JP6303936B2 - Colored composition, colored cured film, and display element - Google Patents

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 of obtaining pixels of each color by irradiation (hereinafter referred to as “exposure”) and development is known (for example, see Patent Documents 1 and 2). In addition, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (for example, see Patent Document 4).

In recent years, there has been a growing social demand for energy saving. For example, a display element that achieves both high-quality display performance and power saving is required. In order to meet this demand, attempts have been made to increase the luminance and contrast of the color filter while suppressing power consumption by suppressing the luminance of the backlight.
As the colorant used in the color filter, a pigment is often used from the viewpoint of heat resistance and solvent resistance. In the case of a coloring composition forming a green pixel, it is known to use a combination of a halogenated zinc phthalocyanine pigment and various yellow pigments. For example, in Patent Documents 5 to 6, a halogenated zinc phthalocyanine pigment and a quinophthalone pigment are used. Are used in combination. In Patent Document 7, brominated zinc phthalocyanine pigment, pigment Y (C.I. Pigment Yellow 150) and C.I. I. It is disclosed that Pigment Yellow 138 is used in combination.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP2012-098712A JP 2013-011867 A JP 2013-037276 A

  However, in the case of the colored compositions described in Patent Documents 5 to 7, it has been found that the thickness of the colored cured film must be increased in order to improve the chromaticity characteristics such as luminance and contrast. If the colored cured film is thick, the display element also becomes thick, which tends to be an obstacle to the reduction in thickness and weight of the display element. Therefore, at present, there is a strong demand for the development of a coloring composition suitable for forming a colored cured film having high brightness and contrast and good chromaticity characteristics even for a thin film.

  Accordingly, an object of the present invention is to provide a coloring composition suitable for forming a colored cured film having high brightness and contrast and good chromaticity characteristics even if it is a thin film. 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-described problems can be solved by using a specific colorant at a certain quantitative ratio.

That is, the present invention provides a colored composition comprising (A) a colorant, (B) a binder resin, and (C) a polymerizable compound, wherein (A) the colorant comprises a zinc halide phthalocyanine pigment, a quinophthalone pigment, , and a azomethine copper pigment, wherein the content of w ₂ quinophthalone pigment, a ratio between the content w ₃ of azomethine copper pigment is _{w 2 / w 3 = 70 /} 30~85 / 15 in mass ratio And providing a coloring composition.

Further, the present invention is a halogenated zinc phthalocyanine pigment, a quinophthalone pigment, and a azomethine copper pigment, the content of w ₂ quinophthalone pigments, w ₂ ratio of the content of w ₃ of azomethine copper pigments in a mass ratio The present invention provides a colored cured film in which / w ₃ = 70/30 to 85/15, and a display element including the colored cured film. Here, the “colored cured film” means a green pixel or the like used for a display element or a solid-state imaging element.

If the coloring composition of this invention is used, even if it is a thin film, a colored cured film with high brightness | luminance and contrast can be formed. Moreover, the colored cured film excellent in heat resistance and solvent resistance can also be formed by using the coloring composition of this invention.
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, a halogenated zinc phthalocyanine pigment as (A) a colorant, and a quinophthalone pigment, and a azomethine copper pigment, the content of w ₂ quinophthalone pigment, a content w ₃ of azomethine copper pigments The ratio of w ₂ / w ₃ = 70/30 to 85/15 in terms of mass ratio.

  As the halogenated zinc phthalocyanine, brominated zinc phthalocyanine or brominated chlorinated zinc phthalocyanine is preferable. Brominated chlorinated zinc phthalocyanine is C.I. in the color index (CI) name. I. It is a pigment classified as Pigment Green 58, and preferably has a structure represented by the following formula (1).

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

The quinophthalone yellow pigment is not particularly limited. I. Pigment Yellow 138 is preferable.
Examples of the azomethine copper pigment include C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 129 and the like. I. Pigment Yellow 129 is preferable.

