JP2019095797A - Coloring composition, colored cured film and display element - Google Patents

Abstract

To provide a colored cured film excellent in both of adhesion and solvent resistance, a coloring composition that gives the cured film and a display element containing the cured film.SOLUTION: A negative coloring composition contains (A) a colorant, (B) a binder resin, (C) a radical polymerizable compound, (D) an O-acyloxime-based compound, and (E) a compound of a trisphenol structural unit having an alkoxyalkyl group.SELECTED DRAWING: None

Description

  The present invention relates to a colored composition, a colored cured film and a display element. Specifically, a colored composition used for forming a colored cured film suitable for a transmissive or reflective color liquid crystal display device, a display device such as an organic EL display device or an 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 having the colored cured film.

In order to produce a color filter using a coloring composition, a pigment-dispersed radiation-sensitive coloring composition is coated on a substrate to form a coating, and then the coating is exposed to a desired pattern shape. There is known a method of obtaining patterned pixels of each color by developing ashes (Patent Documents 1 and 2). As a method of 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). Furthermore, there is also known a method of forming patterned pixels of each color by applying and curing a pigment dispersion type coloring composition by an ink jet method (Patent Document 4).
In the above-described series of operations, in order to expose the coating film in a pattern, the coating film is usually irradiated 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. Here, ideally, in the opening of the photomask, the irradiated light passes directly, and the closed part blocks the light. However, since light is diffracted at the edge portion of the photomask, the coating film in the vicinity of the opening of the closed portion is irradiated with light (leakage light) whose intensity is weaker than the predetermined exposure amount.
For the middle area of the coating film to which the leaked light is irradiated, it is necessary to determine the same behavior as the opening area (exposure area) or the same behavior as the closed area (dark area) depending on the process configuration and product Depends on the purpose of That is, for example, when a negative-type coloring composition is taken as an example, a coloring composition having high photosensitivity, in which the intermediate region cures in the same manner as the exposed portion, may be required. There may also be a need for a colored composition that does not cure as well (i.e. is developed) and has a low mask bias (high mask size reproducibility of the formed pattern). The height of photosensitivity and the smallness of the mask bias are opposite properties, and it is usually difficult to achieve both.

The conventionally known coloring compositions are only by trial and error to know whether this is a type with high light sensitivity or a type with low mask bias, and a high light sensitivity type coloring composition while maintaining the equivalence of other characteristics. It was difficult to make separate products and low mask bias type coloring compositions.
Patent Document 5 relates to a coloring composition containing a specific phenolic compound in the coloring composition, and when the composition is used, it has an excellent pattern shape and has high adhesion to a substrate with high accuracy. It is described that it can be formed. Although this technique is an excellent technique in which improvements in adhesion and pattern shape are certainly seen, the inventors of the present invention have found that the solvent resistance of the formed colored cured film is insufficient. It became clear.
Therefore, it has been recognized in the art that there is a need for a colored composition that can form a colored cured film that is excellent in both adhesion and solvent resistance.

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

The present invention has been made to overcome the above-mentioned current situation.
Therefore, an object of the present invention is to provide a colored cured film which is excellent in both adhesion and solvent resistance, a colored composition which gives the colored cured film, and a display device having the cured film.
It is desirable that the above-mentioned coloring composition can be optionally made by selecting either the type having high photosensitivity or the type having small mask bias.

According to the invention, the above objects and advantages of the invention are, first of all:
(A) Colorant,
(B) Binder resin,
(C) radically polymerizable compound,
This 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 the formula (E0),
R ^I is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ^II is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
x is 1 or 2;
"*" Represents a bond directly bonded to an aromatic ring. ]

The above objects and advantages of the present invention are secondly:
This is achieved by a colored cured film formed using the above-mentioned coloring composition.

The above objects and advantages of the present invention are thirdly:
This is achieved by a display device provided with the above-mentioned colored cured film.

According to the present invention, there are provided a colored cured film which is excellent in both adhesion and solvent resistance, a colored composition which gives the colored cured film, and a display device comprising the cured film.
The above-mentioned coloring composition can make either a type with high photosensitivity or a type with small mask bias depending on the selection of the above-mentioned (E) compound.

<(A) Colorant>
The colorant (A) contained in the coloring composition of the present invention can be used without particular limitation. The coloring agent (A) is used by appropriately selecting and selecting the color, the material and the like according to the application of the coloring composition of the present invention.
As the colorant (A), one or more selected from pigments and dyes can be used.
When using the coloring composition of this invention for formation of each color pixel which comprises a color filter, since a pixel with high brightness | luminance, contrast, and color purity is easily obtained as (A) coloring agent, organic pigment and organic dye It is preferable to use one or more selected from the group consisting of: On the other hand, when using a coloring composition for formation of a black matrix or a black spacer, it is preferable to use an inorganic pigment as (A) coloring agent.
As pigments, organic pigments and inorganic pigments can be mentioned.

