JP6911971B2 - Colored composition, colored cured film and display element - Google Patents

Description

The present invention relates to a colored composition, a colored cured film and a display element. Specifically, a coloring composition used for forming a colored cured film suitable for a transmissive or reflective color liquid crystal display element, an organic EL display element, a display element such as electronic paper, and a solid-state imaging device such as a CMOS image sensor. The present invention relates to a colored cured film formed from the colored composition and a display device including the colored cured film.

To produce a color filter using a coloring composition, a pigment-dispersed radiation-sensitive coloring composition is applied onto a substrate to form a coating film, and then the coating film is exposed to a desired pattern shape. A method of obtaining patterned pixels of each color by developing the film is known (Patent Documents 1 and 2). As a method for producing a black matrix, there is known a method of forming a patterned black matrix by performing the same operation using a carbon black dispersion type radiation-sensitive coloring composition (Patent Document 3). Further, a method of forming patterned pixels of each color by applying and curing a pigment-dispersed coloring composition by an inkjet method is also known (Patent Document 4).
In the above series of operations, in order to expose the coating film in a pattern, it is usual to irradiate the coating film with light through a photomask having a desired pattern. At this time, a predetermined proximity gap (exposure gap) is provided between the coating film and the photomask. Ideally, the irradiated light directly passes through the opening of the photomask, and the closed portion blocks the light. However, since the light is diffracted at the edge portion of the photomask, the coating film in the vicinity of the opening in the closed portion is irradiated with light (leakage light) having an intensity weaker than a predetermined exposure amount.
Of the coating film, whether to obtain the same behavior as the opening region (exposure region) or the same behavior as the closed region (dark region) for the intermediate region irradiated with the leaked light depends on the process configuration and product. It depends on the purpose of. That is, for example, in the case of a negative type coloring composition, a coloring composition having high light sensitivity in which the intermediate region is cured in the same manner as the exposed portion may be required, while the intermediate region is the non-exposed portion. Similarly, a coloring composition that does not cure (that is, is developed), has a small mask bias (high mask size reproducibility of the formed pattern) may be required. High light sensitivity and small mask bias are contradictory characteristics, and it is usually difficult to achieve both.

Conventionally known coloring compositions have only a trial and error process to determine whether this is a high photosensitivity type or a low mask bias type, and a high light sensitivity type coloring composition while maintaining equivalence with respect to other properties. It was difficult to separate the product from the low mask bias type coloring composition.
By the way, Patent Document 5 relates to a coloring composition containing a specific phenol compound in the coloring composition, and when the composition is used, a colored cured film having an excellent pattern shape and high adhesion to a substrate can be obtained with high accuracy. It is explained that it can be formed in. This technique is certainly an excellent technique in which improvement in adhesion and pattern shape can be seen, but according to the study by the present inventors, the solvent resistance of the colored cured film to be formed is insufficient. Became clear.
Therefore, in the art, the need for a coloring composition capable of forming a colored cured film having both excellent adhesion and solvent resistance has been recognized.

Japanese Unexamined Patent Publication No. 2-144502 Japanese Unexamined Patent Publication No. 3-53201 Japanese Unexamined Patent Publication No. 6-35188 Japanese Unexamined Patent Publication No. 2000-310706 Japanese Unexamined Patent Publication No. 2009-204895

The present invention has been made to overcome the above situation.
Therefore, an object of the present invention is to provide a colored cured film having excellent adhesion and solvent resistance, a coloring composition that gives the colored cured film, and a display device including the cured film.
It is desirable that the coloring composition can be arbitrarily prepared by selecting either a type having a high light sensitivity or a type having a small mask bias.

According to the present invention, the above-mentioned objects and advantages of the present invention are, firstly,
(A) Colorant,
(B) Binder resin,
(C) Radical polymerizable compound,
It is achieved by a coloring composition containing (D) a photoradical generator and (E) a compound having a structure in which a group represented by the following formula (E0) is directly linked to an aromatic ring.

*-(CR ^II ₂ ) _x- O-R ^I (E0)

[In equation (E0),
^RI is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ^II is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
x is 1 or 2
"*" Indicates that the bond is a bond that directly binds to the aromatic ring. ]

Secondly, the above object and advantage of the present invention are
It is achieved by a colored cured film formed using the above coloring composition.

Thirdly, the above object and advantage of the present invention are
This is achieved by a display element provided with the above-mentioned colored cured film.

According to the present invention, there is provided a colored cured film having excellent adhesion and solvent resistance, a coloring composition that gives the colored cured film, and a display device including the cured film.
The coloring composition can be made into either a type having a high light sensitivity or a type having a small mask bias by selecting the compound (E).

<(A) Colorant>
The colorant (A) contained in the coloring composition of the present invention can be used without particular limitation. The colorant (A) is used by appropriately selecting and selecting the color, material and the like according to the use of the coloring composition of the present invention.
As the colorant (A), one or more selected from pigments and dyes can be used.
When the coloring composition of the present invention is used for forming each color pixel constituting a color filter, as the colorant (A), pixels having high brightness, contrast and color purity can be easily obtained.
It is preferable to use one or more selected from the group consisting of organic pigments and organic dyes. On the other hand, when the coloring composition is used for forming a black matrix or a black spacer, it is preferable to use an inorganic pigment as the (A) coloring agent.
Examples of the pigment include organic pigments and inorganic pigments.

Preferred examples of organic pigments include, for example, C.I. I. Pigment Red 166, C.I. I. Pigment Red 177, C.I. I. Pigment Red 224, C.I. I. Pigment Red 242, C.I. I. Pigment Red 254, C.I. I. 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 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 211, C.I. I. Pigment Orange 38, C.I. I. Pigment Violet 23 and other pigments with a Color Index (CI) name;
Lake pigments and the like can be mentioned. As the rake pigment, for example, a triarylmethane-based rake pigment obtained by rake-forming a triarylmethane-based dye with an isopolyacid, a heteropolysanoic acid, or the like as disclosed in JP-A-2011-186043;
Examples thereof include xanthene-based lake pigments obtained by rake-forming xanthene-based dyes with isopolyacids, heteropolysanoic acids, etc., as disclosed in JP-A-2010-191304.
Preferred examples of the inorganic pigment include carbon black, titanium black and the like.

The pigment may be used after being purified by, for example, a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof;
The particle surface may be modified with a resin before use;
For example, the primary particles may be miniaturized by salt milling as disclosed in Japanese Patent Application Laid-Open No. 08-179111 and the like before use.

Further, the pigment may be used together with a dispersant, a dispersion aid and the like, if necessary. As the dispersant, for example, an appropriate dispersant such as a cationic type, an anion type, or a nonionic type can be used, but it is preferable to use a polymer dispersant or a pigment derivative. Examples of the polymer dispersant include an acrylic copolymer (acrylic dispersant), a polyurethane (urethane dispersant), a polyester dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, and the like.

