JP2015110726A - Coloring composition, coloring curable film, and display element and solid-state imaging element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition which can form a curable film having excellent chromatic properties and hardly causes defects.SOLUTION: A coloring composition comprises a coloring agent, where the coloring agent includes a pigment represented by formula (1), a phosphate and a dispersant having a nitrogen atom, and further comprises a binder resin and a polymerization compound.

Description

  The present invention relates to a colored composition, a colored cured film, a display element, and a solid-state image sensor. More specifically, the present invention relates 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 to be used, 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 the coloring composition for forming a red colored cured film, from the viewpoint of the chromaticity characteristics of the colored cured film, C.I. I. The use of diketopyrrolopyrrole pigments such as CI Pigment Red 254 as a colorant has been studied (for example, see Patent Document 5). Recently, brominated diketopyrrolopyrrole pigments have been proposed as colorants capable of forming a red colored cured film having more excellent chromaticity characteristics (see, for example, Patent Documents 6 to 8).

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A Japanese Patent Laid-Open No. 11-231516 JP 2012-211969 A JP 2012-21970 A JP2013-014750A

However, according to the study by the present inventors, pixels formed from a colored composition containing a diketopyrrolopyrrole pigment described in Patent Documents 6 to 8 are excellent in chromaticity characteristics but are likely to be chipped. It became clear that there was a problem.
Also, in recent years, in the technical field of color filters, it has become mainstream to reduce the exposure time to shorten the tact time, and it is required to be excellent in the pixel shape formed at a low exposure amount and the pattern shape of the black matrix. ing. However, as a result of studies by the present inventors, a coloring composition containing a diketopyrrolopyrrole pigment is likely to be chipped in the pattern when the exposure amount is reduced, so that it has a good pattern shape while shortening the tact time. It became clear that it was difficult to obtain pixels and black matrix.
Accordingly, an object of the present invention is to provide a colored composition that can form a cured film that uses a diketopyrrolopyrrole pigment as a colorant and is excellent in chromaticity characteristics even at a low exposure amount and hardly causes chipping. . Another object of the present invention is to provide a colored cured film formed using the colored composition, and a display device and a solid-state imaging device including the colored cured film. Furthermore, the subject of this invention is providing the coloring agent dispersion liquid containing a diketopyrrolopyrrole pigment as a coloring agent.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by using a specific compound in combination with a diketopyrrolopyrrole pigment.

  That is, this invention is a coloring composition containing (A) a coloring agent, (C) binder resin, and (D) polymeric compound, Comprising: (A) A coloring agent is represented by following formula (1). And (B1) a phosphoric ester, and (B2) a coloring composition comprising a dispersant having a nitrogen atom.

[In Formula (1), R < ¹ > and R < ² > represents a chlorine atom or a bromine atom mutually independently. ]

  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.

  Furthermore, the present invention is a colorant dispersion containing (A) a colorant and (F) a solvent, wherein (A) the colorant contains a pigment represented by the following formula (1), and (B1) The present invention provides a colorant dispersion containing a phosphate ester and (B2) a dispersant having a nitrogen atom.

[In Formula (1), R < ¹ > and R < ² > represents a chlorine atom or a bromine atom mutually independently. ]

The colorant dispersion of the present invention has good dispersibility of the diketopyrrolopyrrole pigment, the viscosity can be kept low, and the coating property is also excellent. Further, if the colored composition of the present invention is used, a colored cured film that is excellent in chromaticity characteristics even at a low exposure amount and hardly causes chipping can be formed. Furthermore, the colored composition of the present invention is excellent in the developing speed, and the tact time can be shortened.
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 this invention contains the pigment represented by following formula (1) as (A) coloring agent.

[In Formula (1), R < ¹ > and R < ² > represents a chlorine atom or a bromine atom mutually independently. ]

R ¹ and R ² are preferably both chlorine atoms, or R ¹ and R ² are preferably both bromine atoms, more preferably both R ¹ and R ² are bromine atoms. In addition, the pigment represented by the following formula (1) can be produced by a known method. For example, a pigment in which both R ¹ and R ² are bromine atoms is WO 2009/144115 pamphlet. Can be produced by the method described in the above.

