JP2017186523A - Coloring composition, coloring cured film, color filter, display element and solid state imaging device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition having high solvent resistance and suitable for forming a coloring cured film excellent in electrical properties.SOLUTION: There is provided a coloring composition containing (A) a coloring agent, (B) a binder resin and (C) a polymerizable compound, the (A) coloring agent containing a dye, and further having a compound (D) in which an ureylene group and a polymerizable unsaturated bond are contained in the molecule. The polymerizable urea compound can be manufactured by reacting an unsaturated isocyanate compound having a (meth)acryloyl oxy group together with water in a proper solvent.SELECTED DRAWING: None

Description

  The present invention relates to a colored composition, a colored cured film, a color filter, a display element, and a solid-state image sensor, and more specifically, a transmissive or reflective color liquid crystal display element, solid-state image sensor, organic EL display element, electronic Colored composition suitably used for production of colored cured film used for paper, etc., colored cured film formed using the colored composition, and color filter, display element and solid-state imaging provided with the colored cured film It relates to an element.

  In manufacturing 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. (Hereinafter, referred to as “exposure”) and a method of obtaining pixels of each color by development (Patent Documents 1 and 2) are known. A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is also known. Furthermore, a method of obtaining pixels of each color by an inkjet method using a pigment-dispersed colored resin composition is also known.

  By the way, a color filter using a pigment as a colorant tends to cause a decrease in luminance, contrast, and the like of a display element due to light scattering by pigment particles. Therefore, a technique using a dye instead of a pigment as a colorant has been studied. For example, a color composition for a color filter containing a cyanine dye, a triarylmethane dye, a dipyrromethene dye, a xanthene dye, and the like has been proposed (for example, Patent Documents). 3-8). However, since dyes are generally compounds that are easily dissolved in organic solvents, solvent resistance tends to be remarkably insufficient. In addition, when the dye is a charged compound, the electrical characteristics may deteriorate when the display element is manufactured.

Japanese Patent No. 5315984 JP 5609229 A specification JP 2009-235392 A Japanese Patent Laying-Open No. 2015-118267 Japanese Patent Laying-Open No. 2015-199912 JP 2013-083916 A JP 2012-208454 A International Publication No. 2014/192773 Pamphlet

  The subject of this invention is providing the coloring composition suitable for formation of the colored cured film which has high solvent resistance and is excellent in an electrical property. Furthermore, the subject of this invention is providing the color filter, display element, and solid-state image sensor which comprise the colored cured film formed using the said colored composition, and the said colored cured film.

The present inventors have conducted intensive research in view of such circumstances, and found that the above-mentioned problems can be solved by using a specific compound in combination in a coloring composition containing a dye, thereby completing the present invention. It came to.
That is, the present invention is a colored composition containing (A) a colorant, (B) a binder resin and (C) a polymerizable compound, wherein (A) the colorant contains a dye, and (D) The present invention provides a coloring composition containing a compound having a ureylene group and a polymerizable unsaturated bond.

  The present invention also provides a colored cured film containing a dye and a compound having a ureylene group and a polymerizable unsaturated bond in the molecule.

  Furthermore, the present invention provides a colored cured film containing a dye and a compound having a partial structure derived from a compound having a ureylene group and a polymerizable unsaturated bond in the molecule.

  Furthermore, this invention provides a color filter, a display element, and a solid-state image sensor provided with the said colored cured film.

  If the colored composition of the present invention is used, a colored cured film having high solvent resistance and excellent electrical properties can be formed. Therefore, the colored composition of the present invention can be used very suitably for the production of display elements such as color liquid crystal display elements, organic EL display elements, and electronic paper, and solid-state imaging elements.

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, coumarin dyes, pyrazolone dyes, quinoline dyes, nitro dyes, in terms of the structure of the chromophore. And dyes, quinoneimine dyes, phthalocyanine dyes, and the like.

  As the xanthene dye, for example, in addition to the compound described in paragraph [0010] of JP2013-053292A, it is represented by the formulas (A1) to (A6) described in the examples of JP2013-1000046. 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, JP-A No. 2001-011336, JP-A No. 2003-246935, JP-A No. 2008-304766, pamphlet of International Publication No. 2010/123071, and JP-A 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 No. 2011/152379 pamphlet, International Publication No. 2011-162217 pamphlet, JP 2012-014425 A, JP 2012-037740 A, WO 2012/036085 pamphlet, JP 2012-073291 A. International Publication No. 2012/053201, Pamphlet No. 2012-083552, No. 2012-088615, No. 2012-098522, No. 2013-057053, US Patent Application No. 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 the components (A-2) to (A-6) described in Examples of JP2009-235392A, and paragraphs [0096] to [0108] of JP2012-212089A. Compounds described in paragraphs [0054] to [0063] of JP 2012-214718 A, compounds described in paragraphs [0050] to [0054] of JP 2012-214719 A, and the like. 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 No. 2013-053292. Compounds, compounds described in JP 2013-210621 A, and the like can be used.

