JP2016045236A - Coloring composition, colored cured film and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition which has high dissolubility in a dye and does not generate deposits or coating foreign matter.SOLUTION: A coloring composition comprises (A) a colorant, (B) a binder resin, (C) a polymerizable compound and (E) a solvent, where (A) colorant comprises a dye, and (E) solvent comprises glycol.SELECTED DRAWING: None

Description

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

  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 (so-called photolithography method, for example, see Patent Documents 1 and 2) in which pixels of three primary colors of red, green, and blue are arranged on a substrate by irradiation (hereinafter referred to as “exposure”) and development. Are known. 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).

Dyes have been widely studied as colorants used in the production of color filters. This is because when a dye is used as a colorant, the hue and brightness of a display image when an image is displayed can be increased due to the color purity of the dye itself and the vividness of the hue. . As such dyes, xanthene dyes, dipyrromethene dyes, quinophthalone dyes, triarylmethane dyes, quinoneimine dyes and the like are known (see, for example, Patent Documents 5 to 9).
In recent years, there has been a demand for further thinning of color filters, and in order to obtain a color filter having spectral characteristics equivalent to those of conventional ones even if the thickness is reduced, it has been studied to increase the relative amount of colorant in the pixel. Yes.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2010-032999 A JP 2014-066695 A JP 2011-122125 A International Publication No. 2011/152379 Pamphlet JP 2012-155183 A

However, many of the solvents usually used in the color composition for forming a color filter have poor dye solubility. In addition, in a color composition for forming a color filter that uses a dye and a pigment together, when a solvent having a high dye solubility is used, a precipitate or a coating film foreign matter that may be caused by aggregation of the pigment may be generated.
Therefore, the subject of this invention is providing the coloring composition which can form the colored cured film with high solubility of dye, and generation | occurrence | production of the deposit and the coating-film foreign material were suppressed. Furthermore, the subject of this invention is providing the display element which comprises the colored cured film formed using the said colored composition, and this colored cured film.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by using a specific solvent.

That is, the present invention is a colored composition containing (A) a colorant, (B) a binder resin, (C) a polymerizable compound and (E) a solvent,
(A) A coloring composition includes a dye, and (E) a coloring composition in which a solvent includes glycol is provided.

  Moreover, this invention provides the display element which comprises the colored cured film formed using the said coloring composition, and the said colored cured film. Here, the “colored cured film” means each color pixel, protective film, black matrix, spacer, insulating film, and the like used for a display element or a solid-state imaging element.

Since the coloring composition of this invention contains glycol as a solvent, the solubility to the solvent of dye is improved. Therefore, if the coloring composition for color filters of this invention is used, the colored cured film in which generation | occurrence | production of the deposit and the coating-film foreign material was suppressed can be formed.
Therefore, the colored composition of the present invention can be used very suitably for the production of solid-state imaging devices such as color liquid crystal display devices, organic EL display devices, display devices such as electronic paper, and CMOS image sensors.

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 the present invention contains a dye as the colorant (A).
The dye is not particularly limited, and colors and materials can be appropriately selected according to the use such as a color filter, and can be used alone or in combination of two or more. As the dye used in the present invention, for example, a known dye can be used in addition to a compound classified as Dye in the color index (CI; issued by The Society of Dyers and Colorists). .

  Such dyes include, for example, xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, and coumarin dyes in terms of the structure of the chromophore. , Pyrazolone dyes, quinoline dyes, nitro dyes, quinoneimine dyes, phthalocyanine dyes, and the like.

Examples of xanthene dyes include compounds represented by formulas (A1) to (A6) described in Examples of JP2013-100343A, in addition to the compounds described in paragraph [0010] of JP2013-053292A. Compounds described in paragraphs [0038] to [0043] and paragraphs [0048] to [0050] of JP2012-181505A, paragraphs [0036] to [0038] of JP2013-007032A, and the like. Compounds can be used.
Examples of the triarylmethane dye include, for example, Japanese Patent Application Laid-Open No. 2001-011336, Japanese Patent Application Laid-Open No. 2003-246935, Japanese Patent Application Laid-Open No. 2008-304766, International Publication No. 2010/123071, and Japanese Patent Application Laid-Open No. 2010-256598. JP 2011-007847 A, JP 2011-070172 A, JP 2011-116803 A, JP 2011-117995 A, JP 2011-133844 A, JP 2011-227408 A, International Publication. 2011/152379 pamphlet, WO 2011/162217 pamphlet, JP 2012-017425 A, JP 2012-037740 A, WO 2012/036085 pamphlet, JP 2012-073291 A. Gazette, International Publication No. 2012/053201, Pamphlet of JP2012-083552, JP2012-088615, JP2012-098522, JP2013-057053, U.S. Patent Application Publication 2013 / The compounds described in the specification of No. 0418810, International Publication No. 2013/147099, etc. can be used.
Examples of the cyanine dye include components (A-2) to (A-6) described in Examples of JP2009-235392A, paragraphs [0096] to [0108] of JP2012-212089A, and the like. Compounds described in paragraphs [0054] to [0063] of JP 2012-214718 A, compounds described in paragraphs [0050] to [0054] of JP 2012-214719 A, etc. Can be used.