  The colored composition of the present invention can also contain a colorant other than the pigment represented by the formula (1) (hereinafter also referred to as “other colorant”). The other colorant is not particularly limited, and the color and material can be appropriately selected according to the use, and any of pigments other than the pigment represented by formula (1), dyes and natural pigments can be selected. Can also be used. Among these, organic pigments and organic dyes are preferable in terms of obtaining pixels with high luminance and color purity.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), among which JP-A No. 2001-81348 and JP-A No. The rakes described in 2010-026334, 2010-191304, 2010-237384, 2010-237369, 2011-006602, 2011-145346, etc. Pigments, C.I. 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 264, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 80, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 211, C.I. I. Pigment yellow 215, C.I. I. Pigment orange 38, C.I. I. Organic pigments other than lake pigments such as CI Pigment Violet 23 are preferred. Among lake pigments, triarylmethane lake pigments, xanthene lake pigments, and azo lake pigments are preferable, and triarylmethane lake pigments and xanthene lake pigments are more preferable.

  In the present invention, the pigment represented by the formula (1) and other pigments optionally used are purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. You can also Moreover, the pigment surface may be used by modifying the particle surface with a resin if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. As a resin coating method on the carbon black surface, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed. The organic pigment may be used after the primary particles are refined by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

  In the present invention, a known dispersion aid can be further contained together with the pigment represented by the formula (1) and other pigments optionally used. Examples of known dispersing aids include pigment derivatives such as copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. In the present invention, when a dispersion aid is used, a sulfonic acid derivative of diketopyrrolopyrrole is preferable.

  Examples of the organic dye include xanthene dyes, triarylmethane dyes, methine dyes, anthraquinone dyes, and azo dyes. 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.

Among these, xanthene dyes are preferable as the organic dye.
Examples of xanthene dyes include compounds having a structure represented by the following formula.

  When the xanthene dye is cationic, it can have an anion so that the xanthene dye is electrically neutral. Examples of the anion include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, a metide anion, and an anion of a transition metal complex having an azo compound as a ligand. Can do. Examples of the nitrogen anion include nitrogen anions described in JP 2011-133844 A, JP 2011-116803 A, and JP 2010-090341 A. Examples of the anion of the transition metal complex having an azo compound as a ligand include the anions described in JP2009-163226A and JP2012-212089A.

  In addition, a xanthene acid dye having an ammonium cation and a xanthene acid dye having a phosphonium cation can also be preferably used. Here, the xanthene-based acid dye means a xanthene-based dye in which the anion portion becomes a chromophore. Representative examples of the xanthene acid dye having an ammonium cation include, for example, dyes described in Japanese Patent No. 4492760 and Japanese Patent Application Laid-Open No. 2011-242752.

  In the present invention, other colorants can be used alone or in admixture of two or more.

The colored composition of the present invention is preferably used for forming a red pixel. In this case, (A) as the colorant, together with the pigment represented by the formula (1), as other colorants, red pigments other than the pigment represented by the formula (1), red dye, purple pigment, purple dye It is preferable to contain at least one selected from the group consisting of yellow pigments and orange pigments.
Examples of the red pigment include C.I. I. Pigments classified as pigment red are preferred, and C.I. I. Pigment red 177, C.I. I. Pigment red 179, C.I. I. Pigment Red 264 is more preferable. Examples of the purple pigment include C.I. I. Pigment Violet 23 is preferable.
The red dye and purple dye are preferably xanthene dyes, and more specifically, the same dyes as described above can be mentioned.
Examples of the yellow pigment include C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment Yellow 185 is preferable. Examples of the orange pigment include C.I. I. Pigment Orange 38 is preferable.

(A) The content of the colorant is excellent in chromaticity characteristics even at a low exposure amount and is difficult to cause chipping, or from the point of forming a black matrix and a black spacer excellent in light-shielding properties. Usually, it is 5-70 mass%, Preferably it is 10-60 mass%. Here, solid content is components other than the solvent mentioned later.
Moreover, when using another colorant, 99 mass% or less is preferable with respect to the total content of a colorant, and, as for the content rate of another colorant, 95 mass parts or less are more preferable. The lower limit is not particularly limited and may be 0.01% by mass or more.

-(B) component-
The colored composition of the present invention comprises (B1) a phosphoric acid ester (hereinafter also simply referred to as “(B1) component”) and (B2) a dispersant having a nitrogen atom (hereinafter simply referred to as “B”) as the component (B). (B2) also called “dispersant”). The component (B1) and the dispersant (B2) of the present invention act as a dispersant for dispersing the pigment represented by the formula (1) and other pigments optionally used. As a result of intensive studies, the present inventors have used a combination of the component (B1) and the dispersant (B2), whereby the dispersibility of the diketopyrrolopyrrole pigment is good and the viscosity can be kept low. It has been found that an excellent colorant dispersion can be prepared, and as a result, it is possible to form a cured film that is excellent in chromaticity characteristics even at a low exposure amount and hardly causes chipping. Another advantage of the colored composition of the present invention is that the developing speed is high.

