JP5919674B2 - Colorant, coloring composition, color filter and display element - Google Patents

Description

  The present invention relates to a colorant, a coloring composition, a color filter, and a display element. More specifically, the present invention relates 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 colorant that is preferably used, a color composition containing the colorant, a color filter including a color layer containing the colorant, and a display element 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) for obtaining pixels of each color 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).

  By the way, it is known that it is effective to use a dye as a colorant in order to realize high luminance and high color purity of a display element or high definition of a solid-state imaging element. However, when a dye is used as a colorant, there is a problem that heat resistance, light resistance and the like are inferior compared to a case where a pigment is used. In order to solve such a problem, for example, Patent Documents 5 to 6 propose use of a polymerizable triarylmethane dye.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2000-162429 A JP 2003-246935 A

However, when a triarylmethane dye is used, there is a problem in that the solvent resistance of the colored layer constituting the color filter is remarkably lowered, and this problem is caused by using the dyes disclosed in the above Patent Documents 5-6. However, it is not solved. In view of the above background, development of a coloring composition capable of producing a color filter having excellent solvent resistance as well as heat resistance is strongly demanded.
Therefore, the subject of this invention is providing the coloring composition which can manufacture the color filter which can manufacture the color filter which was excellent also in solvent resistance with heat resistance etc., and a coloring composition containing the same. Furthermore, the subject of this invention is providing the display element which comprises the color filter provided with the colored layer excellent also in solvent resistance with heat resistance etc., and the said color filter.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by imparting a specific conjugated ring structure to the cation portion of the triarylmethane dye.

  That is, the present invention is also referred to as (A) a colorant having a cation represented by the following formula (1) (hereinafter referred to as “the present colorant”). ), (B) a binder resin and (C) a cross-linking agent.

[In Formula (1),
R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group or a group having an ethylenically unsaturated bond,
R ^{5 to} R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halo group,
Ring A is an aryl ring having no group represented by —NR ¹³ R ¹⁴ (wherein R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group), Isoindole ring, indolizine ring, quinolidine ring, quinoline ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, β-carboline ring, phenanthridine ring, acridine ring, phenanthroline ring, phenazine ring , Benzofuran ring, isobenzofuran ring, benzothiophene ring, isobenzothiophene ring, isochromene ring, xanthene ring, phenoxathiin ring, thianthrene ring, benzoisothiazole ring, benzoxazole ring, benzothiazole ring, carbazole ring, phenoxazine ring Or a phenothiazine ring is shown. ]

  In addition, the present invention provides a colorant having a cation represented by the above formula (1), a color filter comprising a colored layer containing the colorant, and a display element comprising the color filter. . 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 form a colored layer having excellent solvent resistance as well as heat resistance.
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 This colorant is a compound having a cation represented by the above formula (1), and one of the aryl rings of the amino-substituted triarylmethane colorant is a ring having a conjugated structure having no amino group. It is characterized by that.

In the above formula (1), the ring having a conjugated structure constituting ring A is an aryl ring, isoindole ring, indolizine ring, quinolidine ring, quinoline ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring , Cinnoline ring, β-carboline ring, phenanthridine ring, acridine ring, phenanthroline ring, phenazine ring, benzofuran ring, isobenzofuran ring, benzothiophene ring, isobenzothiophene ring, isochromene ring, xanthene ring, phenoxathiin ring, Thianthrene ring, benzoisothiazole ring, benzoxazole ring, benzothiazole ring, carbazole ring, phenoxazine ring or phenothiazine ring, among which aryl ring, benzofuran ring, benzothiophene ring, benzoxazole ring, benzothia Lumpur ring, carbazole ring, a phenoxazine ring, a phenothiazine ring.
Ring A may have a substituent. The substituent is not particularly limited as long as it is not —NR ¹³ R ¹⁴ , for example, a halo group, a halogenated hydrocarbon group, —OR, —COOR, —SR, —SO ₂ R (where R is A hydrocarbon group.) And the like. When ring A is an aryl ring, it is preferably substituted with these groups.

