JP2013161026A - Colorant composition for color filter, and color filter - Google Patents

Colorant composition for color filter, and color filter Download PDF

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JP2013161026A
JP2013161026A JP2012024877A JP2012024877A JP2013161026A JP 2013161026 A JP2013161026 A JP 2013161026A JP 2012024877 A JP2012024877 A JP 2012024877A JP 2012024877 A JP2012024877 A JP 2012024877A JP 2013161026 A JP2013161026 A JP 2013161026A
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group
parts
colorant
color filter
pigment
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Hisao Saito
悠生 斎藤
Takeshi Nishinaka
健 西中
Hisamitsu Arakawa
久満 荒川
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Toyo Ink Sc Holdings Co Ltd
東洋インキScホールディングス株式会社
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Abstract

PROBLEM TO BE SOLVED: To provide a colorant for color filter that has excellent flowability when being used in a coloring composition, and can obtain high lightness and high contrast ratio when being used in a color filter.SOLUTION: A colorant contains a naphthol azo pigment having a specified structure.

Description

  The present invention relates to a color liquid crystal display device, a color filter colorant used in the production of a color filter used for a color image pickup tube element, a color composition, and a color filter formed using the same. .

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. There is an increasing demand for higher quality and high color reproducibility.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in In general, it is often formed of three color filter segments of red, green, and blue. Each segment is as fine as several microns to several hundreds of microns, and is arranged in a predetermined arrangement for each hue. .

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent heat resistance and light resistance as a colorant is mainly used.

  In the red filter segment of the color filter, C.I. which is a diketopyrrolopyrrole pigment as a main pigment. I. Pigment Red 254 and C.I. an anthraquinone pigment. I. A technique using Pigment Red 177 alone or in combination is common.

  Here, C.I. I. Pigment Red 177 has high contrast and good heat resistance and light resistance, but has a problem of low brightness and poor flowability of the coloring composition.

  In Patent Documents 1 to 3, in order to further improve the brightness of the red filter segment, C.I. I. Pigment red 176, C.I. I. Pigment red 242, and C.I. I. It has been proposed to use an azo pigment such as CI Pigment Orange 38 as a main pigment, but the brightness is not sufficient, and further improvement has been demanded.

JP 2009-237462 A Japanese Patent Laid-Open No. 11-14824 Japanese Patent Laid-Open No. 10-115709

  The problem to be solved by the present invention is a color filter colorant and a color composition which are excellent in fluidity when used in a color filter coloring composition and have high brightness and high contrast ratio when used in a color filter. It is to provide an object and a color filter using the object.

  As a result of intensive studies, the present inventors have found that a naphthol azo pigment having a specific structure can solve the above-described problems, and have reached the present invention.

  That is, this invention relates to the colorant for color filters characterized by containing the azo compound represented by following General formula (1).

General formula (1)

[In General Formula (1), each A independently represents a hydrogen atom, a benzimidazolone group, an optionally substituted phenyl group, or an optionally substituted heterocyclic group.
R 1 represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR 7 , or —COOR 8 . R 2 to R 6 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR 9 , —COOR 10 , —CONHR 11 , or an -SO 2 NHR 12, representative of at least one trifluoromethyl group among R 2 to R 6. R 7 to R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
The present invention also relates to the color filter colorant, wherein A is a phenyl group which may have a substituent.

The present invention further includes C.I. I. Pigment red 254, C.I. I. C. I. Pigment Red 242, or a diketopyrrolopyrrole pigment represented by the following general formula (2) is contained.
General formula (2)
[In general formula (2),
B, C, D and E are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl. group, -CF 3, -OR 13, -SR 14, -N (R 15) R 16, -COOR 17, -CONH 2, -CONHR 18, -CON (R 19) R 20, -SO 2 NH 2, -SO 2 NHR 21, or a -SO 2 N (R 22) R 23,
R 13 to R 23 are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent. ]

  The present invention also relates to the color filter colorant having an average primary particle size of 10 to 50 nm.

  The present invention also relates to a color filter coloring composition comprising at least a colorant and a binder resin, wherein the colorant contains the colorant described above.

  The present invention further relates to the colored composition described above, further comprising a photopolymerizable monomer.

  The present invention also relates to a color filter comprising a filter segment formed from the colored composition described above on a substrate.

  By using the azo compound represented by the general formula (1) of the present invention, it is possible to provide a color filter having excellent lightness and excellent heat resistance and light resistance.

Hereinafter, the present invention will be described in detail.
Note that “CI” described below means a color index (CI).

<Colorant>
First, a color filter colorant (sometimes referred to simply as “colorant”) containing an azo compound represented by the general formula (1) of the present invention will be described. The colorant of the present invention is characterized by containing an azo compound represented by the general formula (1).

  In the general formula (1), in A, the “substituent” of the phenyl group which may have a substituent is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, cyano Of an acidic group selected from a group, a trifluoromethyl group, a nitro group, a hydroxyl group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, an N-substituted sulfamoyl group, a carboxyl group, a sulfo group, a carboxyl group or a sulfo group Trivalent metal salts (for example, sodium salt, potassium salt, aluminum salt, etc.) and the like can be mentioned. Therefore, specific examples of the phenyl group which may have a substituent include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, an o-triphenyl group. Fluoromethylphenyl group, p-chlorophenyl group, p-bromophenyl group, 2,4-dichlorophenyl group, 3-carbamoylphenyl group, 2-chloro-4-carbamoylphenyl group, 2-methyl-4-carbamoylphenyl group, 2 -Methoxy-4-carbamoylphenyl group, 2-methoxy-4-methyl-3-sulfamoylphenyl group, 4-sulfophenyl group, 4-carboxyphenyl group, 2-methyl-4-sulfophenyl group, etc. However, it is not limited to these.

  In A, the “substituent” of the heterocyclic group which may have a substituent is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, or trifluoro group. Monovalent to trivalent metal of an acidic group selected from methyl group, nitro group, hydroxyl group, carbamoyl group, N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, carboxyl group, sulfo group, carboxyl group or sulfo group Salt (for example, sodium salt, potassium salt, aluminum salt etc.) etc. are mentioned. “Heterocycle” means an atom in which one or more heteroatoms other than carbon atoms are contained in the atoms constituting the ring system, and may be a saturated ring or an unsaturated ring. Further, it may be a single ring or a condensed ring. Therefore, the heterocyclic ring includes pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, isoxazole ring, isothiazole ring. , Triazole ring, thiadiazole ring, oxadiazole ring, quinoline ring, benzofuran ring, indole ring, morpholine ring, pyrrolidine ring, piperidine ring, tetrahydrofuran ring and the like. Therefore, the heterocyclic group means a monovalent group derived by removing a hydrogen atom from these heterocycles. Therefore, specific examples of the heterocyclic group which may have a substituent include 2-pyridyl. Group, 3-pyridyl group, 4-pyridyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-imidazolyl group, 2-oxazolyl group Group, 2-thiazolyl group, piperidino group, 4-piperidyl group, morpholino group, 2-morpholinyl group, N-indolyl group, 2-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-quinolino group, N -Carbazolyl group etc. are mentioned.

Examples of the halogen atom in R 1 to R 6 include fluorine, chlorine, bromine, and iodine.

In addition, the alkyl group having 1 to 4 carbon atoms in R 1 to R 12 may be linear or branched, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. , Sec-butyl group, and tert-butyl group.

As the colorant of the present invention, A is preferably a phenyl group which may have a substituent from the viewpoint of lightness. Furthermore, from the viewpoints of lightness and dispersibility, R 1 is preferably an alkyl group having 1 to 4 carbon atoms or —OR 7 , and more preferably R 1 is a methyl group or a methoxy group.

