-10-195119, JP-A-2010-094807, JP-A-2006 Examples thereof include boron anions described in JP-A No. 243594, JP-A No. 2002-341533, JP-A No. 08-015521, and the like.

Examples of phosphate anions include inorganic phosphate anions such as HPO ₄ ²⁻ , PO ₄ ³⁻ , and PF ₆ ⁻ ;
(C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CF] ₃ PF ₃ , (n− C ₃ F ₇ ) ₂ PF ₄ ⁻ , (n-C ₃ F ₇ ) ₃ PF ₃ ⁻ , (n-C ₄ F ₉ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ⁻ , (n-C ₄ F ₉ ) ₂ PF ₄ ⁻ , (n-C ₄ F ₉ ) ₃ PF ₃ ⁻ , (C ₂ F ₄ H) (CF ₃ ) ₂ PF ₃ ⁻ , (C ₂ F ₃ H ₂ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ⁻ , octyl Examples thereof include organic phosphate anions such as phosphate anion, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, and nonylphenyl phosphate anion.

Examples of the carboxylate anion include CH ₃ COO ⁻ , C ₂ H ₅ COO ⁻ , C ₆ H ₅ COO ^{−, and the} like, as well as carboxyl described in JP2009-265641A and JP2008-096680A. Mention may be made of acid anions.

Examples of sulfate anions include sulfate anions and sulfite anions.
Examples of the organic sulfonate anion include alkyl sulfonate anions such as methane sulfonic acid, ethane sulfonic acid, trifluoromethane sulfonic acid, and nonafluorobutane sulfonic acid;
In addition to arylsulfonic acid anions such as benzenesulfonic acid, p-toluenesulfonic acid, p-trifluoromethylsulfonic acid, pentafluorobenzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid ion, 2- (meth) acryloyloxy-1 , 1,2,2-tetrafluoroethanesulfonic acid, 2- (4-vinylphenyloxy) -1,1,2,2-tetrafluoroethanesulfonic acid, International Publication No. 2011/037195, Patent No. 3736221 Examples thereof include organic sulfonate anions described in the specification, Japanese Patent Application Laid-Open No. 2011-007847, Japanese Patent Application Laid-Open No. 2011-070172.

Examples of the nitrogen anion include [(CN) ₂ N] ⁻ , [(FSO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ SO ₂ )] ⁻ , and [(CF ₃ SO ₂ ). ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ CF ₂ SO ₂ )] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₂ CFSO ₂ }] ⁻ , [(FSO ₂ ) N (CF ₃ CF ^{_{2 CF 2 SO 2)] -}} , [(FSO 2) N (CF 3 CF 2 CF 2 CF 2 SO 2)] -, [(FSO 2) N {(CF 3) 2 CFCF 2 SO 2}] -, In addition to [(FSO ₂ ) N {CF ₃ CF ₂ (CF ₃ ) CFSO ₂ }] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₃ CSO ₂ }] ^{− and the} like, JP 2011-133844 A, Nitrogen anions described in JP 2011-116803 A and JP 2010-090341 A can be exemplified.

Examples of the methide anion include (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ CF ₂ SO ₂ ) ₃ C ⁻ , [(CF ₃ ) ₂ CFSO ₂ ] ₃ C ⁻ , and (CF ₃ CF ₂ CF ₂ SO ₂ ) ₃ C ⁻ , (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ ) ₃ C ⁻ , [(CF ₃ ) ₂ CFCF ₂ SO ₂ ] ₃ C ⁻ , [CF ₃ CF ₂ (CF ₃ ) CFSO ₂ ] ₃ C ⁻ , [(CF ₃ ) ₃ CSO ₂ ] ₃ C ⁻ , (FSO ₂ ) ₃ C ^{— and the} like, JP2011-145540 A, US Pat. No. 5,554,664, JP2005-309408 A Examples thereof include the methide anion described in JP-A No. 2004-085657, JP-A-2010-505787, and the like.
Examples of the divalent or higher anion include 3,3′-dithiobis (1-propanesulfonic acid), benzenedisulfonic acid, 1,1,2,2,3,3-hexafluoropropane-1,3-disulfone. Mention may be made of polyvalent sulfonate anions such as acids.

  The coloring agent may be a lake pigment of Si-rhodamine, Ge-rhodamine, or a compound having a cation represented by the above formula (1). Lake pigment refers to a soluble dye made into an insoluble pigment by a precipitating agent. Examples of the precipitating agent include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, and katanol. , Tamol, Complex heteropolyacids (phosphotungstic acid, phosphomolybdic acid, phosphotungsten / molybdic acid, silicotungsten molybdic acid, silicotungstic acid, silicomolybdic acid, phosphotungsten molybdate, phosphotungsten) Acid, phosphomolybdic acid) and the like. The colorant used as a lake pigment can be produced, for example, by lake-forming a compound having a cation represented by the above formula (1) with a precipitant.

