KR20130031787A - Coloring composition, color filter and display device - Google Patents

Abstract

PURPOSE: A coloring composition, a color filter, and a display device are provided to form a green pixel with high luminance and a high contrast ratio. CONSTITUTION: A coloring composition consists of a coloring agent, a binder resin, and a crosslinking agent. The coloring composition contains a green coloring agent and at least one kind selected from quinophthalone-based yellow pigments. The crosslinking agent comprises at least two or more polymerizable unsaturated groups. At least one of the polymerizable unsaturated groups contains a specific compound. [Reference numerals] (AA) Light emitting relative intensity(a.u); (BB) Wavelength(nm)

Description

COLORING COMPOSITION, COLOR FILTER AND DISPLAY DEVICE,

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a coloring composition, a color filter and a display element, and more particularly to the formation of a colored layer useful for color filters used in transmissive or reflective color liquid crystal display elements, solid-state imaging elements, organic EL display elements, electronic papers, and the like. It relates to a color composition for use in a color filter, a color filter having a green pixel formed using the coloring composition, and a display element comprising the color filter.

In manufacturing a color filter using a colored radiation sensitive composition, after apply | coating a colored radiation sensitive composition on a board | substrate and drying, radiation of a dry coating film to a desired pattern shape (hereinafter, referred to as "exposure") And the method (patent document 1-2) which obtains the pixel of each color is known by developing. Moreover, the method (patent document 3) which forms a black matrix using the photopolymerizable composition which disperse | distributed carbon black is also known. There is also known a method of obtaining pixels of respective colors by an inkjet method using a colored thermosetting resin composition (Patent Document 4).

By the way, in forming a green pixel, the coloring composition normally adjusted with the green and yellow coloring agent is used. And the yellow colorant used for formation of a green pixel has conventionally been variously examined in order to raise the transmittance | permeability, ie, brightness of a green pixel. For example, Patent Documents 5 to 7 show C.I. The use of pigment yellow 150 is proposed. Further, in Patent Documents 8 to 9, C.I. Pigment Yellow C.I., which is a quinophthalone pigment, is a yellow colorant with higher brightness than 150. The use of pigment yellow 138 or a yellow dye is proposed.

Japanese Patent Application Laid-Open No. 2-144502 Japanese Patent Laid-Open Publication No. 3-53201 Japanese Patent Application Laid-Open No. 6-35188 Japanese Patent Application Laid-Open No. 2000-310706 Japanese Patent Publication No. 9-269410 Japanese Patent Publication No. 10-160928 Japanese Patent Publication No. 11-14825 Japanese Patent Laid-Open No. 2001-59906 Japanese Patent Laid-Open No. 2010-168531

However, as a yellow colorant, C.I. Even when Pigment Yellow 138 or Yellow dye is used, there is a problem that the luminance of the green pixel is lowered after a high temperature heating step (for example, post-baking step after development). Therefore, C.I. The current situation is that the potential of Pigment Yellow 138 or the yellow dye is not fully available.

Therefore, the subject of this invention is C.I. In the case of using Pigment Yellow 138 or a yellow dye, the present invention provides a coloring composition capable of forming a green pixel whose luminance does not decrease even after a high temperature heating step. Moreover, the subject of this invention is providing the color filter which comprises the green pixel formed using the said coloring composition, and the display element provided with the said color filter.

MEANS TO SOLVE THE PROBLEM The present inventors considered that the cause of a fall of a brightness | luminance by a high temperature heating process is due to the transparency fall of the hardening component with heating, and as a result of earnestly examining, as a result of C.I. It was found that the above problem can be solved by using Pigment Yellow 138 or the like in combination with a specific crosslinking agent.

That is, this invention is a coloring composition containing (A) colorant, (B) binder resin, and (C) crosslinking agent, As (A) colorant, it selects from the group which consists of (a1) a yellow dye and a quinophthalone type yellow pigment. (A) A green colorant, (C) having at least two polymerizable unsaturated groups, and at least one of two or more polymerizable unsaturated groups is a group represented by the following general formula (1) It provides a coloring composition characterized by containing a compound (henceforth a "specific crosslinking agent").

In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkanediyl group having 1 to 10 carbon atoms, m represents an integer of 1 to 5, and "*" represents a bond. ]

Moreover, this invention provides the color filter which comprises the green pixel formed using the said coloring composition, and the display element provided with the said color filter.

According to the coloring composition of this invention, a green pixel with a very high brightness can be formed. Moreover, the green pixel formed with the coloring composition of this invention has high contrast ratio.

Therefore, the coloring composition of this invention is very preferable for preparation of various color filters, including the color filter for color liquid crystal display elements, the color filter for color separation of a solid-state image sensor, the color filter for organic electroluminescent display elements, and the color filter for electronic paper. Can be used.

1 shows the emission spectrum of the cold cathode fluorescent tube used in the example.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Coloring composition

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

- (A) Colorant -

In the present invention, the (A) colorant contains at least one selected from the group consisting of a (a1) quinophthalone-based yellow pigment and a yellow dye, and (a2) a green colorant. Although it does not specifically limit as a quinophthalone type yellow pigment, Although C.I. Pigment Yellow 138 is preferred. Moreover, although it does not specifically limit as a yellow dye, For example, a barbituric acid azo dye, a pyridone azo dye, a pyrazolone azo dye, a quinophthalone dye, a cyanine dye, etc. are mentioned. More specifically, the yellow dye and C.I. disclosed in Japanese Patent Laid-Open No. 2010-168531. And sulfonated derivatives of Pigment Yellow 138. In this invention, a quinophthalone type dye is preferable at the point which a desired effect is acquired more remarkably among these dyes.

