JP5834448B2 - Coloring composition for color filter and color filter - Google Patents

Description

  The present invention relates to a colored composition for a color filter used for a color liquid crystal display device and a solid-state imaging device, and a color filter formed using the colored composition.

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

  A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several μm to several hundreds of μm, and are neatly arranged in a predetermined arrangement for each hue.

  Generally, in a color liquid crystal display device, a transparent electrode for driving liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning liquid crystal in a certain direction is further formed thereon. ing. 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.

  Until now, in order to realize high brightness and high contrast of the color filter, the pigment contained in the filter segment has been 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 finely-divided pigment 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.

  Colored compositions in which pigments that have been made finer are dispersed in a pigment carrier often have a high viscosity due to aggregation of pigment particles over time and exhibit thixotropic properties. Such an increase in viscosity and poor fluidity of the colored composition causes various problems in production work and product value. For example, the filter segment of a color filter is generally formed by spin-coating a colored composition in which a pigment is dispersed in a pigment carrier containing a monomer and a resin on a glass substrate. If a poor coloring composition is used, a coating film having a uniform thickness cannot be obtained due to poor spin coatability, poor leveling, etc., which is not preferable.

  In order to improve the color characteristics, brightness, and high contrast ratio of a color filter, conventionally, a red coloring composition is toned with a red pigment and a yellow pigment, and a green coloring composition is toned with a green pigment and a yellow pigment. Is adopted. However, since many yellow pigments are difficult to disperse, mixing and mixing the yellow pigment dispersion may adversely affect the fluidity and stability of the colored composition. Further, in addition to the above required characteristics, there is a limit to color matching using a yellow pigment dispersion having poor dispersibility when trying to further expand the color reproduction region of the color filter.

  Therefore, recently, a method for obtaining a dispersion having good fluidity by adding a basic resin dispersant to a pigment and dispersing the pigment has been studied. However, in the conventional method, it is necessary to add a large amount of a basic resin type dispersant, which causes yellowing of the dispersant in the heating process for producing a color filter, resulting in a decrease in luminance. Resulting in problems such as insufficient developability due to dilution of the concentration of the alkali-soluble resin in the resist component. Therefore, it is ideal for the photosensitive coloring composition to ensure sufficient pigment dispersibility with as little dispersant as possible, and to disperse the pigment finely and uniformly in the composition.

  Among basic resin type dispersants, a star polymer has been proposed as a dispersant having excellent pigment dispersing ability. (Patent Document 2) However, there is no dispersion example in a toning system containing a yellow pigment, and there are problems in fluidity, stability, etc. in the case of obtaining an expansion of color reproduction range and a high contrast ratio.

Japanese Patent No. 4368134 JP 2010-111781 A

  An object of the present invention is to provide a coloring composition for a color filter excellent in fluidity, storage stability, and developability, and a color filter using the same and having a high contrast ratio.

In a coloring composition containing a colorant [A] containing a yellow pigment, a resin [B], and a basic resin type dispersant [C], the basic resin type dispersant [C] has three or more arms. As a structural unit of the arm, the arm has a segment that dissolves in a non-aqueous solvent and a segment that adsorbs to the pigment, and the segment that dissolves in the non-aqueous solvent is a polymer of an ethylenically unsaturated monomer. It is a compound composed of a star polymer having a urea group as a segment that has a coalescence and adsorbs to the pigment, so that a photosensitive coloring composition excellent in fluidity, storage stability, and developability has become possible. is there.

That is, the present invention provides a basic resin type dispersant [C] in a colored composition containing a colorant [A] containing a yellow pigment, a resin [B], and a basic resin type dispersant [C]. Has a polymer side chain that becomes three or more arms, and has a segment that dissolves in a non-aqueous solvent and a segment that adsorbs to a pigment as a structural unit of the arm, and an ethylenic segment that dissolves in the non-aqueous solvent. The present invention relates to a coloring composition for a color filter comprising a polymer of an unsaturated monomer and a star polymer [C1] having a urea group as a segment adsorbed on the pigment.

  Further, the present invention is characterized in that the yellow pigment contains at least one yellow pigment selected from the group consisting of azo yellow pigments, quinophthalone yellow pigments, isoindoline yellow pigments, and benzimidazolone yellow pigments. It is related with the said coloring composition for color filters.

  In the present invention, the yellow pigment is C.I. I. Pigment Yellow 150 is included, and the present invention relates to the above color filter coloring composition.

  The present invention further relates to the color composition for a color filter, further comprising at least one acidic dispersant [D] selected from the group consisting of an acidic pigment derivative and an acidic resin dispersant.

  In the present invention, the colorant [A] further comprises C.I. I. Pigment green 7, C.I. I. Pigment green 36 or C.I. I. It contains the said pigment | dye green 58, The coloring composition for said color filters characterized by the above-mentioned.

  In the present invention, the colorant [A] further comprises C.I. I. Pigment red 177 or C.I. I. Pigment Red 254 is included, and the present invention relates to the color filter coloring composition.

  The present invention also relates to the above color composition for color filters, which further contains a photopolymerizable monomer [E] and / or a photopolymerization initiator [F].

  The present invention also relates to a color filter comprising a filter segment formed on the substrate with the color filter coloring composition.

  In the photosensitive coloring composition for a color filter of the present invention, in the coloring composition containing a colorant [A] containing a yellow pigment, a resin [B], and a basic resin type dispersant [C], Since the resin-type dispersant [C] is a compound composed of a star polymer having a polymer side chain that forms three or more arms, the fluidity, storage stability, and developability are excellent. Moreover, a high-contrast color filter can be formed by using this coloring composition.

  First, the photosensitive coloring composition for color filters of this invention is demonstrated.

The photosensitive coloring composition for a color filter of the present invention is a coloring composition containing a colorant [A] containing a yellow pigment, a resin [B], and a basic resin type dispersant [C]. The resin-type dispersant [C] has a polymer side chain that becomes three or more arms, and has a segment that dissolves in a non-aqueous solvent and a segment that adsorbs to a pigment as a constituent unit of the arm, and the non-aqueous solvent It is characterized in that it is a compound comprising a polymer of an ethylenically unsaturated monomer as a segment dissolved in the polymer and a star polymer having a urea group as a segment adsorbed on the pigment.

  In the present application, when expressed as “(meth) acrylate”, “(meth) acrylic acid”, or “(meth) acrylamide”, unless otherwise specified, “acrylate and / or methacrylate”, It shall represent “acrylic acid and / or methacrylic acid” or “acrylamide and / or methacrylamide”.

  Further, “CI” mentioned below means a color index (CI).

(Colorant [A])
The colorant [A] used in the photosensitive coloring composition for color filters of the present invention is characterized by containing at least a yellow pigment component. Examples of yellow pigments that can be used 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 Yellow pigments such as 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used. Among them, high brightness and high contrast can be used. From the viewpoint, it is preferable to include at least one kind of yellow pigment selected from the group consisting of azo yellow pigments, quinophthalone yellow pigments, isoindoline yellow pigments, and benzimidazolone yellow pigments. I. Pigment Yellow 138, 139, 150, and 185 are more preferable. In particular, C.I. I. Pigment Yellow 150 is preferred. Further, basic dyes exhibiting yellow, acidic dyes and salt-forming compounds of these dyes can be used in combination.

  Further, in the red coloring composition, a red pigment can be used. 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, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, Red pigments such as 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287 can be used, and among these, C.I. I. Pigment Red 177, 254 is preferred. Further, basic dyes exhibiting red color, acidic dyes, and salt-forming compounds of these dyes can also be used. In addition, other pigments such as orange pigments may be used in combination. I. Pigment Orange 36, 38, 43, 71, 73 or the like. In addition, basic dyes that exhibit an orange color, acidic dyes, and salt-forming compounds of these dyes can also be used.

  Further, in the green coloring composition, a green pigment can be used. I. Pigment Green 7, 10, 36, 37, 58 and the like. Among these, C.I. from the viewpoint of high brightness and high contrast. I. Pigment Green 7, 36, 58 are preferred.

  The preferable concentration of the pigment component in all the non-volatile components of the colored composition according to the present invention is 10 to 90% by weight, more preferably 15 to 90% by weight, from the viewpoint of obtaining sufficient color reproducibility with respect to the entire colored composition. 85% by weight, most preferably 20 to 80% by weight. When the concentration of the pigment component is less than 10% by weight, sufficient color reproducibility may not be obtained. When the concentration exceeds 90% by weight, the concentration of the pigment carrier is lowered, and the stability of the coloring composition is poor. May be.

Particularly preferable pigment ratios in the red coloring composition are, for example, 50 to 99% by weight of the red pigment and 1 to 50% by weight of the yellow pigment based on the total weight of the pigment component.
More preferably, the red pigment is 55 to 95% by weight and the yellow pigment is 5 to 45% by weight, based on the total weight of the pigment component. The chromaticity region can be expanded by such a composition ratio of the pigment.

  Particularly preferable pigment ratios in the green coloring composition are, for example, 50 to 99% by weight of the green pigment and 1 to 50% by weight of the yellow pigment based on the total weight of the pigment component.

  More preferably, the green pigment is 55 to 95% by weight and the yellow pigment is 5 to 45% by weight, based on the total weight of the pigment component. The chromaticity region can be expanded by such a composition ratio of the pigment.

  The pigment used in the present invention can be subjected to a salt milling treatment and used in a refined product, and preferably used in a refined product.

  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 works as a crushing aid, and it is thought that the pigment is crushed using the high hardness of the inorganic salt during salt milling, thereby generating an active surface and causing crystal growth. Yes. Therefore, the crushing of the pigment and the crystal growth occur simultaneously during the kneading, and the primary particle diameter of the pigment obtained varies depending on the kneading conditions.

  In order to promote crystal growth by heating, the heating temperature is preferably 40 to 150 ° C. When the heating temperature is less than 40 ° C., crystal growth does not occur sufficiently, and the shape of the pigment particles becomes close to amorphous, which is not preferable. On the other hand, when the heating temperature exceeds 150 ° C., crystal growth proceeds excessively and the primary particle diameter of the pigment becomes large, which is not preferable as a colorant for the color filter coloring composition. The kneading time for the salt milling treatment is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the salt milling treatment pigment and the cost required for the salt milling treatment.

