JP2012068559A - Coloring composition for color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for a color filter which is excellent in flowability and stable; and a color filter having a good color characteristic and excellent heat resistance which is formed using a red composition having high brightness and a high contrast ratio.SOLUTION: The above problem can be solved by a coloring composition for a color filter which is characterized in that the coloring composition contains a colorant (a), a resin (b), a resin type dispersant (c), an acidic derivative of an organic pigment or a metal salt thereof (d) and a solvent (e), the colorant (a) contains a naphthol AS pigment, and the resin type dispersant (c) is an A-B block copolymer or a B-A-B block copolymer comprising an A block having a quaternary ammonium base and a B block not having a quaternary ammonium base in the side-chain.

Description

  The present invention relates to a color liquid crystal display device, a color filter coloring composition used for the production of a color filter used for a color imaging tube element, and the like, 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. Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  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. Increasing demands are being made.

  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 The filter segments are as fine as several microns to several hundreds of microns, and are regularly 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 light resistance and heat resistance as a colorant is mainly used.

  However, in general, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, since light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state), display devices in the ON state and the OFF state There is a problem that the upper luminance ratio (contrast ratio) is low.

  In order to achieve high brightness and high contrast of the color filter, the pigment contained in the filter segment is often used after being refined. However, various pigments (similarly called crudes having a particle size of 10 to 100 μm produced by chemical reaction, which are made into a mixture of primary particles and aggregated secondary particles by pigmentation treatment) Even if the particles are refined by the refinement treatment method, the pigments whose primary particles or secondary particles have been refined generally tend to agglomerate. When the refinement is too advanced, a huge lump of pigment solid is formed. End up. Furthermore, even if the pigment that has been refined further is dispersed in a pigment carrier containing a resin or the like, and the secondary particles of the pigment are stabilized as close as possible to the primary particles, a stable coloring composition is obtained. It is very difficult.

  In addition, it is difficult to disperse pigments that have been refined into a pigment carrier containing a resin or the like, and it is difficult to disperse pigments stably at high concentrations. It is known to cause various problems.

  For example, pigment compositions containing pigments composed of fine particles often exhibit high viscosity, making it difficult to remove and transport the product from a disperser, and in the worst case, cause gelation during storage, It may even be difficult to use. Furthermore, regarding the surface of the color-developed product of the pigment composition, a poor state such as a decrease in gloss and poor leveling occurs. When different types of pigments are used in combination, color unevenness due to aggregation or phenomena such as sedimentation may cause uneven color and a marked reduction in coloring power.

  Therefore, in general, a resin-type dispersant is used in order to keep the dispersion state good. The resin-type dispersant has a structure of a part that is adsorbed to the pigment and a part that has a high affinity for the solvent as the dispersion medium, and the performance is determined by the balance of these two functional parts. Various types of resin-type dispersants are used according to the surface state of the pigment to be dispersed.

  As the resin-type dispersant, a structure-controlled one having a block type structure (Patent Document 1) or a comb structure (Patent Document 2) is known as having excellent pigment dispersibility. In the case of the block type structure, since the finer pigments have been developed in recent years and the surface area has increased, it is necessary to add a large amount in order to ensure dispersion stability. This causes deterioration in developability and heat resistance. It is. In the case of a comb-shaped structure, the remaining primary or secondary amine is grafted to a polyamine compound having a primary or secondary amino group, which is a comb tooth portion having a functional group such as a carboxyl group or an acryloyl group. However, primary or secondary amines are not preferred because they have highly reactive active hydrogen.

  As described above, the color filter is required to have not only high contrast but also high brightness. In general, in order to obtain high brightness, when dispersing the pigment in the pigment carrier, the transparency of the dispersion is increased to close to the primary particles, and the spectral spectrum of the dispersion has high transmittance, thereby increasing the brightness. It has gained.

  Red, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate, is usually toned using two or more pigments. I. Pigment red 254 and C.I. I. Pigment Red 177 is also a yellow pigment for toning. I. Pigment yellow 150, C.I. I. Pigment yellow 138, C.I. I. It is common to use Pigment Yellow 139. However, as long as the combination of the red pigment and the yellow pigment can be used, it is difficult to obtain both a higher contrast ratio and a higher brightness. Therefore, use of an orange pigment has been proposed as a color material that exhibits a clear color tone and a wide color display area and has high coloring power. (Patent Document 3)

  However, the orange pigment has a solubility in the solvent of the pigment itself, the acidity of the pigment surface, etc. I. Pigment red 254 and C.I. I. Because it is different from CI Pigment Red 177, it is impossible to obtain a colored composition excellent in dispersibility, fluidity, and storage stability even if dispersion is performed using a resin-type dispersant that has been generally used conventionally. There was a problem.

  In the color filter manufacturing process, a transparent electrode for driving the liquid crystal is formed on the color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. However, many of the orange pigments themselves have poor heat resistance, and the use of a large amount of resin-type dispersants causes problems such as a decrease in contrast ratio and a change in hue before and after the process involving high heat. It has become.

JP 2002-31713 A Japanese Patent Laid-Open No. 11-1515 JP-A-9-308794

  The present invention is a stable color filter coloring composition having high brightness and contrast ratio and excellent fluidity, and has good color characteristics and heat resistance formed using the color filter coloring composition. It is to provide an excellent color filter.

  As a result of intensive studies to solve the above problems, the present inventors have found that a colorant (a), a resin (b), a resin-type dispersant (c), an acidic derivative of an organic pigment, or a metal thereof In a colored composition containing a salt (d) and a solvent (e), the colorant (a) contains a naphthol AS pigment, and the resin-type dispersant (c) has a quaternary ammonium base in the side chain. Use of a coloring composition for a color filter, which is an AB block copolymer or a BAB block copolymer comprising an A block and a B block having no quaternary ammonium base As a result, it has been found that the above-mentioned problems can be solved.

In the present invention, the naphthol AS pigment is C.I. I. The present invention relates to a coloring composition for a color filter comprising CI Pigment Orange 38.
The present invention also relates to the coloring composition for a color filter, wherein the acidic derivative of the organic pigment or the metal salt (d) thereof contains a sulfonic acid derivative of quinophthalone or an aluminum salt thereof.
In the present invention, the colorant (a) further comprises C.I. I. Pigment red 254 or C.I. I. Pigment Red 177, and a coloring composition for a color filter.
The present invention also relates to the coloring composition for a color filter, which contains a photopolymerizable monomer and / or a photopolymerization initiator.
The present invention also relates to a color filter comprising a filter segment formed on the substrate with the color filter coloring composition.

  According to the present invention, a color composition for a color filter having high brightness and contrast ratio, excellent dispersibility, fluidity, and storage stability, and a high contrast ratio and brightness and heat resistance using the same. An excellent color filter can be provided.