In the present invention, the quinophthalone-based yellow pigment and the yellow dye may be used alone or in combination of two or more, or may be used by mixing the quinophthalone-based yellow pigment and the yellow dye.

In addition, the green coloring agent in this invention is not specifically limited, It can select suitably according to the use of a color filter. Specifically, any of pigments, dyes, and natural dyes may be used. Organic pigments or organic dyes are preferable in view of high color purity, brightness, contrast ratio, and the like, particularly preferably organic pigments.

Although it does not specifically limit as said green organic pigment, For example, a halogenated metal phthalocyanine can be mentioned, As a specific example, Zinc halide phthalocyanine, Halogenated copper phthalocyanine, Magnesium phthalocyanine, Halogenated aluminum phthalocyanine, Halogenated titanium phthalocyanine, Halogenated vanadium phthalocyanine, Halogenated manganese phthalocyanine, halogenated iron phthalocyanine, halogenated cobalt phthalocyanine, halogenated nickel phthalocyanine, halogenated tin phthalocyanine, halogenated germanium phthalocyanine, halogenated indium phthalocyanine and the like.

Of these, halogenated zinc phthalocyanine, especially zinc bromide phthalocyanine and brominated chlorinated zinc phthalocyanine are preferred. Zinc chlorinated phthalocyanine has C.I. in color index (C.I.) name. It is a pigment classified into pigment green 58, and it is preferable that it is a structure represented by following General formula (4).

In Formula (4), X represents a hydrogen atom, a chlorine atom, or a bromine atom independently of each other. Provided that at least one of all X is a chlorine atom, 10 to 15 bromine atoms, and the rest are hydrogen atoms;

In general formula (4), it is preferable that all the chlorine atoms of X are 1-6. The bromine atom can be appropriately selected within the range of 10 to 15 so that the sum of X is 16, and all X may be constituted by the bromine atom and the chlorine atom.

In this invention, a green coloring agent can be used individually or in mixture of 2 or more types.

In the present invention, known organic pigments, inorganic pigments, oil-soluble dyes, direct dyes, acid dyes, basic dyes and the like can be used together with the above quinophthalone-based yellow pigments and green colorants. As colorants other than a quinophthalone type yellow pigment, a yellow dye, and a green colorant, C.I. It is preferable to use pigment yellow 150 from the point which can improve color purity.

When a pigment is used as a colorant in the present invention, the pigment may be purified and used by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof, if necessary. In addition, a pigment can also be used, modifying the particle surface with resin as needed. As resin which modifies the particle surface of a pigment, the vehicle resin of Unexamined-Japanese-Patent No. 2001-108817, or commercially available various pigment dispersion resin is mentioned, for example. In addition, the pigment is preferably used to refine the primary particles by so-called salt milling. As a method of salt milling, the method disclosed by Unexamined-Japanese-Patent No. 08-179111 can be adopted, for example.

In the present invention, the content ratio of at least one yellow colorant selected from the group consisting of (a1) a quinophthalone-based yellow pigment and a yellow dye is preferably 5 to 65 mass%, particularly preferably in all colorants. 10-30 mass%. In addition, the content rate of the (a2) green colorant is preferably 35 to 95% by mass, particularly preferably 40 to 90% by mass in the appetizer colorant.

(A) The content rate of a coloring agent is 10-70 mass% in solid content of a coloring composition normally from the point which forms the pixel which has high brightness and excellent color purity, Preferably it is 30-60 mass%. In addition, "solid content" here is components other than the solvent mentioned later.

When using a pigment as a coloring agent in this invention, it can be used together with a dispersing agent as needed. As the dispersant, for example, suitable dispersants such as cationic, anionic and nonionic systems can be used. A polymer dispersant is preferable. Specific examples thereof include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene alkyl phenyl ether-based dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants, polyester dispersants, .

Such dispersants are commercially available, for example, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, manufactured by BYK Corporation), urethane-based dispersants As Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Corporation), Solspers 76500 (manufactured by Lubrizol Co., Ltd.), Examples of the polyethyleneimine dispersant include Solsperpers 24000 (manufactured by Lubrizol Co., Ltd.) and polyester dispersants such as Azisper PB821, Azisper PB822, Azisper PB880, and Azisper PB881 (manufactured by Ajinomoto Fine Techno Co., Ltd.). have. In addition, content of a dispersing agent can be suitably determined within the range which does not impair the objective of this invention.

- (B) Binder Resin -

Although it does not specifically limit as binder resin in the coloring composition of this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Especially, the polymer which has a carboxyl group (henceforth a "carboxyl group-containing polymer") is preferable, For example, it differs from the ethylenically unsaturated monomer which has one or more carboxyl groups (henceforth "unsaturated monomer (b1)"), The copolymer of the ethylenically unsaturated monomer copolymerizable (henceforth "unsaturated monomer (b2)") is mentioned.

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 etc. are mentioned.