  By optimizing the conditions at the time of subjecting the pigment to salt milling, it is possible to obtain a pigment having a very fine primary particle diameter, a wide distribution range, and a sharp particle size distribution.

  It is preferable that the primary particle diameter calculated | required by TEM (transmission electron microscope) of the yellow pigment used for the coloring composition of this invention is the range of 20-100 nm. When it becomes smaller than 20 nm, dispersion in an organic solvent becomes difficult. On the other hand, if it exceeds 100 nm, a sufficient contrast ratio cannot be obtained. A particularly preferable range is 25 to 85 nm.

  As the water-soluble inorganic salt used in the salt milling treatment, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, and most preferably 300 to 1000% by weight, based on the total weight of the pigment, in terms 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 easily evaporates. 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, or the like is used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by weight, and most preferably 50 to 500% by weight, based on the total weight of the pigment.

  When performing the salt milling treatment, 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% by weight based on the total weight of the pigment.

  When preparing a pigment dispersion contained in the coloring composition for a color filter of the present invention, it is possible to prevent aggregation of the pigment, maintain a finely dispersed state of the pigment, and provide high brightness, high contrast ratio and high color purity. In order to produce a filter, it is preferable to add a pigment derivative. The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, and most preferably 35 parts by weight or less with respect to 100 parts by weight of the colorant.

  A pigment derivative is a compound in which a basic or acidic substituent is introduced into an organic dye. Organic dyes include light yellow aromatic polycyclic compounds that are not generally called dyes, such as naphthalene, anthraquinone, and acridone. Examples of the pigment derivative include JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-9-9. 176511 gazette etc. can be used, and these can be used individually or in mixture of 2 or more types. In the present invention, it is more preferable to use an acidic derivative obtained by introducing an acidic substituent into an organic dye, which will be described in detail separately.

  When preparing a pigment dispersion contained in the coloring composition for a color filter of the present invention, it is possible to prevent aggregation of the pigment, maintain a finely dispersed state of the pigment, and provide high brightness, high contrast ratio and high color purity. In order to produce a filter, it is necessary to add a resin-type dispersant. The resin-type dispersant contains at least a basic resin-type dispersant [C], and further, the basic resin-type dispersant [C] , Including a star polymer [C1] having a polymer side chain serving as three or more arms. Furthermore, it is preferable from the viewpoint of fluidity and stability that an acidic resin type dispersant is further contained. The resin-type dispersant can be used in an amount of preferably 0.1 to 70 parts by weight, more preferably 1 to 60 parts by weight with respect to 100 parts by weight of the pigment.

  The resin-type dispersant has an acidic group or a basic group because it adsorbs to the surface of the pigment using an acidic group or a basic group as an anchor, and the rebound effect of the polymer acts effectively to express dispersion stability. A polymer is preferred. As the acidic group, a carboxyl group, a sulfone group, and a phosphate group are preferable from the viewpoint of excellent adsorption characteristics, and as the basic group, an amino group is preferable from the viewpoint of excellent adsorption characteristics. Also, a combination of a pigment derivative having an acidic group and a resin type dispersant having a basic group, or a combination of a pigment derivative having a basic group and a resin type dispersant having an acidic group, or a resin type having an acidic group The combined use of the dispersant and the resin-type dispersant having a basic group is more preferable because the compatibility with the resin is good.

  As a resin-type dispersant, a comb polymer having a structure in which a branch polymer portion is graft-bonded to a trunk polymer portion having an acidic group or a basic group is more soluble in an organic solvent due to the excellent steric repulsion effect of the branch polymer portion. preferable. Furthermore, a comb polymer having a molecular structure in which two or more branch polymers are grafted to one molecule of the trunk polymer is more preferable for the above reason.

  Examples of commercially available acidic resin type dispersants include DisPerByk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, manufactured by Big Chemie. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-TerrA-U, 203, 204, or BYK-P104, P104S, 220S, or LACtimon, LACtimon-WS, or Bykumen SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 3184, manufactured by Japan Lubrizol Corporation 32000, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400405, manufactured by Efka Chemicals 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503 and the like.

(Basic resin type dispersant [C])
In the present invention, it is preferable to use a basic resin type dispersant having an amine value of 35 to 100 mgKOH / g. The amine value of the basic resin type dispersant is more preferably 50 to 75 mgKOH / g. If the amine value is less than 35 mgKOH / g, it may not be sufficiently adsorbed by the pigment and may result in poor dispersion. If it exceeds 100 mgKOH / g, the adsorption efficiency to the pigment is poor due to adsorption or reaction to the acidic component in the pigment carrier. May result in poor dispersion. As a number average molecular weight of basic resin type dispersing agent [C] used by this invention, 500-50000 are preferable normally, and 3000-30000 are especially more preferable. When the number average molecular weight is less than 500, the effect of steric repulsion due to the pigment affinity group, the effect of compatibility with the pigment carrier, and the effect of compatibility with the pigment carrier and solvent when using a solvent are small, It may be difficult to prevent aggregation of the pigment, and the viscosity of the dispersion may increase. If the number average molecular weight is 50000 or more, the amount of resin added for dispersion increases, and the pigment concentration in the coating film may be lowered.

  As the basic resin type dispersant [C] having an amine value of 35 to 100 mgKOH / g, various types of resin systems such as vinyl, urethane, polyester, polyether, or polyamide can be used. A urethane monomer copolymer type excellent in pigment dispersibility is preferred.

  The basic resin type dispersant [C] constituting the coloring composition for a color filter of the present invention contains a star polymer [C1] having a polymer side chain serving as three or more arms.

(Star polymer [C1])
The star polymer [C1] as used in the present invention is defined as “a polymer in which polymer chains that form three or more arms (arms) are connected by a core that is the center of each arm”. As a star polymer in which the branch part which is an arm (arm) has two or more different segments, (1) a polymer in which two or more different polymer chains are connected by a core (hetero arm star polymer, Mikto arm star polymer) (2) Polymers in which block copolymers are connected by a core ((AB) n-type star polymer, (ABC) n-type star polymer), and the like.

  The star polymer can be synthesized using a living anionic polymerization method, a living cation polymerization method, a living radical polymerization method, or the like. Among these, a living radical polymerization method capable of copolymerizing various sensitive monomers is preferable. The synthesis method of the star polymer by the living radical polymerization method can be performed with reference to Matyjaszewski Macromolecules. 2006, 39, 7216 and the like.

  The core of the star polymer referred to in the present invention binds a plurality of arms, and the structure is not particularly limited. For example, in constructing the core in the case of synthesizing the arm by living polymerization, it is preferable to use the following branched compound as the starting species for living polymerization. Alternatively, a newly synthesized star starting species may be used. The star-type starting species has a branched structure, and a polymer having, for example, a hydroxy group in each one end region thereof is preferable.

  Examples of the starting species for living polymerization include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (also referred to as thioglycerin or thioglycerol). ), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2, Examples include 2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol.

  Newly synthesized star initiators include, for example, methyl methacrylate (MMA), ethyl 2-bromobutyrate, a polymer having a hydroxy group at one end, polymerized from sparteine, anisole, or ethylene glycol dimethacrylate as a ligand. Type polymers, but the present invention is not limited to these.

  Of the above starting species, 3-mercapto-1,2-propanediol is most preferred.

  The starting species is preferably obtained by bulk polymerization or solution polymerization, more preferably from 1 to 20 parts by weight, more preferably from 0.5 to 30 parts by weight, based on 100 parts by weight of the ethylenically unsaturated monomer. The amount is preferably 2 to 15 parts by weight, particularly preferably 2 to 10 parts by weight. The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C. If the amount is less than 0.5 parts by weight, the molecular weight of the vinyl polymer portion is too high, and the absolute amount increases as an affinity portion for the pigment carrier and the solvent, and the dispersibility effect itself may decrease. When the content exceeds 30% by weight, the molecular weight of the vinyl polymer part (A) is too low, and as an affinity site for the pigment carrier and the solvent, the effect of steric repulsion is lost, and it is difficult to suppress pigment aggregation. There is a case.

  An arm part can be formed by mixing the ethylenically unsaturated monomer and the polymerization initiator with the above starting species and heating, but as the polymerization initiator, an azo compound and an organic peroxide can be used. Can be used. Examples of the azo compounds include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) ), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazoline-2- Yl) propane] and the like.

  Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, or diacetyl peroxide.

These polymerization initiators can be used alone or in combination of two or more.
The star polymer arm constitutional unit preferably has a segment that dissolves in a non-aqueous solvent and a segment that adsorbs to a pigment.

  Segments that are soluble in non-aqueous solvents include ethylenically unsaturated monomers and polymers, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth). Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, Alkyl (meth) acrylates such as trimethylcyclohexyl (meth) acrylate or isobornyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, or Aromatic (meth) acrylates such as enoxydiethylene glycol (meth) acrylate; Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate or oxetane (meth) acrylate; Methoxypolypropylene glycol (meth) Alkoxypolyalkylene glycol (meth) acrylates such as acrylate or ethoxypolyethylene glycol (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl N-substituted (meth) acrylamides such as (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine; N, N-dimethylaminoethyl (meth) acrylate, Are amino group-containing (meth) acrylates such as N, N-diethylaminoethyl (meth) acrylate; or nitriles such as (meth) acrylonitrile.

Moreover, as monomers that can be used in combination with the acrylic monomers, styrenes such as styrene or α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether Or fatty acid vinyls such as vinyl acetate or vinyl propionate.

Moreover, a carboxyl group-containing ethylenically unsaturated monomer can be used in combination. As a carboxyl group-containing ethylenically unsaturated monomer, 1 type (s) or 2 or more types can be selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, or crotonic acid.
Among the ethylenically unsaturated monomers exemplified above, lower alkyl (meth) acrylate (the number of carbon atoms in the lower alkyl moiety is 1 to 4), particularly methyl methacrylate is preferably used from the viewpoint of dispersibility and coating film resistance. In view of affinity with the pigment carrier and the dispersion medium, it is more preferable to use methyl methacrylate in combination with n-butyl methacrylate or t-butyl methacrylate.

  As the segment adsorbed on the pigment, there are diisocyanates. For example, known ones conventionally used as chain extenders in the synthesis of polyurethane and the like can be used, and diisocyanates having an aromatic group, aliphatic groups. And diisocyanates having aromatic groups and aliphatic groups, or diisocyanates having alicyclic groups.

