KR102288373B1 - Coloring composition, colored cured film and display device - Google Patents

Abstract

The subject of this invention is providing the coloring composition suitable for formation of the colored cured film with high brightness|luminance and contrast, and favorable chromaticity characteristic even if it is a thin film.
The solution of the present invention is a coloring composition comprising (A) a colorant, (B) a binder resin, and (C) a polymerizable compound, wherein (A) the colorant is a halogenated zinc phthalocyanine pigment, a quinophthalone pigment, and azomethine copper comprises a pigment, and the content of the quinone Smirnoff etalon pigment w ₂ and azomethine pigment content of copper of ₃ w ratio _{w 2 / w 3 = 70/} 30 to 85/15 in a mass ratio of the coloring composition.

Description

A coloring composition, a colored cured film, and a display element TECHNICAL FIELD

The present invention relates to a colored composition, a colored cured film, and a display element, and more particularly, it is used in the formation of a colored cured film used for a transmissive or reflective color liquid crystal display element, a solid-state image sensor, an organic EL display element, an electronic paper, etc. It is related with the display element provided with the coloring composition used as becomes, the colored cured film formed using the said coloring composition, and the said colored cured film.

In manufacturing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape (hereinafter "exposure"). ) and developing, a method (for example, refer to Patent Documents 1 and 2) for obtaining pixels of each color is known. Moreover, the method of forming a black matrix using the photopolymerizable composition which disperse|distributed carbon black (for example, refer patent document 3) is also known. Moreover, the method (for example, refer patent document 4) which obtains the pixel of each color by an inkjet system using the pigment dispersion type colored resin composition is also known.

In recent years, socially, the request|requirement for energy saving has become strong, for example, the display element which made high-quality display performance and electric power saving compatible is calculated|required. In order to meet this demand, attempts have been made to increase the brightness and contrast of a color filter while suppressing the brightness of the backlight and reducing power consumption.

As a colorant used in a color filter, a pigment is used in many cases from a viewpoint of heat resistance and solvent resistance. In the case of a coloring composition for forming a green pixel, it is known to use a combination of a halogenated zinc phthalocyanine pigment and various yellow pigments. For example, in Patent Documents 5 to 6, a halogenated zinc phthalocyanine pigment and a quinophthalone pigment are used in combination. is disclosed. Moreover, in patent document 7, using a zinc bromide phthalocyanine pigment, pigment Y (C.I. Pigment Yellow 150), and C.I. Pigment Yellow 138 is disclosed in combination.

Japanese Unexamined Patent Publication (Kokai) No. 2-144502 Japanese Patent Laid-Open No. 3-53201 (Hei) Japanese Patent Laid-Open No. 6-35188 Japanese Patent Laid-Open No. 2000-310706 Japanese Patent Laid-Open No. 2012-098712 Japanese Patent Laid-Open No. 2013-011867 Japanese Patent Laid-Open No. 2013-037276

However, in the case of the coloring composition of patent documents 5-7, in order to improve chromaticity characteristics, such as a brightness|luminance and contrast, it became clear that the film thickness of a colored cured film cannot but thicken. Since a display element will also become thick when the film thickness of a colored cured film is thick, when advancing thickness reduction and weight reduction of a display element, it becomes an obstacle easily. Therefore, even if it is a thin film, it is the present situation that the development of the coloring composition suitable for formation of a colored cured film with high brightness|luminance and contrast and a favorable chromaticity characteristic is strongly calculated|required.

Therefore, even if it is a thin film, the subject of this invention is providing the coloring composition suitable for formation of a colored cured film with high brightness|luminance and contrast and favorable chromaticity characteristic. Moreover, the subject of this invention is providing the display element provided with the colored cured film formed using the said coloring composition, and the said colored cured film.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject was solvable by using a specific coloring agent in fixed quantity ratio, as a result of earnestly examining.

That is, the present invention is a coloring composition comprising (A) a colorant, (B) a binder resin, and (C) a polymerizable compound, wherein (A) the colorant contains a halogenated zinc phthalocyanine pigment, a quinophthalone pigment, and an azomethine copper pigment. _{And ratio of content w 2} of a quinophthalone pigment and content w _{3 of an azomethine copper pigment is w 2} /w ₃ =70/30 - 85/15 by mass ratio, The coloring composition characterized by the above-mentioned is provided.

In addition, the present invention includes a halogenated zinc phthalocyanine pigment, a quinophthalone pigment, and an azomethine copper pigment, and the ratio _{of the content w 2} of the quinophthalone pigment to the content w _{3 of the azomethine copper pigment is w 2} /w ₃ = It is providing the colored cured film which is 70/30-85/15, and the display element provided with the said colored cured film. The "colored cured film" here means the green pixel etc. used for a display element and a solid-state image sensor.

If the coloring composition of this invention is used, even if it is a thin film, a colored cured film with high brightness|luminance and contrast can be formed. Moreover, the colored cured film excellent in heat resistance and solvent resistance can also be formed by using the coloring composition of this invention.

Therefore, the coloring composition of this invention can be used suitably for manufacture of solid-state image sensors, such as display elements, such as a color liquid crystal display element, an organic electroluminescent display element, electronic paper, and a CMOS image sensor.

Hereinafter, the present invention will be described in detail.

coloring composition

Hereinafter, the structural component of the coloring composition of this invention is demonstrated in detail.

-(A) Colorant-

The coloring composition of this invention contains a halogenated zinc phthalocyanine pigment, a quinophthalone pigment, and an azomethine copper pigment as (A) coloring agent, The ratio _{of content w 2 of a quinophthalone pigment and content w 3} of an azomethine copper pigment is mass ratio w ₂ /w ₃ =70/30 to 85/15.

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

(In the formula (1), X independently represents a hydrogen atom, a chlorine atom, or a bromine atom, and 10 to 15 of all Xs are bromine atoms, and 1 to 6 are chlorine atoms)

Although it does not specifically limit as a quinophthalone type yellow pigment, C.I. Pigment Yellow 138 is preferable.