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

Moreover, as said unsaturated monomer (b2), N-position substituted maleimide, such as N-phenylmaleimide and N-cyclohexyl maleimide, for example; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl 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 (polymerization degree 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, poly Propylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) Ethylene oxide modified (meth) acrylate of acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, paracumylphenol, glycidyl (meth ) Acrylate, 3,4- (Meth) acrylic acid esters such as foxycyclohexylmethyl (meth) acrylate, 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane ;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) Vinyl ethers such as; And macromonomers having a mono (meth) acryloyl group at the ends of polymer molecular chains 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, Unexamined-Japanese-Patent Japanese Patent Laid-Open No. 10-31308, Japanese Patent Laid-Open No. 10-300922 Japanese Patent Laid-Open No. 11-174224 Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 2000-56118 The copolymer disclosed in Unexamined-Japanese-Patent No. 2002-296778, Unexamined-Japanese-Patent No. 2004-101728, etc. are mentioned.

Moreover, in this invention, for example, Unexamined-Japanese-Patent No. 5-19467, Unexamined-Japanese-Patent No. 6-230212, Unexamined-Japanese-Patent No. 7-207211, Unexamined-Japanese-Patent As disclosed in Japanese Patent Application Laid-Open No. 09-325494, Japanese Patent Application Laid-Open No. Hei 11-140144, Japanese Patent Application Laid-Open No. 2008-181095, and the like, a polymerizable unsaturated bond such as a (meth) acryloyl group is added to a side chain thereof. The carboxyl group-containing polymer which has can also be used as binder resin.

As for the binder resin in this invention, the weight average molecular weight (Mw) of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran) is 1,000-100,000 normally, Preferably it is 3,000-50,000. If Mw is too small, the remaining film ratio or the like of the resulting film may be lowered, the pattern shape, heat resistance, or the like may be impaired, or the electrical properties may be deteriorated. There exists a possibility that a dry foreign material may generate easily at the time of application | coating by a nozzle system.

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

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 Publication No. 07/029871, etc. By the method disclosed, the structure, 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, 10-1,000 mass parts is preferable with respect to 100 mass parts of (A) coloring agents, and, as for content of binder resin, 20-500 mass parts is especially preferable. When there is too little content of binder resin, alkali developability may fall, for example, there exists a possibility that the storage stability of the coloring composition obtained may fall, and when too much, since a coloring agent density | concentration falls relatively, for the purpose as a thin film, There is a possibility that it will be difficult to achieve the color density.

-(C) crosslinking agent-

(C) Crosslinking agent in this invention has a specific crosslinking agent, ie, it has a 2 or more polymerizable unsaturated group, and at least 1 of 2 or more polymerizable unsaturated groups contains the compound represented by the said General formula (1), It is characterized by the above-mentioned. . By using a specific crosslinking agent as the crosslinking agent, a cured film having a low degree of decrease in transmittance at 500 to 600 nm can be obtained even after a high temperature heating step, and as a result, it is possible to form a green pixel with high luminance.

In the formula (1), R ² represents an alkanediyl group having 1 to 10 carbon atoms, preferably a linear alkanediyl group having 1 to 6 carbon atoms, or a branched alkanediyl group having 6 to 8 carbon atoms. . More specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, 2-methylpentane -1,5-diyl group, 4,4-dimethylhexane-2,6-diyl group, 2,4-dimethylhexane-2,6-diyl group, etc. are preferable. In addition, although m represents the integer of 1-5 in the said General formula (1), it is preferable that it is 1 or 2 from the point which improves the curability of a coloring composition. In addition, when m is two or more, two or more R <^2> may be same or different, but the same thing is preferable.

As such a specific crosslinking agent, For example, polymethyl alcohol, such as trimethylol ethane, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, trimethylol melamine, and (meth) acrylic acid and lactones The polyfunctional (meth) acrylate obtained by making it react is mentioned. Examples of the lactones include α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, enantholactone, 4-methylcaprolactone, 3,5,5 -Trimethylcaprolactone, 3,3,5-trimethylcaprolactone, etc. are mentioned. In this invention, the specific crosslinking agent represented by following General formula (2) is preferable at the point which can raise a desired effect.

In formula (2), all 6 R is group represented by the said General formula (1), or 1-5 of 6 R are group represented by the said Formula (1), and the remainder is following formula (3) Group or hydrogen atom represented by

[In Formula (3), R <^3> represents a hydrogen atom or a methyl group, and "*" represents a bond.]

The specific crosslinking agent represented by the above formula (2) is commercially available from Nippon Kayaku Co., Ltd. as a KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3) is represented by formula (1)). The number of groups represented by = 2, R ¹ and R ³ are all hydrogen atoms, R ² is a pentane-1,5-diyl group), DPCA-30 (m = 1 in the formula), and (1) Number of groups represented by = 3, R ¹ and R ³ are all hydrogen atoms, R ² is a pentane-1,5-diyl group), DPCA-60 (m = 1 in the formula), formula (1) The number of groups represented by = 6, R ¹ and R ³ are all hydrogen atoms, R ² is a pentane-1,5-diyl group), DPCA-120 (m = 2 in the formula), formula (1) The number of groups represented by 6 =, R <^1> and R <^3> are all hydrogen atoms, and R <^2> is a pentane- 1, 5- diyl group), etc. are mentioned.

