TWI480689B - Coloring composition, color filter and color liquid crystal display element - Google Patents

Description

Coloring composition, color filter, and color liquid crystal display element

The present invention relates to a coloring composition, a color filter, and a color liquid crystal display element. In particular, it relates to a colored composition which forms a useful colored layer on a color filter for a transmissive or reflective type color liquid crystal display element, a color image tube element, an organic EL display element, an electronic paper or the like. A color filter comprising a coloring layer formed using the coloring composition; and a color liquid crystal display element comprising the color filter.

A method of forming a color filter using a coloring sensitizing radioactive composition, wherein a coating film of a color sensitizing radiation composition is formed on a substrate or a substrate on which a light shielding layer of a desired pattern is formed in advance, and has a pattern The mask is irradiated with radiation (hereinafter referred to as "exposure"), and the unexposed portion is dissolved and removed after development, and then the respective color pixels are obtained by post bake (see, for example, Patent Document 1 and Patent Document 2). Moreover, a method of obtaining each color pixel by an inkjet method using a colored resin composition is also known (see, for example, Patent Document 3).

Conventionally, in the case of forming a coating film of a color sensitizing radioactive composition, a spin coater, a slit, and a spin coater are used. However, in recent years, in order to reduce the liquefaction of the coloring-sensing radioactive composition, and to increase the size of the substrate, a slit die coater using a non-rotating mechanism is mainly used.

For example, in Patent Document 4, a color-sensitive photosensitive resin composition comprising a ruthenium-based surfactant or a fluorine-based surfactant is proposed. However, when a coating film is formed by using a slit die coater, there is a problem in that a coating film around the terminal of the support substrate is damaged by minute irregularities. The conventional colored photosensitive resin composition failed to solve this problem.

On the other hand, in order to meet the demand for high color purity of color liquid crystal display elements in recent years, the content ratio of the coloring agent in the coloring composition tends to be higher. When a coating film is to be formed on a large substrate having a height difference using a related coloring composition, the problem of uneven film thickness of the coating film becomes more remarkable.

Prior technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 2-144502;

Patent Document 2: Japanese Laid-Open Patent No. 3-53201;

Patent Document 3: Japanese Laid-Open Patent Publication No. 2000-310706;

Patent Document 4: Japanese Laid-Open Patent Publication No. 2004-126549.

An object of the present invention is to provide a coloring composition which is formed by using a slit die coater as a coating method, and which does not cause damage by minute irregularities, and can form a flat coating film. Further, a coloring composition is provided which is capable of forming a pixel having excellent flatness even when a pixel having high color purity is formed.

Further, an object of the present invention is to provide a color filter comprising a coloring layer formed of the coloring composition; and a color liquid crystal display element comprising the color filter.

In view of the facts of the present invention, the present inventors have found that the above problems can be solved by including a specific fluorine-based surfactant in the colored composition, and the present invention has been completed.

That is, the present invention provides a coloring composition comprising (A) a colorant, (B) a binder resin, (C) a polyfunctional monomer, and (D) a compound represented by the following formula (1) (hereinafter also referred to as "surfactant (D)"), and the content ratio of the (A) colorant is 20 to 70% by mass in the nonvolatile component.

(In the formula (1), R ¹ to R ⁴ each independently represent C ₆ F ₁₁ -, C ₉ F ₁₇ -, C ₉ F ₁₇ -OC ₆ H ₄ -CO- or a hydrogen atom, but at least 1 of these The line C ₆ F ₁₁ -, C ₉ F ₁₇ - or C ₉ F ₁₇ -OC ₆ H ₄ -CO-, A is independent of each other to indicate an extended ethyl group or a propylene group, and a to d are independent of each other to represent an integer of 0 to 30, but a to d total is 2 to 50, and n is 0 or 1).

Moreover, the present invention provides a color filter comprising a coloring layer formed using the coloring composition, and a color liquid crystal display element comprising the color filter. Here, the "colored layer" means a color pixel, a black matrix, or the like used for a color filter.

The coloring layer formed by using the coloring composition of the present invention is extremely excellent in flatness.

Therefore, the coloring composition of the present invention is extremely suitable for use in color filters for color liquid crystal display elements, color separation color filters for solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. The production of various color filters led by the light sheet.

Embodiment of the invention

Hereinafter, the present invention will be described in detail.

Coloring composition

Hereinafter, the constituent components of the colored composition of the present invention will be described.

- (A) colorant -

The coloring agent (A) in the present invention is not particularly limited as long as it has coloring property, and the color or material can be appropriately selected in accordance with the use of a color filter or the like. Specifically, any pigment, dye, and natural pigment can be used as a coloring agent. However, organic pigments and inorganic pigments are preferred because of the heat resistance of the color filter.

As the organic pigment, for example, a compound classified as a pigment in a color index (C.I.; issued by The Society of Dyers and Colourists) can be cited. Specifically, a color indexer named as follows can be cited.

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 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 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 Red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 1 70, 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, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 262, CI Pigment Red 264, CI Pigment Red 272; CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI pigment purple 38; CI pigment blue 15, CI pigment blue 15:3, CI pigment blue 15:4, CI pigment blue 15:6, CI pigment blue 60, CI pigment blue 80; CI pigment green 7, CI pigment Green 36, CI Pigment Green 58; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, CI Pigment Black 7.

In the present invention, the organic pigment can be purified by a recrystallization method, a reprecipitation solvent washing method, a sublimation method, a vacuum heating method, or the like.