  The component (B1) is not particularly limited as long as it is a phosphate ester, and may be a phosphate monoester, a phosphate diester, a phosphate triester, or a mixture of two or more of these. The phosphate ester may be in the form of a salt. Examples of the salt include amine salts, alkali metal salts, alkaline earth metal salts, and the like. (B1) As a component, what was synthesize | combined by the well-known method can be used, For example, Solsperse 41000 (Lubrisol Co., Ltd. make, a polyether phosphate ester polymer, 100 mass% of non-volatile components, Acid value 50 mgKOH / g), Disperbyk-111 (manufactured by BYK Corporation, phosphate ester polymer, non-volatile component 95% by mass, acid value 129 mgKOH / g), Phosphanol RE-610, Phosphanol RS- 710 (alkyl ether phosphate ester, acid value 65 mgKOH / g) (manufactured by Toho Chemical Co., Ltd.), Disparon PW-36 (nonvolatile component 50% by mass, acid value 55 mgKOH / g), Disparon DA-375 (polyether phosphate) Ester polymer, nonvolatile component 100% by mass, acid value 14 mgKOH g), DISPARLON DA-325 (amine salts of polyether phosphate esters, non-volatile component 100 wt%, acid value 14 mg KOH / g) (more can be used commercially to obtain the Kusumoto Kasei Ltd.). Among these, as the component (B1), a polyether phosphate ester polymer is preferable from the viewpoint of dispersibility, viscosity, and coatability of the diketopyrrolopyrrole pigment.

  The acid value of the component (B1) is preferably 1 to 150 mgKOH / g, more preferably 5 to 90 mgKOH / g, and still more preferably 10 to 60 mgKOH / g. Such an embodiment is preferable from the viewpoints of dispersibility, viscosity, and coatability of the diketopyrrolopyrrole pigment. Here, in the present invention, the “acid value” is the number of mg of KOH required to neutralize 1 g of the nonvolatile content excluding the solvent of the dispersant solution.

The coloring composition of this invention contains (B2) a dispersing agent with (B1) component.
(B2) As a nitrogen atom which a dispersing agent has, a nitrogen atom contained in a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium, an amide group, an imino group, a urethane group, etc. is mentioned.
Examples of the dispersant (B2) in the present invention include polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants, and polyester dispersants. , And (meth) acrylic dispersants having one or more characteristic groups selected from amino groups, quaternary ammonium, amide groups and imino groups, urethane dispersants, polyethyleneimines A system dispersant can be preferably used. The amino group may be a primary amino group, a secondary amino group, or a tertiary amino group.

Among them, as the (B2) dispersant, a (meth) acrylic dispersant or a polyester dispersant having one or more characteristic groups selected from an amino group, a quaternary ammonium group, an amide group, and an imino group. In addition, at least one of urethane dispersants is preferable, and a (meth) acrylic dispersant having one or more characteristic groups selected from an amino group, a quaternary ammonium group, an amide group, and an imino group is more preferable.
The (meth) acrylic dispersant may have a crosslinkable functional group in addition to the above-described characteristic group having a nitrogen atom. Examples of the crosslinkable functional group include oxygen-containing saturated heterocyclic groups such as oxiranyl group, oxetanyl group, tetrahydrofuranyl group, and tetrahydropyranyl group, ethylenically unsaturated group, epithio group, and (dithio) carbonate group. be able to. 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.

(B2) A commercially available dispersant may be used as long as the dispersant has a nitrogen atom. For example, as a (meth) acrylic dispersant, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (non-volatile component 40% by mass), BYK-LPN22102 (above, manufactured by BYK), and the like, urethane dispersing agents such as Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk- 170, Disperbyk-182 (above, manufactured by BYK (BYK)), Solsperse 76500 (manufactured by Lubrizol Co., Ltd., non-volatile component 50% by mass), etc. Perth 24000 (manufactured by Lubrizol Co., Ltd.) etc. In addition, BYK-LPN21324 (non-volatile component 40% by mass) (manufactured by BYK (BYK)) can be exemplified.
(B2) A dispersing agent can be used individually or in mixture of 2 or more types.

In the colored composition of the present invention, the content ratio of the component (B1) and the component (B2) can be appropriately selected. The content w _{1 of the} component (B1) and the content of the dispersant (B2) the ratio w ₁ / w ₂ with w ₂ is preferably 10 / 90-90 / 10 in mass ratio, more preferably from 20/80 to 80/20, more preferably 30 / 70-70 / 30.

  In this invention, 5-300 mass parts is preferable with respect to 100 mass parts of (A) coloring agents, and, as for the total content of (B1) component and (B2) dispersing agent, 10-200 mass parts is more preferable, 20 More preferred is ˜100 parts by mass. By setting it as such an aspect, it becomes easy to obtain the desired effect of this application.