The polymer dispersants are commercially available. As a specific example,
As the above-mentioned acrylic dispersant, for example, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (all manufactured by Big Chemie (BYK)) and the like;
Examples of the urethane-based dispersant include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (all manufactured by Big Chemie (BYK)), Solspers 76500 (Japan Lubrizol Co., Ltd.). ) Made) etc .;
As the polyester-based dispersant, for example, Ajispar PB821, Ajispar PB822, Ajispar PB880, Ajispar PB881 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.) and the like;
Examples of the polyethyleneimine-based dispersant include Solsperse 24000 (manufactured by Japan Lubrizol Co., Ltd.) and BYK-LPN21324 (manufactured by Big Chemie (BYK)).
Examples of the pigment derivative include a sulfonic acid derivative of a pigment. Specifically, for example, a copper phthalocyanine sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, a sulfonic acid derivative of quinophthalone, and the like can be exemplified.

The amount of the dispersant used as described above is preferably 60 parts by mass or less, more preferably 5 to 50 parts by mass, and particularly 10 parts by mass with respect to 100 parts by mass of the pigment in the (A) colorant. It is preferably about 40 parts by mass.

As the dye, it is preferable to use an organic dye, and examples thereof include xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, and azo dyes. More specifically, for example, JP-A-2010-32299, JP-A-2010-254964, JP-A-2011-13894, Pamphlet International Publication No. 2010/123071, JP-A-2011-116803, JP-A. The organic dyes disclosed in JP-A-2011-117995, JP-A-2011-133844, JP-A-2011-174987 and the like are suitable. Specifically, for example, compounds represented by the following formulas (A-2-1) to (A-2-9) can be mentioned.

Of the above, the compounds represented by (A-2-1) and (A-2-3) to (A-2-5) are xanthene dyes;
The compounds represented by (A-2-2) and (A-2-6) are triarylmethane dyes;
The compounds represented by (A-2-7) and (A-2-8) are cyanine dyes; and the compounds represented by (A-2-9) are anthraquinone dyes.

The pigment and dye as the (A) colorant in the coloring composition of the present invention may be used alone or in admixture of any two or more. Further, the pigment and the dye may be mixed and used.

In the art, it is generally recognized that a colored cured film formed by using a coloring composition containing a dye has poor solvent resistance. However, the coloring composition of the present invention can form a colored cured film having excellent solvent resistance even when a dye is contained as the (A) coloring agent. In this case, the content of the dye in the (A) colorant can be 10% by mass or more, more preferably 20% by mass or more, particularly based on the total amount of the (A) colorant. Even if it is 30% by mass or more, a colored cured film having excellent solvent resistance can be obtained.

The content ratio of the (A) colorant in the coloring composition of the present invention is 5% by mass or more based on the total solid content of the coloring composition (meaning components other than the solvent in the coloring composition; the same applies hereinafter). Is more preferable, 10% by mass or more is more preferable, 15% by mass or more is further preferable, 20% by mass or more is further preferable, and 80% by mass or less is more preferable, 60% by mass or less is more preferable, and 55% by mass or less is further preferable. Preferably, 50% by mass or less is further preferable, 45% by mass or less is further preferable, and 40% by mass or less is further preferable. The range of the content ratio of the (A) colorant in the coloring composition of the present invention is preferably 5 to 80% by mass, more preferably 5 to 60% by mass, based on the total solid content of the coloring composition. %, More preferably 10 to 50% by mass, and particularly preferably 15 to 45% by mass. (A) By setting the content ratio of the colorant in the above range, when the colored cured film formed is a pixel, the brightness is high, the color purity and the heat resistance are excellent, and the colored cured film formed is formed. When the film is a black matrix or a black spacer, it is preferable in that it has excellent heat resistance and light-shielding properties.
Further, from the viewpoint of obtaining a coloring composition having even higher sensitivity, the content ratio of the coloring agent (A) in the coloring composition of the present invention is preferably 10 based on the total solid content of the coloring composition. It is ~ 50% by mass, more preferably 15 to 45% by mass, and even more preferably 20 to 40% by mass.
On the other hand, from the viewpoint of obtaining a coloring composition having a smaller mask bias, the content ratio of the coloring agent (A) in the coloring composition of the present invention is preferably 5 based on the total solid content of the coloring composition. It is ~ 50% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 45% by mass.
Since the coloring composition of the present invention can form a colored cured film having excellent solvent resistance and adhesion even if the content ratio of the colorant is high, green pixels and red pixels generally tend to have a high content ratio of the colorant. Can be preferably used for the formation of green pixels, and particularly preferably for the formation of green pixels.

<(B) Binder resin>
The binder resin (B) in the coloring composition of the present invention is not particularly limited, but is preferably a resin having an acidic functional group. A resin having a carboxyl group or a phenolic hydroxyl group is more preferable, and a resin having a carboxyl group is more preferable.

Particularly preferably, the binder resin (B) in the present invention is
(B1) An ethylenically unsaturated monomer having one or more carboxyl groups and
(B2) Copolymer with other copolymerizable ethylenically unsaturated monomer (carboxyl group-containing polymer (1));
Examples thereof include a polymer having a carboxyl group and a polymerizable unsaturated bond (carboxyl group-containing polymer (2)).

Examples of the unsaturated monomer (b1) that is the raw material of the carboxyl group-containing polymer (1) include (meth) acrylic acid, maleic acid, maleic anhydride, and mono oxalic acid [2- (meth) acryloyloxyethyl. ], Ω-carboxypolycaprolactone mono (meth) acrylate, p-vinylbenzoic acid and the like.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

Examples of the unsaturated monomer (b2) include N-position substituted maleimide, aromatic vinyl compounds, (meth) acrylic acid esters, vinyl ethers, macromonomers and the like. Specific examples of these are
As the above N-position substituted maleimide, for example, N-phenylmaleimide, N-cyclohexylmaleimide and the like;
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene and the like;
Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, and benzyl (meth) acrylate. ) Acrylate, polyethylene glycol (polymerization degree 2 to 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, Tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (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) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane, etc.;
Examples of the vinyl ether include cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylvinyl ether, 3-(
Vinyloxymethyl) -3-ethyloxetane, the following formula

Compounds represented by;
Examples of the macromonomer include polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polysiloxane. be able to.
These unsaturated monomers (b2) can be used alone or in admixture of two or more.

The copolymerization ratio of the unsaturated monomer (b1) in the carboxyl group-containing polymer (1) is preferably 5 to 5 based on the total of the unsaturated monomer (b1) and the unsaturated monomer (b2). It is 50% by mass, more preferably 10 to 40% by mass. A coloring composition containing a carboxyl group-containing polymer (1) obtained by copolymerizing an unsaturated monomer (b1) at the above copolymerization ratio is preferable in that it is excellent in storage stability and alkali developability. ..
Specific examples of the carboxyl group-containing polymer (1) include, for example, JP-A-7-140654, JP-A-8-259876, JP-A-10-31308, JP-A-10-300922, and JP-A-11-. It is disclosed in JP-A-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728 and the like.
Examples of the carboxyl group-containing polymer (2) include JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, and JP-A-11-140144. Polymers disclosed in Japanese Patent Application Laid-Open No. 2008-181095 and the like can be used.

