JP2014178676A - Coloring composition, cured coloring film, display element, and solid-state image sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition suitable for forming a cured coloring film having high brightness and coloring power.SOLUTION: A coloring composition contains a colorant (A), a binder resin (B), and a polymerizable compound (C), and the colorant (A) contained includes C.I. Pigment Red 264 and an isoindoline pigment.

Description

  The present invention relates to a colored composition, a colored cured film, a display element, and a solid-state image sensor, and more specifically, to a transmissive or reflective color liquid crystal display element, solid-state image sensor, 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 and a solid-state imaging device 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 demand for higher luminance and expansion of the color reproduction region for display elements. For this reason, it is requested | required to have high brightness | luminance and high color purity also with respect to the coloring composition used in order to form the pixel, black matrix, etc. which comprise a display element. Moreover, in a solid-state image sensor, it is requested | required that it should have coloring power with high color purity with the ultra-thin film thickness of 1 micrometer or less with respect to the colored pixel which comprises this element. In response to such demands, as a coloring composition capable of producing a color filter having high color purity, C.I. I. A coloring composition containing Pigment Red 264 (see, for example, Patent Document 5) has been proposed.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A Japanese Patent Laid-Open No. 10-300920

  However, there is a limit to the improvement in chromaticity characteristics even with such a colored composition, and therefore there is a strong demand for the development of a colored composition suitable for forming a colored cured film having higher luminance and higher color purity. The current situation is.

  Accordingly, an object of the present invention is to provide a coloring composition suitable for forming a colored cured film having high luminance and high coloring power. Furthermore, the subject of this invention is providing the display element and solid-state image sensor which comprise the colored cured film formed using the said coloring composition, and this colored cured film.

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

  That is, the present invention relates to a coloring composition containing (A) a colorant, (B) a binder resin, and (C) a polymerizable compound. I. The present invention provides a coloring composition containing Pigment Red 264 and an isoindoline pigment.

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

If the colored composition of the present invention is used, a colored layer having high luminance and high coloring power can be formed.
Therefore, the colored composition of the present invention can be used very suitably for the production of solid-state imaging devices such as color liquid crystal display devices, organic EL display devices, display devices such as electronic paper, and CMOS image sensors.

It is a figure which shows the emission spectrum of white LED obtained by the color mixture of blue LED and YAG type | system | group fluorescent substance used in the Example. It is a figure which shows the emission spectrum of 3 wavelength LED (white LED obtained by color mixing combining blue LED, red light emission fluorescent substance, and green light emission fluorescent substance) used in the Example.

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 comprises (A) C.I. I. Pigment Red 264 and an isoindoline pigment. Examples of isoindoline pigments include C.I. I. Pigment yellow 139, C.I. I. And CI Pigment Yellow 185. Among them, C.I. I. Pigment Yellow 185 is preferable.

(A ¹ ) C.I. I. The mass ratio [(A ¹ ) / (A ² )] of Pigment Red 264 and (A ² ) isoindoline pigment can be selected as appropriate, but from the viewpoint of further improving the luminance and coloring power, The ratio [(A ¹ ) / (A ² )] is preferably 99/1 to 50/50, more preferably 90/10 to 60/40, and 85/15 to 70/30. Is more preferable.

  The coloring composition of the present invention further contains C.I. I. Other colorants other than CI Pigment Red 264 and isoindoline pigments can also be mixed and used. Other colorants are not particularly limited, and colors and materials can be appropriately selected according to the application.

  Examples of other colorants include pigments, dyes, and natural pigments, and other colorants can be used alone or in combination of two or more. Among them, an organic pigment is preferable as the pigment and an organic dye is preferable as the dye from the viewpoint of obtaining a pixel having high 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 179, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment Red 254, etc. I. Red pigments other than CI Pigment Red 264;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Green pigments such as CI Pigment Green 58;
C. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Blue pigments such as CI Pigment Blue 80;
C. I. Pigment yellow 83, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 179, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211, C.I. I. Yellow pigments other than isoindoline, 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. 10/123071, Pamphlet 2011-116803, JP 2011. Organic dyes described in JP-A No. 117995, JP-A No. 2011-133844, JP-A No. 2011-174987, and the like.
In the present invention, the pigment and the dye can be used alone or in admixture of two or more.