  As ring A, what is represented by either of following formula (2)-(6) is preferable.

[In Formula (2) and Formula (3), X < ¹ > and X < ² > show an oxygen atom or a sulfur atom mutually independently,
In the formula (4), Y represents a single bond, an oxygen atom or a sulfur atom, R ¹⁵ represents a hydrogen atom or an alkyl group,
In formulas (2) to (6), Z ^{1 to} Z ⁵ each independently represent a hydrogen atom, a halo group, a halogenated hydrocarbon group, —OR, —COOR, —SR or —SO ₂ R. However, R is as defined above, and * indicates a bond that bonds to the diphenylmethane skeleton. ]

In the formula (4), the alkyl group in R ¹⁵ is preferably an alkyl group having 1 to 12 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s- Examples thereof include a butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.

Specific examples of the halo group that can be substituted on ring A include a fluoro group, a chloro group, a bromo group, and an iodo group.
As the halogenated hydrocarbon group that can be substituted for ring A, a fluorinated alkyl group is preferable, and a C 1-10 perfluoroalkyl group is particularly preferable. Specific examples thereof include a trifluoromethyl group, a pentafluoroethyl group, a nonafluorobutyl group, and a perfluorooctyl group.
Further, the -OR, -COOR, in -SR and -SO ₂ R, as the hydrocarbon group for R, for example, an alkyl group, a cycloalkyl group, an aryl group, can be exemplified an aralkyl group, and among them the number of carbon atoms 1-12 alkyl groups are preferred. Specific examples thereof include the same groups as those exemplified for R ¹⁵ .
In the above -NR ¹³ R ¹⁴ , the hydrocarbon group in R ¹³ and R ¹⁴ is an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.

In the above formula (1), examples of the alkyl group having 1 to 8 carbon atoms in R ^{1 to} R ¹² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, and a tertiary butyl group. , Isobutyl group, amyl group, tertiary amyl group, hexyl group, heptyl group, octyl group, isooctyl group, tertiary octyl group, 2-ethylhexyl group and the like.
In the above formula (1), the cycloalkyl group having 3 to 8 carbon atoms in R ¹ to R ^4, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group.
In the above formula (1), the group having an ethylenically unsaturated bond in R ^{1 to} R ⁴ is not particularly limited. For example, CH ₂ ═CH—COO—R ¹⁶ —, CH ₂ ═C (CH ₃ ) —COO—R ¹⁶ —, CH ₂ ═CH—Ph—R ¹⁶ —, CH ₂ ═C (CH ₃ ) —Ph—R ¹⁶ — and CH ₂ ═CH—CO— (R ¹⁶ is carbon And an alkanediyl group of formulas 1 to 4 and Ph represents a phenylene group.
Examples of the alkanediyl group having 1 to 4 carbon atoms in R ¹⁶ include a methylene group, an ethylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, Examples include propane-1,3-diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group. .
In the above formula (1), examples of the halo group in R ^{5 to} R ¹² include a fluoro group, a chloro group, a bromo group, and an iodo group.

In the above formula (1), R ^{5 to} R ¹² are preferably all hydrogen atoms.
In the above formula (1), R ^{1 to} R ⁴ are preferably an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms), a phenyl group, or a group having an ethylenically unsaturated bond.

  On the other hand, the anion part of the colorant is not particularly limited, and examples of the colorant include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, and a methide anion. It can be an anion part. The colorant can also be a lake pigment. Lake pigment refers to a soluble dye made into an insoluble pigment by a precipitating agent. Examples of the precipitating agent include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, and katanol. And complex heteropolyacids (phosphotungstic acid, phosphomolybdic acid, phosphotungsten / molybdic acid, silicotungsten molybdic acid, silicotungstic acid, silicomolybdic acid) and the like referred to as tamol and complex acid.