For the binder resin (B) in the coloring composition of the present invention, the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent is preferably 1,000 to 100,000. It is more preferably 3,000 to 50,000. By using such a Mw (B) binder resin, it is possible to suppress the generation of dry foreign matter at the time of coating as much as possible, and a patterned cured film having a good shape can be obtained with high resolution and high residue. It is preferable because it can be formed with a film ratio and the heat resistance, electrical characteristics, solvent resistance, adhesion and the like of the obtained cured film can be further improved.
(B) The ratio (Mw / Mn) of the binder resin Mw to the number average molecular weight Mn is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0. Here, Mn is a polystyrene-equivalent number average molecular weight measured by GPC using tetrahydrofuran as an elution solvent.
The binder resin (B) as described above can be produced by a known method using an appropriate unsaturated monomer or a mixture thereof as a raw material. For example, a binder resin having an appropriately controlled structure, Mw / Mn, etc. is produced by a method disclosed in JP-A-2003-222717, JP-A-2006-259680, Pamphlet No. 2007/029871 and the like. can do.
As the binder resin (B) in the coloring composition of the present invention, the above-mentioned polymers can be used alone or in combination of two or more.

The content of the (B) binder resin in the coloring composition of the present invention is preferably 10 to 1,000 parts by mass, and more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. be. (B) The coloring composition containing the binder resin in the above range has excellent storage stability, good alkali developability of the coating film, and more solvent resistance, adhesion, and chromaticity characteristics of the obtained cured film. It is preferable in that it becomes higher.

<(C) Radical Polymerizable Compound>
The (C) radically polymerizable compound in the coloring composition of the present invention is a compound having two or more radically polymerizable groups in the molecule. Examples of the radically polymerizable group include an ethylenically unsaturated group, an oxylanyl group, an oxetanyl group, an N-alkoxymethylamino group and the like. As the ethylenically unsaturated group, a (meth) acryloyl group is preferable.
The (C) radically polymerizable compound in the present invention is selected from the group consisting of a compound having two or more (meth) acryloyl groups in the molecule and a compound having two or more N-alkoxymethylamino groups in the molecule. It is preferable to use it.

Examples of the compound having two or more (meth) acryloyl groups in the molecule include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with a (meth) acrylic acid, and a caprolactone-modified polyfunctional (? Meta) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting (meth) acrylate with hydroxyl group with polyfunctional isocyanate, (meth) acrylate with hydroxyl group and acid Examples thereof include polyfunctional (meth) acrylates having a carboxyl group obtained by reacting an anhydride.
Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol; trivalent or higher valent or higher such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol. Aliphatic polyhydroxy compounds and the like can be mentioned.

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 dimethacrylate. Etc.;
Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate and the like.
Examples of the acid anhydride include a dibasic acid anhydride and a tetrabasic acid dianhydride, and specific examples thereof include.
As the anhydride of the dibasic acid, for example, oxalic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride and the like are used;
Examples of the tetrabasic acid dianhydride include pyromellitic anhydride, biphenyltetracarboxylic dianhydride, and benzophenonetetracarboxylic dianhydride.

Examples of the caprolactone-modified polyfunctional (meth) acrylate include the compounds described in paragraphs [0015] to [0018] of JP-A-11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide.
Trimethylolpropane tri (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, trimethylolpropane tri (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide,
Pentaerythritol tri (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide,
Pentaerythritol tetra (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide,
Dipentaerythritol penta (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide,
Examples thereof include dipentaerythritol hexa (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide.

Examples of the compound having two or more N-alkoxymethylamino groups in the molecule include a compound having a melamine structure, a benzoguanamine structure, a urea structure, and the like. Here, the melamine structure means a chemical structure having one or more triazine rings as a basic skeleton, and the benzoguanamine structure means one or more phenyl group-substituted triazine rings as a basic skeleton, and includes melamine, benzoguanamine and a condensate thereof. It is a concept. Specific examples of compounds having two or more N-alkoxymethylamino groups in the molecule include, for example, N, N, N', N', N ", N" -hexa (alkoxymethyl) melamine, N, N, N. ', N'-tetra (alkoxymethyl) benzoguanamine, N, N, N', N'-tetra (alkoxymethyl) glycoluryl and the like can be mentioned.

The (C) radically polymerizable compound in the present invention is a polyfunctional (meth) acrylate or caprolactone-modified obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid. Polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N', N', N ", N" -hexa (alkoxymethyl) melamine and N , N, N', N'-tetra (alkoxymethyl) benzoguanamine is a preferred group of compounds. Among the polyfunctional (meth) acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic and an acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and di Pentaerythritol hexaacrylate;
Among the polyfunctional (meth) acrylates having a carboxyl group, compounds obtained by reacting pentaerythritol triacrylate with succinic anhydride and compounds obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride are available. It is particularly preferable because the formed colored cured product has high strength and excellent surface smoothness, and is less likely to cause background stains, film residue, etc. on the substrate and the light-shielding layer of the unexposed portion.
In the coloring composition of the present invention, the radically polymerizable compound (C) can be used alone or in combination of two or more.

The content of the (C) radically polymerizable compound in the coloring composition of the present invention is preferably 10 to 1,000 parts by mass, and more preferably 20 to 700 parts by mass with respect to 100 parts by mass of the (A) colorant. Parts, more preferably 50 to 500 parts by mass.
(C) The coloring composition containing the radically polymerizable compound in the above range is excellent in the developability of the coating film, and causes problems such as background stains and film residue on the substrate or the light-shielding layer of the unexposed portion. Is preferable because it can suppress as much as possible and also has excellent curability of the coating film.

<(D) Photoradical generator>
The (D) photoradical generator contained in the coloring composition of the present invention is a radical of the above (C) radically polymerizable compound by irradiating with light such as visible light, ultraviolet rays, salt ultraviolet rays, electron beams, and X. It is a compound that generates radicals as an active species that can initiate polymerization.
Examples of such (D) photoradical generators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, and benzophenone compounds. , Α-Diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds and the like.
In the coloring composition of the present invention, the photoradical generator (D) can be used alone or in combination of two or more.

As the (D) photoradical generator in the present invention, it is preferable to use at least one selected from the group of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds and O-acyloxime compounds. In particular, it preferably contains an O-acyloxime compound.

Specific examples of the (D) photoradical generator are as follows.
Examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and the like. 2,4-Diisopropylthioxanthone, etc .;
Examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). Butane-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane-1-one, etc.;
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 '-Bimidazole,
2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, etc.;

Examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, and 2- [2- (5-methyl). Fran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (fran-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-ethoxystyryl) -4,6- Triazine compounds having a halomethyl group such as bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine;
Examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), etanone, 1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H -Carbazole-3-yl]-, 1- (O-acetyloxime), etanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl} -9H-carbazole-3-yl]-, 1- (O-acetyloxime) and the like can be mentioned respectively. Examples of commercially available O-acyloxime compounds include NCI-831, NCI-930 (all manufactured by ADEKA Corporation), DFI-020, DFI-091 (all manufactured by Daito Chemix Co., Ltd.) and the like. be able to.