  The colorant of the present invention may have a chemical structure of the general formula (1) or a tautomer thereof, and may be a pigment having any crystal form, and any crystal called a so-called polymorph. It may be a mixed crystal of pigments having a form. The crystal form of these pigments can be confirmed by powder X-ray diffraction measurement or X-ray crystal structure analysis.

  Specific examples of the azo compound used in the colorant of the present invention include the azo compounds shown in Table 1 below, but the present invention is not limited thereto. In Table 1, Ph represents a phenyl group.

(Method for producing colorant)
The colorant of the present invention can be produced by coupling reaction of a diazonium salt and β-naphthol, as is well known in the pigment field.

  First, the amines (diazo component) represented by the following general formula (3) are diazotized with nitrous acid, nitrite or nitrite in an acidic aqueous solution to which hydrochloric acid, sulfuric acid, acetic acid or the like is added. The diazonium salt represented by the following general formula (4) is produced.

General formula (3)

General formula (4)
[In General Formulas (3) and (4), A and R 1 have the same meanings as in General Formula (1). X represents an inorganic or organic anion. ]

Examples of the inorganic or organic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, CH 3 COO , C 6 H 5 COO −, and the like. Preferred are chloride ion, bromide ion, and CH 3 COO 2 .

  Next, the diazonium salt represented by the general formula (4) and the β-naphthols (coupling component) represented by the following general formula (5) are usually reacted at 5 ° C. to 70 ° C. in an aqueous solvent. The azo pigment of the general formula (1) is produced by post-treatment according to a conventional method. Further, the coupling reaction may be performed in the presence of a surfactant, a resin, a pigment derivative, or an inert solvent. Moreover, the manufacturing method of the azo pigment of this invention is not limited to these methods.

General formula (5)
[In General Formula (5), R < 2 > -R < 6 > is synonymous with the thing in General formula (1). ]

(Other pigments)
The colorant for a color filter of the present invention is used in combination with other coloring matter such as a pigment other than the azo pigment of the above general formula (1) or a dye within a range not impairing the effects of the present invention in order to adjust chromaticity. Also good.

  For example, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, Mention may be made of red pigments such as 279, 280, 281, 282, 283, 284, 285, 286 or 287. Examples of red dyes include xanthene series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, and anthraquinone series. Specifically, C.I. I. And salt forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  In addition, C.I. I. Pigment orange 43, 71, or 73 and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or a yellow pigment 221 and the like can be used in combination. Examples of the orange dye and / or yellow dye include quinoline series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, and methine series.

  Preferred dyes to be used in combination include azo dyes, naphtholazo dyes, diketopyrrolopyrrole dyes, anthraquinone dyes, quinophthalone dyes, and perylene dyes from the viewpoint of brightness. Specifically, C.I. I. Pigment red 176, 177, 254, 242, C.I. I. Pigment Yellow 138, 139, 150, 185. Among these, particularly preferred dyes are C.I. I. Pigment Red 254.

Moreover, as a pigment | dye used together, the diketopyrrolopyrrole pigment represented by following General formula (2) is preferable.
General formula (2)
[In general formula (2),
B, C, D and E are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl. group, -CF 3, -OR 13, -SR 14, -N (R 15) R 16, -COOR 17, -CONH 2, -CONHR 18, -CON (R 19) R 20, -SO 2 NH 2, -SO 2 NHR 21, or a -SO 2 N (R 22) R 23,
R 13 to R 23 are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent. ]

  Specific examples of the diketopyrrolopyrrole pigment represented by the general formula (2) that can be used in the present invention are listed below, but are not limited thereto.

Among the diketopyrrolopyrrole pigments represented by the general formula (2) that can be used in the present invention, the formula (2-1), the formula (2-2), the formula (2-3), and the formula (2-4) ), Formula (2-19), and Formula (2-20) are preferable from the viewpoints of brightness, contrast, and crystal precipitation suppression effect. In particular, from the viewpoint of brightness, the formulas (2-19) and (2-20) are preferable. Further, R 18 to R 20 in the formulas (2-3) and (2-4) are an alkyl group having 4 or more carbon atoms, or a phenyl group which may have a substituent. From the point of view, it is preferable. The reason why these are effective in increasing contrast and suppressing crystal precipitation is because of the steric hindrance effect due to bulky substituents such as carboamide groups, phenyl groups, and t-butyl groups having an alkyl group having 4 or more carbon atoms. This is thought to be due to the suppression of aggregation. Moreover, the diketopyrrolopyrrole pigment having a carboamide group, a phenyl group, or a t-butyl group has excellent color characteristics.

  When a colorant other than the azo compound represented by formula (1) is used in combination with the colorant of the present invention, the azo compound of the present invention is 10% by weight to 100% by weight in the total amount of the colorant (100% by weight). It is preferable to be in the range. More preferably, it is in the range of 30 wt% to 100 wt%. When the azo pigment of the present invention is 10% by mass or less, the effect of excellent brightness cannot be exhibited sufficiently.

(Miniaturization of colorant)
The color filter colorant of the present invention provides high brightness and high contrast in the case of a colored composition. Therefore, if necessary, the color filter particle is refined by a salt milling process or the like, if necessary. It can be suitably used as a colorant. The primary particle diameter of the colorant is preferably 10 nm or more in order to improve dispersibility in the colorant carrier. Moreover, in order to obtain a filter segment with high contrast, the thickness is preferably 50 nm or less.

  Salt milling is a process of heating a mixture of a colorant, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the colorant is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions at the time of subjecting the colorant to salt milling, it is possible to obtain a colorant having a sharp particle size distribution in which the primary particle size is very fine and the width of the distribution is widened.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, and most preferably 300 to 1000% by weight based on the total weight of the pigment (100% by weight) from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the colorant and water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, those having a high boiling point of 120 ° C. or higher are preferable from the viewpoint of safety. Such as, for example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol , Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. Is used. These water-soluble organic solvents are preferably used in an amount of 5 to 1000% by weight, and most preferably 50 to 500% by weight, based on the total weight of the colorant (100% by weight).

  When salt milling the colorant, a resin may be added as necessary. Here, the type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the water-soluble organic solvent. The amount of resin used is preferably in the range of 2 to 200% by weight based on the total weight of the colorant (100% by weight).

<Coloring composition for color filter>
The coloring composition for a color filter of the present invention is composed of a binder resin and an organic solvent in addition to the colorant described above.
(Binder resin)
Examples of the binder resin contained in the colored composition for a color filter of the present invention include conventionally known thermoplastic resins and thermosetting resins.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

  When used as a coloring composition for a color filter, the spectral transmittance is preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Energy ray curable resins having ethylenically unsaturated active double bonds include reactive substitution of isocyanate groups, aldehyde groups, epoxy groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, etc. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a group or cinnamic acid is used. In addition, polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer are half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferable as the photosensitive coloring composition for color filters.

  The following are mentioned as a monomer which comprises the said thermoplastic resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene Glycol (meth) acrylate of (meth) acrylates,

  Alternatively, (meth) acrylamide (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, etc. Acrylamides, styrenes, styrenes such as α-methylstyrene, ethyl vinyl ethers, n-propyl vinyl ethers, isopropyl vinyl ethers, n-butyl vinyl ethers, vinyl ethers such as isobutyl vinyl ethers, fatty acid vinyls such as vinyl acetate or vinyl propionate Kind.

  Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-sc N-imidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine.