  In the present invention, C.I. I. Pigment Red 264, the isoindoline-based pigment, and other pigments that are optionally mixed may 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. 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. 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, C.I. I. In addition to Pigment Red 264, the isoindoline pigment, and other colorants that are optionally mixed, known dispersants and dispersion aids may also be included. 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. Dispersing agents, polyester dispersants, (meth) acrylic dispersants and the like can be mentioned, and examples of the dispersion aid include pigment derivatives. Here, “(meth) acryl” means one or both of “acryl” and “methacryl”.

  Such a dispersant is commercially available. For example, as a (meth) acrylic dispersant, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, Big Chemie ( BYK)), and the like, Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 Lubrizol Co., Ltd.), polyethylene imine dispersant, Solsperse 24000 (Lubrisol Co., Ltd.), etc., polyester dispersant, Ajispa PB821, Adisper PB822, Adisper PB880, Adisper PB881 (or more, Ajinomoto Fine-Techno Co., Ltd.), and the like, can be mentioned, respectively.

Among such dispersants, (meth) acrylic dispersants are preferable.
As the (meth) acrylic dispersant, in addition to the commercially available (meth) acrylic dispersant, a (meth) acrylic dispersant having a crosslinkable functional group is also 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, an oxygen-containing saturated heterocyclic group is preferable, and an oxetanyl group and a tetrahydrofuranyl group are more preferable. 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.

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

  The colored composition of the present invention is usually used for forming a red pixel. I. Other colorants can be mixed and used together with Pigment Red 264 and the isoindoline pigment. In that case, C.I. I. It is preferable to include a red colorant other than CI Pigment Red 264. I. Pigment Red 177 is preferably included.

  The content of other colorants is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less, with respect to the total content of colorants. The lower limit is not particularly limited and may be 0.01% by mass or more. In particular, C.I. I. In the case of including Pigment Red 177, C.I. I. 20 mass% or more is preferable with respect to the total content of a coloring agent, and, as for the lower limit of the content rate of pigment red 177, 30 mass% or more is more preferable.

The coloring composition of the present invention has 0.660 ≦ x ≦ 0.690 and 0.300 ≦ in the chromaticity coordinates (x, y) in the XYZ color chromaticity diagram measured in a field of view twice using a C light source. It can be preferably used for forming a colored cured film satisfying y ≦ 0.320. From the viewpoint of further improving the chromaticity characteristics, the lower limit value of the chromaticity coordinate value x is preferably 0.665, more preferably 0.668, and the upper limit value of x is preferably 0.688. Preferably it is 0.686, More preferably, it is 0.682. The lower limit value of the chromaticity coordinate value y is preferably 0.302, more preferably 0.304, still more preferably 0.308, and the upper limit value of y is preferably 0.318, and more preferably 0. .315.
Further, the coloring composition of the present invention also has 0.660 ≦ x ≦ 0.690 and 0.300 ≦ y in the chromaticity coordinates (x, y) in the XYZ color chromaticity diagram measured using a white LED. It can be preferably used for forming a colored cured film satisfying ≦ 0.320.

When the colored composition of the present invention is used for a colored cured film of a display element, the content ratio of (A) the colorant is usually from the point of forming a pixel having high luminance and excellent coloring power, or a black matrix having excellent light shielding properties. The solid content of the coloring composition is 5 to 70% by mass, preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and particularly preferably 20 to 50% by mass. The colored composition of the present invention has a high luminance even when the content of the (A) colorant is 40% by mass or less, further 30% by mass or less, particularly 25% by mass or less in the solid content of the colored composition. A colored cured film having high coloring power can be produced.
Moreover, when using the coloring composition of this invention for the colored cured film of a solid-state image sensor, the content rate of (A) colorant is normal from the point which forms the pixel pattern which is excellent in color separation property, and suppresses a development residue. The solid content of the coloring composition is 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, and particularly preferably 50% by mass or more. On the other hand, the upper limit is usually 70% by mass or less from the viewpoint of suppression of development residue and good pattern formation. Here, the “solid content” is a component other than the solvent described later.

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

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

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

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 -10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) ) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (b2) can be used alone or in admixture of two or more.

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

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

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

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

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

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

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

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

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

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

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

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

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

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

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

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

  Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound etc. can be mentioned.

