JP2016170324A - Coloring composition for color filter, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for a color filter that has excellent dispersibility, temporal stability, chemical resistance and heat resistance even when a fine pigment and a dye are used as a coloring agent, and is further excellent in developability to alkali aqueous solution in the case of a photosensitive coloring composition; and a color filter using the same.SOLUTION: A coloring composition for a color filter contains: a coloring agent; a binder resin; an epoxy compound; a solvent; and a dispersant (X) that has a polyester portion X1' which is obtained by reaction of an acid anhydride group in one or more acid anhydrides (b) selected from a tetracarboxylic acid anhydride (b1) and a tricarboxylic acid anhydride (b2) with a hydroxyl group in a hydroxyl group-containing compound (a), and has a carboxyl group, and a vinyl polymer portion X2' which is obtained by radical polymerization of an ethylenically unsaturated monomer (c) and has any group selected from groups consisting of structural units represented by general formulae (1) to (4).SELECTED DRAWING: None

Description

  The present invention relates to a color liquid crystal display device, a color composition for a color filter used for the production of a color filter used for a color imaging device, and the like, and a color filter including a filter segment formed using the same. is there.

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

  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.

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

  For this reason, for example, pigment compositions containing pigments composed of fine particles often exhibit high viscosity, making it difficult to remove and transport the product from a disperser, and in the worst case gelation occurs during storage. It may wake up and become difficult to use. Therefore, dispersibility can be achieved by using a structure-controlled one having a block structure (Patent Document 1) or a comb structure (Patent Document 2) or a resin-type dispersant (Patent Document 3) such as a polyester dispersant having a specific structure. A coloring composition having excellent storage stability and a high contrast ratio has been studied. However, even if these resin-type dispersants are used, it is not sufficient to improve the resistance of pigments whose surface area is increasing due to the progress of finer pigments. The present situation is that it is not sufficient with respect to resistance such as heat resistance, light resistance, and solvent resistance, resulting in poor state and poor leveling.

In addition, in order to realize a high contrast ratio and high brightness that cannot be achieved with pigments in recent years, attention is also focused on dyes as coloring materials.
The dye is generally soluble in a solvent or a polymer, and is stable without causing aggregation or the like even in a color filter coloring composition. In addition, a color filter obtained using a coloring liquid in which the dye is dispersed has no depolarizing action and excellent light transmittance because the dye is dispersed at the molecular level. However, a coloring composition containing a dye as compared with a coloring composition containing a pigment as a colorant often has the disadvantages of being inferior in heat resistance, light resistance, and chemical resistance.

  Thus, in a color filter manufactured by photolithography technology, it has high contrast ratio, high definition, high transparency, high color purity by using finely divided organic pigments and dyes, and also has heat resistance, A practical color filter excellent in light resistance, chemical resistance and sublimation resistance has not been obtained.

JP 2002-31713 A Japanese Patent Laid-Open No. 11-1515 International Publication No. 2008/007776 Pamphlet

  The object of the present invention is to have excellent dispersibility, stability over time, chemical resistance and heat resistance even when a finer pigment or dye is used as a colorant. In the case of a photosensitive coloring composition, an alkali is further added. An object of the present invention is to provide a coloring composition for a color filter excellent in developability for an aqueous solution, and a color filter using the same.

  As a result of intensive studies to solve the above problems, the present inventors have used a specific resin-type dispersant as a coloring composition for a color filter, and further contain an epoxy compound, whereby dispersibility, The inventors have found that a color filter that is very excellent in contrast ratio, brightness, heat resistance, and solvent resistance and that also satisfies developability can be produced, and the present invention has been achieved.