Examples of the azomethine copper pigment include C.I. Pigment Yellow 117 and C.I. Pigment Yellow 129, and among these, C.I. Pigment Yellow 129 is preferable.

In this invention, although ratio of content w ₂ of a quinophthalone pigment and content w _{3 of azomethine copper pigment requires that it be w 2} /w ₃ =70/30 - 85/15 in mass ratio _{, this ratio is w 2} / It is more preferable that w ₃ =70/30 - 80/20, and it is still more preferable that it is 70/30 - 75/25. By setting it as such a form, even if it is a thin film, a luminance and contrast are high, and the colored cured film excellent also in heat resistance and solvent resistance can be formed.

_{The content w 1} of the halogenated zinc phthalocyanine pigment and the content w ₃ of the azomethine copper pigment content mass ratio (w ₁ /w _{3 ) can be appropriately selected, but w 1} /w ₃ =65 from the viewpoint of further improvement in luminance and contrast. It is preferable that it is /35-90/10, It is more preferable that it is 70/30-90/10, It is still more preferable that it is 75/25-88/12, It is especially preferable that it is 80/20-86/14.

The coloring composition of this invention is normally used for formation of a green pixel. In this case, other colorants may be mixed together with the halogenated zinc phthalocyanine pigment, the quinophthalone pigment and the azomethine copper pigment. It does not specifically limit as another coloring agent, According to a use, a color and a material can be selected suitably.

Pigments and dyes are mentioned as other colorants, and other colorants can be used individually or in combination of 2 or more types. Among them, from the viewpoint of obtaining a pixel having high brightness, contrast, and coloring power, an organic pigment is preferable as a pigment, and an organic dye is preferable as a dye.

As an organic pigment, the compound classified as a pigment in the color index (C.I.; issued by The Society of Dyers and Colorists), ie, the thing to which the following color index (C.I) number is given, is mentioned, for example.

Red pigments, such as C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 264;

green pigments such as C.I. Pigment Green 7 and C.I. Pigment Green 36;

blue pigments such as C.I. Pigment Blue 15:6, C.I. Pigment Blue 16, and C.I. Pigment Blue 80;

Yellows, such as CI Pigment Yellow 83, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Yellow 215 pigment;

orange pigments such as C.I. Pigment Orange 38;

Purple pigments such as C.I. Pigment Violet 23.

In addition, Japanese Patent Laid-Open No. 2001-081348, Japanese Patent Application Laid-Open No. 2010-026334, Japanese Patent Application Laid-Open No. 2010-191304, Japanese Patent Application Laid-Open No. 2010-237384, and Japanese Patent Application Laid-Open No. 2010-237569 The lake pigment of Unexamined-Japanese-Patent No. 2011-006602, Unexamined-Japanese-Patent No. 2011-145346, etc. are mentioned.

Moreover, as said dye, a xanthene type dye, a triarylmethane type dye, a cyanine type dye, anthraquinone type dye, an azo type dye, etc. are preferable. More specifically, Japanese Patent Laid-Open No. 2010-32999, Japanese Patent Application Laid-Open No. 2010-254964, Japanese Patent Application Laid-Open No. 2011-138094, International Publication No. 10/123071, Japanese Patent Laid-Open No. 2011- The organic dye of Unexamined-Japanese-Patent No. 116803, 2011-117995, Unexamined-Japanese-Patent No. 2011-133844, Unexamined-Japanese-Patent No. 2011-174987, etc. are mentioned.

In the present invention, the pigment and the dye may be used alone or in combination of two or more.

Among these, as another colorant, green colorants other than halogenated zinc phthalocyanine pigments, yellow colorants other than quinophthalone pigments and azomethine copper pigments are preferable.

In the present invention, halogenated zinc phthalocyanine pigments, quinophthalone pigments, azomethine copper pigments and other pigments optionally mixed are purified by recrystallization method, reprecipitation method, solvent washing method, sublimation method, vacuum heating method, or a combination thereof. may be In addition, these pigments may be used by modifying the particle surface thereof with a resin if necessary. As resin which modifies the particle|grain surface of a pigment, the vehicle resin of Unexamined-Japanese-Patent No. 2001-108817, or commercially available resin for various pigment dispersions is mentioned, for example. In addition, the organic pigment may be used by refining the primary particles by so-called salt milling. As a method of salt milling, the method disclosed by Unexamined-Japanese-Patent No. Hei 08-179111 is employable, for example.

Moreover, in this invention, a well-known dispersing agent and a dispersing auxiliary agent can also be contained with a halogenated zinc phthalocyanine pigment, a quinophthalone pigment, an azomethine copper pigment, and other colorants to be mixed arbitrarily.

As a well-known dispersing agent, For example, a urethane type dispersing agent, a polyethyleneimine type dispersing agent, a polyoxyethylene alkyl ether type dispersing agent, a polyoxyethylene alkylphenyl ether type dispersing agent, a polyethylene glycol diester type dispersing agent, a sorbitan fatty acid ester type dispersing agent, a polyester type. A dispersant, an acrylic dispersing agent, etc. are mentioned, As a commercial item, For example, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, Big Chemie (BYK) company), etc. (Met) ) Acrylic dispersant, Dispervic-161, Dispervic-162, Dispervic-165, Dispervic-167, Dispervic-170, Dispervic-182 (above, manufactured by BYK), Solsperse 76500 (Lubry) Urethane-based dispersants such as Sol Co., Ltd.), Polyethylenimine-based dispersants such as Solsperse 24000 (Lubrizol Co., Ltd.), Azisper PB821, Azisper PB822, Azisper PB880, Azisper PB881 (above, Ajinomo) Moreover, in addition to polyester-type dispersing agents, such as Fine Techno Co., Ltd. make), dispersing agents, such as BYK-LPN21324 (made by BYK), can be used.