  In particular, it is preferable to have a structural unit derived from an N-substituted maleimide, and among them, cyclohexylmaleimide, methylmaleimide, ethylmaleimide, and 1,2-bismaleimideethane are preferable from the viewpoint of heat resistance, and cyclohexylmaleimide is particularly preferable.

  Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.

  The coloring composition for a color filter of the present invention preferably includes a thermosetting resin in terms of heat resistance, for example, among them, an epoxy resin and a melamine resin can be more suitably used, and a melamine resin is particularly preferable. Of these, a melamine compound having a methylolimino group or a condensate thereof is more preferable.

  The thermosetting resin is preferably added in the range of 5 to 60 parts by weight with respect to 100 parts by weight of the colorant. If the amount is less than 10 parts by weight, the effect of improving heat resistance and light resistance is reduced, and if it exceeds 60 parts by weight, the developability deteriorates during alkali development, which is not preferable.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 8,000 to 50,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are connected to four separation columns in series in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation. This is a polystyrene equivalent molecular weight measured using “TSK-GEL SUPER H5000”, “H4000”, “H3000”, and “H2000” manufactured by the company and using tetrahydrofuran as the mobile phase.

  When using a binder resin as a coloring composition for a color filter, from the viewpoint of dispersibility, developability, and heat resistance, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, a colorant carrier, and The balance of the aliphatic group and aromatic group acting as an affinity group for the organic solvent is important for dispersibility, developability, and durability, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin can be used in an amount of 20 to 500% by weight based on the total weight of the colorant. If it is less than 30% by weight, the film formability and various resistances are insufficient, and if it exceeds 500% by weight, the colorant concentration is low and color characteristics cannot be expressed.

(Organic solvent)
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent can be included to facilitate the formation.

  Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl -1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m -Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Methylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol mono Ethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

  Among them, because of good dispersion of the colorant of the present invention, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, benzyl It is preferable to use aromatic alcohols such as alcohol and ketones such as cyclohexanone.

  An organic solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, since the solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment with a desired uniform film thickness, the total weight of the colorant is 100% by weight (500% to 4000% by weight). It is preferable to use it in the quantity.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.

(Dye derivative)
Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in combination of two or more.

  The blending amount of the pigment derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, most preferably based on the total amount of the additive colorant (100% by weight) from the viewpoint of improving the dispersibility of the additive colorant. Preferably it is 3 weight% or more. Further, from the viewpoint of heat resistance and light resistance, the total amount of the added colorant is preferably 40% by weight or less, more preferably 35% by weight or less, based on the total amount (100% by weight).

(Resin type dispersant)
The resin-type dispersant has a colorant affinity part that has the property of adsorbing to the added colorant, and a part that is compatible with the colorant carrier, and adsorbs to the added colorant to disperse in the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

  Among the above-mentioned dispersants, a polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion is lowered and a high contrast is exhibited with a small addition amount, and a nitrogen atom-containing graft copolymer or side chain is preferable. Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles and the like are preferred.

  The resin-type dispersant is preferably used in an amount of about 5 to 200% by weight relative to the total amount of the pigment, and more preferably about 10 to 100% by weight from the viewpoint of film formability.

  Commercially available resin-type dispersants include Dsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., Ciba Japan EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 755 , 1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

(Surfactant)
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate , Anionic surfactants such as monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate, chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts, alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  The compounding amount in the case of adding the resin type dispersant and the surfactant is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight based on the total amount of the added colorant (100% by weight). %. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 55% by weight, the dispersion is adversely affected by the excessive dispersant. May affect.

(Method for producing colored composition)
The coloring composition of the present invention is a mixture of at least an azo pigment represented by the general formula (1), a binder resin, and an organic solvent, such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. It can be produced by dispersing using various dispersers. Moreover, the coloring composition of this invention can also be manufactured by mixing the colorant separately dispersed in a binder resin and an organic solvent.

  In this way, when the colorant is dispersed in the binder resin using a disperser, the dispersed particle size becomes smaller as the dispersion proceeds, the transparency increases, and the contrast ratio increases. In particular, a good contrast ratio can be obtained from about 300 nm. On the other hand, when the dispersion progresses and the dispersed particle size becomes small, the viscosity of the dispersion increases and the thixotropic property tends to increase. When used as a photosensitive coloring composition for a color filter, it is required to have a low viscosity and a Newtonian flow because it is required to be coated with a thin film and to have a smooth coating surface. For this reason, it is preferable to suppress the dispersed particle size to about 100 nm in consideration of the viscosity and thixotropic property preferable for normal use. Thus, by using a colorant having an average primary particle size of 100 nm or less and controlling the degree of dispersion so that the average particle size of the dispersed particles is in the range of 50 nm to 150 nm, the increase in viscosity and thixotropic property are minimized. A colorant dispersion with a very high contrast ratio can be obtained.

(Removal of coarse particles)
The colored composition for a color filter of the present invention is 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more by centrifugal separation or filtration using a sintered filter or a membrane filter. It is preferable to remove coarse particles and mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it does not contain particles of 0.3 μm or less.

<Photosensitive coloring composition for color filter>
The coloring composition for a color filter of the present invention can be used as a photosensitive coloring composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

(Photopolymerizable monomer)
The photopolymerizable monomer that can be added to the coloring composition for a color filter of the present invention includes a monomer or an oligomer that forms a transparent resin by being cured by ultraviolet rays or heat, and these are used alone or in combination. Two or more kinds can be mixed and used. The amount of the monomer is preferably 5 to 400% by weight based on the total weight of the colorant (100% by weight), and more preferably 10 to 300% by weight from the viewpoint of photocurability and developability. preferable.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

(Photopolymerization initiator)
The photosensitive coloring composition for a color filter of the present invention is a solvent development type or alkali development type coloring by adding a photopolymerization initiator or the like when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method. It can be prepared in the form of a resist material. The blending amount when using the photopolymerization initiator is preferably 2 to 200% by weight based on the total amount of the colorant, and 5 to 150% by weight from the viewpoint of photocurability and developability. More preferred.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-meth) Cyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxy) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 2 to 200% by weight based on the total amount of the colorant in the color filter coloring composition (100% by weight), and 5 from the viewpoint of photocurability and developability. More preferably, it is -150 weight%.

(Sensitizer)
Furthermore, the photosensitive coloring composition for a color filter of the present invention can contain a sensitizer.

  Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzo Phenone, 4,4'-diethylaminobenzophenone, etc. are mentioned.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  Two or more kinds of sensitizers may be used in any ratio as required. The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the colored composition (100% by weight). From the viewpoint of developability, it is more preferably 5 to 50% by weight.

(Amine compounds)
Moreover, the coloring composition for color filters of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

(Leveling agent)
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the coloring composition for a color filter of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

  Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

(Curing agent, curing accelerator)
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition for color filters of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01 to 15 weight% is preferable with respect to the thermosetting resin whole quantity.

(Other additive components)
The coloring composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of the colorant (100% by weight).

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the colorant in the coloring composition (100% by weight).

<Color filter>
Next, the color filter of the present invention will be described. The color filter of this invention comprises the filter segment formed using the coloring composition for color filters of this invention. Examples of the color filter include those having a red filter segment, a green filter segment, and a blue filter segment. The filter segment is coated with a color filter coloring composition by a spin coat method or a die coat method, and then ultraviolet rays or the like. The active energy rays are irradiated to cure the portion that becomes the filter segment, and then developed to form on the substrate. The red filter segment therein is formed from a coloring composition or a photosensitive coloring composition containing the azo pigment of the present invention.