  In the present invention, the anion moiety preferably has at least one electron-withdrawing group selected from the group consisting of a halo group (preferably a fluoro group) and a cyano group from the viewpoint of heat resistance. Examples of such anions include organic sulfonate anions having a fluoro group, and specific examples include the anions shown in the following anion group α and anion group β.

Moreover, as a nitrogen anion having at least one electron-withdrawing group selected from the group consisting of a fluoro group and a cyano group, for example, [(CN) ₂ N] ⁻ , [( FSO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ SO ₂ )] ⁻ , [(FSO ₂ ) N (CF ₃ CF ₂ SO ₂ )] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₂ CFSO ₂ }] ⁻ , [(FSO ₂ ) N (CF ₃ CF ₂ CF ₂ SO ₂ )] ⁻ , [(FSO ₂ ) N (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ )] ⁻ , [( FSO ₂ ) N {(CF ₃ ) ₂ CFCF ₂ SO ₂ }] ⁻ , [(FSO ₂ ) N {CF ₃ CF ₂ (CF ₃ ) CFSO ₂ }] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₃ CSO ₂ }] ^{-and the} like.

Further, as phosphate anions having a fluoro group, for example, PF ₆ ⁻ , (C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF] ₂ PF _{4 ^{-, [(CF 3) 2}} CF] 3 PF 3, (n-C 3 F 7) 2 PF 4 -, (n-C 3 F 7) 3 PF 3 -, (n-C 4 F 9) 3 PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ⁻ , (nC ₄ F ₉ ) ₂ PF ₄ ⁻ , (nC ₄ F ₉ ) ₃ PF ₃ ⁻ , (C ₂ F ₄ H) (CF ₃ ) ₂ PF ₃ ⁻ , (C ₂ F ₃ H ₂ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF _3- ^{and the} like.

Examples of boron anions having at least one electron-withdrawing group selected from the group consisting of a fluoro group and a cyano group include, for example, BF ₄ ⁻ , (CF ₃ ) ₄ B ⁻ , (CF ₃ ) ₃ BF ⁻ , (CF ₃ ) ₂ BF ₂ ⁻ , (CF ₃ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₄ B ⁻ , (C ₂ F ₅ ) ₃ BF ⁻ , (C ₂ F ₅ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₂ BF ₂ ⁻ , (CF ₃ ) (C ₂ F ₅ ) ₂ BF ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ , (CF ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ F ₅ ) ₂ BF ₂ ⁻ , (C ₆ F ₅ ) BF ₃ ⁻ , (C ₆ H ₃ F ₂ ) ₄ B ⁻ , B (CN) ₄ ⁻ , B (CN ) F ₃ ⁻ , B (CN) ₂ F ₂ ⁻ , B (CN) ₃ F ⁻ , (CF ₃ ) ₃ B (CN) ⁻ , (CF ₃ ) ₂ B (CN) ₂ ⁻ , (C ₂ F _{5 ^{) 3 B (CN) -,}} (C 2 F 5) 2 B (CN) 2 -, (n-C 3 F 7) 3 ^{(CN) -, (n-} C 4 F 9) 3 B (CN) -, (n-C 4 F 9) 2 B (CN) 2 -, (n-C 6 F 13) 3 B (CN) - , (CHF ₂ ) ₃ B (CN) ⁻ , (CHF ₂ ) ₂ B (CN) ₂ ⁻ , (CH ₂ CF ₃ ) ₃ B (CN) ⁻ , (CH ₂ CF ₃ ) ₂ B (CN) ₂ ⁻ , (CH ₂ C ₂ F ₅ ) ₃ B (CN) ⁻ , (CH ₂ C ₂ F ₅ ) ₂ B (CN) ₂ ⁻ , (CH ₂ CH ₂ C ₃ F ₇ ) ₂ B (CN) ₂ ⁻ , _{(n-C 3 F 7 CH} 2) 2 B (CN) 2 - and the like can be given ^{_{-, (C 6 H 5)}} 3 B (CN).