Especially, as a dispersing agent, at least 1 sort(s) selected from the group which consists of a (meth)acrylic-type dispersing agent, a urethane-type dispersing agent, and a polyester-type dispersing agent is preferable, and a (meth)acrylic-type dispersing agent is more preferable.

Among the (meth)acrylic dispersing agents, a (meth)acrylic dispersing agent having a crosslinkable functional group is preferable. Examples of the crosslinkable functional group include an oxygen-containing saturated heterocyclic group such as an oxiranyl group, an oxetanyl group, a tetrahydrofuranyl group and a tetrahydropyranyl group, an ethylenically unsaturated group, an epithio group, and a (dithio)carbonate group. and the like. Among these crosslinkable functional groups, an oxygen-containing saturated heterocyclic group is preferable, an oxetanyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group are more preferable, and an oxetanyl group and a tetrahydrofuranyl group are still more preferable.

The (meth)acrylic dispersing agent having a crosslinkable functional group means a compound containing a (co)polymer of a (meth)acrylic monomer having a crosslinkable functional group. In addition, "(meth)acrylic monomer" means a polymeric compound which has a (meth)acryloyl group in a molecule|numerator, and "(meth)acryloyl group" shall mean an acryloyl group or a methacryloyl group .

As a (meth)acrylic-type dispersing agent which has a crosslinkable functional group, the copolymer of the (meth)acrylic-type monomer which has a crosslinkable functional group, and another copolymerizable (meth)acrylic-type monomer is mentioned, for example. As another copolymerizable (meth)acrylic monomer, for example, (meth)acrylate having an oxyalkylene group, (meth)acrylate having a hydroxyl group, (meth)acrylate having a 1-3 amino group, (meth) Acrylic acid alkylester, (meth)acrylic acid aryl ester, etc. are mentioned, These can have 1 type, or 2 or more types.

It is preferable that it is 5-50 mass % in all the monomers, and, as for the ratio of the (meth)acrylic-type monomer which has a crosslinkable functional group, it is more preferable that it is 10-30 mass %. Moreover, the (meth)acrylic-type dispersing agent which has a crosslinkable functional group can be synthesize|combined by the method of Unexamined-Japanese-Patent No. 2012-118505, for example.

With this aspect, the desired effect of the present invention can be further obtained.

In this invention, 5-300 mass parts is preferable with respect to 100 mass parts of (A) coloring agents, as for content of (B) dispersing agent, 10-200 mass parts is more preferable, 20-100 mass parts is still more preferable. By setting it as such a form, it becomes easy to acquire the desired effect of this application.

Moreover, a pigment derivative etc. are mentioned as a dispersing auxiliary agent. Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

(A) The content rate of a coloring agent is 5-70 mass %, Preferably it is 5-60 mass %, More preferably, it is 10-50 mass in solid content of a coloring composition at the point which forms the pixel which is high in a brightness|luminance and is excellent in coloring power. %, particularly preferably 20 to 50 mass%. Here, solid content is components other than the solvent mentioned later.

Moreover, when another coloring agent is included, 50 mass % or less is preferable with respect to the total content of a coloring agent, and, as for the content rate of another coloring agent, 30 mass parts or less are more preferable. A lower limit is not specifically limited, What is necessary is just 0.01 mass % or more.

-(B) binder resin-

Although it does not specifically limit as (B) binder resin in this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as a "carboxyl group-containing polymer") is preferable, for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as "unsaturated monomer (b1)") and different and copolymers of copolymerizable ethylenically unsaturated monomers (hereinafter also referred to as "unsaturated monomers (b2)").

Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, monosuccinic acid [2-(meth)acryloyloxyethyl], ω-carboxypolycaprolactone mono(meth)acrylate , p-vinyl benzoic acid, and the like.

These unsaturated monomers (b1) can be used individually or in mixture of 2 or more types.

In addition, as said unsaturated monomer (b2), for example,

N-position substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, and acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate , Polyethylene glycol (degree of polymerization 2 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, poly Propylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) Acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of paracumyl phenol, glycidyl ( Meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyl (meth)acrylic acid esters such as oxetane;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^{2, 6} ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane vinyl ethers such as;

and macromonomers having a mono(meth)acryloyl group at the terminal of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane.

These unsaturated monomers (b2) can be used individually or in mixture of 2 or more types.

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

As a specific example of the copolymer of an unsaturated monomer (b1) and an unsaturated monomer (b2), For example, Unexamined-Japanese-Patent No. 7-140654, Unexamined-Japanese-Patent No. 8-259876, and Unexamined-Japanese-Patent No. Hei (Hei), for example. )10-31308, Japanese Patent Laid-Open (Hei)10-300922, Japanese Patent Laid-Open (Hei)11-174224, Japanese Patent Laid-Open (Hei)11-258415, Japanese Patent Laid-Open No. 2000-56118 and copolymers disclosed in Japanese Patent Application Laid-Open No. 2004-101728 and the like.

Further, in the present invention, for example, Japanese Patent Laid-Open No. Hei 5-19467, Japanese Patent Laid-Open No. Hei 6-230212, Japanese Unexamined Patent Application Laid-Open No. Hei 7-207211, and Japanese Patent Laid-Open (Kokai) ( As disclosed in Japanese Patent Application Laid-Open No. Hei 9-325494, Japanese Patent Application Laid-Open No. Hei 11-140144, and Japanese Patent Application Laid-Open No. 2008-181095, a polymerizable unsaturated bond such as a (meth)acryloyl group in the side chain A carboxyl group-containing polymer having

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

Moreover, ratio (Mw/Mn) of the weight average molecular weight (Mw) of binder resin in this invention and number average molecular weight (Mn) becomes like this. Preferably it is 1.0-5.0, More preferably, it is 1.0-3.0. In addition, Mn here means the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran).