  Examples of the diisocyanate having an aromatic group include xylylene diisocyanate, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and 2,4-tolylene diisocyanate. 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, naphthylene diisocyanate, 1,3-bis (isocyanatomethyl) benzene, and the like.

  Examples of the diisocyanate having an aliphatic group include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodeca. Examples thereof include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the diisocyanate having an aromatic group and an aliphatic group include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1, Examples include 4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, or 1,3-tetramethylxylylene diisocyanate.

  Examples of the diisocyanate having an alicyclic group include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Examples include methyl-2,4-cyclohexane diisocyanate or methyl-2,6-cyclohexane diisocyanate.

As described above, the listed diisocyanates are not necessarily limited to these, and two or more kinds can be used in combination.
In addition, as a segment adsorbed on the pigment, there is a polyamine, which is a compound having at least two primary and / or secondary amino groups, and is used for reacting with an isocyanate group to form a urea bond. A diamine is mentioned as such an amine.

  As the diamine having two primary amino groups, a conventionally known chain extender can be used as a chain extender during the synthesis of polyurethane or the like. Specifically, ethylenediamine, propylenediamine [also known as : 1,2-diaminopropane or 1,2-propanediamine], trimethylenediamine [alias: 1,3-diaminopropane or 1,3-propanediamine], tetramethylenediamine [alias: 1,4-diaminobutane] 2-methyl-1,3-propanediamine, pentamethylenediamine [alias: 1,5-diaminopentane], hexamethylenediamine [alias: 1,6-diaminohexane], 2,2-dimethyl-1,3- Fats such as propanediamine, 2,2,4-trimethylhexamethylenediamine, or tolylenediamine Family diamine; alicyclic diamines such as isophorone diamine, or dicyclohexylmethane-4,4'-diamine; or, may be mentioned aromatic diamines such as phenylene diamine, or xylylene diamine and the like.

  In addition, as the diamine having two secondary amino groups, known ones conventionally used as chain extenders can be used during the synthesis of polyurethane and the like. Specifically, N, N -Dimethylethylenediamine, N, N-diethylethylenediamine, N, N'-di-tert-butylethylenediamine, etc. can be mentioned.

  As the diamine having primary and secondary amino groups, a conventionally known chain extender can be used as a chain extender during the synthesis of polyurethane and the like. Specifically, N-methyl Ethylenediamine [alias: methylaminoethylamine], N-ethylethylenediamine [alias: ethylaminoethylamine], N-methyl-1,3-propanediamine [alias: N-methyl-1,3-diaminopropane or methylaminopropylamine] N, 2-methyl-1,3-propanediamine, N-isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl-1,3-diaminopropane [alias: N-isopropyl-1,3-propanediamine or Isopropylaminopropylamine] or N-lauryl 1,3-propanediamine: mention may be made of the Alias N- lauryl-1,3-diaminopropane or lauryl amino propylamine], and the like.

  The polyamine of the present invention is a compound having at least two primary and / or secondary amino groups, and the primary and / or secondary amine reacts with an isocyanate group to form a urea group, and this urea group serves as a pigment adsorption site. However, when the polyamine is a compound having two primary and / or secondary amino groups at both ends and further having a secondary and / or tertiary amino group at both ends, This is particularly preferable because the adsorptivity to the surface is improved.

  Examples of such polyamines include polyamines having two primary and / or secondary amino groups at both ends as shown below, and further having secondary and / or tertiary amino groups at both ends.

  Polyamines include methyliminobispropylamine [alias: N, N-bis (3-aminopropyl) methylamine], lauryliminobispropylamine [alias: N, N-bis (3-aminopropyl) laurylamine], Iminobispropylamine [alias: N, N-bis (3-aminopropyl) amine], N, N′-bisaminopropyl-1,3-propylenediamine, or N, N′-bisaminopropyl-1,4 -Butylene diamine etc. can be mentioned, The methyliminobispropylamine or lauryliminobispropylamine which has two primary amino groups and one tertiary amino group is easy to control reaction with diisocyanate, and is preferable.

  An iminobispropylamine having two primary amino groups and one secondary amino group is preferable because of its good adsorptivity to pigments.

  In addition, as the polyamine of the present invention, a polymer having two or more primary and / or secondary amino groups can also be used.

  Polymers having primary and / or secondary amino groups include ethylenically unsaturated monomers having primary amino groups and ethylenically unsaturated monomers having secondary amino groups, such as vinylamine and allylamine monopolymers. Copolymers (so-called polyvinylamine and polyallylamine), copolymers thereof with other ethylenically unsaturated monomers, ethyleneimine ring-opening polymers, polycondensates of ethylene chloride and ethylenediamine, and oxazolidone- It is preferably selected from the ring-opening polymers (so-called polyethyleneimine). The content of primary and / or secondary amino groups in the polymer is preferably 10 to 100% by weight, more preferably 20 to 100% by weight, in terms of monomer units, based on the polymer. If the content is 10% by weight or more, it is effective for preventing aggregation of pigments and suppressing an increase in viscosity.

Examples of the ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monomer having a primary amino group and an ethylenically unsaturated monomer having a secondary amino group include (meth) acrylic acid, croton Unsaturated carboxylic acid such as acid, itaconic acid, maleic acid or fumaric acid; aromatic vinyl compound such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, indene or vinyltoluene; methyl (meth) (Meth) acrylic acid alkyl esters such as acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, or 2-ethylhexyl (meth) acrylate; (Meth) acrylic acid alkyl aryl ester; glycidyl (meth) acrylate Or a (meth) acrylic acid-substituted alkyl ester having a functional group such as 2-hydroxyethyl (meth) acrylate; a tertiary amino group such as dimethylaminoethyl (meth) acrylate or dimethylaminopropyl (meth) acrylate ( (Meth) acrylic acid substituted alkyl ester; (meth) acrylamide, dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide, or tert-octyl (meth) Alkyl (meth) acrylamides such as acrylamide; substituted alkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide, or dimethylaminopropyl (meth) acrylamide; 1,3-butadiene, or iso Diene compounds such as polyne; one-end methacryloylated polymethyl methacrylate oligomer, one-end methacryloylated polystyrene oligomer, or polymerizable oligomer (macromonomer) such as one-end methacryloylated polyethylene glycol; or vinyl cyanide .

  The weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography) of the polymer having a primary and / or secondary amino group is preferably 300 to 75,000, and preferably 300 to 20,000. It is more preferable that it is, and it is especially preferable that it is 500-5,000. When the weight average molecular weight is 300 to 75,000, it is effective to suppress the viscosity increase of the pigment dispersion by preventing the aggregation of the pigment.

In addition to polyamines, monoamines can also be used as the amine compound constituting the dispersant of the present invention. The monoamine is a monoamine compound having one primary amino group or secondary amino group in the molecule, and the monoamine is used as a reaction terminator in order to suppress excessively high molecular weight in the reaction of diisocyanate and polyamine. Is done. The monoamine may have a polar functional group other than the primary amino group or the secondary amino group in the molecule. Examples of such a polar functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a cyano group, and a nitroxyl group.

As the monoamine, known ones conventionally used as a reaction terminator can be used when synthesizing polyurethane or the like. Specifically, aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1 -Aminobutane, 2-aminobutane, 1-aminopentane, 2-aminopentane, 3-aminopentane, isoamylamine, N-ethylisoamylamine, 1-aminohexane, 1-aminoheptane, 2-aminoheptane, 2-octylamine 1-aminononane, 1-aminodecane, 1-aminododecane, 1-aminotridecane, 1-aminohexadecane, stearylamine, aminocyclopropane, aminocyclobutane, aminocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino- 2-ethyl hex 1-amino-2-methylpropane, 2-amino-2-methylpropane, 3-amino-1-propene, 3-aminomethylheptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-iso Butoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine, 3-lauryloxypropylamine, 3-myristoxypropylamine, 2-aminomethyltetrahydrofuran, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, disec-butylamine, N-ethyl-1,2-dimethylpropylamine, piperidine, 2-pipecoline, 3 -Pipette Phosphorus, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, Pipecolic acid, Isonipecotic acid, Methyl isonipecotate, Ethyl isonipeco Tate, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinebutyric acid hydrochloride, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, indoline, aniline, N-butylaniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1-anilinonaphthalene, 1-aminoanthraquinone, 2-aminoanthraquinone, 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline , o-aminodiphenyl, 4-aminodiphenyl ether, β-aminoethylbenzene, 2-aminobenzophenone, 4-aminobenzophenone, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, N-methylbenzylamine, 3 -Benzylaminopropionic acid ethyl ether, 4-benzylpiperidine, α-phenylethylamine, phenesylamine, p-methoxyphenesylamine, furfurylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine 2-amino-2-methyl-propanol or diphenylamine.

  Among these, a monoamine compound having only a secondary amino group as an aliphatic amine is preferable because it improves the dispersibility of the dispersant.

  Aliphatic monoamine compounds having only secondary amino groups include dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n-butylamine. , Disec-butylamine, N-ethyl-1,2-dimethylpropylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, Examples include 3-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, or 3-pyrrolidinol.

  Moreover, since the tertiary amino group does not have an active hydrogen that reacts with an isocyanate group, a diamine having a primary or secondary amino group and a tertiary amino group is used as a reaction terminator in the same manner as a monoamine. In addition, a tertiary amino group having an effect of improving the pigment adsorption ability can be introduced into the polymer terminal of the dispersant according to the present invention.

  Examples of the diamine having a primary or secondary amino group and a tertiary amino group include N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dimethyl-1,3-propanediamine, or N, N. Diamine having a primary amino group and a tertiary amino group such as 1,2,2-tetramethyl-1,3-propanediamine; or a secondary amino group such as N, N, N′-trimethylethylenediamine and a tertiary amino group And diamines having a group.

  These amine amine compounds acting as a reaction terminator may be used singly or in combination of two or more.

  At the time of synthesis, a known catalyst that has been conventionally used as a synthesis catalyst for polyurethane and the like can be used, and examples thereof include a tertiary amine compound or an organometallic compound.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU), and the like. Examples of organometallic compounds include tin compounds and non-tin compounds.

  Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyl Examples thereof include tin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.