  The coloring composition for a color filter of the present invention contains a naphthol AS pigment as a colorant (a), an A block having a quaternary ammonium base in the side chain as a resin-type dispersant (c), and a quaternary ammonium base. High fluidity by containing an AB block copolymer or a B-A-B block copolymer, and an acidic pigment derivative or a metal salt (d) thereof, consisting of a B block not present In addition, the use of this composition not only provides high brightness and high contrast ratio, but also improves heat resistance. Thus, it is possible to form a color filter that does not cause a decrease in contrast ratio or change in hue.

First, various components of the coloring composition for a color filter of the present invention will be described.
<Colorant (a)>
When the colorant (a) in the coloring composition for a color filter of the present invention is represented by a color index (CI) number, C.I. I. Pigment orange 4, 24, 38, C.I. I. It includes naphthol AS pigments such as CI Pigment Red 170 and 188. Among these, C.I. I. Pigment Orange 38 is preferable because of its high contrast ratio and high brightness.

The colorant (a) in the coloring composition for a color filter of the present invention can be used alone or in combination of two or more naphthol AS pigments.
Moreover, when using as a red coloring composition for red filter segment formation, since color adjustment becomes easy, you may use together with another red pigment, a yellow pigment, etc.

  Examples of the red pigment that can be used in combination when the coloring composition for a color filter of the present invention is used for a red filter segment include 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, Red pigments such as 168, 176, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, and 279 can be used in combination. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment red 254 or C.I. I. Pigment Red 177 is preferably used, and these may be used together.

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, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, and the like.
Among these, C.I. I. It is preferable to use together CI Pigment Yellow 138, 139, 150 in that the chromaticity region can be expanded.

  When using together with the said red pigment or yellow pigment, the ratio of a naphthol AS pigment is 10 to 90 weight% in all the coloring agents (a), Preferably it is 10 to 70 weight%, More preferably, it is 40 to 60 weight%. The chromaticity region can be expanded by such a composition ratio of the pigment.

  The naphthol AS pigment used in the coloring composition of the present invention is C.I. I. Pigment red 254, C.I. I. It is yellowish than CI Pigment Red 177, and the rising wavelength of the transmission spectrum is in the range of 530 to 560 nm. Therefore, it effectively acts on the bright line of the backlight generally used in liquid crystal display devices, and high brightness is obtained. . Also, an AB block copolymer or a BAB block copolymer comprising a naphthol AS pigment, an A block having a quaternary ammonium base in the side chain, and a B block having no quaternary ammonium base. By using a certain resin-type dispersant (c) in combination with an acidic pigment derivative or a metal salt thereof (d), it becomes possible for the pigment to exist stably in the state of primary particles, and a high contrast ratio is obtained at the same time. I can do it.

[Miniaturization of pigment]
The pigment used in the present invention can be refined by a salt milling treatment. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with a high contrast ratio, it is preferably 100 nm or less. A particularly preferable range is a range of 25 to 85 nm.
The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). 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 pigment particles. Next, for 100 or more pigment particles, the volume of each particle is approximated to a cube having the obtained particle diameter to obtain an average volume, and the length of one side of the cube having this average volume is determined as the average primary The particle size.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After 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 pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  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 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the 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, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. 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 and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. 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 organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Resin (b)>
The resin (b) contained in the coloring composition for a color filter of the present invention disperses the colorant (a), and examples thereof include thermoplastic resins and thermosetting resins. The resin (b) described above is preferably a transparent resin having a spectral transmittance of 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 photosensitive coloring composition, 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 active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  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, and polyimide resins.

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

  Examples of the vinyl-based alkali-soluble resin copolymerized with 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.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and further reacting a polybasic acid anhydride with the generated hydroxyl group to convert an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3
-Hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate may be mentioned. The above may be used in combination. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

  In order to disperse the colorant (a) preferably, the weight average molecular weight (Mw) of the resin (b) is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. is there. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When used in a color filter coloring composition, from the viewpoint of dispersibility, stability, developability, and heat resistance of the colorant (a), a carboxyl that acts as a colorant-adsorbing group and an alkali-soluble group during development. The balance of aliphatic and aromatic groups acting as affinity groups for groups, colorant carriers and solvents is important for pigment dispersibility, penetrability, developability, and durability, and an acid value of 20-300 mg KOH / It is preferable to use g resin. 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. If it exceeds 300 mgKOH / g, no fine pattern remains.

  The resin (b) is preferably used in an amount of 30 parts by weight or more with respect to 100 parts by weight of the total weight of the colorant (a) because the film formability and various resistances are good, and the colorant concentration is high. From the viewpoint that good color characteristics can be expressed, it is preferably used in an amount of 500 parts by weight or less.

<Resin type dispersant (c)>
The resin-type dispersant (c) in the present invention is an AB block copolymer or BA composed of an A block having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base. It is a -B block copolymer. By using a resin type dispersant of AB block copolymer or BAB block copolymer, it is possible to achieve both high heat resistance and dispersibility and prevent coloring due to reaction with other components. it can. The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. However, since the pigment adsorbing groups are randomly arranged in the random type dispersant, the viscosity tends to increase by crosslinking. On the other hand, in the block copolymer, the pigment adsorbing groups are arranged at high density, so that the adsorption to the pigment is strong and there is no crosslinking. For this reason, the block copolymer can ensure higher dispersion stability. Further, the introduction of a quaternary ammonium base increases the polarity of the dispersant and increases the adsorption ability, thereby further improving the dispersion stability.

The A blocks constituting the block copolymer of the resin dispersant of the present invention, for example, quaternary ammonium bases, preferably ^{_{-N + R 1 R 2 R 3}} · Y - ( where, R _1, R ₂ and R ₃ each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group, or two or more of R ₁ , R ₂ and R ₃ are bonded to each other to form a cyclic structure Y ⁻ represents a counter anion.) And has a quaternary ammonium base. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

In -N ⁺ R ₁ R ₂ R ₃ , as a cyclic structure formed by combining two or more of R ₁ , R ₂ and R ₃ with each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Further, these cyclic structures may further have a substituent.

As R ₁ to R ₃ in the ^{_{-N + R 1 R 2 R 3}} , and more preferably may have an alkyl group, or a substituent having carbon atoms of 1 to 3 may have a substituent It is a phenyl group.

A block containing a partial structure represented by the following general formula (1) is particularly preferable.
General formula (1)

(Wherein R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group, or R ₁ , R ₂ and R ₃ are Two or more are bonded to each other to form a cyclic structure, R ₄ represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y ⁻ represents a counter anion.)

In the general formula (1), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH—R ₇ — group, a —COO—R ₈ — group (provided that R ₇ And R ₈ is a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R′—O—R ″ —: R ′ and R ″ are each independently an alkylene group). And is preferably a —COO—R ₈ — group.

Examples of the counter anion Y ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .

  The partial structure containing the specific quaternary ammonium base as described above may be contained in one or more A blocks. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base may be contained in the A block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later. It is done. The content of the partial structure containing no quaternary ammonium base in the A block is preferably 0 to 50% by weight, more preferably 0, based on the weight of all the structural units in the resin-type dispersant (c). Although it is ˜20% by weight, it is most preferable that such a partial structure not containing a quaternary ammonium base is not contained in the A block.