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

  Among preferred photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

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

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′. -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In this invention, a hydrogen donor can be used individually or in mixture of 2 or more types. Among these, it is preferable to use one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors in combination because the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like. As commercial products of O-acyloxime compounds, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), DFI-020, DFI-091 (above, manufactured by Daito Chemix Corporation), etc. may be used. it can.

  In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) polymeric compounds, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. By setting it as such an aspect, sclerosis | hardenability and a film characteristic can be improved further.

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

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

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

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

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

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

  In this invention, a solvent can be used individually or in mixture of 2 or more types. When used in combination, mix at least (poly) alkylene glycol monoalkyl ethers and (poly) alkylene glycol monoalkyl ether acetates, (poly) alkylene glycol monoalkyl ether acetates and alkoxycarboxylic acid esters. Are preferably used.

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

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- 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.
Among them, the colored composition of the present invention preferably contains an antioxidant, more preferably contains a hindered phenol-based antioxidant, and particularly pentaerythritol tetrakis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate].

  The colored composition of the present invention can be prepared by an appropriate method. For example, the components (A) to (C) are mixed together with a solvent and other components optionally added. Can be prepared. Among them, the pigment is mixed and dispersed in a solvent in the presence of a dispersant, optionally together with a part of the component (B), for example, using a bead mill, a roll mill or the like, to obtain a pigment dispersion, A method in which the components (B) to (C) and, if necessary, an additional solvent and other components are further added to the pigment dispersion and mixed is preferred.

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

Hereinafter, a colored cured film used for a color filter and a method for forming the same will be described.
As a method for 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 a pixel array of the three primary colors of blue, green and red is arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

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

Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  When applying the radiation-sensitive coloring composition to the substrate, an appropriate coating method such as spraying, roll coating, spin coating (spin coating), slit die coating (slit coating), bar coating, etc. Can be adopted. Among these, it is preferable to employ a spin coating method or a slit die coating method.

  Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.

  The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying.

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

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

For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

  Further, as a second method for producing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723 and JP-A-2000-310706 can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a blue liquid composition of the thermosetting coloring composition of the present invention is ejected into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, the coating film is exposed as necessary, and then cured by post-baking to form a blue pixel pattern.

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

In addition, since the partition plays not only a light shielding function but also a function for preventing the color mixing of the thermosetting coloring compositions discharged in the respective sections, it is compared with the black matrix used in the first method described above. The film thickness is thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming such a black spacer.
The colored composition of the present invention can be suitably used in forming any colored cured film such as each color pixel, black matrix, and black spacer used in the color filter.

  Since the color filter including the colored cured film of the present invention thus formed has extremely high luminance and coloring power, it can be used in color liquid crystal display elements, color imaging tube elements, color sensors, organic EL display elements, electronic papers, and the like. Very useful. In addition, the display element mentioned later should just have at least 1 or more of the colored cured film formed using the coloring composition of this invention.

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. Can be taken. Furthermore, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (indium oxide doped with tin) electrode or an IZO (mixture of acid value indium and zinc oxide) electrode It is also possible to adopt a structure in which the formed substrate is opposed to the liquid crystal layer. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained. 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 on the substrate side on which the ITO electrode or IZO 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
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, 38 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 resin (A-1) solution (solid content concentration = 40% by mass). Obtained resin (A-1) was Mw = 10500, Mn = 5900, and Mw / Mn = 1.78.

Synthesis example 2
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, 15 parts by mass of methacrylic acid, 10 parts by mass of styrene, 12.5 parts by mass of 2-hydroxyethyl methacrylate, 38 parts by mass of 2-ethylhexyl methacrylate, A mixed solution of 12 parts by mass of N-phenylmaleimide and 12.5 parts by mass of mono (2-acryloyloxyethyl) succinate, and 20 parts by mass of propylene glycol monomethyl ether acetate and 2,2′-azobis (2,4-dimethyl) A mixed solution of 6 parts by weight of valeronitrile) was added dropwise over 3 hours, and polymerization was performed for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and polymerization was further performed for 1 hour. Thereafter, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the solid content concentration was 40% by mass to obtain a resin (A-2) solution (solid content concentration = 40% by mass). Obtained resin (A-2) was Mw = 10,800, Mn = 5,900, and Mw / Mn = 1.83.