  Examples of non-tin compounds include titanium-based compounds such as dibutyltitanium dichloride, tetrabutyltitanate, or butoxytitanium trichloride; lead oleates; lead-based compounds such as lead 2-ethylhexanoate, lead benzoate, or lead naphthenate. Iron-based such as iron 2-ethylhexanoate or iron acetylacetonate; cobalt-based such as cobalt benzoate or cobalt 2-ethylhexanoate; zinc-based such as zinc naphthenate or zinc 2-ethylhexanoate; Alternatively, a zirconium system such as zirconium naphthenate can be used.

  Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate or the like is preferable in terms of reactivity and hygiene.

  Catalysts such as the tertiary amine compounds or organometallic compounds can be used alone or in combination depending on the case.

  The number of arms (arms) of the star polymer of the present invention is preferably 3-50. The number of arms can be estimated from the number of branches of the starting species used in the synthesis and the amount of polyamine, but the molecular weight measured by gel permeation chromatography (GPC) having a differential refractometer as a detector is the ethylene used in the synthesis. It can also be roughly calculated by dividing by the theoretical molecular weight calculated from the polymerizable unsaturated monomer, isocyanate, and polyamine.

  The present invention uses a star polymer [C1] having a polymer side chain with three or more arms as a dispersant for a yellow pigment, whereby a coloring composition for a color filter having excellent fluidity, storage stability, and developability. It has been found that can be produced.

  The surface of yellow pigments usually used in coloring compositions for color filters often have both acid and base properties, but the acidic properties are stronger, and for good dispersion, for example, comb-shaped or block-shaped basic dispersion It is generally known that the use of agents is effective. In the present invention, by using a star polymer [C1] having a polymer side chain with three or more arms as a yellow pigment dispersant, a yellow pigment dispersion particularly excellent in fluidity and storage stability is prepared. The reason for this is that the yellow pigment is prevented from being adsorbed by the steric hindrance effect caused by the arms extending in three or more directions from the center. The effect of the steric hindrance is greater than that of a comb-shaped polymer or a block-shaped polymer spreading in the horizontal direction. In addition, it is possible to adsorb more yellow pigments and sometimes acidic dispersants by the arms extending in three or more directions from the center. In particular, when adsorbing with an acidic dispersant, it is considered to play a role of bridging the yellow pigment and the acidic dispersant.

(Acid dispersant [D])
When preparing a pigment dispersion contained in the coloring composition for a color filter of the present invention, it is possible to prevent aggregation of the pigment, maintain a finely dispersed state of the pigment, and provide high brightness, high contrast ratio and high color purity. In order to produce a filter, it is preferable to add at least one acidic dispersant [D] selected from the group consisting of an acidic pigment derivative [D1] and an acidic resin type dispersant [D2]. The content of the acidic dispersant [D] in the color filter coloring composition is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 40 parts by weight, and still more preferably 5 to 5 parts by weight with respect to 100 parts by weight of the pigment. 30 parts by weight. When the content of the acidic resin dispersant [D] is less than 0.01 parts by weight, the dispersion effect is insufficient, and when it exceeds 100 parts by weight, the dispersibility may be deteriorated.

(Acid pigment derivative [D1])
It is preferable to add an acidic pigment derivative [D1] that is excellent in pigment dispersibility and has a large effect of preventing reaggregation of the pigment after dispersion to the coloring composition for a color filter of the present invention. The acidic pigment derivative [D1] is a compound in which an acidic substituent is introduced into an organic dye. Organic dyes include light yellow aromatic polycyclic compounds that are not generally called dyes, such as naphthalene, anthraquinone, and acridone. Examples of the pigment derivative include JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-9-9. 176511 gazette etc. can be used, and these can be used individually or in mixture of 2 or more types. The content of the acidic pigment derivative [D1] is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, and most preferably 35 parts by weight or less with respect to 100 parts by weight of the colorant.

(Acid resin type dispersant [D2])
It is preferable to add an acidic resin dispersant [D2] that is excellent in pigment dispersibility and has a large effect of preventing re-aggregation of the pigment after dispersion to the coloring composition for a color filter of the present invention. The acidic resin dispersant [D2] can be used in an amount of preferably 0.1 to 70 parts by weight, more preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the pigment.

  As the acidic group of the acidic resin dispersant [D2], a carboxy group, a sulfone group, and a phosphoric acid group are preferable from the viewpoint of excellent adsorption characteristics, and a carboxy group is more preferable from the viewpoint of excellent fluidity. Also, a combination of a pigment derivative having an acidic group and a resin type dispersant having a basic group, or a combination of a pigment derivative having a basic group and a resin type dispersant having an acidic group, or a resin type having an acidic group The combined use of the dispersant and the resin-type dispersant having a basic group is more preferable because the compatibility with the resin is good.

  As an acidic resin type dispersant having an acidic group, a comb polymer having a structure in which a branch polymer portion is graft-bonded to a trunk polymer portion having an acidic group has more organic solvent solubility due to the excellent steric repulsion effect of the branch polymer portion. Therefore, it is preferable. Furthermore, a comb polymer having a molecular structure in which two or more branch polymers are grafted to one molecule of the trunk polymer is more preferable for the above reason.

  Commercially available resin-type dispersants include DisPerByk-101, 102, 103, 106, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171 manufactured by Big Chemie. 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-TerrA-U, 203, 204, or BYK-P104, P104S, 220S, or LACtimon, LACtimon-WS or Bykumen, etc. SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, manufactured by Nippon Lubrizol 2000, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402 manufactured by Efka Chemicals , 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, and the like.

  The acidic dispersant [D] can be used in an amount of preferably 10 to 400 parts by weight, more preferably 100 to 400 parts by weight with respect to 100 parts by weight of the basic resin type dispersant [C]. The basic resin type dispersant [C] of the present invention has a good compatibility with the acidic dispersant [D], and the more the acidic dispersant [D] is added, the better the dispersibility. A colored composition having at least the basic resin type dispersant [C] having good fluidity and stability can be obtained. That is, by using the basic resin type dispersant [C] of the present invention, in the heating step for producing a color filter, the dispersant is yellowed, resulting in a decrease in luminance, or the alkali-soluble resin in the resist component. The density can be diluted to prevent problems such as insufficient developability.

(Resin [B])
It is preferable that the coloring composition for color filters of this invention contains resin [B]. By including the resin [B], the dispersion stability of the colored composition of the present invention becomes better. When the filter segment is formed using the colored composition for a color filter, there are few pigment aggregates, developability, A filter segment having a good pattern shape can be obtained.

  Resin [B] includes thermoplastic resin [B1], thermosetting resin [B2], alkali-soluble vinyl resin [B3] copolymerized with an acidic group-containing ethylenically unsaturated monomer, and ethylenically unsaturated. The energy ray curable resin [B4] having an active double bond is preferable, and the spectral transmittance is preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, each resin may be used independently and may be used together.

  The thermoplastic resin [B1] includes, for example, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, Examples include 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 [B2] include benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, epoxy resin, urea resin, and phenol resin.

  When the coloring composition for a color filter of the present invention is used in the form of a coloring composition for an alkali development type color filter, an acidic group-containing ethylenically unsaturated monomer such as (meth) acrylic acid is used as the resin [B]. It is preferable to use a polymerized alkali-soluble vinyl resin [B3]. Examples of the alkali-soluble vinyl resin [B3] obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Moreover, the energy beam curable resin [B4] which has an ethylenically unsaturated active double bond can also be used. Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin into which an ethylenically unsaturated double bond is introduced by the following methods (a) and (b).

[Method (a)]
As the method (a), 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, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these 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. Moreover, when an etrahydrophthalic 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 (a), 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 (b)]
As the method (b), 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- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. 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 particular, the resin [B] contains a carboxyl group such as an unsaturated monocarboxylic acid such as (meth) acrylic acid, crotonic acid, or α-chloroacrylic acid, or an unsaturated dicarboxylic acid such as maleic acid or fumaric acid. And a group consisting of a carboxyl group-containing monomer such as a compound having an ethylenically unsaturated double bond, and methyl (meth) methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (Meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl acrylate, neopentyl (meth) acrylate, t-pentyl (meth) acrylate , 1-methylbutyl (meth) ac Rate, hexyl (meth) acrylate, hepta (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, allyl (meth) acrylate, or oleyl (meth) acrylate and other alkyl or alkenyl (meth) acrylates, etc. .

  Among the resins [B], those having both alkali-soluble performance and energy ray curing performance can be used as having both the performance of the resin [B3] and the resin [B4].

  The weight average molecular weight (Mw) of the resin [B] is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 80,000, still more preferably 5,000 to 30,000. Range. 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 the weight average molecular weight (Mw) of the resin [B] exceeds 100,000, the interaction between the resins becomes strong, and the viscosity of the colored composition for color filter becomes high, so that the handling tends to be difficult. Further, if the weight average molecular weight (Mw) is less than 5,000, problems may occur in developability and adhesion to a substrate such as glass.

  The resin [B] can be used in an amount of 3 to 500 parts by weight with respect to 100 parts by weight of the total weight of the colorant [A]. The amount is preferably 30 to 500 parts by weight, and if it is less than 3 parts by weight, the developability, film formability and various resistances tend to be insufficient, and if it exceeds 500 parts by weight, the colorant concentration is low and color characteristics cannot be expressed.

Resin [B] is an aliphatic group that functions as a pigment adsorbing group and a carboxyl group that functions as an alkali-soluble group during development and an affinity group for the pigment carrier and solvent from the viewpoint of pigment dispersibility, developability, and heat resistance. Since the balance of groups and aromatic groups is important for pigment dispersibility, developability, and durability, the acid value is preferably in the range of 20 to 300 mgKOH / g.
More preferably, the acid value is in the range of 30 to 150 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern may not remain.

(Photopolymerizable monomer [E])
The photopolymerizable monomer [E] is a resin that is cured by ultraviolet rays or heat, and includes a monomer or an oligomer, which can be used alone or in combination of two or more. . Examples of monomers and oligomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and β-carboxyethyl (meth). Acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester Acrylate and methylolated melamine (meth) acrylic ester, epoxy (meth) acrylate, urethane acrylate and other acrylic and methacrylic esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol di Vinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide And acrylonitrile, but are not necessarily limited thereto.
Further, the photopolymerizable monomer [E] is preferably 25 to 700 parts by weight with respect to 100 parts by weight of the pigment in total, and an amount of 50 to 400 parts by weight from the viewpoint of photocurability and developability. It is more preferable to use in.