Preferred examples of the organic pigment 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. Pigments given a color index (CI) name such as CI Pigment Violet 23;
Lake pigment etc. can be mentioned. As the lake pigment, for example, a triarylmethane lake pigment obtained by lakeing a triarylmethane dye with isopolyacid, heteropolysanic acid or the like as disclosed in, for example, JP-A-2011-186043;
Examples thereof include xanthene-based lake pigments obtained by lake-forming xanthene-based dyes with isopolyacid, heteropolysanic acid and the like as disclosed in JP-A-2010-191304 and the like.
As a preferable example of an inorganic pigment, carbon black, titanium black etc. can be mentioned, for example.

The pigment may be used after being purified by, for example, a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, etc., or a combination thereof;
The surface of the particles may be modified with a resin and used;
For example, the primary particles may be used after being refined by salt milling as disclosed in JP-A-08-179111.

  The pigment may be used together with a dispersing agent, a dispersing aid and the like as required. As the dispersing agent, for example, an appropriate dispersing agent such as a cationic type, an anionic type or a nonionic type can be used, but it is preferable to use a polymer dispersing agent or a pigment derivative. Examples of the polymer dispersant include acrylic copolymers (acrylic dispersants), polyurethanes (urethane dispersants), polyester dispersants, polyethyleneimine dispersants, polyallylamine dispersants, and the like.

The above polymeric dispersants are commercially available. As a specific example,
Examples of the acrylic dispersant include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN 21116, BYK-LPN 22102 (all manufactured by BYK Corporation (BYK)), etc .;
Examples of the above urethane-based dispersants include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (all by BYK Chemie, BYK), Solsparse 76500 (Japan Lubrizol (a stock) ) Made etc);
Examples of the above-mentioned polyester-based dispersants include Adisper PB 821, Adisper PB 822, Azisper PB 880, Azisper PB 881 (all manufactured by Ajinomoto Fine Techno Co., Ltd.), etc .;
As said polyethylenimine type dispersing agent, BYK-LPN21324 (made by a BIC Chemie (BYK) company) other than Sols spars 24000 (made by Nippon Lubrisol Co., Ltd.) etc. can be mentioned, respectively.
As said pigment derivative, the sulfonic acid derivative of a pigment etc. can be mentioned, for example. Specific examples thereof include copper phthalocyanine sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and sulfonic acid derivatives of quinophthalone.

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

  As the above-mentioned dye, it is preferable to use an organic dye, for example, xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes and the like can be mentioned as preferable examples. More specifically, for example, JP-A-2010-32999, JP-A-2010-254964, JP-A-2011-138094, International Publication No. 2010/123071 brochure, JP-A-2011-116803, JPA The organic dyes disclosed in JP-A-2011-117995, JP-A-2011-133844, JP-A-2011-174987, etc. are suitable. Specifically, for example, compounds represented by the following formulas (A-2-1) to (A-2-9) can be mentioned.

Among the above, the compounds represented by (A-2-1) and (A-2-3) to (A-2-5) are xanthene dyes;
The compounds represented by each of (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 compound represented by (A-2-9) is an anthraquinone dye.

  The pigment and the dye as the (A) coloring agent in the coloring composition of the present invention may be used alone or in combination of two or more. Moreover, you may mix and use a pigment and dye.

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

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

<(B) Binder resin>
Although the (B) binder resin in the coloring composition of this invention is not specifically limited, It is preferable that it is resin which has an acidic functional group. The resin is more preferably a resin having a carboxyl group or a phenolic hydroxyl group, and still more preferably a resin having a carboxyl group.

Particularly preferably as the (B) binder resin in the present invention,
(B1) an ethylenically unsaturated monomer having one or more carboxyl groups,
(B2) a copolymer with another copolymerizable ethylenically unsaturated monomer (carboxyl group-containing polymer (1));
The polymer (carboxyl group containing polymer (2)) etc. which have a carboxyl group and a polymerizable unsaturated bond can be mentioned.

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

Examples of unsaturated monomers (b2) include N-substituted maleimide, aromatic vinyl compounds, (meth) acrylic esters, vinyl ethers, macromonomers and the like. Examples of these are
Examples of the N-position-substituted maleimide include N-phenyl maleimide, N-cyclohexyl maleimide and the like;
Examples of the above aromatic vinyl compounds include styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl 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, benzyl (meth) acrylate ) Acrylate, polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree of 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate DOO, tricyclo [5.2.1.0 ^{2, 6]} decene-8-yl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, para-cumylphenol ethylene oxide-modified (meth ) Acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyl oxetane, etc. ;
Examples of the above vinyl ethers include cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, 3- (vinyloxymethyl) -3-ethyl oxetane, the following formula

A compound etc. represented by
Examples of the above macromonomers include macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane. be able to.
These unsaturated monomers (b2) can be used alone or in combination 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. The coloring composition containing the carboxyl group-containing polymer (1) obtained by copolymerizing the 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) are disclosed in, for example, JP-A Nos. 7-140654, 8-259876, 10-31308, 10-300922, and 11- No. 174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, and the like.
As the carboxyl group-containing polymer (2), for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144. The polymers disclosed in Japanese Patent Application Publication No. 2008-181095 and the like can be used.