Examples of the anthraquinone dyes are described in paragraphs [0071] of JP-A Nos. 2000-129150 and 2008-015530 in addition to the compounds described in paragraph [0049] of JP-A-2013-053292. The compounds described in JP 2013-210621 A and the like can be used.
Examples of the azo dye include Japanese Patent Application Laid-Open No. 2003-510398, Japanese Patent Application Laid-Open No. 2005-226022, Japanese Patent Application Laid-Open No. 2007-212539, Japanese Patent Application Laid-Open No. 2010-152160, Japanese Patent Application Laid-Open No. 2010-170073, and Japanese Patent Application No. 2011. 148993, JP2011-148994, JP2011-148995, JP2012-041461, JP2012-062461, WO2012 / 039361, Pamphlet 2012 Pyridone azo dyes described in JP-A No. 194200; for example, JP-A Nos. 04-249549, 2005-120132, 2005-298636, 2007-197538, 2010-275531 JP, 2012-2012 Diazo dyes described in Japanese Patent No. 41429; monoazo dyes described in Japanese Patent Application Laid-Open Nos. 2004-325864 and 2010-275533; Japanese Patent Application Laid-Open Nos. 2005-274788 and 2005-290351, for example. JP, 2006-039301, JP 2007-041076, JP 2007-04-1050, JP 2009-067748, 2010-170116, 2010-170117, etc. Pyrazole azo dyes described in JP-A-2007-293127, paragraphs [0058] to [0061], JP-A 2011-219655, paragraph [0014], JP-A 2013-145258, etc. In addition to azomethine dyes, JP 2010-150416 A JP, 2010-152159, JP, 2010-170074, JP, 2011-016974, JP, 2011-074270, JP, 2011-145540, US Patent Application Publication No. 2013/0164681. The compounds described in the specification can be used.

Examples of the dipyrromethene dye include dipyrromethene compounds containing a polymerizable group described in JP2011-180306A, in addition to the compounds described in JP2008-292970A.
Examples of the quinophthalone dye include compounds represented by the formula (2) described in JP-A-5-039269, JP-A-6-220339, JP-A-8-171201, and JP-A-2006-126649. A compound represented by the formula (1) described in JP 2010-250291 A or a compound represented by the formula (1) described in JP 2013-209614 A can be used.
Examples of the coumarin dye include a compound described in Example 4 of JP-A-4-179955, a compound represented by the formula (1) described in JP2013-151668A, and JP2013-231165A. And a compound represented by the formula (1) described in JP 2014-044419 A can be used.
As the pyrazolone dye, for example, a compound represented by the formula (1) described in JP-A-2006-016564 and a compound represented by the formula (1) described in JP-A-2006-0663171 are used. Can do.
Examples of the phthalocyanine dye are described in paragraphs [0147] to [0155] of JP-A-2007-094181, in addition to the compounds described in JP-A-2004-233504 and JP-A-2006-047497. A compound or the like can be used.

  As the dye, any of acidic dyes, basic dyes, and nonionic dyes can be suitably used. Here, in the present specification, the “acidic dye” means an ionic dye in which the anion part becomes a chromophore, and the ionic dye forming a salt with the anion part is also an acid dye. In the present specification, the “basic dye” means an ionic dye having a cation moiety as a chromophore, and an ionic dye forming a salt with the cation moiety is also a basic dye. “Nonionic dye” means a dye other than an acid dye and a basic dye.

  Examples of the acid dye include azo acid dyes, triarylmethane acid dyes, anthraquinone acid dyes, xanthene acid dyes, quinoline acid dyes, nitro acid dyes, and cyanine acid dyes. These can be used alone or in combination of two or more, and can be arbitrarily combined when two or more are used in combination.

Specific examples of the azo acid dye include C.I. 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 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. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Moldant Black 7, C.I. I. Direct green 28 etc. can be mentioned.
Specific examples of triarylmethane acid dyes include C.I. I. Acid Blue 9 etc. can be mentioned.
Specific examples of anthraquinone acid dyes include C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. And reactive blue 49.
Specific examples of xanthene acid dyes include C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. In addition to Acid Red 388, Synthesis Examples 1 to 3 in JP 2010-32999 A and dyes disclosed in JP 2011-138094 A can be exemplified.
Specific examples of quinoline acid dyes include C.I. I. Acid Yellow 3 etc. can be mentioned.
Specific examples of the nitro acid dye include C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3 etc. can be mentioned.
Specific examples of cyanine acid dyes include C.I. I. Reactive yellow 1 etc. can be mentioned.