Further, examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, chrome yellow, zinc yellow, and iron oxide red (red iron oxide (III)). ), cadmium red, ultramarine, indigo, chrome oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black, and the like.

These colorants may also be modified with a polymer whose surface is modified by a polymer as desired. For example, a polymer described in Japanese Laid-Open Patent Publication No. Hei 8-259876, or a commercially available polymer or oligomer for pigment dispersion can be used. As a method of coating the surface of the carbon black, a method described in, for example, JP-A-H09-71733, JP-A-9-95625, JP-A-9-124969, and the like can be employed.

In the present invention, the coloring agent (A) may be used singly or in combination of two or more kinds.

When the coloring composition of the present invention is used to form a pixel, it is preferable to use a coloring agent having a high coloring property as the (A) coloring agent because of the high fine coloring of the pixel. Specifically, it is preferred to use an organic pigment. When forming a red pixel, it is preferable to use at least one group selected from the group consisting of CI Pigment Red 254 and CI Pigment Red 177; when forming a green pixel, in particular, at least one selected from the group consisting of CI Pigment Green 7, CI Pigment Green The group of 36 and CI Pigment Green 58 is preferred; when forming blue pixels, it is preferable to use CI Pigment Blue 15:6.

On the other hand, when the coloring composition of the present invention is used for the formation of a black matrix, it is preferable to use an organic pigment or carbon black as the (A) coloring agent because of the light shielding property of the black matrix.

In the present invention, the content ratio of the (A) coloring agent is 20 to 70% by mass in the nonvolatile content. The non-volatile component is a component that removes a volatile component of a solvent as a main component, and the total mass thereof can be measured by, for example, heating and drying the colored composition. The heating temperature at the time of heating and drying the colored composition can be appropriately set in consideration of the boiling point of the solvent or the decomposition temperature of the components (B) to (E) described below.

In general, when forming each color pixel, it will be close to the NTSC specification of the CRT standard color reproduction field (red: x=0.670, y=0.330/green: x=0.210, y=0.710/blue: x=0.140, y=0.080) ) or sRGB specification (red: x = 0.640, y = 0.330 / green: x = 0.300, y = 0.60 / blue: x = 0.150, y = 0.060) after chromaticity after baking, achieving 1.0 μm ~ 3.0 μm The film thickness is preferred. In this case, the content ratio of the (A) coloring agent is preferably 25% by mass or more based on the nonvolatile content, and particularly preferably 30% by mass or more. Further, when a black matrix is formed, an OD value (optical density) of 3.5 to 4.0 / μm is preferably obtained after post-baking to a film thickness of 1.0 μm. In this case, the content ratio of the coloring agent (A) in the black coloring composition is preferably 40% by mass or more based on the nonvolatile content. When the content ratio of the (A) coloring agent is too small, the thickness of the film must be increased when the pixel or the black matrix is to be formed. Therefore, it is difficult to form a coloring layer having excellent flatness on a large substrate. According to the coloring composition of the present invention, even when the content ratio of the coloring agent (A) is high, a coloring layer excellent in flatness can be formed on a large substrate. On the other hand, if the content ratio of the (A) coloring agent is too large, it is difficult to ensure the development of the image forming property. In view of the fact that the image forming property is further improved, the content ratio of the (A) coloring agent is preferably 60% by mass or less based on the solid content.

The coloring agent in the present invention can be used together with a dispersing agent and a dispersing aid as needed. A suitable dispersing agent such as a cationic system, an anionic system, or a nonionic system can be used, and a polymer dispersant is preferred. Specific examples thereof include an acrylic copolymer, a polyurethane, a polyester, a polyethyleneimine, and a polyalylamine.

Such dispersants are commercially available, and for example, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (hereinafter, BYK-Chemie GmbH) (BYK) as an acrylic copolymer )Company system); Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, BYK), Solsperse76500 (Lubricol) Group (The Lubrizol Corporation); Solsperse 24000 (made by Lubrizol Group) as polyethyleneimine; Ajisper-PB821, Ajisper-PB822, Ajisper-PB880, Ajisper-PB881 (Ajinomoto) Ajinomoto Fine-Techno Co., Inc., etc.).

These dispersing agents may be used singly or in combination of two or more kinds. The content of the dispersant is usually 100 parts by mass or less, preferably 1 to 70 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the (A) colorant. When the content of the dispersing agent is too large, the developing property or the like is impaired.

The above-mentioned dispersing aid may, for example, be a pigment derivative. Specific examples thereof include copper phthalocyanine (CuPC), diketopyrrolopyrrole, and a sulfonic acid derivative of quinophthalone.

In addition, by using the aromatic carboxylic acid-based compound proposed in JP-A-2010-14961 together with the dispersing agent and the dispersing aid, the storage stability of the colored composition can be further improved.

- (B) Adhesive Resin -

The (B) binder resin which is the present invention is not particularly limited, but is preferably an acid functional group resin having a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as "carboxy group-containing polymer") is preferable, and particularly an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (b1)") and A copolymer of other ethylenically unsaturated monomers (hereinafter referred to as "unsaturated monomers (b2)") which may be copolymerized is preferred.

As the above unsaturated monomer (b1), (meth)acrylic acid, maleic acid, maleic anhydride, mono [2-(meth)acrylic acid ethyl] succinate, ω-carboxypoly Indoleamine mono(meth)acrylate and the like. These unsaturated monomers (b1) may be used singly or in combination of two or more kinds.