-(C) Binder resin-
The (C) binder resin in the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as “unsaturated monomer (c2)”). .

Examples of the unsaturated monomer (c1) 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 (c1) can be used alone or in admixture of two or more.

Moreover, as said unsaturated monomer (c2), 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 (c2) can be used alone or in admixture of two or more.

  In the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2), the copolymerization ratio of the unsaturated monomer (c1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (c1) within 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 (c1) and the unsaturated monomer (c2) 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.

-(D) 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, (D) polymeric compound can be used individually or in mixture of 2 or more types.

  The content of the polymerizable compound (D) in the present invention is preferably 10 to 1,000 parts by weight, more preferably 20 to 700 parts by weight, and further 80 to 500 parts by weight with respect to 100 parts by weight of the (D) 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.

-(E) 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 this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (D) polymeric compounds, and, as for content of (E) 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.

-(F) Solvent-
Although the coloring composition of this invention contains the said (A)-(D) component and the other component added arbitrarily, normally, a solvent is mix | blended and it prepares as a liquid composition.
(F) As a solvent, as long as (A)-(D) component and other components which comprise a coloring composition are disperse | distributed or melt | dissolved, and it does not react with these components, 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.

  (F) 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 fluorine surfactants and silicone surfactants; vinyltrimethoxysilane Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyl Adhesion promoters such as limethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- t-butylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-t-butyl-4-hydroxy) -5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxa-spiro [5 · 5] undecane, thiodiethylenebis [3- (3,5-di- antioxidants such as t-butyl-4-hydroxyphenyl) propionate]; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) Nyl) -5-chlorobenzotriazole, alkoxybenzophenones, etc .; anti-aggregation agents such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol Residue improving agents such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. An improving agent etc. can be mentioned.

The coloring composition of the present invention can be prepared by an appropriate method, but a more preferable method for preparing the coloring composition is a method using the colorant dispersion of the present invention. That is, (A) a colorant containing the pigment represented by the formula (1) is used in (F) a solvent, (B1) component and (B2) dispersant, and optionally a dispersion aid, (C) binder resin Along with a part, for example, a bead mill, a roll mill, etc., mixed and dispersed while being pulverized to form a colorant dispersion, and (C) a binder resin and (D) a polymerizable compound are added to the colorant dispersion. According to the method, (E) a photopolymerization initiator, an additional (F) solvent, or an additive may be further added and mixed. In addition, (A) colorant, (B1) component, (B2) dispersant and (F) solvent in the colorant dispersion of the present invention, and a dispersion aid added as necessary, (C) binder resin The specific configuration is as described above.
In addition, the colorant dispersion of the present invention can be obtained by using the component (B1) and the component (B2) in combination, compared with the case where the component (B1) and the component (B2) are each used alone. A colored composition capable of forming a cured film having good dispersibility of ketopyrrolopyrrole pigments, low viscosity, excellent coating properties, and excellent chromaticity characteristics even at a low exposure amount and hardly causing chipping. Can be prepared. Specifically, the viscosity of the colorant dispersion is preferably 20 mPa · s or less, more preferably 16 mPa · s or less, still more preferably 13 mPa · s or less, and particularly preferably 11 mPa · s or less. Here, the viscosity is a value measured using an E-type viscometer at 25 ° C.

  Moreover, when using both the dye and the pigment as the colorant, the coloring composition of the present invention, as disclosed in JP 2010-132874 A, after passing the dye solution through the first filter, A method can be employed in which the dye solution that has passed through the first filter is mixed with a separately prepared pigment dispersion or the like, and the resulting colored composition is passed through a second filter. In addition, the dye, the above components (B) to (D), and other components used as necessary are dissolved in a solvent, and the obtained solution is passed through the first filter, and then the first filter is used. You may employ | adopt the method prepared by mixing the solution which passed through with the pigment dispersion liquid prepared separately, and passing the obtained coloring composition through a 2nd filter. Also, after passing the dye solution through the first filter, the dye solution that has passed through the first filter, the above components (B) to (D), and other components used as necessary are mixed and dissolved. The obtained solution is passed through a second filter, and the solution that has passed through the second filter is further mixed with a separately prepared pigment dispersion, and the resulting colored composition is passed through a third filter. It is also possible to adopt a method to do this.

Colored cured film and formation 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. constituting the color filter Means.

Hereinafter, the colored cured film used for the color filter which comprises a display element and a solid-state image sensor, and its formation method are demonstrated.
As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, after applying a red liquid composition of the radiation-sensitive colored composition of the present invention on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns (colored cured films) are arranged in a predetermined arrangement.