  The coloring composition of this invention can also contain another coloring agent with this coloring agent as a coloring agent. Other colorants are not particularly limited, and colors and materials can be appropriately selected according to the application.

  Examples of other colorants include pigments, dyes, and natural pigments, and other colorants can be used alone or in combination of two or more. Among them, an organic pigment is preferable as the pigment and an organic dye is preferable as the dye from the viewpoint of obtaining a pixel having high brightness, contrast, and color purity.

  Preferable specific examples of the organic pigment include C.I. as a color index (CI) name. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment red 264, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 80, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 211, C.I. I. Pigment yellow 215, C.I. I. Pigment orange 38, C.I. I. And CI Pigment Violet 23. Preferable specific examples of the inorganic pigment include carbon black and titanium black.

  As the pigment, a lake pigment is also preferable, and specific examples include triarylmethane dyes and xanthene dyes which are insoluble pigments with the same precipitant as described above. Triarylmethane-based lake pigments are disclosed in, for example, Japanese Patent Application Laid-Open No. 2011-186043. Xanthene-based lake pigments are disclosed in, for example, JP 2010-191304 A.

The dyes are preferably xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, and the like. More specifically, JP 2010-32999 A, JP 2010-254964 A, JP 2011-138094 A, International Publication No. 10/123071, Pamphlet 2011-116803, JP 2011. Organic dyes described in JP-A No. 117995, JP-A No. 2011-133844, JP-A No. 2011-174987, and the like.
In the present invention, the pigment and the dye can be used alone or in admixture of two or more.

  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, the pigment surface may be used by modifying the particle surface with a resin if desired. Further, the organic pigment can be used 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.

  In the present invention, when a pigment is used as a colorant, it 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 dispersants are commercially available. For example, acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK Corporation (BYK)) Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (Lubrizol) As a polyethylenimine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc. As a polyester-based dispersant, Azisper PB8 1, Adisper PB822, Adisper PB880, Adisper PB881 (or more, Ajinomoto Fine-Techno Co., Ltd.), and the like, can be mentioned, respectively.

  Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, sulfonic acid derivatives of quinophthalone, and the like.

  The colored composition of the present invention can be preferably used for forming a green pixel. In this case, it is preferable to use the present colorant in combination with another colorant. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 211, and C.I. I. At least one selected from the group consisting of CI Pigment Yellow 215 is preferable. Moreover, it is preferable that it is 10-95 mass% in all the coloring agents, and, as for the content rate of this coloring agent, it is preferable that it is 30-90 mass%, and also 50-80 mass%.

  (A) The content ratio of the colorant is usually 5 to 70% by mass in the solid content of the coloring composition, preferably from the point of forming a pixel having high luminance and excellent color purity, or a black matrix having excellent light shielding properties. 5 to 60% by mass.

-(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 also referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as “unsaturated monomer (b2)”). .

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, 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 (degree of polymerization 2 -10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 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 Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) 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 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

  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. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence 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 weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably Is 3,000 to 50,000. By setting it as such an aspect, the remaining-film rate of a film, a pattern shape, heat resistance, an electrical property, and the resolution can be improved further, and generation | occurrence | production of the dry foreign material at the time of application | coating can be suppressed at a high level.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3. .0. In addition, Mn here says the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

  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. By setting it as such an aspect, alkali developability, the storage stability of a coloring composition, and chromaticity characteristic can be improved further.

-(C) Polymerizable compound-
In the present invention, the polymerizable compound refers to 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 polymerizable compound 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 polyfunctional (meta) modified with caprolactone. ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-functional (meth) acrylate and polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group obtained by making a product 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; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that. 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. The alkylene oxide-modified polyfunctional (meth) acrylate is at least one selected from bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from modified isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide Pen modified with at least one selected from pentaerythritol tri (meth) acrylate, ethylene oxide and propylene oxide. Dipentaerythritol modified with at least one selected from dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from taerythritol tetra (meth) acrylate, ethylene oxide and propylene oxide Examples include 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. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. 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.

Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethanes (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 this invention, (C) polymeric compound can be used individually or in mixture of 2 or more types.

  The content of the polymerizable compound (C) in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, and further 100 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. preferable. By setting it as such an aspect, sclerosis | hardenability and alkali developability can be improved further and generation | occurrence | production of a ground stain, a film | membrane residue, etc. on the board | substrate of a non-exposed part or a light shielding layer can be suppressed at a high level.

-Photopolymerization initiator-
The coloring composition of the present invention can contain a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.

  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. As commercially available O-acyloxime compounds, NCI-831, NCI-930 (manufactured by ADEKA Corporation) and the like can also be used.