  Examples of the basic dye include azo-based basic dyes, triarylmethane-based basic dyes, xanthene-based basic dyes, quinoneimine-based basic dyes, and cyanine-based basic dyes. These can be used alone or in combination of two or more, and can be arbitrarily combined when two or more are used in combination.

Specific examples of the azo basic dye include C.I. I. Basic Blue 41, C.I. I. In addition to the basic red 18, dyes described in JP 2011-145540 A can be exemplified.
Specific examples of the triarylmethane basic dye include C.I. I. In addition to Basic Blue 7, there can be mentioned dyes described in WO2010 / 123071, pamphlet, JP2011-116803A, JP2011-117995A, and JP2011-133844A.
Specific examples of the xanthene-based basic dye include C.I. I. Basic violet 11 and the like can be mentioned.
Specific examples of the quinoneimine basic dye include C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 etc. can be mentioned.
Specific examples of the cyanine basic dye include C.I. I. Basic Red 12, C.I. I. Basic Red 13, C.I. I. Basic Red 14, C.I. I. Basic Violet 7, C.I. I. Basic Violet 16, C.I. I. Basic Yellow 1, C.I. I. Basic Yellow 11, C.I. I. Basic Yellow 13, C.I. I. Basic Yellow 21, C.I. I. Basic Yellow 28, C.I. I. Basic yellow 51 etc. can be mentioned.
In addition, various basic dyes described in JP-T-2007-503477 can be exemplified.

  Examples of nonionic dyes include azo nonionic dyes, anthraquinone nonionic dyes, phthalocyanine nonionic dyes, nitro nonionic dyes, and methine nonionic dyes. These can be used alone or in combination of two or more, and can be arbitrarily combined when two or more are used in combination.

Specific examples of the azo nonionic dye include C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. In addition to Disperse Blue 165, dyes described in JP 2010-170073 A, JP 2010-170074 A, JP 2010-275531 A, and JP 2010-275533 A may be mentioned.
Specific examples of the anthraquinone nonionic dye include C.I. I. Bat Blue 4, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. can be mentioned.
Specific examples of the phthalocyanine-based nonionic dye include C.I. I. Pad blue 5 etc. can be mentioned.
Specific examples of quinoline-based nonionic dyes include C.I. I. Solvent Yellow 33, C.I. I. Disperse Yellow 64 and the like.
Specific examples of the nitro nonionic dye include C.I. I. Disperse Yellow 42 etc. can be mentioned.
Specific examples of the methine nonionic dye include C.I. I. Solvent Yellow 179, Disperse Yellow 201, etc. can be mentioned.
In addition, various nonionic dyes described in claim 3 or claim 4 of JP2010-168531A can be mentioned.

  In the present invention, these dyes can be appropriately selected and used, among which acidic dyes and basic dyes are preferable. In terms of the structure of the chromophore, triarylmethane dyes, xanthene dyes, azo dyes, methine dyes, and cyanine dyes are preferable, and xanthene dyes are more preferable.

  The coloring composition of the present invention may contain a colorant other than the dye. Examples of such other colorants include pigments, and these other colorants can be used alone or in combination of two or more.

  As the pigment, for example, a compound classified as a pigment in the color index (CI; issued by The Society of Dyers and Colorists), that is, the following color index (CI) number is attached. You can list what you have.

C. 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. Red pigments such as CI Pigment Red 264;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Green pigments such as CI Pigment Green 58;
C. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Blue pigments such as CI Pigment Blue 80;
C. I. Pigment yellow 83, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 179, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 211, C.I. I. Yellow pigments such as CI Pigment Yellow 215;
C. I. Orange pigments such as CI Pigment Orange 38;
C. I. Purple pigment such as CI Pigment Violet 23.

  In addition, the brominated diketopyrrolopyrrole pigment represented by the formula (Ic) of JP-T-2011-523433 can also be used as a red pigment. JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-191304, JP-A-2010-237384, JP-A-2010-237569, JP-A-2011-006602, Examples include lake pigments described in JP-A-2011-145346.

  In the present invention, when the pigment is contained as the colorant (A), 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. 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. The organic pigment may be used after the primary particles are refined 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 contained as the colorant (A), at least one selected from known dispersing agents and dispersing aids may be further contained.
Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. Dispersants, polyester-based dispersants, (meth) acrylic-based dispersants and the like can be mentioned. Examples of commercially available products include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above, Big Chemie BYK))) and other (meth) acrylic dispersants, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-17 , Dispersbyk-182 (above, manufactured by BYK Corporation), urethane dispersants such as Solsperse 76500 (manufactured by Lubrizol Corporation), and polyethyleneimine dispersions such as Solsperse 24000 (manufactured by Lubrizol Corporation) Other than polyester dispersants such as the additives, Azisper PB821, Azisper PB822, Azisper PB880, Azisper PB881 (Ajinomoto Fine Techno Co., Ltd.), BYK-LPN21324 (Bikchemy (BYK) Co.) it can.