  Examples of the azo dye include Japanese Patent Application Laid-Open Nos. 2003-510398, 2005-226022, 2007-212539, 2010-152160, 2010-201073, and 2011- No. 148993, JP 2011-148994, JP 2011-148995, JP 2012-046161, JP 2012-062461, WO 2012/039361, Pamphlet 2012-194200 Pyridone azo dyes described in JP-A No. 04-249549, JP-A No. 2005-120132, JP-A No. 2005-298636, JP-A No. 2007-197538, JP-A No. 2010-275531, JP2012-14 Diazo dyes described in Japanese Patent Application Laid-Open No. 429; 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, JP-A-2006-039301, JP-A-2007-041076, JP-A-2007-041050, JP-A-2009-067748, JP-A-2010-170116, JP-A-2010-170117, etc. Of the azomethine dyes described in JP-A 2007-293127, paragraphs [0058] to [0061], JP-A 2011-219655, paragraph [0014], JP-A 2013-145258, and the like. In addition, JP 2010-150416 A, JP 20 Nos. 0-152159, 2010-170074, 2011-016974, 2011-074270, 2011-145540, and US 2013/0164681. The described compounds and the like can be used.

  As the dipyrromethene dye, for example, a dipyrromethene compound containing a polymerizable group described in JP-A-2011-180306 as well as a compound described in JP-A-2008-292970 can be used.

  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 and 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. A compound represented by the formula (1) described above and a compound represented by the formula (1) described in JP-A-2014-044419 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-2006-063171 may be used. it can.

  Examples of the phthalocyanine dye include compounds described in paragraphs [0147] to [0155] of JP 2007-094181 A, in addition to the compounds described in JP 2004-233504 A and JP 2006-047497 A, for example. Etc. can be used.

  As the dye, any of acidic dyes, basic dyes, and nonionic dyes can be suitably used. Here, the “acid dye” in the present specification means an ionic dye having an acidic group, and an ionic dye forming a salt with the acidic group is also an acid dye. In the present specification, the “basic dye” means an ionic dye having no acidic group among ionic dyes, and is usually a dye having a basic group. The “nonionic dye” means a dye other than an acid dye and a basic dye.

  Examples of acid dyes 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 the triarylmethane acid dye include C.I. I. Acid Blue 9 etc. can be mentioned.

  Specific examples of the anthraquinone acid dye 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 the xanthene acid dye 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 the cyanine acid dye include C.I. I. Reactive yellow 1 etc. can be mentioned.

  Among these, as the acid dye, a xanthene acid dye is preferable.

  Examples of basic dyes include azo basic dyes, triarylmethane basic dyes, xanthene basic dyes, quinoneimine basic dyes, and cyanine 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 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.

  Of these, triarylmethane basic dyes and cyanine basic dyes are preferable as the basic dye.

  Examples of nonionic dyes include azo nonionic dyes, anthraquinone nonionic dyes, phthalocyanine nonionic dyes, nitro nonionic dyes, methine nonionic dyes, and dipyrromethene 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 nonionic dye include C.I. I. Pad blue 5 etc. can be mentioned.

  Specific examples of the quinoline nonionic dye 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 methine nonionic dyes 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, cyanine dyes, xanthene dyes, and dipyrromethene dyes are preferable, and triarylmethane dyes, cyanine dyes, 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. Pigment green 58, C.I. I. Green pigments such as CI Pigment Green 59;
C. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 79, C.I. I. Blue pigments such as CI Pigment Blue 80;
C. I. Pigment yellow 83, C.I. I. Pigment yellow 138, 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. Pigment violet 19, C.I. 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 additive, Azisper PB821, Azisper PB822, Azisper PB880, Azisper PB881 (Ajinomoto Fine Techno Co., Ltd.), and BYK-LPN21324 (Bikchemy (BYK) Co., Ltd.) may be used. 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 10 to 60% by mass, more preferably in the solid content of the colored composition, from the viewpoint of forming a pixel having high luminance and excellent coloring power. Is 15 to 50% by mass, and particularly preferably 20 to 50% by mass. 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. Moreover, although (A) a dye may be contained alone as a colorant, the content of the dye is preferably 90% by mass or less, more preferably 70% by mass or less, and more preferably 50% by mass or less with respect to the total colorant. Further preferred.