That is, the present invention relates to a color filter coloring composition comprising a colorant, a dispersant, a binder resin, a thermosetting compound, and a solvent, wherein the dispersant is a tetracarboxylic acid anhydride (b1) and a tricarboxylic acid. A polyester portion X1 ′ having a carboxyl group, obtained by reacting an acid anhydride group in one or more acid anhydrides (b) selected from the anhydride (b2) and a hydroxyl group in the hydroxyl group-containing compound (a); A vinyl polymer portion X2 ′ formed by radical polymerization of an ethylenically unsaturated monomer (c) and having any one selected from the group consisting of structural units represented by the following general formulas (1) to (4): The coloring composition for color filters characterized by containing the dispersing agent (X) which has, and a thermosetting compound containing an epoxy compound.
General formula (1)

[In general formula (1), n1 represents an integer of 1 to 4, R ₁ represents hydrogen or a methyl group, X represents a direct bond, or —CR ₆ R ₇ —Z—, and Z represents a direct bond or -CR ₈ R ₉ - is represented by,
R _{2 to} R ₉ are a hydrogen atom, a halogen atom, a phthalimide group, —CH ₂ CH ₂ COOH, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and —CH ₂ — contained in these groups may be substituted with —O—, —CO— or —OCO—,
R ₂ and R ₄ may be directly bonded to form an unsaturated double bond, R ₂ and R ₃ and / or R ₄ and R ₅ may be combined to form ═CH ₂ , R ₂ and R ₆ and R ₄ and R ₈ may be combined with the carbon atom to which they are bonded to form a ring having 6 to 10 carbon atoms, and “*” indicates a bond. ]
General formula (2)

[In General Formula (2), n2 represents an integer of 1 to 4, W ₁ represents —CR ₁₁ or a nitrogen atom, W ₂ represents —CR ₁₄ or a nitrogen atom, Y represents —COOH, —SO ₃ H, R ₁₀ represents hydrogen or a methyl group, and R _{11 to} R ₁₄ represent a hydrogen atom, a halogen atom, a nitro group, an ethynyl group, —SO ₃ H, —COOH, —COCl, —NHCOCH ₃ , substituted or unsubstituted carbon. Represents an alkyl group of 1 to 20, R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₁₃ and R ₁₄ together with the carbon atom to which they are bonded form a ring of 6 to 10 carbon atoms. “*” Indicates a bond. ]
General formula (3)

[In General Formula (3), n3 represents an integer of 1 to 3, R ₁₅ represents hydrogen or a methyl group, and R _{16 to} R ₂₅ represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. R ₁₇ and R ₁₉ and / or R ₂₃ and R ₂₅ may be directly bonded to form an unsaturated double bond, and R ₁₇ and R ₂₃ may be combined with the carbon atom to which they are bonded. May form a ring, and “*” indicates a bond. ]
General formula (4)

[In General Formula (4), n4 is an integer of 1 to 3, R ₂₆ represents hydrogen or a methyl group, R ₃₁ represents a hydrogen atom or a methyl group, R _{27 to} R ₃₀ represent a hydrogen atom, a halogen atom, A nitro group, —COOH, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and “*” represents a bond. ]

  The present invention also relates to the color composition for color filters, wherein the colorant contains a dye.

  The present invention also relates to the colored composition for a color filter, wherein the number of functional groups of the epoxy compound is 3 or more.

  In addition, the present invention relates to the coloring composition for a color filter, wherein the acid value of the dispersant (X) is 6 to 100 mgKOH / g.

  In addition, the present invention relates to the coloring composition for a color filter, wherein methyl (meth) acrylate is 40 to 80% by weight in 100% by weight of the ethylenically unsaturated monomer (c).

In the present invention, the dispersant (X) is a structural unit in which R _{2 to} R _{5 in} the general formula (1) are hydrogen atoms, or a structure in which R _{11 to} R _{14 in} the general formula (2) are hydrogen atoms. It has a unit, It is related with the said coloring composition for color filters characterized by the above-mentioned.

  The present invention also relates to the color composition for color filters, further comprising a photopolymerization initiator.

  Moreover, this invention comprises the filter segment formed from the said coloring composition for color filters on a base material, The color filter characterized by the above-mentioned.

  With the color filter coloring composition of the present invention, it is possible to provide a color filter coloring composition and a color filter that are very excellent in dispersibility, contrast ratio, lightness, heat resistance, and satisfying developability.

Hereinafter, the present invention will be described in detail.
In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described, Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent.
Further, “CI” in this specification means a color index (CI).