It is preferable that it is a compound which has 4 or more groups represented by the said General formula (1) from a point which raises a desired effect, and it is especially preferable that it is a compound which has 4-6 groups represented by the said General formula (1). In addition, when a specific crosslinking agent has two or more groups represented by the said General formula (1), R <^1> , R <^2> and m may be same or different in each group.

In this invention, a specific crosslinking agent can be used individually or in mixture of 2 or more types.

In this invention, another crosslinking agent can be used together with a specific crosslinking agent, and the curability of a coloring composition can be improved by it. As another crosslinking agent, the polyfunctional (meth) acrylate which does not have a group represented by the said General formula (1), the compound which has two or more epoxy groups, the compound which has two or more N-alkoxymethylamino groups, etc. are mentioned, for example. . Among them, a polyfunctional (meth) acrylate having no group represented by the above formula (1) is preferable at the point of improving photocurability, and a compound having two or more N-alkoxymethylamino groups is preferable at the point of increasing thermosetting. .

As a specific example of the polyfunctional (meth) acrylate which does not have the group represented by the said General formula (1), the polyfunctional (meth) acrylate obtained by making an aliphatic polyhydroxy compound and (meth) acrylic acid react, and alkylene oxide is modified | denatured. Polyfunctional urethane (meth) acrylate obtained by making functional (meth) acrylate, (meth) acrylate which has a hydroxyl group, and polyfunctional isocyanate react, and having a carboxyl group obtained by making (meth) acrylate which has a hydroxyl group, and an acid anhydride react Polyfunctional (meth) acrylate etc. are mentioned.

Moreover, as a compound which has the said 2 or more N-alkoxy methylamino group, the compound etc. which have a melamine structure, a benzoguanamine structure, 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 a basic skeleton, and is a concept including melamine, benzoguanamine, or their condensate. 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 (alkoxy Methyl) benzoguanamine, N, N, N ', N'- tetra (alkoxy methyl) glycoluril, etc. are mentioned.

Among these other crosslinking agents, the polyfunctional (meth) acrylate which has a polyfunctional (meth) acrylate obtained by making a trivalent or more aliphatic polyhydroxy compound and (meth) acrylic acid react, the polyfunctional urethane (meth) acrylate, and a carboxyl group, N, N, N ', N', N ", N" -hexa (alkoxymethyl) melamine, N, N, N ', N'-tetra (alkoxymethyl) benzoguanamine is preferred. In the polyfunctional (meth) acrylate obtained by making a trivalent or more aliphatic polyhydroxy compound and (meth) acrylic acid react, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipenta In the polyfunctional (meth) acrylate which erythritol hexaacrylate has a carboxyl group, the compound obtained by making pentaerythritol triacrylate and succinic anhydride react, and the compound obtained by making dipentaerythritol pentaacrylate and succinic anhydride react In particular, the intensity of the green pixel is high, the surface smoothness of the green pixel is excellent, and it is particularly preferable in that it is difficult to generate background contamination, film residue, etc. on the substrate and the light shielding layer of the unexposed part.

In this invention, another crosslinking agent can be used individually or in mixture of 2 or more types.

As for content of (C) crosslinking agent in this invention, 10-1,000 mass parts is preferable with respect to 100 mass parts of (B) binder resin, and 20-500 mass parts is especially preferable. In this case, when there is too little content of a crosslinking agent, there exists a possibility that sufficient sclerosis | hardenability may not be obtained. On the other hand, when there is too much content of a crosslinking agent, when alkali developability is provided to the coloring composition of this invention, alkali developability will fall and it will become easy to generate a ground contamination, film | membrane residue, etc. on the board | substrate or light shielding layer of an unexposed part. There is a tendency.

In addition, in this invention, content of the specific crosslinking agent becomes like this. Preferably it is 10-98 mass parts with respect to 100 mass parts of (B) binder resin, Especially preferably, it is 20-90 mass parts. By setting it as such a form, a desired effect can be heightened more.

-(D) photoinitiator-

The coloring composition of this invention can be made to contain (D) photoinitiator. Thereby, the coloring composition can be imparted with radiation sensitivity. The (D) photoinitiator used for this invention is a compound which generate | occur | produces the active species which can start superposition | polymerization of the said (C) crosslinking agent by exposure of radiation, such as visible light, an ultraviolet-ray, an ultraviolet-ray, an electron beam, X-rays.

As such a photoinitiator, For example, thioxanthone type compound, acetophenone type compound, biimidazole type compound, triazine type compound, O-acyl oxime type compound, onium salt type compound, benzoin type compound, benzophenone type compound, α-diketone compounds, polynuclear quinone compounds, diazo compounds, imidesulfonate compounds, onium salt compounds and the like.

In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. As a photoinitiator, at least 1 sort (s) chosen from the group of a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, and an O-acyl oxime type compound is preferable.

As a specific example of a thioxanthone type compound among the preferable photoinitiators in this invention, thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxide Santone, 2, 4- dichloro thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- diisopropyl thioxanthone, etc. are mentioned.

In addition, specific examples of the acetophenone-based compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 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 type 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 type compound as a photoinitiator, using a hydrogen donor together is preferable at the point which can improve a sensitivity. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a nonimidazole-based compound by exposure. Examples of the hydrogen donors include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis (di Amine hydrogen donors, such as ethylamino) benzophenone, are mentioned. In the present invention, the hydrogen donors may be used alone or in combination of two or more thereof, but the combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors may further improve the sensitivity. It is preferable at the point.