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

Further, as the unsaturated monomer (b2), for example, an N-position substituted horse of N-phenylmaleimide N-cyclohexylmaleimide may be mentioned. Anthranil; such as styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ester, aromatic vinyl compound of acenaphthylene; (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (methyl) Acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ]decane-8-yl (methyl ) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, p-cumyl phenol, ethylene oxide denatured (meth) acrylate, shrinkage Glycerol (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(methyl) propylene fluorenylmethyl] propylene oxide, 3-[(meth) propylene An unsaturated carboxylic acid ester of mercaptomethyl]-3-ethyl propylene oxide; such as polyphenylene Ethylene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, polymer polymer chain ends with a single (meth) acrylonitrile group Body and so on.

These unsaturated monomers (b2) may be used alone or in combination of two or more.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) are disclosed in, for example, JP-A-7-140654, JP-A-8-259876, and JP-A 10 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

In the present invention, it is also possible to use, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. 5-19467, No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain such as JP-A-2008-181095 is used as a binder resin.

The polyethylene-converted weight average molecular weight (hereinafter also referred to as "Mw") measured by a gel permeation chromatography (GPC; elution solvent: tetrahydrofuran) in the present invention is usually 1,000 to 50,000, and is 3,000 to 30,000. It is better. When the Mw is too small, the obtained film residual film ratio or the like is lowered, or the pattern shape, heat resistance, and the like are impaired, and the electrical characteristics are deteriorated. On the other hand, when the film is too large, the resolution is lowered, or the pattern shape is impaired, and the slit is formed by the slit. When the die coater is applied by a nozzle, it is likely to cause dry foreign matter.

Further, the ratio of the Mw of the binder resin in the present invention to the polyethylene-converted number average molecular weight (hereinafter also referred to as "Mn") measured by a gel permeation chromatography (GPC; elution solvent: tetrahydrofuran) (Mw/Mn) It is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0.

The binder resin in the present invention can be produced by a conventional method, but can also be disclosed in, for example, Japanese Laid-Open Patent Publication No. 2003-222717, JP-A-2006-259680, and International Publication No. 07/029871. Etc., control its structure or Mw, Mw / Mn.

The binder resin in the present invention may be used singly or in combination of two or more kinds.

The content of the binder resin in the present invention is usually 10 to 1,000 parts by mass, and preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. When the content of the binder resin is too small, for example, the alkali developability is lowered, or the storage stability of the resulting colored composition is lowered. On the other hand, when the amount is too large, the concentration of the colorant is relatively lowered, and it is difficult to achieve a desired color concentration of the film.

-(C) polyfunctional monomer -

The (C) polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.

As such a polyfunctional monomer, for example, a di(meth)acrylate such as ethylene glycol or a propylene glycol alkylene glycol; a polyalkylene glycol such as polyethylene glycol or polypropylene glycol Di(meth)acrylate; poly(methyl) of a trivalent or higher polyvalent alcohol such as glycerin, trimethylolpropane, pentalinerhritol, dipentaerithritol An acrylate or a dicarboxylic acid denature thereof; such as a polyester, an epoxy resin, a polyurethane resin, an alkyd resin, an anthracene resin, an oligo (meth) acrylate of a spiran resin; a terminal (hydroxy) poly-1,3-butadiene, a bis(meth) acrylate of a hydroxyl polymer at both ends of the terminal hydroxypolyisoprene; having a (meth) acrylate having a hydroxyl group and a polyfunctional Poly(meth)acrylate having an amine ester structure obtained by a cyanic acid reaction; poly(meth)acrylic acid having a caprolactam structure described in paragraphs [0015] to [0018] of JP-A-11-44955 Ester; tris[2-(meth)acrylic acid ethyl]phosphate, ethylene oxide isocyanurate denatured triacrylate, etc.

Among these polyfunctional monomers, a poly(meth)acrylate of a polyvalent alcohol having a trivalent or higher value or a dicarboxylic acid denatured product thereof, a poly(meth)acrylate having an amine ester structure, and A poly(meth)acrylate having a caprolactam structure is preferred. As a poly(meth) acrylate of a polyvalent alcohol having a valence of 3 or more or a dicarboxylic acid denatured product thereof, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, new Pentaerythritol triacrylate, neopentyl alcohol trimethacrylate, neopentyl alcohol tetraacrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl alcohol triacrylate and monoester of succinic acid, pentaerythritol trimethacrylate a monoester of succinic acid, a monoester of dipentaerythritol pentaacrylate and succinic acid, a monoester of dipentaerythritol pentamethyl acrylate and succinic acid, particularly trimethylolpropane Triacrylate, neopentyl alcohol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, neopentyl alcohol triacrylate and monoester of succinic acid and dipentaerythritol a monoester of pentaacrylate and succinic acid, because of the high strength of the colored layer, the surface of the colored layer Excellent smoothness, ink (greasing) of the upper portion of the substrate and the light-shielding layer and not exposed, and so easy to produce the film residue preferred.

These polyfunctional monomers may be used singly or in combination of two or more kinds.

The content of the (C) polyfunctional monomer in the present invention is preferably 5 to 500 parts by mass, particularly preferably 20 to 300 parts by mass, per 100 parts by mass of the (B) binder resin. In this case, when the content of the polyfunctional monomer is too small, sufficient curing property may not be obtained. On the other hand, when the content of the polyfunctional monomer is too large, when the coloring composition of the present invention is provided with alkali developability, the alkali is used. The developing property is lowered, and ink or film residue on the unexposed portion or on the light shielding layer tends to be easily generated.