Although the binder resin in this invention can be manufactured by a well-known method, For example, Unexamined-Japanese-Patent No. 2003-222717, Unexamined-Japanese-Patent No. 2006-259680, International Unexamined-Japanese-Patent No. 07/029871, etc. By the disclosed method, the structure and Mw and Mw/Mn can also be controlled.

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

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

-(C) polymerizable compound-

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

Specific examples of the compound having two or more (meth)acryloyl groups include polyfunctional (meth)acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylate, Polyfunctional urethane (meth)acrylate obtained by reacting alkylene oxide-modified polyfunctional (meth)acrylate, (meth)acrylate having a hydroxyl group and polyfunctional isocyanate, (meth)acrylate having a hydroxyl group and an acid anhydride The polyfunctional (meth)acrylate etc. which have a carboxyl group obtained by making it react are mentioned.

Here, as an aliphatic polyhydroxy compound, For example, a bivalent aliphatic polyhydroxy compound like ethylene glycol, propylene glycol, polyethyleneglycol, and polypropylene glycol; and trivalent or higher aliphatic polyhydroxy compounds such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol. As (meth)acrylate which has the said hydroxyl group, 2-hydroxyethyl (meth)acrylate, trimethylol propane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta (meth)acrylate, glycerol dimethacrylate, etc. are mentioned. As said polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate etc. are mentioned, for example. Examples of the acid anhydride include an anhydride of a dibasic acid such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, pyromellitic anhydride, and biphenyltetracarboxylic acid 2 and tetrabasic acid dianhydride such as anhydride and benzophenonetetracarboxylic dianhydride.

Further, examples of the caprolactone-modified polyfunctional (meth)acrylate include compounds described in paragraphs [0015] to [0018] of Japanese Patent Application Laid-Open No. 11-44955. The alkylene oxide-modified polyfunctional (meth)acrylate is selected from bisphenol A di(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Trimethylolpropane tri(meth)acrylate modified with at least one selected from isocyanuric acid tri(meth)acrylate, ethylene oxide, and propylene oxide modified by at least one Pentaerythritol tri (meth) acrylate modified with at least one selected from 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, dipentaerythritol hexa modified with at least one selected from ethylene oxide and propylene oxide (meth)acrylate etc. are mentioned.

Moreover, as a compound which has two or more N-alkoxy methylamino groups, the compound etc. which have a melamine structure, a benzoguanamine structure, and a urea structure are mentioned, for example. In addition, a melamine structure and a benzoguanamine structure mean the chemical structure which has one or more triazine ring or a phenyl-substituted triazine ring as basic skeleton, It is a concept including melamine, benzoguanamine, or those condensates. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, N,N,N',N'-tetra( Alkoxymethyl) benzoguanamine, N,N,N',N'- tetra(alkoxymethyl) glycoluril, etc. are mentioned.

Among these polymerizable compounds, polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylate, and polyfunctional urethane (meth)acryl rate, polyfunctional (meth)acrylate having a carboxyl group, N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, N,N,N',N'-tetra(alkoxymethyl ) benzoguanamine is preferred. Among the polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, Among polyfunctional (meth)acrylates in which pentaerythritol hexaacrylate has a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, dipentaerythritol pentaacrylate obtained by reacting with succinic anhydride The compound is particularly preferable from the viewpoints of high strength of the colored layer, excellent surface smoothness of the colored layer, and difficulty in generating background contamination, film residue, and the like on the substrate and light-shielding layer of the unexposed portion.

In this invention, (C) polymeric compound can be used individually or in mixture of 2 or more types.

10-1,000 mass parts is preferable with respect to 100 mass parts of (A) coloring agents, and, as for content of the (C) polymeric compound in this invention, 20-700 mass parts is further, 80-500 mass parts is more preferable. By setting it as such a form, curability and alkali developability are further improved, and generation|occurrence|production of a background contamination, a film|membrane residue, etc. on the board|substrate of an unexposed part or a light shielding layer can be suppressed to a high level.

-(D) Photoinitiator-

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

Examples of the photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an O-acyloxime compound, an onium salt compound, a benzoin compound, a benzophenone compound, an α-diketone compound, A polynuclear quinone compound, a diazo compound, an imide sulfonate compound, etc. are mentioned.

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more. As a photoinitiator, at least 1 sort(s) selected from the group of a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, and an O- acyl oxime compound is preferable.

Among the preferable photoinitiators in the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and 4-isopropylthiok. Santhone, 2,4-dichlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, etc. are mentioned.

Further, specific examples of the acetophenone compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc. are mentioned.

Moreover, as a specific example of the said biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2' -bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl) -4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc. are mentioned.

Moreover, when using a biimidazole compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The "hydrogen donor" here means a compound which can donate a hydrogen atom with respect to the radical which generate|occur|produced from the biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzooxazole, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(di and amine hydrogen donors such as ethylamino)benzophenone. In the present invention, the hydrogen donor may be used alone or in combination of two or more, but using a combination of one or more mercaptan hydrogen donors and one or more amine hydrogen donors can further improve the sensitivity preferred in

Further, specific examples of the triazine compound include 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2- [2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4 ,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine , 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis (trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)- and triazine compounds having a halomethyl group such as 4,6-bis(trichloromethyl)-s-triazine.

Specific examples of the O-acyloxime compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), ethanone, 1-[9-ethyl- 6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), ethanone,1-[9-ethyl-6-(2-methyl-4-tetrahydro) furanylmethoxybenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), ethanone,1-[9-ethyl-6-{2-methyl-4-(2,2-) Dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-,1-(O-acetyloxime), etc. are mentioned. As a commercial item of an O-acyl oxime compound, NCI-831, NCI-930 (above, ADEKA Corporation make), DFI-020, DFI-091 (above, Daitokemix Corporation make) etc. can also be used.