In addition, examples of the methide anion having a fluoro group include (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ CF ₂ SO ₂ ) ₃ C ⁻ , [(CF ₃ ) ₂ CFSO ₂ ] ₃ C ⁻ , (CF ₃ CF ₂ CF ₂ SO ₂ ) ₃ C ⁻ , (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ ) ₃ C ⁻ , [(CF ₃ ) ₂ CFCF ₂ SO ₂ ] ₃ C ⁻ , [CF ₃ CF ₂ (CF ₃ ) CFSO ₂ ] ₃ C ⁻ , [(CF ₃ ) ₃ CSO ₂ ] ₃ C ⁻ , (FSO ₂ ) ₃ C ⁻ , (ClSO ₂ ) ₃ C ⁻ , (BrSO ₂ ) ₃ C ⁻ , (ISO ₂ ) ₃ C ^-, and the like can be given.

  This colorant can be produced by a known method, for example, by reacting a bisaminoaryl ketone compound with a cyclic compound corresponding to ring A in the presence of phosphoryl chloride. For the production of this colorant, you can refer to Hosoda Toyou Station's “Theoretical Manufacturing Dye Science” published by Gihodo Co., Ltd.

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.
As other colorants, colors and materials can be appropriately selected according to applications. Specifically, any of pigments, dyes and natural pigments can be used. However, since the color layer constituting the color filter is required to have high color purity, luminance, contrast, light shielding properties, etc. It is preferable to use a dye.

  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 Dyers and Colorists). . Specific examples include those with the following color index (CI) names.

C. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment blue 1, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 80, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211, C.I. I. Pigment orange 38, C.I. I. Pigment Violet 23.

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

  When a pigment is used as the colorant in the present invention, the pigment can 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 particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and 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.

  The total content of the present colorant and other colorants used as required is usually in the solid content of the color composition from the viewpoint of forming a pixel having high luminance and excellent color purity, or a black matrix having excellent light shielding properties. It is 5-70 mass%, Preferably it is 5-60 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 a urethane-based dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by Big Chemie (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 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 -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. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, 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) of 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.

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

  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 in total of the present colorant and other colorants used as required. is there. 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.

  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 (meth) acrylate having a hydroxyl group 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 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.

Among these crosslinking agents, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, polyfunctional urethanes ( (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 Among polyfunctional (meth) acrylates having a carboxyl group, erythritol hexaacrylate is obtained by reacting pentaerythritol triacrylate and succinic anhydride, and 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, and 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 crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, if the content of the crosslinking agent is too large, when the coloring composition of the present invention is imparted with alkali developability, the alkali developability is deteriorated, and the soil or film on the unexposed portion of the substrate or on the light shielding layer is deteriorated. There is a tendency for the rest to occur easily.

-(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 -A diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound etc. can be mentioned.

  In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. 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, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. 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-based compounds having a halomethyl group such as xystyryl) -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 compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 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 this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 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 this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) crosslinking agents, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, 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 that are optionally added, but is usually prepared as a liquid composition by blending a solvent.
As said solvent, (A)-(C) component which comprises a coloring composition, and another component are disperse | distributed or melt | dissolved, and it does not react with these components, but suitably has appropriate volatility. 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, 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.

  Although content of a solvent is not specifically limited, From viewpoints of the applicability | paintability of a coloring composition obtained, stability, etc., the total density | concentration of each component remove | excluding the solvent from the said coloring composition is 5-50. An amount of mass% is preferred, and an amount of 10 to 40 mass% is particularly preferred.

-Additives-
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); fluorine-based surfactants, silicon-based surfactants, and phosphate-based surfactants. , Surfactants such as sulfonic acid surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropro Adhesion promoters such as rumethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-t- Butylphenol), 2,6-di-t-butylphenol and other antioxidants; UV absorption of 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones, etc. Agent; anti-aggregation agent such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pen Tanol, 3-amino-1,2-propanediol, 2-amino-1,3-pro Diol, 4-amino-1,2-butanediol, etc .; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω- Examples include developability improvers such as carboxypolycaprolactone mono (meth) acrylate; siloxane oligomers having a reactive functional group disclosed in Japanese Patent Application Laid-Open No. 2008-2242078 and the like.

