KR20110065348A - Coloring composition, color filter and display device - Google Patents

Abstract

PURPOSE: A coloring composition is provided to form pixels which does not occur a coating remainder and to ensure excellent flatness. CONSTITUTION: A coloring composition comprises (A) a coloring agent, (B) a cross-linking agent, (C) a binder resin, (D) a compound represented by chemical formula 1, and (E) a solvent. In chemical formula 1, R^21 and R^22 independently represent a radical having an alkyl fluoride group; R^23 and R^24 independently represent a methyl group or an ethyl group; X is a divalent linker excluding fluorine; and m and n are an integer of 1-100.

Description

Coloring composition, color filter and display element {COLORING COMPOSITION, COLOR FILTER AND DISPLAY DEVICE}

This invention relates to a coloring composition, a color filter, and a display element, More specifically, formation of the colored layer useful for the color filter used for a transmissive or reflective color liquid crystal display device, a color image tube element, an organic electroluminescent display element, an electronic paper, etc. It relates to a color composition having a colored composition used in the present invention, a color filter having a colored layer formed from the coloring composition, and the color filter.

Conventionally, in manufacturing a color filter using a colored radiation-sensitive composition, after drying a colored radiation-sensitive composition on a substrate or on a substrate on which a light shielding layer having a desired pattern is formed in advance, the dried coating film is dried. The method (for example, patent document 1, patent document 2) which obtains the pixel of each color is known by irradiating a radiation with a desired pattern shape (henceforth "exposure"), and developing. Moreover, the method (for example, refer patent document 3) of forming a black matrix using the photopolymerizable composition containing a black material is also known. Moreover, the method (for example, refer patent document 4) of obtaining the pixel of each color by the inkjet system using a coloring thermosetting resin composition is also known.

As for the colored composition used to form the pixel by the inkjet method, it is known to contain a specific solvent in the resin composition (for example, refer to Patent Document 5) in order to improve the stability of the ink, the ejectability, and the like. However, when the pixel is to be formed in the narrow area partitioned by the partition formed on the transparent substrate by the inkjet method, the shape of the pixel is at or near the periphery of the pixel due to the affinity between the ink and the partition wall surface. Therefore, there is a problem in that the film thickness becomes thin, the shape is the same as having the maximum portion of the film thickness on the center side of the pixel, or the surface may be irregular, such as the irregularities in the film thickness. . In addition, due to the affinity between the ink and the transparent substrate or the size of the opening area partitioned by the partition wall, the ink may not be applied and diffused in the pixel, and may be referred to as a coating remaining part (pin hole, discoloration, white defect, etc.). ) Occurred.

Japanese Patent Laid-Open No. 2-144502 Japanese Patent Laid-Open No. 3-53201 Japanese Patent Laid-Open No. 6-35188 Japanese Patent Laid-Open No. 2000-310706 Japanese Patent Laid-Open No. 2006-299090

An object of the present invention is to provide a coloring composition that is excellent in flatness and suitable for an inkjet method capable of forming a pixel that does not generate a coating residue.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched, and found that the said subject could be solved by using a specific surfactant, and completed this invention.

That is, this invention is a (A) coloring agent, (B) crosslinking agent, (C) binder resin, (D) the compound represented by following formula (1) (Hereinafter, it may be called "surfactant (D)"), and ( E) It is to provide the coloring composition characterized by containing a solvent.

(Formula 1, R ²¹ and R ²² independently represent a group having an alkyl fluoride group, R ²³ and R ²⁴ independently represent a methyl group or an ethyl group, X represents a divalent linking group containing no fluorine, m And n independently of each other represent an integer from 1 to 100)

Moreover, this invention provides the color filter which comprises the colored layer formed using the said coloring composition, and the display element provided with this color filter. Here, "colored layer" means each color pixel used for a color filter, a black matrix, etc.

According to the coloring composition of this invention, the pixel which is excellent in flatness and does not generate | occur | produce application | coating remainder can be formed by the inkjet method.

Therefore, the coloring composition of this invention is various color filters, including the color filter for color liquid crystal display elements in the electronic industry, 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. It can be used very well for the production of.

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

Coloring composition

-(A) colorant-

It will not specifically limit, if it has coloring property as (A) coloring agent in this invention, A color and a material can be selected suitably according to a use. Specifically, any of pigments, dyes, and natural dyes can be used as the colorant, but since the heat resistance is required for the color filter, an organic pigment or an inorganic pigment is preferable as the colorant in the present invention.

Examples of the organic pigments include compounds classified as pigments in the color index (C. I .; issued by The Society of Dyers and Colorists), and specifically those having the following color index (C. I.) names.

CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 180, CI Pigment Yellow 211;

CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment CI Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, CI Pigment Orange 72, CI Pigment Orange 73, CI Pigment Orange 74;

CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 41, CI Pigment Red 122, CI Pigment CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 243, C. I. Pigment Red 254, C. I. Pigment Red 255, C. I. Pigment Red 262, C. I. Pigment Red 264, C. I. Pigment Red 272;

C. I. Pigment Violet 1, C. I. Pigment Violet 19, C. I. Pigment Violet 23, C. I. Pigment Violet 29, C. I. Pigment Violet 32, C. I. Pigment Violet 36, C. I. Pigment Violet 38;

C. I. Pigment Blue 15, C. I. Pigment Blue 15: 3, C. I. Pigment Blue 15: 4, C. I. Pigment Blue 15: 6, C. I. Pigment Blue 60, C. I. Pigment Blue 80;

C. I. Pigment Green 7, C. I. Pigment Green 36, C. I. Pigment Green 58.

These organic pigments can be used individually or in mixture of 2 or more types.

In the present invention, the organic pigment may be purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof. In addition, it is preferable to use an organic pigment refine | purifying primary particle by what is called salt milling. Salt milling methods are disclosed, for example, in Japanese Patent Application Laid-Open No. 08-179111.

Examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, bengal (red iron oxide (III)), cadmium, ultramarine blue, blue blue, and chromium oxide. And cobalt rust, amber, titanium black, synthetic iron black, carbon black and the like.