Synthesis example 3
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, 29 parts by mass of 2-ethylhexyl methacrylate, N- A mixed solution of 12 parts by weight of phenylmaleimide and 14 parts by weight of benzyl methacrylate, and a mixed solution of 20 parts by weight of propylene glycol monomethyl ether acetate and 3 parts by weight of azobisisobutyronitrile are added dropwise over 3 hours, and this temperature is maintained. And polymerized for 1 hour. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and polymerization was further performed for 1 hour. Thereafter, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the solid content concentration was 40% by mass to obtain a resin (A-3) solution (solid content concentration = 40% by mass). The obtained resin (A-3) was Mw = 9.700, Mn = 5,700, and Mw / Mn = 1.70.

<Synthesis of dispersant>
Synthesis example 4
To a 1000 mL flask were added 521.03 g of tetrahydrofuran (THF), 48.20 g of lithium chloride (3.59 mass% concentration in THF) and 2.11 g of diisopropylamine, and the mixture was cooled to −60 ° C. Thereafter, 8.67 g (15.36 mass% hexane solution) of n-butyllithium was added and aged for 15 minutes.
Next, 44.75 g of dimethylaminoethyl methacrylate (DMMA) was added dropwise, and the reaction was continued for 20 minutes after the addition. And GC (gas chromatography) was measured and the loss | disappearance of the monomer was confirmed. A part of the reaction solution was sampled and analyzed by GPC (mobile phase THF, PMMA standard). As a result, the molecular weight (Mw) was 3,060 and the molecular weight distribution (Mw / Mn) was 1.09.
Next, a mixed solution of 27.80 g of methyl methacrylate (MMA), 39.31 g of n-butyl methacrylate (nBMA) and 28.15 g of tetrahydrofurfuryl methacrylate (hereinafter sometimes abbreviated as THFMA) was dropped over 60 minutes. The reaction was continued for 30 minutes after the dropping. After measuring GC and confirming the disappearance of the monomer, 3.29 g of methanol was added to stop the reaction.
When the obtained copolymer was analyzed by GPC (mobile phase DMF, PMMA standard), the molecular weight (Mw) was 9,020 and the molecular weight distribution (Mw / Mn) was 1.12. Further, the obtained copolymer is a block copolymer of DMMA- [MMA / nBMA / THFMA], and the composition ratio (mass%) is DMMA / MMA / nBMA / THFMA = 32/20/28/20. I confirmed that there was.
The reaction solution was diluted with ethyl acetate, washed three times with water, and then the solvent was distilled off. After replacing the solvent in propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether was added, and the mixture was adjusted to be propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 7/3 (w / w). The tertiary amine structure was quaternized by adding 0.8 equivalent of benzyl chloride (BzCl) to DMMA and reacting at 70 ° C. for 7 hours. Finally, a resin solution (X-1) of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 7/3 (w / w) having a solid content concentration of 40% by mass was obtained. This resin corresponds to a dispersant having a tetrahydrofuranyl group as a crosslinkable functional group.

<Preparation of colorant dispersion>
Preparation Example 1
As a coloring agent, C.I. I. Pigment Red 264 in 10.7 parts by mass, C.I. I. 2.3 parts by weight of Pigment Yellow 185, 13.0 parts by weight (solid content concentration = 40% by weight) of BYK-LPN21116 (manufactured by BYK) as a dispersant, and 10. of the resin (A-1) solution. Using 0 parts by mass, 62.0 parts by mass of propylene glycol monomethyl ether acetate and 16.0 parts by mass of propylene glycol monoethyl ether as solvents, a red pigment dispersion (R-1) was prepared by mixing and dispersing with a bead mill. .

Preparation Examples 2-13
In Preparation Example 1, red pigment dispersions (R-2) to (R-13) were prepared in the same manner as in Preparation Example 1, except that the type and amount of the colorant were changed as shown in Table 1. In Preparation Example 4 and Preparation Examples 7 to 9, no matter what ratio the colorant described in Table 1 is mixed, evaluation of chromaticity characteristics using a C light source and a white LED emission spectrum described later as the light source In Example 1, a cured film satisfying chromaticity coordinate values of x ≧ 0.660 and y ≦ 0.320 could not be produced, and therefore the preparation of the pigment dispersion was abandoned.