Examples of the B block constituting the block copolymer of the resin-type dispersant (c) of the present invention include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate , Propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, N, N- (Meth) acrylic acid ester monomers such as dimethylaminoethyl (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N-methylolacrylamide, N, N-dimethyl Acrylamide, N, N-dimethylami Such as acrylamide (meth) acrylamide monomer; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; N- methacryloyl morpholine, polymer structure obtained by copolymerizing comonomers such.
Moreover, for example, a polymer having a structure disclosed in JP-A-2004-287298 can be given. Moreover, as a commercial item of the block type dispersing agent which has a quaternary ammonium base, BYK2001, 2000, BYK-LPN-21324 (Bic Chemie Japan Co., Ltd. product) etc. can be mentioned. In this invention, a block type dispersing agent can be used individually or in mixture of 2 or more types.

  The content of the pigment dispersant (c) is preferably 10 to 70 parts by weight, and more preferably 20 to 55 parts by weight with respect to 100 parts by weight of the naphthol AS pigment. When the blending amount of the resin-type dispersant (c) is less than 10 parts by weight, it is difficult to obtain the pigment dispersibility effect. On the other hand, when the amount exceeds 70 parts by weight, alkali developability may be lowered when a pixel dispersion pattern containing the pigment dispersion composition is used and a pixel pattern of a color filter is formed by a photolithography method.

  Resin-type dispersants that can be used in combination include polyurethanes, polyacrylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, 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 polymer Acrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, it can be used alone or in admixture of two or more.

  Commercially available resin-type dispersants that can be used in the present invention include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, manufactured by Big Chemie. 165, 166, 167, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2025, 2155, 9076, 9077, or BYK-LPN6919, 21324 or Anti-Terra-U , 203, 204, or BYK-P104, P104S, 220S, or SOLPERSE-3000, 9000, 13240, 13650, 139 manufactured by Lubrizol Japan, Inc., such as Lactimon, Lactimon-WS, or Bykumen. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, 76500, etc., EFKA-46 manufactured by Fuka Chemicals 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, 4300, 4330 Etc., Ajinomoto Fine Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824 and the like.

<Acid derivative of organic pigment or metal salt thereof (d)>
The coloring composition for a color filter of the present invention is characterized by containing an acidic derivative of an organic pigment or a metal salt (d) thereof. The acidic derivative of the organic pigment or the metal salt (d) thereof has a great effect of preventing re-aggregation of the pigment after dispersion because the pigment adsorption of the pigment and the resin-type dispersant is further promoted and the dispersibility of the pigment is improved. . Therefore, when a colored composition obtained by dispersing a pigment in a pigment carrier using an acidic derivative of an organic pigment or a metal salt (d) thereof, a color filter having excellent stability can be obtained. Further, a resin mold which is an AB block copolymer or a BAB block copolymer, comprising an A block having a quaternary ammonium base in a side chain and a B block having no quaternary ammonium base. It has high heat resistance when used at the same time as the dispersant (c). This is because the acidity of the derivatives decreases due to the acid-base interaction between the acidic substituent and the basic substituent of the dispersant, so that each crystal structure can be formed more densely and the apparent molecular weight is increased. it is conceivable that.

The structure of the acidic derivative of the organic pigment or the metal salt (d) thereof is a compound represented by the following general formula (2).
P-Lx General formula (2)
(However,
P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue L: acidic substituent,
x: hydrogen or metal ion. )

Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; copper phthalocyanine, halogenated copper phthalocyanine, zinc phthalocyanine, halogenated zinc phthalocyanine, Phthalocyanine pigments such as metal-free phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigment; dioxazine pigment; perinone pigment; Thioindigo pigments; isoindoline pigments; isoindolinone pigments; selenium pigments; quinophthalone pigments; dioxazine pigments; metal complex pigments.
Among them, quinophthalone dyes, particularly quinophthalone yellow pigments C.I. I. Pigment Yellow 138 is preferable because it is excellent in productivity, dispersion stability, heat resistance, light resistance, solvent resistance, and the like of the coloring composition.

Examples of the substituent constituting the acidic substituent of L include sulfonic acid, carboxylic acid, phosphoric acid and the like.

Examples of the metal ion of x include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as magnesium, calcium and barium, amphoteric metal ions such as aluminum and zinc, and transition metal ions such as iron and nickel. .
Of these, alkaline earth metal ions such as calcium and barium, amphoteric metal ions such as aluminum and zinc, and transition metal ions such as iron and nickel are preferable. Of these, aluminum ions are particularly preferred because of their high heat resistance and dispersibility.

[Sulphonic acid derivative of quinophthalone or its aluminum salt]
Particularly preferred as an acidic derivative of an organic pigment or a metal salt (d) thereof is a sulfonic acid derivative of quinophthalone or an aluminum salt thereof. The sulfonic acid derivative of quinophthalone or its aluminum salt is excellent in dispersion of the colorant (a) and has a great effect of preventing reaggregation of the colorant after dispersion. Therefore, a colored composition obtained by dispersing a colorant (a) in a colorant carrier such as a resin or an organic solvent using a sulfonic acid derivative of quinophthalone or an aluminum salt thereof is excellent in stability.

  Quinophthalone yellow pigment C.I. I. A sulfonic acid derivative of quinophthalone composed of CI Pigment Yellow 138 is a compound represented by the following formula (3), and an aluminum salt thereof is a compound represented by the following formula (4).

Formula (3):

Formula (4):

  The aluminum salt of the sulfonic acid derivative of quinophthalone is synthesized by a conventional method, but the following method is industrially advantageous. That is, a dye is added to concentrated sulfuric acid or fuming sulfuric acid, and the mixture is heated to perform sulfonation. Next, the reaction solution is poured into a large amount of ice water, and the sulfonic acid derivative precipitated is filtered off with a filter press or the like and washed with water. The resulting aqueous paste of sulfonic acid derivative was redispersed in a large amount of water, adjusted to a weak alkali with aqueous sodium hydroxide solution, and then gradually added with aqueous aluminum sulfate solution to form sulfonic acid, This is a method of forming a salt. Thereafter, the aluminum salt of the sulfonic acid derivative of quinophthalone in powder form can be obtained through steps of filtration, washing with water, drying and pulverization.

  In the present invention, the total amount of the acidic pigment derivative or the metal salt (d) thereof is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, most preferably 100 parts by weight of the naphthol AS pigment. 3 parts by weight or more. When the amount is less than 0.5 part by weight, the contrast ratio may decrease due to a process involving high heat during the production of the color filter. Moreover, it is preferably 40 parts by weight or less, and most preferably 20 parts by weight or less. If it exceeds 40 parts by weight, the light resistance deteriorates, which is not preferable.

  The acidic derivative of the organic pigment or the metal salt (d) thereof may be used alone or may contain both an acidic derivative and a metal salt, and each of them may be used as a mixture of two or more or other pigment derivatives.