(Photopolymerization initiator [F])
When the colored composition is cured by ultraviolet irradiation, a photopolymerization initiator [F] or the like is added to the photosensitive colored composition for a color filter of the present invention.
As the photopolymerization initiator [F], 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, etc. Acetophenone compounds, benzoin, benzoin methyl ether, benzoin ethyl ether, Benzoin compounds such as zoin isopropyl ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3, Benzophenone compounds such as 3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4- Thioxanthone compounds such as diethylthioxanthone, 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, 2,4- Triazine compounds such as trichloromethyl (4′-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-ben) Oxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine and the like, bis (2,4,6- Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl -1,2'-biimidazole, 2,2'-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4 , 4 ′, 5,5′-tetra (p-methylphenyl) biimidazole, imidazole compounds, 9,10-phenanthrenequinone, camphor Quinones, quinone-based compounds such as ethyl anthraquinone, borate compounds, carbazole-based compounds, titanocene compounds and the like.
Among these, it is more preferable to include at least one photopolymerization initiator selected from the group consisting of acetophenone compounds, phosphine compounds, and imidazole compounds.

  The photopolymerization initiator [F] is preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight from the viewpoint of photocurability and developability, with respect to 100 parts by weight of the total pigment. .

(Sensitizer)
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer. The content of the sensitizer can be used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the photopolymerization initiator [F].

  Sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by 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, Michler's ketone derivatives and the like.

Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.
Among the sensitizers, particularly preferred sensitizers include thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.
The sensitizer may contain two or more sensitizers in any ratio.

In the coloring composition for color filter of the present invention, the pigment is sufficiently dispersed in a dye carrier such as a resin or a photopolymerizable compound so that the dry film thickness is 0.2 to 10 μm on a transparent substrate such as a glass substrate. In order to make it easy to form a filter segment or a black matrix by applying to a solvent, a solvent is contained. Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 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 mono Hexyl ether, ethylene glycol monomethyl ether Ter, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone , Dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dip Pyrene 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, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, Isobutyl, propyl acetate, include dibasic acid esters such as, used alone or in combination.
The solvent can be used in an amount of 100 to 10,000 parts by weight, preferably 500 to 5000 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

(Multifunctional thiol)
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol (SH) groups.
By using polyfunctional thiol together with the above-mentioned photopolymerization initiator, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates a thiyl radical that is less susceptible to polymerization inhibition by oxygen. The composition becomes highly sensitive. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.

  For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tris Thioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), Pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaeryth Tallhexakis (3-mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- ( N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.

The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the pigment.
By using 0.05 part by weight or more of polyfunctional thiol, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

(UV absorber, polymerization inhibitor)
The coloring composition for a color filter of the present invention can contain an ultraviolet absorber or a polymerization inhibitor. By containing an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled. Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, etc. Hydroxyphenyltriazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, Benzotriazoles such as 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4- Benzophenone series such as hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, salicylate series such as phenyl salicylate, p-tert-butylphenyl salicylate, Cyanoacrylates such as ethyl-2-cyano-3,3′-diphenylacrylate, 2,2,6,6, -tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis (2, 2,6,6-tetramethyl-4-piperidyl) -sebacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl] And hindered amines such as [(2,2,6,6-tetramethyl-4-piperidinyl) imino] and the like. Or in a mixture used. Examples of the polymerization inhibitor include methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol. Hydroquinone derivatives and phenol compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. Copper and manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxyl Min such nitroso compounds and their ammonium salts or aluminum salts and the like, and used alone or in combination.

The ultraviolet absorber and the polymerization inhibitor can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.
By using 0.01 part by weight or more of the ultraviolet absorber or the polymerization inhibitor, better resolution can be obtained.

(Storage stabilizer)
The coloring composition for a color filter of the present invention can contain a storage stabilizer. By containing a storage stabilizer, the viscosity with time of the composition can be stabilized. Examples of the storage stabilizer include 2,6-bis (1,1-dimethylethyl) -4-methylphenol, pentaerystyryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl). Propionate], hindered phenols such as 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, tetraethylphosphine, tri Organic phosphines such as phenylphosphine and tetraphenylphosphine, phosphites such as zinc dimethyldithiophosphate, zinc dipropyldithiophosphate and molybdenum dibutyldithiophosphate, sulfurs such as dodecyl sulfide and benzothiophene, benzyltrimethyl chloride, Quaternary ammonium chloride such as diethylhydroxyamine , Lactic acid, and organic acids and their methyl ethers such as oxalic acid. Used alone or in combination.

  The storage stabilizer can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

  By using 0.01 parts by weight or more of the storage stabilizer, the temporal stability of the color filter coloring composition is improved.

(Antioxidant)
The colored composition for a color filter of the present invention contains an antioxidant in order to increase the transmittance of the coating film. Antioxidant is used to prevent the photopolymerization initiator and thermosetting resin contained in the color filter coloring composition from being oxidized and yellowed by the thermal process during thermal curing and ITO annealing. Can be high. That is, the coloring composition for a color filter of the present invention contains an antioxidant, thereby preventing yellowing due to oxidation during the heating step and obtaining a high coating film transmittance.

  Preferable antioxidants include hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, sulfide antioxidants, and the like. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants. These can be used alone or in combination of two or more.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5- And di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

  In the hindered amine antioxidant, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N , N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4- Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3,4 -Butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6- Tetramethyl-4-piperidyl) Mino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2,2 , 6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl) -4 Polycondensate with -hydroxy-2,2,6,6-tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2, 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine and the like are preferable, and these include one or more. Can be used.

  As the phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine- 6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2- Yl) oxy] ethyl] amine, ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl), and is preferably at least one compound selected from the group consisting of these, Can use 1 type (s) or 2 or more types.

  As sulfide-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol and 2,4-bis [(laurylthio) methyl] -o-cresol are mentioned.

  The antioxidant is preferably used in an amount of 0.1 to 5% by weight in a total of 100% by weight of the solid content of the color filter coloring composition. When the amount of the antioxidant is less than 0.1% by weight, the effect of increasing the transmittance is small, and when it is more than 5% by weight, the hardness is greatly lowered, and the sensitivity of the coloring composition for the color filter is greatly decreased.

(Other ingredients)
The coloring composition for a color filter of the present invention can contain an adhesion improving agent such as a silane coupling agent in order to enhance the adhesion to the transparent substrate.
Examples of the silane coupling agent include vinyl silanes such as vinyl tris (β-methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane, (meth) acryl silanes such as γ-methacryloxypropyl trimethoxy silane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy (Cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-amino Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, Examples include aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

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 thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine and the like.

(Manufacturing method of coloring composition)
The coloring composition for a color filter of the present invention finely disperses a pigment in a dye carrier such as a resin and / or a solvent using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. To produce a pigment dispersion, and to the pigment dispersion, a photopolymerization initiator, a resin, a photopolymerizable compound, and in some cases, other photopolymerization initiators, sensitizers, polyfunctional thiols, ultraviolet absorbers, polymerization inhibitors. , A storage stabilizer, a solvent, and other components can be mixed and stirred. In addition, the coloring composition for color filter containing two or more pigments is prepared by mixing each pigment dispersion separately in a dye carrier and / or a solvent, and further mixing a photopolymerization initiator or photopolymerizability. It can be produced by mixing and stirring compounds and the like.

When the pigment is dispersed in the resin and / or solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. The dispersion aid is excellent in dispersion of the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, the color composition for a color filter is obtained by dispersing the pigment in a resin and / or solvent using the dispersion aid. When an object is used, a color filter excellent in transparency can be obtained.
The dispersing aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment.

(Removal of coarse particles and dust)
The green coloring composition 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. When coarse particles are present, foreign matters remain in the color filter, causing problems in practical use, and in the coating process, foreign matters are clogged in the piping and nozzles, resulting in serious manufacturing problems.

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

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, a fine pattern having high dimensional accuracy and smoothness can be printed 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 the fluidity of the ink on the printing machine is also important, and the ink viscosity can be adjusted with a dispersant or extender pigment.

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

In the 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. An antifoaming agent or a surfactant can also be added to the developer.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition due to oxygen. Thereafter, ultraviolet exposure can also be performed.

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

  The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

(Color filter)
Next, the color filter of the present invention will be described. The color filter of the present invention is provided with a filter segment or a black matrix formed from the coloring composition for a color filter of the present invention on a transparent substrate, and a general color filter includes at least one red filter segment, At least one green filter segment and at least one blue filter segment, or at least one magenta color filter segment, at least one cyan color filter segment, and at least one yellow color filter segment, the at least one The red, green, or yellow color filter segment is formed using the coloring composition for a color filter of the present invention.
As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

  The red filter segment can be formed using a normal red coloring composition. Examples of the red coloring composition 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, 166, 168, 169, 176, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, Red pigments such as 279, 280, 281, 282, 283, 284, 285, 286, or 287 are used.

  The red coloring composition includes C.I. I. Pigment orange 38, 43, 71, 73 or the like and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 181,182,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like.

The green filter segment can be formed using a normal red coloring composition. For example, CI Pigment Green 7, 10, 36, 37, 58 or the like can be used for the green coloring composition. A yellow pigment can be used in combination with the green coloring composition.
As the yellow pigment added to the green coloring composition, the pigment used in the red filter segment can be used. Of these, CI Pigment Yellow 138, 139, 150, and 185 are preferred.

  The blue filter segment can be formed using a normal blue coloring composition. Examples of the blue coloring composition include C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60 and 64 are used. The blue coloring composition includes C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” means “parts by weight”.
Prior to Examples, viscosity characteristic measurement method, measurement method of increase in viscosity with time, measurement method of contrast ratio of coating film, measurement method of development rate, method of manufacturing acrylic resin solution, method of manufacturing basic resin type dispersant, A method for producing the acidic dispersant will be described.

(Evaluation method)
Using the obtained alkali developing resist material, viscosity characteristics are evaluated for evaluating fluidity, brightness, contrast ratio for evaluating brightness and contrast ratio (CR), and stability are also evaluated. In order to evaluate, the ratio of change in contrast ratio with time and the rate of increase in viscosity with time were measured.