When a biimidazole-based compound is used as the (D) photoradical generator in the present invention, it is preferable to use a hydrogen donor together with the compound in that the photosensitivity can be further increased. Here, the "hydrogen donor" is a compound capable of donating a hydrogen atom to a radical generated from a biimidazole-based compound by light irradiation. Examples of such hydrogen donors include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; and 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino). ) Amine-based hydrogen donors such as benzophenone can be mentioned. These hydrogen donors can be used alone or in combination of two or more, but at least one of the mercaptan hydrogen donors and at least one of the amine hydrogen donors should be used in combination. However, it is preferable in that the light sensitivity can be extremely high.

On the other hand, the photoradical generator (D) in the present invention is selected from the group consisting of photoradical generators other than biimidazole compounds, preferably thioxanthone compounds, acetophenone compounds, triazine compounds and O-acyloxime compounds. When at least one of these photoradical generators is used, a sensitizer may be used together with these photoradical generators. Examples of such a sensitizer include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethylamino. Ethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. At least one selected from these can be used.

The content ratio of the (D) photoradical generator in the coloring composition of the present invention is preferably 0.01 to 120 parts by mass, and more preferably 1 to 1 part by mass with respect to 100 parts by mass of the (C) radically polymerizable compound. It is 100 parts by mass. (D) By setting the content ratio of the photoradical generator in the above range, the curability of the coloring composition can be improved, which is preferable.
(D) When a biimidazole-based compound is used as the photoradical generator and a hydrogen donor is used together with the biimidazole-based compound, the content of the hydrogen donor is preferably based on 100 parts by mass of the biimidazole-based compound. Is less than or equal to 500 parts by mass, more preferably 50 to 300 parts by mass;
(D) When a photoradical generator other than the biimidazole compound is used as the photoradical generator and a sensitizer is used together with the photoradical generator, the content of the sensitizer is other than the biimidazole compound. It is preferably 300 parts by mass or less, and more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the photoradical generator.

<(E) Compound>
The compound (E) in the present invention is a compound having a structure in which the group represented by the above formula (E0) is directly linked to an aromatic ring.
The alkyl group of the definitive ^{R I} of the formula (E0), such as methyl group, ethyl group, n- propyl group, i- propyl, n- butyl group, sec- butyl group, be mentioned t- butyl group Can be done. R ^I is preferably an alkyl group, and more preferably a methyl group or an ethyl group.
R ^II is independently, it can be the alkyl group of which a hydrogen atom and R ^I is one of the groups exemplified above, and is preferably a hydrogen atom.
x is preferably 1.

The compound (E) in the present invention is preferably a compound having two or more groups represented by the above formula (E0) in the molecule, and more preferably a compound having four or more groups. Particularly preferably, the number is 6 to 10. Two or more groups represented by the above formula (E0) may be bonded to one aromatic ring.
The compound (E) in the present invention is at least one selected from the group consisting of a monovalent group represented by the following formula (E0-1) and a divalent group represented by the following formula (E0-2). It is preferably a compound having a group of.

[E0 in the formulas (E0-1) and (E0-2) are groups represented by the above formula (E0), respectively.
Z is independently a hydroxyl group or a monovalent organic group.
Each "+" indicates that it is a bond;
In equation (E0-1), a1 is an integer from 1 to 5, b1 is an integer from 0 to 4, but satisfies the relationship a1 + b1 = 1 to 5; and in (E0-2), a2 is. It is an integer of 1 to 4, b2 is an integer of 0 to 3, but satisfies the relationship of a2 + b2 = 1 to 4. ]

The a1 in the above formula (E0-1) and the a2 in the above formula (E0-2) are preferably 1 or 2 independently, and more preferably 2.
Z in the above formulas (E0-1) and (E0-2) is a hydroxyl group or a monovalent organic group. Examples of the organic group include an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkoxy group having 2 to 8 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, a glycidyloxy group, and a 2,3-dihydroxypropoxy group. Can be done. Z is a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkoxyalkoxy group having 2 to 6 carbon atoms, or an acyloxy group having 2 to 4 carbon atoms from the viewpoint of increasing the stability of the obtained coloring composition. It is preferable to have. Specific examples of these include, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like as an alkoxy group;
As the alkoxyalkoxy group, for example, 1-methoxyethoxy group, 2-methoxyethoxy group, 1-ethoxyethoxy group, 2-ethoxyethoxy group, 1-butoxyethoxy group and the like; as an acyloxy group, for example, an acetyloxy group and the like, respectively. Can be mentioned.
It is preferable that b1 in the above formula (E0-1) and b2 in the above formula (E0-2) are independently 0 or 1, respectively.

The compound (E) in the present invention having the above-mentioned group is at least one compound selected from the group consisting of the compounds represented by the following formulas (E-1) to (E-5). Is preferable.

[E0 and Z in the formulas (E-1) to (E-5) have the same meaning as E0 and Z in the above formulas (E0-1) and (E0-2), respectively.
R is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, a phenyl group or a naphthyl group.
A is a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -SO-, -SO _2- , -CR _2- (where R is the above) independently of each other. It has the same meaning.) Or the following formula (T-1)

(In the above formula (T-1), Z has the same meaning as Z in the above formulas (E0-1) and (E0-2), n is an integer of 0 to 4, and "+" is a bond. Indicates that there is.)
It is a group represented by;

C1, c2, d1 and d2 in the formula (E-1) are independently integers of 0 to 5, except that c1 + d1 = 0 to 5 and c2 + d2 = 0 to 5 are satisfied, and c1 and c1 and d2 are satisfied. At least one of c2 is not 0;
E1 to e3 and f1 to f3 in the formula (E-2) are independently integers of 0 to 5, except that the conditions of e1 + f1 = 0 to 5, e2 + f2 = 0 to 5 and e3 + f3 = 0 to 5. And at least one of e1 to e3 is not 0;
G1 to g4 and h1 to h4 in the formula (E-3) are independently integers of 0 to 5, except that g1 + h1 = 0 to 5, g2 + h2 = 0 to 5, g3 + h3 = 0 to 5 and g4 + h4. = The condition 0 to 5 is satisfied, and at least one of g1 to g4 is not 0;
In the formula (E-4), i1 to i3 and j1 to j3 are independently integers of 0 to 5, and i4 and j4 are independently integers of 0 to 4, where i1 + j1 =. The conditions 0-5, i2 + j2 = 0-5, i3 + j3 = 0-5, and i4 + J4 = 0-4 are satisfied, and at least one of i1 to i4 is not 0;
In the formula (E-5), k1, k2, L1 and L2 are independently integers of 0 to 5, and k3 and L3 are independently integers of 0 to 4, where k1 + L1 =. The conditions 0 to 5, k2 + L2 = 0 to 5, and k3 + L3 = 0 to 4 are satisfied, and at least one of k1 to k3 is not 0;
m is an integer of 1-5. ]

The R in the above formulas (E-2) to (E-5) is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably. It is a hydrogen atom.
As A, a single bond, a methylene group, a propane-2,2-diyl group or a group represented by the above formula (T-1) is preferable.
C1, c2, e1 to e3, g1 to g4, i1 to i3, and k1 to k3 in the above formulas (E-1) to (E-5) are preferably 1 or 2, respectively, and are 2. Is more preferable;
i4 is preferably 0;
d1, d2, f1 to f3, h1 to h4, j1 to j3 and L1 to L3 are preferably 0 or 1, respectively, and more preferably 1.
j4 is preferably 0.