  Subsequently, using each radiation sensitive coloring composition of green or blue, application of each radiation sensitive coloring composition, pre-baking, exposure, development, and post-baking are performed in the same manner as described above to obtain a green pixel array and blue color. Are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  The black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithographic method. However, the radiation sensitive material in which a black colorant is dispersed is used. 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. In particular, it is preferable to employ a spin coating method or a slit die coating method.

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

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

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

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

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

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

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

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

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

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

The radiation-sensitive 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 formed in this way has extremely high luminance and color purity, it can be used in color liquid crystal display elements, color imaging tube elements, color sensors, organic EL display elements, electronic paper, and the like. Very useful. In addition, the display element mentioned later should just have at least 1 or more of colored cured films formed using the radiation sensitive 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. In addition, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (tin-doped indium oxide) electrode is formed face each other through a liquid crystal layer. A structure can also be adopted. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained. When the latter structure is adopted, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed or the substrate side on which the ITO electrode is formed.

  The color liquid crystal display element including the colored cured film of the present invention can include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

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

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

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 and forming a colored pixel (colored cured film) on a semiconductor substrate such as a CMOS substrate by the same operation as described above, particularly color reproduction is achieved. 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 (B2) dispersant>
Synthesis example 1
According to Synthesis Example 5 of JP2012-118505A, A block in which about 80 mol% of repeating units derived from dimethylaminoethyl methacrylate are quaternized ammonium, normal butyl methacrylate, methyl methacrylate and tetrahydrofurfuryl methacrylate. A block copolymer solution (non-volatile component 40% by mass) consisting of B block having repeating units was obtained. The obtained block copolymer is referred to as “dispersant (B-1)”.

<Synthesis of (C) binder resin>
Synthesis example 2
In a flask equipped with a condenser and a stirrer, 25.0 g of 3-methacryloyloxymethyl-3-ethyloxetane, 18.0 g of methacrylic acid, 14.0 g of 2-hydroxylethyl ester of methacrylic acid, 24.0 g of benzyl methacrylate, N-phenyl 10.0 g of maleimide and 9.0 g of mono-2-acryloxyethyl succinate were dissolved in 300 g of propylene glycol monomethyl ether acetate, and 5.3 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added. Thereafter, nitrogen was purged for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling and polymerized for 5 hours to obtain a solution containing 25% by mass of the precursor copolymer [c-1]. This precursor copolymer [c-1] had a polystyrene-reduced weight average molecular weight (Mw) of 10,000.
Next, 200 g of a solution containing the precursor copolymer [c-1], 15.9 g of 2-methacryloyloxyethyl isocyanate, and 0.2 g of phenothiazine as a polymerization inhibitor were placed in a flask and reacted at a temperature of 110 ° C. for 9 hours. . This reaction solution was washed with 75 g of ion-exchanged water four times and concentrated under reduced pressure to obtain a binder resin solution (C-1) (solid content concentration: 33% by mass). The obtained binder resin had Mw of 11,500.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate 23 parts by mass, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) The solution was added dropwise over a period of time and polymerized for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a binder resin solution (C-2) (solid content concentration: 33% by mass). The obtained binder resin had Mw of 12,200 and Mn of 6,500.

<Synthesis of colorant>
Synthesis example 4
In a 200 mL eggplant-shaped flask containing a stirring bar, C.I. I. 2.9 g (5.0 mmol) of Acid Red 52 and 29 mL of ion-exchanged water were added, and the mixture was heated to a bath temperature of 85 ° C. in an oil bath while stirring. To this solution, a solution obtained by dissolving 5.2 g (10.26 mmol) of tributylhexadecylphosphonium bromide in 60 g of ion exchange water at room temperature was added little by little at the same temperature. When all were added, it was confirmed that a water-insoluble colored oily substance was formed. Then, after stirring at the same temperature for 1 hour, it cooled to room temperature vicinity using the ice bath. The supernatant was removed by decantation, and then the residue was washed with ion-exchanged water. The residue was dissolved in methanol and collected, and then concentrated under reduced pressure using a rotary evaporator. The obtained oily residue was dried under reduced pressure at 50 ° C. for 12 hours to obtain 6.1 g of a reddish purple solid.
It was confirmed by ¹ H-NMR spectrum (solvent: deuterated chloroform) that the obtained compound was a compound represented by the following formula (A-2). Let the obtained compound be a coloring agent (A-2).

Synthesis example 5
A compound represented by the following formula (A-3) was synthesized with reference to Synthesis Example 3 in JP2010-032999A. This compound is defined as a colorant (A-3).