  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) polymeric compounds, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. By setting it as such an aspect, sclerosis | hardenability and a film characteristic can be improved further.

-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.

Among such solvents, 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;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

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;
Alkoxycarboxylic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate ;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

  Of these solvents, (poly) alkylene glycol monoalkyl ethers, lactic acid alkyl esters, (poly) alkylene glycol monoalkyl ether acetates, and other ethers from the viewpoints of solubility, pigment dispersibility, coatability, etc. , Ketones, diacetates, alkoxycarboxylic acid esters, and other esters are preferred, especially 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-hept Non, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 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 and the like are preferable.

  In this invention, a solvent can be used individually or in mixture of 2 or more types. When used in combination, it is preferable to use a mixture of at least (poly) alkylene glycol monoalkyl ether acetates and ketones or (poly) alkylene glycol monoalkyl ethers.

  Although content of a solvent is not specifically limited, The quantity from which the total density | concentration of each component except the solvent of the coloring composition becomes 5-50 mass% is preferable, and the quantity used as 10-40 mass% More preferred. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability and the coloring composition with favorable coating property and stability can be obtained.

-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- Antioxidant of t-butylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) ) -5-chlorobenzotriazole, UV absorbers such as 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- Residue improvers such as mino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono [2- (meth) acryloyloxyethyl] And developability improvers such as mono [2- (meth) acryloyloxyethyl] phthalate and ω-carboxypolycaprolactone mono (meth) acrylate.

  The coloring composition of the present invention can be prepared by an appropriate method, and examples of the preparation method include methods disclosed in JP 2008-58642 A, JP 2010-132874 A, and the like. be able to. When both a dye and a pigment are used as the colorant, as disclosed in JP 2010-132874 A, after passing the dye solution through the first filter, the dye solution that has passed through the first filter is used. Alternatively, it is possible to employ a method of preparing by mixing with a separately prepared pigment dispersion and passing the obtained colored composition through a second filter. In addition, the dye, the above components (B) to (C), and other components to be used as necessary are dissolved in a solvent, and the obtained solution is passed through the first filter, and then the first filter is used. You may employ | adopt the method prepared by mixing the solution which passed through with the pigment dispersion liquid prepared separately, and passing the obtained coloring composition through a 2nd filter. Also, after passing the dye solution through the first filter, the dye solution that has passed through the first filter, the above components (B) to (C), and other components used as necessary are mixed and dissolved. The obtained solution is passed through a second filter, and the solution that has passed through the second filter is further mixed with a separately prepared pigment dispersion, and the resulting colored composition is passed through a third filter. The method of doing can also be employ | adopted.

Color filter and production method thereof The color filter of the present invention comprises a colored layer containing the present colorant.

  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 green liquid composition of the radiation-sensitive colored composition of the present invention 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 green pixel patterns are arranged in a predetermined arrangement.

  Subsequently, each radiation-sensitive colored composition of red or blue is used, and the radiation-sensitive colored composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above, so that the red 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 photolithographic method. It can also be formed in the same manner as in the case of forming the above-mentioned pixel using a sexually colored composition.

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 applying the radiation-sensitive coloring composition 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 μm, preferably 1.2 to 5 μm, as the film thickness after drying.

  Examples of the radiation light source used when forming at least one selected from the pixel and the black matrix include, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure. Examples thereof include a lamp light source such as a mercury lamp, and a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably radiation in the range of 190 to 450 nm.

Exposure of the radiation is generally preferred 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-. An aqueous solution of undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene or the like is preferable.

For example, 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 μm, preferably 1.0 to 3 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, a green liquid composition of the thermosetting coloring composition of the present invention is discharged into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a green pixel pattern.

  Subsequently, red or blue thermosetting coloring compositions are used to sequentially form a red pixel pattern and a blue pixel pattern 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 pixels of each color is not limited to the above.

In addition, since the partition plays not only a light shielding function but also a function for preventing the color mixing of the thermosetting coloring compositions discharged in the respective sections, it is compared with the black matrix used in the first method described above. The film thickness is 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. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming such a black spacer.
Since the color filter of the present invention thus obtained has extremely high luminance and color purity, it is useful for color liquid crystal display elements, color imaging tube elements, color sensors, organic EL display elements, electronic paper, etc. It is useful as a color filter for liquid crystal display elements and a color filter for organic EL display elements. When the color filter of the present invention is used for a color liquid crystal display element, it is particularly preferable to use it as a color filter for a white light emitting diode light source liquid crystal display device.

