WO2012023474A1 - Coloring agent, coloring composition, color film, and display element - Google Patents

Abstract

Provided is a novel coloring agent capable of realizing higher brightness and higher color purity than in the past. The coloring agent of the present invention is a triarylmethane coloring agent or xanthene coloring agent having anions represented by formula (1). [In the formula (1), R is an aliphatic hydrocarbon group or alicyclic hydrocarbon group, and the hydrogen atoms of the aliphatic hydrocarbon group and alicyclic hydrocarbon group can be substituted by at least one selected from the group comprising hydroxyl groups, sulfanyl groups, carboxyl groups, alkoxy groups, oxo groups, halo groups, and -X-NR¹R² (where R¹ and R² each independently are hydrogen atoms or optionally substituted hydrocarbon groups and X is a single bond or carbonyl group).]

Description

Colorant, coloring composition, color filter and display element

The present invention relates to a colorant, a coloring composition, a color filter, and a display element, and more particularly, to a color filter such as a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, and electronic paper. The present invention relates to a suitably used triarylmethane colorant or xanthene colorant, a color composition containing the colorant, a color filter including a color layer containing the colorant, and a display device including the color filter.

In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. There is known a method (Patent Documents 1 and 2) in which pixels of each color are obtained by irradiation (hereinafter referred to as “exposure”) and development. A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3) is also known. Furthermore, a method of obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (Patent Document 4).

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A

By the way, color liquid crystal display elements such as televisions and monitors are required to have high brightness and an expanded color reproduction area. Therefore, the color filters constituting the color liquid crystal display elements have recently been increasing in light transmittance. What has high color purity is required.

However, the conventional pigment-dispersed coloring composition has limitations in increasing luminance and color purity. Against the background as described above, there is a strong demand for the development of a color filter coloring composition that can achieve higher brightness and higher color purity than conventional pigment-dispersed coloring compositions.
Therefore, the subject of this invention is providing the novel coloring agent and coloring composition which can implement | achieve high brightness and high color purity compared with the past. Furthermore, the subject of this invention is providing the display element which comprises the color filter provided with the colored layer containing the said coloring agent, and the said color filter.

The present inventors have found that a triarylmethane colorant or a xanthene colorant having a specific structure can solve the above problems.

That is, the present invention provides a triarylmethane colorant or xanthene colorant (hereinafter also referred to as “the present colorant”) having an anion represented by the following formula (1).

[In the formula (1), R represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and the hydrogen atoms of the aliphatic hydrocarbon group and the alicyclic hydrocarbon group are a hydroxyl group, a sulfanyl group, a carboxyl group, An alkoxy group, an oxo group, a halo group, and —X—NR ¹ R ² (R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and X represents a single bond or a carbonyl group; It may be substituted with at least one selected from the group consisting of: ]

Moreover, this invention is a coloring composition containing (A) a coloring agent, (B) binder resin, and (C) a crosslinking agent, Comprising: (A) The coloring composition containing this coloring agent as a coloring agent, this A color filter provided with a colored layer containing a colorant, and a display element including the color filter are provided. Here, the “colored layer” means each color pixel, black matrix, black spacer, etc. used in the color filter.

If this colorant is used, it is possible to achieve higher brightness and higher color purity than before, and this colorant is also superior in solubility in organic solvents and heat resistance. Moreover, if the coloring composition of this invention containing this coloring agent is used, the color filter which has each color pixel with a high contrast can be obtained.
Therefore, this colorant is extremely useful for the production of various color filters including color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be preferably used. The colorant can also be suitably used for coloring plastic moldings, colorants for inkjet inks, colorants for color toners, colorants for electrophoretic display elements, and the like.

Hereinafter, the present invention will be described in detail.
This colorant First, the definitions of the symbols in the formula (1).
R represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group, and among them, an alkyl group is preferable. The number of carbon atoms of the aliphatic hydrocarbon group is preferably from 1 to 50, and particularly preferably from 2 to 20, from the viewpoints of solubility in organic solvents and coloring power. The aliphatic hydrocarbon group may be linear or branched.
Examples of the alicyclic hydrocarbon group include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged ring hydrocarbon group, a spiro hydrocarbon group, and a cyclic terpene hydrocarbon group. Of these, a cycloalkyl group, a bridged ring hydrocarbon group, and a cyclic terpene hydrocarbon group are preferable. Specific examples of the cycloalkyl group include a cyclohexyl group, and specific examples of the bridged ring hydrocarbon group include a bicyclo [2.2.1] heptyl group and a tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl group, adamantyl group and the like, and specific examples of the cyclic terpene hydrocarbon group include isobornyl group and the like. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 30, and particularly preferably 3 to 20, from the viewpoints of solubility in organic solvents and coloring power. Here, in the present invention, the “alicyclic hydrocarbon group” is a general term for hydrocarbon groups having a structure in which carbon atoms are bonded in a cyclic manner, excluding an aromatic hydrocarbon group. Those having the above-mentioned aliphatic hydrocarbon group as a substituent or a linkage part with —SO ₃ ^— , such as —yl group, are also included.