Synthesis Example 6
A compound represented by the following formula (A-4) was synthesized with reference to Synthesis Example 3 of JP2012-181505A. This compound is defined as a colorant (A-4).

Synthesis example 7
With reference to the synthesis example of Japanese Patent No. 4492760, a compound represented by the following formula (A-5) was synthesized. This compound is defined as a colorant (A-5).

<Preparation and Evaluation of Colorant Dispersion>
Example 1
(A) 13 parts by mass of a pigment represented by the following formula (2) as a colorant (hereinafter also referred to as “colorant (A-1)”), and Solsperse 41000 (Lubrisol Co., Ltd.) as a component (B1) 2 parts by mass (non-volatile component 100% by mass), 5 parts by mass of dispersant (B-1) solution (non-volatile component 40% by mass) as (B2) dispersant, and propylene glycol monomethyl ether acetate as solvent The colorant dispersion (R-1) was prepared by mixing and dispersing with a bead mill using the colorant dispersion at 100 parts by mass.

Viscosity of colorant dispersion The viscosity of the obtained colorant dispersion was measured at 25 ° C. using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). The evaluation results are shown in Table 1.

Examples 2-30 and Comparative Examples 1-14
In Example 1, the colorant dispersions (R-2) to (R-44) were prepared in the same manner as in Example 1 except that the types and amounts of the components to be mixed and dispersed were changed as shown in Table 1. Prepared. In the same manner as in Example 1, the viscosity of the colorant dispersion was measured. The evaluation results are shown in Table 1.
However, in Examples 22-25, 15 mass parts of binder resin solution (C-1) (solid content concentration 33 mass%) was added as (C) binder resin. In Example 26, a 9/1 (mass ratio) mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether was used as a solvent.

The symbols in Table 1 are as follows.
R177: C.I. I. Pigment Red 177
R179: C.I. I. Pigment Red 179
Y150: C.I. I. Pigment Yellow 150
R254: C.I. I. Pigment Red 254
S41000: Solsperse 41000 (Lubrisol Co., Ltd., non-volatile component 100% by mass)
BYK111: Disperbyk-111 (manufactured by BYK Corporation, non-volatile component 95% by mass)
Dispersant (B-1): Dispersant (B-1) solution synthesized in Synthesis Example 1 (nonvolatile component 40 mass%)
LPN21324: BYK-LPN21324 (BIC Chemie (BYK), nonvolatile component 40% by mass)
LPN21116: BYK-LPN21116 (Bikchemy (BYK), non-volatile component 40% by mass)
S76500: Solsperse 76500 (manufactured by Lubrizol Corp., nonvolatile component 50 mass%)
PB821: Ajisper PB821 (Ajinomoto Fine Techno Co., Ltd., nonvolatile component 100% by mass)

In Table 1, “colorant (A-1) / R177 = 50/50” means a mixture of colorant (A-1) and R177 at 50/50 (mass ratio). Similarly, “colorant (A-1) / R177 / Y150 = 25/70/5” is a mixture of colorant (A-1), R177, and Y150 at 25/70/5 (mass ratio). “Colorant (A-1) / R179 = 50/50” means a mixture of colorant (A-1) and R179 at 50/50 (mass ratio), and “colorant (A -1) / R179 / R177 = 50/30/20 "means a mixture of colorant (A-1), R179 and R177 at 50/30/20 (mass ratio). -1) / colorant (A-2) = 85/15 "means a mixture of colorant (A-1) and colorant (A-2) at 85/15 (mass ratio). “R254 / R177 = 50/50” means a mixture of R254 and R177 at 50/50 (mass ratio).
In Comparative Examples 7 and 14, since the colorant could not be dispersed, the viscosity could not be measured.

<Preparation and evaluation of coloring composition>
Example 101
100 parts by weight of the pigment dispersion (R-1), (C) 35 parts by weight of the binder resin solution (C-1) as the binder resin, and (D) a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as the polymerizable compound. (Hereinafter referred to as “(D-1)” manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as 13 parts by mass, 2-methyl-1- [4- (methylthio) phenyl]-as a photopolymerization initiator 10 parts by mass of 2-morpholinopropan-1-one, 0.05 parts by mass of Megafac F-554 (manufactured by DIC Corporation) as a surfactant, and propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate as solvents Were mixed so as to have a solid content concentration of 15% by mass to prepare a colored composition (S-1). The content of 3-methoxybutyl acetate was adjusted to 30% by mass in the total solvent contained in the colored composition (S-1).