If desired, these colorants may be used by modifying the particle surface thereof with a resin. 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. As a resin coating method of the carbon black surface, the method as described in Unexamined-Japanese-Patent No. 9-71733, Unexamined-Japanese-Patent No. 9-95625, Unexamined-Japanese-Patent No. 9-124969, etc. are mentioned, for example. Can be adopted.

The said coloring agent can be used individually or in mixture of 2 or more types.

When the coloring composition of this invention is used for formation of a pixel, since high color development is calculated | required by a pixel, as (A) coloring agent, the coloring agent with high color development property is preferable, and an organic pigment is specifically used preferably. On the other hand, when the coloring composition of this invention is used for formation of a black matrix, since a light shielding property is calculated | required for a black matrix, organic pigment or carbon black is used suitably as (A) coloring agent.

By the way, the blue pixel formed using the blue coloring agent, especially the coloring composition containing a blue pigment, is accompanied by the high temperature heating at the time of a post-baking process, with yellowing of a binder resin component or a crosslinking component, or crystal transition of a blue pigment itself, etc. There exists a problem that transparency and a color characteristic fall.

In addition, a pixel formed by using a coloring composition containing a colorant having an azo bond has a problem in that the azo bond is decomposed by high temperature heating during the post-baking process, and the color purity is lowered. As a coloring agent which has an azo bond, For example, the monoazo pigment represented by CI pigment yellow 150, the pigment disclosed by Unexamined-Japanese-Patent No. 2001-354869, the disazo pigment represented by CI pigment red 242, etc. are mentioned, for example. Although a monoazo pigment is especially easy to fade by high temperature heating. Among monoazo pigments, a compound represented by the following formula (I) or a tautomer thereof, a molecular compound consisting of a compound represented by the following formula (II), in particular a compound represented by the following formula (I) or a host which is a tautomer thereof, A clathrate compound (hereinafter sometimes referred to as a "specific yellow pigment") composed of the displayed guest is a yellow pigment excellent in transparency and color purity, but is easily faded by high temperature heating.

According to the coloring composition of the present invention, the problem of the above heat resistance is surprisingly solved.

<Formula I>

<Formula II>

(In Formula II, R ^a to R ^c represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted independently of each other.)

According to the coloring composition of the present invention, the problem of the above heat resistance is surprisingly solved.

In addition, a green pixel formed using a zinc halide phthalocyanine pigment represented by C. I. Pigment Green 58 has a problem that, when exposed to an organic solvent, the colored component elutes and the color purity is lowered. According to the coloring composition of the present invention, the problem of the solvent resistance is surprisingly solved.

In the present invention, the content ratio of the colorant (A) is preferably 5 to 70% by mass in the total solids of the coloring composition, in that a pixel having excellent transparency and color purity or a black matrix having excellent light shielding properties is formed. It is more preferable that it is-60 mass%. Here, solid content is components other than the solvent mentioned later.

The colorant in the present invention can be used together with a dispersant and a dispersing aid, if desired. As the dispersant, for example, suitable dispersants such as cationic, anionic, and nonionic systems can be used, but a polymer dispersant is preferable. Specifically, an acryl-type copolymer, a polyurethane, polyester, polyethyleneimine, polyallylamine, etc. are mentioned.

Such dispersants are commercially available, for example Disperbyk-2000, Dispervik-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK), poly As urethane dispervic -161, dispervic -162, dispervic -165, dispervic -167, dispervic -170, dispervic -182 (above, product made by Big Chemie (BYK) company), Solsper 7676 (Lubrissol Co., Ltd.) as a polyethyleneimine, Solspersper 24000 (made by Lubrizol Co., Ltd.), polyester as azisper PB821, azisper PB822, azisper PB823, azisper PB824, azisper PB827, azisper PB880 And Azisper PB881 (above, Ajinomoto Fine Techno Co., Ltd.).

These dispersants can be used individually or in mixture of 2 or more types. Content of a dispersing agent is 100 mass parts or less normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 1-70 mass parts, More preferably, it is 10-50 mass parts. In this case, when content of a dispersing agent exceeds 100 mass parts, there exists a possibility that the intensity | strength etc. of the colored layer obtained may be impaired.

Examples of the dispersion aid include pigment derivatives, and specific examples thereof include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

-(B) crosslinking agent-

The crosslinking agent (B) in the present invention is not particularly limited as long as it is a monomer having two or more polymerizable groups. As a group which can superpose | polymerize, an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, an N-alkoxy methylamino group, etc. are mentioned, for example. In this invention, as (B) crosslinking agent, the compound (b1) which has two or more N-alkoxymethylamino groups (henceforth a "crosslinking agent (b1)"), and (b2) polyfunctional (meth) acrylate At least 1 sort (s) chosen from the group which consists of (the following may be called "crosslinking agent (b2)") is preferable. When the coloring composition of this invention is used for formation of the colored layer by an inkjet system, especially when it is set as a thermosetting inkjet ink, it is preferable to use these together from a viewpoint of the heat resistance and flatness of the colored layer formed. Moreover, when providing radiation sensitivity to the coloring composition of this invention, it is preferable to use a crosslinking agent (b2) from a viewpoint of a sensitivity.

The crosslinking agent (b1) is not particularly limited as long as it has two or more N-alkoxymethylamino groups, and examples thereof include a melamine structure, a benzoguanamine structure and a urea structure. In addition, a "melamine structure and a benzoguanamine structure" means the chemical structure which has one or more triazine ring or a phenyl substituted triazine ring as a basic skeleton, and is a concept containing melamine, benzoguanamine, or these condensates. Since the crosslinking reaction of a crosslinking agent (b1) gives the colored layer excellent sclerosis | hardenability, and has the characteristic which is hard to yellow even with high temperature heating, it gives outstanding heat resistance to a colored layer. As a specific example of a crosslinking agent (b1), the compound represented by following General formula (b1-1)-(b1-5) is mentioned.

In formula (b1-2), R <^5> -R <^6> represents a C1-C4 linear or branched alkyl group independently of each other.