The hydrogen atom of the aliphatic hydrocarbon group and the alicyclic hydrocarbon group includes a hydroxyl group, a sulfanyl group (—SH), a carboxyl group, an alkoxy group, an oxo group, a halo group, and —X—NR ¹ R ² (R ¹ and R ² independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and X represents a single bond or a carbonyl group, and may be substituted with at least one selected from the group consisting of . R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cyclo group, and the like. Examples thereof include an alkenyl group and an aryl group, and among them, an alkyl group and a cycloalkyl group are preferable. In addition, examples of the substituent in R ¹ and R ² include a hydroxyl group, a carboxyl group, an alkoxy group, and a carbamoyl group. In addition, the carbon number referred to in the previous paragraph is the total carbon number including the carbon atoms constituting the substituents in the above R ¹ and R ² .

When this coloring agent is used as a coloring agent contained in the coloring composition described later, the substituent in R is, from the viewpoint of heat resistance, a hydroxyl group, a sulfanyl group, a carboxyl group, an oxo group, a halo group, and —X—. At least one selected from the group consisting of NR ¹ R ² is preferred. Since the substituent which this coloring agent has reacts with the binder resin and / or crosslinking agent mentioned later, interaction, or exposure and / or heating, it is thought that the heat resistance of a coloring composition is improved.

As a representative example of the anion represented by the above formula (1), for example, an anion represented by the following formula can be given.

On the other hand, as a cation which this coloring agent has, what is represented by following formula (2) or Formula (3) is preferable. In addition, although various resonance structures exist in the cation represented by the following formula (2) or formula (3), in the present invention, the cation represented by the following formula (2) or formula (3) Equivalent.

[In Formula (2),
Ar represents an aromatic hydrocarbon group,
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group,
R ⁷ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, —COOR ′ (R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) or a chlorine atom,
R ⁸ and R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a chlorine atom,
Y represents a hydrogen atom or a group represented by the following formula (4). ]

[In the formula (3), Ar, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are Ar, R ³ , R ⁴ , R ⁵ , R ⁶ in the formula (2), respectively] , R ⁷ , R ⁹ and R ¹⁰ . ]

[In Formula (4), R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

The aromatic hydrocarbon group in Ar is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms (more preferably 6 to 10 carbon atoms), specifically, a benzene ring, a naphthalene ring, a biphenyl ring, an anthracene ring. And groups in which 2 to 4 hydrogen atoms are removed from the arene ring such as
R ³ to R ¹¹ (including —COOR ′ in R ⁷ ) according to the above formula (2) or (3), and alkyl groups having 1 to 8 carbon atoms in R ¹² and R ^{13 according} to the above formula (4) As, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, tertiary butyl group, isobutyl group, amyl group, tertiary amyl group, hexyl group, heptyl group, octyl group, An isooctyl group, a tertiary octyl group, a 2-ethylhexyl group, etc. can be mentioned.

In the present invention, among the cations represented by the above formula (2), a cation represented by the following formula (5) is particularly preferable from the viewpoint of improving luminance and color purity.

In [Equation ^{(5), R 3, R} 4, R 5, R 6, R 12 and R ^13, R ³ in the formula (2) and ^{(4), R 4, R} 5, R 6, R the same meaning as ¹² and R ^13. ]

In the above formula (5), R ³ , R ⁴ , R ¹² and R ¹³ are preferably alkyl groups having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms), and R ⁵ is preferably a carbon number. An alkyl group or phenyl group having 1 to 8 (more preferably 1 to 6 carbon atoms) is preferable, and R ⁶ is an alkyl group or hydrogen atom having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms). preferable.

Among the cations represented by the above formula (3), a cation represented by the following formula (6) is particularly preferable from the viewpoint of improving luminance and color purity.

In [Equation ^{(6), R 3, R} 4, R 5, R 6 and R ⁷ have the same meanings as ^{R 3, R 4, R 5} , R 6 and R ⁷ in the formula (3). ]

In the above formula (6), R ³ and R ⁴ are preferably alkyl groups having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms), and R ⁵ is preferably 1 to 8 carbon atoms (more preferably Is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ⁶ is preferably an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms) or a hydrogen atom. R ⁷ is preferably —COOR ′ (R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms).