(Measurement method of viscosity characteristics)
The viscosity of the obtained pigment dispersion was measured using an H-type viscometer (“H-type viscometer” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and a rotation speed of 60 rpm.
The viscosity of the dispersion of each production example was measured and evaluated in three stages according to the following criteria.
A: Viscosity less than 10.0 mPa · s B: Viscosity 10.0 mPa · s or more, less than 50.0 mPa · s ×: Viscosity 50.0 mPa · s or more The viscosity of the obtained colored composition is an E-type viscometer (East Using an “ELD viscometer” manufactured by Koki Sangyo Co., Ltd., the viscosity was measured at 25 ° C. under the condition of a rotational speed of 20 rpm.
The viscosities of the colored resin compositions of the examples and comparative examples were measured and evaluated in three stages according to the following criteria.
A: Viscosity less than 4.0 mPa · s B: Viscosity of 4.0 mPa · s or more, less than 5.0 mPa · s ×: Viscosity of 5.0 mPa · s or more (Measurement method of viscosity increase rate with time)
The initial viscosity of the next day after the pigment dispersion was prepared and the viscosity with time accelerated at 40 ° C. for 1 week were rotated at 25 ° C. using an H-type viscometer (“H-type viscometer” manufactured by Toki Sangyo Co., Ltd.). The measurement was performed under the condition of several 60 rpm. The initial viscosity thus measured and the viscosity with time were applied to the following equation, and the rate of increase in viscosity with time was measured. The viscosity increase rate with time for the colored resin compositions of each Example and Comparative Example was measured and evaluated in three stages according to the following criteria.
[Rate of increase in viscosity with time] = (Viscosity with time / initial viscosity) × 100
◎: Viscosity increase rate with time less than 120% ○: Viscosity increase rate with time 120% or more, less than 200% ×: Viscosity increase rate with time 200% or more The initial viscosity of the next day after the coloring composition was prepared, and one week at 40 ° C The accelerated viscosity with time was measured using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. under the condition of a rotation speed of 20 rpm. The initial viscosity thus measured and the viscosity with time were applied to the following equation, and the rate of increase in viscosity with time was measured. The viscosity increase rate with time for the colored resin compositions of each Example and Comparative Example was measured and evaluated in three stages according to the following criteria.
[Rate of increase in viscosity with time] = (Viscosity with time / initial viscosity) × 100
A: Increased viscosity over time less than 120% B: Increased viscosity over time 120% or more, less than 150% X: Increased viscosity over time 150% or more (Measurement method of contrast ratio of coating film)
When the pigment dispersion and the coloring composition are spin coated, the chromaticity of the dry film thickness in the CIE color system is y = 0.62, 0.6, 0.58 in the case of the green pigment dispersion and the coloring composition. Thus, in the case of the red pigment dispersion and the coloring composition, x = 0.64, 0.62, and 0.60, and in the case of the yellow pigment dispersion and the coloring composition, x = 0.42. , 0.44, 0.46 so that y = 0.11, 0.13, 0.15 in the case of a blue pigment dispersion, and x = 0.0.1 in the case of an orange pigment dispersion. Three coated substrates were prepared so as to be 64, 0.62, and 0.60. After coating and drying at 80 ° C. for 30 minutes in a hot air oven, the respective film thicknesses are measured. In the case of green pigment dispersion and coloring composition, y = 0.6, in the case of red pigment dispersion and coloring composition x = 0.62, x = 0.44 for yellow pigment dispersion and colored composition, y = 0.13 for blue pigment dispersion, x = 0.62 for orange pigment dispersion The contrast ratio was determined by the first order correlation method. The chromaticity was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.).

An apparatus for measuring the contrast ratio of the coating film and a method for calculating the value will be described.
The light emitted from the backlight unit for liquid crystal display (7) passes through the polarizing plate (6), is polarized, and is applied onto the glass substrate (5). 4) to reach the polarizing plate (3). If the polarization planes of the polarizing plate (6) and the polarizing plate (3) are parallel, light is transmitted through the polarizing plate (3), but if the polarization plane is perpendicular, the light is transmitted by the polarizing plate (3). Blocked. However, when light polarized by the polarizing plate (6) passes through the dried coating film (4) of the colored composition, scattering by pigment particles or the like occurs, and a part of the polarization plane is displaced. Is parallel, the amount of light transmitted through the polarizing plate (3) is reduced, and when the polarizing plate is orthogonal, a part of the light is transmitted through the polarizing plate (3). 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)
Accordingly, when scattering occurs due to the pigment dispersion and the pigment of the dried coating film (4) of the coloring composition, the brightness when parallel is lowered and the brightness when orthogonal is increased, and the contrast ratio is lowered.

  A color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used as the luminance meter (1), and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, a black mask (2) having a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

(Development speed measurement method)
The colored resin composition is applied to a glass substrate by a spin coat method so that the dry film thickness is 2.0 μm, and the coated substrate is exposed to 60 mJ / cm 2 through a mask pattern with a high-pressure mercury lamp, and then 0.04 weight. Spray development was performed at a pressure of 0.25 MPa using a% potassium hydroxide aqueous solution (developer temperature: 26 ° C.), and the time until the colored resin film was dissolved and the substrate surface was exposed (development dissolution time) was measured. The development dissolution time for the colored resin compositions of each Example and Comparative Example was measured and evaluated in three stages according to the following criteria.
◎: Less than 20 seconds ○: 20 seconds or more, less than 40 ×: 40 seconds or more (weight average molecular weight of resin)
It measured by polystyrene conversion using the gel permeation chromatograph measuring apparatus ("Shodex GPC System-21H" Showa Denko make).

(Acid value)
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the resin solution and stirred to dissolve uniformly, and an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) is used with a 0.1 mol / L KOH aqueous solution as a titrant. ) And the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

(Method for producing alkali-soluble vinyl resin solution)
(Preparation of alkali-soluble vinyl resin solution (B3-1))
70.0 parts of PGMEA was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer, and the temperature was raised to 80 ° C. 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 dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a solid content of 30% by weight and a weight average molecular weight of 26000.

  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 PGMEA was added to the previously synthesized resin solution so that the nonvolatile content was 20 wt%. Thus, an alkali-soluble vinyl resin solution (B3-1) was prepared.

(Method for producing energy ray curable resin having ethylenically unsaturated active double bond)
(Preparation of energy ray-curable resin solution (B4-1) having an ethylenically unsaturated active double bond)
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was dropped over 2.5 hours from the dropping tube at a temperature to polymerize. Reaction was performed.

  Next, the inside of the flask was purged with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours. The reaction was terminated when it reached 0.8, and a resin solution having a weight average molecular weight of about 12000 (measured by GPC) was obtained.

  Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added and reacted at 120 ° C. for 4 hours, and propylene glycol monomethyl ether acetate was added so that the non-volatile content was 20%. An energy beam curable resin solution (B4-1) having a bond was prepared.

(Production Example of Basic Resin Type Dispersant C1-A)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 500 parts of methyl methacrylate, 11 parts of thioglycerol, and 511 parts of methoxypropyl acetate (PGMAc) and replaced with nitrogen gas. The inside of the reaction vessel was heated to 90 ° C., and 0.50 part of AIBN [2,2′-azobis (isobutyronitrile)] was added, followed by reaction for 7 hours. After confirming that 95% had reacted by solid content measurement, it was cooled to room temperature, and the solid content of vinyl polymer (C1A-1) having a weight average molecular weight of 9,500 and having two free hydroxyl groups in one end region A 50% solution was obtained.

In another reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 1022 parts of a 50% solid content solution of the vinyl polymer (C1 A -1), 45.3 parts of isophorone diisocyanate, and PGMAc 45 .2 parts and 0.11 g of dibutyltin dilaurate as a catalyst were charged and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C. and reacted for 3 hours, and then cooled to 40 ° C. to obtain a colorless transparent solution (B-1). Furthermore, the inside of reaction container was heated at 50 degreeC, 7.5 parts of Jeffamine T403 was dripped, 7.5 parts of PGMAc was added, and the colorless and transparent solution (C1A-2) was obtained.
In yet another reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, a mixed solution of 11.8 parts of methyliminobispropylamine and 694.2 parts of PGMAc was heated and heated to 100 ° C. to be colorless and transparent 1000.0 parts of the solution (C1 A- 2) was added dropwise over 30 minutes, and the reaction was further continued for 1 hour, followed by cooling to room temperature to complete the reaction. The solid content was adjusted to 30% to obtain a colorless transparent solution of the basic resin type dispersant (C1-A). The weight average molecular weight of the basic resin dispersant (C1-A) was 43,200, and the amine value was 10.5 mgKOH / g.

(Production Example of Basic Resin Type Dispersant C1-B)
A four-necked flask equipped with a condenser, a stirring motor, and a thermometer was charged with 1.3 g of copper (I) chloride and 0.9 g of copper (II) chloride, cooled with dry ice / methanol, and purged with nitrogen. While cooling, 55 g of methyl methacrylate, 5 g of ethyl 2-bromoisobutyrate, 9 g of spartein, and 100 g of anisole were mixed, and a liquid well substituted with nitrogen was added. Further, nitrogen bubbling was performed for 20 minutes under cooling. The mixture was heated to an internal temperature of 70 ° C. with nitrogen flow and stirring and polymerized for 6 hours. Thereafter, 60 g of anisole solution containing 5 g of ethylene glycol dimethacrylate was further added and polymerized at 80 ° C. for 13 hours. The reaction solution is diluted with anisole, and after removing the copper complex with an activated alumina column, it is reprecipitated with hexane and dried.
A star-shaped starting species (C1B-1) was obtained.
The same four-necked flask as above was charged with 0.3 g of copper (I) chloride and 0.2 g of copper (II) chloride, sufficiently substituted with nitrogen, then cooled with dry ice / methanol, and synthesized as described above. Star-shaped starting species (C1B-1) 14.3 g, N, N, N ′, N ′, N ″, N ′ ″-hexamethyltriethyltetraamine as a ligand (HMTETA: Sigma Aldrich, reagent) 1 0.1 g, a mixed solution of 2- (dimethylaminoethyl) methacrylate (DMAEMA: Wako Pure Chemical Industries, Ltd., reagent) 7.5 g and anisole 14 g were added, and polymerization was performed at 40 ° C. for 16 hours while stirring. The reaction solution was diluted with anisole, and after removing the copper complex with a neutral activated alumina column, it was reprecipitated with hexane and dried to obtain a basic resin type dispersant (C1-B). The molecular weight Mn was 20000, and Mw / Mn was 1.3.