  Examples of the dye derivatives that can be used in combination include JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, and JP-B-5 The thing described in 9469 gazette etc. is mentioned.

<Solvent (e)>
The solvent (e) is a filter segment in which a colorant is sufficiently dispersed in a resin, and the colored composition of the present invention is applied on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. Is used to facilitate the formation.
As the solvent (e), 1,2,3-trichloropropane, 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-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate N-methylpyrrolidone, 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, ethyl Lenglycol 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 Nopropyl 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 monoethyl 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, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, vinegar n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters and the like. These may be used singly or in combination.

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

  A solvent (e) can be used individually by 1 type or in mixture of 2 or more types. In addition, the solvent (e) can adjust the colored composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness. Therefore, the solvent (e) is 800 to 4000 parts by weight with respect to 100 parts by weight of the colorant (a). It is preferable to use it in an amount.

  The coloring composition for a color filter of the present invention can be used as a photosensitive coloring composition (resist material) for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

<Photopolymerizable monomer>
The photopolymerizable monomer used in the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to form a resin, and these can be used alone or in combination of two or more. The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant (a), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. Is more preferable.

  Examples of the photopolymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and β-carboxy. Ethyl (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 diglycidyl ether di (meth) acrylate, bisphenol A Glycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (Meth) acrylic esters of methylolated melamine, various acrylic esters and methacrylic esters such as epoxy (meth) acrylate, urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, Pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, Although acrylonitrile etc. are mentioned, it is not necessarily limited to these.

<Photopolymerization initiator>
In the coloring composition for a color filter of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithography method, a photopolymerization initiator or the like is added to add a solvent development type or an alkali development type photosensitive. Can be prepared in the form of an ionic coloring composition. The amount of the photopolymerization initiator used is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the colorant (a), and 10 to 150 parts by weight from the viewpoint of photocurability and developability. More preferably.

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 ben Benzoin compounds such as rudimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4 Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -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- (4 Triazine compounds such as' -methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O Oxime ester compounds such as (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds Or a titanocene compound or the like is used.
These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required.

<Sensitizer>
Furthermore, the 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, tetraphyrin 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) benzopheno And 4,4′-diethylaminobenzophenone.

  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. It is preferable that the compounding quantity at the time of using a sensitizer is 3-60 weight part with respect to 100 weight part of photoinitiators contained in a coloring composition, and it is 5 from a viewpoint of photocurability and developability. More preferably, it is -50 weight part.

<Surfactant>
The coloring composition for a color filter of the present invention can contain a 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 lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; 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 may be used alone or in admixture of two or more, but are not necessarily limited thereto.

<Amine compound>
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. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight in 100% by weight of the total weight of the coloring composition.

  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. The content of the curing accelerator is preferably 0.01 to 15 parts by weight based on the total weight of the thermosetting resin (100 parts by weight).

<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 parts by weight relative to 100 parts by weight of the total weight of the colorant (a).

  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 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total weight of the colorant (a).

<Method for producing colored composition>
The coloring composition for a color filter of the present invention comprises a colorant (a) containing a naphthol AS pigment, an A block having a quaternary ammonium base in the side chain, and a B block having no quaternary ammonium base. A pigment dispersant (c) containing an A-B block copolymer or a B-A-B block copolymer, an acidic derivative of an organic pigment or a metal salt thereof (d), and, if necessary, a resin (b), The solvent (e) can be produced by finely dispersing together (pigment dispersion) using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. The colored composition for color filters of the present invention may be produced by dispersing naphthol AS pigments and other colorants such as red pigments and yellow pigments used together, or by mixing separately dispersed ones. Can also

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, additives, and the like. Can be mixed and adjusted.

  The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

<Removal of coarse particles>
The colored composition for a color filter of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that the coloring composition for color filters substantially does not contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
The color filter of the present invention is a color filter comprising at least one filter segment formed from the coloring composition for a color filter of the present invention.
The color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one red filter segment is a coloring composition for a color filter of the present invention. It is preferable to form using.
The green filter segment can be formed using a normal green coloring composition. Examples of the green coloring composition include C.I. I. Pigment Green 7, 10, 36, 37, 58, and the like. Green coloring compositions 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 It can be used in combination with the yellow pigments such as 181,182,185,187,188,193,194,198,199,213,214.

  Moreover, a blue filter segment can be formed using a normal blue coloring composition. Examples of the blue coloring composition include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and the like. Blue coloring compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.
[Printing 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.

[Photolithography]
When forming a filter segment by a photolithography method, the photosensitive coloring composition prepared as the solvent development type or alkali development type coloring composition is spray coated, spin coated, slit coated, roll coated, etc. on a transparent substrate. The coating method is applied so that the dry film thickness is 0.2 to 5 μm. 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 | stimulate superposition | polymerization of a coloring composition, it can also heat as needed. 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 composition, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can 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 color filter coloring 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.

  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 acid value and polymerization average molecular weight (Mw) of the resin, the amine value and quaternary ammonium salt value of the resin type dispersant, the fineness of the pigment, and the contrast ratio of the coating film are as follows.

<Resin acid value>
The acid value of the resin was determined by potentiometric titration using a 0.1N potassium hydroxide / ethanol solution. The acid value of the resin indicates the acid value of the solid content.

<Resin polymerization average molecular weight (Mw)>
Polymerization average molecular weight (Mw) of the acrylic resin was converted to polystyrene using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. The weight average molecular weight (Mw).

<Amine value of resin-type dispersant>
The amine value of the resin-type dispersant was determined by potentiometric titration using a 0.1N hydrochloric acid aqueous solution, and then converted to an equivalent of potassium hydroxide. The amine value of the resin-type dispersant indicates the amine value of the solid content.

<Quaternary ammonium salt value of resin-type dispersant>
The quaternary ammonium salt value of the resin-type dispersant was determined by titrating with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted into an equivalent of potassium hydroxide. The quaternary ammonium salt value of the following resin type dispersant indicates the quaternary ammonium salt value of the solid content.

<Pigment refinement>
The fineness of the pigment was evaluated by the specific surface area of the pigment particles. The specific surface area was measured with an automatic vapor adsorption amount measuring apparatus (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) using the BET method of nitrogen adsorption.

<Measurement method of contrast ratio of coating film>
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing planes of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but if the polarizing plane is perpendicular, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dried coating film of the colored composition, scattering by the pigment particles occurs, resulting in deviation in a part of the polarization plane. When the amount of light transmitted through the plate is reduced and the polarizing plate is perpendicular, a part of the light is transmitted through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.
(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)
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, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

  First, acrylic resin solutions, resin-type dispersants, pigment derivatives, fine pigments, pigment dispersions other than naphthol AS pigments used in Examples and Comparative Examples, and green coloring compositions used for the production of color filters, blue coloring The method for producing the composition and the yellow coloring composition will be described.