Further, in the present invention, a part of the polyfunctional monomer may be substituted with a monofunctional monomer having one polymerizable unsaturated bond.

The monofunctional monomer may, for example, be a monovalent [2-(meth)acrylic acid ethyl] succinate or a mono [2-(meth)acrylic acid ethyl] phthalate. Mono[(meth)acrylic acid alkyl]ester of a polyvalent carboxylic acid; such as mono(meth)acrylic acid having a polymer of a carboxyl group and a hydroxyl group at both ends of ω-carboxypolycaprolactam mono(meth)acrylate M-5600 (trade name; manufactured by Toagosei Co., Ltd.), which is a commercial product, other than N-(methyl) propylene decylmorpholine, N-vinylpyrrolidone, and N-vinyl-ε-caprolactam. Wait.

These monofunctional monomers may be used singly or in combination of two or more kinds.

The content ratio of the monofunctional monomer in the present invention is preferably 90% by mass or less, and more preferably 50% by mass or less based on the total of the polyfunctional monomer and the monofunctional monomer. At this time, when the ratio of use of the monofunctional monomer is too large, the curability tends to be lowered.

- surfactant (D) -

The compound represented by the above formula (1), that is, the surfactant (D), is a component having a surfactant function in the coloring composition of the present invention. The colored composition of the present invention can form a coloring layer excellent in flatness by containing the specific surfactant. Specific examples of the surfactant (D) include compounds represented by the following formulas.

(Formula (1-1) to (1-4), R ¹ ~ R ⁴ and lines with a ~ d of formula (R 1) in the ¹ ~ R ⁴ synonymous and a ~ d).

In the above formula (1), R ¹ to R ⁴ are preferably at least two of C ₆ F ₁₁ -, C ₉ F ₁₇ - or C ₉ F ₁₇ -OC ₆ H ₄ -CO-, particularly R ¹ - All of R ⁴ is preferably C ₆ F ₁₁ -, C ₉ F ₁₇ - or C ₉ F ₁₇ -OC ₆ H ₄ -CO-. The C ₆ F ₁₁ -, C ₉ F ₁₇ - is a residue derived from a dimer or a trimer of hexafluoropropylene, and examples thereof include a structure represented by the following formula.

(In the above formula, "*" indicates the key).

In the present invention, R ¹ to R ^{4 are} preferably C ₉ F ₁₇ -.

Further, in the above formula (1), A represents an exoethyl group or a propyl group, and any one of a to d is 2 or more, that is, any of (AO) _a to (AO) _d forms a polyalkylene oxide. In the case of a (polyoxyalkylene) bond, the oxyalkylene bond may contain both a vinyl group and a propylene group.

Further, in the above formula (1), the total of a to d is preferably 5 to 30, particularly preferably 8 to 18.

The method for producing the surfactant (D) is not particularly limited, and it can be produced, for example, according to the method described in JP-A-4-145041.

The content of the surfactant (D) in the colored composition of the present invention is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the (B) binder resin. By including the surfactant (D) in such a range, even if the slit die coating method is employed as the coating method, the flatness of the colored layer is extremely excellent.

In the present invention, as the surfactant, a conventional fluorine-based surfactant other than the surfactant (D), a lanthanoid surfactant, or the like may be used together with the surfactant (D).

-(E) Photopolymerization Initiator -

In the colored composition of the present invention, by containing a photopolymerization initiator, it is possible to impart a radiation-sensitivity to the colored composition. Here, "radiation" means including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, and the like.

The (E) photopolymerization initiator used in the present invention is a compound which is exposed to radiation of visible light, ultraviolet rays, far ultraviolet rays, electron rays, X-rays or the like to produce the above (C) polyfunctional monomer and The active species from which the polymerization of the monofunctional monomer used can be initiated.

Examples of such a photopolymerization initiator include a thioxanthone-based compound, an acetophenone-based compound, a biimidazole-based compound, and three. (triazine)-based compound, O-acyloxime-based compound, onium salt-based compound, benzoin-based compound, diphenylketone-based compound, α-diketene-based compound, multinuclear An anthraquinone compound, a diazo compound, a sulfoxide compound, or the like.

In the present invention, the photopolymerization initiator may be used singly or in combination of two or more kinds. As the photopolymerization initiator, at least one selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three A group of a compound or an O-mercapto lanthanide compound is preferred.

Among the preferred photopolymerization initiators in the present invention, specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxene. Ketone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Ketyl ketone and the like.

Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinan-1-one and 2-benzyl- 2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholine Phenyl) butan-1-one and the like.

Further, specific examples of the above bisimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole. , 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis (2,4 , 6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, and the like.

Further, when the bisimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor to improve the sensitivity. Here, the "hydrogen donor" means a compound which can supply a hydrogen atom to a group derived from a bisimidazole compound by exposure. As the hydrogen donor, for example, 2-sulfhydrylbenzothiazole or 2-sulfhydrylbenzone can be cited. a thiol-based hydrogen donor such as azole; an amine-based hydrogen supply such as 4,4'-bis(dimethylamino)diphenyl ketone or 4,4'-bis(diethylamino)diphenyl ketone Subject. In the present invention, the hydrogen donors may be used singly or in combination of two or more kinds, and one or more types of thiol-based hydrogen donors and one or more amine-based hydrogen donors may be used in combination to further improve the sensitivity. good.