Evaluation of Development Speed After applying the colored composition (S-1) on a soda glass substrate having a diameter of 4 inches on which a SiO ₂ film for preventing elution of sodium ions was formed using a slit die coater, Pre-baking was performed at 90 ° C. for 1 minute on a hot plate to form a coating film having a thickness of 2.0 μm. The elution end time (braking time) is measured by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm). The test was performed with “◯” for less than 25 seconds, “Δ” for 25 seconds or more and less than 30 seconds, and “X” for 30 seconds or more. The evaluation results are shown in Table 2. The faster this time is, the faster the development speed is, and there is an advantage that the tact time for manufacturing the color filter can be shortened.

Evaluation of pattern chipping The colored composition (S-1) was applied on a glass substrate using a slit die coater and then allowed to stand at room temperature for 20 minutes. After prebaking with a 90 ° C. hot plate for 1 minute to form a coating film having a thickness of 2.0 μm, the substrate was cooled to room temperature. Using a high-pressure mercury lamp, through a photomask having a stripe pattern with a width of 90 μm, radiation including each wavelength of 365 nm, 405 nm, and 436 nm, exposure illuminance of 17 mW, exposure dose of 400 J / m ² , distance between the substrate and the mask Exposure was performed under conditions of 350 μm. Thereafter, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was applied to the coating film on the substrate at a development pressure of 1.5 kgf / cm ² (nozzle diameter 1 mm), and the coating film in the unexposed area was Shower development was performed by completely discharging and discharging until 30 seconds passed. Next, after rinsing is performed by discharging ultrapure water at a rinse pressure of 1.5 kgf / cm ² (nozzle diameter 1 mm) for 60 seconds, water on the substrate surface on which the stripe pattern is formed is removed by air blowing. As a result, a 90 μm-wide strap pattern was formed.
The five stripe patterns were observed using an optical microscope. “X” indicates that 10 or more chips are observed in five stripe patterns, “△” indicates that one to nine chips are observed, and “◯” indicates that no chip is observed at all. evaluated. The evaluation results are shown in Table 2.

Evaluation of contrast The colored composition (S-1) was applied on a glass substrate using a slit die coater and then pre-baked on an 80 ° C. hot plate for 10 minutes to form a coating film. Three coating films having different film thicknesses were formed by the same operation while changing the rotation speed of the spin coater.
Next, after cooling these substrates to room temperature, a high-pressure mercury lamp is used, and a radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without using a photomask at an exposure dose of 2,000 J / m ² . And exposed. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and further post-baked in a clean oven at 200 ° C. for 30 minutes to form a cured film for evaluation.
A substrate on which a 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 a luminance meter LS-100 (Minolta Co., Ltd.) is rotated. The maximum value and the minimum value of the light intensity transmitted through (made by)) 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 = 0.650 was obtained. The evaluation results are shown in Table 2. The larger the numerical value, the better the contrast ratio.

Examples 102-130 and Comparative Examples 101-114
In Example 1, colored compositions (S-2) to (S-44) were prepared in the same manner as in Example 101 except that the colorant dispersion was changed as shown in Table 2. Next, various evaluations were performed in the same manner as Example 101 using the obtained colored composition. The results are shown in Table 2. However, regarding the contrast evaluation, in Examples 109 to 126, Example 128, and Comparative Examples 108 to 114, the contrast ratio at the chromaticity coordinate value y = 0.663 was obtained.

In Comparative Example 107 and Comparative Example 114, since the colorant dispersion (R-35) and the colorant dispersion (R-44) could not be dispersed, various evaluations of the color composition could not be performed.
In Comparative Example 105 and Comparative Example 112, a uniform coating film could not be obtained with a slit die coater, and evaluation was difficult.