-(B) Binder resin-
The binder resin of the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or 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)”). . Binder resin can be used 1 type or in mixture of 2 or more types.

  Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth). Examples thereof include acrylate and p-vinylbenzoic acid.

  An unsaturated monomer (b1) can be used 1 type or in mixture of 2 or more types.

Moreover, as an unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide, 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.

  An unsaturated monomer (b2) can be used 1 type or in mixture of 2 or more types.

  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-10-300922, 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. In the colored composition of the present invention, a highly sensitive colored composition can be obtained by using a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain as a binder resin. Moreover, it is preferable at the point that sclerosis | hardenability of a coating film can be improved.

  The binder resin in the present invention has an Mw measured by GPC of usually 1,000 to 100,000, preferably 3,000 to 50,000. By setting it as such an aspect, while solvent resistance is improved further, transferability and foreign material generation | occurrence | production can be suppressed effectively.

  The Mw / Mn of the binder resin is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. Here, Mw and Mn are polystyrene-reduced number average molecular weights measured by GPC (elution solvent: tetrahydrofuran).

  The binder resin can be produced by a known method, for example, by a method disclosed in JP2003-222717A, JP2006-259680A, International Publication No. 2007/029871, etc. The structure, Mw, and Mw / Mn can also be controlled.

  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, More preferably, it is 50-200 mass parts. . By setting it as such an aspect, not only the colored cured film excellent in solvent resistance can be formed, but it is excellent in pattern shape, and generation | occurrence | production of a deposit and a coating-film foreign material 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 (C) is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups. (C) A polymeric compound can be used 1 type or in mixture of 2 or more types.

  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 dihydrate. 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. A compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and foreign matter is hardly generated.

  The content of the polymerizable compound (C) in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 800 parts by mass, and 100 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. Is more preferable. By setting it as such an aspect, the pixel excellent in solvent resistance and pattern shape, or the black matrix and black spacer excellent in light-shielding property can be formed.

-(D) Compound having a ureylene group and a polymerizable unsaturated bond in the molecule-
The component (D) is a compound having a ureylene group in the molecule and an unsaturated bond that is polymerized by exposure to radiation in the presence of a photopolymerization initiator (hereinafter also referred to as “polymerizable urea compound”). As a result of intensive studies, the inventors of the present invention have surprisingly surprisingly realized that the dye is charged by including a polymerizable urea compound having a ureylene group (—NH—CO—NH—) in the coloring composition containing the dye. It has been found that even a compound having a high electrical property is excellent. Since the polymerizable urea compound having a ureylene group has a high affinity with the dye, it is easy to hold the dye in the colored cured film, and as a result, it is considered that the electrical characteristics of the display element are improved.

  This polymerizable urea compound is preferably a compound represented by the following formula.

[In Formula (1),
n independently represents an integer of 1 to 3,
R ¹ represents, independently of each other, an n + 1 valent organic group,
R ² independently represents a hydrogen atom or a methyl group. ]
Examples of the organic group related to R ¹ in the above formula (1) include a methylene group, an alkylene group having 2 to 10 carbon atoms, a phenylene group,-(C ₂ H ₄ O) _m C ₂ H ₄ -,-( C ₃ H ₆ O) _m C ₂ H ₄ — (m represents an integer of 1 to 5), a group represented by the following formula, and the like can be given.

[In Formula (1)-(2),
a, b, c, p, q, r and s each independently represent an integer of 0 to 12. ]
Specific examples of the polymerizable urea compound include 1,3-bis (acryloyloxyethyl) urea, 1,3-bis (methacryloyloxyethyl) urea, 1,3-bis (methacryloyloxybutyl) urea, 1,3-bis (methacryloyloxy-2-ethoxyethyl) urea, 1,3-bis (m-methacryloyloxyphenyl) urea, 1,3-bis (1,1-bis (acryloyloxymethyl) ethyl) Examples include urea.

  A polymerizable urea compound can be used individually or in mixture of 2 or more types.

  The polymerizable urea compound can be produced, for example, by reacting an unsaturated isocyanate compound having a (meth) acryloyloxy group with water in an appropriate solvent. As the unsaturated isocyanate compound having a (meth) acryloyloxy group, known compounds can be used, but 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 4-methacryloyloxybutyl isocyanate, 2-methacrylic acid 2- (2-Isocyanatoethoxy) ethyl is preferred from the viewpoint of reactivity.

  In the colored composition of the present invention, the content of the (D) polymerizable urea compound is usually 1 to 300 parts by mass with respect to 100 parts by mass of the dye which is (A) the colorant. Especially, the colored cured film which is excellent in a voltage retention can be formed by setting it as 10-200 mass parts with respect to 100 mass parts of dyes, especially 30-150 mass parts.