In the present invention, the content of w ₂ quinophthalone pigments, but requires that the ratio between the content w ₃ of azomethine copper pigment is _{w 2 / w 3 = 70 /} 30~85 / 15 in mass ratio, the The ratio is more preferably w ₂ / w ₃ = 70/30 to 80/20, and still more preferably 70/30 to 75/25. By setting it as such an aspect, even if it is a thin film, the colored cured film which has high brightness | luminance and contrast, and is excellent also in heat resistance and solvent resistance can be formed.
The content mass ratio (w ₁ / w ₃ ) between the content w ₁ of the halogenated zinc phthalocyanine pigment and the content w ₃ of the azomethine copper pigment can be selected as appropriate, but the viewpoint of further improving the brightness and contrast Therefore, it is preferable that w ₁ / w ₃ = 65/35 to 90/10, more preferably 70/30 to 90/10, still more preferably 75/25 to 88/12, and 80 Particularly preferred is / 20 to 86/14.

  The colored composition of the present invention is usually used for forming a green pixel. In this case, other colorants can be mixed together with the halogenated zinc phthalocyanine pigment, the quinophthalone pigment and the azomethine copper pigment. Other colorants are not particularly limited, and colors and materials can be appropriately selected according to the application.

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

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), that is, the following color index (CI) numbers. Can be mentioned.

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. Green pigments such as CI Pigment Green 36;
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, JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-191304, JP-A-2010-237384, JP-A-2010-237469, JP-A-2011-006602, Examples include lake pigments described in JP-A-2011-145346.

The dyes are preferably xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, and the like. More specifically, JP 2010-32999 A, JP 2010-254964 A, JP 2011-138094 A, International Publication No. 2010/123071, Pamphlet 2011-116803, JP 2011. Organic dyes described in JP-A No. 117995, JP-A No. 2011-133844, JP-A No. 2011-174987, and the like.
In the present invention, the pigment and the dye can be used alone or in admixture of two or more.
Among these, as other colorants, green colorants other than halogenated zinc phthalocyanine pigments, yellow colorants other than quinophthalone pigments and azomethine copper pigments are preferable.

  In the present invention, a zinc halide phthalocyanine pigment, a quinophthalone pigment, an azomethine copper pigment, and other pigments that are optionally mixed can be obtained by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. It can also be used after purification. Further, these pigments 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. 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 Laid-Open No. 8-179111 can be employed.

Moreover, in this invention, a well-known dispersing agent and dispersion | distribution adjuvant can also be included with a halogenated zinc phthalocyanine pigment, a quinophthalone pigment, an azomethine copper pigment, and the other colorant mixed arbitrarily.
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, acrylic-based dispersants and the like can be mentioned. Examples of commercially available products include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK Chemy (BYK)). (Meth) acrylic dispersants, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 , Manufactured by BYK Co., Ltd.), urethane dispersants such as Solsperse 76500 (manufactured by Lubrizol Corp.), polyethyleneimine dispersants such as Solsperse 24000 (manufactured by Lubrizol Corp.), Ajisper PB821, Ajisper In addition to polyester-based dispersants such as PB822, Azisper PB880, and Azisper PB881 (manufactured by Ajinomoto Fine Techno Co., Ltd.), dispersants such as BYK-LPN21324 (manufactured by BYK Chemy (BYK)) can be used.