<Method for producing acrylic resin solution>
(Adjustment 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, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Acrylic resin solution 1 was prepared by adding ether acetate.

(Adjustment of acrylic resin solution 2)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are put into 9.3 parts of acrylic acid (100% of glycidyl group) and the container is placed at 120 ° C. The reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 19000. Obtained. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Then, an acrylic resin solution 2 which is an active energy ray curable resin was prepared.

<Method for producing resin-type dispersant>
(Preparation of resin-type dispersant A)
A 4-neck separable flask equipped with a thermometer, stirrer, distillation tube, and condenser was charged with 80 parts of methyl ethyl ketone, 92.0 parts of butyl acrylate, 2.8 parts of sparteine, and 1.9 parts of ethyl bromoisobutyrate. The temperature was raised to 40 ° C. 1.1 parts of cuprous chloride was added and the temperature was raised to 75 ° C. to initiate polymerization. After polymerization for 3 hours, the polymerization solution was sampled, and it was confirmed that the polymerization yield was 95% or more from the solid content of the polymerization, and the weight average molecular weight (Mw) was 6860, 8.0 parts of dimethylaminoethyl methacrylate, Then, 20.0 parts of methyl ethyl ketone was added, and polymerization was further performed. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. 100 parts of the resulting resin solution was diluted with 100 parts of methyl ethyl ketone, 60 parts of cation exchange resin “Diaion PK228LH (Mitsubishi Chemical Corporation)” was added and stirred at room temperature for 1 hour. 6 parts of 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 30 minutes. The polymerization catalyst residue was removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a resin type dispersant A solution having a solid content of 50% by weight (amine value 29 mgKOH / g, quaternary ammonium salt value 0 mgKOH / g). .

(Preparation of resin-type dispersant B)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 50.0 parts of methyl methacrylate and 50.0 parts of 2-methoxyethyl acrylate, and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile were added to propylene glycol monoethyl ether acetate 45 The solution dissolved in 4 parts was added and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. At this time, the weight average molecular weight was 4000. Next, 9.7 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 31.7 parts of propylene glycol monoethyl ether acetate, and 1,8-diazabicyclo- [5.4.0]-as a catalyst 0.2 part of 7-undecene was added and reacted at 120 ° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After completion of the reaction, propylene glycol monoethyl ether acetate was added so that the nonvolatile content was 50% by weight, and a solution of resin-type dispersant B having an acid value of 75 mgKOH / g and a weight average molecular weight of 9500 was obtained (amine) 0 mg KOH / g, quaternary ammonium salt value 0 mg KOH / g).

(Preparation of resin-type dispersant C)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 62.4 parts of methyl ethyl ketone and heated to 75 ° C. under a nitrogen stream. Separately, 19.5 parts of methyl methacrylate, 11.7 parts of n-butyl methacrylate, 11.7 parts of 2-ethylhexyl methacrylate, 7.8 parts of diethylene glycol monomethacrylate (trade name: Bremer PE90 "manufactured by NOF Corporation) are added to the dropping funnel. , 27.3 parts of dimethylaminoethyl methacrylate, 4.7 parts of 2,2′-azobis (2,4-dimethylvaleronitrile), and 15.6 parts of methyl ethyl ketone were mixed and made uniform. The flask was attached to the flask and dropped over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7130, and the mixture was cooled to 50 ° C. To this, 22.0 parts of benzyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thereafter, 150 parts of diethylene glycol was added, ethanol and methyl ethyl ketone were distilled off under reduced pressure at 100 ° C., and the solvent was replaced with propylene glycol monoethyl ether acetate. Thus, a resin type dispersant C solution having a solid content of 50% by weight was obtained (amine value 3 mgKOH / g, quaternary ammonium salt value 97 mgKOH / g).

(Preparation of resin-type dispersant D)
The flask was equipped with a mechanical stirrer, thermometer, nitrogen inlet, drying tube outlet, and addition funnel. The flask was kept at room temperature under a nitrogen atmosphere, and 3000 parts by weight of tetrahydrofuran (THF) was charged into the flask. Next, 200 parts by weight of a solution prepared by dissolving 6 parts by weight of 1-pyrrolidinocyclohexene as an initiator and 92 parts by weight of methylaluminum bis (2,6-di-t-butyl-4-methylphenoxide) in 102 parts by weight of a THF solution was added. Feed I [dimethylaminoethyl methacrylate 200 parts by weight] was slowly added dropwise and stirred for 40 minutes. Completion of Feed I (
After 99% or more of the monomers had reacted), Feed II [benzyl methacrylate (BzMA) 200 parts by weight] was slowly added dropwise and stirred for 30 minutes. After completion of Feed II, Feed III [2-ethylhexyl methacrylate (2EHMA) 100 parts by weight] was slowly added dropwise and stirred for 20 minutes. After completion of Feed III, Feed IV [100 parts by weight of butyl methacrylate (BMA)] was slowly added dropwise and stirred for 20 minutes. After completion of Feed IV, Feed V [100 parts by weight of methyl methacrylate (MMA)] was slowly added dropwise and stirred for 20 minutes. After completion of Feed V, Feed VI [ω-carboxydicaprolactone monoacrylate (ω-capro) 200 parts by weight] was slowly added dropwise and stirred for 30 minutes. After completion of Feed VI, Feed VII [100 parts by weight of methacrylic acid (MAA)] was slowly added dropwise and stirred for 20 minutes. 30 minutes later, 100 parts by weight of methanol was added to obtain a polymer solution. The polymer solution was returned to room temperature, 500 parts by weight of a solution prepared by dissolving 160 parts by weight of benzyl chloride in 340 parts by weight of THF was slowly added dropwise, and then heated to reflux at 80 ° C. for 2 hours. Distillation was started, and the concentrate was added to hexane for reprecipitation purification. 1000 parts by weight of the obtained solid was dissolved in 1500 parts by weight of a 1/1 mixed solution of butyl glycol / propylene glycol monoethyl ether acetate, and thus a resin type dispersant D solution having a solid content of 50% by weight was obtained ( (Amine value 4 mgKOH / g, quaternary ammonium salt value 90 mgKOH / g).

Table 1 summarizes the resin structure and pigment adsorption group of each resin type dispersant synthesized.