-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 (C) by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. . A photoinitiator can be used 1 type or in mixture of 2 or more types.

  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 compound, a polynuclear quinone compound, a diazo compound, an imide sulfonate compound, an onium salt compound, etc. can be mentioned. Among these, at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds is preferable.

  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 acetophenone compounds 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-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, the hydrogen donor can be used singly or in combination 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 compounds described in paragraphs [0063] to [0065] of JP-B-57-6096 and JP-A-2003-238898.

  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 commercial products of O-acyloxime compounds, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), OXE-03, OXE-04 (above, manufactured by BASF 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 still more preferable. By setting it as such an aspect, not only suppression of the generation | occurrence | production of a foreign material but sclerosis | hardenability and a film characteristic can be made favorable.

-Solvent-
The colored composition of the present invention contains the above components (A) to (D) and other components optionally added, but is usually prepared as a liquid composition by blending an organic solvent. .

  As an organic solvent, as long as (A)-(D) component and other components which comprise a coloring composition are disperse | distributed or melt | dissolved, and it does not react with these components and has moderate volatility, it is suitably You can choose to use. A solvent can be used 1 type or in mixture of 2 or more types.

Among such organic 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, (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;
Cyclic 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 Fatty acid alkyl 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, at least one selected from (poly) alkylene glycol monoalkyl ether and (poly) alkylene glycol monoalkyl ether acetate is preferable from the viewpoints of solubility, pigment dispersibility, coatability and the like.

  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 composition which is excellent in a dispersibility and stability, and favorable applicability | paintability 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 silicone 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-chloropro Adhesion promoters such as rutrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butane Such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. Examples include developability improvers.

Preparation Method of Colored Composition The colored composition of the present invention can be prepared by an appropriate method. For example, the components (A) to (D) can be added to a solvent or optionally added. It can prepare by mixing with the component of. (A) When the colorant contains a pigment, the pigment is mixed and dispersed in a solvent in the presence of a dispersant, optionally with (B) a part of the binder resin, for example, using a bead mill, a roll mill or the like. Then, a pigment dispersion is prepared, and then the components (C) to (D) and, if necessary, a photopolymerization initiator, an additional (B) binder resin, a solvent and other components are added to the pigment dispersion. However, the method of preparing by mixing is preferable.

Colored cured film and method for forming the same The colored cured film of the present invention contains a polymerizable urea compound and a dye, and such a colored cured film can be formed using the colored composition of the present invention. . In addition, when forming a colored cured film using the colored composition of the present invention, a compound having a structural unit derived from a ureylene group and a polymerizable unsaturated bond, which is a polymer of the polymerizable urea compound, is included. May be. That is, the colored cured film of the present invention may contain a compound having a structural unit derived from a ureylene group and a polymerizable unsaturated bond, and a dye. Hereinafter, a colored cured film used for a color filter constituting a display element and a method for forming the same will be described.

  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 red 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 red pixel patterns (colored cured films) are arranged in a predetermined arrangement.

  Subsequently, using each radiation sensitive coloring composition of green or blue, 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 blue color. 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. However, it is a radiation sensitive material in which a black colorant is dispersed. A colored composition can be used in the same manner as in the case of forming the pixel.

  Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. 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.

Prebaking is usually about 1 to 10 minutes at 70 to 110 ° C.
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, and 1,8-diazabicyclo- [5.4.0] -7-undecene. An aqueous solution of 1,5-diazabicyclo- [4.3.0] -5-nonene 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 liquid composition of a red thermosetting coloring composition 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 red pixel pattern.

  Subsequently, using each thermosetting coloring composition of green or blue, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming 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 radiation-sensitive colored 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 a color filter. Since the color filter having the colored cured film of the present invention formed in this way is excellent in solvent resistance, it is extremely useful for display elements such as color liquid crystal display elements, organic EL display elements, electronic paper, and solid-state imaging elements. is there. In addition, the display element and solid-state image sensor which are mentioned later should just have at least 1 or more of colored cured films formed using the coloring composition of this invention.

Color filter The color filter of the present invention comprises the colored cured film of the present invention. Specifically, what is necessary is just to comprise the colored cured film of this invention as members, such as each color pixel used for a color filter, a black matrix, a black spacer.

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 take 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 take an appropriate structure, and examples thereof include a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

Solid-state image sensor The solid-state image sensor of the present invention comprises the colored cured film of the present invention. In addition, the solid-state imaging device of the present invention can take an appropriate structure. For example, as one embodiment, by using the colored composition of the present invention to form a colored pixel (colored cured film) on a semiconductor substrate such as a CMOS substrate by the same operation as described above, particularly color separation is performed. It is possible to manufacture a solid-state imaging device having excellent properties.