In the formulas (b1-1) and (b1-3) to (b1-5), R ¹ to R ⁴ and R ⁷ to R ²⁰ are each independently a hydrogen atom or a linear or branched C 1-4 carbon atom. An alkyl group of. Provided that at least two of R ¹ to R ⁴ in formula (b1-1), at least two of R ⁷ to R ¹⁰ in formula (b1-3), and R ¹¹ to R in formula (b1-4) ^At least two of ¹⁶ and at least two of R ¹⁷ to R ²⁰ in the formula (b1-5) are linear or branched alkyl groups having 1 to 4 carbon atoms.

Specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, etc. are mentioned.

In the present invention, the crosslinking agent (b1) is preferably a compound having a melamine structure, a benzoguanamine structure, or both from the viewpoints of solubility in a solvent, heat resistance of a colored layer to be formed, and solvent resistance. 4) or a compound represented by the formula (b1-5) or a condensate thereof is preferable.

In this invention, a crosslinking agent (b1) can be used individually or in mixture of 2 or more types.

The crosslinking agent (b2) is not particularly limited as long as it is a compound having two or more (meth) acryloyl groups. For example, an aliphatic polyhydroxy compound and an ester of (meth) acrylic acid, and a caprolactone-modified polyfunctional (meth) ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by making (meth) acrylate which has a hydroxyl group, and polyfunctional isocyanate react, (meth) acrylate which has a hydroxyl group And polyfunctional (meth) acrylates having a carboxyl group obtained by reacting an acid anhydride. The hardening reaction by bridge | crosslinking between the (meth) acryloyl groups of a crosslinking agent (b2) gives the flatness excellent to a colored layer, when using the coloring composition of this invention for formation of the colored layer by an inkjet system.

Here, as the aliphatic polyhydroxy compound, for example, divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and The same trivalent or more aliphatic polyhydroxy compound is mentioned, As a (meth) acrylate which has the said hydroxyl group, 2-hydroxyethyl (meth) acrylate, trimethylolpropanedi (meth) acrylate, penta, for example. Erythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol dimethacrylate, etc. are mentioned, As said polyfunctional isocyanate, for example, tolylene diisocyanate, hexamethylene diisocyanate, Diphenylmethylene diisocyanate, isophorone diisocyanate, etc. are mentioned Examples of the acid anhydride include succinic anhydride, maleic anhydride, glutaric anhydride, anhydrides of dibasic acids such as itaconic anhydride, phthalic anhydride, hexahydro phthalic anhydride, pyromellitic anhydride, and biphenyltetracarboxylic anhydride. Tetrabasic dianhydrides, such as an acid dianhydride and a benzophenone tetracarboxylic dianhydride, are mentioned.

Moreover, as said caprolactone modified polyfunctional (meth) acrylate, the compound described in Paragraph [0015]-[0018] of Unexamined-Japanese-Patent No. 11-44955 is mentioned, for example, The said alkylene oxide is mentioned. Modified polyfunctional (meth) acrylates include ethylene oxide and / or propylene oxide modified di (meth) acrylates of bisphenol A, ethylene oxide and / or propylene oxide modified di (meth) acrylates of isocyanuric acid. Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of isocyanuric acid, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of trimethylolpropane, ethylene of pentaerythritol Oxide and / or propylene oxide modified tri (meth) acrylates, ethylene oxide of pentaerythritol and / or propylene oxide modified tetra (meth) acrylates Ethylene oxide and / or propylene oxide modified penta (meth) acrylate of dipentaerythritol, ethylene oxide and / or propylene oxide modified hexa (meth) acrylate of dipentaerythritol, and the like. .

Among these crosslinking agents (b2), esters of aliphatic polyhydroxy compounds and (meth) acrylic acid, caprolactone modified polyfunctional (meth) acrylates, polyfunctional urethane (meth) acrylates, or polyfunctional (meth) s having a carboxyl group As an acrylate, it is preferable to have 3 or more (meth) acryloyl groups.

In this invention, a crosslinking agent (b2) can be used individually or in mixture of 2 or more types.

When using a crosslinking agent (b1) and a crosslinking agent (b2) together, from the viewpoint of the solvent resistance and heat resistance of the colored layer formed as a crosslinking agent (b2), the trifunctional or more than trifunctional polyfunctional (meth) acrylate which has a hydroxyl group, and a carboxyl group The branch is preferably at least one selected from the group consisting of trifunctional or higher polyfunctional (meth) acrylates. It is thought that reaction with the hydroxyl group and / or carboxyl group of a crosslinking agent (b2), and the N-alkoxy methylamino group of a crosslinking agent (b1) gives the color layer excellent solvent resistance.

Especially as trifunctional or more than trifunctional polyfunctional (meth) acrylate which has a hydroxyl group, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable. Moreover, it is preferable that acid value is 30-300 mg KOH / g, and, as for trifunctional or more than trifunctional polyfunctional (meth) acrylate which has a carboxyl group, it is more preferable that it is 50-250 mg KOH / g. In particular, a reactant of pentaerythritol tri (meth) acrylate with succinic anhydride and a reactant of dipentaerythritol penta (meth) acrylate with succinic anhydride are preferable.

In this invention, the polyfunctional (meth) acrylate which has a hydroxyl group, and the polyfunctional (meth) acrylate which has a carboxyl group can be used individually or in mixture of 2 or more types, respectively. Of course, the polyfunctional (meth) acrylate which has independent or 2 or more types of hydroxyl groups, and the polyfunctional (meth) acrylate which has individual or 2 or more types of carboxyl groups can also be mixed and used.

The total content of the crosslinking agent (B) in the present invention is preferably 5 to 1,000 parts by mass, and more preferably 20 to 300 parts by mass with respect to 100 parts by mass of the (A) colorant. In this case, when there is too little content of a crosslinking agent, there exists a tendency for the intensity | strength and surface smoothness of a colored layer to fall, and when too much, since a pigment concentration falls relatively, it is difficult to achieve the target color density as a thin film. There is a risk of loss.