<Method for producing pigment derivative>
(Production of derivative A)
30 parts of quinophthalone yellow pigment (CI Pigment Yellow 138) was dissolved in 300 parts of 98% sulfuric acid and stirred at 70 ° C. for 8 hours to carry out sulfonation reaction. The end point of the reaction was defined as the point at which no change in the spectrum was observed by measuring the spectrum of the sulfuric acid solution. Next, this reaction solution was poured into 3000 parts of ice water, and the precipitated sulfonated dye derivative was filtered off, washed with water and dried. I. A derivative A having a structure represented by the formula (5), which is a sulfonated derivative of CI Pigment Yellow 138, was obtained. The yield after drying was 334 parts and the yield was 99% (5)

(Production of derivative B)
The paste of derivative A was redispersed in 10,000 parts of water (pH 2.5). Next, the solution was adjusted to pH 11 with an aqueous sodium hydroxide solution and dissolved to give a red solution. To this solution, 278 parts of an aqueous aluminum sulfate solution (liquid sulfuric acid band) was gradually added. Precipitates appear one after another from the dropped portion, and the pH decreases with the addition, and the pH is 3.6 at the end of the addition. No bleed was seen. The slurry containing this precipitate was filtered off and washed with water. I. A derivative B having a structure represented by the formula (6), which is an aluminum salt of a sulfonated derivative of CI Pigment Yellow 138, was obtained. The yield after drying was 334 parts, and the yield was 99%.
Formula (6)

(Production of derivative C)
In 300 parts of 96% sulfuric acid, 30 parts of a benzimidazolone pigment (CI Pigment Yellow 180) was dissolved at 10 ° C. or lower and stirred at 15 ° C. for 2 hours. The mixture was poured into 3000 parts of ice water, filtered, washed with a 1% aqueous sodium chloride solution, and then washed with water to such an extent that bleeding was observed, to obtain an aqueous paste of a sulfonated benzimidazolone dye.
The resulting benzimidazolone dye sulfonated water paste was reslurried in 10,000 parts of water and adjusted to pH 10 with an aqueous sodium hydroxide solution, and then 20 parts of an aqueous aluminum sulfate solution (liquid sulfuric acid band) was gradually added. The reaction slurry was heated at 90 ° C. for 2 hours, filtered, washed with water, and dried to obtain 25 parts of derivative C having the structure represented by formula (7), which is an aluminum salt of a sulfonated derivative of a benzimidazolone dye. Obtained.
Formula (7)

(Production of derivative D)
To 300 parts of 95% sulfuric acid, 20 parts of a condensed azo pigment (CI Pigment Red 214) was added at 20 ° C. or lower, and the mixture was stirred at 25 ° C. for 3 hours for sulfonation. The reaction solution was poured into 2000 parts of ice water, filtered and washed with dilute hydrochloric acid to obtain a water paste of a sulfonated product of condensed azo dye.
The obtained water paste of the sulfonated condensed azo dye was reslurried in 2000 parts of water, heated to 60 ° C. and adjusted to pH 9, and then 50 parts of an aqueous aluminum sulfate solution (liquid sulfuric acid band) was gradually added. After stirring at 90 ° C. for 2 hours, filtration, washing with water and drying were performed to obtain 25 parts of derivative D having a structure represented by the formula (8), which is an aluminum salt of a sulfonated derivative of a condensed azo dye.
Formula (8)

(Production of derivative E)
30 parts of a dianthraquinone pigment (CI Pigment Red 177) was added to 240 parts of chlorosulfonic acid, heated at 90 ° C. for 3 hours, and poured into 2000 parts of ice water. The resulting suspension was filtered and washed with water to obtain 180 parts of a water paste of a chlorsulfonated dianthraquinone dye.
The obtained water paste of chlorsulfonated dianthraquinone dye was reslurried in 10,000 parts of water, adjusted to pH 11 with an aqueous sodium hydroxide solution, and stirred at 90 ° C. for 6 hours while appropriately adding to maintain pH 11. . Adjust the pH to 10 using hydrochloric acid, add 50 g of an aqueous aluminum sulfate solution (liquid sulfuric acid band), and stir at 90 ° C. for 2 hours. Then, precipitate deposited is filtered, washed with water, dried, and sulfonated derivative of dianthraquinone dye. 25 parts of derivative E having the structure represented by the formula (9) which is an aluminum salt was obtained.
Formula (9)

(Production of derivative F)
In 300 parts of chlorosulfonic acid, 30 parts of 1,4-diketo-3,6-diphenylpyrrolo- [3,4-c] -pyrrole (CI Pigment Red 255) was dissolved at 20 ° C. or lower over 20 minutes. The mixture was stirred at 50 ° C. for 2 hours to effect chlorsulfonation. The reaction solution was added to 5000 parts of ice water, and the resulting precipitate was filtered and washed with water to obtain an aqueous paste of chlorsulfonated diketopyrrolopyrrole pigment.
The obtained diketopyrrolopyrrole pigment chlorosulfonated water paste was reslurried in 3000 parts of water, adjusted to pH 11 using an aqueous sodium hydroxide solution and heated to 80 ° C., and a red solution was obtained. 120 parts of an aqueous aluminum sulfate solution (liquid sulfuric acid band) is gradually added, stirred at 90 ° C. for 2 hours, filtered, washed with water and dried to obtain an aluminum salt of a sulfonated derivative of a diketopyrrolopyrrole dye ( 25 parts of derivative F having the structure shown in 10) was obtained.
Formula (10)

(Structure of derivative G)
As the derivative G, a derivative having a structure represented by the formula (11) was used.
Formula (11)

Derivatives A to G are summarized in Table 2.

<Production method of fine pigment>
(Preparation of refined pigment 1 (PC-1))
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by Ciba Japan), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of diketopyrrolopyrrole-based refined pigment 1 (PC-1) was obtained. The specific surface area of the micronized pigment 1 was 70 m ² / g.

(Preparation of refined pigment 2 (PC-2))
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“Chromophthalred A2B” manufactured by Ciba Japan Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of anthraquinone-based micronized pigment 2 (PC-2) were obtained. The specific surface area of the micronized pigment 2 was 80 m ² / g.

(Preparation of fine pigment 3 (PC-3))
Azo pigment C.I. I. 200 parts of CI Pigment Orange 64 (“Chromophthal Orange GP” manufactured by CSC), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of azo-based fine pigment 3 (PC-3) were obtained. The specific surface area of the micronized pigment 3 was 75 m ² / g.

(Preparation of refined pigment 4 (P-1))
Naphthol AS pigment C.I. I. 200 parts of Pigment Orange 38 (“Novoperm Red HFG” manufactured by Clariant), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , 190 parts of naphthol AS pigment refined pigment 4 (P-1). The specific surface area of the micronized pigment 4 was 65 m ² / g.

(Preparation of refined pigment 5 (P-2))
Naphthol AS pigment C.I. I. 200 parts of Pigment Orange 4 (“Helio Fast Orange G” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , 190 parts of naphthol AS pigment refined pigment 5 (P-2). The specific surface area of the micronized pigment 5 was 75 m ² / g.

(Preparation of refined pigment 6 (P-3))
Naphthol AS pigment C.I. I. 200 parts of Pigment Orange 24 (“Suimei Fast Orange MC” manufactured by Sansui Color Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , 190 parts of naphthol AS pigment refined pigment 6 (P-3). The specific surface area of the micronized pigment 6 was 60 m ² / g.

(Preparation of refined pigment 7 (P-4))
Naphthol AS pigment C.I. I. 200 parts of Pigment Red 170 (“Permanent Red FGR” manufactured by Clariant), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of naphthol AS pigment refined pigment 7 (P-4) were obtained. The specific surface area of the fine pigment 7 was 80 m ² / g.