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

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

-(E) solvent-

Although the coloring composition of this invention contains the said (A)-(C) component and other components added arbitrarily, it mixes a solvent normally, and is manufactured as a liquid composition.

(E) As the solvent, components (A) to (C) and other components constituting the coloring composition are dispersed or dissolved, and they do not react with these components and can be appropriately selected and used as long as they have moderate volatility. .

Among these solvents, for example

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene Glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monomethyl ether (poly)alkylene glycol monoalkyl ethers such as propylene glycol monoethyl 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, and 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 (poly)alkylene glycol monoalkyl ether acetates such as acetate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate;

other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Alkoxycarboxyl such as 3-methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate acid esters;

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-propyl butyrate , other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate;

aromatic hydrocarbons such as toluene and xylene;

and amides or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

Among these solvents, (poly) alkylene glycol monoalkyl ethers, lactic acid alkyl esters, (poly) alkylene glycol monoalkyl ether acetates, other ethers, ketones, from the viewpoint of solubility, pigment dispersibility, applicability, etc. , diacetates, alkoxycarboxylic acid esters, and other esters are preferable, and in particular, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl are preferred. 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, 3-methoxyethyl propionate, 3-ethoxy methyl propionate, 3-ethoxypropionate ethyl, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, acetic acid i -Butyl, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate, etc. are preferable.

In the present invention, the solvent may be used alone or in combination of two or more.

(E) Although content of a solvent is not specifically limited, The quantity used as 5-50 mass % of the total density|concentration of each component except the solvent of a coloring composition is preferable, and the quantity used as 10-40 mass % is more preferable. By setting it as such a form, a coloring agent dispersion liquid with favorable dispersibility and stability, and a coloring composition with favorable applicability|paintability and stability can be obtained.

-additive-

The coloring composition of this invention may contain various additives as needed.

As an additive, For example, fillers, such as glass and alumina; high molecular compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and silicone-based surfactants; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl) -3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclo hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. adhesion promoter; 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, pentaerythritoltetrakis[3-(3,5-di-t-butyl-4) -Hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl] -2,4,8,10-tetraoxa-spiro[5·5]undecane, thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], etc. antioxidants; UV absorbers such as 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenones; Aggregation inhibitors, 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-propane residue improving agents such as diol, 2-amino-1,3-propanediol, and 4-amino-1,2-butanediol; Developability improving agents, such as succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], and omega -carboxy polycaprolactone mono(meth)acrylate, etc. are mentioned can

The coloring composition of this invention can be manufactured by a suitable method, As its manufacturing method, for example, (A)-(C) component can be manufactured by mixing with the (E) solvent or other component added arbitrarily. . Among them, the pigment is mixed and dispersed in the solvent (E) in the presence of a dispersing agent, optionally together with a part of the component (B), using, for example, a bead mill, a roll mill, etc. while pulverizing to obtain a pigment dispersion. Then, the method of manufacturing by adding (B)-(C) component, and the solvent and other components further added as needed to this pigment dispersion liquid, and mixing is preferable.

coloring cured film and a method for preparing the same

The colored cured film of this invention is formed using the coloring composition of this invention, and there exists a green pixel used for a color filter, for example.

Hereinafter, the colored cured film used for a color filter and its formation method are demonstrated.

As a method of forming the colored cured film which comprises a color filter, the following method is mentioned first. First, on the surface of the substrate, a light blocking layer (black matrix) is formed so as to partition a portion where pixels are to be formed, if necessary. Then, on this board|substrate, after apply|coating the liquid composition of the radiation-sensitive coloring composition of this invention of green, for example, prebaking is performed, a solvent is evaporated, and a coating film is formed. Then, after exposing this coating film through a photomask, it develops using an alkali developing solution, and melt|dissolves and removes the unexposed part of a coating film. Thereafter, by post-baking, a pixel array in which a green pixel pattern (colored cured film) is arranged in a predetermined arrangement is formed.

Then, using each of the red or blue radiation-sensitive coloring compositions, in the same manner as above, each radiation-sensitive coloring composition is applied, prebaked, exposed, developed, and post-baked, and a red pixel array and a blue pixel are applied. Arrays are sequentially formed on the same substrate. Thereby, the color filter in which the three primary color pixel array of red, green, and blue is arrange|positioned on the board|substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

In addition, the black matrix can be formed by forming a metal thin film such as chromium formed into a film by sputtering or vapor deposition into a desired pattern using a photolithography method. Using a radiation-sensitive coloring composition in which a black pigment is dispersed, the pixel It can also be formed in the same manner as in the case of formation of .

As a board|substrate used when forming a colored cured film, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, a polyimide, etc. are mentioned, for example.

In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction method, vacuum deposition, or the like, if necessary.

When the radiation-sensitive coloring composition is applied to a substrate, an appropriate application method such as a spray method, roll coating method, spin coating method (spin coating method), slit die coating method (slit coating method), bar coating method, etc. can be adopted. In particular, it is preferable to employ a spin coating method or a slit die coating method.

Prebaking is usually performed by combining drying under reduced pressure and drying by heating. Drying under reduced pressure is usually performed until it reaches 50 to 200 Pa. In addition, the conditions of heat-drying are about 1 to 10 minutes at 70-110 degreeC normally.

Application thickness is 0.6-8 micrometers normally as a film thickness after drying, Preferably it is 1.2-5 micrometers.

As a light source of the radiation used when forming at least 1 sort(s) selected from a pixel and a black matrix, For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury-vapor lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, etc. and laser light sources such as lamp light sources, argon ion lasers, YAG lasers, XeCl excimer lasers, and nitrogen lasers. As the exposure light source, an ultraviolet LED may be used. The wavelength is preferably radiation in the range of 190 to 450 nm.

The exposure amount of radiation is generally preferably 10 to 10,000 J/m 2 .