When using a crosslinking agent (b1) and a crosslinking agent (b2) together, these mixing ratios are 90: 10-10: 90 by mass ratio, More preferably, they are 80: 20-20: 80. In this case, the content ratio of at least one selected from the group consisting of a polyfunctional (meth) acrylate having a hydroxyl group and a polyfunctional (meth) acrylate having a carboxyl group in the crosslinking agent (b2) is preferably 5 mass. % Or more, More preferably, it is 10-80 mass%. By using each crosslinking agent in such an aspect, the heat resistance, solvent resistance, and flatness of a colored layer become excellent.

(C) binder resin

Although it does not specifically limit as (C) binder resin in 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, and it is copolymerizable different from the ethylenically unsaturated monomer which has one or more carboxyl groups (henceforth "unsaturated monomer (c1)"). Copolymers of ethylenically unsaturated monomers (hereinafter referred to as "unsaturated monomers (c2)") are preferred.

Examples of the unsaturated monomer (c1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth) acrylate. Etc. can be mentioned. These unsaturated monomers (c1) can be used individually or in mixture of 2 or more types.

In the copolymer of an unsaturated monomer (c1) and an unsaturated monomer (c2), the copolymerization ratio of an unsaturated monomer (c1) becomes like this. Preferably it is 5-50 mass%, More preferably, it is 10-40 mass%. By copolymerizing an unsaturated monomer (c1) in such a range, the coloring composition excellent in storage stability and alkali developability can be obtained.

Moreover, as said unsaturated monomer (c2), for example

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

Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxy-α-methylstyrene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate , Polyethylene glycol (n = 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (n = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylic Latex, polypropylene glycol (n = 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5. 2. 1.0 ^2,6 ] decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, para Unsaturated carboxylic acid esters such as ethylene oxide modified (meth) acrylate of cumylphenol;

The macromonomer which has a mono (meth) acryloyl group in the terminal of polymer molecular chains, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane, etc. are mentioned.

These unsaturated monomers (c2) can be used individually or in mixture of 2 or more types.

As a specific example of the copolymer of an unsaturated monomer (c1) and an unsaturated monomer (c2), 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. 2004-101728, etc. are mentioned.

In addition, in this invention, Unexamined-Japanese-Patent No. 5-19467, Unexamined-Japanese-Patent No. 6-230212, Unexamined-Japanese-Patent No. 7-207211, Unexamined-Japanese-Patent A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as the binder resin, as disclosed in Japanese Patent Application Laid-Open No. 11-140144, Japanese Patent Laid-Open No. 2008-181095, and the like. .

The polystyrene reduced weight average molecular weight (hereinafter sometimes referred to as "Mw") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the binder resin in the present invention is usually 1,000 to 300,000, preferably Preferably 3,000 to 100,000. 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 characteristics may be deteriorated. There is concern.

In addition, the ratio (Mw) of Mw of binder resin in this invention and the polystyrene conversion number average molecular weight (henceforth "Mn") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

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

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

In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. In this case, when there is too little content of binder resin, there exists a possibility that the storage stability and alkali developability of the coloring composition obtained may fall, for example, and when too much, the coloring agent concentration will fall comparatively, and therefore, the target color density as a thin film There is a fear that it will be difficult to achieve.

Surfactant (D)

The coloring composition of this invention contains surfactant (D), ie, the compound represented by the said General formula (1). Since the surfactant (D) has a hydroxyl group, the affinity for the glass substrate of the colored composition is increased, and the coating diffusion is improved, thereby forming a pixel which does not generate a coating residue in the partition by the inkjet method. It becomes possible. Moreover, it is thought that hardening reaction by the thermal crosslinking of the hydroxyl group of surfactant (D) and the N-alkoxy methylamino group of the said crosslinking agent (b1) further improves the solvent resistance and heat resistance of a colored layer.

In the above formula (1), examples of the divalent linking group represented by X include a divalent group in which a substituted or unsubstituted divalent hydrocarbon group and a plurality of divalent hydrocarbon groups are connected to at least one linker containing a hetero atom. have. As an example of the said bivalent hydrocarbon group, an alkylene group, a cycloalkylene group, an alkendiyl group, a cycloalkenediyl group, an arylene group, etc. are mentioned. In addition, the alkylene group may be linear or branched. In addition, specific examples of the linking group containing the hetero atom include -O-, -S-, -CO-, -SO _2- , -COO-, -SO _3- , -CONH-, -OCONH-, and -SO ₂ NH -Etc. can be mentioned. When X is a divalent group in which a plurality of hydrocarbon groups are connected to at least one linking group containing a hetero atom, the plurality of hydrocarbon groups may be the same or different, and even when there are a plurality of linking groups including a hetero atom, Including linking groups may be the same or different.

In this invention, it is preferable that it is 1-50, and, as for the sum total carbon number which X has, the thing which is 1-20 is more preferable. When the total carbon number which X has is too high, since the hydroxyl value of surfactant (D) will become low, there exists a possibility that the coating | diffusion diffusion property of a coloring composition on a board | substrate may deteriorate. It is further more preferable that X is a C1-C20 bivalent hydrocarbon group, and it is especially preferable that it is a C1-C10 bivalent hydrocarbon group.

In addition, in Formula 1, R ²¹ and R ²² are preferably groups having a perfluoroalkyl group having 1 to 4 carbon atoms in terms of enhancing a desired effect, and in particular, CF ₃ CH _2- , CF ₃ CH ₂ CH _2- , CF ₃ CF ₂ CH _2- , CF ₃ CF ₂ CH ₂ CH _2- , CF ₃ CF ₂ CF ₂ CH _2- , CF ₃ CF ₂ CF ₂ CH ₂ CH _2- , CF ₃ CF ₂ CF ₂ CF ₂ CH _2- , CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ -is preferred.

In addition, in Formula 1, m + n is preferably 2 to 40, more preferably 3 to 30. In this case, when m + n is too small, there is a possibility that the flatness of the pixel may deteriorate. On the other hand, since the hydroxyl value of the surfactant (D) is lowered, the coating diffusion of the coloring composition on the substrate may be deteriorated, or There is a fear that the compatibility of the.