Especially, as a dispersing agent, at least 1 sort (s) chosen from the group which consists of a (meth) acrylic-type dispersing agent, a urethane type dispersing agent, and a polyester-type dispersing agent is preferable, and a (meth) acrylic-type dispersing agent is more preferable.
Among the (meth) acrylic dispersants, (meth) acrylic dispersants having a crosslinkable functional group are preferable. Examples of the crosslinkable functional group include oxygen-containing saturated heterocyclic groups such as oxiranyl groups, oxetanyl groups, tetrahydrofuranyl groups, and tetrahydropyranyl groups, ethylenically unsaturated groups, epithio groups, and (dithio) carbonate groups. it can. Among these crosslinkable functional groups, oxygen-containing saturated heterocyclic groups are preferable, oxetanyl groups, tetrahydrofuranyl groups, and tetrahydropyranyl groups are more preferable, and oxetanyl groups and tetrahydrofuranyl groups are more preferable.
The (meth) acrylic dispersant having a crosslinkable functional group refers to a compound comprising a (co) polymer of a (meth) acrylic monomer having a crosslinkable functional group. Further, “(meth) acrylic monomer” means a polymerizable compound having a (meth) acryloyl group in the molecule, and “(meth) acryloyl group” means an acryloyl group or a methacryloyl group. And
Examples of the (meth) acrylic dispersant having a crosslinkable functional group include a copolymer of a (meth) acrylic monomer having a crosslinkable functional group and another copolymerizable (meth) acrylic monomer. A polymer can be mentioned. Other copolymerizable (meth) acrylic monomers include, for example, (meth) acrylate having an oxyalkylene group, (meth) acrylate having a hydroxyl group, and (meth) acrylate having a primary to tertiary amino group. , (Meth) acrylic acid alkyl ester, (meth) acrylic acid aryl ester, and the like, and these may be used alone or in combination.
The ratio of the (meth) acrylic monomer having a crosslinkable functional group is preferably 5 to 50% by mass and more preferably 10 to 30% by mass in the total monomers. In addition, the (meth) acrylic-type dispersing agent which has a crosslinkable functional group is compoundable by the method of Unexamined-Japanese-Patent No. 2012-118505, for example.
By such an aspect, the desired effect of this invention can be acquired more.

  In this invention, 5-300 mass parts is preferable with respect to 100 mass parts of (A) colorants, and, as for content of (B) dispersing agent, 10-200 mass parts is more preferable, and 20-100 mass parts is further. preferable. By setting it as such an aspect, it becomes easy to obtain the desired effect of this application.

  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% 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.
Moreover, when another colorant is included, the content ratio of the other colorant is preferably 50% by mass or less, and more preferably 30 parts by mass or less with respect to the total content of the colorant. The lower limit is not particularly limited and may be 0.01% by mass or more.

-(B) Binder resin-
Although it does not specifically limit as (B) binder resin in this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as “unsaturated monomer (b2)”). .

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

Moreover, as said unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (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 admixture of two or more.

  In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

  Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

  The binder resin in the present invention has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably Is 3,000 to 50,000. By setting it as such an aspect, the remaining-film rate of a film, a pattern shape, heat resistance, an electrical property, and the resolution can be improved further, and generation | occurrence | production of the dry foreign material at the time of application | coating can be suppressed at a high level.

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

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in 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 individually or in mixture of 2 or more types.

  In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. By setting it as such an aspect, alkali developability, the storage stability of a coloring composition, pattern shape, and chromaticity characteristic can be improved further.

-(C) Polymerizable compound-
In the present invention, the polymerizable compound refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

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

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. The alkylene oxide-modified polyfunctional (meth) acrylate is at least one selected from bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from modified isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide Pen modified with at least one selected from pentaerythritol tri (meth) acrylate, ethylene oxide and propylene oxide. Dipentaerythritol modified with at least one selected from dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from taerythritol tetra (meth) acrylate, ethylene oxide and propylene oxide Examples include hexa (meth) acrylate.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril and the like.

Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethanes (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate is a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, among polyfunctional (meth) acrylates having a carboxyl group, obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.
In this invention, (C) polymeric compound can be used individually or in mixture of 2 or more types.

  The content of the polymerizable compound (C) in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, and further 80 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. preferable. By setting it as such an aspect, sclerosis | hardenability and alkali developability can be improved further and generation | occurrence | production of a ground stain, a film | membrane residue, etc. on the board | substrate of a non-exposed part or a light shielding layer can be suppressed at a high level.

-(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 individually or in mixture 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 the 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, hydrogen donors can be used alone or in admixture of two or more, but one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. 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 weight, particularly preferably 1 to 100 parts by weight, with respect to 100 parts by weight of the polymerizable compound (C). By setting it as such an aspect, sclerosis | hardenability and a film characteristic can be improved further.

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

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

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

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate ;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

  Of these solvents, (poly) alkylene glycol monoalkyl ethers, lactic acid alkyl esters, (poly) alkylene glycol monoalkyl ether acetates, and other ethers from the viewpoints of solubility, pigment dispersibility, coatability, etc. , Ketones, diacetates, alkoxycarboxylic acid esters, and other esters are preferred, especially propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-hept Non, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3- Methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, Ethyl pyruvate and the like are preferable.