  The green filter segment can be formed using a normal green coloring composition or a green photosensitive coloring composition containing a green pigment and a pigment carrier. Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58, etc. are used. Blue pigments such as aluminum phthalocyanine can also be used.

  Moreover, a yellow pigment can be used together with a green coloring composition or a green photosensitive coloring composition. Examples of yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, Mention may be made of yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.

  The blue filter segment can be formed using a normal blue coloring composition or a blue photosensitive coloring composition containing a blue pigment and a pigment carrier. Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. A purple pigment can be used in combination with the blue coloring composition or the blue photosensitive coloring composition. Examples of purple pigments that can be used in combination include C.I. I. And violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50. In addition, a basic dye or a salt-forming compound of an acid dye exhibiting blue or purple can be used. When using a dye, a xanthene dye is preferable in terms of heat resistance and lightness.

(Color filter manufacturing method)
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, or the like in addition to the above method, but the colored composition or the photosensitive colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

  The average primary particle diameter of the pigment, the identification method of the azo pigment, the weight average molecular weight (Mw) of the resin, and the acid value of the resin are as follows.

(Average primary particle diameter of pigment)
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

(Azo pigment identification method)
The identification of the azo pigment of the present invention was carried out using a MALDI mass spectrometer autoflex III (hereinafter referred to as TOF-MS) manufactured by Bruker Daltonics, and the molecular ion peak of the obtained mass spectrum, the mass number obtained by calculation, Identified with the agreement.

(Resin polymerization average molecular weight (Mw))
Polymerization average molecular weight (Mw) of the resin is TSKgel column (manufactured by Tosoh Corporation), GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC), and measured in terms of polystyrene measured using THF as a developing solvent. It is a weight average molecular weight (Mw).

(Resin acid value)
To 0.5 to 1.0 part of the resin solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly, and a 0.1 mol / L KOH aqueous solution is used as a titrant and an automatic titrator (“COM-555”). Titration using Hiranuma Sangyo) and the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

(Method for producing binder resin solution)
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

[Example 1]
(Production of red colorant 1 (R-1))
Below, the specific synthesis method of the said azo compound 1 is shown with the reaction scheme (the following reaction scheme A). Other azo compounds according to the present invention can be synthesized according to a similar scheme. In addition, the manufacturing method (synthesis method) of an azo compound is not limited to the following method.

(1) Synthesis of Compound (B) 90 parts of 2,3-hydroxynaphthoic acid and 1.2 parts of N, N-dimethylformamide were added to 573 parts of toluene, heated to 85 ° C., and 556.3 parts of thionyl chloride. Was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was refluxed for 1 hour. The above reaction solution was added dropwise over 30 minutes to a solution in which 80.9 parts of separately prepared compound (A) and 264 parts of toluene were heated to 85 ° C., and the mixture was heated to reflux for 2 hours. After cooling this reaction liquid to 95 ° C., 8.0 parts of 28% ammonia aqueous solution and 20 parts of water were added and stirred at 95-100 ° C. for 15 minutes, and then toluene and unreacted compound (A) were removed by steam distillation. did. The precipitated reaction product was collected by filtration, washed with hot water, and dried to obtain 152 parts (yield: 95.8%) of compound (B).

(2) Synthesis of Azo Compound 1 After adding 36.3 parts of Compound (C) to 252.2 parts of glacial acetic acid, 39.1 parts of 35% hydrochloric acid was added and cooled to −2 to 0 ° C. After adding 42.2 parts of 25% aqueous sodium nitrite solution to this solution, the mixture was stirred for 30 minutes while maintaining at 0-5 ° C. This reaction solution was added to a mixed solution consisting of 50.7 parts of the compound (B) prepared separately by the previous method, 67.1 parts of 25% sodium hydroxide solution, 772 parts of water and 680 parts of isopropyl alcohol for 15 minutes. It was dripped at. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and further stirred while maintaining at 80 ° C. The precipitated reaction product was collected by filtration, washed with hot water and methanol, and dried to obtain 85.9 parts of azo dye 1. (Yield: 98%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 1.

  Next, 80 parts of the azo compound 1, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 1 (R-1) were obtained. The average primary particle size was 38 nm.

[Example 2]
<Production of Red Colorant 2 (R-2)>
(Synthesis of Azo Compound 2)
The same procedure as in Example 1 was carried out except that 66.8 parts of 3-aminobenztrifluoride was used instead of 80.9 parts of compound (A) used in Example 1, and 80 parts of azo compound 2 were obtained. 0.0 part (yield 98%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 2.

  Next, 80 parts of the azo compound 2, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 2 (R-2) were obtained. The average primary particle size was 42 nm.

[Example 3]
<Production of Red Colorant 3 (R-3)>
(Synthesis of Azo Compound 3)
The same operation as in Example 1 was carried out, except that 24.9 parts of 3-amino-4-methoxybenzamide was used instead of 36.3 parts of 3-amino-4-methoxybenzanilide used in Example 1. Thus, 80.0 parts (yield 97%) of azo compound 3 was obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 3.

  Next, 80 parts of the azo compound 3, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 3 (R-3) were obtained. The average primary particle size was 45 nm.

[Example 4]
<Production of Red Colorant 4 (R-4)>
(Synthesis of Azo Compound 4)
Instead of 80.9 parts of compound (A) used in Example 1, 66.8 parts of 3-aminobenztrifluoride, and 3-amino-4 instead of 3-amino-4-methoxybenzanilide The same operation as in Example 1 was carried out except that 24.9 parts of -methoxybenzamide was used to obtain 80.0 parts (yield 97%) of azo compound 4. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 4.

  Next, 80 parts of the azo compound 4, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 4 (R-4) were obtained. The average primary particle size was 39 nm.

[Example 5]
<Production of Red Colorant 5 (R-5)>
(Synthesis of Azo Compound 5)
Instead of the compound (A) used in Example 1, 66.8 parts of 2-aminobenztrifluoride and 3-amino-4-methoxybenzamide instead of 3-amino-4-methoxybenzanilide The same operation as in Example 1 was carried out except that 24.9 parts were used to obtain 80.0 parts (yield 95%) of azo compound 5. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 5.

  Next, 80 parts of the azo compound 5, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 5 (R-5) were obtained. The average primary particle size was 38 nm.

[Example 6]
<Production of Red Colorant 6 (R-6)>
(Synthesis of Azo Compound 6)
Instead of the compound (A) used in Example 1, instead of 5-chloro-2-aminobenztrifluoride and 3-amino-4-methoxybenzanilide, 3-amino-4-methoxybenzamide was replaced with 24 The same operation as in Example 1 was carried out except that 9 parts were used to obtain 80.0 parts of azo compound 6. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 6.

  Next, 80 parts of the azo compound 6, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 6 (R-6) were obtained. The average primary particle size was 42 nm.

[Example 7]
<Production of Red Colorant 7 (R-7)>
(Synthesis of Azo Compound 7)
Instead of the compound (A) used in Example 1, 95.1 parts of 3,5-bis (trifluoromethyl) aniline, and 3-amino-4-methoxybenzanilide instead of 3-amino- The same operation as in Example 1 was carried out except that 24.9 parts of 4-methoxybenzamide was used to obtain 80.0 parts (yield 96%) of azo compound 7. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 7.

  Next, 80 parts of the azo compound 7, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 7 (R-7) were obtained. The average primary particle size was 47 nm.