Specific examples of such compound (E) include
As the compound (E-1), for example, a compound represented by each of the following formulas (E-1-1) to (E-1-3);
As the compound (E-2), for example, a compound represented by each of the following formulas (E-2-1) and (E-2-2);
As the compound (E-3), for example, a compound represented by the following formula (E-3-1) and the like;
As the compound (E-4), for example, a compound represented by each of the following formulas (E-4-1) to (E-4-8); and as the compound (E-5), for example, the following formula. The compounds represented by (E-5-1) and the like can be mentioned respectively.

[In equation (E-5-1),
m, n, r and s are independently integers from 0 to 5, respectively.
p and q are independently integers from 0 to 4, respectively.
l is 0 or any natural number representing the number of repeating units.
However, m + n and r + s are each in the range of 0 to 5, p + q is in the range of 0 to 4, and at least one of m, r and p is not 0. ]

The amount of the compound (E) used in the coloring composition of the present invention is preferably 0.1 to 50 parts by mass, preferably 1 to 45 parts by mass with respect to 100 parts by mass of the binder resin (B). More preferably, it is 3 to 40 parts by mass.
As described above, the preferred compound (E) in the present invention has both a group represented by the above formula (E0) and a group Z. Here, when a compound having a hydroxyl group as the group Z is used as the compound (E), a coloring composition having a small mask bias can be obtained. In this case, the amount of the compound (E) used is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, and 5 parts by mass with respect to 100 parts by mass of the binder resin (B). The above is even more preferable, and 40 parts by mass or less is preferable, 35 parts by mass or less is more preferable, and 30 parts by mass or less is further preferable. The content of the compound (E) in the coloring composition of the present invention is preferably 1 to 40 parts by mass, more preferably 2 to 35 parts by mass, based on 100 parts by mass of the binder resin (B). It is preferably 3 to 30 parts by mass.
On the other hand, when a compound in which the group Z is a monovalent organic group is used as the compound (E), a coloring composition having high photosensitivity can be obtained. In this case, the amount of the compound (E) used is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, and 45 parts by mass with respect to 100 parts by mass of the binder resin (B). It is preferably parts or less, 43 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less. The content of the compound (E) in the coloring composition of the present invention is preferably 1 to 45 parts by mass, more preferably 2 to 40 parts by mass, based on 100 parts by mass of the binder resin (B). It is preferably 3 to 35 parts by mass, and may be 20 to 45 parts by mass, further 25 to 43 parts by mass, and further 30 to 40 parts by mass.

<Other ingredients>
The coloring composition of the present invention contains the above-mentioned components (A) to (E) as essential components, but may optionally contain other components as long as the effects of the present invention are not impaired. Such other components include fillers such as glass and alumina;
Polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate);
Surfactants such as fluorine-based surfactants and silicon-based surfactants;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;

2,2-thiobis (4-methyl-6-t-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- Antioxidants such as tetraoxa-spiro [5.5] undecane, thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate];
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones;
Anti-aggregation agent 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 and other residue improvers;
Developable improvers such as mono-succinate [2- (meth) acryloyloxyethyl], mono-phthalate [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. Can be done.

<Solvent>
The coloring composition of the present invention contains the above-mentioned components (A) to (E) as essential components and optionally contains other components, but is preferably a liquid composition further containing a solvent. Prepared.
Here, as the solvent, a solvent in which the above-mentioned components are dispersed or dissolved, does not react with these components, and has appropriate volatility is preferable, and a solvent having such characteristics is appropriately selected and used. can do.

Examples of the solvent contained in the coloring composition of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and 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, Dipropylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono (Poly) alkylene glycol monoalkyl ethers such as ethyl 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;
Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-
Alkoxycarboxylic acid esters such as 3-methoxybutyl propionate;

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 butyrate 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 thereof include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and lactams.

Of these solvents, (poly) alkylene glycol monoalkyl ethers, lactic acid alkyl esters, (poly) alkylene glycol monoalkyl ethers, from the viewpoint of solubility, coatability, etc., and dispersibility of pigments when contained. Acetates, other ethers, ketones, diacetates, alkoxycarboxylic acid esters, and other esters are preferable, and propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether are particularly preferable. Acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 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-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n formic acid It is more preferable to use −amyl, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate and the like.
In the coloring composition of the present invention, the solvent can be used alone or in combination of two or more.

The most preferable solvent for the coloring composition of the present invention is
At least one selected from the group consisting of (poly) alkylene glycol monoalkyl ethers and (poly) alkylene glycol monoalkyl ether acetates, or (poly) alkylene glycol monoalkyl ethers and (poly) alkylene This is the case when it contains a mixture of glycol monoalkyl ether acetates.

The content of the solvent in the coloring composition of the present invention is not particularly limited, but the solid content concentration of the coloring composition (the total mass of the components other than the solvent of the coloring composition is the total mass of the coloring composition. The proportion) is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. A coloring composition containing the solvent in the above amount is preferable in that the dispersibility of each component contained therein is excellent, and therefore the stability of the composition is excellent and the coating property is excellent.

<Preparation method of coloring composition>
The coloring composition of the present invention can be prepared by an appropriate method. For example, it can be prepared by mixing the above-mentioned components (A) to (E) and optionally other components together with a solvent.
For example, when the (A) colorant in the coloring composition of the present invention contains a pigment, the (A) colorant is preferably one of the (B) binder resins in the presence of a dispersant. In the solvent, for example, a bead mill, a roll mill, or the like is used to pulverize and mix and disperse the parts together with the pigment dispersion liquid to obtain a pigment dispersion liquid, and then the residue of the binder resin (B) and (C) to (E) are added to the pigment dispersion liquid. ) Ingredients and optionally other ingredients can be added and mixed.

<Method of forming a colored cured film>
A colored cured film can be formed by using the coloring composition of the present invention as described above. The colored cured film in the present invention is a concept including pixels of each color used in a display element and a solid-state image pickup device; a black matrix, a black spacer, and the like.
In order to form a colored cured film using the coloring composition of the present invention, it is preferable to use any of the following methods.
In the first method, the coloring composition of the present invention is applied onto a substrate to form a coating film, and then at least a part of the coating film is irradiated with light, then developed, and preferably further heated (post-baked). ) Is a way to do it;
The second method is to apply the coloring composition of the present invention in a pattern on a substrate by an inkjet method to form a coating film, optionally irradiate the coating film with light, and then preferably further heat (post). It is a method of baking).
In any of the above methods, a color filter is formed by sequentially forming a colored cured film as pixels of each color using a colored composition of three colors of red, green and blue or three colors of cyan, magenta and yellow. be able to. On the other hand, a black matrix or a black spacer can be formed by forming a black colored cured film using a black coloring composition.
Examples of the substrate include a substrate made of glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide and the like. If necessary, these substrates are subjected to chemical (for example, silane coupling agent) treatment, plasma treatment, ion plating treatment, sputtering treatment, vapor phase reaction treatment, vacuum deposition treatment, etc. It may be processed.