  In this invention, a solvent can be used individually or in mixture of 2 or more types.

  (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, the coloring agent dispersion liquid with favorable dispersibility and stability and the coloring composition with favorable coating property and stability can be obtained.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- 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-hydroxy 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.

  The coloring composition of the present invention can be prepared by an appropriate method. Examples of the preparation method include (A) to (C) components together with (E) a solvent and other components optionally added. , Can be prepared by mixing. Among them, in the presence of a dispersant in the solvent (E) in the solvent, and optionally with a part of the component (B), for example, using a bead mill, a roll mill or the like, the pigment is mixed and dispersed while being pulverized to obtain a pigment dispersion. Next, a method of preparing the pigment dispersion by adding (B) to (C) components and, if necessary, additional solvent and other components and mixing them is preferable.

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, and includes, for example, a green pixel used for a color filter.

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, after applying a green liquid composition of the radiation-sensitive colored composition of the present invention on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which green pixel patterns (colored cured films) are arranged in a predetermined arrangement.

  Subsequently, each radiation-sensitive colored composition of red or blue is used, and the radiation-sensitive colored composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above, so that the red pixel array and blue Are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithographic method. It can also be formed in the same manner as in the case of forming the above-mentioned pixel using a sexually colored composition.

Examples of the substrate used when forming the 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 green liquid composition of the thermosetting coloring composition of the present invention is discharged into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a green pixel pattern.

  Subsequently, red or blue thermosetting coloring compositions are used to sequentially form a red pixel pattern and a blue pixel pattern on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

In addition, since the partition plays not only a light shielding function but also a function for preventing the color mixing of the thermosetting coloring compositions discharged in the respective sections, it is compared with the black matrix used in the first method described above. The film thickness is thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used 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.

  Since the color filter including the colored cured film of the present invention thus formed has extremely high luminance, contrast, and coloring power, a color liquid crystal display element, a color imaging tube element, a color sensor, an organic EL display element, and electronic paper It is extremely useful for such as.

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.

  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
Binder resin (B-1)
A flask equipped with a condenser and a stirrer was charged with 80 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 50 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 15 parts by mass of 2-hydroxyethyl methacrylate, 28 parts by mass of 2-ethylhexyl methacrylate, N- A mixed solution of 12 parts by weight of phenylmaleimide and 15 parts by weight of mono (2-acryloyloxyethyl) succinate, and 20 parts by weight of propylene glycol monomethyl ether acetate and 2,2′-azobis (2,4-dimethylvaleronitrile) 6 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 further polymerized for 1 hour to obtain a binder resin (B-1) solution (solid content concentration = 40% by mass). The obtained binder resin (B-1) was Mw = 10500, Mn = 5900, and Mw / Mn = 1.78.

<Synthesis of dispersant>
Synthesis example 2
Dispersant (1)
To a flask purged with argon, 80 parts by mass of tetrahydrofuran, 45 parts by mass of dimethylaminoethyl methacrylate and 5 parts by mass of sec-butyllithium were added, and the mixture was maintained and stirred at -78 ° C. for 3 hours with COOLNICS using ethylene glycol as a refrigerant. It was. Next, 23 parts by mass of methyl methacrylate, 17 parts by mass of methoxy-terminated polyethylene glycol methacrylate (manufactured by NOF Corporation, product name: Blenmer PME-200), tetrahydrofurfuryl methacrylate (Kyoeisha Chemical Co., Ltd., product name: Wright) Ester (THF) (15 parts by mass) and propylene glycol monomethyl ether acetate (70 parts by mass) were added, polymerization was carried out for 3 hours while maintaining this temperature, and the reaction was stopped with methanol, followed by extraction and purification with ultrapure water and ethyl acetate. The organic layer was collected, and ethyl acetate was distilled off under reduced pressure using an evaporator. The obtained resin solid was dissolved and diluted with propylene glycol monomethyl ether acetate to prepare a solid content concentration of 40%. The obtained resin had Mw = 10000, Mn = 7700, and Mw / Mn = 1.30. Let the obtained resin solution be a dispersing agent (1) solution. The dispersant (1) is a (meth) acrylic dispersant having a tetrahydrofuranyl group as a crosslinkable functional group.