In this invention, a dispersing agent can be used 1 type or in combination of 2 or more types.
In this invention, 5-300 mass parts is preferable with respect to 100 mass parts of pigments, as for content of a dispersing agent, 10-200 mass parts is more preferable, 20-100 mass parts is further more preferable, 20-50 mass parts. Is even more preferable.

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

(A) The content of the colorant is usually 5 to 70% by mass, preferably 5 to 60% by mass, more preferably 5% to 60% by mass in the solid content of the colored composition from the viewpoint of forming a pixel having high luminance and excellent coloring power. Is 10-50 mass%, and 20-50 mass% is particularly preferable. Here, solid content is components other than the solvent mentioned later.
When the coloring composition of the present invention contains both a dye and a pigment as the colorant (A), the content of the dye is 5% by mass or more with respect to the total colorant from the viewpoint of further enjoying the effects of the present invention. It is preferable that the content is 10% by mass or more, more preferably 15% by mass or more. In addition, the coloring composition of this invention may contain dye independently as (A) coloring agent. Even if the coloring composition of the present invention has a high content ratio of the dye relative to the solid content of the coloring composition, or (A) a combination of a dye and a pigment as the coloring agent, It is possible to form a colored cured film in which the generation of coating film foreign matter is suppressed.

-(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 combination 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 (polymerization degree 2 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 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 combination 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 adopting such an embodiment, the balance between coloring power and luminance, the remaining film ratio of the coating, the pattern shape, heat resistance, electrical characteristics, and resolution can be further enhanced, and the occurrence of precipitates and coating foreign matter can be increased. Can be suppressed at a 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 JP2003-222717A, JP2006-259680A, International Publication No. 2007/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

  In this invention, binder resin can be used 1 type or in combination of 2 or more types.

  In this invention, content of (B) 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, More preferably, it is 50-200 mass. Part, more preferably 80 to 150 parts by weight. By adopting such an embodiment, the balance between coloring power and luminance, alkali developability, storage stability of the colored composition, pattern shape, and chromaticity characteristics can be further enhanced, and the occurrence of precipitates and coating film foreign matter Can be suppressed.

-(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 has an excellent balance between coloring power and brightness, and the strength of the colored layer is high, the surface of the colored layer is excellent, and stains and film residue are generated on the unexposed substrate and the light shielding layer. This is particularly preferable because of difficulty.
In this invention, (C) polymeric compound can be used 1 type or in combination of 2 or more types.

  The content of the polymerizable compound (C) in the present invention is 10 to 1 with respect to 100 parts by mass of the colorant (A) from the viewpoint of the balance between coloring power and luminance, and the suppression of generation of precipitates and coating film foreign matter. 1,000 parts by mass is preferable, 20 to 500 parts by mass is more preferable, and 30 to 300 parts by mass is still more preferable.

-(D) 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-diketone compounds, polynuclear quinone compounds, A diazo compound, an imide sulfonate compound, etc. can be mentioned.

  In this invention, a photoinitiator can be used 1 type or in combination of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, and an O-acyloxime compound.

  Among preferred photopolymerization initiators in the present invention, specific examples of the thioxanthone compound 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 can be mentioned.

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

  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) -4,4 Examples include ', 5,5'-tetraphenyl-1,2'-biimidazole.

  In addition, when using a biimidazole compound as a photoinitiator, using a hydrogen donor together is preferable at the point which can improve a sensitivity. The term “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 hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, and 4,4′-bis (diethylamino) benzophenone. Mention may be made of amine hydrogen donors. In the present invention, the hydrogen donor can be used alone or in combination of two or more, but it is possible to use one or more mercaptan hydrogen donors and one or more amine hydrogen donors in combination. It is preferable in 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 (trichloromethyl) ) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-eth Triazine compounds having a halomethyl group such as cistyryl) -4,6-bis (trichloromethyl) -s-triazine and 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, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) ) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3- And dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime). As commercially available O-acyloxime compounds, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), DFI-020, DFI-091 (above, manufactured by Daito Chemix Corporation), and the like can also be used. .

  In this invention, when using photoinitiators other than biimidazole compounds, such as an acetophenone 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 the present invention, the content of the (D) photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, with respect to 100 parts by mass of the (C) polymerizable compound. 50 parts by mass is more preferable. By setting it as such an aspect, sclerosis | hardenability and a film characteristic can be improved further.