When the coloring composition of the present invention is used for forming pixels of a color filter, it is preferable that a black matrix is formed so as to partition a pixel region on the substrate. The black matrix can be a thin film of a metal (such as chromium) having a desired pattern, a colored cured film formed from a coloring composition, or the like. The patterned metal thin film can be formed, for example, by applying photolithography to a metal thin film formed on a substrate by a sputtering method, a vapor deposition method, or the like. The patterned colored cured film formed from the coloring composition can be formed by the same method as in the present invention using the black coloring composition. In the second method using the inkjet method, the black matrix also functions as a barrier to prevent the color compositions ejected by the inkjet method from mixing in addition to the light-shielding function. Therefore, the black matrix in this case preferably has a film thickness of a certain value or more, and therefore the black matrix in this case is preferably a black cured film formed by using the black coloring composition.
When the coloring composition of the present invention is used for forming a black matrix, it is preferable that the substrate is a substrate on which a black matrix for partitioning a pixel region has not yet been formed.
Further, the substrate used when the coloring composition of the present invention is used for forming a black spacer is preferably a substrate on which both a black matrix for partitioning a pixel region and pixels are formed.

In the above first method, examples of the method of applying the coloring composition on the substrate include a spray method, a roll coating method, a rotary coating method (spin coating method), a slit die coating method (slit coating method), and a bar coating method. And so on. Of these, it is preferable to adopt the spin coating method or the slit die coating method.
After coating by the above method or an inkjet method, a coating film thereof can be preferably applied by heating (prebaking) the coated coloring composition to remove the solvent. The pre-baking conditions are preferably 70 to 110 ° C., preferably about 1 to 10 minutes, and the pre-baking is preferably performed under reduced pressure. The degree of decompression is preferably set so that the ultimate pressure (absolute pressure) is 50 to 200 Pa.
The thickness of the coating film is preferably 0.6 to 12 μm, more preferably 1.2 to 10 μm as the thickness after removing the solvent.

Examples of the light source used for irradiating the formed coating film with light include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps, and argon. Examples thereof include an ion laser, a YAG laser, an XeCl excimer laser, a nitrogen laser, and an ultraviolet LED. The light to be irradiated is preferably light having a bright line in the range of 190 to 450 nm. Light irradiation amount is preferably from 10~10,000J / ^{m 2,} and more preferably 50~5,000J / ^{m 2.}

The above development is carried out using an alkaline developer. By the developing process, the unexposed portion of the coating film is removed to form a patterned coating film. Examples of this alkaline developer include sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1 , 5-Diazabicyclo- [4.3.0] -5-Nonene or the like is preferably used. If necessary, a water-soluble organic solvent such as methanol or ethanol; a surfactant or the like may be added to the aqueous solution in an appropriate range.
As the developing method, for example, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid filling) developing method and the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature. The developed coating film is preferably washed with water.
The post-baking can be performed, for example, at a temperature of 180 to 280 ° C. for, for example, 10 to 60 minutes.

The film thickness of the colored cured film formed as described above is as follows depending on the application.
Pixel: preferably 0.5-5 μm, more preferably 1-3 μm
Black matrix: preferably 0.5-10 μm, more preferably 0.8-5 μm
Black spacer: preferably 0.5 to 10 μm, more preferably 1 to 7 μm

The pixel pattern obtained by forming the pixels of each color as described above is obtained by forming a protective film on the pixel pattern as needed, and then forming a transparent conductive film and a spacer in this order to form a display element. It can be used as a color filter.

<Display element>
The display element in the present invention includes at least one colored cured film selected from the group consisting of the pixels formed as described above, the color filter, the black matrix, and the black spacer. 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 includes a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, an IPS (In-Planes Switching) type, a VA (Vertical Birefringence) type, an OCB (Optical Birefringence) type, etc. Appropriate liquid crystal mode can be applied.

The color liquid crystal display element may be a transmissive type or a reflective type, and may have a liquid crystal cell having an appropriate structure. As the structure of the liquid crystal cell, for example, a driving substrate on which a thin film transistor (TFT) is arranged and an opposing substrate on which a color filter is formed are used as a pair, and a liquid crystal layer is sandwiched between the pair of substrates;
A substrate having both a thin film transistor (TFT) and a color filter and a substrate on which an ITO (tin-doped indium oxide) electrode is formed are used as a pair, and a structure in which a liquid crystal layer is sandwiched between the pair of substrates is formed. It can be exemplified.
The color liquid crystal display device may include a backlight unit in addition to the above liquid crystal cell. Examples of the light source in the backlight unit include a cold cathode fluorescent tube and a white LED.
The organic EL display element can have an appropriate structure, for example, the structure disclosed in Japanese Patent Application Laid-Open No. 11-307242.
The electronic paper can have an appropriate structure, for example, the structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.
The solid-state image sensor can have an appropriate structure, for example, the structure disclosed in Japanese Patent No. 4480740.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
<(B) Synthesis of binder resin>
Synthesis example B1
A flask equipped with a cooling tube and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and substituted with nitrogen. The contents of the flask are heated 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 by mass. Consists of 23 parts by mass of -ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono (2-acryloyloxyethyl) oxalate and 6 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile). The mixed solution was added dropwise over 1 hour, and the mixture was maintained at this temperature and polymerized for 2 hours. Then, the temperature of the reaction solution was raised to 100 ° C., and the temperature was maintained for another 1 hour to polymerize to obtain a solution containing the binder resin (B-1) (solid content concentration 33% by mass). .. The Mw of the obtained binder resin (B-1) was 12,200, and the Mn was 6,500.

<Preparation of pigment dispersion liquid>
Preparation Example P1
(A) As a colorant, C.I. I. Pigment Green 58 by 9.1 parts by mass and C.I. I. Pigment Yellow 138 by 3.9 parts by mass, BYK-LPN21116 as a dispersant (manufactured by Big Chemie, solid content concentration 40% by mass) in a solution of 12.5 parts by mass, (B) Synthetic example B1 as a part of a binder resin A mixed solution containing 15.2 parts by mass of the solution containing the binder resin (B-1) obtained in 1 and 59.3 parts by mass of propylene glycol methyl ether acetate as a solvent is mixed and dispersed for 12 hours using a bead mill. As a result, a pigment dispersion liquid (A-1-1) was prepared.

Preparation Examples P2 to P6
Pigment dispersions (A-1-2) to (A-1) in the same manner as in Preparation Example P1 except that the pigments of the type and amount shown in Table 1 were used as the colorant in Preparation Example P1. -6) were prepared respectively.

The abbreviations for pigments in Table 1 have the following meanings.
G58: C.I. I. Pigment Green 58
Y138: C.I. I. Pigment Yellow 138
G7: C.I. I. Pigment Green 7
Y129: C.I. I. Pigment Yellow 129
Y185: C.I. I. Pigment Yellow 185
R254: C.I. I. Pigment Red 254
R177: C.I. I. Pigment Red 177
B15: 6: C.I. I. Pigment Blue 15: 6

<Dye synthesis>
Synthesis example SD1
A compound represented by the above formula (A-2-1) (Compound (A-2-1)) was synthesized according to Synthesis Example 1 of JP2013-190776A.