  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 binder resin Synthesis Example 1
In a reagent bottle, normal butyl methacrylate 24.0 g, methacrylic acid 18.0 g, succinic acid mono 2-acryloxyethyl 13.5 g, N-phenylmaleimide 12.0 g, benzyl methacrylate 22.5 g, hydroxyethyl methacrylate 45.0 g and 60 g of propylene glycol monomethyl ether acetate was weighed and mixed. This is a monomer solution.
Next, 10.50 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 63 g of propylene glycol monomethyl ether acetate. This is an initiator solution.
Into a flask equipped with a condenser and a stirrer, 177 g of propylene glycol monomethyl ether acetate was added, and a monomer solution and an initiator solution were added dropwise over 120 minutes, followed by reaction at 90 ° C. for 120 minutes.

  To 200 g of the obtained precursor copolymer solution, 13.4 g of glycidyl methacrylate and 0.2 g of 4-methoxyphenol as a polymerization inhibitor were dropped and reacted at 90 ° C. for 2 hours. The reaction solution was washed twice with 75 g of ion exchange water per time and concentrated under reduced pressure to obtain a solution containing 33% by mass of the binder resin (B-1). The binder resin (B-1) had a polystyrene-equivalent weight average molecular weight measured by GPC (elution solvent: tetrahydrofuran) of 11,000, and the ratio of the weight average molecular weight to the number average molecular weight was 1.9.

Synthesis of component D Synthesis example 2 (synthesis of 1,3-bis (methacryloyloxyethyl) urea)
A flask equipped with a condenser and a stirrer was charged with 10 parts of 2-methacryloyloxyethyl isocyanate and 30 parts of tetrahydrofuran. Subsequently, 2 parts of distilled water was added, the temperature of the solution was raised to 40 ° C., and the mixture was gently stirred for 1 hour. Tetrahydrofuran and distilled water were removed by distillation under reduced pressure, followed by recrystallization from 50 parts of ethanol to obtain needle-like white crystals.
It was confirmed by ¹ H-NMR that the obtained compound was 1,3-bis (methacryloyloxyethyl) urea.

Synthesis Example 3 (Synthesis of 1,3-bis (acryloyloxyethyl) urea)
In Synthesis Example 2, acicular white crystals were obtained in the same manner as Synthesis Example 2 except that 2-acryloyloxyethyl isocyanate was used instead of 2-methacryloyloxyethyl isocyanate.
It was confirmed by ¹ H-NMR that the obtained compound was 1,3-bis (acryloyloxyethyl) urea.

Synthesis Example 4 (Synthesis of 1,3-bis (methacryloyloxy-2-ethoxyethyl) urea)
A flask equipped with a condenser and a stirrer was charged with 12 parts of 2-methacryloyloxy-2-ethoxyethyl isocyanate and 30 parts of tetrahydrofuran. Subsequently, 2 parts of distilled water was added, the temperature was raised to 40 ° C., and the mixture was gently stirred for 1 hour. Tetrahydrofuran and distilled water were removed by distillation under reduced pressure to obtain a colorless liquid.
It was confirmed by ¹ H-NMR that the obtained compound was 1,3-bis (methacryloyloxy-2-ethoxyethyl) urea.

Preparation of pigment dye dispersion Preparation Example 1
(A) C.I. I. Pigment Red 254 (manufactured by Ciba Specialty Chemicals, trade name BK-CF) is 9.0 parts by mass and cyanine dye-1 is 2.0 parts by mass, and as a dispersant, BYK-LPN21116 (by BYK (BYK), solid content) (Concentration 40% by mass) is 8.0 parts by mass, (B) 7.7 parts by mass of the binder resin (B-1) solution as the binder resin, and propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether = 75.6 as the solvent. A pigment dye dispersion (A-1) was prepared by mixing / dispersing with a /1.6 (mass ratio) mixed solvent for 12 hours by a bead mill and then filtering with a Millipore filter having a pore size of 0.5 μm.

Preparation Examples 2-8
In Preparation Example 1, pigment dye dispersions (A-2) to (A-8) were prepared in the same manner as Preparation Example 1, except that the type and amount of each component were changed as shown in Table 1.