-(E) Solvent-
The coloring composition of this invention needs to contain glycol as (E) solvent. Examples of such glycols include ethylene glycol (1,2-ethanediol), propylene glycol (1,2-propanediol), 1,2-butylene glycol, 1,3-butylene glycol, and 1,4-butylene. Examples include alkylene glycols such as glycol; dialkylene glycols such as diethylene glycol and dipropylene glycol; trialkylene glycols such as triethylene glycol and tripropylene glycol; and polyalkylene glycols having a polymerization degree of 4 or more, and trimethylene glycol. .

Among such glycols, alkylene glycol and dialkylene glycol are preferable, alkylene glycol is more preferable, ethylene glycol and propylene glycol are further preferable, and propylene glycol is particularly preferable.
In this invention, glycol can be used 1 type or in combination of 2 or more types.

The content ratio of glycol is preferably 0.01% by mass or more with respect to the total solvent, and more preferred embodiments are as follows.
When the coloring composition of the present invention contains (A) a dye as a coloring agent, preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more, based on the total coloring agent. The content ratio is preferably 0.03 to 30% by mass, and 0.05 to 20% by mass with respect to the total solvent, from the viewpoints of workability such as applicability and post-baking, and suppression of occurrence of precipitates and coating film foreign matter. % Is more preferable, 0.1 to 14% by mass is further preferable, and 0.5 to 10% by mass is particularly preferable.

The colored composition of the present invention preferably contains a solvent other than glycol together with glycol.
As such other solvents, the components (A) to (C) constituting the coloring composition and other components are dispersed or dissolved, and do not react with these components and have appropriate volatility. As long as it is, it can be appropriately selected and used.

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

Among these solvents, (poly) alkylene glycol monoalkyl ether, lactate alkyl ester, (poly) alkylene glycol monoalkyl ether acetate, other ethers, ketones, diesters from the viewpoint of solubility, pigment dispersibility, coatability, etc. Acetate, alkoxycarboxylic acid ester, and other esters are preferred, particularly propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-hept Non, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3- Methoxybutyl propionate, 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, etc. Is preferred.
In this invention, another solvent can be used 1 type or in combination of 2 or more types.

  When the coloring composition of the present invention contains a dye and a pigment as the colorant (A), it is preferable that the solvent other than glycol contains at least one selected from the group consisting of propylene glycol monomethyl ether and ethyl lactate. In this case, the content ratio of at least one solvent selected from the group consisting of propylene glycol monomethyl ether and ethyl lactate is preferably 1 to 40% by mass, and more preferably 3 to 30% by mass with respect to the total solvent.

  (E) 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 it is 10-40 mass%. Is more preferred. By setting it as such an aspect, since it is excellent in the solubility of the dye to the solvent, a colorant dispersion having good dispersibility and stability, and a coloring composition having good coatability 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 fluorine surfactants and silicone surfactants; vinyltrimethoxysilane Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyl Adhesion promoters such as limethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- t-butylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-t-butyl-4-hydroxy) -5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxa-spiro [5 · 5] undecane, thiodiethylenebis [3- (3,5-di- antioxidants such as t-butyl-4-hydroxyphenyl) propionate]; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) Nyl) -5-chlorobenzotriazole, alkoxybenzophenones, etc .; anti-aggregation agents such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol Residue improving agents such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. An improving agent etc. can be mentioned.

Method for Producing Colored Composition The colored composition of the present invention comprises, for example, (A) a dye solution obtained by dissolving a dye in a solvent containing glycol when (D) is used alone as a colorant, and (B) It can be prepared by adding and mixing a binder resin, (C) a photopolymerization initiator, an additional (E) solvent and other components. When the coloring composition of the present invention contains a pigment and a dye as (A) the colorant, the pigment is (E) in a solvent in the presence of a dispersant, and optionally with (B) a part of the binder resin, For example, using a bead mill, a roll mill, etc., mixing and dispersing while pulverizing to obtain a pigment dispersion, and then, in this pigment dispersion, a dye solution obtained by dissolving a dye in a (E) solvent containing glycol; It can be prepared by adding (C) a polymerizable compound, (B) a binder resin, (D) a photopolymerization initiator as required, and further adding (E) a solvent and other components and mixing them. . In addition, the pigment is mixed and dispersed with a dye in a solvent (E) containing glycol in the presence of a dispersant to obtain a pigment dispersion, and then the (C) polymerizable compound is added to the colorant dispersion. It can also be prepared by adding (B) a binder resin, and (D) a photopolymerization initiator, if necessary, an additional (E) solvent and other components and mixing them.

Colored cured film and production method thereof The colored cured film of the present invention is formed using the colored composition of the present invention, specifically, each color pixel, black matrix, black spacer, etc. used in the color filter. Means.

Hereinafter, a colored cured film used for a color filter and a method for forming the same will be described.
As a method for forming the colored cured film constituting the color filter, the following method is first exemplified. 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, a blue liquid composition of the radiation-sensitive colored composition of the present invention is applied on the substrate, and then pre-baked to evaporate the solvent to form 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 blue pixel patterns (colored cured films) are arranged in a predetermined arrangement.