(Preparation of fine pigment 8 (P-5))
Naphthol AS pigment C.I. I. 200 parts of Pigment Red 188 (“Novoperm Red HF3S” manufactured by Clariant), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , 190 parts of naphthol AS pigment refined pigment 8 (P-5). The specific surface area of the micronized pigment 8 was 70 m ² / g.

(Preparation of green fine pigment 1)
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. . Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of green fine pigment 1 were obtained. The specific surface area of the green fine pigment 1 was 75 m ² / g.

(Preparation of yellow fine pigment 1)
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a yellow fine pigment 1 were obtained. The specific surface area of the yellow fine pigment 1 was 65 m ² / g.

(Preparation of blue fine pigment 1)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Ink Manufacturing Co., Ltd., specific surface area 60 m 2 / g), 200 parts of sodium chloride, 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) It knead | mixed at 80 degreeC for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of blue fine pigment 1 were obtained. The specific surface area of the blue fine pigment 1 was 80 m ² / g.

(Preparation of purple fine pigment 1)
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of purple fine pigment 1 were obtained. The specific surface area of the purple fine pigment 1 was 95 m ² / g.

<Manufacture of pigment dispersions other than naphthol AS pigments>
(Preparation of pigment dispersion (DC-1))
The following mixture 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) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-1) was produced by filtering with a filter.
Fine pigment 1 (PC-1): 10.0 parts (CI Pigment Red 254)
Acrylic resin solution 1: 7.0 parts propylene glycol monomethyl ether acetate (PGMAC): 77.0 parts Resin-type dispersant solution (dispersant D): 6.0 parts

(Preparation of pigment dispersion (DC-2))
The following mixture 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) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a pigment dispersion (DC-2) was produced.
Fine pigment 2 (PC-2): 10.0 parts (CI Pigment Red 177)
Acrylic resin solution 1: 7.0 parts propylene glycol monomethyl ether acetate (PGMAC): 77.0 parts Resin-type dispersant solution (dispersant D): 6.0 parts

(Preparation of pigment dispersion (DC-3))
The following mixture 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) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a pigment dispersion (DC-3) was produced.
Fine pigment 3 (PC-3): 10.0 parts (CI Pigment Orange 64)
Acrylic resin solution 1: 7.0 parts propylene glycol monomethyl ether acetate (PGMAC): 77.0 parts Resin-type dispersant solution (dispersant D): 6.0 parts

<Manufacture of green coloring composition, blue coloring composition, yellow coloring composition>
[Green pigment dispersion]
The following mixture 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) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a pigment dispersion (DP-1) was produced.
Green fine pigment 1 (CI Pigment Green 36): 11.0 parts acrylic resin solution 1: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin-type dispersant (manufactured by Ciba Japan) "EFKA4300"): 1.0 part

[Yellow pigment dispersion]
A yellow pigment dispersion was obtained in the same manner as the green pigment dispersion, except that the green fine pigment 1 (CI Pigment Green 36) was changed to the yellow fine pigment 1 (CI Pigment Yellow 150).

[Blue pigment dispersion]
A blue pigment dispersion was obtained in the same manner as the green pigment dispersion except that the green fine pigment 1 (CI Pigment Green 36) was changed to the blue fine pigment 1 (CI Pigment Blue 15: 6). It was.

[Purple pigment dispersion]
A purple pigment dispersion was obtained in the same manner as the green pigment dispersion, except that the green fine pigment 1 (CI Pigment Green 36) was changed to the purple fine pigment 1 (CI Pigment Violet 23).

[Production of Green Coloring Composition 1]
A mixture of the following composition containing the pigment dispersion shown below was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a green colored composition 1.
Green pigment dispersion: 35.0 parts Yellow pigment dispersion: 10.0 parts Acrylic resin solution 2: 15.0 parts Dipentaerythritol hexaacrylate: 9.0 parts Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan) )): 2.0 parts “2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one”
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.2 part "4,4'-diethylaminobenzophenone"
Cyclohexanone: 28.8 parts

[Production of blue coloring composition 1]
A green colored composition except that 35.0 parts of the green pigment dispersion and 10.0 parts of the yellow pigment dispersion were replaced with a total of 45.0 parts of 36 parts of the blue dispersion and 9 parts of the purple dispersion. In the same manner as in Example 1, a blue colored composition 1 was obtained.

[Production of yellow coloring composition 1]
The yellow colored composition 1 was the same as the green colored composition 1 except that 35.0 parts of the green pigment dispersion and 10.0 parts of the yellow pigment dispersion were replaced with 45.0 parts of the yellow dispersion. Got.

[Example 1]
(Pigment dispersion (D-1))
The following mixture 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) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (D-1) was produced by filtering with a filter.
Fine pigment 4 (P-1): 9.0 parts (CI Pigment Orange 38)
Acrylic resin solution 1: 7.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 77.0 parts Resin type dispersant solution (dispersant D): 6.0 parts Acidic pigment derivative (derivative A): 1.0 part

[Examples 2 to 10, Comparative Examples 2 to 5]
Hereinafter, the pigment dispersions (D-2 to 10 and 12 to 15) were made in the same manner as the pigment dispersion (D-1) except that the pigment, the resin-type dispersant solution and the derivative were changed to the compositions shown in Table 3. It was adjusted.

[Comparative Example 1]
The following mixture 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) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a pigment dispersion (DP-11) was produced.
Fine pigment 4 (P-1): 10.0 parts (CI Pigment Orange 38)
Acrylic resin solution 1: 7.0 parts propylene glycol monomethyl ether acetate (PGMAC): 77.0 parts Resin-type dispersant solution (dispersant D): 6.0 parts

[Evaluation of coloring composition (pigment dispersion) for color filter]
The viscosity and contrast ratio of the pigment dispersions (D-1 to 15) obtained in the examples and comparative examples were evaluated by the following methods.

<Viscosity characteristics>
As for the viscosity of the pigment dispersion, an initial viscosity at 25 ° C. was measured using an E type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.). Separately, 25 g of the pigment dispersion was allowed to stand at 40 ° C. for 24 hours in a sealed state in a glass container, and then the viscosity was measured by the same method as described above to obtain the time-dependent viscosity.

<Contrast ratio (CR)>
Using the obtained pigment dispersion, a spin coater was used to produce three coated substrates so that the dry film thickness was about 1 μm by changing the number of rotations. After coating, the film was dried in a hot air oven at 80 ° C. for 30 minutes, and the film thickness and the contrast ratio were measured. The contrast ratio (CR) at a film thickness of 1 μm was determined from the three points of data by the primary correlation method.
The results are shown in Table 4 below.