Moreover, as said alkaline developing solution, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1 Aqueous solutions, such as ,5-diazabicyclo-[4.3.0]-5-nonene, are preferable.

An appropriate amount of water-soluble organic solvents, surfactants, etc., such as methanol and ethanol, can also be added to alkaline developing solution, for example. In addition, after alkali development, it washes with water normally.

As a developing treatment method, a shower developing method, a spray developing method, a dipping (immersion) developing method, a puddle (liquid pooling) developing method, etc. are applicable. The developing conditions are preferably 5 to 300 seconds at room temperature.

The conditions of post-baking are about 10 to 60 minutes at 180-280 degreeC normally.

The film thickness of the pixel formed in this way is 0.5-5 micrometers normally, Preferably it is 1.0-3 micrometers.

Moreover, as a 2nd method of forming the colored cured film which comprises a color filter, the pixel of each color by the inkjet method disclosed by Unexamined-Japanese-Patent No. 7-318723, Unexamined-Japanese-Patent No. 2000-310706, etc. A method to obtain can be employed. In this method, first, a barrier rib also serving as a light-shielding function is formed on the surface of the substrate. Then, in the partition formed, after discharging the liquid composition of the thermosetting coloring composition of this invention green, for example with an inkjet apparatus, prebaking is performed and a solvent is evaporated. Then, after exposing this coating film as needed, it hardens|cures by post-baking, and a green pixel pattern is formed.

Then, using each red or blue thermosetting coloring composition, it carries out similarly to the above, and a red pixel pattern and a blue pixel pattern are sequentially formed on the same board|substrate. Thereby, the color filter in which the three primary color pixel patterns of red, green, and blue are arrange|positioned on the board|substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

In addition, since the barrier rib functions not only as a light-shielding function but also as a function for preventing color mixing of the thermosetting coloring composition of each color discharged into the compartment, the barrier rib has a larger film thickness than the black matrix used in the first method described above. Accordingly, the barrier ribs are usually formed using a black radiation-sensitive composition.

The board|substrate used when forming a colored cured film, the light source of a radiation, and the method and conditions of a pre-baking and a post-baking are the same as that of an above-mentioned 1st method. In this way, the film thickness of the pixel formed by the inkjet method is about the same as the height of the partition wall.

On the pixel pattern obtained in this way, after forming a protective film as needed, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to obtain a color filter. The spacer is usually formed using a radiation-sensitive composition, but a spacer having light-shielding properties (black spacer) can also be used. In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used.

The color filter comprising the colored cured film of the present invention formed in this way has very high luminance, contrast and coloring power, so it is very useful for a color liquid crystal display element, a color image tube element, a color sensor, an organic EL display element, electronic paper, and the like.

display element

The display element of this invention is equipped with the colored cured film of this invention. As a display element, a color liquid crystal display element, an organic electroluminescent display element, electronic paper, etc. are mentioned.

Transmissive type or reflective type may be sufficient as the color liquid crystal display element provided with the colored cured film of this invention, and an appropriate structure can be employ|adopted. For example, a structure may be adopted in which the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed face each other with a liquid crystal layer interposed therebetween. In addition, a structure in which a substrate on which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed and a substrate on which an ITO (tin-doped indium oxide) electrode is formed face each other through a liquid crystal layer. may be The latter structure can improve the aperture ratio remarkably, and has the advantage that a bright and high-definition liquid crystal display element is obtained. In addition, when the latter structure is employ|adopted, a black matrix and black spacer may be formed in any one of the board|substrate side in which the color filter was formed, and the board|substrate side in which the ITO electrode was formed.

The color liquid crystal display element provided with the colored cured film of this invention can be equipped with the backlight unit which uses a white LED as a light source other than a cold cathode fluorescent tube (CCFL) (CCFL). As the white LED, for example, a white LED that obtains white light by mixing a red LED, a green LED, and a blue LED, a white LED that obtains white light by mixing a blue LED, a red LED and a green phosphor, and a blue LED A white LED that obtains white light by mixing a red light-emitting phosphor and a green light-emitting phosphor, a white LED that obtains white light by mixing a blue LED and a YAG-based phosphor, and a blue LED, an orange light-emitting phosphor and a green light-emitting phosphor and a white LED that obtains white light by a combination of an ultraviolet LED, a red light-emitting phosphor, a green light-emitting phosphor, and a blue light-emitting phosphor, and a white LED that obtains white light by color mixing.

In the color liquid crystal display element provided with the colored cured film of this invention, TN(Twisted Nematic) type, STN(Super Twisted Nematic) type, IPS(In-Planes Switching) type, VA(Vertical Alignment) type, OCB(Optically Compensated) type An appropriate liquid crystal mode such as a birefringence type may be applied.

Moreover, although an appropriate structure can be employ|adopted for the organic electroluminescent display element provided with the colored cured film of this invention, the structure currently disclosed by Unexamined-Japanese-Patent No. 11-307242 is mentioned, for example.

Moreover, although an appropriate structure can be employ|adopted for the electronic paper provided with the colored cured film of this invention, the structure currently disclosed by Unexamined-Japanese-Patent No. 2007-41169 is mentioned, for example.

<Example>

Hereinafter, an Example is given and embodiment of this invention is described more concretely. However, the present invention is not limited to the following examples.