Again, as the above three Specific examples of the compound include 2,4,6-tris(trichloromethyl)-s-three. 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three , 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three Three of the halogenated methyl groups a compound.

Further, specific examples of the O-indenyl lanthanide compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, and 2-(O-benzamide). , Ethyl Ketone, 1-[9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetamidine), Ethyl Ketone, 1 -[9-ethyl-6-(2-methyl-4-(2,2-dimethyl-1,3-dioxalyl)methoxybenzylidene]-9H-carbazole-3 -yl-, 1-(O-acetamidine) and the like.

In the present invention, when a photopolymerization initiator other than a bisimidazole compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. Examples of the sensitizer include 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, and 4-diethylamino acetophenone. , 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene) Cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone, and the like.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the (C) polyfunctional monomer. In this case, when the content of the photopolymerization initiator is too small, the curing by exposure is insufficient. On the other hand, when the amount is too large, the formed color layer tends to fall off from the substrate during development.

- solvent -

The colored composition of the present invention is usually prepared by mixing a solvent to form a liquid composition. As the above solvent, it is possible to appropriately disperse or dissolve the other components such as (A) to (D) or (E) components constituting the colored composition, and do not react with the components, and have moderate volatility. use.

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and Ethylene 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 single Ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol single (poly)alkylene glycol monoalkyl ethers such as methyl ether, tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether Acid ester, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl (poly)alkyl glycol monoalkyl ether acetates such as diacetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Class; methyl ethyl ketone, cyclohexanone, 2-heptanone, a ketone such as 3-heptanone; a diacetate such as propylene glycol diacetate, 1,3-butanediol diacetate or 1,6-hexanediol diacetate; methyl lactate or lactic acid Ethyl lactate such as ethyl ester; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl ester, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl Propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amylformate, i- Amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, pyruvic acid Other esters such as ethyl ester, n-propylpyruvate, methyl acetonitrile, ethyl acetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; A guanamine or an indoleamine such as N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether B are used in terms of solubility, pigment dispersibility, and coating properties. Acid ester, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butane Alcohol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ester, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amylformate, i-pentyl acetate, Preferably, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate or the like.

These solvents may be used singly or in combination of two or more kinds.

Further, together with the above solvent, benzyl ether, di-n-hexyl ether, acetoacetone, isophorone, caproic acid, eranidic acid, 1-octanol, 1-nonanol, benzyl b may be used in combination. High-boiling solvent of acid ester, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate .

The content of the solvent is not particularly limited. The total concentration of each component of the solvent-removing component of the composition is preferably from 5 to 50% by mass, particularly preferably from 10 to 40% by mass, from the viewpoints of coatability and stability of the obtained coloring composition. the amount.

-additive-

The coloring composition of the present invention may contain various additives as necessary.

Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); vinyl trimethoxy decane or vinyl triethoxy decane; Vinyl tris(2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxy Baseline, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropene a adhesion promoter such as methoxypropyltrimethoxydecane or 3-hydrothiopropyltrimethoxydecane; 2,2-thiobis(4-methyl-6-t-butylphenol), An antioxidant such as 2,6-di-t-butylphenol; 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, alkoxy Ultraviolet absorbers such as phenyl ketones; anti-agglomerating agents such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and Zhongkang , 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4 - a residue improving agent such as amino-1,2-butanediol or the like.

In the present invention, the colored composition can be prepared by an appropriate method, and can be prepared, for example, by mixing the components (A) to (D) with a solvent or any other component added arbitrarily. As a preparation method of a preferred coloring composition, the (A) coloring agent may be used in the presence of a solvent or a dispersing agent, and, for example, a part of the component (B) may be used, for example, powder polishing or roller polishing. The pulverized mixed dispersion is used as a colorant dispersion. Next, a preparation method of mixing the components (B) to (D) and, if necessary, further adding a solvent or other components to the colorant dispersion is added.

Color filter and manufacturing method thereof

The color filter of the present invention is provided with a coloring layer formed of the colored composition of the present invention.

As a method of producing a color filter, the following methods are first mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate, if necessary, by forming a partial division of the pixels. Next, on the substrate, for example, a liquid composition of the color-sensitive radiation composition of the present invention in which a red coloring agent is dispersed is applied, and then pre-baked to evaporate the solvent to form a coating film. Next, after the coating film was exposed through a photomask, an alkali developing solution was used for development to dissolve and remove the unexposed portion of the coating film. Thereafter, by post-baking, a pixel array in which the red pixel patterns are arranged in a certain order is formed.

Next, the liquid composition of each of the coloring radiation-releasing compositions of the green or blue coloring agent is dispersed, and the coating, pre-baking, exposure, development, and post-baking of each liquid composition are performed as described above. A green pixel array and a blue pixel array are sequentially formed on the same substrate. Thereby, a color filter in which three primary color pixel arrays of red, green, and blue are arranged on the substrate can be obtained. However, in the present invention, the order in which the respective color pixels are formed is not limited to the above.

Further, the black matrix can be formed by a photolithography method in which a metal thin film such as chromium or the like which is formed by sputtering or evaporation is formed into a desired pattern. However, it is also possible to form a color-sensing radiation linear composition in which a black colorant is dispersed, in the same manner as in the case of forming the above-mentioned pixel. The height difference between the black matrix and the substrate of the metal thin film is usually 0.1 to 0.2 μm, but the difference between the resin black matrix formed by using the black radiation-sensitive composition and the substrate is 1 μm. According to the color-sensing radiation composition of the present invention, even on a substrate having a high difference in height of the resin black matrix, a pixel having excellent flatness can be formed.