Preparation Example 9
(A) C.I. I. 9.5 parts by mass of CI Pigment Blue 15: 6 and 0.5 parts by mass of xanthene dye-2, and 8.5 parts by mass of BYK-LPN21116 (manufactured by BYK Corporation (solid content concentration 40% by mass)) as a dispersant. , (B) 6.3 parts by mass of the binder resin (B-1) solution as the binder resin, and propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether = 62.0 / 6.6 (mass ratio) mixed solvent as the solvent. And mixed and co-dispersed by a bead mill for 12 hours. To this was added a solution prepared by dissolving 1.6 parts by mass of xanthene dye-2 in 6.4 parts by mass of propylene glycol monoethyl ether, and filtered through a Millipore filter having a pore size of 0.5 μm to obtain a pigment dye dispersion (A- 9) was prepared.

In Table 1, each component is as follows.
BrDPP: Compound represented by the following formula (BrDPP) Cyanine dye-1: A salt containing a cationic chromophore (cat-1) described later and p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt are exchanged. And a dye represented by the following formula (Cya-1) (basic cyanine dye). Cyanine dye-1 can be produced by salt exchange of a salt containing a cationic chromophore (cat-1) and p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt by a known method.
Xanthene dye-1: “salt-forming compound (A-1)” (acidic xanthene dye) obtained according to the method described in paragraph [0163] of JP2012-208454A
Dipyrromethene dye-1: Exemplified compound (11) of JP 2013-083916 A (dipyrromethene metal complex dye)
Triarylmethane dye-1: “Triarylmethane 1” (basic triarylmethane dye) described in Chemical formula 57 of JP-A-2015-199912
Triarylmethane dye-2: “Triarylmethane 3” (basic triarylmethane dye) described in Chemical Publication No. 59 of JP-A-2015-199912
Xanthene Dye-2: Compound represented by Formula (Ia-7) (acidic xanthene dye) obtained according to Example 1a of International Publication No. 2014/192773 pamphlet
PGMEA: Propylene glycol monomethyl ether acetate PGEE: Propylene glycol monoethyl ether

Preparation and evaluation of coloring composition Example 1
(A) Pigment dye dispersion (A-1) 100 parts by mass as a colorant, (B) 5.5 parts by mass (solid content concentration 33% by mass) of a binder resin (B-1) solution as a binder resin, (C) Aronix M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Toagosei Co., Ltd. as a polymerizable compound, NCI-930 (manufactured by ADEKA) 0.7 as a photopolymerization initiator Parts by mass and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholyl) phenyl] -1-butanone (trade name Irgacure 379EG, manufactured by BASF) Obtained in Synthesis Example 2 as 4 parts by mass, 0.05 part by mass of Megafac F-554 (manufactured by DIC Corporation) as a surfactant , 3-bis (methacryloyloxyethyl) urea (0.46 parts by mass) and propylene glycol monomethyl ether acetate (65 parts by mass) as a solvent were mixed and then filtered through a Millipore filter having a pore size of 0.5 μm to obtain a colored composition. Prepared.

The solvent resistance evaluation <br/> obtained colored composition, the SiO ₂ film on a soda glass substrate formed on the surface to prevent the elution of sodium ions was applied using a spin coater, 90 ° C. Was pre-baked for 2 minutes on a hot plate to form a coating film.
Subsequently, after cooling this board | substrate to room temperature, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed to the coating film with the exposure amount of 60 mJ / cm < ² > without using a high pressure mercury lamp. Then, shower development was performed for 60 seconds 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 further post-baked in a clean oven at 230 ° C. for 20 minutes to form a strip pattern on the substrate. About this strip-like pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate value (x, y) and the stimulus value (Y) in the CIE color system with a C light source and a 2-degree field of view. It was measured.

Next, the substrate was immersed in an N-methylpyrrolidone solution at 25 ° C. for 5 minutes. About the strip-shaped pattern after immersion, the chromaticity coordinate value (x, y) and the stimulus value (Y) in the CIE color system were measured in the same manner as described above. 2. Color change before and after immersion, that is, ΔE ^* _ab is calculated, “AA” when the value of ΔE ^* _ab is 2.0 or less, “A” when the value is greater than 2.0 and 3.0 or less. The case where it was larger than 0 and 4.0 or less was evaluated as “B” and the case where it was larger than 4.0 was evaluated as “C”. The results are shown in Table 2. It can be said that the smaller the ΔE ^* _ab value, the better the solvent resistance.