Preparation Example 14
As a coloring agent, C.I. I. Pigment Red 264 in 10.7 parts by mass, C.I. I. Pigment Yellow 185 (2.3 parts by mass), BYK-LPN6919 (manufactured by BYK Corporation) as a dispersing agent (4.0 parts by mass) (solid content concentration = 60% by mass), and resin solution (X-1) (7. 0 parts by mass (solid content concentration = 40% by mass), 10.0 parts by mass of the resin (A-1) solution, 64.0 parts by mass of propylene glycol monomethyl ether acetate and 16.0 parts by mass of propylene glycol monoethyl ether as solvents Was mixed and dispersed by a bead mill to prepare a red pigment dispersion (R-14).

Preparation Example 15
In Preparation Example 1, C.I. I. Pigment Red 264 in an amount of 8.8 parts by mass and C.I. I. A red pigment dispersion (R-15) was prepared in the same manner as in Preparation Example 1, except that 4.2 parts by mass of Pigment Yellow 185 was used.

In Table 1, each component is as follows.
R264: C.I. I. Pigment Red 264
R254: C.I. I. Pigment Red 254
R242: C.I. I. Pigment Red 242
R177: C.I. Pigment Red 177
Y185: C.I. I. Pigment Yellow 185
Y139: C.I. I. Pigment Yellow 139
Y150: C.I. I. Pigment Yellow 150
Y129: C.I. I. Pigment Yellow 129

<Preparation and evaluation of coloring composition>
Example 1
Preparation of coloring composition 624 parts by mass of red pigment dispersion (R-1) as a colorant, 91 parts by mass of resin (A-1) solution as a binder resin, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as polymerizable compounds 90 parts by mass (Aronix M-402, manufactured by Toagosei Co., Ltd.), 4.0 parts by mass of Adeka Arcles NCI-831 (manufactured by ADEKA) as a photopolymerization initiator, and pentaerythritol tetrakis as an antioxidant [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010, manufactured by BASF) 1.0 part by mass, Megafac F-554 (manufactured by DIC Corporation) as a surfactant ) 5% by mass of propylene glycol monomethyl ether acetate 9.7 parts by mass, and 321 parts by mass of propylene glycol monomethyl ether acetate, 70 parts by mass of methoxybutyl acetate, and 30 parts by mass of ethyl 3-ethoxypropionate as a solvent are mixed, and a red coloring composition having a solid content concentration of 20% by mass (S-1) was obtained.

Evaluation of Chromaticity Properties After applying the red coloring composition (S-1) on a glass substrate using a spin coater, pre-baking was performed for 1 minute on a hot plate at 90 ° C. A coating film was formed.
Next, after cooling the substrate to room temperature, the coating film on the substrate was exposed to radiation containing each wavelength of 365 nm, 405 nm, and 436 nm without using a photomask, and an exposure dose of 600 J / m ² . And exposed. Thereafter, shower development was performed on the coating film on the substrate by discharging a developer composed of a 0.04% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm). 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 red cured film.
Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinates (x, y) and the stimulus value in the CIE color system with a C light source and a 2-degree field of view were obtained for the obtained three cured films. Y) was measured. From the measurement result, the chromaticity coordinate value y and the stimulus value (Y) when the chromaticity coordinate value x = 0.675 were obtained. Moreover, the film thickness of the obtained cured film was measured using the alpha step IQ made from KLA-Tencor. The evaluation results are shown in Table 2.
It can be said that the greater the stimulus value (Y), the higher the luminance, and the thinner the film thickness, the greater the coloring power of the colorant.

Examples 2-6 and Comparative Examples 1-9
In Example 1, red colored compositions (S-2) to (S-15) were prepared in the same manner as in Example 1 except that the type of the red pigment dispersion was changed as shown in Table 2. Then, the obtained red coloring compositions (S-2) to (S-15) were evaluated in the same manner as in Example 1. The results are shown in Table 2. However, in Comparative Examples 2, 5, 6 and 7, when chromaticity coordinate value x = 0.675, y> 0.320 and a cured film satisfying 0.300 ≦ y ≦ 0.320 was not obtained. .