Examples of the substrate used for forming the pixel and/or the black matrix include glass, ruthenium, polycarbonate, polyester, aromatic polyamine, polyamidamine, polyamine, and the like.

Further, for these substrates, an appropriate pretreatment such as a drug treatment such as a decane coupling agent, a plasma treatment, an ion deposition, a sputtering, a gas phase reaction method, or a vacuum evaporation may be applied as desired.

When the liquid composition of the coloring radiation-sensitive composition is applied to the substrate, a suitable coating method such as a spray method, a roll coating method, a spin coating method, a slit die coating method, or a rod coating method can be employed. However, it is preferable to use a slit die coating method in particular.

The coating thickness and the film thickness after drying are usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm.

As the radiation used for forming the pixels and/or the black matrix, for example, visible light, ultraviolet light, far ultraviolet light, electron light, X-ray, or the like can be used. However, it is preferred to use radiation in the wavelength range of 190 to 450 nm.

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

Further, as the above-mentioned alkali developing solution, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diindole bicyclo-[5.4.0]-7- eleven An aqueous solution of carbene or 1,5-diindole bicyclo-[4.3.0]-5-nonene is preferred.

A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkali developing solution in an appropriate amount. Further, after alkali development, it is usually washed with water.

As the development processing method, a shower imaging method, a spray imaging method, an immersion imaging method, a paddle (liquid) development method, or the like can be applied. The development condition is preferably 5 to 300 seconds at normal temperature.

Moreover, as a second method of producing a color filter, a method of obtaining each color pixel by an inkjet method, such as Japanese Laid-Open Patent Publication No. Hei 7-318723, and No. 2000-310706, is also known.

The color filter of the present invention thus obtained is excellent in flatness of a colored layer, and is extremely useful for a color liquid crystal display element, a color image tube element, a color sensor, an organic EL display element, an electronic paper, or the like.

Color liquid crystal display element

The color liquid crystal display element of the present invention is provided with the color filter of the present invention.

The color liquid crystal display element of the present invention can be suitably constructed. For example, the color filter is formed on a substrate other than the substrate for driving the thin film transistor (TFT), and the substrate for driving and the substrate on which the color filter is formed can be in a facing structure via the liquid crystal layer. Further, the substrate on which the color filter is formed on the surface of the substrate for driving the thin film transistor (TFT) and the substrate on which the ITO (tin-doped indium oxide) electrode is formed may also have an opposite structure via the liquid crystal layer. The latter structure can particularly improve the aperture ratio and has the advantage of obtaining a bright, high-definition liquid crystal display element.

Hereinafter, embodiments of the present invention will be further specifically described by way of examples. However, the invention is not limited to the following examples.

Synthesis of surfactant (D)

The following compounds were synthesized according to the method described in JP-A-4-145041.

Surfactant (D-1): In the above formula (1-3), R ¹ to R ⁴ are each a compound in which C ₉ F ₁₇ - and a to d are 5 in total.

Surfactant (D-2): In the above formula (1-3), R ¹ to R ⁴ are each a compound in which C ₉ F ₁₇ - and a to d are 8 in total.

Surfactant (D-3): In the above formula (1-3), R ¹ to R ⁴ are each a compound in which C ₉ F ₁₇ - and a to d are 12 in total.

Surfactant (D-4): In the above formula (1-3), R ¹ to R ⁴ are each a compound in which C ₉ F ₁₇ - and a to d are 18 in total.

Surfactant (D-5): In the above formula (1-1), R ¹ to R ³ are each a compound in which C ₉ F ₁₇ - and a to c are 24 in total.

Surfactant (D-6): In the above formula (1-3), R ¹ to R ⁴ are each a compound in which C ₉ F ₁₇ - and a to d are 30 in total.

Modulation of colorant dispersion

Modulation example 1

Ajisper-PB821 (manufactured by Ajinomoto Fine Technology Co., Ltd.) 4 as a dispersing agent, using 12 parts by mass of a mixture of a mixture of a color of a color of a color of a mixture of a color of a color of The mass fraction of propylene glycol monomethyl ether acetate as a solvent was adjusted to have a solid content of 16% by mass, and dispersed by powder grinding for 12 hours to prepare a colorant dispersion (A-1).

Modulation example 2

11 parts by mass of a 60/40 (mass ratio) mixture of CI Pigment Green 36 and CI Pigment Yellow 150 as (A) colorant, and BYK-LPN21116 (manufactured by BYK) 2 as a dispersing agent 2 parts by mass of Ajisper-PB880 (manufactured by Ajinomoto Fine Chemical Co., Ltd.), propylene glycol monomethyl ether acetate as a solvent, and a solid content concentration of 15% by mass, and by mass The mixture was mixed by grinding for 12 hours to prepare a colorant dispersion (A-2).

Modulation example 3

Using 10 parts by mass of a mixture of CI Pigment Blue 15:6 and CI Pigment Violet 23 as a dispersant, Disperbyk-2000 (by BYK) 2 parts by mass (solid content conversion) and BYK-LPN21324 (by BYK) 2 parts by mass (solid content conversion), as solvent propylene glycol monomethyl ether acetate, the solid concentration is 14 mass %, and dispersed by powder milling for 12 hours to prepare a colorant dispersion (A-3).