In addition, specific examples of the triazine-based 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)- Triazine type compounds which have halomethyl groups, such as 4, 6-bis (trichloromethyl) -s-triazine, are mentioned.

In addition, specific examples of the O-acyl oxime 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-tetra Hydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2 -Dimethyl-1,3-dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime), in addition to International Publication No. 08/078678, Japanese Patent Laid-Open The oxime ester compound etc. which are described in 2011-132215 are mentioned.

In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. As such a sensitizer, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylamino acetophenone, 4-dimethylamino propiophenone, for example. Ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl ) Coumarin, 4- (diethylamino) chalcone, and the like.

In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) crosslinking agents, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, when there is too little content of a photoinitiator, there exists a possibility that hardening by exposure may become inadequate, and when too large, there exists a tendency for the formed colored layer to fall off from a board | substrate at the time of image development.

-(E) solvent-

The coloring composition of this invention contains the said (A)-(C) component and the other component added arbitrarily, Usually, a solvent is mix | blended and it is manufactured as a liquid composition.

As said solvent, (A)-(C) component and other components which comprise a coloring composition are disperse | distributed or dissolved, and it can select suitably, and can use suitably, as long as it does not react with these components and has suitable volatility.

As such a solvent, 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, (Poly) alkyls such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether Glycol monomethyl 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;

Alkoxycarboxylates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate and 3-methyl- Acid esters;

Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, 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 acetic acid, ethyl acetate, ethyl 2-oxobutyrate;

Aromatic hydrocarbons such as toluene and xylene;

Amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

Propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, from these viewpoints of solubility, pigment dispersibility, applicability | paintability, etc. -Methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol di Acetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, formic acid n-amyl, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate and the like are preferred.

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

Although content of a solvent is not specifically limited, From the viewpoint of the applicability | paintability, stability, etc. of the coloring composition obtained, the quantity by which the total concentration of each component except the solvent of the said coloring composition becomes 5-50 mass% is preferable, Especially 10 It is preferable that the amount will be from 40% by mass.

-additive-

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

As an additive, For example, fillers, such as glass and an 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; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; An anti-aggregation agent such as sodium polyacrylate; Amino-1-pentanol, 3-amino-1,2-propane, 3-amino-1-pentanol, Diol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and the like; Developability improvers such as monosuccinate mono [2- (meth) acryloyloxyethyl], monophthalate [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth) acrylate; And siloxane oligomers having a reactive functional group disclosed in JP-A-2008-242078.

The coloring composition of this invention can be manufactured by a suitable method, As a manufacturing method, it can manufacture by mixing (A)-(C) component with (E) solvent and the other component added arbitrarily, for example. . (A) When using a pigment as a colorant, the pigment is mixed with a part of component (B), optionally in the presence of a dispersant in (E) solvent, for example, while grinding using a bead mill, a roll mill, or the like. -It disperse | distributes to make a pigment dispersion liquid, Then, the method of manufacturing by adding and mixing (B)-(C) component further as needed, and a further solvent or another component as needed is preferable.

Color filter and its manufacturing method

The color filter of this invention is equipped with the pixel formed using the coloring composition of this invention.

As a method of manufacturing a color filter, the following method is mentioned first. First, on the surface of a board | substrate, a light shielding layer (black matrix) is formed so that the part which forms a pixel may be divided as needed. Subsequently, after apply | coating the liquid composition of the green radiation sensitive composition of this invention, on this board | substrate, for example, prebaking is performed and the solvent is evaporated and a coating film is formed. Subsequently, after exposing through a photomask to this coating film, it develops using alkaline developing solution, and removes and removes the unexposed part of a coating film. Thereafter, by post-baking, a pixel array in which green pixel patterns are arranged in a predetermined arrangement is formed.

Subsequently, using each colored radiation-sensitive composition of red or blue, applying, prebaking, exposure, developing and post-baking of each colored radiation-sensitive composition were carried out in the same manner as described above to perform a red pixel array and a blue pixel. Arrays are sequentially formed on the same substrate. As a result, a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, in this invention, the order which forms the pixel of each color is not limited to the above-mentioned thing.

In addition, the black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a port lithography method, and using the colored radiation-sensitive composition containing a black colorant, the pixel It can also be formed in the same manner as in the case of forming.

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

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

When the colored radiation-sensitive composition is applied to the substrate, suitable coating methods such as spraying, roll coating, rotary coating (spin coating), slit die coating, and bar coating can be adopted. It is preferable to adopt the slit die coating method.

Prebaking is normally performed combining pressure reduction drying and heat drying. The reduced-pressure drying is usually carried out until 50 to 200 Pa is reached. The conditions for heating and drying are usually about 70 to 110 DEG C for about 1 to 10 minutes.

Coating thickness is 0.6-8.0 micrometers normally as a film thickness after drying, Preferably it is 1.2-5.0 micrometers.

As a light source for radiation used when forming a pixel and / or a black matrix, for example, a light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, or an argon Laser light sources, such as an ion laser, a YAG laser, an XeCl excimer laser, and a nitrogen laser, etc. are mentioned, The radiation whose wavelength is 190-450 nm is preferable.

In general, the exposure dose of radiation is preferably 10 to 10,000 J / m ² .