  Subsequently, using each radiation sensitive coloring composition of green or red, application of each radiation sensitive coloring composition, pre-baking, exposure, development, and post-baking are performed in the same manner as described above to obtain a green pixel array and red color. Are sequentially formed on the same substrate. Thereby, a color filter in which a pixel array of the three primary colors of blue, green and red is 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 by using the coloring composition.

Examples of the substrate used when forming the colored cured film 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 spraying, roll coating, spin coating (spin coating), slit die coating (slit coating), bar coating, etc. 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 forming a colored cured film constituting a color filter, a method for obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723, JP-A-2000-310706, etc. Can be adopted. In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a blue liquid composition of the thermosetting coloring composition of the present invention is ejected into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, the coating film is exposed as necessary, and then cured by post-baking to form a blue pixel pattern.

  Next, using the green or red thermosetting coloring composition, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as described above. As a result, a color filter in which the pixel patterns of the three primary colors of blue, green and red 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 for forming the colored cured film, 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.
The colored composition of the present invention can be suitably used in forming any colored cured film such as each color pixel, black matrix, and black spacer used in the color filter.

  Since the color filter including the colored cured film of the present invention thus formed has extremely high luminance and coloring power, it can be used in color liquid crystal display elements, color imaging tube elements, color sensors, organic EL display elements, electronic papers, and the like. Very useful.

Display element The display element of the present invention comprises the colored cured film 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 colored cured film 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. Further, 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 (tin-doped indium oxide) 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. When the latter structure is adopted, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed or the substrate side on which the ITO electrode is formed.

  The color liquid crystal display element including the colored cured film of the present invention can 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 element having the colored cured film of the present invention includes TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Plane Switching) type, VA (Vertical Alignment) type, OCB (Optical). An appropriate liquid crystal mode such as a Compensated Birefringence type is applicable.

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

  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 colorant>

Synthesis example 1
In a 200 mL eggplant-shaped flask containing a stirring bar, C.I. I. 2.9 g (5.0 mmol) of Acid Red 52 and 29 mL of ion-exchanged water were added, and the mixture was heated to a bath temperature of 85 ° C. in an oil bath while stirring. To this solution, a solution obtained by dissolving 3.3 g (10.26 mmol) of tetrabutylammonium bromide in 60 g of ion-exchanged water at room temperature was added little by little at the same temperature. When all were added, it was confirmed that a water-insoluble colored oily substance was formed. Then, after stirring at the same temperature for 1 hour, it cooled to room temperature vicinity using the ice bath. The supernatant was removed by decantation, and then the residue was washed with ion-exchanged water. This residue was recovered by dissolving in methanol and concentrated under reduced pressure using a rotary evaporator. The obtained oily residue was dried under reduced pressure at 50 ° C. for 12 hours to obtain 6.1 g of a reddish purple solid.
It was confirmed by ¹ H-NMR spectrum (solvent: deuterated chloroform) that the obtained compound was a compound represented by the following formula (A-1). Let the obtained compound be dye (A-1).

Synthesis example 2
In Synthesis Example 1, a dye represented by the following formula (A-2) was prepared using the same method as Synthesis Example 1 except that tetrabutylphosphonium bromide was used instead of tetrabutylammonium bromide. Let the obtained compound be dye (A-2).

Synthesis example 3
In Synthesis Example 1, C.I. I. In place of Acid Red 52, C.I. I. A dye (A-3) was produced in the same manner as in Synthesis Example 1 except that Acid Red 87 was used.

Synthesis example 4
In Synthesis Example 1, C.I. I. In place of Acid Red 52, C.I. I. A dye (A-4) was produced in the same manner as in Synthesis Example 1 except that Acid Red 92 was used.

Synthesis example 5
In Synthesis Example 1, C.I. I. In place of Acid Red 52, C.I. I. A dye (A-5) was produced in the same manner as in Synthesis Example 1 except that Acid Red 289 was used.

Synthesis Example 6
In Synthesis Example 1, C.I. I. In place of Acid Red 52, C.I. I. A dye (A-6) was produced in the same manner as in Synthesis Example 1 except that Acid Red 388 was used.

Synthesis example 7
A compound represented by the following formula (A-7) was synthesized according to the method described in Synthesis Example 1 of JP2013-100343A. This compound is referred to as “dye (A-7)”. The dye (A-7) is a xanthene dye.

Synthesis Example 8
20 parts by mass of the compound represented by the following formula (8) and 200 parts by mass of N-dodecylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed under shading conditions, and the resulting solution was stirred at 110 ° C. for 6 hours. The obtained reaction liquid was cooled to room temperature, added to a mixed liquid of 800 parts by mass of water and 50 parts by mass of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystals were subjected to suction filtration, and the obtained residue was dried to obtain 24 parts by mass of the compound represented by the formula (A-8).
It was confirmed by MS spectrum measurement that the obtained compound was a compound represented by the following formula (A-8). Let the obtained compound be dye (A-8). The dye (A-8) is a xanthene dye.