Display element The display element of the present invention comprises the color filter of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.
The color liquid crystal display element provided with the color filter of the present invention may be a transmissive type or a reflective type, and can take 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 an ITO (indium oxide doped with tin) electrode or IZO (acid value indium and zinc oxide) It is also possible to adopt a structure in which the substrate on which the electrode is formed is opposed to the liquid crystal layer. 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 device including the color filter 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 by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

  The color liquid crystal display device having the color filter of the present invention includes a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, an IPS (In-Plane Switching) type, a VA (Vertical Alignment) type, and an OCB (Optical Optical). An appropriate liquid crystal mode such as a birefringence type can be applied.

Moreover, the organic EL display element provided with the color filter of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.
In addition, the electronic paper including the color filter of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-2007-41169.

  Among these display elements, the display element of the present invention is particularly preferably applied as a display element having a backlight unit using an organic EL display element or a white LED as a light source.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
<Synthesis of this coloring agent>

Synthesis example 1
The following compound A1 was synthesized with reference to Journal Of The American Chemical Society, 2012, 134, 5029-5031. This compound is defined as a colorant (A-1).

<Synthesis of binder resin>
Synthesis example 2
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 23 parts by mass, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) The solution was added dropwise over a period of time and polymerized for 2 hours while maintaining this temperature. 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% by mass). The obtained binder resin had Mw of 12,200 and Mn of 6,500. This binder resin is referred to as “binder resin (B1)”.

<Preparation of colorant 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 Then, a green pigment dispersion (a-1) was prepared by treatment with a bead mill.

Preparation Example 2
In Preparation Example 1, C.I. I. In place of Pigment Green 58, C.I. I. A yellow pigment dispersion (a-2) was prepared in the same manner as in Preparation Example 1, except that CI Pigment Yellow 150 was used.

Preparation Example 3
15 parts by mass of the colorant (A-1) synthesized in Synthesis Example 1 and 85 parts by mass of cyclohexanone were mixed to prepare a dye solution (A-1).

<Preparation and evaluation of coloring composition>
Example 1
Preparation of coloring composition 27.2 parts by mass of dye solution (A-1) and 13.6 parts by mass of pigment dispersion (a-2) as colorants, 21.6 parts by mass of binder resin (B1) solution as binder resin, M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Toagosei Co., Ltd. as a polymerizable compound, and 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, trade name IRGACURE369) 1.7 parts by mass and NCI-930 (manufactured by ADEKA Corporation) 0.1 part by mass, as a surfactant Megafac F-554 (manufactured by DIC Corporation) 0.05 parts by mass and cyclohexanone as a solvent Te was prepared having a solid content concentration of 20 mass% of the coloring composition.

Evaluation of Chromaticity Characteristics The obtained colored composition 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 200 ° C. for 30 minutes to form a green cured film for evaluation.
Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate values (x, y) and stimuli in the CIE color system with a C light source and a 2-degree field of view for the three green cured films obtained The value (Y) was measured. From the measurement result, the stimulus value (Y) when the chromaticity coordinate value y = 0.666 was obtained.

Comparative Example 1
In Example 1, a green cured film was formed in the same manner as in Example 1 except that the pigment dispersion (a-1) was used instead of the dye solution (A-1). Next, the chromaticity characteristics were evaluated in the same manner as in Example 1. As a result, Example 1 showed a higher stimulation value (Y) than Comparative Example 1. It can be said that the green pixel containing the present colorant has higher luminance than the green pixel containing the conventional colorant.

Claims (5)

  (A) A coloring composition for a color filter comprising a coloring agent containing at least one selected from Si-rhodamine and Ge-rhodamine, (B) a binder resin, and (C) a polymerizable compound. (A) A coloring composition for a color filter comprising a colorant comprising a compound having a cation represented by the following formula (1), (B) a binder resin, and (C) a polymerizable compound.

[In Formula (1),
Z represents a silicon atom or a germanium atom.
R ¹ and R ² each independently represent a hydrogen atom or an organic group. However, R ¹ and R ² may be bonded to each other to form a ring structure together with the silicon atom or germanium atom to which they are bonded, and the ring structure may have a substituent.
R ³ represents a hydrogen atom or an organic group.
Ar independently represents a substituted or unsubstituted arylene group. ]   A color filter comprising a colored layer containing at least one selected from Si-rhodamine and Ge-rhodamine. The color filter provided with the colored layer containing the compound which has the cation represented by following formula (1).

[In Formula (1),
Z represents a silicon atom or a germanium atom.
R ¹ and R ² each independently represent a hydrogen atom or an organic group. However, R ¹ and R ² may be bonded to each other to form a ring structure together with the silicon atom or germanium atom to which they are bonded, and the ring structure may have a substituent.
R ³ represents a hydrogen atom or an organic group.
Ar independently represents a substituted or unsubstituted arylene group. ]   A display device comprising the color filter according to claim 3.