The (B) binder resin in the coloring composition of the present invention preferably has a polystyrene-equivalent weight average molecular weight (Mw) of 1,000 to 100,000 as measured by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent. More preferably, it is 3,000-50,000. By using such a Mw (B) binder resin, it is possible to suppress as much as possible the generation of dry foreign matter during coating, and a pattern-like cured film having a good shape has high resolution and high residue. It is preferable at the point which can be formed by a film rate, and the heat resistance of the cured film obtained, an electrical property, solvent resistance, adhesiveness, etc. are further improved.
The ratio (Mw / Mn) of Mw of the binder resin 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 (B) binder resin 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, the binder resin whose structure, Mw / Mn, etc. are appropriately controlled is manufactured by the method disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 2007/029871 etc. can do.
As the (B) binder resin in the coloring composition of the present invention, the polymers as described above 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, more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. is there. (B) The coloring composition which contains binder resin in said range is excellent in storage stability, the alkali developability of a coating film is favorable, and the solvent resistance of the cured film obtained, adhesiveness, and a chromaticity characteristic are more than it is. It is preferable in that it becomes higher.

<(C) Radically 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 oxiranyl group, an oxetanyl group, an N-alkoxymethylamino group and the like. As said 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 preferred to use.

Examples of the compound having two or more (meth) acryloyl groups in the molecule include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, and caprolactone-modified polyfunctional ( Meta) acrylates, alkylene oxide-modified polyfunctional (meth) acrylates, polyfunctional urethane (meth) acrylates obtained by reacting (meth) acrylates having hydroxyl groups with polyfunctional isocyanates, (meth) acrylates having hydroxyl groups (meth) acrylate and acids The polyfunctional (meth) acrylate etc. which have a carboxyl group obtained by making an anhydride react can be mentioned.
Examples of the aliphatic polyhydroxy compounds include bivalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol; trivalent or more 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 isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate and the like.
Examples of the above acid anhydrides include anhydrides of dibasic acids, dianhydrides of tetrabasic acids, and the like.
As the anhydride of the above dibasic acid, for example, succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride etc .;
Examples of the dianhydride of the above-mentioned tetrabasic acid include pyromellitic anhydride, biphenyltetracarboxylic acid dianhydride, benzophenonetetracarboxylic acid dianhydride and the like.

As said caprolactone modified polyfunctional (meth) acrylate, the compound etc. which are described in stage-of Unexamined-Japanese-Patent No. 11-44955 can be mentioned, for example. The above-mentioned alkylene oxide-modified polyfunctional (meth) acrylate is, for example, bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide,
Isocyanuric acid 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 compounds having a melamine structure, a benzoguanamine structure or a urea structure. The term "melamine structure" as used herein means a chemical structure having one or more triazine rings and one or more benzoguanamine structures as one or more phenyl group-substituted triazine rings as a basic skeleton, and includes melamine, benzoguanamine and their condensates. It is a concept. Specific examples of the compound 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 And N, N'-tetra (alkoxymethyl) benzoguanamine, N, N, N ', N'-tetra (alkoxymethyl) glycoluril and the like.

Among the above, the (C) radical polymerizable compound in the present invention is a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, and caprolactone modified. Multifunctional (meth) acrylate, multifunctional 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, (meth) acryl and acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, Pentaerythritol hexaacrylate;
Among the polyfunctional (meth) acrylates having a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride and a compound obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride are The colored cured product to be formed is particularly preferable in that it is high in strength and excellent in surface smoothness, and hardly causes background stain, film residue and the like on the substrate and the light shielding layer in the unexposed area.
In the coloring composition of the present invention, the (C) radically polymerizable compound 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, more preferably 20 to 700 parts by mass with respect to 100 parts by mass of the (A) colorant. Part, more preferably 50 to 500 parts by mass.
(C) The colored composition containing the radically polymerizable compound in the above range is excellent in the developability of the coating film, and problems such as ground stains and film residue occur on the substrate of the unexposed area or on the light shielding layer. And the curability of the coating film is excellent, which is preferable.

<(D) photo radical generator>
The (D) light radical generator contained in the coloring composition of the present invention is a radical of the above (C) radically polymerizable compound when irradiated with light such as visible light, ultraviolet light, salt ultraviolet light, electron beam, X and the like. It is a compound which generates a radical as an active species capable of initiating polymerization.
Examples of such (D) photoradical generators 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, diazo compounds, imidosulfonate compounds and the like can be mentioned.
In the coloring composition of the present invention, the (D) photoradical generator can be used alone or in combination of two or more.

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

Specific examples of the photoradical generator (D) are as follows.
Examples of the above thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dichloro thioxanthone, 2,4- dimethyl thioxanthone, 2,4- diethyl thioxanthone, 2,4-diisopropylthioxanthone etc .;
Examples of the above acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like;
Examples of the above-mentioned biimidazole compounds include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,2, 4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 5'-tetraphenyl-1,2'-biimidazole etc .;

Examples of the triazine compounds include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methyl) Furan-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-ethoxysty) Triazine compounds having a halomethyl group such as 4-, 4-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Etc;
Examples of the above O-acyloxime compounds 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-dioxolanyl) methoxy] Benzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) etc. can be mentioned respectively. Examples of commercially available products of O-acyloxime compounds include NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), DFI-020, DFI-091 (above, manufactured by Daitoke Mix Co., Ltd.), etc. be able to.