  The coloring composition of the present invention can be prepared by an appropriate method. When the coloring agent is a dye, it is disclosed in, for example, JP-A-2008-58642, JP-A-2010-132874, and the like. Can be prepared by any method. When using a pigment together with a dye (the present colorant), as disclosed in JP 2010-132874 A, after passing the dye solution containing the present colorant through the first filter, the first filter A method can be employed in which the dye solution that has passed through 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 (the present colorant), the above components (B) to (C), and, if necessary, the above component (D) and the additive component are dissolved in the solvent (E), and the resulting solution is used as the first solution. It is also possible to employ a method in which the solution passed through the first filter is mixed with a separately prepared pigment dispersion and the resulting colored composition is passed through the second filter. Moreover, after passing the dye solution containing this coloring agent through a 1st filter, the dye solution which passed the 1st filter, said (B)-(C) component, and said (D) component as needed And the additive component is mixed and dissolved with the solvent (E), the obtained solution is passed through the second filter, and the solution passed through the second filter is further mixed with a separately prepared pigment dispersion. A method of preparing the colored composition by passing it through a third filter can also be adopted.

Color filter and manufacturing method thereof The color filter of the present invention comprises a colored layer formed using the colored composition of the present invention.

  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 a specific colorant 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 combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.

  The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 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.

Exposure of the radiation is generally preferred 10~10,000J / 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 such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.

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, but from the viewpoint of the heat resistance of the specific 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 μm, preferably 1 to 3 μm.

  Further, as a second method for producing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723 and JP-A-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 a specific colorant is discharged into the formed partition wall by an ink jet 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.

  Subsequently, using each coloring 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 the 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.
The color liquid crystal display element provided with the color filter of the present invention may be a transmissive type or a reflective type, and 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 may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a 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-Plane Switching) type, a VA (Vertical Alignment) type, and an OCB (Optical Optical). An appropriate liquid crystal mode such as a birefringence type can be applied.

  Moreover, the organic EL display element provided with the color filter of the present invention can take an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.

  In addition, the electronic paper including 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 embodiment 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 of this coloring agent>
Example 1
To an eggplant-shaped flask, 0.55 g (1.7 mmol) of 4,4′-bis (diethylamino) benzophenone, 0.28 g (1.8 mmol) of 1-methoxynaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) and 16 mL of toluene were added. . To this mixture, 0.27 g (1.8 mmol) of phosphoryl chloride was added at room temperature, and the mixture was stirred at 85 ° C. for 5.5 hours. After cooling to room temperature, 1 g of ethanol was added to the reaction solution to stop the reaction, the supernatant was removed by decantation, and the resulting viscous solid was washed with a small amount of toluene. The solid was dissolved in ethanol and collected as a solution. After concentration under reduced pressure, ethanol was removed by vacuum drying at room temperature. The obtained solid was washed with about 20 mL of water and collected by filtration. After vacuum drying at 50 ° C., 0.48 g of a solid was obtained (yield 56%). ¹ H-NMR analysis confirmed that the obtained solid was a compound represented by the following formula (7). This compound is defined as a colorant (A-1).

Example 2
A colorant was synthesized in the same manner as in Example 1 except that 1-thiomethoxynaphthalene (manufactured by Energy Chemical Co.) was used instead of 1-methoxynaphthalene in Example 1, and the following was found by ¹ H-NMR analysis. It was confirmed that it was a compound represented by Formula (8). Let this compound be a coloring agent (A-2).

Example 3
A colorant was synthesized in the same manner as in Example 1 except that 1-methylsulfonylnaphthalene (manufactured by ChemPacific Corporation) was used instead of 1-methoxynaphthalene in Example 1, and the following was found by ¹ H-NMR analysis. It was confirmed that it was a compound represented by Formula (9). This compound is defined as a colorant (A-3).