(Production Example of Acidic Dispersant D1-1)
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 quinophthalone skeleton sulfonic acid having a structure represented by the formula ( 1 ), which is a sulfonated derivative of CI Pigment Yellow 138, was obtained. The yield after drying was 334 parts, and the yield was 99%.

Formula (1)

The paste of quinophthalone skeleton sulfonic acid 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. An acidic dispersant (D1-1) having a structure represented by the formula ( 2 ) 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 (2)

(Preparation of the acidic dispersing agent D 1-2)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer is charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone and 0.1 part of monobutyltin (IV) oxide as a catalyst, and nitrogen gas. Then, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 73.3 parts of pyromellitic anhydride was added and reacted at 120 ° C. for 2 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated to obtain an acidic resin type dispersant ( D1-2 ). The obtained dispersing agent was white solid at normal temperature, and the acid value was 49 mgKOH / g.

(Method for measuring volume average primary particle diameter (MV) of pigment)
Further, the volume average primary particle diameter (MV) of the pigment was measured by measuring the short axis diameter and the long axis diameter of 100 primary particles of the pigment using a transmission (TEM) electron micrograph. The average of the axial diameter is defined as the particle diameter (d) of the pigment particles, and then the volume (V) of each particle is determined assuming that each pigment is a sphere having the determined particle diameter. It calculated about the pigment particle from the following formula.
MV = Σ (V · d) / Σ (V)
(Manufacture of refined pigments)
(Preparation of red micronized pigment (PR-1))
Red pigment C.I. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by Ciba Japan Co., Ltd.) 152 parts, 8 parts of pigment derivative of formula (3) , 1600 parts of sodium chloride, and 190 parts of diethylene glycol 1 gallon kneader made of stainless steel (Inoue Manufacturing Co., Ltd.) And kneaded at 60 ° C. for 10 hours. Next, the mixture is poured into 3 liters of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and solvent, and then 80 It was dried for 1 day at 0 ° C. to obtain a red refined pigment (PR-1). The obtained pigment had a volume average primary particle size of 30 nm.

(Preparation of red refined pigment (PR-2))
Red pigment C.I. I. 500 parts of Pigment Red 177 (“Chromophthaled A2B” manufactured by Ciba Japan), 3500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a red refined pigment (PR-2) was obtained. The obtained pigment had a volume average primary particle size of 35 nm.

Formula (3)

(Production of green refined pigment (PG-1))
Green pigment C.I. I. 500 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. . Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green refined pigment (PG-1) was obtained. The obtained pigment had a volume average primary particle size of 32 nm.

(Production of green refined pigment (PG-2))
Green pigment C.I. I. 500 parts of Pigment Green 58 (“First Gain Green A110” manufactured by DIC Corporation), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green refined pigment (PG-2) was obtained. The obtained pigment had a volume average primary particle size of 25 nm.

(Production of green refined pigment (PG-3))
Green pigment C.I. I. 500 parts of Pigment Green 7 (“First Gain Green S” manufactured by DIC Corporation), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green refined pigment (PG-3) was obtained. The obtained pigment had a volume average primary particle size of 32 nm.

(Manufacture of yellow refined pigment (PY-1))
Metal complex yellow pigment C.I. I. 500 parts of Pigment Yellow 150 (LANXESS "E4GN"), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C for 6 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a yellow refined pigment (PY-1) was obtained. The obtained pigment had a volume average primary particle size of 26 nm.

(Manufacture of yellow refined pigment (PY-2))
Quinophthalone yellow pigment C.I. I. 500 parts of Pigment Yellow 138 ("Pariotol Yellow K0960-HD" manufactured by BASF), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C for 6 hours. . Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a yellow refined pigment (PY-2) was obtained. The obtained pigment had a volume average primary particle size of 28 nm.

(Manufacture of yellow refined pigment (PY-3))
Yellow pigment C.I. I. 500 parts of Pigment Yellow 139 (“Irgafore Yellow 2R-CF” manufactured by Ciba Japan), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C. for 6 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a yellow refined pigment (PY-3) was obtained. The obtained pigment had a volume average primary particle size of 36 nm.

(Production of yellow refined pigment (PY-4))
Yellow pigment C.I. I. 500 parts of Pigment Yellow 185 (“Pariotor Yellow D1155” manufactured by BASF), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C. for 6 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a yellow refined pigment (PY-4) was obtained. The obtained pigment had a volume average primary particle size of 40 nm.

(Manufacture of orange refined pigment (PO-1))
C. I. 500 parts of Pigment Orange 38 (PO38) ("Novoperm Red HFG" manufactured by Clariant), 2500 parts of sodium chloride, and 250 parts of polyethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho). The mixture was kneaded at 120 ° C. for 12 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, The resultant was dried at 80 ° C. for a whole day and night to obtain an orange finely-treated pigment PO-1. The obtained pigment had a volume average primary particle size of 39 nm.

  Table 1 summarizes the volume average primary particle diameters of the respective color-reduced pigments produced.

(Preparation of pigment dispersant solution (X-1))
A pigment dispersant (“Ajisper PB821” manufactured by Ajinomoto Fine Techno Co., Ltd.) was diluted with propylene glycol monomethyl ether acetate to prepare a pigment dispersant solution (X-1) having a solid content of 30%.

(Production of pigment dispersion containing Colorant A)
[Production of red pigment dispersion (P-R1)]
10.0 parts of red micronized pigment (PR-1), 42.5 parts of alkali-soluble vinyl resin solution (B3-1), 5.0 parts of pigment dispersant solution (X-1), ethylene glycol monomethyl ether After stirring and mixing 42.5 parts of acetate uniformly, using a zirconia bead with a diameter of 0.5 mm, the mixture was dispersed for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), and then filtered with a 5 μm filter. Filtration was performed to prepare a PR254 pigment dispersion (P-R1).

[Production of Red Pigment Dispersion (P-R2)]
The PR177 pigment dispersion (P-R1) was prepared in the same manner as the pigment dispersion (P-R1) except that the red refinement-treated pigment (PR-1) was changed to the red refinement-treated pigment (PR-2). R2) was prepared.

[Production of Red Pigment Dispersion (P-R3)]
10.0 parts of red refined pigment (PR-1), 42.5 parts of alkali-soluble vinyl resin solution (B3-1), 1.5 parts of basic resin type dispersant (C1- A ), ethylene glycol After uniformly stirring and mixing 46.0 parts of monomethyl ether acetate, using a zirconia bead having a diameter of 0.5 mm, the mixture was dispersed for 3 hours in an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), and then 5 μm Filtration through a filter produced a PR254 pigment dispersion (P-R3).

[Production of Red Pigment Dispersion (P-R4)]
The PR177 pigment dispersion (P-R) was prepared in the same manner as the pigment dispersion (P-R3) except that the red refinement-treated pigment (PR-1) was changed to the red refinement-treated pigment (PR-2). R4) was prepared.

[Production of Green Pigment Dispersion (P-G1)]
The pigment dispersion of PG36 (P-) was prepared by the same production method as that of the pigment dispersion (P-R1) except that the red refinement-treated pigment (PR-1) was changed to the green refinement-treated pigment (PG-1). G1) was prepared.

[Production of Green Pigment Dispersion (P-G2)]
PG58 pigment dispersion (P--) was prepared in the same manner as the pigment dispersion (P-R1) except that the red refinement-treated pigment (PR-1) was changed to the green refinement-treated pigment (PG-2). G2) was prepared.

[Production of Green Pigment Dispersion (P-G3)]
The PG7 pigment dispersion (P-R1) was prepared in the same manner as the pigment dispersion (P-R1) except that the red refined pigment (PR-1) was changed to the green refined pigment (PG- 3 ). G 3) was prepared.

[Production of Green Pigment Dispersion (P-G4)]
The pigment dispersion of PG36 (P-R) was prepared in the same manner as the pigment dispersion (P-R3) except that the red refinement-treated pigment (PR-1) was changed to the green refinement-treated pigment (PG-1). G4) was prepared.

[Production of Green Pigment Dispersion (P-G5)]
The pigment dispersion of PG58 (P--) was prepared in the same manner as the pigment dispersion (P-R3) except that the red refinement-treated pigment (PR-1) was changed to the green refinement-treated pigment (PG-2). G5) was produced.

[Production of Green Pigment Dispersion (P-G6)]
The PG7 pigment dispersion (P-R3) was prepared in the same manner as the pigment dispersion (P-R3) except that the red refined pigment (PR-1) was changed to the green refined pigment (PG- 3 ). G6) was produced.

[Production of Yellow Pigment Dispersion (P-Y1)]
10.0 parts yellow refined pigment (PY-1), 25.0 parts alkali-soluble vinyl resin solution (B3-1), 5.0 parts basic resin dispersant (C1- A ), ethylene After uniformly mixing 60.0 parts of glycol monomethyl ether acetate with zirconia beads having a diameter of 0.5 mm, the mixture is dispersed for 1 hour in an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), and then 0 Using a 1 mmφ zirconia bead, the mixture was dispersed for 3 hours in a picoglen mill (manufactured by Asada Tekko Co., Ltd.), and then filtered through a 5 μm filter to prepare a PY150 pigment dispersion (P-Y1).

[Production of Yellow Pigment Dispersion (P-Y2)]
The PY138 pigment dispersion (PY-1) was prepared in the same manner as the pigment dispersion (P- Y1 ), except that the yellow colorization-treated pigment (PY-1) was changed to the yellow finer-treated pigment (PY-2). P-Y2) was prepared.

[Production of Yellow Pigment Dispersion (P-Y3)]
The PY139 pigment dispersion (PY-1) was prepared in the same manner as the pigment dispersion (P- Y1 ), except that the yellow colorization-treated pigment (PY-1) was changed to the yellow-sized refined pigment (PY-3). P-Y3) was prepared.

[Production of Yellow Pigment Dispersion (P-Y4)]
The PY185 pigment dispersion (PY-1) was prepared in the same manner as the pigment dispersion (P- Y1 ), except that the yellow colorization-treated pigment (PY-1) was changed to the yellow-sized refined pigment (PY-4). P-Y4) was prepared.