Evaluation of voltage holding ratio On a soda glass substrate on which a SiO2 film for preventing elution of sodium ions is formed on the surface, and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape, the obtained coloring is obtained. After spin-coating the composition, it was pre-baked for 1 minute on a hot plate at 100 ° C. to form a coating film having a thickness of 2.0 μm. Subsequently, the coating film was exposed at an exposure amount of 60 mJ / cm ² without using a photomask. Thereafter, the substrate was developed by being immersed in a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, washed with ultrapure water, and air-dried. Further, post-baking was performed at 230 ° C. for 30 minutes to cure the coating film to form a permanent cured film.
Next, the substrate on which the permanent cured film is formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealing agent mixed with 1.8 mm glass beads, and then Merck liquid crystal (MLC6608) is injected. Thus, a liquid crystal cell was produced. Next, the liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system (VHR-1A type, Toyo Technica Co., Ltd.). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio is a value obtained by (liquid crystal cell potential difference after 16.7 milliseconds / voltage immediately after application). The case where the voltage holding ratio of the liquid crystal cell is 93% or more is “AA”, the case where it is less than 93% and 90% or more is “A”, the case where it is less than 90% and 85% or more is “B”, and less than 85%. The case was evaluated as “C”. The results are shown in Table 2.

Examples 2-9 and Comparative Examples 1-5
In Example 1, a colored composition was prepared in the same manner as in Example 1 except that the type and amount of the color material solution were changed as shown in Table 2. Then, the obtained colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

In Table 2, each component is as follows.
C-1: Aronix M-402 (manufactured by Toagosei Co., Ltd.)
D-1: 1,3-bis (methacryloyloxyethyl) urea D-2: 1,3-bis (acryloyloxyethyl) urea D-3: 1,3-bis (methacryloyloxy-2-ethoxyethyl) urea E -1: NCI-930 (made by ADEKA)
E-2: Irgacure 379EG (manufactured by BASF)
E-3: NCI-831 (made by ADEKA)
E-4: Irgacure 907 (manufactured by BASF. 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one)
E-5: 2,4-diethylthioxanthone F-1: Megafax F-554 (manufactured by DIC Corporation)
G-1: Propylene glycol monomethyl ether acetate G-2: 3-methoxybutyl acetate G-3: Propylene glycol monomethyl ether

Preparation Examples 10-28
In Preparation Example 1, pigment dye dispersions (A-10) to (A-28) were prepared in the same manner as Preparation Example 1, except that the type and amount of each component were changed as shown in Table 3.

In Table 3, each component is as follows, and components not described here are the same as those in Table 1.
Azo dye-1: C.I. I. Solvent Orange 62
Azo dye-2: C.I. I. Salt Formation Compound of Solvent Orange 62 and Tetrabutylphosphonium Azo Dye-3: C.I. I. Solvent Orange 62 sodium salt azo dye-4: C.I. I. Salt Orange Compound of Solvent Orange 62 and Tetrabutylammonium Cyanine Dye-2: Has a basic cyanine chromophore which is a salt of a cationic chromophore (cat-1) described later and an anion (ani-1) described later Dye multimer (basic cyanine dye). Cyanine dye-2 is obtained by subjecting a salt containing a cationic chromophore (cat-1) and an “anion (ani-1) triethylamine salt” obtained according to Synthesis Example 6 described below to salt exchange by a known method. Can be manufactured.
Cyanine dye-3: a salt (basic cyanine dye) of a cationic chromophore (cat-2) and p- (vinylphenyl) trifluoromethanesulfonylimide acid described later. Cyanine dye-3 can be produced by the same salt exchange as cyanine dye-1.
Cyanine dye-4: a salt (basic cyanine dye) of a cationic chromophore (cat-3) and a bis (trifluoromethanesulfonyl) imide anion described later. Cyanine dye-4 can be produced by salt exchange of a salt containing a cationic chromophore (cat-3) and bis (trifluoromethanesulfonyl) imide lithium by a known method.
Cyanine dye-5: a dye multimer (basic cyanine dye) having a basic cyanine chromophore, which is a salt of a cationic chromophore (cat-4) described later and an anion (ani-1) described later. Cyanine dye-5 can be produced by the same salt exchange as cyanine dye-2.
Cyanine dye-6: a dye multimer (basic cyanine dye) having a basic cyanine chromophore, which is a salt of a cationic chromophore (cat-5) described later and an anion (ani-1) described later. Cyanine dye-6 can be produced by the same salt exchange as cyanine dye-2.
Cyanine dye-7: a dye multimer (basic cyanine dye) having a basic cyanine chromophore, which is a salt of a cationic chromophore (cat-6) described later and an anion (ani-1) described later. Cyanine dye-7 can be produced by the same salt exchange as cyanine dye-2.
Cyanine dye-8: a dye multimer (basic cyanine dye) having a basic cyanine chromophore, which is a salt of a cationic chromophore (cat-7) described later and an anion (ani-1) described later. Cyanine dye-8 can be produced by the same salt exchange as cyanine dye-2.
Xanthene Dye-3: “Dye (A-1)” (acidic xanthene dye) obtained according to Synthesis Example 1 of JP2013-19077A
Dipyrromethene dye-2: “Exemplary Compound B-2” (dipyrromethene metal complex dye) described in Chemical Publication 12 of International Publication No. 2012/137888 Pamphlet
Cyanine dye-9: a pigment multimer (basic cyanine dye) having a basic cyanine chromophore obtained according to Synthesis Example 5 described later