Example 7
About three red cured films produced using the red coloring composition (S-1) produced in Example 1, instead of the C light source, a blue LED and a YAG phosphor as shown in FIG. Chromaticity coordinates (x, y) and stimulation value (Y) were measured in the same manner as in Example 1 except that a white LED emission spectrum obtained by color mixing was used as a light source. From the measurement result, the chromaticity coordinate value y and the stimulus value (Y) when the chromaticity coordinate value x = 0.663 were obtained. Moreover, the film thickness of the obtained cured film was measured using the alpha step IQ made from KLA-Tencor. The evaluation results are shown in Table 3.

Examples 8-12 and Comparative Examples 10-18
About the red cured film of 3 sheets produced using Examples 2-6 and Comparative Examples 1-9 using the red coloring composition (S-2)-(S-15), it is the same as that of Example 7. And evaluated. The results are shown in Table 3. However, in Comparative Examples 11, 14, 15, and 16, a cured film satisfying y ≦ 0.320 was not obtained when the chromaticity coordinate value x = 0.663.

Example 13
About three red cured films produced using the red coloring composition (S-1) produced in Example 1, instead of the C light source, a three-wavelength LED (blue LED and red color as shown in FIG. 2) A white LED obtained by color mixing using a combination of a light-emitting phosphor and a green light-emitting phosphor) Except that the light emission spectrum was used as a light source, the chromaticity coordinates (x, y) and the stimulus value (Y) were determined in the same manner as in Example 1. It was measured. From the measurement result, the chromaticity coordinate value y and the stimulus value (Y) when the chromaticity coordinate value x = 0.85 were obtained. Moreover, the film thickness of the obtained cured film was measured using the alpha step IQ made from KLA-Tencor. The evaluation results are shown in Table 4.

Examples 14-18 and Comparative Examples 19-27
About the red cured film of 3 sheets produced using Examples 2-6 and Comparative Examples 1-9 using the red coloring composition (S-2)-(S-15), it is carried out similarly to Example 13. And evaluated. The results are shown in Table 4. However, in Comparative Examples 20, 23, 24, and 25, a cured film satisfying y ≦ 0.315 was not obtained when the chromaticity coordinate value x = 0.685.

<Preparation and evaluation of colored cured film for solid-state imaging device>
Preparation Example 16
(Preparation of composition for forming undercoat film)
After the atmosphere in the flask was replaced with nitrogen, 200 parts by mass of a methyl-3-methoxypropionate solution in which 0.6 parts by mass of 2,2′-azobisisobutyronitrile was dissolved was charged. Subsequently, 37.5 parts by mass of tert-butyl methacrylate and 62.5 parts by mass of glycidyl methacrylate were charged, stirred, and heated at 70 ° C. for 6 hours. After cooling, a resin solution containing a polymer was obtained.
Next, after diluting 33.3 parts by mass (containing 10 parts of the polymer) of this resin solution, 31.9 parts by mass of methyl-3-methoxypropionate, and 3.4 parts by mass of propylene glycol monomethyl ether. , 0.3 parts by mass of trimellitic acid, 0.5 parts by mass of 3-glycidoxypropyltrimethoxysilane, and 0.005 parts by mass of the trade name “FC-4432” (manufactured by Sumitomo 3M Limited) Then, a composition for forming a base film was prepared.

Example 19
As a coloring agent, C.I. I. 8.8 parts by mass of CI Pigment Red 264, C.I. I. Pigment Yellow 185 (2.2 parts by mass), BYK-LPN21324 (manufactured by BYK Corporation) as a dispersant, 8.45 parts by mass (solid content concentration = 40% by mass), and resin (A-2) solution in 8. 45 parts by mass (solid content concentration = 40% by mass), 67.87 parts by mass of propylene glycol monomethyl ether acetate and 4.23 parts by mass of propylene glycol monoethyl ether as a solvent, and mixed and dispersed by a bead mill to disperse a red pigment A liquid (R-16) was prepared.
Next, 455 parts by mass of the red pigment dispersion (R-16) prepared above as a colorant, 0.28 parts by mass (solid content concentration = 40% by mass) of a resin (A-3) solution as a binder resin, polymerizability Kayrad DPEA-12 (Nippon Kayaku Co., Ltd., ethylene oxide-modified dipentaerythritol hexaacrylate) 15.07 parts by mass as a compound, Adeka Arcles NCI-930 (manufactured by ADEKA Co., Ltd.) 4.07 as a photopolymerization initiator Part by mass, 0.02 part by mass of Fantent FTX-218 (manufactured by Neos Co., Ltd.) as a fluorosurfactant and propylene glycol monomethyl ether acetate are mixed, and the solid content concentration is 20% by mass and the pigment concentration is 50 masses. % Red coloring composition (S-16) was obtained.