As the alkaline developer, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydrooxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-dia Aqueous solutions, such as xabicyclo- [4.3.0] -5-nonene, are preferable.

A suitable amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like can also be added to the alkaline developer. After the alkali development, it is usually washed with water.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid pooling) developing method, and the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature.

Post-baking conditions are usually about 10 to 60 minutes at 120 to 280 ° C. Using the coloring composition of the present invention, a green pixel having high luminance and contrast ratio can be formed even at a postbaking temperature of 200 ° C or higher and 220 ° C or higher. . More specifically, the transmittance (%) at wavelength 545 nm when the green pixel of y = 0.600 is formed in the chromaticity coordinate y in the CIE1931 colorimeter (XYZ colorimeter) measured by using a cold cathode fluorescent tube as a light source. This 86.0% or more, Preferably it is 87.0% or more, Especially preferably, it becomes 87.5% or more, and a green pixel with high Y value and contrast ratio is obtained.

The film thickness of the pixel formed in this way is 0.5-5.0 micrometers normally, Preferably it is 1.0-3.0 micrometers.

Further, as a second method of manufacturing a color filter, a method of obtaining pixels of each color by an inkjet method disclosed in Japanese Patent Laid-Open No. 7-318723, Japanese Patent Laid-Open No. 2000-310706, or the like is adopted. can do. In this method, the partition which also has a light shielding function is first formed on the surface of a board | substrate. Subsequently, after discharging the liquid composition of the green thermosetting composition of the present invention by, for example, an inkjet device into the formed partition wall, prebaking is performed to evaporate the solvent. Subsequently, this coating film is exposed as needed, and then post-baked to form a green pixel pattern.

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

In addition, the partition wall has a function of preventing the mixing of the coloring composition of each color discharged in the compartment as well as the light shielding function, and thus has a larger film thickness than the black matrix used in the first method. Therefore, a partition is normally formed using a black radiation sensitive composition.

The method and conditions of the substrate, the light source of the radiation used for forming the color filter, the prebaking and the postbaking are the same as those of the first method described above. Thus, the film thickness of the pixel formed by the inkjet system is about the same as the height of a partition.

After forming a protective film on the pixel pattern obtained in this way as needed, a transparent conductive film is formed by sputtering. After a transparent conductive film is formed, a spacer may be further formed to form a color filter. Although a spacer is normally formed using a radiation sensitive composition, it can also be set as the spacer (black spacer) which has light shielding property.

Since the color filter of this invention obtained in this way is extremely high in brightness | luminance and contrast ratio, it is very useful for a color liquid crystal display element, a color image tube element, a color sensor, an organic EL display element, an electronic paper, etc.

Display element

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

The color liquid crystal display device having the color filter of the present invention can take an appropriate structure. For example, the color filter may be formed on a substrate separate from the driving substrate on which the thin film transistor TFT is disposed, and the substrate on which the driving substrate and the color filter are formed may have an opposite structure via the liquid crystal layer. The substrate in which the color filter is formed on the surface of the driving substrate on which the thin film transistor (TFT) is disposed, and the substrate in which the ITO (indium oxide doped with tin) electrode is formed via the liquid crystal layer face each other. You can also take The latter structure can remarkably improve the aperture ratio, and has the advantage that a bright and high precision liquid crystal display element is obtained.

The color liquid crystal display element provided with the color filter 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: Cold Cathode Fluorescent Lamp). As a white LED, for example, a white LED which combines a red LED, a green LED, and a blue LED to obtain white light by mixing, and a white LED and a blue LED which combines a blue LED, a red LED and a green phosphor to obtain white light by mixing White LED that obtains white light by mixing color by combining red light emitting phosphor and green light emitting phosphor, white LED which obtains white light by mixing blue LED and YAG-based phosphor, The white LED which obtains white light, the ultraviolet-ray LED, the red light emitting fluorescent substance, the green light emitting fluorescent substance, and the blue light emitting fluorescent substance are combined, and the white LED etc. which obtain white light by mixing are mentioned.

The color liquid crystal display device including the color filter of the present invention includes a twisted nematic (TN) type, a super twisted nematic (STN) type, an in-plane switching (IPS) type, a vertical alignment (VA) type, and an optically compacted irefringence (OCB) type. Appropriate liquid crystal modes such as a mold can be applied.

Moreover, the organic electroluminescent display element provided with the color filter of this invention can adopt a suitable structure, For example, the structure disclosed by Unexamined-Japanese-Patent No. 11-307242 is mentioned.

Moreover, the electronic paper provided with the color filter of this invention can adopt a suitable structure, for example, the structure disclosed by Unexamined-Japanese-Patent No. 2007-41169.

<Examples>

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

&Lt; Synthesis of binder resin >

Synthesis Example 1

100 mass parts of propylene glycol monomethyl ether acetates were thrown into the flask provided with the cooling tube and the stirrer, and it substituted by nitrogen. It heats at 80 degreeC, 50 mass parts of propylene glycol monomethyl ether acetates, 20 mass parts of methacrylic acid, 10 mass parts of styrene, 5 mass parts of benzyl methacrylate, and 15 mass parts of 2-hydroxyethyl methacrylate. , 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono (2-acryloyloxyethyl) succinate and 2,2'-azobis (2,4-dimethylvalle Ronitrile) 6 parts by mass of a mixed solution was added dropwise over 1 hour, and maintained at this temperature to polymerize for 2 hours. Then, the binder solution was obtained by heating up the temperature of reaction solution at 90 degreeC and superposing | polymerizing for 1 hour. Obtained binder resin was Mw = 11900, Mn = 5700 and solid content concentration = 40 mass%. This binder resin is called "binder resin (B-1)."