The cationic chromophore (cat-1) is “compound (C1-2-1)” described in Chemical formula 27 of JP-A-2015-049482.
The cationic chromophore (cat-2) is a chromophore of “cationic cyanine dye A-1” described in Chemical Formula 20 of JP-A-2015-118267.
The cationic chromophore (cat-3) is “compound (C1-3-1)” described in Chemical Formula 27 of JP-A No. 2015-049482.
The cationic chromophore (cat-4) is a chromophore of “cationic cyanine dye A-2” described in Chemical formula 21 of JP-A-2015-118267.
The cationic chromophore (cat-5) is a chromophore of a cyanine compound described in Chemical Formula 7 of JP-A-2015-004014.
The cationic chromophore (cat-6) is a chromophore of “Chemical formula 16” described in Chemical formula 12 of JP-A-2015-004014.
The cationic chromophore (cat-7) is a chromophore of “cationic cyanine dye F-5” described in Chemical formula 71 of JP-A-2014-224970.

Synthesis Example 5 (Synthesis of cyanine dye-9)
In a reaction vessel equipped with a cooling pipe, 5.46 g of bis (trifluoromethanesulfonyl) imide anion salt of “Compound No. 14” described in Japanese Patent No. 5955584, 2.51 g of methacrylic acid, 3,4-epoxy 2.00 g of cyclohexylmethyl methacrylate and 0.130 g of α-thioglycerol were added and dissolved in 20 g of cyclohexanone. The solution was heated to 100 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, a solution prepared by dissolving 98.0 mg of α, α'-azobisisobutyronitrile in 10.4 g of cyclohexanone was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours. Continued. After the reaction solution was cooled to room temperature, 60 g of acetone was added to make a uniform solution, which was added dropwise to 1.1 L of hexane. The produced precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C. to obtain a polymer represented by the following structural formula. This is designated as “cyanine dye-9”.

Synthesis Example 6 (Synthesis of triethylamine salt of anion (ani-1))
In a reaction vessel equipped with a condenser tube, 5.46 g of p- (vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt, 2.51 g of methacrylic acid, 2.00 g of 3,4-epoxycyclohexylmethyl methacrylate and 0.130 g of α-thioglycerol. And dissolved in 20 g of cyclohexanone. The solution was heated to 100 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, a solution prepared by dissolving 98.0 mg of α, α'-azobisisobutyronitrile in 10.4 g of cyclohexanone was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours. Continued. After the reaction solution was cooled to room temperature, 60 g of acetone was added to make a uniform solution, which was added dropwise to 1.1 L of hexane. The produced precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C. to obtain a polymer represented by the following structural formula. This is referred to as “triethylamine salt of anion (ani-1)”.

Examples 10-28
A colored composition was prepared in the same manner as in Example 1 except that the type and amount of the color material solution were changed as shown in Table 4 in Example 1. Then, the obtained colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 4.

Claims (10)

A coloring composition containing (A) a colorant, (B) a binder resin, and (C) a polymerizable compound,
(A) the colorant contains a dye,
Further, (D) a coloring composition containing a compound having a ureylene group and a polymerizable unsaturated bond in the molecule.   (D) The coloring composition of Claim 1 whose content of the compound which has a ureylene group and a polymerizable unsaturated bond in a molecule | numerator is 1-300 mass parts with respect to 100 mass parts of dyes.   The coloring composition according to claim 1 or 2, wherein the dye contains a basic dye or an acid dye.   The coloring composition according to any one of claims 1 to 3, wherein the dye is selected from a triarylmethane dye, a cyanine dye, a xanthene dye, and a dipyrromethene dye. (D) The coloring composition of any one of Claims 1-4 whose compound which has a ureylene group and a polymerizable unsaturated bond in a molecule | numerator is a compound represented by following formula (1).


[In Formula (1),
n independently represents an integer of 1 to 3,
R ¹ represents, independently of each other, an n + 1 valent organic group,
R ² independently represents a hydrogen atom or a methyl group. ]   A colored cured film comprising a dye and a compound having a ureylene group and a polymerizable unsaturated bond in the molecule.   A colored cured film comprising a dye and a compound having a structural unit derived from a ureylene group and a polymerizable unsaturated bond.   A color filter comprising the colored cured film according to claim 6.   A display element provided with the colored cured film according to claim 6. A solid-state imaging device comprising the colored cured film according to claim 6.