<Preparation of colorant dispersion>
Preparation Example 1
Colorant dispersion (A-1)
(A) C.I. I. Pigment Green 58 in an amount of 7.33 parts by mass, C.I. I. Pigment Yellow 129 in 0.94 parts by mass, and C.I. I. Pigment Yellow 138 (4.46 parts by mass), BYK-LPN21116 (manufactured by BYK) (non-volatile component 40% by mass) as a dispersant, 11.25 parts by mass, (B) binder resin (B-1) as binder resin 11.25 parts by mass of the solution (solid content concentration 40%) and (E) 76.5 parts by mass of propylene glycol monomethyl ether acetate and 1.50 parts by mass of propylene glycol monomethyl ether as a solvent were mixed and dispersed by a bead mill. Thus, a green colorant dispersion (A-1) was prepared.

Preparation Examples 2 to 10
Colorant dispersions (A-2) to (A-10)
In Preparation Example 1, green colorant dispersions (A-2) to (A-10) 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. .

In Table 1, each component is as follows.
G58: C.I. I. Pigment Green 58
Y138: C.I. I. Pigment Yellow 138
Y129: C.I. I. Pigment Yellow 129
Y150: C.I. I. Pigment Yellow 150
LPN21116: BYK-LPN21116 (Bikchemy (BYK), non-volatile component 40% by mass)
Dispersant (1): Dispersant (1) solution synthesized in Synthesis Example 2 (solid content concentration 40%)
E-1: Propylene glycol monomethyl ether acetate E-2: Propylene glycol monomethyl ether

<Preparation and evaluation of coloring composition>
Example 1
Preparation of coloring composition (A) 510 parts by mass of a colorant dispersion (A-1) as a colorant, (B) 100 parts by mass of a binder resin (B-1) solution as a binder resin, (C) 90 parts by mass of pentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA), (D) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1 as a photopolymerization initiator -3 parts by weight of ON (Ciba Specialty Chemicals, trade name Irgacure 369) and ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime)] (BASF, trade name IRGACURE OXE02) 12 parts by mass, 3-methacryloilo as an adhesion promoter 5 parts by mass of cyclopropyltrimethoxysilane, 5 parts by mass of a 5% by mass propylene glycol monomethyl ether acetate solution of Emulgen A-60 (manufactured by Kao Corporation) as a surfactant, and 155 propylene glycol monomethyl ether acetate as a solvent (E) A green coloring composition (S-1) was prepared by mixing part by mass and 420 parts by mass of ethyl 3-ethoxypropionate.

(1) Evaluation of chromaticity characteristics The color composition (S-1) was applied on a glass substrate using a spin coater, and then pre-baked on a 90 ° C hot plate for 1 minute to obtain a film thickness of 2.5 µm. The coating film was formed. 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, the coating film on the substrate was irradiated with radiation including each wavelength of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp without passing through a photomask at an illuminance of 35 mW, 600 J / m. The exposure amount was ² . After that, shower development was performed by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 25 ° C. at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm) onto the coating film on the substrate. . Thereafter, these substrates were washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 20 minutes to produce a green cured film.
Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate value (x, y) and the stimulus value in the CIE color system with a C light source and a 2-degree visual field for the three cured films obtained. (Y) was measured. From the measurement results, the chromaticity coordinate value x and the stimulus value (Y) when the chromaticity coordinate value y = 0.590 were obtained. The evaluation results are shown in Table 3. It can be said that the larger the stimulus value (Y), the higher the luminance.
Moreover, the film thickness of the obtained cured film was measured using the alpha step IQ made from KLA-Tencor. In Table 3, the film thickness of the comparative example 1 was set to 100, and it put together as a relative value with respect to this. It can be said that the thinner the film thickness, the greater the coloring power of the colorant.