Synthesis Example 9
A xanthene-based dye, C.I. I. 1.29 g (2.71 mmol) of basic violet 10, 1.30 g (4.07 mmol) of potassium bis (trifluoromethanesulfonyl) imide, 20 mL of chloroform and 10 mL of water were added and stirred at room temperature for 7 hours. After separating and removing the aqueous layer, the organic layer was washed twice with water. The solid obtained by concentrating under reduced pressure was dried under reduced pressure to obtain 1.43 g of solid.
¹ H-NMR spectrum (solvent: deuterated chloroform) measurement confirmed that the obtained solid was a compound represented by the following formula (A-9). Let the obtained compound be dye (A-9).

<Preparation of pigment dispersion>
Preparation example a
As a coloring agent, C.I. I. 15 parts by weight of CI Pigment Blue 15: 6, 12.5 parts by weight of BYK-LPN22102 (produced by BYK) as a dispersant (solid content concentration 40% by weight), 72.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent Was used to prepare a pigment dispersion (a-1).
BYK-LPN22102 is a (meth) acrylic dispersant, and the (meth) acrylic dispersant is a propylene glycol methyl ether acetate / propylene glycol methyl ether of a modified (meth) acrylic block copolymer = 1. / 1 (mass ratio) solution (acid value = 0 mgKOH / g, amine value = 29 mgKOH / g). The modified (meth) acrylic block copolymer comprises a block having repeating units derived from methacryloyloxyethylbenzyldimethylammonium chloride and dimethylaminoethyl methacrylate, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate and triethylene. It consists of a block having repeating units derived from glycol ethyl ether methacrylate.

<Synthesis of binder resin>
Synthesis Example 10
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 (B-1)”.

Synthesis Example 11
A flask equipped with a condenser and a stirrer was charged with 144 parts by mass of cyclohexanone and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 48 parts by mass of cyclohexanone, 28.8 parts by mass of methacrylic acid, 18 parts by mass of butyl methacrylate, 18 parts by mass of methyl methacrylate, 2-ethylhexyl EO modified acrylate (manufactured by Toagosei Co., Ltd.) , M-120), 18 parts by mass of cyclohexyl methacrylate and 37.2 parts by mass of glycerol methacrylate, and 48 parts by mass of cyclohexanone and 2,2′-azobis (2,4-dimethylvaleronitrile) 8.4. Part by mass of the mixed solution was added dropwise over 2 hours, and polymerization was performed for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and polymerization was further performed for 1 hour. Next, this solution was cooled to room temperature, and cyclohexanone was added so that a non-volatile content might be 33 mass%, and the resin (B-2 ') solution was obtained. The obtained resin (B-2 ′) had Mw = 10,700, Mn = 5,600, and Mw / Mn = 1.91.
Into a flask equipped with a condenser and a stirrer, the entire amount of the resin (B-2 ′) solution was put and the temperature of the solution was raised to 90 ° C., and then 2-methacryloyloxyethyl isocyanate (Karenz MOI, Showa Denko KK) ) A mixed solution of 34.3 parts by mass (95 mol% with respect to the number of moles of glycerol methacrylate) and 0.36 parts by mass of 4-methoxyphenol was added dropwise over 15 minutes under air bubbling conditions, and this temperature was maintained. The addition reaction was carried out for 1.5 hours. Next, this solution was cooled to room temperature, and cyclohexanone was added so that a non-volatile content might be 36 mass%, and the binder resin solution was obtained. The obtained binder resin was Mw = 12,800, Mn = 6,000, and Mw / Mn = 2.13. This binder resin is referred to as “binder resin (B-2)”.

<Preparation of dye solution>
Preparation Example 1
A dye solution (1) was prepared by mixing 10 parts by mass of the dye (A-1) and 90 parts by mass of a mixed solvent of propylene glycol / ethyl lactate = 10/90 (mass ratio).

Preparation Examples 2-17
Dye solutions (2) to (17) were prepared in the same manner as in Preparation Example 1 except that the types and amounts of the dye and solvent were changed as shown in Table 1 in Preparation Example 1. In Preparation Example 17, the dye was not completely dissolved.

  In Table 1, “EL” represents ethyl lactate, “PG” represents propylene glycol, “EG” represents ethylene glycol, “PGME” represents propylene glycol monomethyl ether, and “PGMEA” represents propylene glycol monomethyl ether. Acetate is shown.