Formation and Evaluation of Pixel Pattern Using an automatic coating and developing apparatus (clean track manufactured by Tokyo Electron Ltd., trade name “MARK-Vz”) on a 6-inch silicon wafer, the composition for forming the base film is spin-coated. After coating, the substrate was baked at 230 ° C. for 300 seconds to form a base film having a thickness of 0.6 μm.
A red coloring composition (S-16) was applied onto the undercoat film by spin coating, and then prebaked at 90 ° C. for 150 seconds to form a coating film having a thickness of 0.75 μm. Thereafter, the obtained substrate is cooled to room temperature, and a reduction projection exposure machine (NSR-2005i10D manufactured by Nikon Corporation, lens numerical aperture = 0.63) is applied to the coating film on the substrate via a photomask. It was exposed to light exposure amount of 30~500mJ / cm ² at 10 mJ / cm ² intervals at a wavelength of 365 nm (i line). Subsequently, in an automatic coating phenomenon apparatus, paddle development is performed for 90 seconds with 0.05% tetramethylammonium hydroxide aqueous solution, rinsed with ultrapure water, spin-dried, and then 230 ° C. on a hot plate. Was post-baked for 300 seconds to form a red colored pattern.
It was confirmed that the red coloring pattern is excellent in color separation even if it is an ultrathin film required for a solid-state imaging device. Therefore, it can be said that the colored composition of the present invention has high color purity and can produce a color filter suitable for a solid-state imaging device.

Example 20
As a coloring agent, C.I. I. 8.8 parts by mass of CI Pigment Red 264, C.I. I. Pigment Yellow 185 (2.2 parts by mass), BYK-LPN6919 (manufactured by BYK Corporation) as a dispersing agent (5.63 parts by mass (solid content concentration = 60% by mass)), and resin (A-2) solution (8. 8). 45 parts by mass (solid content concentration = 40% by mass), 70.69 parts by mass of propylene glycol monomethyl ether acetate and 4.23 parts by mass of propylene glycol monoethyl ether as a solvent, mixed and dispersed by a bead mill to disperse a red pigment A liquid (R-17) was prepared.
Next, in the same manner as in Example 19 except that the red pigment dispersion (R-17) prepared above was used instead of the red pigment dispersion (R-16), the solid content concentration was 20% by mass and the pigment A red colored composition (S-17) having a concentration of 50% by mass was obtained. When a pixel pattern was formed in the same manner as in Example 19, it was confirmed that the color separation was excellent. Therefore, it can be said that a color filter having high color purity and suitable for a solid-state imaging device can be produced.

Claims (9)

In a coloring composition containing (A) a colorant, (B) a binder resin and (C) a polymerizable compound,
(A) C.I. I. A coloring composition comprising Pigment Red 264 and an isoindoline pigment. (A ¹ ) C.I. I. Pigment Red 264 (A ²⁾ containing a mass ratio of the isoindoline-based pigment ^{[(A 1) / (A 2} ) ] is 99 / 1-50 / 50, colored composition according to claim 1.   Isoindoline pigments are C.I. I. Pigment yellow 139 and C.I. I. The coloring composition according to claim 1 or 2 which is at least one sort chosen from pigment yellow 185.   Further, (A) C.I. I. The coloring composition of any one of Claims 1-3 containing red coloring agents other than pigment red 264.   C. above. I. Red colorants other than CI Pigment Red 264 are C.I. I. The coloring composition according to claim 4, which is CI Pigment Red 177.   Coloring satisfying 0.660 ≦ x ≦ 0.690 and 0.300 ≦ y ≦ 0.320 in the chromaticity coordinates (x, y) in the XYZ color chromaticity diagram measured in the field of view twice using a C light source The coloring composition of any one of Claims 1-5 used for formation of a cured film.   The colored cured film formed using the coloring composition of any one of Claims 1-6.   A display element comprising the colored cured film according to claim 7.   A solid-state imaging device comprising the colored cured film according to claim 7.

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