As typical examples of the cation represented by the above formula (2) or formula (3), for example, cations represented by the following formulas can be cited. Among them, compound b, compound c, compound d, compound f Compound g, Compound h, Compound i, Compound j, Compound k, and Compound l are preferable.

The colorant can be produced by a known method, and examples thereof include the same methods as in Examples in JP-A-2003-206415. In the case where the present colorant is produced by a salt exchange reaction using a basic dye whose anion portion is a halogen ion as a starting material, as in the examples of JP-A-2003-206415, the heat resistance of the obtained colorant is obtained. From the viewpoint of further improving the properties, it is preferable to purify so that halogen ions do not remain as much as possible.
The colorant thus obtained is soluble in various organic solvents including ketones such as cyclohexanone and has excellent heat resistance. In addition, in order to improve heat resistance more, it is preferable that the halogen ion contained in the coloring composition of this invention is as few as possible. That is, it is preferable to use a component having as little halogen ion content as possible in other components described later.

Coloring composition will be described components of the colored composition of the present invention.

-(A) Colorant-
The coloring composition of this invention contains this coloring agent as (A) coloring agent. This coloring agent can be used individually or in mixture of 2 or more types.
Since the present colorant exhibits a blue to red color when dissolved in an organic solvent, the present colorant can be used alone or in combination with other colorants as appropriate, for example, blue pixels, red pixels, black colors. It can be applied to a colored composition for forming a colored layer.
As colorants other than the present colorant, colors and materials can be appropriately selected according to the application. Specifically, as the colorant other than the present colorant, any of pigments, dyes, and natural pigments can be used, but the color layer constituting the color filter has high color purity, brightness, contrast, and light shielding properties. Therefore, it is preferable to use pigments and / or dyes.

The pigment may be either an organic pigment or an inorganic pigment, and examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyer's and Colorists). . Specific examples include those with the following color index (CI) names.

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

C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

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

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 1, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

Examples of the inorganic pigment include, for example, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, and chromium oxide. Examples include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

In the present invention, the pigment may be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, the pigment surface may be used by modifying the particle surface with a resin if desired. Examples of the resin that modifies the pigment particle surface include a vehicle resin described in JP-A No. 2001-108817, or various commercially available resins for dispersing pigments. As a resin coating method on the carbon black surface, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969, and the like can be employed. The organic pigment is preferably used by refining primary particles by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

In addition, the dye can be appropriately selected from various oil-soluble dyes, direct dyes, acid dyes, metal complex dyes, and the like. For example, the following color index (CI) names are attached. Can be mentioned.

C. I. Solvent Yellow 4, C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 15, C.I. I. Solvent Yellow 24, C.I. I. Solvent Yellow 82, C.I. I. Solvent Yellow 88, C.I. I. Solvent Yellow 94, C.I. I. Solvent Yellow 98, C.I. I. Solvent Yellow 162, C.I. I. Solvent yellow 179;
C. I. Solvent Red 45, C.I. I. Solvent red 49;
C. I. Solvent Orange 2, C.I. I. Solvent Orange 7, C.I. I. Solvent Orange 11, C.I. I. Solvent Orange 15, C.I. I. Solvent Orange 26, C.I. I. Solvent orange 56;
C. I. Solvent Blue 35, C.I. I. Solvent Blue 37, C.I. I. Solvent Blue 59, C.I. I. Solvent blue 67;

C. I. Acid Yellow 17, C.I. I. Acid Yellow 29, C.I. I. Acid Yellow 40, C.I. I. Acid Yellow 76;
C. I. Acid Red 91, C.I. I. Acid Red 92, C.I. I. Acid Red 97, C.I. I. Acid Red 114, C.I. I. Acid Red 138, C.I. I. Acid Red 151;
C. I. Acid Orange 51, C.I. I. Acid Orange 63;
C. I. Acid Blue 80, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90;
C. I. Acid Green 9, C.I. I. Acid Green 16, C.I. I. Acid Green 25, C.I. I. Acid Green 27.

In the present invention, other colorants can be used alone or in admixture of two or more.

In the present invention, when the colorant having a cation represented by the formula (2) is used in combination with another colorant to form a colored composition, the content of the colorant is preferably 20 to 80% by mass. In addition, when the coloring agent having a cation represented by the formula (3) and another coloring agent are used in combination to form a coloring composition, the content of the coloring agent is preferably 5 to 40 in all coloring agents. % By mass.