Synthesis Example 2

100 mass parts of propylene glycol monomethyl ether acetates were thrown into the flask provided with the cooling tube and the stirrer, and it substituted by nitrogen. It heats at 80 degreeC, and 50 mass parts of propylene glycol monomethyl ether acetates, 20 mass parts of methacrylic acid, 10 mass parts of styrene, 5 mass parts of benzyl methacrylate, and 15 mass parts of 2-hydroxyethyl methacrylate , 38 mass parts of 2-ethylhexyl methacrylate, 12 mass parts of N-phenylmaleimide, and 6 mass parts of 2,2'- azobis (2, 4- dimethylvaleronitrile) are dripped over 1 hour, The polymerization was carried out for 2 hours while maintaining this temperature. Then, the temperature of the reaction solution was heated up at 100 degreeC and the binder resin solution was obtained by superposition | polymerization for 1 hour. Obtained binder resin was Mw = 11,000, Mn = 6,000, solid content concentration = 40 mass%. This binder resin is referred to as "binder resin (B-2)".

Preparation of Pigment Dispersion

Production Example 1

(A) As a coloring agent, C.I. Pigment Green 58 / C.I. Pigment Yellow 150 (Azo pigment yellow) /C.I. Pigment Yellow 138 = 52/36/12 (mass ratio) 15 parts by mass of a mixture, 11 parts by mass of BYK-LPN21116 (manufactured by BYK Co., Ltd.) as a dispersant (solid content concentration = 40 mass%), binder resin (B- 1) The solution was mixed and dispersed with a bead mill using 14 parts by mass of 60 parts by mass of propylene glycol monomethyl ether acetate as a solvent to prepare a pigment dispersion (A-1).

Production Example 2

(A) As a coloring agent, C.I. Pigment Green 58 / C.I. Pigment Yellow 138 / C.I. 15 parts by mass of a sulfonated derivative = 46/52/2 (mass ratio) mixture of Pigment Yellow 138, 11 parts by mass of BYK-LPN21116 (by BYK Co., Ltd.) as a dispersant (solid content concentration = 40% by mass), a binder A pigment dispersion (A-2) was prepared by mixing and dispersing the resin (B-1) solution with a bead mill using 14 parts by mass and 60 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Production Example 3

(A) As a coloring agent, C.I. Pigment Green 58 / C.I. Pigment Yellow 150 (Azo-based yellow pigment) = 55/45 (mass ratio) 15 parts by mass of a mixture, 11 parts by mass of BYK-LPN21116 (manufactured by Vickemy (BYK)) as a dispersant (solid content concentration = 40% by mass), a binder A pigment dispersion (A-3) was prepared by mixing and dispersing the resin (B-1) solution with a beads mill using 14 parts by mass and 60 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

&Lt; Preparation and evaluation of colored composition >

Example 1

Nippon Kayaku Co., Ltd. product KAYARAD DPCA-60 (formulas (1) to (1) to (210) above) 25 mass parts of m = 1, the number of groups represented by General formula (1) = 6, R <^1> and R <^3> are all hydrogen atoms, and R <^2> is a pentane- 1, 5- diyl group), (D) As a photoinitiator, it is 20 mass parts of 2-benzyl-2- dimethylamino-1- (4-morpholinophenyl) -butan-1-one (BASF Corporation make, brand name Irgacure 369), and a fluorine-type surfactant 0.60 mass part and 3-methoxybutyl acetate were mixed for DIC Corporation Megaface F-554, and the liquid coloring composition (S-1) of 20 mass% of solid content concentration was manufactured.

After apply | coating liquid coloring composition (S-1) to a predetermined | prescribed film thickness on a glass substrate using a spin coater, it prebaked for 1 minute on the 90 degreeC hotplate, and formed the coating film. Subsequently, after cooling this board | substrate to room temperature, the radiation which contains each wavelength of 365 nm, 405 nm, and 436 nm was exposed to each coating film at the exposure amount of 600 J / m <^2> using a high pressure mercury lamp, without passing through a photomask. . Then, shower development was performed by discharging the developing solution containing the 0.04 mass% potassium hydroxide aqueous solution of 23 degreeC with respect to this board | substrate at 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 further post-baking for 20 minutes in a 230 degreeC clean oven.

About each of the cured film before postbaking and the cured film after postbaking, the transmission spectrum was measured using the color analyzer (MCPD2000 by Otsuka Denshi Co., Ltd.), and the transmittance | permeability in wavelength 545nm was confirmed. In addition, chromaticity coordinate values (x, y) and magnetic pole values (Y) in the CIE1931 color system (XYZ color system) were obtained from the obtained transmission spectrum and the emission spectrum of the cold cathode fluorescent tube shown in FIG. 1. The evaluation results are shown in Table 2.

Subsequently, the board | substrate after postbaking was sandwiched with two deflection plates, the deflection plate of the front side was rotated, irradiating a fluorescent lamp (wavelength range 380-780 nm) from the back side, and the luminance meter LS-100 ( The maximum value and minimum value of the light intensity transmitted by Minolta Co., Ltd. were measured. And the value which divided the maximum value by the minimum value was made into contrast ratio. The evaluation results are shown in Table 2.