Modulation example 4

Ajisper-PB821 (Ajinomoto) used as a dispersing agent for CI Pigment Red 254/CI Pigment Red 177/CI Pigment Yellow 139=50/35/15 (mass ratio) mixture as (A) colorant 6.0 parts by mass of 1,3-butanediol diacetate as a solvent, the solid content concentration was 19.5% by mass, and was mixed and dispersed by powder grinding for 12 hours to prepare a colorant dispersion. (A-4).

Modulation example 5

By using 15 parts by mass of a 50/50 (mass ratio) mixture of CI Pigment Green 36 and CI Pigment Yellow 150 as (A) colorant, BYK-LPN21116 (manufactured by BYK) 3 as a dispersing agent 3 parts by mass of Ajisper-PB880 (manufactured by Ajinomoto Fine Chemical Co., Ltd.), and 1,3-butanediol diacetate as a solvent to have a solid content concentration of 21% by mass, and The colorant dispersion (A-5) was prepared by mixing and dispersing for 12 hours by powder milling.

Modulation example 6

Disperbyk-2000 (by BYK), which is a dispersant of 12 parts by mass of a mixture of CI Pigment Blue 15:6 and CI Pigment Violet 23 as a dispersant (A) 3 parts by mass (solid content conversion) and BYK-LPN21324 (manufactured by BYK) 3 parts by mass (solid content conversion), 1,3-butanediol diacetate as a solvent to form a solid fraction The concentration was 18% by mass, and the colorant dispersion (A-6) was prepared by mixing and dispersing for 12 hours by powder milling.

Modulation example 7

13 parts by mass of CI pigment green 58 as (A) coloring agent, and 4 parts by mass (solid content conversion) of BYK-LPN21116 (manufactured by BYK) as a dispersing agent, and propylene glycol single as a solvent The methyl ether acetate had a solid content concentration of 17% by mass, and was mixed and dispersed by powder grinding for 12 hours to prepare a colorant dispersion (A-7).

Modulation example 8

As a dispersing agent, BYK-LPN21116 (manufactured by BYK Co., Ltd.) 4 using a mixture of CI pigment green 58 as a coloring agent (A) and an 80/20 (mass ratio) mixture of CI pigment yellow 150 The mass fraction (solid fraction conversion) was used as a solvent of propylene glycol monomethyl ether acetate to have a solid content concentration of 17% by mass, and was mixed and dispersed by powder grinding for 12 hours to prepare a colorant dispersion (A-8).

(B) Synthesis of binder resin

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 2 parts by mass of 2,2'-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate were charged, followed by charging 15 parts by mass of methacrylic acid and N-benzene. 20 parts by mass of kamalimide, 55 parts by mass of benzyl methacrylate, 10 parts by mass of styrene, and 2,4-diphenyl-4-methyl-1-pentene as a molecular weight regulator ( 3 parts by mass of a product manufactured by Nippon Oil & Fat Co., Ltd.; trade name: Novumma-MSD, and substituted with nitrogen. Thereafter, the mixture was slowly stirred, the temperature of the reaction solution was raised to 80 ° C, and polymerization was carried out by maintaining the temperature for 5 hours to obtain a binder resin solution (solid content concentration = 32.3% by weight). The obtained binder resin was Mw = 16,000 and Mn = 7,000. This binder resin is used as "adhesive resin (B-1)".

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 136 parts by mass of propylene glycol monomethyl ether acetate was charged, and nitrogen gas was injected while heating to 80 °C. 20 parts by mass of methacrylic acid, 12 parts by mass of N-phenylmaleimide, 5 parts by mass of benzyl methacrylate, 10 parts by mass of styrene, 2-hydroxyethyl methacrylate at the same temperature 15 parts by mass and 38 parts by mass of 2-ethylhexyl methacrylate dissolved in 40 parts by mass of propylene glycol monomethyl ether acetate, and 6 parts by mass of 2,2-azobisisobutyronitrile dissolved in propylene glycol A solution of 24 parts by mass of methyl ether acetate was added dropwise at 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and polymerization was carried out by maintaining the temperature for 1 hour to obtain a binder resin solution (solid content concentration = 33.0% by weight). The obtained binder resin was Mw = 11,000 and Mn = 6,000. This binder resin is referred to as "binder resin (B-2)".

Example 1

Modulation of coloring radiation composition

100 parts by mass of the (A) colorant dispersion (A-1), and 10 parts by mass of the binder resin (B-1) of the (B) binder resin (solid content conversion), as (C) polyfunctional 15 parts by mass of the divalent pentaerythritol hexaacrylate, 0.05 parts by mass of the surfactant (D-1), and 2-benzyl-2-dimethylamino group as the (E) photopolymerization initiator - 4 parts by mass of 1-(4-morpholinyl)butan-1-one and 1 part by mass of 4,4'-bis(diethylamino)diphenyl ketone, and propylene glycol monomethyl ether B as a solvent The acid ester was mixed at a solid concentration of 15% by mass to prepare a liquid composition (S-1). The liquid composition (S-1) was weighed on an aluminum pan and heated on a hot plate at 180 ° C for 1 hour. The concentration of the nonvolatile component was measured by measuring the weight before and after heating, and the concentration of the nonvolatile component was 14.8% by mass. In the liquid composition (S-1), the content ratio of the coloring agent in the nonvolatile matter was 26% by mass.

The liquid composition (S-1) was evaluated in the following order. The evaluation results are shown in Table 1.