[Example 8]
<Production of Red Colorant 8 (R-8)>
(Synthesis of Azo Compound 8)
Instead of the compound (A) used in Example 1, 0.050 mol amount of 4-fluoro-3-aminobenztrifluoride, and 3-amino-4 instead of 3-amino-4-methoxybenzanilide The same operation as in Example 1 was carried out except that 0.015 mol of -methoxybenzamide was used, to obtain 7.97 g (yield 96%) of azo compound 8. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 8.

  Next, 80 parts of the azo compound 8, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to a salt milling treatment. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 8 (R-8) were obtained. The average primary particle size was 42 nm.

[Example 9]
<Production of Red Colorant 9 (R-9)>
(Synthesis of Azo Compound 9)
Instead of the compound (A) used in Example 1, 74.3 parts of 2-chloro-5-aminobenztrifluoride and 3-amino-4 instead of 3-amino-4-methoxybenzanilide The same operation as in Example 1 was carried out except that 24.9 parts of -methoxybenzamide was used to obtain 80.0 parts (yield 97%) of azo compound 9. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 9.

  Next, 80 parts of the azo compound 9, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 9 (R-9) were obtained. The average primary particle size was 41 nm.

[Example 10]
<Production of Red Colorant 10 (R-10)>
(Synthesis of Azo Compound 10)
Instead of the compound (A) used in Example 1, 66.8 parts of 4-aminobenztrifluoride and 3-amino-4-methoxybenzamide instead of 3-amino-4-methoxybenzanilide The same operation as in Example 1 was carried out except that 24.9 parts were used to obtain 80.0 parts (yield 95%) of azo compound 10. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 10.

  Next, 80 parts of the azo compound 10, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 10 (R-10) were obtained. The average primary particle size was 48 nm.

[Example 11]
<Production of Red Colorant 11 (R-11)>
(Synthesis of Azo Compound 11)
An azo compound 11 was prepared in the same manner as in Example 1 except that 24.9 parts of 3-amino-4-methylbenzamide was used instead of 3-amino-4-methoxybenzanilide used in Example 1. Of 80.0 parts (yield 97%). As a result of mass spectrometry by TOF-MS, it was identified as azo compound 11.

  Next, 80 parts of the azo compound 11, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 11 (R-11) were obtained. The average primary particle size was 50 nm.

[Example 12]
<Production of Red Colorant 12 (R-12)>
(Synthesis of Azo Compound 12)
Aside from using 51.6 parts of 3-amino-4-methoxybenz- (2′-chloro-5′-trifluoromethyl) anilide instead of 3-amino-4-methoxybenzanilide used in Example 1. Performed the same operation as in Example 1 to obtain 80.0 parts of azo compound 12 (yield 96%). As a result of mass spectrometry by TOF-MS, it was identified as azo compound 12.

  Next, 80 parts of the azo compound 12, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 12 (R-12) were obtained. The average primary particle size was 38 nm.

[Example 13]
<Production of Red Colorant 13 (R-13)>
(Synthesis of Azo Compound 13)
Instead of the compound (A) used in Example 1, 66.8 parts of 3-aminobenztrifluoride and 3-amino-4-methoxybenz- instead of 3-amino-4-methoxybenzanilide The same operation as in Example 1 was carried out except that 46.5 parts of (3′-trifluoromethyl) anilide was used to obtain 80.0 parts (yield 95%) of azo compound 13. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 13.

  Next, 80 parts of the azo compound 13, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 13 (R-13) were obtained. The average primary particle size was 36 nm.

[Example 14]
<Production of Red Colorant 14 (R-14)>
(Synthesis of Azo Compound 14)
The same operation as in Example 1 was carried out except that 44.7 parts of the following compound (D) was used instead of 3-amino-4-methoxybenzanilide used in Example 1, and azo compound 14 was changed to 80. 0 parts (yield 95%) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 14.

  Next, 80 parts of the azo compound 14, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 14 (R-14) were obtained. The average primary particle size was 40 nm.

Compound (D)

[Example 15]
<Production of Red Colorant 15 (R-15)>
(Synthesis of Azo Compound 15)
Instead of (A) used in Example 1, 66.8 parts of 3-aminobenztrifluoride and 44.7 parts of compound (D) instead of 3-amino-4-methoxybenzanilide Except for the above, the same operation as in Example 1 was carried out to obtain 80.0 parts (yield 97%) of azo compound 15. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 15.

Next, 80 parts of the azo compound 1, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 15 (R-15) were obtained. The average primary particle size was 43 nm.
[Example 16]
<Production of Red Colorant 16 (R-16)>
(Synthesis of Azo Compound 16)
The azo compound 16 was prepared in the same manner as in Example 1 except that 27.0 parts of 3-amino-N-methylbenzamide was used instead of 3-amino-4-methoxybenzanilide used in Example 1. Of 80.0 parts (yield 97%). As a result of mass spectrometry by TOF-MS, it was identified as azo compound 16.

  Next, 80 parts of the azo compound 16, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 16 (R-16) were obtained. The average primary particle size was 43 nm.

[Example 17]
<Production of Red Colorant 17 (R-17)>
80 parts of the azo compound 17 obtained in Example 1 was added to 1200 parts of concentrated sulfuric acid and stirred at 40 ° C. for 3 hours, and then this sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The produced precipitate was filtered, washed with water, and dried overnight at 80 ° C. to obtain 78 parts of red colorant 17 (R-17). The average primary particle size was 65 nm.

(Manufacturing method of other red colorants)
[Production Example 1]
(Production of red colorant 18 (RC-1))
Commercially available C.I. I. Pigment Red 254 (PR254) (“Irgafoa Red B-CF” manufactured by Ciba Specialty Chemicals), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 60 ° C. And kneaded for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red colorant 18 (RC-1) were obtained. The average primary particle size was 33 nm.

[Production Example 2]
(Production of red colorant 19 (RC-2))
C. I. Pigment Red 254 ("Irgafore Red B-CF" manufactured by Ciba Specialty Chemicals) I. Pigment Red 177 (PR177) (“CROMOPHTAL RED A2B” manufactured by BASF) was used in the same manner as in the production of Red Colorant 1 (RC-1), and 97 parts of Red Colorant 19 (RC-2) was used. Obtained. The average primary particle size was 37 nm.

[Production Example 3]
(Production of red colorant 20 (RC-3))
C. I. Pigment Red 254 ("Irgafore Red B-CF" manufactured by Ciba Specialty Chemicals) I. Except having changed to pigment red 242 (PR242) (Clariant's SandorinScallet 4RF), it carried out similarly to manufacture of the red coloring agent 1 (RC-1), and obtained 98 parts of red coloring agent 20 (RC-3). The average primary particle size was 39 nm.

[Production Example 4]
(Production of red colorant 21 (RC-4))
C. I. Pigment Red 254 ("Irgafore Red B-CF" manufactured by Ciba Specialty Chemicals) I. Pigment Red 176 (PR176) (“Novoperm Carmine HF3C” manufactured by Clariant) was used in the same manner as in the production of Red Colorant 1 (RC-1), and 98 parts of Red Colorant 21 (RC-4) was used. Obtained. The average primary particle size was 35 nm.

[Production Example 5]
(Production of red colorant 22 (RC-5))
C. I. Pigment Red 254 ("Irgafore Red B-CF" manufactured by Ciba Specialty Chemicals) I. Pigment Orange 38 (PO38) ("Novoperm Red HF part" manufactured by Clariant) was used in the same manner as in the production of Red Colorant 1 (RC-1), and 97 parts of Red Colorant 22 (RC-5) Got. The average primary particle size was 39 nm.