The content of the colorant (A) is usually 5 to 70% by mass, preferably 5 to 70% by mass in the solid content of the coloring composition from the viewpoint of forming a pixel having high luminance and excellent color purity, or a black matrix having excellent light shielding properties. 5 to 60% by mass. Solid content here is components other than the solvent mentioned later.

In the present invention, when a pigment is used as a colorant, it can be used together with a dispersant and a dispersion aid as desired. As the dispersing agent, for example, an appropriate dispersing agent such as a cationic type, an anionic type, or a nonionic type can be used, and a polymer dispersing agent is preferable. Specifically, urethane dispersant, polyethyleneimine dispersant, polyoxyethylene alkyl ether dispersant, polyoxyethylene alkylphenyl ether dispersant, polyethylene glycol diester dispersant, sorbitan fatty acid ester dispersant, polyester Examples thereof include an acrylic dispersant and an acrylic dispersant.

Such dispersants are commercially available. For example, acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK Corporation (BYK) And the like as urethane dispersants such as Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (Lubrisol) Etc.) as a polyethyleneimine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc. as a polyester-based dispersant. B821, Adisper PB822, Adisper PB880, the Ajisper PB881 (Ajinomoto Fine-Techno Co., Ltd.), and the like, can be mentioned, respectively.
Examples of the dispersion aid include pigment derivatives, and specific examples include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. The contents of the dispersant and the dispersion aid can be appropriately determined within a range that does not impair the object of the present invention.

-(B) Binder resin-
Although it does not specifically limit as binder resin in the coloring composition of this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). (B1) ") and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as" unsaturated monomer (b2) ").

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

Moreover, as said unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 To 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) ) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.
These unsaturated monomers (b2) can be used alone or in admixture of two or more.

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

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 1, JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2002-296778, JP-A-2004-101728. And the like.

In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-09-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, 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 a binder resin.

The binder resin in the present invention has a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (elution solvent: tetrahydrofuran) is usually 1,000 to 100,000, preferably 3,000 to 50,000. If Mw is too small, the remaining film rate of the resulting film may be reduced, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, resolution may be reduced. In addition, the pattern shape may be damaged, and dry foreign matter may be easily generated during application by the slit nozzle method.

In addition, the ratio (Mw / Mn) of the weight average molecular weight of the binder resin in the present invention to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC (elution solvent: tetrahydrofuran) is preferably 1.0 to 5. 0, more preferably 1.0 to 3.0.

The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

In the present invention, the binder resins can be used alone or in admixture of two or more.

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. If the content of the binder resin is too small, for example, the alkali developability may be decreased, or the storage stability of the resulting colored composition may be decreased. On the other hand, if the content is too large, the colorant concentration is relatively high. Therefore, it may be difficult to achieve the target color density as a thin film.

-(C) Crosslinking agent-
In the present invention, (C) a crosslinking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, (C) the crosslinking agent is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups, and particularly two or more (meth). It is preferable to use a combination of a compound having an acryloyl group and a compound having two or more N-alkoxymethylamino groups.

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

Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

Examples of the caprolactone-modified polyfunctional (meth) acrylate include the compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include ethylene oxide of bisphenol A and / or propylene oxide modified di (meth) acrylate, ethylene oxide of isocyanuric acid and / or propylene oxide modified tri (meth) acrylate, tri Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of methylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modified tetra (meth) acrylate of pentaerythritol Dipentaerythritol ethylene oxide and / or propylene oxide modified penta (meth) acrylate, di It can be mentioned pointer ethylene oxide erythritol and / or propylene oxide-modified hexa (meth) acrylate.

Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N Examples include '-tetra (alkoxymethyl) benzoguanamine, N, N, N', N'-tetra (alkoxymethyl) glycoluril and the like.

Of these polyfunctional monomers, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, Polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N '-Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate is a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, among polyfunctional (meth) acrylates having a carboxyl group, and obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.
In the present invention, the crosslinking agent (C) can be used alone or in admixture of two or more.

In the present invention, the content of the (C) crosslinking agent is preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass, with respect to 100 parts by mass of the (A) colorant. In this case, if the content of the polyfunctional monomer is too small, sufficient curability may not be obtained. On the other hand, if the content of the polyfunctional monomer is too large, when the color composition of the present invention is imparted with alkali developability, the alkali developability is lowered, and on the unexposed portion of the substrate or the light shielding layer. There is a tendency that dirt, film residue, etc. are likely to occur.

-(D) Photopolymerization initiator-
The coloring composition of the present invention can contain (D) a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The (D) photopolymerization initiator used in the present invention generates an active species capable of initiating the polymerization of the above (C) crosslinking agent by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. A compound.

Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -Diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, onium salt compounds, and the like.