Example 4
A colorant was synthesized in the same manner as in Example 1 except that 1-chloronaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1-methoxynaphthalene in Example 1, and ¹ H-NMR analysis was performed. It was confirmed that it was a compound represented by following formula (10). This compound is defined as a colorant (A-4).

Example 5
A colorant was synthesized in the same manner as in Example 1 except that 1-trifluoromethylnaphthalene (manufactured by Meryer Chemical Technology Shanghai Company) was used instead of 1-methoxynaphthalene in Example 1, and ¹ H-NMR was synthesized. Analysis confirmed that it was a compound represented by the following formula (11). This compound is defined as a colorant (A-5).

Example 6
Instead of the 1-methoxy-naphthalene in Example 1, azulene except for using (manufactured by Tokyo Kasei Kogyo Co., Ltd.), a colorant was synthesized in the same manner as in Example 1, by ¹ H-NMR analysis, the following formula ( It was confirmed that the compound is represented by 12). This compound is defined as a colorant (A-6).

Example 7
Instead of the 1-methoxy-naphthalene in Example 1, benzofuran except for using (manufactured by Tokyo Kasei Kogyo Co., Ltd.), to synthesize a colorant in the same manner as in Example 1, by ¹ H-NMR analysis, the following formula ( It was confirmed that the compound was represented by 13). This compound is defined as a colorant (A-7).

Example 8
A colorant was synthesized in the same manner as in Example 1 except that benzothiophene (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1-methoxynaphthalene in Example 1, and the following formula was obtained by ¹ H-NMR analysis. It was confirmed that it was a compound represented by (14). This compound is defined as a colorant (A-8).

Example 9
A colorant was synthesized in the same manner as in Example 1 except that benzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1-methoxynaphthalene in Example 1, and the following formula was obtained by ¹ H-NMR analysis. It was confirmed that it was a compound represented by (15). This compound is defined as a colorant (A-9).

Example 10
A colorant was synthesized in the same manner as in Example 1 except that phenoxazine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1-methoxynaphthalene in Example 1, and the following formula was obtained by ¹ H-NMR analysis. It was confirmed that it was a compound represented by (16). This compound is defined as a colorant (A-10).

Example 11
Instead of the 1-methoxy-naphthalene in Example 1, phenothiazines except for using (manufactured by Tokyo Kasei Kogyo Co., Ltd.), to synthesize a colorant in the same manner as in Example 1, by ¹ H-NMR analysis, the following formula ( It was confirmed that the compound is represented by 17). This compound is defined as a colorant (A-11).

Example 12
Instead of the 1-methoxy-naphthalene in Example 1, except for using the carbazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.), the colorant was synthesized in the same manner as in Example 1, by ¹ H-NMR analysis, the following formula ( It was confirmed that the compound is represented by 18). This compound is defined as a colorant (A-12).

Example 13
1.4 g (2.73 mmol) of the colorant (A-12), 0.703 g (4.09 mmol) of sodium trifluoromethanesulfonate, 20 mL of chloroform, and 10 mL of water are added to the screw tube into which the stirrer is charged. Stir for hours. After separating and removing the aqueous layer, the organic layer was washed twice with water, concentrated under reduced pressure, and the obtained solid was dried under reduced pressure to obtain 1.45 g of a dark blue solid (yield 85.0%). ¹ H-NMR analysis confirmed that the obtained solid was a compound in which the anion moiety was trifluoromethanesulfonate ion in the above formula (18). This compound is defined as a colorant (A-13).

Example 14
In Example 13, a colorant was synthesized in the same manner as in Example 13 except that bis (trifluoromethanesulfonyl) imide lithium was used instead of sodium trifluorosulfonate. ^{From the 1} H-NMR measurement, it was confirmed that the obtained solid was a compound in which the anion moiety was bis (trifluoromethanesulfonyl) imide ion in the above formula (18). This compound is defined as a colorant (A-14).