An AB block copolymer or a BAB block copolymer comprising a naphthol AS pigment, an A block having a quaternary ammonium base in the side chain, and a B block having no quaternary ammonium base. Examples 1 to 10 of the colored composition for color filter comprising a resin type dispersant, an acidic derivative of an organic pigment or a metal salt thereof, a solvent, and a resin have a lower viscosity than Comparative Examples 1 to 5. Good results with high CR were obtained.
In Examples 1 to 6 containing an acidic derivative of an organic pigment or a metal salt thereof, the viscosity and CR are better than those of Comparative Example 1 that does not contain the organic pigment and Comparative Example 2 that contains a basic derivative. On the other hand, an AB block comprising an A block having an acidic derivative of an organic pigment or a metal salt thereof and having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base. Comparative Examples 3 to 5 containing no dispersant, which is a polymer or a B-A-B block copolymer, are greatly inferior to Example 2 in viscosity and CR.
Among the naphthol AS pigments, C.I. I. Example 2 containing Pigment Orange 38 has a higher CR than Examples 7-10 containing other naphthol AS pigments. Also, Examples 1 and 2 using quinophthalone skeleton sulfonic acid or metal salt thereof are more preferable because CR and viscosity are better than Examples 3 to 6 containing other acidic derivatives or metal salts thereof. It was a result.

[Example 11]
(Photosensitive coloring composition (R-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a photosensitive coloring composition (R-1).
Colorant dispersion (60 parts in total)
Pigment dispersion (D-1): 24.0 parts Pigment dispersion (DC-1): 26.0 parts Acrylic resin solution 2: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (Shin Nakamura Chemical Co., Ltd.) "NK ester ATMPT"
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan Co., Ltd.): 1.2 parts sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts ethylene glycol monomethyl ether acetate: 23.2 parts

[Examples 12 to 22, Comparative Examples 6 to 12]
(Photosensitive coloring composition (R-2 to 19))
A photosensitive colored composition (R-2 to 19) was obtained in the same manner as the photosensitive colored composition (R-1) except that the pigment dispersion was changed to the type and blending amount of the pigment dispersion shown in Table 5. . In the photosensitive coloring composition, a pigment dispersion is used in combination, but the total amount as the colorant dispersion is 50 parts in all the photosensitive coloring compositions.

[Evaluation of Color Filter Coloring Composition (Photosensitive Coloring Composition)]
Evaluation of chromaticity contrast ratio and heat resistance of the photosensitive colored compositions (R-1 to 19) obtained in Examples and Comparative Examples was performed by the following methods.

<Color characteristic evaluation>
A photosensitive coloring composition was applied on a glass substrate so that x = 0.581, y = 0.335 using a C light source, and this substrate was heated at 230 ° C. for 20 minutes. Thereafter, the brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

<Contrast ratio (CR)>
Using a spin coater, the obtained resist was changed in three rotations so that the chromaticity x at the C light source in the CIE color system was 0.560, 0.581, 0.600. Produced. After coating and drying in a hot air oven at 80 ° C. for 30 minutes, the chromaticity and contrast ratio were measured, respectively, and the contrast ratio (CR) at a chromaticity x of 0.581 was determined from the three points by the primary correlation method. .

<Heat resistance of coating film>
A resist material is applied on a transparent substrate so that the dry coating thickness is about 2.0 μm, and UV exposure is performed through a mask having a predetermined pattern. Then, an alkali developer is sprayed to remove uncured parts. Thus, a desired pattern was formed. Then, after heating in an oven at 230 ° C. for 1 hour and allowing to cool, the color difference 1 (L * (1), a * (1), b * (1)) of the obtained coating film with a C light source was measured by a microspectrophotometer. (Olympus Optical Co., Ltd. “OSP-SP200”). Then, as a heat resistance test, the sample was heated in an oven at 250 ° C. for 1 hour, and a color difference 2 (L * (2), a * (2), b * (2)) with a C light source was measured.

Using the measured color difference value, the color difference change rate ΔEab * was calculated by the following formula, and the heat resistance of the coating film was evaluated in the following four stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
：: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 3.0 Δ: ΔEab * is 3.0 or more and less than 5.0 ×: ΔEab * is 5.0 or more, Table 6 The results are shown in.

  An AB block copolymer or a BAB block copolymer comprising a naphthol AS pigment, an A block having a quaternary ammonium base in the side chain, and a B block having no quaternary ammonium base. Examples 11 to 22 of coloring compositions for color filters containing a certain dispersant, an acidic derivative of an organic pigment or a metal salt thereof have better lightness than Comparative Examples 11 and 12, which do not contain a naphthol AS pigment. Yes, CR and heat resistance were good for Comparative Examples 6 and 7 not containing an acidic derivative of an organic pigment or a metal salt thereof.

  In addition, Examples 11 and 12 using quinophthalone skeleton sulfonic acid or metal salt thereof had better CR, viscosity, and heat resistance than Examples 13 to 16 containing other acidic derivatives or metal salts thereof. It was.

[Production example 1 of color filter]
The red colored composition of the present invention, the green colored composition 1 and the blue colored composition 1 were applied onto a substrate by spin coating so as to have a dry film thickness of 1.7 μm. UV exposure is performed through a mask having a predetermined pattern provided in a contact state, and then an alkali developer is sprayed by spraying to remove an uncured portion to form a desired pattern, followed by heating at 230 ° C. for 1 hour. . By repeating the same operation for each color of RGB to produce a color filter, it was possible to produce a color filter having high brightness and excellent heat resistance.

[Production example 2 of color filter]
Using the red coloring composition of the present invention, the green coloring composition 1, the yellow coloring composition 1, and the blue coloring composition 1, it is applied on the substrate by spin coating so that the dry film thickness becomes 1.7 μm. Then, UV exposure is performed through a mask having a predetermined pattern provided in a non-contact state with this film, and then an alkaline developer is sprayed to remove uncured portions to form a desired pattern by spraying at 230 ° C. For 1 hour. By repeating the same operation for each color of RGBY to produce a color filter, it was possible to produce a color filter having high brightness and excellent heat resistance.

Claims (6)

In a coloring composition containing a colorant (a), a resin (b), a resin-type dispersant (c), an acidic derivative of an organic pigment or a metal salt thereof (d), and a solvent (e),
The colorant (a) comprises a naphthol AS pigment;
AB block copolymer or BAB block in which the resin-type dispersant (c) is composed of an A block having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base. A coloring composition for a color filter, which is a copolymer.   Naphthol AS pigments are C.I. I. The coloring composition for color filters according to claim 1, which is CI Pigment Orange 38.   The coloring composition for a color filter according to claim 1 or 2, wherein the acidic derivative of the organic pigment or the metal salt (d) thereof is a sulfonic acid derivative of quinophthalone or an aluminum salt thereof.   The colorant (a) further contains C.I. I. Pigment red 254 or C.I. I. The coloring composition for a color filter according to any one of claims 1 to 3, comprising Pigment Red 177.   Furthermore, the coloring composition for color filters of any one of Claims 1-4 containing a photopolymerizable monomer and / or a photoinitiator.   A color filter comprising a filter segment formed on the substrate by the color filter coloring composition according to claim 1.