In the present invention, the photopolymerization initiators can be used alone or in admixture of two or more. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

Among preferred photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

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 and the like can be mentioned.

In addition, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in terms of improving sensitivity. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole 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, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine compounds having a halomethyl group, such as toxistyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

Specific examples of the O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -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 the present invention, when using a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound, a sensitizer can be used in combination. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

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, with respect to 100 parts by mass of the (C) cross-linking agent. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

-(E) Solvent-
The colored composition of the present invention contains the above components (A) to (C) and other components optionally added, but is usually prepared as a liquid composition by blending a solvent.
As the solvent, as long as the components (A) to (C) and other components constituting the colored composition are dispersed or dissolved and do not react with these components and have appropriate volatility, the solvent is appropriately used. You can choose to use.

As such a solvent, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;
Alkoxycarboxylic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate ;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Pioneto acetate n- butyl acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
In this invention, a solvent can be used individually or in mixture of 2 or more types.

The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the colored composition is 5 to 50 from the viewpoint of the coating property and stability of the obtained colored composition. An amount of mass% is preferable, and an amount of 10 to 40 mass% is particularly preferable.

-Additive-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitors: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanedio Development of succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. And the like, and the like.

The colored composition of the present invention can be prepared by an appropriate method, and examples of the preparation method include methods disclosed in Japanese Patent Application Laid-Open Nos. 2008-58642 and 2010-132874. be able to. When both the present colorant and pigment are used as the colorant, as disclosed in JP 2010-132874 A, after passing the dye solution containing the present colorant through the first filter, A method is preferred in which the dye solution that has passed through the filter is mixed with a separately prepared pigment dispersion or the like, and the resulting colored composition is passed through a second filter. In addition, the dye containing the present colorant, the components (B) to (C), and the component (D) and the additive component, if necessary, are dissolved in the solvent (E), and the resulting solution is dissolved in the first solution. Also preferred is a method of preparing a solution obtained by passing the first filter after passing through the first filter and mixing with a separately prepared pigment dispersion and passing the resulting colored composition through the second filter. Further, the dye solution containing the present colorant is passed through the first filter and then passed through the first filter, the above components (B) to (C), and, if necessary, the above (D) to (D) (E) Component and additive component were mixed and dissolved, and the resulting solution was passed through a second filter, and the solution that passed through the second filter was further mixed with a separately prepared pigment dispersion. A method of preparing the colored composition by passing it through a third filter is also preferred.

Color filter and production method thereof The color filter of the present invention comprises a colored layer containing the present colorant.

As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, after applying a liquid composition of a blue radiation-sensitive composition containing the coloring agent on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which blue pixel patterns are arranged in a predetermined arrangement.

Next, each colored radiation-sensitive composition of green or red is used, and each colored radiation-sensitive composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above, so that a green pixel array and red color are obtained. Are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

A 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. Using the radiation-sensitive composition, it can be formed in the same manner as in the case of forming the pixel. The colored composition of the present invention can also be suitably used for forming such black tricks.

Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

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

Pre-baking is usually performed by a combination of vacuum drying and heat drying. The drying under reduced pressure is usually performed until reaching 50 to 200 Pa. The conditions for heat drying are usually about 70 to 110 ° C. and about 1 to 10 minutes.

The coating thickness is usually 0.6 to 8.0 μm, preferably 1.2 to 5.0 μm, as the film thickness after drying.

Examples of radiation light sources used in forming pixels and / or black matrices include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, and low pressure mercury lamps. Examples of the light source include a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. Radiation having a wavelength in the range of 190 to 450 nm is preferable.

In general, the exposure dose of radiation is preferably 10 to 10,000 J / m ² .
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution of 5-diazabicyclo- [4.3.0] -5-nonene or the like is preferable.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually 120 to 280 ° C. for about 10 to 60 minutes. From the viewpoint of heat resistance of the present colorant, the post-baking temperature is preferably 240 ° C. or less, particularly preferably 230 ° C. or less. is there.
The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

Further, as a second method for producing a color filter, a method for obtaining pixels of each color by an ink jet method disclosed in Japanese Patent Laid-Open Nos. 7-318723 and 2000-310706 can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a liquid composition of a blue coloring composition containing the present coloring agent is discharged into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, the coating film is exposed as necessary, and then cured by post-baking to form a blue pixel pattern.

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

In addition, the partition has not only a light shielding function but also a function for preventing the color composition of each color discharged in the section from being mixed, so that the film is a film compared to the black matrix used in the first method described above. Thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming such a black spacer.
Since the color filter of the present invention thus obtained has extremely high luminance and color purity, it is extremely useful for color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like.