<Synthesis of binder resin>

Synthesis Example 1

Binder Resin (B-1)

In a flask equipped with a cooling tube and a stirrer, 80 parts by mass of propylene glycol monomethyl ether acetate was introduced and nitrogen-substituted. It heats to 80 degreeC, and at the same temperature, 50 mass parts of propylene glycol monomethyl ether acetate, 20 mass parts of methacrylic acid, 10 mass parts of styrene, 15 mass parts of 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate A mixed solution of 28 parts by mass, 12 parts by mass of N-phenylmaleimide, and 15 parts by mass of mono(2-acryloyloxyethyl succinate), and 20 parts by mass of propylene glycol monomethyl ether acetate and 2,2'-azobis(2) (, 4-dimethylvaleronitrile) 6 mass parts of mixed solutions were dripped each over 2 hours, and it superposed|polymerized for 1 hour while maintaining this temperature. Then, the temperature of the reaction solution was raised to 90 degreeC, and the binder resin (B-1) solution (solid content concentration = 40 mass %) was obtained by superposing|polymerizing again for 1 hour. The obtained binder resin (B-1) had Mw=10500, Mn=5900, and Mw/Mn=1.78.

<Synthesis of dispersant>

Synthesis Example 2

Dispersant (1)

To a flask substituted with argon, 80 parts by mass of tetrahydrofuran, 45 parts by mass of dimethylaminoethyl methacrylate, and 5 parts by mass of sec-butyllithium were added, and at -78°C by Coolnics using ethylene glycol as a refrigerant. Maintenance stirring was performed for 3 hours. Next, 23 parts by mass of methyl methacrylate, 17 parts by mass of methoxy-terminated polyethylene glycol methacrylate (manufactured by Nichiyu Corporation, product name: Brenma PME-200), tetrahydrofurfuryl methacrylate (Kyoe) Shah Chemical Co., Ltd., product name: Light Ester THF) 15 parts by mass and propylene glycol monomethyl ether acetate 70 parts by mass were added, polymerization was carried out while maintaining this temperature for 3 hours, and the reaction was stopped with methanol, followed by ultrapure water (超純水) and ethyl acetate extracted and purified 3 times, the organic layer was collect|recovered, and ethyl acetate was distilled off under reduced pressure with the evaporator. With respect to the obtained resin solid, it melt|dissolved and diluted with propylene glycol monomethyl ether acetate, and it manufactured so that solid content concentration might be set to 40 %. The obtained resin was Mw=10000, Mn=7700, and Mw/Mn=1.30. Let the obtained resin solution be a dispersing agent (1) solution. The dispersing agent (1) is a (meth)acrylic dispersing agent having a tetrahydrofuranyl group as a crosslinkable functional group.

<Preparation of colorant dispersion>

Preparation Example 1

Colorant Dispersion (A-1)

(A) CI Pigment Green 58 as 7.33 mass parts, CI Pigment Yellow 129 as 0.94 mass parts and CI Pigment Yellow 138 as 4.46 mass parts, as a dispersing agent BYK-LPN21116 (by BYK company make, non-volatile) 11.25 mass parts of component 40 mass %), 11.25 mass parts of binder resin (B-1) solution (40% of solid content concentration) as (B) binder resin, and (E) 76.5 mass parts of propylene glycol monomethyl ether acetate as a solvent. And using 1.50 mass parts of propylene glycol monomethyl ether, it mixed and disperse|distributed with the bead mill, and the green coloring agent dispersion liquid (A-1) was prepared.

Preparation Examples 2 to 10

Colorant dispersions (A-2) to (A-10)

In Production Example 1, green colorant dispersions (A-2) to (A-10) were prepared in the same manner as in Production Example 1 except that the type and amount of each component were changed as shown in Table 1.

In Table 1, each component is as follows.

G58: C.I. Pigment Green 58

Y138: C.I. Pigment Yellow 138

Y129: C.I. Pigment Yellow 129

Y150: C.I. Pigment Yellow 150

LPN21116: BYK-LPN21116 (by Big Chemie (BYK), 40 mass % of non-volatile components)

Dispersant (1): Dispersant (1) solution synthesized in Synthesis Example 2 (solid content concentration: 40%)

E-1: propylene glycol monomethyl ether acetate

E-2: propylene glycol monomethyl ether

<Preparation and evaluation of coloring composition>

Example 1

Preparation of coloring composition

(A) 510 parts by mass of a colorant dispersion (A-1) as a colorant, (B) 100 parts by mass of a binder resin (B-1) solution as a binder resin, (C) dipentaerythritol hexaacrylate (Nippon) 90 parts by mass of Kayaku Corporation, trade name KAYARAD DPHA, (D) 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (D) as a photoinitiator 3 parts by mass of Ciba Specialty Chemicals, trade name Irgacure 369) and ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O- Acetyloxime)] (manufactured by BASF, trade name IRGACURE OXE02) 12 parts by mass, as an adhesion promoter 5 parts by mass of 3-methacryloyloxypropyltrimethoxysilane, Emulgen A- as a surfactant 60 (manufactured by Kao Corporation) 5 parts by mass of a 5% by mass solution of propylene glycol monomethyl ether acetate, and (E) 155 parts by mass of propylene glycol monomethyl ether acetate and 420 parts by mass of ethyl 3-ethoxypropionate are mixed as a solvent Thus, a green coloring composition (S-1) was prepared.

(1) Evaluation of chromaticity characteristics

After apply|coating a coloring composition (S-1) on a glass substrate using a spin coater, it prebaked for 1 minute with a 90 degreeC hotplate, and formed the coating film with a film thickness of 2.5 micrometers. The same operation was performed by changing the rotation speed of the spin coater to form three coating films having different film thicknesses.

Subsequently, after cooling these substrates to room temperature, using a high-pressure mercury lamp for the coating film on the substrate, without interposing a photomask, the radiation including the wavelengths of 365 nm, 405 nm and 436 nm is irradiated with an irradiance of 35 mW, It was exposed with the exposure dose of 600 J/m<2>. Then, shower development was performed by discharging the developing solution containing the 0.04 mass % potassium hydroxide aqueous solution at 25 degreeC with respect to the coating film on the board|substrate with a developing pressure of 1 kgf/cm<2> (nozzle diameter 1mm). Then, after wash|cleaning these board|substrates with ultrapure water and air-drying, the green cured film was produced by performing post-baking again in 230 degreeC clean oven for 20 minutes.