(2) Contrast evaluation The substrate on which the cured film is formed is sandwiched between two deflecting plates, and the front deflecting plate is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and the luminance meter LS- The maximum value and the minimum value of the light intensity transmitted through 100 (Minolta Co., Ltd.) were measured. And about each cured film, the value which remove | divided the maximum value by the minimum value was made into the contrast ratio. From the measurement result, the contrast ratio at the chromaticity coordinate value y = 0.590 was determined. The evaluation results are shown in Table 3. Note that the larger the numerical value, the better the contrast ratio.

(3) Evaluation of heat resistance The colored composition (S-1) was applied on a glass substrate using a slit die coater, and then pre-baked on a 90 ° C hot plate for 4 minutes to obtain a film thickness of 2.0 µm. The coating film was formed. Next, after cooling the substrate to room temperature, each coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 400 J / m ² through a photomask using a high-pressure mercury lamp. Thereafter, shower development was performed on these substrates using a 0.04 mass% potassium hydroxide aqueous solution at 25 ° C. for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes to form a green dot pattern on the substrate.
About the obtained dot pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a C light source, a chromaticity coordinate value (x, y) and a stimulus value (Y) in the CIE color system with a 2-degree field of view. Was measured. Subsequently, the chromaticity coordinate value (x, y) and the stimulus value (Y) after additional baking at 230 ° C. for 90 minutes were measured, and the color change before and after the additional baking, that is, ΔE _ab was evaluated. As a result, a value of ΔE _ab less than 2 was evaluated as “」 ”, a value of 2 or more and less than 3 as“ ◯ ”, a value of 3 or more and less than 5 as“ Δ ”, and a value of 5 or more as“ x ”. . The evaluation results are shown in Table 3. It can be said that the smaller the value of ΔE _ab, the better the heat resistance.

(4) Evaluation of solvent resistance Using the colored composition (S-1), a green dot pattern was formed on the substrate in the same manner as in the above “evaluation of heat resistance”. The substrate on which the dot pattern was formed was immersed in N-methylpyrrolidone at 25 ° C. for 30 minutes, and ΔE _ab before and after immersion was evaluated in the same manner as in the above “Evaluation of heat resistance”. As a result, a value of ΔE _ab that was smaller than 3 was evaluated as “◯”, a value between 3 and 5 as “Δ”, and a value larger than 5 as “×”. The evaluation results are shown in Table 3. It can be said that the smaller the value of ΔE _ab, the better the solvent resistance.

Examples 2-5 and Comparative Examples 1-5
In Example 1, coloring compositions (S-2) to (S-10) were prepared in the same manner as in Example 1 except that the types and amounts of the colorant dispersion and the solvent were changed as shown in Table 2. did. Then, the obtained colored compositions (S-2) to (S-10) were evaluated in the same manner as in Example 1. The results are shown in Table 3.

In Table 2, each component is as follows.
C-1: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA)
D-1: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (product name: Irgacure 369, manufactured by Ciba Specialty Chemicals)
D-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime)] (manufactured by BASF, trade name IRGACURE OXE02)
F-1: 3-methacryloylpropyltrimethoxysilane F-2: 5% by mass of propylene glycol monomethyl ether acetate in Emulgen A-60 (manufactured by Kao Corporation) E-1: propylene glycol monomethyl ether acetate E-3: 3- Ethyl ethoxypropionate E-4: Methoxybutyl acetate

Claims (5)

A coloring composition comprising (A) a colorant, (B) a binder resin and (C) a polymerizable compound,
(A) colorant comprises a halogenated zinc phthalocyanine pigment, a quinophthalone pigment, an azomethine copper pigment, the content of w ₂ quinophthalone pigments, w ratio is the mass ratio of the content of w ₃ of azomethine copper pigments ₂ / w is ₃ = 70/30 to 85/15, colored composition. The content of w ₁ of the halogenated zinc phthalocyanine pigment, the ratio between the content w ₃ of azomethine copper pigment is _{w 1 / w 3 = 65 /} 35~90 / 10 in mass ratio, coloration according to claim 1 Composition.   Furthermore, the coloring composition of Claim 1 or 2 containing the (meth) acrylic-type dispersing agent which has a crosslinkable functional group. A colored cured film, which is a cured product of the colored composition according to claim 1 .   A display element comprising the colored cured film according to claim 4.