Display element The display element of the present invention comprises the color filter of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.
A color liquid crystal display device including the color filter of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. In addition, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

The color liquid crystal display device including the color filter of the present invention can include a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp) and a backlight unit using a white LED as a light source. As the white LED, for example, a white LED that obtains white light by mixing red LED, green LED, and blue LED, a white LED that obtains white light by mixing blue LED, red LED, and green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

The color liquid crystal display device having the color filter of the present invention includes a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, an IPS (In-Planes Switching) type, a VA (Vertical Alignment) type, and an OCB (Optic Optical An appropriate liquid crystal mode such as a birefringence type can be applied.

In addition, the organic EL display element having the color filter of the present invention can adopt an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.

In addition, the electronic paper provided with the color filter of the present invention can adopt an appropriate structure, and examples thereof include a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Synthesis and Evaluation of the Colorant>
1. Synthesis Example 1 of the present colorant

Into the screw tube into which the stirrer is charged, C.I. I. (Cl of the compound b ^- salt) Basic Blue 7 1.4 g (2.72 mmol), potassium 3-mercapto-1-propanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) 0.728 g (4.08 mmol), chloroform 20mL and 10 mL of water was added and stirred at room temperature for 7 hours. After separating and removing the aqueous layer, the organic layer was washed twice with water, concentrated under reduced pressure, and the resulting solid was dried under reduced pressure to obtain 1.38 g of a blue-black solid (yield 79.8%). This is designated Compound A. ¹ H-NMR (solvent: deuterated chloroform) spectrum was as follows, and it was confirmed to be the objective compound.

¹ H-NMR: δ 8.68 (brs, 1H), 8.62 (d, 1H), 7.10-7.55 (m, 8H), 6.70 (d, 4H), 6.65 (d, 1H), 3.70 (q, 2H) , 3.56 (q, 8H), 3.05 (t, 2H), 2.75 (q, 2H), 2.49 (brs, 1H), 2.24 (q, 2H), 1.45 (t, 3H), 1.30 (t, 12H)

Example 2
A colorant was synthesized in the same manner as in Example 1 except that potassium 1-hexadecanesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of potassium 3-mercapto-1-propanesulfonate in Example 1. Is compound B. ^{By 1} H-NMR (solvent: deuterated chloroform) measurement, it was confirmed to be the target compound.

¹ H-NMR: δ8.85-9.41 (brs, 1H), 8.72 (d, 1H), 7.10-7.65 (m, 8H), 6.70 (d, 4H), 6.60 (d, 1H), 3.70 (q, 2H), 3.52 (q, 8H), 2.95 (t, 2H), 2.10-2.65 (brs, 1H), 1.95 (q, 2H), 1.00-1.68 (m, 41H), 0.89 (t, 3H)

Example 3
A colorant was prepared in the same manner as in Example 1 except that potassium 3-hydroxy-1-propanesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of potassium 3-mercapto-1-propanesulfonate in Example 1. It was synthesized and confirmed to be the target compound by ¹ H-NMR (solvent: deuterated chloroform) measurement.

Example 4
The colorant was prepared in the same manner as in Example 1 except that potassium 3-amino-1-propanesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of potassium 3-mercapto-1-propanesulfonate in Example 1. It was synthesized and confirmed to be the target compound by ¹ H-NMR (solvent: deuterated chloroform) measurement.

Example 5
Example 1 was the same as Example 1 except that potassium N- (2-acetamido) -2-aminoethanesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of potassium 3-mercapto-1-propanesulfonate. Then, a colorant was synthesized and confirmed to be the target compound by ¹ H-NMR (solvent: deuterated chloroform) measurement.

Example 6
In Example 1, C.I. I. Instead of Basic Blue 7, C.I. I. Basic Blue 11 (Cl of the compound d ^- salt) except for using synthesizes a colorant in the same manner as in Example ^1, 1 H-NMR: by (solvent deuterated chloroform) measuring, in the compound of interest I confirmed that there was.

Example 7
A colorant was synthesized in the same manner as in Example 1 except that sodium camphorsulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of potassium 3-mercapto-1-propanesulfonate in Example 1, and ¹ H— NMR (solvent: deuterated chloroform) measurement confirmed that the compound was the target compound.

Example 8
In Example 1, C.I. I. Instead of Basic Blue 7, C.I. I. A colorant was synthesized in the same manner as in Example 1 except that Basic Violet 11: 1 was used, and the compound was confirmed to be the target compound by ¹ H-NMR (solvent: deuterated chloroform) measurement.