As a specific example of surfactant (D), the compound represented by a following formula is mentioned.

(In the formula, R ²¹ to R ^24, m and n are the same as R ²¹ to R ^24, m and n in the general formula (1), and, R represents an ethylene group or a methylethylene, l is an integer from 1 to 40 Indicates

Surfactant (D) is commercially available, for example PF-7002 sold by OMNOVA (R ²¹ and R ²² in formula (1-1) are CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ —, R ²³ and R ²⁴ are methyl groups, surfactants having m + n = 4 to 5), PF-151N (R ²¹ and R ²² in formula (1-2) are CF ₃ CF ₂ And CH ₂ —, R ²³ and R ²⁴ are methyl groups, R is an ethylene group, and surfactants in which the average values of m and n are all 4 and 1 are 21).

In this invention, surfactant (D) can be used individually or in mixture of 2 or more types.

Content of surfactant (D) is 0.01-2.0 mass parts normally with respect to 100 mass parts of solid content except the solvent mentioned later, Preferably it is 0.02-1.5 mass parts, More preferably, it is 0.05-1.0 mass part. If the content of the surfactant (D) is too small, the desired effect may not be obtained. On the other hand, if the content of the surfactant (D) is too high, the surface of the colored layer may be rough.

In this invention, well-known fluorine-type surfactant other than surfactant (D), silicone type surfactant, etc. can also be used with surfactant (D).

-(E) solvent-

The coloring composition of this invention is manufactured as a liquid composition normally by mix | blending a solvent. As a solvent, (A)-(D) component which comprises a coloring composition, and the additive component mentioned later are disperse | distributed or melt | dissolved, and it does not react with these components, It can select suitably, and can use as long as it has a suitable volatility.

When using the coloring composition of this invention for formation of the colored layer by the inkjet system, the boiling point in 1 atmosphere is preferably 180 degreeC or more (Hereinafter, it is also called a "high boiling point solvent"), More preferably, it is 200 degreeC- The solvent which is 290 degreeC, Especially preferably, the solvent which is 220 degreeC-280 degreeC or less, Preferably it contains 70 mass% or more, More preferably, 80-100 mass%, Especially preferably, 90-100 mass% in all solvents. . When the content ratio of the high boiling point solvent is too small, the coloring composition tends to be dried, and not only the ink ejectability deteriorates, but also the balance between the leveling speed and the drying speed of the coloring composition is broken. There is a possibility that the coating diffusibility on the substrate is also deteriorated.

As said high boiling point solvent, For example, the solvent which has two acetate structures represented by glycol diacetate, such as a propylene glycol diacetate, 1, 3- butylene glycol diacetate, and 1, 6- hexanediol diacetate;

Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol mono Solvents having one acetate structure such as methyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, propylene glycol butyl ether acetate and 3-methyl-3-methoxybutyl acetate;

Ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl 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, 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 monoethyl ether, benzyl ethyl ether, dihexyl ether, diethylene glycol diethyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1 Nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, carbonic acid Propylene, N-methylpyrrolidone, and the like.

Among them, from the viewpoint of dispersion stability of the coloring composition, a solvent having two acetate structures is preferable, glycol diacetate is more preferable, diacetate of glycol having 2 to 6 carbon atoms is more preferable, and 1,3-butyl Lenglycol diacetate is particularly preferred.

The said high boiling point solvent can be used individually or in mixture of 2 or more types.

Moreover, when using the coloring composition of this invention for formation of the colored layer by an inkjet system, you may use together the high boiling point solvent and the solvent whose boiling point at 1 atmosphere is less than 180 degreeC.

As a solvent whose boiling point in 1 atmosphere is less than 180 degreeC, for example

Alcohols such as methanol, ethanol and benzyl alcohol;

(Poly) alkylene glycol mono, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether Alkyl ethers;

(Poly) alkyl such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate Lenglycol monoalkyl ether acetates;

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

Methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexan-2-one Ketones such as these;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate N-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, Esters such as n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl 2-oxobutyrate and the like;

Aromatic hydrocarbons such as toluene and xylene;

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

Among these other solvents, benzyl alcohol, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl from the viewpoint of solubility and pigment dispersibility. Ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, n-butyl acetate, acetic acid i-butyl, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate and ethyl pyruvate are preferable.

The solvent whose boiling point in said 1 atmosphere is less than 180 degreeC can be used individually or in mixture of 2 or more types.

On the other hand, when using the coloring composition of this invention for rotation coating or slit die application, the boiling point in 1 atmosphere is preferably the solvent below 180 degreeC, More preferably, the solvent which is 100 to 180 degreeC, Especially preferably, it is 120 degreeC Preferably it is 70 mass% or more, More preferably, it is 80-100 mass%, Especially preferably, 90-100 mass% of the solvent which is -180 degreeC or less is contained in all the solvents.

When using the coloring composition of this invention for rotational coating or slit die coating, as a solvent whose boiling point in 1 atmosphere is less than 180 degreeC, the said (poly) alkylene glycol monoalkyl ether and (poly) alkylene glycol mono | mono are from a coatability viewpoint. Alkyl ether acetates, ethers, ketones and esters are preferable, and ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, cyclohexanone, n-butyl acetate, i-butyl acetate, i-pentyl acetate, 3-methoxy Butyl acetate, n-butyl propionate, ethyl 3-methoxypropionate, 3-ethoxypropion Methyl acid and ethyl 3-ethoxypropionate are particularly preferred.

These solvents can be used individually or in mixture of 2 or more types.

The content of the solvent is preferably an amount such that the total concentration of each component excluding the solvent is from 5 to 35% by mass from the viewpoints of ink ejectability, coating property, storage stability, and the like of the colored composition obtained, and becomes from 10 to 30% by mass. Amount is more preferable.

Photoinitiator

Radiation sensitivity can be provided to the coloring composition of this invention by containing a photoinitiator. The photoinitiator in this invention is a compound which can generate the active species which can start the crosslinking reaction of the said (B) crosslinking agent by radiation exposure, such as visible light, an ultraviolet-ray, an ultraviolet-ray, an electron beam, X-rays.

Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone compound, a multinuclear quinone compound, a diazo compound, an imide sulfonate compound, 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, a 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.

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, and the like.

Further, specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2' -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 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 "hydrogen donor" here means the compound which can donate a hydrogen atom with respect to the radical which generate | occur | produced in the biimidazole type compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis ( Amine hydrogen donors, such as diethylamino) benzophenone, are mentioned. In the present invention, the hydrogen donor 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. Preferred at

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) -4 Triazine type compounds which have halomethyl groups, such as a 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-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) and the like.

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, content of a photoinitiator is 0.01-120 mass parts normally with respect to 100 mass parts of (B) crosslinking agents, Preferably it is 1-100 mass parts.

Additive component

The resin composition of this invention may further contain various additive components as needed.

As the additive component, for example

Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyl dimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyl Adhesion promoters such as trimethoxysilane;

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;

Aggregation inhibitors such as sodium polyacrylate;

Thermal radical generators such as 1,1'-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile;

Inkjet ejection performance stabilizers, such as methanol, ethanol, i-propanol, n-butanol, and glycerin, etc. are mentioned.

Furthermore, the coloring composition of this invention can contain a thermal acid generator. A thermal acid generator is a component which generates an acid by heating, and for example, onium salts such as sulfonium salt, benzothiazolium salt, ammonium salt and phosphonium salt can be mentioned. Of these thermal acid generators, sulfonium salts and benzothiazolium salts are preferred.

Specific examples of the sulfonium salt and the benzothiazolium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, 4-hydroxyphenyl benzyl methylsulfonium hexafluoroantimonate, 4-acetoxyphenyl benzyl Methylsulfonium hexafluoroantimonate, 4-hydroxyphenyldibenzylsulfonium hexafluoroantimonate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexa Fluoroantimonate, and the like.

The said thermal acid generator can be used individually or in mixture of 2 or more types.

In this invention, a coloring composition can be manufactured by a suitable method, for example, can be manufactured by mixing (A)-(E) component with the other component added arbitrarily. As a manufacturing method of a preferable coloring composition, (A) coloring agent is grind | pulverized in the presence of a dispersing agent with a part of (C) component in the presence of a dispersing agent, for example using a bead mill, a roll mill, etc. The method of mixing and disperse | distributing to make a coloring agent dispersion liquid, and then adding and mixing (B)-(D) component and the (E) solvent and other components which are further added as needed to this coloring agent dispersion liquid is mentioned. .

Color filter

The color filter of this invention has a colored layer 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. Next, after apply | coating the liquid composition of the colored radiation-sensitive composition of this invention in which the red coloring agent was disperse | distributed, for example, preliminary baking is performed and the solvent is evaporated and a coating film is formed. Subsequently, after exposing to this coating film through a photo mask, 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 the red pixel patterns are arranged in a predetermined arrangement is formed.

Subsequently, using the liquid composition of each colored radiation-sensitive composition in which the green or blue colorant is dispersed, in the same manner as described above, coating, preliminary baking, exposure, development, and post-baking of each liquid composition are carried out to produce a green pixel array. And a blue pixel array are sequentially formed on the same substrate. Thereby, a color filter is obtained in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate. However, in this invention, the order which forms the pixel of each color is not limited to said thing.

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 photolithography method, but using the colored radiation-sensitive composition in which the black colorant is dispersed, the pixel It may be formed in the same manner as in the case of formation. The film thickness of the black matrix which consists of a metal thin film is 0.1-0.2 micrometer normally, while the film thickness of the resin black matrix formed using the black radiation sensitive composition is around 1 micrometer.

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

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

When the liquid composition of the radiation sensitive composition is applied to a substrate, appropriate coating methods such as spraying, roll coating, spin coating (spin coating), slit die coating, and bar coating can be employed. The coating method and the slit die coating method are preferable.

Prebaking is normally performed combining a reduced pressure drying and heat drying. Drying under reduced pressure is usually carried out until it reaches 0.1 to 1 Torr. In addition, the conditions of heat drying are about 1 to 10 minutes at 70-110 degreeC normally.

The coating thickness is a film thickness after drying, which is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm.

As a light source of radiation used when forming a color filter, for example, a lamp 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, an argon ion laser, YAG Laser light sources, such as a laser, an XeCl excimer laser, and a nitrogen laser, etc. are mentioned, The radiation in which wavelength is 190-450 nm is preferable.

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 hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- Aqueous solutions, such as diazabicyclo- [4.3.0] -5-nonene, are preferable.

An appropriate amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may be added to the alkaline developer. In addition, after alkali development, water washing is normally performed.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle developing method and the like can be applied. As for image development conditions, 5 to 300 second is preferable at normal temperature.

The conditions of the post-baking are usually about 10 to 60 minutes at 180 to 280 ° C.

The film thickness of the pixel thus formed is usually 0.5 to 5.0 m, preferably 1.0 to 3.0 m.

Moreover, as a 2nd method of manufacturing a color filter, the method of obtaining the pixel of each color by the inkjet system is also known. In this method, a partition wall which also serves as a light shielding function is first formed on the surface of the substrate. Next, after discharging the liquid composition of the coloring composition of this invention in which the red coloring agent was disperse | distributed, for example in the formed partition by inkjet apparatus, prebaking is performed and the solvent is evaporated. Subsequently, this coating film is exposed as needed, and then cured by post-baking to form a red pixel pattern.

Subsequently, using the liquid composition of each coloring composition in which the green or blue coloring agent was disperse | distributed, it carried out similarly to the above, and green pixel pattern and blue pixel pattern are formed sequentially on the same board | substrate. Thereby, a color filter in which the three primary color pixel patterns of red, green and blue are arranged on the substrate is obtained. However, in this invention, the order which forms the pixel of each color is not limited to the above.

In addition, the partition wall has not only a light shielding function but also a function for preventing the coloring composition of each color discharged into the compartment from mixing. Thus, the film has a thicker film than the black matrix used in the first method. The film thickness is usually 1-3 micrometers. Therefore, a partition is normally formed using a black radiation sensitive composition.