Synthesis example SD2
A compound represented by the above formula (A-2-2) (compound (A-2-2)) was synthesized according to the method described in Colorant Synthesis Example 3 of JP2012-108469A.

<Preparation of dye solution>
Preparation Example SD1
A dye solution (A-2-1) was prepared by dissolving 10 parts by mass of the compound (A-2-1) obtained in the above Synthesis Example SD1 in 90 parts by mass of propylene glycol monomethyl ether.

Preparation Example SD2
A dye solution (A-2-2) was prepared by dissolving 10 parts by mass of the compound (A-2-2) obtained in the above Synthesis Example SD2 in 90 parts by mass of propylene glycol monomethyl ether.

Example 1
<Preparation of coloring composition>
100 parts by mass of the pigment dispersion liquid (A-1-1) obtained in Preparation Example P1, 15 parts by mass of a solution containing the binder resin (B-1) as the binder resin (B) obtained in Synthesis Example B1 above. (C
) KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as a radically polymerizable compound, 13 parts by mass, (D) IRGACURE 369 as a photoradical generator (commodity) Name, manufactured by BASF, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1) 0.7 parts by mass and Adecca radicals NCI-831 (trade name, O-acyloxime compound) , Manufactured by ADEKA Co., Ltd.) 0.6 parts by mass, (E) 1.0 part by mass of the compound represented by the above formula (E-4-1) as a compound, and Megafuck F-554 as a radical surfactant. (Product name, manufactured by DIC Co., Ltd.) 0.05 parts by mass is mixed, 3-methoxybutyl acetate (MBA) and propylene glycol monomethyl ether acetate (PGMEA) are added, and a solvent containing a component brought in from the pigment dispersion. A coloring composition (S-1) having a composition of MBA: PGMEA = 15: 85 (parts by mass) and a solid content concentration of 17% by mass was prepared.
This coloring composition was evaluated according to the following procedure.
The evaluation results are shown in Table 5.

<Evaluation of coloring composition>
(1) Evaluation of solvent resistance After applying the coloring composition (S-1) on a glass substrate using a spin coater, prebaking was performed on a hot plate at 90 ° C. for 100 seconds to obtain a film thickness of 2.5 μm. A coating film was formed. After allowing the substrate with the coating film to cool to room temperature, the coating film was irradiated with a high-pressure mercury lamp at an ^{exposure amount of 400 J / m 2} via a photomask having a line-and-space pattern with a slit width of 90 μm and a space width of 210 μm. (Exposure gap = 300 μm). Next, with respect to the substrate with a coating film after light irradiation, a potassium aqueous solution having a temperature of 23 ° C. and a concentration of 0.04% by mass was used as a developing solution, and the developing pressure was 110 kPa and the developing solution flow rate was 1.2 liters / minute. It was discharged for a second and shower-developed. The developed substrate with a coating film was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 30 minutes to form a pixel pattern consisting of a line-and-space pattern on the substrate.
The substrate on which the pixel pattern was formed was immersed in N-methylpyrrolidone at 25 ° C. for 30 minutes, and the pixel pattern shape and film thickness before and after the immersion were observed with a scanning electron microscope and evaluated according to the following criteria.

Evaluation Criteria When the pixel pattern is not chipped and the film thickness after immersion is 95% or more of the film thickness before immersion: Solvent resistance "good"
When a part of the pixel pattern is chipped, or the film thickness after immersion is 80% or more and less than 95% of the film thickness before immersion: Solvent resistance "poor"
When a part of the pixel pattern is chipped and the film thickness after immersion is less than 80% of the film thickness before immersion: Solvent resistance "impossible"

(2) Evaluation of Sensitivity and Mask Bias By the same operation as in "(1) Evaluation of Solvent Resistance" above, a pixel pattern consisting of a line-and-space pattern was formed on a glass substrate.
The pixel pattern obtained above was observed with an optical microscope to check for chipping of the pattern edge, and evaluated according to the following criteria.

If no chipping is found in the evaluation criteria pattern: Sensitivity "excellent"
If the pattern is slightly chipped: Sensitivity "good"
If there are many chips in the pattern: Sensitivity "poor"

Further, the line width of the pixel pattern obtained above was measured, a value obtained by subtracting the slit width (90 μm) of the photomask from the line width measurement value was obtained, and the mask bias property was evaluated based on this value.
The mask bias property can be evaluated by the following criteria.

Evaluation criteria When the subtraction value is a negative value: Curing is poor and the sensitivity is significantly inferior. When the subtraction value is 0 μm or more and less than 10 μm: The mask bias property is small (excellent mask bias property).
When the subtraction value is 10 μm or more: The mask bias property is large (the mask bias property is inferior).

Here, if the light sensitivity of the coloring composition is sufficiently high, a pattern (colored cured film) having excellent curability and adhesion to the substrate is formed, so that the formed pattern is not chipped or peeled off. ..
On the other hand, when the mask bias property is small, a pattern having a size that reproduces the photomask size is formed.
Therefore, the coloring composition can be suitably used after selecting the process design to be adopted, the application of the liquid crystal display element, and the like, as long as it is excellent in either one of the above-mentioned light sensitivity and mask bias property.

Examples 2-4, 8-10 and 12-15
In Example 1 above, a coloring composition was prepared in the same manner as in Example 1 except that the types and amounts of the components (A) to (E) were as shown in Table 2, and various evaluations were performed.
The evaluation results are shown in Table 5.

Example 5
85 parts by mass of the pigment dispersion (A-1-5) obtained in Preparation Example P5 (containing 11 parts by mass of the pigment and 4.2 parts by mass of the binder resin (B-1)) and the dye obtained in Preparation Example SD1. 20 parts by mass of the solution (A-2-1) (containing 2 parts by mass of the dye), and 31 parts by mass of the solution (binder) containing the binder resin (B-1) as the (B) binder resin obtained in the above synthesis example B1. KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate and dipentaerythritol) as a (C) radically polymerizable compound (corresponding to 10.2 parts by mass in terms of resin (B-1)) 19 parts by mass (mixture of pentaacrylate), (D) IRGACURE 369 as a photoradical generator (trade name, manufactured by BASF, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1) 1) .0 parts by mass and Adeca Arclus NCI-831 (trade name, O-acyloxime compound, manufactured by ADEKA Co., Ltd.) 0.9 parts by mass, represented by the above formula (E-4-1) as the (E) compound. MBA, PGMEA and propylene glycol monomethyl ether (PGME) are mixed with 1.5 parts by mass of the compound to be used and 0.05 parts by mass of Megafuck F-554 (trade name, manufactured by DIC Co., Ltd.) as a fluorine-based surfactant. ) Was added to prepare a coloring composition having a solvent composition of MBA: PGMEA: PGME = 15: 75:10 (parts by mass) and a solid content concentration of 17% by mass, including the amount brought in from the pigment dispersion.
Various evaluations were carried out in the same manner as in Example 1 using this coloring composition.
The evaluation results are shown in Table 5.