  When a biimidazole 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 light sensitivity can be further enhanced. Here, the "hydrogen donor" is a compound capable of donating a hydrogen atom to a radical generated from a biimidazole compound by light irradiation. Such hydrogen donors include, for example, mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; and 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) And amine hydrogen donors such as benzophenone. These hydrogen donors may be used alone or in combination of two or more, but at least one of mercaptan hydrogen donors and at least one of amine hydrogen donors may be used in combination. Is preferable in that the light sensitivity can be extremely high.

  On the other hand, as the photoradical generator (D) in the present invention, it 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 the foregoing is used, a sensitizer may be used together with these photoradical generators. Such sensitizers include, for example, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 4-dimethylamino Ethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. There can be mentioned and 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 120 parts by mass with respect to 100 parts by mass of the (C) radically polymerizable compound. 100 parts by mass. By setting the content ratio of the photoradical generator (D) in the above range, the curability of the colored composition can be further improved, which is preferable.
(D) When a biimidazole compound is used as the photoradical generator and a hydrogen donor is used together with the biimidazole compound, the content of the hydrogen donor is preferably 100 parts by mass of the biimidazole compound. Is 500 parts by mass or less, more preferably 50 to 300 mass;
(D) When a photoradical generator other than a 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 Preferably it is 300 parts by mass or less, more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the photo radical generator.

<(E) compound>
The (E) compound 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.
Examples of the alkyl group of R ^{I in} the above formula (E0) include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group and the like. Can. R ^I is preferably an alkyl group, more preferably a methyl group or an ethyl group.
R ^II can be each independently a hydrogen atom and any of the groups exemplified above as an alkyl group of R ^I , but is preferably a hydrogen atom.
Preferably, x is 1.

The compound (E) in the present invention is preferably a compound having two or more groups represented by the above formula (E0) in a molecule, and more preferably a compound having four or more groups. The number is particularly preferably 6 to 10. Two or more groups represented by the above formula (E0) may be bonded to one aromatic ring.
The (E) compound 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 preferable that it is a compound which has these groups.

[E0 in the formulas (E0-1) and (E0-2) is a group represented by the above formula (E0), respectively
Z is each independently a hydroxyl group or a monovalent organic group,
"+" Each represents a bond;
In formula (E0-1), a1 is an integer of 1 to 5 and b1 is an integer of 0 to 4, provided that a1 + b1 = 1 to 5 is satisfied; and in (E0-2), a2 is It is an integer of 1-4, b2 is an integer of 0-3, However, the relationship of a2 + b2 = 1-4 is satisfy | filled. ]

Each of a1 in the formula (E0-1) and a2 in the formula (E0-2) is independently preferably 1 or 2, 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 this 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. Z is a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkoxy alkoxy group having 2 to 6 carbon atoms, or an acyloxy group having 2 to 4 carbon atoms from the viewpoint of further enhancing the stability of the obtained coloring composition Is preferred. As specific examples of these, as an alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like;
As an alkoxy alkoxy group, for example, 1-methoxyethoxy group, 2-methoxyethoxy group, 1-ethoxyethoxy group, 2-ethoxyethoxy group, 1-butoxyethoxy group etc .; As an acyloxy group, for example, acetyloxy group etc. It can be mentioned.
It is preferable that b1 in said Formula (E0-1) and b2 in said Formula (E0-2) are 0 or 1 each independently.

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

[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 each independently represents 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 each independently represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -SO-, -SO _2- , -CR _2- (wherein R is the same as above) It is 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 from 0 to 4 and “+” is a bond Indicates that there is a)
A group represented by

C1, c2, d1 and d2 in formula (E-1) are each independently an integer of 0 to 5, provided that c1 + d1 = 0 to 5 and c2 + d2 = 0 to 5 are satisfied, and c1 and at least one of c2 is not 0;
Each of e1 to e3 and f1 to f3 in the formula (E-2) is independently an integer of 0 to 5, provided that 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 formula (E-3) are each independently an integer of 0 to 5, provided that g1 + h1 = 0 to 5, g2 + h2 = 0 to 5, g3 + h3 = 0 to 5 and g4 + h4 Satisfy the condition of 0 to 5 and at least one of g1 to g4 is not 0;
I1 to i3 and j1 to j3 in formula (E-4) are each independently an integer of 0 to 5, and i4 and j4 are each independently an integer of 0 to 4, provided that i1 + j1 = Meet the conditions of 0-5, i2 + j2 = 0-5, i3 + j3 = 0-5, and i4 + J4 = 0-4, and at least one of i1 to i4 is not 0;
K1, k2, L1 and L2 in formula (E-5) are each independently an integer of 0 to 5, and k3 and L3 are each independently an integer of 0 to 4, provided that k1 + L1 = Meet the conditions of 0-5, k2 + L2 = 0-5, and k3 + L3 = 0-4, and at least one of k1 to k3 is not 0;
m is an integer of 1 to 5; ]

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, particularly preferably It is a hydrogen atom.
As A, a single bond, a methylene group, 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 each preferably 1 or 2, and 2 Is more preferred;
i4 is preferably 0;
Each of d 1, d 2, f 1 to f 3, h 1 to h 4, j 1 to j 3 and L 1 to L 3 is preferably 0 or 1, and more preferably 1;
j4 is preferably 0.