Example 15
In Example 13, a colorant was synthesized in the same manner as in Example 13 except that K [BF (CN) ₃ ] was used instead of sodium trifluorosulfonate. ^{From the 1} H-NMR measurement, it was confirmed that the obtained solid was a compound having an anion moiety of BF (CN) ₃ ^— in the above formula (18). This compound is defined as a colorant (A-15).

<Preparation of pigment dispersion>
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 of dye solution>
About each of coloring agent (A-1)-coloring agent (A-15) synthesize | combined in the said Examples 1-15, 20 mass parts of coloring agents and 80 mass parts of propylene glycol monomethyl ether are mixed, and dye solution (A- 1) to dye solution (A-15) were prepared. Further, 20 parts by mass of Basic Blue 7 as a colorant and 80 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution a.

<Synthesis of binder resin>
Synthesis example 1
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. Heat to 80 ° C., and 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 16
13.6 parts by mass of the pigment dispersion (A-1), 27.2 parts by mass of the dye solution (A-1), 21.6 parts by mass of the binder resin (B1) solution as the binder resin, manufactured by Toagosei Co., Ltd. M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 9.2 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1 as a photopolymerization initiator -ON (product name IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.2 parts by mass, benzyl-4-hydroxyphenylmethylsulfonium as thermal acid generator Fluorosurfactant Megafac manufactured by DIC Corporation as surfactant 0.2 parts by mass of F-554 and propylene glycol monomethyl ether as a solvent A colored composition having a solid content concentration of 20% by mass was prepared by mixing ether.

The obtained colored composition was applied on a glass substrate using a spin coater and then pre-baked for 10 minutes on a hot plate at 80 ° C. to form a coating film having a thickness of about 2.5 μm.
Next, after cooling the substrate to room temperature, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 2,000 J / m ² without using a high pressure mercury lamp. did. In this way, a blue evaluation cured film was formed on the substrate.

Evaluation of heat resistance The obtained substrate was post-baked in a clean oven at 230 ° C. for 1 hour. The color difference (ΔEab *) was measured for the substrates before and after post-baking. The case where ΔEab * was less than 3.0 was evaluated as ◎, the case where 3.0 or more and less than 5.0 was evaluated as ◯, and the case where 5.0 or more was evaluated as ×. The evaluation results are shown in Table 1.

Evaluation of solvent resistance The obtained substrate was immersed in propylene glycol monomethyl acetate at 25 ° C. for 30 minutes. The film thickness before and after this treatment was measured with a stylus-type film thickness measuring machine (Alphastep IQ, KLA Tencor), and the remaining film ratio (film thickness after treatment / film thickness before treatment × 100) was calculated. The case where the remaining film ratio was 90% or more was evaluated as ◎, the case where it was 80% or more and less than 90% was evaluated as ○, and the case where it was less than 80% was evaluated as ×. The evaluation results are shown in Table 1.

Examples 16 to 30 and Comparative Example 1
In Example 1, a colored composition was prepared in the same manner as in Example 1, except that the types and amounts of the pigment dispersion and the dye solution were changed as shown in Table 1. The obtained colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Claims (6)

(A) a colorant having a cation represented by the following formula (1),
A coloring composition comprising (B) a binder resin and (C) a crosslinking agent.

[In Formula (1),
R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group or a group having an ethylenically unsaturated bond,
R ^{5 to} R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halo group,
Ring A, -NR ¹³ R ¹⁴ (where, R ¹³ and R ¹⁴ mutually independently represent a monovalent hydrocarbon group having a hydrogen atom or a substituted or unsubstituted.) Group having no formula represented by ( 5);

(In the formula (5), Z ⁴ represents a halogenated hydrocarbon group, —COOR, —SR or —SO ₂ R (where R represents a monovalent hydrocarbon group), where * represents diphenylmethane. (Indicates that the bond is bonded to the skeleton.)
An aryl ring represented by the following formula (6);