[Production of Yellow Pigment Dispersion (P-Y5)]
10.0 parts of yellow color-refined pigment (PY-1), 25.0 parts of energy ray curable resin solution (B4-1), 5.0 parts of basic resin type dispersant (C1- A ), ethylene After uniformly mixing 60.0 parts of glycol monomethyl ether acetate with zirconia beads having a diameter of 0.5 mm, the mixture is dispersed for 1 hour in an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), and then 0 Using a 1 mmφ zirconia bead, the mixture was dispersed for 3 hours in a picoglen mill (manufactured by Asada Tekko Co., Ltd.) and then filtered through a 5 μm filter to prepare a PY150 pigment dispersion (P-Y5).

[Production of Yellow Pigment Dispersion (P-Y6)]
10.0 parts of yellow color-refined pigment (PY-1), 25.0 parts of alkali-soluble vinyl resin solution (B3-1), 5.0 parts of basic resin type dispersant (C1 -B ), After uniformly stirring and mixing 60.0 parts of ethylene glycol monomethyl ether acetate, using a zirconia bead having a diameter of 0.5 mm, the mixture is dispersed for 1 hour with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan). Using 0.1 mmφ zirconia beads, the mixture was dispersed for 3 hours with a pico-glen mill (manufactured by Asada Tekko Co., Ltd.) and then filtered with a 5 μm filter to prepare a PY150 pigment dispersion (P-Y6).

[Production of Yellow Pigment Dispersion (P-Y7)]
10.0 parts of yellow refined pigment (PY-1), 35.0 parts of alkali-soluble vinyl resin solution (B3-1), 2.0 parts of basic resin type dispersant (C1- A ), acidic After uniformly stirring and mixing 1.0 part of the dispersant (D1-1) and 52.0 parts of ethylene glycol monomethyl ether acetate, using a zirconia bead having a diameter of 0.5 mm, an Eiger mill ("Mini Model M" manufactured by Eiger Japan) was used. -250 MKII ") for 1 hour, then using a 0.1 mmφ zirconia bead for 3 hours in a Pico Glen Mill (manufactured by Asada Tekko Co., Ltd.), filtered through a 5 μm filter, and a PY150 pigment dispersion (P-Y7) was produced.

[Production of Yellow Pigment Dispersion (P-Y8)]
10.0 parts of yellow refined pigment (PY-1), 25.0 parts of alkali-soluble vinyl resin solution (B3-1), 2.0 parts of basic resin type dispersant (C1- A ), acidic After uniformly stirring and mixing 3.0 parts of the dispersant (D1-2) and 60.0 parts of ethylene glycol monomethyl ether acetate, using a zirconia bead having a diameter of 0.5 mm, an Eiger mill ("Mini Model M" manufactured by Eiger Japan) was used. -250 MKII ") for 1 hour, then using a 0.1 mmφ zirconia bead for 3 hours in a Pico Glen Mill (manufactured by Asada Tekko Co., Ltd.), filtered through a 5 μm filter, and a PY150 pigment dispersion (P-Y8) was produced.

[Production of Yellow Pigment Dispersion (P-Y9)]
After uniformly mixing 10.0 parts of yellow color-refined pigment (PY-1), 50.0 parts of alkali-soluble vinyl resin solution (B3-1), and 40.0 parts of ethylene glycol monomethyl ether acetate, Using a zirconia bead with a diameter of 0.5 mm, it is dispersed for 1 hour with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), and then using a 0.1 mmφ zirconia bead, a picoglen mill (Asada Tekko Co., Ltd.) Manufactured for 3 hours, and filtered through a 5 μm filter to prepare a PY150 pigment dispersion (P-Y9).

[Production of Yellow Pigment Dispersion (P-Y10)]
10.0 parts of yellow color-refined pigment (PY-1), 25.0 parts of alkali-soluble vinyl resin solution (B3-1), 16.7 parts of pigment dispersant solution (X-1), ethylene glycol monomethyl After 48.3 parts of ether acetate was uniformly stirred and mixed, it was dispersed for 1 hour 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 0.1 mmφ. Then, using a zirconia bead, the mixture was dispersed for 3 hours with a picoglen mill (manufactured by Asada Tekko Co., Ltd.) and then filtered with a 5 μm filter to prepare a PY150 pigment dispersion (P-Y10).

[Production of Orange Pigment Dispersion (P-O1)]
The PO38 pigment dispersion (P-R) was prepared in the same manner as the pigment dispersion (P-R1) except that the red refinement-treated pigment (PR-1) was changed to the orange refinement-treated pigment (PO-1). O1) was prepared.

[Production of Orange Pigment Dispersion (P-O2)]
The PO38 pigment dispersion (P--) was prepared in the same manner as the pigment dispersion (P-R3) except that the red refinement-treated pigment (PR-1) was changed to the orange refinement-treated pigment (PO-1). O2) was prepared.

[Production of Blue Pigment Dispersion (P-B1)]
Other red finer treated pigment (PR-1) was changed to blue color finer treated pigment (PB-1) is in the same preparation method and pigment dispersion (P-R1), PB15: 6 pigment dispersion (P-B1) was produced.

[Production of Blue Pigment Dispersion (P-B2)]
Other red finer treated pigment (PR-1) was changed to blue color finer treated pigment (PB-1) is in the same preparation method and pigment dispersion (P-R3), PB15: 6 pigment dispersion (P-B2) was produced.

Table 3 shows the evaluation results of the initial viscosity, the viscosity with time, and the contrast ratio of these pigment dispersions.

(Example 1-68 and Comparative Example 1 to 5)
Table 2 shows pigment dispersions produced by the various pigment dispersion production methods. Using these pigment dispersions, the other types and amounts of the materials shown in Table 4 were mixed to prepare colored compositions 1 to 63 for color filters. Moreover, the symbol in a table | surface represents the material as shown below.
However, Examples 21 and 66 are reference examples.

Alkali-soluble vinyl-based resin solution (B3-1): Energy ray-curable resin (B4-1) having the above synthetic ethylenically unsaturated active double bond: Synthetic photopolymerizable monomer ( E1 ): Dipentaerythritol Hexaacrylate
("Aronix M-402" manufactured by Toagosei Co., Ltd.)
Photopolymerizable monomer ( E2 ): a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate and a mixture of succinic acid derivatives of dipentaerythritol pentaacrylate
TO-2349 (manufactured by Toagosei Co., Ltd., acid value: 68)
Photopolymerization initiator (F1): 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one
("Irgacure 907" manufactured by Ciba Japan)
Photopolymerization initiator (F2): ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime)
("Irgacure OXE02" manufactured by Ciba Japan)
Organic solvent (G1): cyclohexanone sensitizer (H1): 2,4-diethylthioxanthone
(“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Multifunctional thiol (I1): trimethylolpropane tri (3-mercaptobutyrate)
("TPMB" manufactured by Showa Denko KK)
Ultraviolet absorber (J1): 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine
("TINUVIN400" manufactured by Ciba Japan)
Polymerization inhibitor (K1): N-nitrosophenylhydroxylamine aluminum salt
("Q-1301" manufactured by Wako Pure Chemical Industries, Ltd.)
Storage stabilizer (L1): Triphenylphosphine
("TPP" manufactured by Hokuko Chemical Co., Ltd.)
Antioxidant (M1); hindered phenol antioxidant 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)
Antioxidant (M2); hindered amine antioxidant bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate antioxidant (M3); phosphorus antioxidant ethyl bisphosphite (2,4 -Di-tert-butyl-6-methylphenyl)
Antioxidant (M4); sulfide antioxidant 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
Examples 1 to 60 and Comparative Examples 1 to 3 The obtained colored compositions were applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, dried at 70 ° C. for 20 minutes, Using a high-pressure mercury lamp, ultraviolet exposure was performed with an integrated light amount of 150 mJ. Tables 5 and 6 show the contrast ratios of the coating films obtained after heating and cooling the coated substrate at 230 ° C. for 60 minutes. Further, the development speed evaluation and the viscosity characteristic evaluation are performed, and the results at that time are also shown.

  As shown in Examples 1 to 21 in Table 5, in the red coloring composition, the green coloring composition, and the yellow coloring composition containing a yellow pigment, by using a basic resin type dispersant having a star polymer structure, A colored composition having a good initial viscosity could be obtained. Furthermore, as shown in Examples 22 to 27 in Table 5, by using a combination of a basic polymer type dispersant having a star polymer structure and an acidic dispersant, a good initial viscosity, a good stability over time, and a high contrast ratio. Thus, it was possible to obtain a colored composition having good developability.

In addition, as shown in Comparative Examples 1 to 3 in Table 6, when the basic resin type dispersant is not contained or the basic resin type dispersant does not have a star polymer structure, there is a problem in viscosity characteristics, contrast ratio, and developability. Happens.

Claims (8)

  In a coloring composition containing a colorant [A] containing a yellow pigment, a resin [B], and a basic resin type dispersant [C], the basic resin type dispersant [C] contains three or more basic resin type dispersants [C]. It has a polymer side chain to be an arm, and has a segment that dissolves in a non-aqueous solvent and a segment that adsorbs to a pigment as a structural unit of the arm, and an ethylenically unsaturated monomer as a segment that dissolves in the non-aqueous solvent. A coloring composition for a color filter comprising a star polymer [C1] having a polymer and having a urea group as a segment adsorbed to the pigment.   The yellow pigment includes at least one yellow pigment selected from the group consisting of azo yellow pigments, quinophthalone yellow pigments, isoindoline yellow pigments, and benzimidazolone yellow pigments. Coloring compositions for color filters.   The yellow pigment is C.I. I. The coloring composition for a color filter according to claim 1, comprising Pigment Yellow 150.   The coloring for color filter according to any one of claims 1 to 3, further comprising at least one acidic dispersant [D] selected from the group consisting of an acidic pigment derivative and an acidic resin dispersant. Composition.   The colorant [A] is further added to C.I. I. Pigment green 7, C.I. I. Pigment green 36 or C.I. I. The coloring composition for a color filter according to claim 1, comprising Pigment Green 58.   Colorant [A] is further added to C.I. I. Pigment red 177 or C.I. I. The coloring composition for a color filter according to any one of claims 1 to 4, comprising Pigment Red 254.   The colored composition for a color filter according to any one of claims 1 to 6, further comprising a photopolymerizable monomer [E] and / or a photopolymerization initiator [F].   A color filter comprising a filter segment formed on the substrate by the color filter coloring composition according to claim 1.