[Production Example 6]
(Production of red colorant 23 (RC-6))
(Brominated diketopyrrolopyrrole pigment formula (2-19))
To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium-tert-amyl alkoxide are added in a nitrogen atmosphere and heated to 100 ° C. with stirring to obtain an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating to 90 ° C. with stirring to prepare a solution of these mixtures. The heated solution of the mixture was slowly dropped into the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropwise addition, heating and stirring were continued for 2 hours at 90 ° C. to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Furthermore, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel with a glass jacket, and cooled to -10 ° C. While cooling this mixture with a high-speed stirring disperser and rotating a shear disk having a diameter of 8 cm at 4000 rpm, the alkali metal salt of the diketopyrrolopyrrole compound obtained above was cooled to 75 ° C. The solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid and water is always kept at −5 ° C. or lower. Was added in small portions over approximately 120 minutes. After addition of the alkali metal salt, red crystals were precipitated to form a red suspension. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and then filtered to obtain a red paste. This paste was re-dispersed in 3500 parts of methanol cooled to 0 ° C. to make a suspension with a methanol concentration of about 90%, and stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the resulting diketopyrrolopyrrole compound aqueous paste was filtered off with an ultrafiltration machine, dried at 80 ° C. for 24 hours, and pulverized, thereby bromination represented by the formula (2-19). 150.8 parts of diketopyrrolopyrrole pigment were obtained.

  100 parts of the brominated diketopyrrolopyrrole pigment represented by the formula (2-19) obtained above, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) at 60 ° C. And kneaded for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red colorant 23 (RC-6) were obtained. The average primary particle size was 45 nm.

[Production Example 7]
(Production of red colorant 24 (RC-7))
(Heterodiketopyrrolopyrrole pigment formula (2-1))
While adding 220 parts of tert-amyl alcohol to the reaction vessel 1 and cooling with a water bath, 32 parts of 60% NaH was added and heated and stirred at 90 ° C. Next, 100 parts of tert-amyl alcohol, 85.0 parts of compound (E) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl are heated and dissolved in the reaction vessel 2, This was dropped into the reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, cooling to 60 ° C., adding 400 parts of methanol and 50 parts of acetic acid, filtering off and washing with methanol, the heterodiketo represented by formula (2-1) 88.1 parts of pyrrolopyrrole pigment were obtained.

Compound (E)

  80 parts of the heterodiketopyrrolopyrrole pigment represented by the formula (2-1) obtained above, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), 60 The mixture was kneaded at 6 ° C. for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 24 (RC-7) were obtained. The average primary particle size was 40 nm.

[Production Example 8]
(Production of red colorant 25 (RC-8))
(Heterodiketopyrrolopyrrole pigment formula (2-2))
Except for changing 60.9 parts of 4-cyanobiphenyl to 54.1 parts of 4-tert-butylbenzonitrile, this was carried out in the same manner as in the production of the heterodiketopyrrolopyrrole pigment formula (2-1), and the formula (2-2 ) 83.9 parts of a heterodiketopyrrolopyrrole pigment represented by the following formula:

  80 parts of the heterodiketopyrrolopyrrole pigment represented by the formula (2-2) obtained above, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), 60 The mixture was kneaded at 6 ° C. for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 25 (RC-8) were obtained. The average primary particle size was 46 nm.

[Production Example 9]
(Production of red colorant 26 (RC-9))
(Heterodiketopyrrolopyrrole pigment formula (2-3a))
Except that 60.9 parts of 4-cyanobiphenyl was changed to 68.7 parts of N-butyl-4-cyanobenzamide, this was carried out in the same manner as in the production of the heterodiketopyrrolopyrrole pigment formula (2-1), and the formula (2- 87.0 parts of a heterodiketopyrrolopyrrole pigment represented by 3a) were obtained.

  80 parts of the heterodiketopyrrolopyrrole pigment represented by the formula (2-3a) obtained above, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), 60 The mixture was kneaded at 6 ° C. for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 26 (RC-9) were obtained. The average primary particle size was 45 nm.

[Production Example 10]
(Production of red colorant 27 (RC-10))
(Heterodiketopyrrolopyrrole pigment formula (2-4a))
Except that 60.9 parts of 4-cyanobiphenyl was changed to 87.8 parts of N, N-dibutyl-4-cyanobenzamide, this was carried out in the same manner as in the production of the heterodiketopyrrolopyrrole pigment formula (2-1), and the formula (2-1) 27.1 parts of heterodiketopyrrolopyrrole pigment represented by 2-4a) was obtained.

  80 parts of the heterodiketopyrrolopyrrole pigment represented by the formula (2-4a) obtained above, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), 60 The mixture was kneaded at 6 ° C. for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 27 (RC-10) were obtained. The average primary particle size was 40 nm.

[Production Example 11]
(Production of Red Colorant 28 (RC-11))
(Heterodiketopyrrolopyrrole pigment formula (2-9a))
Heterodiketopyrrolopyrrole pigment Except that 60.9 parts of 4-cyanobiphenyl was changed to 84.1 parts of 4- (octylthio) benzonitrile, this was carried out in the same manner as in the production of the heterodiketopyrrolopyrrole pigment formula (2-1). ) 85.5 parts of a heterodiketopyrrolopyrrole pigment represented by the following formula:

  80 parts of the heterodiketopyrrolopyrrole pigment represented by the formula (2-9a) obtained above, 800 parts of sodium chloride, and 90 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), 60 The mixture was kneaded at 6 ° C. for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 28 (RC-11) were obtained. The average primary particle size was 43 nm.

(Method for producing colored composition)
[Example 18]
(Preparation of colored composition 1 (RP-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0.0 micrometer filter, and the coloring composition 1 (RP-1) was produced.
Red colorant 1 (R-1) 10.0 parts Resin type dispersant (“PB821” manufactured by Ajinomoto Fine Techno Co., Ltd.) 3.0 parts Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

[Examples 19 to 34, Comparative Examples 1 to 3]
(Preparation of colored compositions 2-12 (RP-2-12))
Colored compositions 2 to 20 (RP-2 to 20) were the same as colored composition 1 (RP-1) except that red colorant 1 (R-1) was changed to the red colorant described in Table 1. Produced.

(Evaluation of coating film of colored composition)
The heat resistance, light resistance, and foreign material evaluation of the coating film produced using the obtained colored composition (RP-1 to 20) were performed by the following methods. Moreover, initial viscosity evaluation of the colored composition (RP-1 to 20) was also performed. Table 2 shows the evaluation results.
(Heat resistance evaluation)
The coloring composition (RP-1 to 20) was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that the dry film thickness was 2.0 μm, and then at 70 ° C. The coated substrate was prepared by drying for 20 minutes and then heating and cooling at 230 ° C. for 60 minutes. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 250 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following three stages.
ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)
○: ΔEab * is less than 2.5 Δ: ΔEab * is 2.5 or more and less than 5.0 ×: ΔEab * is 5.0 or more

(Light resistance evaluation)
A coated substrate is prepared in the same manner as in the heat resistance evaluation, and the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source is measured with a microspectrophotometer ( Measurement was performed using “OSP-SP100” manufactured by Olympus Optical Co., Ltd. Subsequently, an ultraviolet cut filter (“COLORED OPTICAL part LASS L38” manufactured by Hoya Co., Ltd.) was applied on the substrate, and irradiated with ultraviolet rays for 100 hours using a 470 W / m 2 xenon lamp, and then the chromaticity ( [L * (2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was determined by the above formula and evaluated according to the same criteria as for heat resistance.