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

[In the formula (E-5-1),
m, n, r and s are each independently an integer of 0 to 5,
p and q are each independently an integer of 0 to 4,
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 0-5, p + q is in the range of 0-4, and at least one of m, r and p is not 0. ]

The use amount of the compound (E) in the coloring composition of the present invention is preferably 0.1 to 50 parts by mass, and 1 to 45 parts by mass with respect to 100 parts by mass of the (B) binder resin. More preferably, it is preferably 3 to 40 parts by mass.
As described above, the preferred (E) compound in the present invention has both the group represented by the above formula (E0) and the group Z. Here, when a compound in which the group Z is a hydroxyl group is used as the (E) compound, a colored composition having a small mask bias can be obtained. The amount of the compound (E) used in this case 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 still more preferable. The range of 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, further preferably 100 parts by mass of the binder resin (B). Preferably it is 3-30 mass parts.
On the other hand, when a compound in which the group Z is a monovalent organic group is used as the (E) compound, a colored composition with high photosensitivity can be obtained. The amount of the compound (E) used in this case 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 100 parts by mass of the binder resin (B). The amount is preferably not more than 43 parts by mass, more preferably 40 parts by mass or less, and still more preferably 35 parts by mass or less. The range of 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, further preferably 100 parts by mass of the binder resin (B). The amount is preferably 3 to 35 parts by mass, and can be 20 to 45 parts by mass, further 25 to 43 parts by mass, and further 30 to 40 parts by mass.

<Other ingredients>
Although the coloring composition of this invention contains the said (A)-(E) component as an essential component, you may contain the other component arbitrarily in the range which does not impair the effect of this invention. Such other components include, for example, fillers such as glass and alumina;
Polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate);
Surfactants such as fluorosurfactants and silicone surfactants;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrithiol 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, etc .;

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, thiodiethylene bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate];
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones and the like;
Anticoagulant 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 Residue improving agents such as 2-amino-1,3-propanediol and 4-amino-1,2-butanediol;
Examples include developability improvers such as mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] phthalate, and ω-carboxypolycaprolactone mono (meth) acrylate. Can.

<Solvent>
The coloring composition of the present invention contains the above components (A) to (E) as essential components and optionally contains other components, but preferably further contains a solvent as a liquid composition Be prepared.
Here, as the solvent, one which disperses or dissolves the above components, does not react with these components, and has appropriate volatility, is preferably selected from solvents having such characteristics 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, 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 (Poly) alkylene glycol mono such as dimonomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. Alkyl ethers;
Alkyl lactates such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol and the like;
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 and the like;
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 acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-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, butyrate i -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;
Amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like can be mentioned.

Among these solvents, (poly) alkylene glycol monoalkyl ethers, lactic acid alkyl esters, (poly) alkylene glycol monoalkyl ethers from the viewpoint of solubility, coatability, etc., and when contained, the dispersibility of the pigment. Acetates, other ethers, ketones, diacetates, alkoxycarboxylic acid esters, other esters are preferred, in particular 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, Rohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy propionic acid Ethyl, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, butyric acid It is more preferable to use n-butyl, ethyl pyruvate and the like.
In the coloring composition of the present invention, the solvents may be used alone or in combination of two or more.

Most preferably as a solvent of the coloring composition of the present invention,
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 In the case of containing 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 components other than the solvent of the coloring composition is the total mass of the coloring composition It is preferable to set it as the quantity which will be 5-50 mass%, and it is more preferable to set it as the quantity which becomes 10-40 mass%. The coloring composition containing the solvent in the above amount is preferable in that it is excellent in the dispersibility of each component contained, and hence excellent in stability as a composition and excellent in coatability.

<Method of Preparing Colored 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 with a solvent.
For example, when the colorant (A) in the coloring composition of the present invention contains a pigment, the colorant (A) is preferably one of (B) binder resin, preferably in the presence of a dispersant. The pigment dispersion is mixed and dispersed in a solvent, for example, using a bead mill, a roll mill, etc., to obtain a pigment dispersion, and then the remainder of the binder resin (B) and (C) to (E) Can be prepared by adding and mixing components) and optionally other components.

<Method for forming colored cured film>
A colored cured film can be formed using the colored 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 for a display device and a solid-state imaging device; black matrix; black spacer and the like.
In order to form a colored cured film using the colored 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, and then at least a part of the coating is irradiated with light, then developed, and preferably further heated (post-baked) How to do it;
In the second method, the colored composition of the present invention is applied in a pattern on an ink jet system to form a coating on a substrate, and the coating is optionally irradiated with light and then preferably heated (posted) Baking).
In any of the above methods, a color filter is formed by sequentially forming a colored cured film to be a pixel of each color using a coloring composition of red, green and blue three colors or cyan, magenta and yellow three colors. 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 substrates made of glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide and the like. For these substrates, if necessary, appropriate treatments such as chemical treatment (eg, silane coupling agent) treatment, plasma treatment, ion plating treatment, sputtering treatment, treatment by a gas phase reaction method, treatment by a vacuum evaporation method, etc. It may be treated.