2. Evaluation of the present colorant Compound A obtained in Example 1 was dissolved in cyclohexanone in an amount of 10% by mass or more, and the solution exhibited a blue color. All the colorants obtained in Examples 2 to 8 were dissolved in cyclohexanone by 10% by mass or more. Further, the obtained cyclohexanone solution was stored at 5 ° C. for a whole day and night, but no precipitate was confirmed.
Further, the 5% mass reduction temperatures based on the thermogravimetric-differential heat simultaneous measurement analysis of the colorants obtained in Examples 1 to 8 were all 230 ° C. or higher. On the other hand, C.I. I. Basic Blue 7 and C.I. I. The 5% mass loss temperature based on thermogravimetric-differential thermal simultaneous measurement analysis of Basic Blue 11 was all less than 200 ° C.

<Preparation of pigment dispersion>
Preparation Example 1
As a coloring agent, C.I. I. 15 parts by weight of Pigment Blue 15: 6, 12.5 parts by weight of BYK-LPN21116 (produced by BYK) as a dispersant (solid content concentration = 40% by weight), 72.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent The pigment dispersion (A-1) was prepared by processing with a bead mill.

Preparation Example 2
As a coloring agent, C.I. I. Pigment Blue 15: 6 instead of C.I. I. A pigment dispersion (A-2) was prepared in the same manner as in Preparation Example 1, except that CI Pigment Violet 23 was used.

<Preparation of dye solution>
Preparation Example 3
A dye solution A was prepared by mixing 5 parts by mass of Compound A as a colorant and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Preparation Example 4
A dye solution B was prepared by mixing 5 parts by mass of Compound B as a colorant and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Adjustment example 5
As a coloring agent, C.I. I. A dye solution C was prepared by mixing 5 parts by weight of Basic Blue 7 and 95 parts by weight of propylene glycol monomethyl ether as a solvent.

<Synthesis of binder resin>
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heated to 80 ° C., at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate 23 parts by mass, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) The solution was added dropwise over a period of time and polymerized for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C. and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 12,200 and Mn = 6,500. This binder resin is referred to as “binder resin (B1)”.

<Preparation and evaluation of coloring composition>
Example 9
13.6 parts by mass of pigment dispersion (A-1), 25.4 parts by mass of dye solution A, 16.1 parts by mass of binder resin (B1) solution as a binder resin, and M-402 manufactured by Toagosei Co., Ltd. as a crosslinking agent (Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 5.5 parts by mass and MW-30 (N, N, N ′, N ′, N ″, N ″ -hexa) manufactured by Sanwa Chemical Co., Ltd. (Methoxymethyl) melamine as a main component, weight average polymerization degree 1.3) 2.4 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-as photopolymerization initiator ON (Ciba Specialty Chemicals, trade name IRGACURE 369) 2.2 parts by mass and propylene glycol monomethyl ether acetate as solvent To a solid content concentration of 20 mass% of the coloring composition (CR1) was prepared.

The coloring composition (CR1) was applied on a glass substrate using a spin coater, and then pre-baked on an 80 ° C. hot plate for 10 minutes to form a coating film. Three coating films having different film thicknesses were formed by the same operation while changing the rotation speed of the spin coater.
Next, after cooling these substrates to room temperature, a high-pressure mercury lamp is used, and a radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without using a photomask at an exposure dose of 2,000 J / m ² . And exposed. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 30 minutes to form a cured film for evaluation.

Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate value (x, y) and the stimulus value in the CIE color system with a C light source and a 2-degree visual field for the three cured films obtained. (Y) was measured. Further, the thickness of the obtained cured film was measured using an alpha step IQ manufactured by KLA-Tencor. From the measurement results, the chromaticity coordinate value x, the stimulus value (Y), and the film thickness at the chromaticity coordinate value y = 0.080 were obtained. The evaluation results are shown in Table 1. The larger the stimulus value (Y), the higher the light transmittance (brightness), and the thinner the film thickness, the higher the coloring power.

The substrate on which the cured film is formed is sandwiched between two deflection plates, and the front side deflection plate is rotated while irradiating with a fluorescent lamp (wavelength range: 380 to 780 nm) from the rear side to obtain a luminance meter LS-100 (Minolta Co. The maximum value and the minimum value of the light intensity transmitted through (made by)) were measured. And about each cured film, the value which remove | divided the maximum value by the minimum value was made into the contrast ratio. From the measurement result, the contrast ratio at the chromaticity coordinate value y = 0.080 was obtained. The evaluation results are shown in Table 1.