(Coating foreign material evaluation)
The coloring composition (RP-1 to 20) was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that the dry film thickness was 2.0 μm, and then at 70 ° C. The coated substrate was prepared by drying for 20 minutes and then heating and cooling at 230 ° C. for 60 minutes. The evaluation was performed using a Olympus system metal microscope “BX60”). The magnification was 500 times, and the number of particles that were observable in arbitrary 5 fields of view through transmission was counted. Evaluation was made in the following three stages. ○ indicates that the number of foreign matters is small and good, and Δ indicates that there is a large number of foreign matters but there is no problem in use, and × indicates that the coating cannot be used because of uneven coating due to foreign matters.
○: Number of foreign matter is less than 10 Δ: Number of foreign matter is 10 or more, less than 60 ×: Number of foreign matter is 60 or more

(Initial viscosity evaluation)
The viscosity of the coloring composition was measured at 25 ° C. on the adjustment day using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 20 rpm. Evaluation was made in the following three stages.
○: Less than 20.0 [mPa · s]
Δ: 20.0 or more and less than 40.0 [mPa · s]
×: 40.0 or more [mPa · s]

  As shown in Table 2, the colored composition using the azo compound of the present invention had good results in the heat resistance, light resistance, coating foreign matter, and initial viscosity of the coating film.

(Preparation method of photosensitive coloring composition)
The coloring composition used for preparation of the photosensitive coloring composition was prepared.

(Preparation of colored composition 21 (RP-21))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0.0 micrometer filter, and the coloring composition 21 (RP-21) was produced.
Red colorant 18 (RC-1) 10.0 parts Resin type dispersant ("PB821" manufactured by Ajinomoto Fine Techno Co., Ltd.) 3.0 parts Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of colored composition 22 (RP-22))
A colored composition 22 (RP-22) was produced in the same manner as the colored composition 21 (RP-21) except that the red colorant 18 (RC-1) was changed to the red colorant 20 (RC-3).
(Preparation of colored composition 23 (RP-23))
A colored composition 23 (RP-23) was produced in the same manner as the colored composition 21 (RP-21) except that the red colorant 18 (RC-1) was changed to the red colorant 23 (RC-6).
(Preparation of colored composition 24 (RP-24))
A colored composition 24 (RP-24) was produced in the same manner as the colored composition 21 (RP-21) except that the red colorant 18 (RC-1) was changed to the red colorant 24 (RC-7).
(Preparation of colored composition 25 (RP-25))
A colored composition 25 (RP-25) was produced in the same manner as the colored composition 21 (RP-21) except that the red colorant 18 (RC-1) was changed to the red colorant 25 (RC-8).
(Preparation of colored composition 26 (RP-26))
A colored composition 26 (RP-26) was produced in the same manner as the colored composition 21 (RP-21) except that the red colorant 18 (RC-1) was changed to the red colorant 26 (RC-9).
(Preparation of colored composition 27 (RP-27))
A colored composition 27 (RP-27) was produced in the same manner as the colored composition 21 (RP-21) except that the red colorant 18 (RC-1) was changed to the red colorant 27 (RC-10).
(Preparation of colored composition 28 (RP-28))
A colored composition 28 (RP-28) was produced in the same manner as the colored composition 21 (RP-21) except that the red colorant 18 (RC-1) was changed to the red colorant 28 (RC-11).
[Example 35]
(Preparation of photosensitive coloring composition 1 (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare photosensitive coloring composition 1 (RR-1).
Coloring composition 1 (RP-1) 20.5 parts Coloring composition 5 (RP-5) 22.5 parts Acrylic resin solution 2 8.2 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Propylene glycol monomethyl ether acetate 43 .6 parts

[Examples 36 to 72, Comparative Examples 4 to 7]
(Photosensitive coloring composition 2 to 42 (RR-2 to 42))
Except for changing coloring composition 1 (RP-1) and coloring composition 5 (RP-5) to the combination and ratio of coloring compositions shown in Table 2 (ratio within 43 parts of the total amount of coloring composition) In the same manner as in Example 35, photosensitive colored compositions 36 to 72 (RR-2 to 42) were obtained. In addition, about the ratio change, it was made to match | combine the chromaticity of x = 0.640, y = 0.330 with C light source in the case of coating-film evaluation.

(Evaluation of coating film of photosensitive coloring composition)
The brightness (color characteristic) and contrast of the red coating film produced using the obtained photosensitive coloring compositions 1-42 (RR-1 to 42) were evaluated by the following methods. Table 3 shows the evaluation results.

(Brightness evaluation)
The photosensitive coloring compositions 1-42 (RR-1 to 42) are applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then dried at 70 ° C. for 20 minutes. Using a high-pressure mercury lamp, UV exposure was performed with an integrated light amount of 150 mJ / cm 2 and development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Then, after heating and cooling at 230 ° C. for 60 minutes, the brightness Y (C) of the obtained coating film substrate was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The prepared coated substrate was adjusted to chromaticity of x = 0.640 and y = 0.330 with a C light source after heat treatment at 230 ° C. The alkali developer is composed of 8.0% by mass of sodium carbonate 1.5% by mass, sodium hydrogen carbonate 0.5% by mass, an anionic surfactant (“PERILEX NBL” manufactured by Kao Corporation) and 90% by mass of water. Was used. Regarding brightness Y (C), it can be said that there is a clear difference if it is 0.1 point or more.

(Contrast ratio evaluation)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.

(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)

Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low.

  A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, the measurement was performed through a black mask having a 1 cm square hole in the measurement portion. As the substrate, the same substrate as that for which the brightness evaluation was performed was used.

  From the results in Table 3, it was revealed that the examples using the azo pigments of the present invention were excellent in brightness and contrast in forming color filters. In particular, C.I. conventionally used as a bluish pigment. I. Pigment red 177 and C.I. I. By using instead of Pigment Red 176, the effect of improving the brightness was confirmed.

(Production of color filter)
The green photosensitive coloring composition and the blue photosensitive coloring composition used for preparation of a color filter were produced. In addition, about the red, the photosensitive coloring composition 1 (RR-1) of this invention was used.

(Preparation of green coloring composition 1 (GP-1))
A mixture having the composition shown below was stirred and mixed uniformly, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The green colored composition 1 (GP-1) was produced by filtering with a filter.
Green pigment (CI Pigment Green 36) 6.8 parts Yellow pigment (CI Pigment Yellow 150) 5.2 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin Solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of green photosensitive coloring composition 1 (GR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare green photosensitive coloring composition 1 (GR-1).
Green coloring composition 1 (GP-1) 42.0 parts Acrylic resin solution 2 13.2 parts Photopolymerizable monomer (“Aronix M402” manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907" manufactured by the company) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 39.6 parts ethylene glycol monomethyl ether acetate

(Preparation of blue coloring composition 1 (BP-1))
A mixture having the composition shown below was stirred and mixed uniformly, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The blue colored composition 1 (BP-1) was produced by filtering with a filter.
Blue pigment (CI Pigment Blue 15: 6) 7.2 parts Purple Pigment (CI Pigment Violet 23) 4.8 parts Resin type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of blue photosensitive coloring composition 1 (BR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a blue photosensitive coloring composition 1 (BR-1).
Blue coloring composition 1 (BP-1) 34.0 parts Acrylic resin solution 2 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (Ciba Japan) “Irgacure 907” manufactured by the company) 2.0 parts Sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 45.1 parts ethylene glycol monomethyl ether acetate

  A black matrix was patterned on a glass substrate, and the photosensitive coloring composition 1 (RR-1) of the present invention was applied onto the substrate with a spin coater to form a colored film. The coating was irradiated with 300 mJ / cm 2 of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. The formed red filter segment was x = 0.640 and y = 0.330 with a C light source. By the same method, green photosensitive coloring composition 1 (part R-1) x = 0.300, y = 0.600, blue photosensitive coloring composition 1 (BR-1) x = 0.150, A color filter was obtained by forming a green filter segment and a blue filter segment so that y = 0.060.