It is preferable that a black matrix is formed on the substrate used when the coloring composition of the present invention is used to form the pixels of the color filter so as to partition the pixel region. This black matrix can be a thin film of a metal (such as chromium) having a desired pattern, a colored cured film formed from a colored composition, and 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 colored composition can be formed by the same method as the present invention using a black colored composition. In the second method using the ink jet method, the black matrix also functions as a barrier for preventing color mixing of each color composition discharged by the ink jet method in addition to the light shielding function. Therefore, it is preferable that the black matrix in this case has a certain thickness or more, and accordingly, it is preferable that the black matrix in this case is a black cured film formed using a black coloring composition.
It is preferable that the substrate used when the coloring composition of the present invention is used to form a black matrix is a substrate on which a black matrix that defines a pixel area has not been formed yet.
Furthermore, the substrate used when the coloring composition of the present invention is used to form a black spacer is preferably a substrate on which both a black matrix and pixels are formed to define the pixel area.

In the above first method, as a method of applying the coloring composition on the substrate, for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), a bar coating method Etc. can be mentioned. Among these, spin coating or slit die coating is preferably employed.
After coating by the above method or the ink jet system, a coating can be applied preferably by heating (prebaking) the colored composition after coating to remove the solvent. The conditions for this prebaking are preferably 70 to 110 ° C., preferably about 1 to 10 minutes. The prebaking is preferably performed under reduced pressure. As a pressure reduction degree, it is preferable to set so that an ultimate pressure (absolute pressure) may be 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 solvent removal.

Examples of light sources used for irradiating the formed coating film with light include xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, lamp light source such as medium pressure mercury lamp and low pressure mercury lamp Ion laser, YAG laser, XeCl excimer laser, nitrogen laser, ultraviolet LED etc. can be mentioned. It is preferable that it is light which has a bright line in the range of 190-450 nm as light to irradiate. 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 development treatment, the unexposed part of the coating film is removed to form a pattern-like coating film. Examples of the alkaline developer include sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1 It is preferred to use an aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene. If necessary, a water-soluble organic solvent such as methanol, ethanol and the like; a surfactant etc. may be added to the aqueous solution in an appropriate range and used.
As a development method, for example, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, etc. can be applied. The development condition is preferably 5 to 300 seconds at normal temperature. The coated film after development is preferably washed with water.
The post-baking can be performed, for example, at a temperature of 180 to 280 ° C., for example, for 10 to 60 minutes.

The film thickness of the colored cured film formed as mentioned above is as follows according to the use.
Pixel: preferably 0.5 to 5 μm, more preferably 1 to 3 μm
Black matrix: preferably 0.5 to 10 μm, more preferably 0.8 to 5 μm
Black spacer: preferably 0.5 to 10 μm, more preferably 1 to 7 μm

  In the pixel element obtained by forming the pixels of each color as described above, a protective film is formed on this, and then a transparent conductive film and a spacer are formed in this order to obtain a display device. It can be used as a color filter.

<Display element>
The display element in the present invention comprises at least one colored cured film selected from the group consisting of the pixel and the color filter formed as described above, a black matrix and a black spacer. As said display element, a color liquid crystal display element, an organic electroluminescent display element, electronic paper etc. can be mentioned, for example.
The color liquid crystal display device may be a known TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Planes Switching) type, VA (Vertical Alignment) type, OCB (Optically Compensated Birefringence) type, etc. The appropriate liquid crystal mode can be applied.

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

Hereinafter, the embodiments of the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following examples.
<(B) Synthesis of binder resin>
Synthesis example B1
In a flask equipped with a condenser and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was charged and purged with nitrogen. The contents of the flask are heated to 80 ° C., and 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 at the same temperature 23 parts by mass of ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono (2-acryloyloxyethyl) succinate, and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) The mixed solution was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and polymerization was carried out for an additional hour while maintaining this temperature to obtain a solution (solid content concentration: 33 mass%) containing the binder resin (B-1). . Mw of obtained binder resin (B-1) was 12,200, and Mn was 6,500.

<Preparation of pigment dispersion>
Preparation Example P1
(A) As a coloring agent, C.I. I. Pigment green 58 and 9.1 parts by mass and C.I. I. Pigment Yellow 138, 3.9 parts by mass, BYK-LPN 21116 (manufactured by Bick Chemie, solid content concentration 40 mass%) as a dispersant, 12.5 parts by mass in a solution, and (B) the above-mentioned Synthesis Example B1 as a part of a binder resin A mixed solution consisting of 15.2 parts by mass of the solution containing the binder resin (B-1) obtained above and 59.3 parts by mass of propylene glycol methyl ether acetate as a solvent is mixed and dispersed using a bead mill for 12 hours Thus, pigment dispersion (A-1-1) was prepared.

Preparation Examples P2 to P6
In the above Preparation Example P1, pigment dispersions (A-1-2) to (A-1) were prepared in the same manner as in Preparation Example P1 except that a pigment of the type and amount listed in Table 1 was used as the colorant (A). -6) were prepared respectively.