<Preparation and evaluation of colored cured film for solid-state imaging device>
Preparation Example 1
(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 131
9.0 parts by weight of a colorant (A-1) as a colorant, C.I. I. Pigment Yellow 139 (6.0 parts by mass), (B2) BYK-LPN22102 (manufactured by BYK (BYK)) as a dispersant, 10.0 parts by mass (solid content concentration = 40% by mass), and (B1) component as phosphor Nord RS-710 (manufactured by Toho Chemical Industry Co., Ltd.) 2.0 parts by mass, binder resin solution (C-1) 5.0 parts by mass (solid content concentration = 40% by mass), and propylene glycol monomethyl ether acetate 68 as a solvent Using 0.0 part by mass, a colorant dispersion (R-45 was prepared by mixing and dispersing with a bead mill.
BYK-LPN22102 is a (meth) acrylic dispersant having an amino group and a quaternary ammonium group, and the (meth) acrylic dispersant is a propylene glycol methyl ether acetate / modified acrylic block copolymer. Propylene glycol methyl ether = 1/1 (mass ratio) 40% by mass solution (acid value = 0, amine value = 29 mgKOH / g). The modified acrylic block copolymer comprises a block having repeating units derived from methacryloyloxyethylbenzyldimethylammonium chloride and dimethylaminoethyl methacrylate, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate and triethylene glycol ethyl ether. It consists of a block having repeating units derived from methacrylate.
Next, 66.7 parts by mass of the colorant dispersion (R-45) prepared above, and 4.48 parts by mass of the binder resin solution (C-1) as the binder resin (C) (solid content concentration = 40% by mass) (D) 2.81 parts by mass of Kayrad DPEA-12 (manufactured by Nippon Kayaku Co., Ltd., ethylene oxide-modified dipentaerythritol hexaacrylate) as a polymerizable compound, Adeka Arcles NCI-930 (ADEKA Co., Ltd.) as a photopolymerization initiator 0.37 parts by mass), 0.004 parts by mass of Fentent FTX-218 (manufactured by Neos Co., Ltd.) and 25.67 parts by mass of propylene glycol monomethyl ether acetate as a fluorosurfactant A colored composition (S-45) having a partial concentration of 20% by mass and a pigment concentration of 50% by mass 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 colored composition (S-45) was applied onto the base film by a spin coating method 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 was cooled to room temperature, and a reduction projection exposure machine (NSR-2205i12D manufactured by Nikon Corporation, lens numerical aperture = 0.50) was applied to the coating film on the substrate through 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 (liquid accumulation) development was performed for 90 seconds with a 0.6% tetramethylammonium hydroxide aqueous solution, rinsed with ultrapure water, spin-dried, and then 200 ° C. on a hot plate. Was post-baked for 300 seconds to form a red pixel pattern.
It has been confirmed that the red pixel pattern is excellent in color separation even if it is an ultra-thin film required for a solid-state imaging device. Therefore, it can be said that the colored composition of the present invention is excellent in color reproducibility and can produce a color filter suitable for a solid-state imaging device.

Comparative Example 115
9.0 parts by weight of a colorant (A-1) as a colorant, C.I. I. Pigment Yellow 139 (6.0 parts by mass), (B2) 15.0 parts by mass (solid content concentration = 40% by mass) of BYK-LPN22102 (produced by BYK (BYK)) as a dispersant, binder resin solution (C-1) ), 5.0 parts by mass (solid content concentration = 40% by mass), 65.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and mixed and dispersed by a bead mill to obtain a colorant dispersion (R-46). Prepared.
Next, in the same manner as in Example 131 except that the colorant dispersion (R-46) prepared above was used instead of the colorant dispersion (R-45), the solid content concentration was 20% by mass and the pigment was used. A colored composition (S-46) having a concentration of 50% by mass was obtained. A red pixel pattern was formed in the same manner as in Example 131.
As a result, many development residues were recognized on the red pixel pattern. If a color filter for a solid-state imaging device is created using the red pixel pattern, color mixing caused by a development residue may occur and color reproducibility may deteriorate.

Claims (10)

A coloring composition comprising (A) a colorant, (C) a binder resin and (D) a polymerizable compound,
(A) The colorant contains a pigment represented by the following formula (1),
Furthermore, the coloring composition containing (B1) phosphate ester and (B2) the dispersing agent which has a nitrogen atom.

[In Formula (1), R < ¹ > and R < ² > represents a chlorine atom or a bromine atom mutually independently. ]   (B2) The dispersant having a nitrogen atom is a (meth) acrylic dispersant or a polyester dispersant, and has one or more characteristic groups selected from an amino group, a quaternary ammonium group, an amide group, and an imino group The coloring composition of Claim 1 which is at least 1 sort (s) of an agent and a urethane type dispersing agent. The ratio (w ₁ / w ₂ ) between the content w _{1 of the} (B1) phosphate ester and the content w ₂ of the dispersant (B2) having a nitrogen atom is 10/90 to 90/10 by mass ratio. The coloring composition according to claim 1 or 2.   (B1) The coloring composition of any one of Claims 1-3 whose acid value of phosphate ester is 1-150 mgKOH / g.   The colored composition according to any one of claims 1 to 4, wherein the (B1) phosphate ester is a polyether phosphate ester polymer.   The coloring composition of any one of Claims 1-5 in which the said (A) coloring agent contains coloring agents other than the pigment represented by the said Formula (1).   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. A colorant dispersion comprising (A) a colorant and (F) a solvent,
(A) The colorant contains a pigment represented by the following formula (1),
Furthermore, the coloring agent dispersion liquid containing (B1) phosphate ester and (B2) the dispersing agent which has a nitrogen atom.

[In Formula (1), R < ¹ > and R < ² > represents a chlorine atom or a bromine atom mutually independently. ]