Example 10
15.2 parts by mass of pigment dispersion (A-1), 23.8 parts by mass of dye solution B, 16.1 parts by mass of binder resin (B1) solution as a binder resin, and M-402 manufactured by Toagosei Co., Ltd. as a crosslinking agent 5.5 parts by weight and 2.4 parts by weight of MW-30 manufactured by Sanwa Chemical Co., Ltd., 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1- A colored composition (CR2) having a solid content of 20% by mass was prepared by mixing 2.2 parts by mass of ON and propylene glycol monomethyl ether acetate as a solvent.
Evaluation was performed in the same manner as in Example 9 except that the colored composition (CR2) was used instead of the colored composition (CR1). The evaluation results are shown in Table 1.

Comparative Example 1
18.1 parts by mass of the pigment dispersion (A-1), 4.5 parts by mass of the pigment dispersion (A-2), 16.1 parts by mass of the binder resin (B1) solution as the binder resin, and Toagosei Co., Ltd. as the crosslinking agent 5.5 parts by mass of M-402 and 2.4 parts by mass of MW-30 manufactured by Sanwa Chemical Co., Ltd., 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) as a photopolymerization initiator Butane-1-one (trade name: IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.2 parts by mass and propylene glycol monomethyl ether acetate as a solvent are mixed to form a colored composition (CR3 ) Was prepared.
Evaluation was performed in the same manner as in Example 9 except that the colored composition (CR3) was used instead of the colored composition (CR1). The evaluation results are shown in Table 1.

Comparative Example 2
18.1 parts by mass of pigment dispersion (A-1), 24.2 parts by mass of dye solution C, 16.1 parts by mass of binder resin (B1) solution as a binder resin, and M-402 manufactured by Toagosei Co., Ltd. as a crosslinking agent 5.5 parts by weight and 2.4 parts by weight of MW-30 manufactured by Sanwa Chemical Co., Ltd., 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1- 2.2 parts by mass of ON (manufactured by Ciba Specialty Chemicals, trade name: IRGACURE 369) and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a colored composition (CR4) having a solid content concentration of 20% by mass. .
Evaluation was performed in the same manner as in Example 9 except that the colored composition (CR4) was used instead of the colored composition (CR1). The evaluation results are shown in Table 1.

In Table 1, “B15: 6” means C.I. I. Pigment Blue 15: 6, “V23” means C.I. I. Pigment Violet 23, “BB-7” is C.I. I. Each means Basic Blue 7.

Claims (8)

1. A triarylmethane colorant or a xanthene colorant having an anion represented by the following formula (1).
   

   

   [In the formula (1), R represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and the hydrogen atoms of the aliphatic hydrocarbon group and the alicyclic hydrocarbon group are a hydroxyl group, a sulfanyl group, a carboxyl group, An alkoxy group, an oxo group, a halo group, and —X—NR ¹ R ² (R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and X represents a single bond or a carbonyl group; It may be substituted with at least one selected from the group consisting of: ]
2. The colorant of Claim 1 which has a cation represented by either the following formula (2) or Formula (3).
   

   

   [In Formula (2),
   Ar represents an aromatic hydrocarbon group,
   R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group,
   R ⁷ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, —COOR ′ (R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) or a chlorine atom,
   R ⁸ and R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
   R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a chlorine atom,
   Y represents a hydrogen atom or a group represented by the following formula (4). ]
   

   

   [In Formula (3),
   Ar, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are Ar, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ⁹ in the formula (2). It has the same meaning as R ^10. ]
   

   

   [In Formula (4), R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group. ]
3. The colorant according to claim 2, wherein the cation is represented by any one of the following formulas (5) and (6).
   

   

   In [Equation ^{(5), R 3, R} 4, R 5, R 6, R 12 and R ^13, the formula (2) and R ³ in the formula ^{(4), R 4, R} 5, R 6, R the same meaning as ¹² and R ^13. ]
   

   

   In [Equation (6), R ^3, R ^4, R ^5, R ⁶ and R ^7, R ^3, R ^4, the same meaning as R ^5, R ⁶ and R ⁷ in formula (2). ]
4. R represents a hydroxyl group, a sulfanyl group, a carboxyl group, an oxo group, a halo group, and —X—NR ¹ R ² (R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group. X represents a single bond or a carbonyl group), which is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group substituted with at least one selected from the group consisting of: The coloring agent according to item.
5. A coloring composition containing (A) a coloring agent, (B) a binder resin and (C) a crosslinking agent,
   (A) A colored composition containing the colorant according to any one of claims 1 to 4 as a colorant.
6. The coloring composition according to claim 5, further comprising (D) a photopolymerization initiator.
7. A color filter comprising a colored layer containing the colorant according to any one of claims 1 to 4.
8. A display element comprising the color filter according to claim 7.