The abbreviations of 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

<Synthesis of dye>
Synthesis example SD1
The compound (compound (A-2-1)) represented by the said Formula (A-2-1) was synthesize | combined according to the synthesis example 1 of Unexamined-Japanese-Patent No. 2013-190776.

Synthesis example SD2
The compound (compound (A-2-2)) represented by the said Formula (A-2-2) was synthesize | combined in accordance with the method as described in the coloring agent synthesis example 3 of Unexamined-Japanese-Patent No. 2012-108469.

<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 Colored Composition>
100 parts by mass of the pigment dispersion (A-1-1) obtained in Preparation Example P1 and 15 parts by mass of a solution containing the binder resin (B-1) as the binder resin (B) obtained in Synthesis Example B1 (C) 13 parts by mass of KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as a radically polymerizable compound, (D) IRGACURE 369 as a photoradical generator (Trade name, manufactured by BASF, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1) 0.7 parts by mass and Adeka Acrulus NCI-831 (trade name, O-acyloxime Compound, 0.6 parts by mass (manufactured by ADEKA Co., Ltd.), and a compound represented by the above formula (E-4-1) as the (E) compound 1.0 part by mass and 0.05 parts by mass of Megafac F-554 (trade name, manufactured by DIC Corporation) as a fluorosurfactant are mixed, and 3-methoxybutyl acetate (MBA) and propylene glycol monomethyl ether are mixed. Acetate (PGMEA) was added to prepare a colored composition (S-1) having a solvent composition including carry-over from the pigment dispersion of MBA: PGMEA = 15: 85 (parts by mass) and a solid content concentration of 17% by mass. did.
The color composition was evaluated according to the following procedure.
The evaluation results are shown in Table 5.

<Colored composition evaluation>
(1) Evaluation of Solvent Resistance The above-mentioned coloring composition (S-1) is applied on a glass substrate using a spin coater, and then prebaked for 100 seconds on a hot plate at 90 ° C. to a film thickness of 2.5 μm. A coating was formed. The coated substrate was allowed to cool to room temperature, and then the coated film was irradiated with a high pressure mercury lamp at a dose of 400 J / m ² through 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 coated substrate after the light irradiation, using a potassium aqueous solution having a temperature of 23 ° C. and a concentration of 0.04 mass% as a developer, the developing pressure is 110 kPa and the developer flow rate is 60 liters / minute. Discharge was performed for a second to perform shower development. The coated film-coated substrate after development was washed with ultrapure water and air-dried, and then post-baked for 30 minutes in a clean oven at 230 ° C. to form a pixel pattern consisting of a line and space pattern on the substrate.
The substrate on which the pixel pattern was formed as described above was immersed in N-methylpyrrolidone at 25 ° C. for 30 minutes, and the pixel pattern shape and film thickness before and after immersion were observed with a scanning electron microscope and evaluated based on the following criteria.

Evaluation criteria No chipping is observed in the pixel pattern, and the film thickness after immersion is 95% or more of the film thickness before immersion: Solvent resistance "good"
When chipping was observed in part of the pixel pattern, or the film thickness after immersion was 80% or more and less than 95% of the film thickness before immersion: Solvent resistance "defect"
When chipping is observed in part of the pixel pattern 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 property The pixel pattern which consists of a line and space pattern was formed on the glass substrate by operating similarly to said "(1) evaluation of solvent resistance".
The pixel pattern obtained above was observed using an optical microscope to check for the presence or absence of a chipped pattern edge, and evaluated according to the following criteria.

Evaluation criteria If no defects were found in the pattern: sensitivity "excellent"
If there is a slight chipping in the pattern: sensitivity "good"
If there are many missing parts in the pattern: sensitivity "bad"

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

Evaluation criteria When the subtraction value is a negative value: curing failure 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 (the mask bias property is excellent)
When the subtraction value is 10 μm or more: The mask bias property is large (poor to the mask bias property)

Here, when the photosensitivity of the coloring composition is sufficiently high, a pattern (colored cured film) excellent in curability and adhesion to a substrate is formed, so chipping and peeling are not observed in the formed pattern. .
On the other hand, when the mask bias property is small, a pattern having a size reproducing the photomask size is formed.
Therefore, if the coloring composition is excellent in any one of the photosensitivity and the mask bias property, it can be suitably used after selecting the process design to be employed, the use of the liquid crystal display element, and the like.