The substrate and the light source of the radiation used in forming the color filter, and the method and conditions of pre-baking or post-baking are the same as in the first method. In this way, the film thickness of the pixel formed by the inkjet method is about the same as the film thickness of a partition.

The coloring composition of this invention can form the pixel which was very excellent in flatness, without generating an application | coating remainder in a partition by the inkjet system. Moreover, even when hardening only by post-baking, the pixel which has very excellent solvent resistance can be formed. In addition, since the pixel formed by the coloring composition of the present invention has very excellent heat resistance, no deterioration in transparency or color characteristics is seen even when high temperature post-baking is performed. Therefore, the coloring composition of this invention is especially suitable for formation of the colored layer by the inkjet system.

Since the color filter of this invention is excellent in transparency and a color characteristic, it is very useful for a solid-state image sensor, an organic electroluminescence display, an electronic paper, etc. besides a transmissive or reflective color liquid crystal display device.

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 liquid crystal display element provided with the color filter of this invention can take a suitable structure. For example, the color filter is formed on a substrate separate from the driving substrate on which the thin film transistor (TFT) is arranged, and the substrate on which the driving substrate and the color filter are formed has an opposite structure via the liquid crystal layer. The substrate on 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 on which the ITO (indium oxide doped tin) electrode is formed are opposed to each other via a liquid crystal layer. The structure can be taken. The latter structure has the advantage that the aperture ratio can be significantly improved, and a bright and high precision liquid crystal display device is obtained.

Moreover, the organic electroluminescent display element provided with the color filter of this invention can employ | adopt an appropriate 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 employ | adopt an appropriate 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, the present invention is not limited to the following examples.

Preparation of Colorant Dispersion

<Manufacture example 1>

(A) 13.0 parts by mass of CI Pigment Red 254 as a coloring agent, 7.5 parts by mass of Azisper PB880 (manufactured by Ajino Moto Fine Techno Co., Ltd.) as a dispersant, and (E) 1,3-butylene glycol diacetate as a solvent. 79.5 parts by mass were treated with a bead mill to prepare a colorant dispersion (R1).

<Manufacture example 2>

(A) C. I. Pigment Red 254 / C. As colorant. I. Pigment Red 177 / Specific yellow pigment whose guest represented by the formula (II) is melamine = 25/47/28 (mass ratio) 13.0 parts by mass of a mixture, Azisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a dispersant 7.5 mass parts and 79.5 mass parts of 1, 3- butylene glycol diacetates as a (E) solvent were processed by the bead mill, and the coloring agent dispersion liquid (R2) was produced.

<Manufacture example 3>

(A) C. I. Pigment Red 242 / C. As colorant. I. Pigment Red 177 = 40/60 (mass ratio) 13.0 parts by mass of the mixture, 7.5 parts by mass of Azisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a dispersant, and (E) 1,3-butylene as a solvent 79.5 parts by mass of glycol diacetate was treated with a bead mill to prepare a colorant dispersion (R3).

&Lt; Preparation Example 4 &

(A) CI pigment green 58 as a coloring agent / specific yellow pigment whose guest represented by said formula (II) is melamine = 60/40 (mass ratio) 13.0 mass parts of mixtures, Azisper PB881 (Ajinomoto fine techno Kabushiki Kaisha) as a dispersing agent Preparation) 6.9 mass parts and 80.1 mass parts of 1, 3- butylene glycol diacetates as a (E) solvent were processed by the bead mill, and the coloring agent dispersion liquid (G1) was manufactured.

Production Example 5

(A) CI pigment green 36 as a coloring agent / specific yellow pigment whose guest represented by said formula (II) is melamine = 65/35 (mass ratio) 13.0 mass parts of mixtures, Azisper PB881 (Ajinomoto fine techno Kabushiki Kaisha) as a dispersing agent Preparation) 6.9 mass parts and 80.1 mass parts of 1, 3- butylene glycol diacetates as a (E) solvent were processed by the bead mill, and the coloring agent dispersion liquid (G2) was produced.

<Manufacture example 6>

(A) C. I. Pigment Blue 15: 6 / C as colorant. I. Pigment Violet 23 = 83/17 (mass ratio) 12.0 parts by mass of the mixture, 6.8 parts by mass of Azisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a dispersant, and (E) 1,3-butylene as a solvent 81.2 parts by mass of glycol diacetate was treated with a bead mill to prepare a colorant dispersion (B1).

Synthesis of Binder Resin

3 parts by mass of 2,2'-azobisisobutyronitrile and 200 parts by mass of diethylene glycol monobutyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 10 parts by mass of methacrylic acid and N-. 25 parts by mass of phenylmaleimide, 15 parts by mass of styrene, 40 parts by mass of diethylene glycol methyl ether methacrylate (manufactured by Nichi Oil Co., Ltd., product name: Bremermer ^R PME-100), 10 parts by mass of dicyclopentenyl acrylate And 5 parts by mass of α-methylstyrene dimer as a molecular weight regulator were carried out for nitrogen substitution. Thereafter, the mixture was stirred slowly, the temperature of the reaction solution was raised to 80 ° C, and the binder resin solution (solid content concentration = 29.8%) was obtained by maintaining the temperature for 5 hours and polymerizing. Obtained binder resin was Mw = 8,200 and Mn = 3300. This binder resin solution is referred to as "resin solution 1".

&Lt; Example 1 >

(A) 567 mass parts of colorant dispersion liquid (R1) as a coloring agent, (B) Crosslinking agent which has as a main component the compound whose R <^11> -R <^16> of said general formula (b1-4) is a methyl group as a crosslinking agent (The acid and the chemical company make, brand name MW) -30, weight average degree of polymerization 1.3) 25 parts by mass, 7 parts by mass of the reactant of dipentaerythritol pentaacrylate and succinic anhydride, 18 parts by mass of dipentaerythritol hexaacrylate, and (C) resin solution 1 as binder resin 111 parts by mass, manufactured by Ohmova Corp. as a surfactant (D), PF-7002 (in the formula (1-1), R ²¹ and R ²² are CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH _2- , R ²³ and R; 0.9 mass part of ²⁴ -valent methyl groups, surfactant of m + n = 4-5), and 272 mass parts of 1, 3- butylene glycol diacetates as a solvent were mixed, and the coloring composition (IJ-1) was produced.