<Preparation and evaluation of coloring composition>
Example 1
21.3 parts by mass of the pigment dispersion (a-1) and 8.0 parts by mass of the dye solution (1), (B) 12.2 parts by mass of the binder resin (B-1) solution as the binder resin (solid content concentration 33 masses) %), (C) M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Toagosei Co., Ltd. as a polymerizable compound, (D) 2-benzyl as a photopolymerization initiator 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, trade name IRGACURE369) 0.8 parts by mass and NCI-930 (manufactured by ADEKA Corporation) 0 .1 part by mass, 0.02 part by mass of Megafac F-554 (manufactured by DIC Corporation) as a fluorosurfactant, and (E) a solvent and Using propylene glycol monomethyl ether acetate Te, solid content of 20 wt% of the coloring composition (CR1) was prepared. The content ratio of propylene glycol contained in the coloring composition (CR1) is 1.0% by mass with respect to the total solvent.

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. The same operation was performed by changing the rotation speed of the spin coater to form three coating films having different film thicknesses.
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 230 ° C. for 30 minutes to form a cured film for evaluation.

Evaluation of coating film foreign matter The cured film for evaluation described above was observed at a magnification of 50 times using an optical microscope, and the number of foreign matters that could be confirmed in the visual field was counted. This operation was performed at arbitrary five locations on the cured film for evaluation, and the following criteria were evaluated from the total of confirmed foreign substances. The results are shown in Table 2.
○: Less than 5 △: 5 or more and less than 50 ×: 50 or more

Examples 2-9
Colored compositions (CR2) to (CR9) were prepared in the same manner as in Example 1, except that the dye solutions (2) to (9) were used in place of the dye solution (1). Next, evaluation was performed in the same manner as in Example 1 except that the colored compositions (CR2) to (CR9) were used instead of the colored composition (CR1). The results are shown in Table 2.

Example 10
In Example 1, instead of 21.3 parts by mass of the pigment dispersion (a-1) and 8.0 parts by mass of the dye solution (1), 29.3 parts by mass of the dye solution (10) was used. A colored composition (CR10) was prepared using the same procedure as in 1. Subsequently, evaluation was performed in the same manner as in Example 1 except that the colored composition (CR10) was used instead of the colored composition (CR1). The results are shown in Table 2.

Example 11
In Example 1, instead of using propylene glycol monomethyl ether acetate as a solvent for adjusting the solid content concentration to 20% by mass, a mixed solvent of propylene glycol and propylene glycol monomethyl ether acetate was used, and in the colored composition A colored composition (CR11) was prepared using the same method as in Example 1 except that the content ratio of propylene glycol was adjusted to 15% by mass with respect to the total solvent. Subsequently, evaluation was performed in the same manner as in Example 1 except that the colored composition (CR11) was used instead of the colored composition (CR1). The results are shown in Table 2.

Examples 12-14
In Example 1, coloring compositions (CR12) to (CR14) were prepared using the same method as in Example 1 except that the dye solutions (11) to (13) were used instead of the dye solution (1). Subsequently, evaluation was performed in the same manner as in Example 1 except that the colored compositions (CR12) to (CR14) were used in place of the colored composition (CR1). The results are shown in Table 2.

Example 15
In Example 1, 29.3 parts by mass of the dye dispersion (a-1) and 8.0 parts by mass of the dye solution (1) were used, and 29.3 parts by mass of the dye solution (14) was used. Instead of using propylene glycol monomethyl ether acetate as a solvent for adjusting the concentration to 20% by mass, a mixed solvent of propylene glycol and propylene glycol monomethyl ether acetate is used, and the content of propylene glycol in the colored composition is all A colored composition (CR15) was prepared using the same method as in Example 1 except that the content was 14% by mass with respect to the solvent. Next, evaluation was performed in the same manner as in Example 1 except that the colored composition (CR15) was used instead of the colored composition (CR1). The results are shown in Table 2.

Comparative Examples 1-2
In Example 1, colored compositions (CR16) to (CR17) were prepared using the same method as in Example 1 except that the dye solutions (15) to (16) were used instead of the dye solution (1). . Subsequently, evaluation was performed in the same manner as in Example 1 except that the colored compositions (CR16) to (CR17) were used in place of the colored composition (CR1). The results are shown in Table 2.

Claims (7)

A coloring composition comprising (A) a colorant, (B) a binder resin, (C) a polymerizable compound and (E) a solvent,
(A) The coloring composition contains a dye, and (E) the coloring composition contains a glycol.   The coloring composition of Claim 1 whose content rate of glycol is 0.01 mass% or more with respect to all the solvents.   The coloring composition of Claim 1 or 2 in which glycol contains alkylene glycol.   The coloring composition of any one of Claims 1-3 in which dye contains a xanthene dye.   The coloring composition of any one of Claims 1-4 in which a coloring agent contains a pigment.   The colored cured film formed using the coloring composition of any one of Claims 1-5.   A display element comprising the colored cured film according to claim 6.