Appearance evaluation of the film

The liquid composition (S-1) prepared above was applied onto a 550×650 mm chromium film-forming glass using a slit die coater (manufactured by Tokyo Ohka Kogyo Co., Ltd.; form “TR632105-CL”). The arrival pressure was set to 100 Pa, and the solvent was removed by vacuum drying, and further baked at 80 ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm.

For this coating film, the occurrence state of the damage of the pre-bake Procci needle was visually evaluated under a sodium lamp. When the damage was almost no damage, the appearance of the coating film was "excellent", and when the damage was slightly observed, the appearance was "good", and when the damage was clearly visible, the appearance was "poor".

Evaluation of film thickness uniformity of coating film

In the above-mentioned "Appearance Evaluation of Coating Film", the 550 × 650 mm chromium film-forming glass is replaced with the 550 × 650 mm alkali-free glass which is formed into a resin black matrix having a thickness of 1 μm, and is the same as the "Appearance Evaluation of the Coating Film". A coating film is formed on the substrate. With respect to this coating film, the film thickness was measured at the measurement point at 20 o'clock, and the film thickness uniformity was calculated from the following formula.

Film thickness uniformity (%) = (maximum value of coating film thickness - minimum value) × 100 / ((average coating film thickness of 20 points) × 2) When the coating film thickness uniformity calculated by this is 1% or less, It can be said that the film thickness uniformity is good.

Moreover, the above 20 point measurement points are as follows. In other words, the inner region (450 × 550 mm) in the range of 50 mm from the end portions of the long side and the short side of the substrate (550 × 650 mm) is removed as a measurement region in which the long side direction and the short side direction are in a straight line. 10 points (20 points in total) were set at 40 mm apart, and the measurement points were used as such.

Examples 2 to 13 and Comparative Examples 1 to 9

In the first embodiment, the type and amount of the colorant dispersion, the binder resin, the polyfunctional monomer, and the surfactant were changed as shown in Table 1, and the liquid composition (S-2) was prepared in the same manner as in Example 1. )~(S-22).

Next, the evaluation was carried out in the same manner as in Example 1 except that the liquid compositions (S-1) were used instead of the liquid compositions (S-2) to (S-22). The results are shown in Table 1. Further, the following coating films were respectively formed and evaluated: in Comparative Example 5, the film thickness of the same color gradation x as that of the coating film formed in Example 3; and Comparative Example 6, the same chromaticity y as the coating film formed in Example 7. The thickness of the film was the same as that of the coating film formed in Example 8 in Comparative Example 7.

In Table 1, each component is as follows.

D-1: a commercially available fluorine-based surfactant (manufactured by Dainippon Ink and Chemicals Co., Ltd.; trade name: Megafac R08);

D-2: commercially available lanthanide surfactant (manufactured by Toray Dow Corning Co., Ltd.; trade name: SH8400);

In addition, the "colorant concentration" in Table 1 means the content ratio (% by mass) in the nonvolatile component of the colorant.

Example 14

Inkjet ink modulation

(A) 545 parts by mass of the colorant dispersion (A-4), and (B) 19 parts by mass of the binder resin (B-2) of the binder resin (solid content conversion), as (C) polyfunctional 78 parts by mass of dipentaerythritol hexaacrylate, 0.15 parts by mass of surfactant (D-3), and 310 parts by mass of 1,3-butanediol diacetate as (E) solvent Mix and modulate inkjet inks.

Evaluation of pixel flatness

The inkjet device Nanoprinter-1500S (manufactured by Microjet Co., Ltd.) was used to form a film having a height of 2.0 μm, a length of 500 μm, and a width of 150 μm, and the film thickness near the center of the pixel after drying was 2.0 μm, the inkjet ink prepared as described above was sprayed. The thickness of the central portion of the pixel was measured in the width direction by using α-step IQ (manufactured by KLA Tencor Co., Ltd.), and it was confirmed that the flatness of the pixel was good.

Examples 15 to 16

In the same manner as in Example 14, except that the colorant dispersion (A-4) was changed to the colorant dispersion (A-5) or the colorant dispersion (A-6), the inkjet ink was prepared. Evaluate pixel flatness. It was confirmed that any of the inkjet inks was used, and the flatness of the pixels was good. It was found that the coloring composition of the present invention is excellent in leveling.

Claims (7)

A colored composition comprising (A) a colorant, (B) a binder resin, (C) a polyfunctional monomer, and (D) a compound represented by the following formula (1), and (A) coloring The proportion of the agent is 20 to 70% by mass of the non-volatile component. In the formula (1), R ¹ to R ⁴ each independently represent C ₆ F ₁₁ -, C ₉ F ₁₇ -, C ₉ F ₁₇ -OC ₆ H ₄ -CO- or a hydrogen atom, but at least 1 of these C ₆ F ₁₁ -, C ₉ F ₁₇ - or C ₉ F ₁₇ -OC ₆ H ₄ -CO-, A is independent of each other to indicate an extended ethyl group or a propyl group, and a to d are independent of each other to represent an integer of 0 or more. However, a~d totals 8~18, and n is 0 or 1. The coloring composition of claim 1, wherein in the formula (1), at least one of R ¹ to R ⁴ is C ₉ F ₁₇ -. The colored composition according to any one of claims 1 to 2, further comprising (E) a photopolymerization initiator. The colored composition of claim 3 of the patent application is used for a slit die coating method. A colored composition according to any one of claims 1 to 2, which is used for forming a pixel of a color filter. A color filter comprising a coloring layer formed using the colored composition according to any one of claims 1 to 5. A color liquid crystal display element comprising a color filter as in claim 6 of the patent application.