About the coloring composition (IJ-1), it evaluated by the following points. The evaluation results are shown in Table 2.

Evaluation of color characteristics

After apply | coating a coloring composition (IJ-1) using a spin coater on a soda glass board | substrate, it vacuum-dried at 0.2 Torr, prebaking for 5 minutes on a 90 degreeC hotplate, and also 230 degreeC clean oven. Post-baking was performed within 30 minutes, and the cured film was formed.

About the obtained cured film, chromaticity coordinate value (x, y) and stimulus value (Y) in a CIE colorimeter are measured by a C light source and a 2-degree visual field using a color analyzer (MCPD 2000 manufactured by Otsuka Denshi Co., Ltd.). It was. Moreover, about the obtained cured film, the contrast ratio was measured using the contrast system (CT-1 by Tsubosaka Denki Co., Ltd., blank 20000). In addition, the film thickness of the obtained cured film was measured using the alpha step IQ by KLA-Tencor.

Solvent-resistant  evaluation

The test piece which cut out the glass substrate in which the cured film manufactured by the evaluation of the said color characteristic was formed by the 2 cm x 4 cm side was manufactured. The obtained test piece was immersed in 25 degreeC N-methylpyrrolidone for 30 minutes, and the color change (DELTA) Eab ^* before and behind immersion was calculated | required. Solvent resistance is good if (DELTA) Eab ^* is less than 3, and it can be said that it is very favorable if it is less than 2.5.

Evaluation of heat resistance

The test piece which cut out the glass substrate with a cured film manufactured by the evaluation of the said color characteristic into 2 cm x 4 cm side was manufactured. The obtained test piece was heated in 250 degreeC clean oven for 1 hour, and color change (DELTA) Eab ^* before and behind heating was calculated | required. Heat resistance is good if (DELTA) Eab ^* is less than 5, and it may be said that it is very favorable if it is less than 3.

Pixel Flatness and Coating Diffuse  evaluation

Using a inkjet device Nanoprinter-1500S (manufactured by MicroJet Co., Ltd.), the film thickness after drying was 2.0 in a pixel partitioned by a partition having a height of 2.0 μm, a length of 500 μm, and a width of 150 μm. The coloring composition was discharged so that it became μm. After vacuum drying at 0.2 Torr, prebaking was carried out for 5 minutes on a hot plate at 90 ° C, and post-baking for 30 minutes in a clean oven at 230 ° C. The film thickness of the pixel center part was measured in the width direction and the length direction using (alpha) -step IQ (made by KLA-Tencor).

At this time, (DELTA) H = A- (B + C) / 2 was calculated | required as the maximum value of the film thickness of the width direction, A and the film thickness of both ends of a pixel as B and C. The flatness of a pixel is good if this value is less than 0.60 micrometer, and it can be said that it is very favorable if it is less than 0.40 micrometer.

In addition, the horizontal distance ΔL from the point closest to the end of the pixel with the maximum film thickness in the longitudinal direction was measured. The application | coating diffusivity is good in this value being 50 micrometers or less, and it can be said that it is very favorable in it being 30 micrometers or less.

Evaluation of the viscosity

The viscosity (25 degreeC) of a coloring composition was measured using Tokyo Keiki Co., Ltd. ELD type viscometer.

Evaluation of Surface Tension

The surface tension of the coloring composition was measured using a dynometer (manufactured by BYK-Gardner GmbH).

<Examples 2 to 12, and Comparative Examples 1 to 6>

In Example 1, resin compositions (IJ-2) to (IJ-18) were produced like Example 1 except having changed the kind and quantity of constituent components as shown in Table 1. Each composition is shown in Table 1.

Next, it evaluated like Example 1 except having used resin compositions (IJ-2)-(IJ-18) instead of resin composition (IJ-1), respectively. The evaluation results are shown in Table 2.

Each component in Table 1 is as follows.

MW-30: a crosslinking agent containing a compound in which all of R ¹¹ to R ^{16 in} the formula (b1-4) are methyl groups (acid and chemical company make, trade name MW-30, weight average polymerization degree 1.3)

b2-1: Reaction product of dipentaerythritol pentaacrylate with succinic anhydride

b2-2: dipentaerythritol pentaacrylate

b2-3: dipentaerythritol hexaacrylate

PF-7002: Surfactant wherein R ²¹ and R ²² in formula (1-1) are CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH _2- , R ²³ and R ²⁴ are methyl groups, m + n = 4-5 (Om Nova Corporation make)

F475: fluorine-based surfactant having no hydroxyl group (manufactured by DIC Corporation)

FT-250: Fluorine-type surfactant which does not have a hydroxyl group (made by Neos)

1,3-BGDA: 1,3-butylene glycol diacetate

BCTAC: diethylene glycol mono-n-butyl ether acetate

Claims (7)

A coloring composition containing (A) a coloring agent, (B) crosslinking agent, (C) binder resin, (D) the compound represented by following formula (1), and (E) solvent.
<Formula 1>

(Formula 1, R ²¹ and R ²² independently represent a group having an alkyl fluoride group, R ²³ and R ²⁴ independently represent a methyl group or an ethyl group, X represents a divalent linking group containing no fluorine, m And n independently of each other represent an integer from 1 to 100) The coloring composition according to claim 1, wherein in Formula 1, R ²¹ and R ²² independently of each other have a C 1 to C 4 perfluoroalkyl group. The coloring composition according to claim 1 or 2, wherein m + n in Formula 1 is 2 to 40. The coloring composition according to any one of claims 1 to 3, wherein X in Formula 1 is a divalent hydrocarbon group having 1 to 20 carbon atoms. The coloring composition of any one of Claims 1-4 used for formation of the colored layer by the inkjet system. The color filter provided with the colored layer formed using the coloring composition of any one of Claims 1-5. The display element provided with the color filter of Claim 6.