  By using the photosensitive coloring composition 1 (RR-1) of the present invention, it was possible to produce a color filter with high brightness.

The present invention relates to a color filter formed by using color liquid crystal display device, and a color image pickup tube device for a color filter colorant set used for manufacturing a color filter used in such Narubutsu, and it.

An object of the present invention is to provide excellent flowability when used in the coloring composition for a color filter, high brightness, high contrast for ratio color filter is obtained colorant set when used in color filters Narubutsu And a color filter using the same.

That is, the present invention provides a color filter coloring composition comprising at least a colorant and a binder resin, wherein the colorant is a colorant containing an azo compound represented by the following general formula (1) : The weight average molecular weight (Mw) is 8,000 to 50,000, the binder resin is 20 to 500% by weight based on the total weight of the colorant, and further contains a resin-type dispersant. The resin-type dispersant relates to a coloring composition for a color filter, which is 0.1 to 45% by weight based on the total amount of the coloring agent (100% by weight) .

General formula (1)

[In General Formula (1), each A independently represents a hydrogen atom, a benzimidazolone group, an optionally substituted phenyl group, or an optionally substituted heterocyclic group.
R 1 represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR 7 , or —COOR 8 . R 2 to R 6 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR 9 , —COOR 10 , —CONHR 11 , or an -SO 2 NHR 12, representative of at least one trifluoromethyl group among R 2 to R 6. R 7 to R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
The present invention also relates to the color filter coloring composition, wherein A is a phenyl group which may have a substituent.

The present invention further includes C.I. I. Pigment red 254, C.I. I. C. I. Pigment Red 242 or the following formula wherein the color filter coloring composition characterized by containing the diketopyrrolopyrrole pigment represented by (2) relates.
General formula (2)

[In general formula (2),
B, C, D and E are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl. group, -CF 3, -OR 13, -SR 14, -N (R 15) R 16, -COOR 17, -CONH 2, -CONHR 18, -CON (R 19) R 20, -SO 2 NH 2, —SO 2 NHR 21 or —
SO 2 N (R 22 ) R 23 ,
R 13 to R 23 are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent. ]

Moreover, this invention relates to the said coloring composition for color filters whose average primary particle diameter of a coloring agent is 10-50 nm.

The present invention further relates to the colored composition described above, further comprising a photopolymerizable monomer.
Moreover, this invention relates to the said coloring composition whose photopolymerizable monomer is 10-300 weight% on the basis (100 weight%) of the total weight of a coloring agent.

<Colorant>
First, a description will be given for a color filter coloring agent containing an azo compound represented by a general formula (1) (simply referred to as "colorant"). Wear colorant is characterized in that contains an azo compound represented by the general formula (1).

The wear colorant, from the viewpoints of lightness, A is preferably a substituent is also a phenyl group. Furthermore, from the viewpoints of lightness and dispersibility, R 1 is preferably an alkyl group having 1 to 4 carbon atoms or —OR 7 , and more preferably R 1 is a methyl group or a methoxy group.

Wear colorant is, the chemical structure is formula (1), or may be a tautomer may be a pigment having any crystalline form, any crystal form called a so-called polymorphism It may be a mixed crystal of pigments. The crystal form of these pigments can be confirmed by powder X-ray diffraction measurement or X-ray crystal structure analysis.

Specific examples of the azo compound used in the wear coloring agent, there may be mentioned azo compounds shown in Table 1, the present invention is not limited thereto. In Table 1, Ph represents a phenyl group.

(Method for producing colorant)
Wear colorant, as is well known in the pigment art, it can be prepared by coupling reaction of the diazonium salt and β- naphthols.

(Other pigments)
The color filter colorants, or the like to prepare the chromaticity, without impairing the effect of the present invention may be used in combination with other dyes such as pigments or dyes other than an azo pigment of the general formula (1) .

If the destination color material used in combination coloring agent other than the azo compound represented by the general formula (1), in the colorant total amount (100 wt%), the A zone compound is in the range of 10% to 100% by weight It is preferable. More preferably, it is in the range of 30% by weight to 100% by weight. If A zone pigment is 10 wt% or less, it can not sufficiently exhibit the excellent effect of lightness.

That is, the present invention provides a color filter coloring composition comprising at least a colorant and a binder resin, wherein the colorant is a colorant containing an azo compound represented by the following general formula (1): The weight average molecular weight (Mw) is 8,000 to 50,000, the binder resin is 20 to 500% by weight based on the total weight of the colorant, and further contains a resin-type dispersant. The resin-type dispersant is 0.1 to 45% by weight based on the total amount of the colorant (100% by weight), and the binder resin is a resin copolymerized with paracumylphenol ethylene oxide-modified acrylate as a monomer. The present invention relates to a colored composition for a color filter.

Claims (7)

  1. The coloring agent for color filters characterized by containing the azo compound represented by following General formula (1).
    General formula (1)

    [In General Formula (1), each A independently represents a hydrogen atom, a benzimidazolone group, an optionally substituted phenyl group, or an optionally substituted heterocyclic group.
    R 1 represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR 7 , or —COOR 8 . R 2 to R 6 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR 9 , —COOR 10 , —CONHR 11 , or an -SO 2 NHR 12, representative of at least one trifluoromethyl group among R 2 to R 6. R 7 to R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
  2.   The colorant for a color filter according to claim 1, wherein A is a phenyl group which may have a substituent.
  3. Furthermore, C.I. I. Pigment red 254, C.I. I. C. I. The colorant for a color filter according to claim 1 or 2, comprising Pigment Red 242 or a diketopyrrolopyrrole pigment represented by the following general formula (2).
    General formula (2)

    [In general formula (2),
    B, C, D and E are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl. group, -CF 3, -OR 13, -SR 14, -N (R 15) R 16, -COOR 17, -CONH 2, -CONHR 18, -CON (R 19) R 20, -SO 2 NH 2, -SO 2 NHR 21, or a -SO 2 N (R 22) R 23,
    R 13 to R 23 are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent. ]
  4.   The colorant for a color filter according to any one of claims 1 to 3, wherein the average primary particle size is 10 to 50 nm.
  5.   A color composition for color filters comprising at least a colorant and a binder resin, wherein the colorant contains the colorant according to any one of claims 1 to 4.
  6.   Furthermore, the coloring composition of Claim 5 containing a photopolymerizable monomer.
  7.   A color filter comprising a filter segment formed from the colored composition according to claim 5 or 6 on a substrate.
JP2012024877A 2012-02-08 2012-02-08 Colorant composition for color filter, and color filter Pending JP2013161026A (en)

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JPH08510009A (en) * 1993-02-05 1996-10-22 サウスウォール テクノロジーズ,インコーポレイテッド Plastics have an adhesion promoting layer - metal laminate film
JPH08327809A (en) * 1995-05-31 1996-12-13 Ricoh Co Ltd Plastic reflecting mirror
JP2000081505A (en) * 1998-09-04 2000-03-21 Nikon Corp Reflection mirror and production of reflection mirror
JP2001013309A (en) * 1999-04-30 2001-01-19 Matsushita Electric Works Ltd Reflection mirror
JP2002139610A (en) * 2000-10-31 2002-05-17 Mitsubishi Chemicals Corp Method for manufacturing projection lens
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