In (Equation (6), Z ⁵ represents a hydrogen atom, halo, halogenated hydrocarbon group, -OR, -COOR, -SR or -SO ₂ R (where, R represents a monovalent hydrocarbon group. However, * indicates a bond that bonds to the diphenylmethane skeleton.)
In either an aryl ring represented, isoindole ring, an indolizine ring, a quinolizine ring, off Tarajin ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, beta-carboline ring, a phenanthridine ring, an acridine ring, phenanthroline ring, phenazine ring, showing Lee Sobenzofuran ring, Lee Seo benzothiophene ring, isochromene ring, xanthene ring, phenoxathiin ring, thianthrene ring, a benzisothiazole ring or base Nzochiazoru ring. ]   The anion part of the colorant having a cation represented by the formula (1) is selected from the group consisting of a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion and a methide anion. The coloring composition according to claim 1, wherein   Furthermore, (D) The coloring composition of Claim 1 or 2 containing a photoinitiator. A color filter comprising a colored layer containing a colorant having a cation represented by the following formula (1).

[In Formula (1),
R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group or a group having an ethylenically unsaturated bond,
R ^{5 to} R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halo group,
Ring A, -NR ¹³ R ¹⁴ (where, R ¹³ and R ¹⁴ mutually independently represent a monovalent hydrocarbon group having a hydrogen atom or a substituted or unsubstituted.) Group having no formula represented by ( 5);

(In the formula (5), Z ⁴ represents a halogenated hydrocarbon group, —COOR, —SR or —SO ₂ R (where R represents a monovalent hydrocarbon group), where * represents diphenylmethane. (Indicates that the bond is bonded to the skeleton.)
An aryl ring represented by the following formula (6);

In (Equation (6), Z ⁵ represents a hydrogen atom, halo, halogenated hydrocarbon group, -OR, -COOR, -SR or -SO ₂ R (where, R represents a monovalent hydrocarbon group. However, * indicates a bond that bonds to the diphenylmethane skeleton.)
In either an aryl ring represented, isoindole ring, an indolizine ring, a quinolizine ring, off Tarajin ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, beta-carboline ring, a phenanthridine ring, an acridine ring, phenanthroline ring, phenazine ring, showing Lee Sobenzofuran ring, Lee Seo benzothiophene ring, isochromene ring, xanthene ring, phenoxathiin ring, thianthrene ring, a benzisothiazole ring or base Nzochiazoru ring. ]   A display element comprising the color filter according to claim 4. The coloring agent which has a cation represented by following formula (1).

[In Formula (1),
R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group or a group having an ethylenically unsaturated bond,
R ^{5 to} R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halo group,
Ring A, -NR ¹³ R ¹⁴ (where, R ¹³ and R ¹⁴ mutually independently represent a monovalent hydrocarbon group having a hydrogen atom or a substituted or unsubstituted.) Group having no formula represented by ( 5);

(In the formula (5), Z ⁴ represents a halogenated hydrocarbon group, —COOR, —SR or —SO ₂ R (where R represents a monovalent hydrocarbon group), where * represents diphenylmethane. (Indicates that the bond is bonded to the skeleton.)
An aryl ring represented by the following formula (6);

In (Equation (6), Z ⁵ represents a hydrogen atom, halo, halogenated hydrocarbon group, -OR, -COOR, -SR or -SO ₂ R (where, R represents a monovalent hydrocarbon group. However, * indicates a bond that bonds to the diphenylmethane skeleton.)
In either an aryl ring represented, isoindole ring, an indolizine ring, a quinolizine ring, off Tarajin ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, beta-carboline ring, a phenanthridine ring, an acridine ring, phenanthroline ring, phenazine ring, showing Lee Sobenzofuran ring, Lee Seo benzothiophene ring, isochromene ring, xanthene ring, phenoxathiin ring, thianthrene ring, a benzisothiazole ring or base Nzochiazoru ring. ]