Examples 2 to 4, 8 to 10 and 12 to 15
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) in Example 1 were as described 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 pigment and 4.2 parts by mass of binder resin (B-1)) and the dye obtained in Preparation Example SD1 Solution (A-2-1) 20 parts by mass (containing 2 parts by mass of dye), 31 parts by mass of solution containing binder resin (B-1) as binder resin (B) obtained in Synthesis Example B1 (binder (C) equivalent to 10.2 parts by mass in terms of resin (B-1)), (C) KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate and dipentaerythritol as a radically polymerizable compound) 19 parts by mass of a mixture of pentaacrylates, (D) IRGACURE 369 (trade name, manufactured by BASF, 2-benzyl-2-dimethylamino-1- (4-mol) as a photoradical generator (E) Orinophenyl) butanone-1) 1.0 parts by mass and 0.9 parts by mass of Adeka Acrulus NCI-831 (trade name, O-acyloxime compound, manufactured by ADEKA) as the (E) compound 1.5 parts by mass of a compound represented by the formula (4) -1), and 0.05 parts by mass of Megafac F-554 (trade name, manufactured by DIC Corporation) as a fluorosurfactant, and then MBA, PGMEA And propylene glycol monomethyl ether (PGME), and the solvent composition including carry-over from the pigment dispersion is MBA: PGMEA: PGME = 15: 75: 10 (parts by mass), and the coloring composition has a solid content concentration of 17% by mass Prepared.
Various evaluations were performed in the same manner as in Example 1 using this coloring composition.
The evaluation results are shown in Table 5.

Example 6
A colored composition was prepared in the same manner as in Example 5 except that the type and amount of the component (A) were as described in Table 2 in Example 5 above, 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), (B) Binder resin (B-1) as a binder resin obtained in the above Synthesis Example B1 62 parts by mass of solution (equivalent to 20.5 parts by mass converted to binder resin (B-1)), (C) KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd.), as a radically polymerizable compound 27 parts by mass of a 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 2.5 parts by mass of Linophenyl) butanone-1) and Adeka Acrulus NCI-831 (trade name, O-acyloxime compound, 2. 2 parts by mass of ADEKA), 2.0 parts by mass of the compound represented by the above-mentioned formula (E-4-1) as the compound (E), and Megafac F-554 (trade name) as the fluorochemical surfactant A mixed solution of 0.05 parts by mass of DIC Corporation and MBA, PGMEA and PGME is added, and the solvent composition including the carry-in from the pigment dispersion is MBA: PGMEA: PGME = 15: 40: 45 (mass) Part), the coloring matter composition whose solid content concentration is 17 mass% was prepared.
Various evaluations were performed in the same manner as in Example 1 using this coloring composition.
The evaluation results are shown in Table 5.

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

Examples 16, 17 and 20 to 24 and Comparative Examples 1 and 4
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) in Example 1 were as described 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
A colored 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 described in Table 3 in Example 5 above, and various evaluations were performed.
The evaluation results are shown in Table 6.

Example 19 and Comparative Examples 3 and 6
A colored 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 described in Table 3 in Example 7 above, 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
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) in Example 1 were as described 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
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 described in Table 4 in Example 5 above, and various evaluations were performed.
The evaluation results are shown in Table 7.

Examples 28, 29 and Comparative Example 9
A colored 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 described in Table 4 in Example 7 above, and various evaluations were performed.
The evaluation results are shown in Table 7.

The abbreviation of each component in the above Tables 2 to 4 has the following meanings.
[(C) radically 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 ARKRUZ NCI-831 (trade name, O-acyloxime compound, manufactured by ADEKA Co., Ltd.)
[(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: above formula (E) -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: Above formula (E) Compound E-4-5: Compound Represented by Formula (E-4-5) E-5-1: Compound Represented by Formula (E-5-1) [Other compounds]
R-1: a compound represented by the following formula (R-1)

  Although the compounds represented by the above-mentioned formula (R-1) used in Comparative Examples 1 to 3 do not correspond to the compounds (E) defined in the present invention, in Table 3, they are described in the column of the compounds (E) for convenience. .

Claims (7)

(A) Colorant,
(B) Binder resin,
(C) radically polymerizable compound,
(D) An O-acyloxime compound and (E) a negative coloring composition comprising a compound represented by the following formula (E-4)

[In the formula (E-4),
E0 each independently represents the following formula (E0);
*-(CR ^II ₂ ) _x -O-R ^I (E0)
(In the formula (E0),
R ^I is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ^II is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
x is 1 or 2;
"*" Represents a bond directly bonded to an aromatic ring. )
Is a group represented by
Z is each independently a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkoxy group having 2 to 8 carbon atoms, or an acyloxy group having 2 to 6 carbon atoms,
Each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
i1 to i3 and j1 to j3 are each independently an integer of 0 to 5, and
i4 and j4 are each independently an integer of 0 to 4, provided that i1 + j1 = 0-5, i2 + j2 = 0-5, i3 + j3 = 0-5, and i4 + J4 = 0-4, and i1 At least one of i4 is not zero.
However, at least one of a plurality of Z is a hydroxyl group. ]   The negative type coloring composition according to claim 1, wherein a content ratio of the compound represented by the (E) formula (E-4) is 0.1 to 50 parts by mass with respect to 100 parts by mass of the (B) binder resin. object.   The negative type coloring composition of Claim 1 or 2 whose content rate of the said (A) coloring agent is 15-45 mass% on the basis of the sum total of solid content of a coloring composition.   The negative type coloring composition as described in any one of Claims 1-3 whose said (A) coloring agent contains a dye.   A colored cured film formed using the negative-type coloring composition according to any one of claims 1 to 4.   The colored cured film according to claim 5, which is a pixel, a black matrix or a black spacer.   A display element comprising the colored cured film according to claim 5 or 6.