Example 6
In Example 5 above, a coloring composition was prepared in the same manner as in Example 5 except that the type and amount of the component (A) were as shown in Table 2, and various evaluations were performed.
The evaluation results are shown in Table 5.

Example 7
130 parts by mass of the dye solution (A-2-2) obtained in the above Preparation Example SD2 (containing 13 parts by mass of the dye), and the binder resin (B-1) as the (B) binder resin obtained in the above Synthesis Example B1. 62 parts by mass of the contained solution (corresponding to 20.5 parts by mass in terms of binder resin (B-1)), (C) KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., dye) as a radically polymerizable compound. 27 parts by mass of (mixture of pentaerythritol hexaacrylate and dipentaerythritol pentaacrylate), (D) IRGACURE 369 (trade name, manufactured by BASF, 2-benzyl-2-dimethylamino-1- (4-morpho)) as a photoradical generator. Renophenyl) Butanon-1) 2.5 parts by mass and Adeca Arckles NCI-831 (trade name, O-acyloxime compound, manufactured by ADEKA Co., Ltd.) 2.2 parts by mass, as the compound (E) above formula (E) 2.0 parts by mass of the compound represented by E-4-1) and 0.05 parts by mass of Megafuck F-554 (trade name, manufactured by DIC Co., Ltd.) as a fluorine-based surfactant are mixed, and MBA, PGMEA and PGME were added to prepare a coloring composition having a solvent composition of MBA: PGMEA: PGME = 15: 40: 45 (parts by mass) and a solid content concentration of 17% by mass, including the amount brought in from the pigment dispersion.
Various evaluations were carried out in the same manner as in Example 1 using this coloring composition.
The evaluation results are shown in Table 5.

Example 11
In Example 7, a coloring composition was prepared in the same manner as in Example 7 except that the type and amount of the component (E) were as shown in Table 2, and various evaluations were performed.
The evaluation results are shown in Table 5.

Examples 16, 17 and 20-24 and Comparative Examples 1 and 4
In Example 1, a coloring composition was prepared in the same manner as in Example 1 except that the types and amounts of the components (A) to (E) were as shown in Table 3, and various evaluations were performed.
The evaluation results are shown in Table 6.

Examples 18 and 25 and Comparative Examples 2 and 5
In Example 5, a coloring composition was prepared in the same manner as in Example 5 except that the types and amounts of the components (A) to (E) were as shown in Table 3, and various evaluations were performed.
The evaluation results are shown in Table 6.

Example 19 and Comparative Examples 3 and 6
In Example 7, a coloring composition was prepared in the same manner as in Example 7 except that the types and amounts of the components (A) to (E) were as shown in Table 3, and various evaluations were performed.
The evaluation results are shown in Table 6.

Examples 26, 27, 33 and 34 and Comparative Examples 7, 8, 11 and 12
In Example 1, a coloring composition was prepared in the same manner as in Example 1 except that the types and amounts of the components (A) to (E) were as shown in Table 4, and various evaluations were performed.
The evaluation results are shown in Table 7.

Examples 30-32, 35 and 36 and Comparative Examples 10, 13 and 14
In Example 5, a coloring composition was prepared in the same manner as in Example 5 except that the types and amounts of the components (A) to (E) were as shown in Table 4, and various evaluations were performed.
The evaluation results are shown in Table 7.

Examples 28 and 29 and Comparative Example 9
In Example 7, a coloring composition was prepared in the same manner as in Example 7 except that the types and amounts of the components (A) to (E) were as shown in Table 4, and various evaluations were performed.
The evaluation results are shown in Table 7.

The abbreviations for each component in Tables 2 to 4 above have the following meanings.
[(C) Radical Polymerizable Compound]
C-1: KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)
[(D) Photoradical generator]
D-1: IRGACURE 369 (trade name, manufactured by BASF, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1)
D-2: ADEKA ARKULS NCI-831 (trade name, O-acyloxime compound, manufactured by ADEKA Corporation)
[(E) Compound]
E-1-1: Compound represented by the above formula (E-1-1) E-2-1: Compound represented by the above formula (E-2-1) E-2-2: Compound represented by the above formula (E-2-1) -2-2) Compound E-3-1: Compound represented by the above formula (E-3-1) E-4-1: Compound represented by the above formula (E-4-1) E-4-2: Compound represented by the above formula (E-4-2) E-4-3: Compound represented by the above formula (E-4-3) E-4-4: The above formula (E) -4-4) Compound E-4-5: Compound represented by the above formula (E-4-5) E-51: Compound represented by the above formula (E-5-1) [Other compounds]
R-1: Compound represented by the following formula (R-1)

The compound represented by the above formula (R-1) used in Comparative Examples 1 to 3 does not correspond to the compound (E) specified in the present invention, but is described in the column of the compound (E) for convenience in Table 3. ..

Claims (8)

(A) Colorant,
(B) Binder resin,
(C) Radical polymerizable compound,
It is characterized by containing (D) a photoradical generator and (E) at least one compound selected from the group consisting of compounds represented by the following formulas (E-3) and (E-5). , Coloring composition.

[In formulas (E-3) and (E-5),
E0 is independently expressed by the following equation (E0);
*-(CR ^II ₂ ) _x- O-R ^I (E0)
(In equation (E0),
^RI is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ^II is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
x is 1 or 2
"*" Indicates that the bond is a bond that directly binds to the aromatic ring. )
It is a group represented by
Z is independently a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkoxy group having 2 to 8 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, a glycidyloxy group or a 2,3-dihydroxypropoxy group. ,
R is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, a phenyl group or a naphthyl group.
A is a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -SO-, -SO _2- , -CR _2- (where R is the above). It has the same meaning.) Or the following formula (T-1);

(In the above formula, Z is synonymous with the above, n is an integer of 0 to 4, and "+" indicates a bond.)
It is a group represented by;
g1 to g4 and h1 to h4 are independently integers of 0 to 5, but satisfy the conditions of g1 + h1 = 0 to 5, g2 + h2 = 0 to 5, g3 + h3 = 0 to 5, and g4 + h4 = 0 to 5. And at least one of g1 to g4 is not 0;
k1, k2, L1 and L2 are independently integers of 0 to 5, respectively.
k3 and L3 are independently integers of 0 to 4, but satisfy the conditions of k1 + L1 = 0 to 5, k2 + L2 = 0 to 5, and k3 + L3 = 0 to 4, and at least one of k1 and k3. One is not 0;
m is an integer of 1-5. ] The (E) 0.1 to 50 parts by mass with respect to the content of the compound (B) Binder resin 100 parts by weight, the coloring composition of the placing serial to claim 1. The coloring composition according to claim 1 or 2 , wherein the (D) photoradical generator contains an O-acyloxime compound. The coloring composition according to any one of claims 1 to 3, wherein the content ratio of the coloring agent (A) is 15 to 45% by mass based on the total solid content of the coloring composition. The coloring composition according to any one of claims 1 to 4 , wherein the coloring agent (A) contains a dye. A colored cured film, which is formed by using the coloring composition according to any one of claims 1 to 5. The colored cured film according to claim 6 , which is a pixel, a black matrix, or a black spacer. A display element comprising the colored cured film according to claim 6 or 7.