About the obtained cured film of 3 sheets, using a color analyzer (MCPD2000 manufactured by Otsuka Denshi Co., Ltd.), the chromaticity coordinate values (x, y) and the stimulus values (Y) in the CIE color system in a C light source and a 2 degree field of view. ) was measured. From the measurement results, when the chromaticity coordinate value y = 0.590, the chromaticity coordinate value x and the stimulus value (Y) were obtained. Table 3 shows the evaluation results. It can be said that the greater the stimulus value Y, the higher the luminance.

In addition, the film thickness of the obtained cured film was measured using alpha step IQ made from KLA-Tencor. In Table 3, the film thickness of the comparative example 1 was set to 100, and was integrated as a relative value with respect to this. It can be said that the coloring power of a coloring agent is so large that a film thickness is thin.

(2) Contrast evaluation

The substrate on which the cured film was formed was sandwiched between two deflection plates, and the deflector plate on the front side was rotated while irradiated with a fluorescent lamp (wavelength range 380 to 780 nm) from the back side, and the luminance meter LS-100 (Minolta Co., Ltd.) ), the maximum and minimum values of the transmitted light intensity were measured. And the value which divided the maximum value by the minimum value about each cured film was made into contrast ratio. From the measurement result, the contrast ratio at the chromaticity coordinate value y = 0.590 was obtained. Table 3 shows the evaluation results. In addition, it means that a contrast ratio is so favorable that a numerical value is large.

(3) Evaluation of heat resistance

After apply|coating a coloring composition (S-1) on a glass substrate using the slit-die coater, it prebaked for 4 minutes with a 90 degreeC hotplate, and formed the coating film with a film thickness of 2.0 micrometers. Subsequently, after cooling the substrate to room temperature, using a high-pressure mercury lamp, through a photomask, each coating film was subjected to radiation containing wavelengths of 365 nm, 405 nm and 436 nm at an exposure dose of 400 J/m2. exposed Then, shower development was performed for 90 second with respect to this board|substrate using the 0.04 mass % potassium hydroxide aqueous solution at 25 degreeC. Then, after wash|cleaning this board|substrate with ultrapure water and air-drying, the green dot pattern was formed on the board|substrate by performing post-baking again in 230 degreeC clean oven for 30 minutes.

With respect to the obtained dot pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Denshi Co., Ltd.), chromaticity coordinate values (x, y) and stimulus values (Y) in the CIE color space system were measured with a C light source and a 2 degree field of view. . Subsequently, the chromaticity coordinate values (x,y) and stimulus values (Y) after additional baking at 230°C for 90 minutes were measured, and color change before and after additional baking, ie, ΔE _{ab ,} was evaluated. As a result, _{a value of ΔE ab} of less than 2 was evaluated as "double-circle", that of 2 or more and less than 3 was evaluated as "○", that of 3 or more and less than 5 was evaluated as "Δ", and that of 5 or more was evaluated as "x". Table 3 shows the evaluation results. It can be said that heat resistance is favorable, so that the value of ΔE _{ab is small.}

(4) Evaluation of solvent resistance

Using the coloring composition (S-1), it carried out similarly to the said "heat resistance evaluation", and formed the green dot pattern on the board|substrate. The substrate on which the dot pattern was formed was immersed in N-methylpyrrolidone at 25° C. for 30 minutes, and ΔE _ab before and after immersion was evaluated in the same manner as in the above “evaluation of heat resistance”. As a result, those having _{a value of ΔE ab} smaller than 3 were evaluated as “○”, those between 3 and 5 were evaluated as “Δ”, and those larger than 5 were evaluated as “×”. Table 3 shows the evaluation results. It can be said that solvent resistance is so favorable that the value of ΔE _{ab is small.}

Examples 2 to 5 and Comparative Examples 1 to 5

In Example 1, the coloring compositions (S-2) to (S-10) were prepared in the same manner as in Example 1 except that the type and amount of the colorant dispersion and solvent were changed as shown in Table 2. And about the obtained coloring composition (S-2) - (S-10), it carried out similarly to Example 1, and evaluated.

A result is shown in Table 3.

In Table 2, each component is as follows.

C-1: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name Kyarrad DPHA)

D-1: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (manufactured by Ciba Specialty Chemicals, trade name Irgacure 369)

D-2: Ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime)] (manufactured by BASF, trade name Irgacure) OXE02)

F-1: 3-methacryloylpropyltrimethoxysilane

F-2: 5 mass % solution of propylene glycol monomethyl ether acetate of emulgen A-60 (made by Kao Corporation)

E-1: propylene glycol monomethyl ether acetate

E-3: 3-ethoxy ethyl propionate

E-4: methoxybutyl acetate

Claims (5)

A coloring composition comprising (A) a colorant, (B) a binder resin, and (C) a polymerizable compound,
(A) A coloring agent contains a halogenated zinc phthalocyanine pigment, a quinophthalone pigment, and an azomethine copper pigment, The ratio _{of content w 2} of a quinophthalone pigment and content w _{3 of an azomethine copper pigment is w 2} /w _{3 in mass ratio} =70/30 to 85/15, the coloring composition. _{The coloring composition of Claim 1} whose ratio _{of content w 1} of a halogenated zinc phthalocyanine pigment and content w ₃ of an azomethine copper pigment is w 1 /w ₃ =65/35 - 90/10 in mass ratio. The coloring composition of Claim 1 or 2 which further contains the (meth)acrylic-type dispersing agent which has a crosslinkable functional group. A halogenated zinc phthalocyanine pigment, a quinophthalone pigment, and an azomethine copper pigment are included, and _{the ratio of the content w 2} of the quinophthalone pigment to the content w _{3 of the azomethine copper pigment is w 2} /w ₃ =70/30 to 85 in mass ratio. /15 people, colored cured film. A display element provided with the colored cured film of Claim 4.