Examples 2 to 4, Comparative Examples 1 to 6 and Reference Examples 1 to 2

In Example 1, except having changed into the pigment dispersion liquid, crosslinking agent, etc. which are shown in Table 1, it carried out similarly to Example 1, and manufactured liquid coloring composition (S-2)-(S-12).

Subsequently, the board | substrate with each cured film was evaluated like Example 1 except having used liquid coloring compositions (S-2)-(S-12) instead of liquid coloring composition (S-1), respectively. . The evaluation results are shown in Table 2.

In Table 1, each component is as follows.

C-1: m = 1 in the formulas (1) to (3), the number of groups represented by the formula (1) = 6, R ¹ and R ³ are all hydrogen atoms, R ² is pentane-1,5 Compound which is diyl group (brand name KAYARAD DPCA-60, Nippon Kayaku Co., Ltd. product)

C-2: In said Formula (1)-(3), m = 2, the number of groups represented by Formula (1) = 6, R <^1> and R <^3> are all hydrogen atoms, R <^2> is pentane-1,5 Compound which is diyl group (brand name KAYARAD DPCA-120, Nippon Kayaku Co., Ltd. product)

C-3: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD MAX-3510, manufactured by Nippon Kayaku Co., Ltd.)

C-4: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name Aronix M-450, manufactured by Toagosei Co., Ltd.)

C-5: ethylene oxide modified dipentaerythritol hexaacrylate (trade name KAYARAD DPEA-12, manufactured by Nippon Kayaku Co., Ltd.)

C-6: Mixture of the monoester of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate (trade name Aronix TO-1382, manufactured by Toagosei Co., Ltd.)

C-7: mixture of isocyanuric acid ethylene oxide modified diacrylate and triacrylate (trade name Aronix M-315, manufactured by Toagosei Co., Ltd.)

As can be seen from Table 2, in the case of using the pigment dispersion (A-1), in Examples 1 to 2 to which a specific crosslinking agent was applied, the transmittance (%) at 545 nm was reduced only by 0.6 to 0.7 points before and after postbaking. not. On the other hand, in Comparative Examples 1 to 5 without applying a specific crosslinking agent, both the transmittance (%) and the Y value were low (Comparative Example 3) at the time point before the postbaking, or the transmittance (%) was 1.2 to before and after the postbaking. 2.1 points are reduced, and as a result, the Y value is also significantly decreased (Comparative Examples 1 to 2 and 4 to 5).

This tendency becomes more remarkable when the pigment dispersion liquid (A-2) with more content ratio of a quinophthalone type yellow pigment and a yellow dye is used than a pigment dispersion liquid (A-1). That is, in Comparative Example 6 in which the specific crosslinking agent was not applied, the transmittance (%) was reduced by 3 points or more before and after postbaking, while in Examples 3 to 4 to which the specific crosslinking agent was applied, only 0.9 to 1.0 point was reduced. As can be seen from Reference Examples 1 and 2, when neither quinophthalone-based yellow pigment nor yellow dye is used as a yellow colorant, even if a specific crosslinking agent is applied, the transmittance (%) before postbaking is not applied. And the Y value, the transmittance (%) before and after the postbaking, and the degree of decrease of the Y value are all about the same and no difference is observed. That is, the effect that the fall of the transmittance | permeability (%) and Y value can be suppressed by applying a specific crosslinking agent is peculiar when using a quinophthalone type yellow pigment and a yellow dye as a yellow colorant.

Claims (7)

It is a coloring composition containing (A) a coloring agent, (B) binder resin, and (C) crosslinking agent,
(A) As a coloring agent, (a1) contains at least 1 sort (s) chosen from the group which consists of a yellow dye and a quinophthalone type yellow pigment, and (a2) a green coloring agent,
(C) As a crosslinking agent, it has two or more polymerizable unsaturated groups, and at least 1 of 2 or more polymerizable unsaturated groups contains the compound represented by following General formula (1), The coloring composition characterized by the above-mentioned.

In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkanediyl group having 1 to 10 carbon atoms, m represents an integer of 1 to 5, and "*" represents a bond. ] The coloring composition of Claim 1 containing the polyfunctional (meth) acrylate obtained by making a polyhydric alcohol, (meth) acrylic acid, and lactones react as said (C) crosslinking agent. The coloring composition of Claim 1 containing the compound represented by following General formula (2) as said (C) crosslinking agent.

In formula (2), all 6 R is group represented by the said General formula (1), or 1-5 of 6 R are group represented by the said Formula (1), and the remainder is following formula (3) Group or hydrogen atom represented by

[In Formula (3), R <^3> represents a hydrogen atom or a methyl group, and "*" represents a bond.] The content of the compound which has at least 2 polymerizable unsaturated groups, and at least 1 of 2 or more polymerizable unsaturated groups is represented by the said General formula (1) is 100 mass parts of said (B) binder resins of Claim 1 The coloring composition which is 10-98 mass parts with respect to. The coloring composition according to any one of claims 1 to 4, wherein the coloring composition contains zinc halide phthalocyanine as the (a2) green colorant. The color filter which comprises the pixel formed using the coloring composition of any one of Claims 1-4. A display element comprising the color filter of claim 6.

Images