The color filter coloring composition of the present invention is a color filter coloring composition containing a colorant, a dispersant, a binder resin, a thermosetting compound, and a solvent, and the dispersant is a tetracarboxylic acid anhydride ( Polyester having a carboxyl group obtained by reacting an acid anhydride group in one or more acid anhydrides (b) selected from b1) and a tricarboxylic acid anhydride (b2) with a hydroxyl group in the hydroxyl group-containing compound (a) A vinyl polymer obtained by radical polymerization of the moiety X1 ′ and the ethylenically unsaturated monomer (c) and having any one selected from the group consisting of structural units represented by the general formulas (1) to (4) A coloring composition for a color filter comprising a dispersant (X) having a moiety X2 ′, wherein the thermosetting compound contains an epoxy compound.
It is characterized by that.
Hereinafter, each component which comprises the coloring composition for color filters of this invention is explained in full detail.

<Colorant>
The colorant that can be used in the coloring composition of the present invention can be arbitrarily selected from conventionally known various pigments and dyes. These pigments / dyes can be used alone or in admixture of two or more at any ratio as required.

The content of the colorant is preferably 10% by weight or more, more preferably 15% by weight or more from the viewpoint of obtaining sufficient color reproducibility, based on the total nonvolatile components of the coloring composition (100% by weight), and most preferably Preferably it is 20 weight% or more. Further, from the viewpoint of the stability of the coloring composition, the preferred colorant content is 90% by weight or less, more preferably 80% by weight or less, and most preferably 70% by weight or less.
In addition, when a coloring agent contains dye, it is preferable that content of dye is 1-800 weight part with respect to 100 weight part of pigments. More preferably, it is 5 to 400 parts by weight. When the addition amount of the dye is within this range, the lightness and contrast ratio can be excellent.

<Organic pigment>
Specific examples of pigments that can be used when forming color filter pixels as colorants are shown.
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254, more preferably C.I. I. Pigment Red 177, 209, 224, 242, or 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6. Moreover, it is also preferable to use an aluminum phthalocyanine pigment, and the aluminum phthalocyanine pigment described in JP-A No. 2004-333817, Japanese Patent No. 4893859 and the like can also be used.

  Examples of the green pigment include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36 or 58.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, or 185.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

[Miniaturization of pigment]
When the pigment is used in the present invention, it is preferably used after being refined, but the refinement method is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation can be used, and examples are given in the present invention. Thus, a salt milling process by a kneader method, which is a kind of wet grinding, can be performed. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Further, it is preferably 100 nm or less because a color filter having a high contrast ratio can be formed. A particularly preferable range is a range of 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is obtained by approximating it to a cube of the obtained particle size, and the volume average particle size is defined as the average primary particle size.
The colored composition of the present invention is excellent in resistance even when such a finely-treated pigment is used by containing an epoxy compound together with a specific pigment dispersant containing a heat-crosslinkable functional group. In addition, a coloring composition for a color filter having a high luminance and contrast ratio can be obtained.

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

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

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

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

"dye"
The coloring composition of this invention can also use dye as a coloring agent. As the dye, any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes and the like can be used. Moreover, it may be in the form of a lake pigment obtained by lacquering these derivatives or dyes.
In general, a coloring composition using a dye often has a problem in durability, but a coloring composition containing the dispersant (X) of the present invention and an epoxy compound uses such a dye. In addition, since it is excellent in heat resistance and solvent resistance, a high-quality color filter can be obtained.

Furthermore, in the case of an acid dye having an acid group such as sulfonic acid or carboxylic acid, or in the form of a direct dye, an inorganic salt of an acid dye, an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, Alternatively, use a salt-forming compound with a nitrogen-containing compound such as a primary amine compound, or salt formation using a resin component having these functional groups, or use it as a salt-forming compound after sulfonamidation. Therefore, it is possible to obtain a colored composition having excellent fastness, which is preferable.
A salt-forming compound of an acid dye and a compound having an onium base is also preferable because of excellent fastness. More preferably, the compound having an onium base is a resin having a cationic group in the side chain.

  In the case of a basic dye, it can be used after salt formation using an organic acid, perchloric acid or a metal salt thereof. Among them, a salt forming compound of a basic dye is preferable because of its resistance and excellent compatibility with pigments, and further, a basic dye and organic sulfonic acid, organic sulfuric acid, fluorine group-containing phosphorus, which are counter components that function as counter ions. It is possible to use a salt-forming compound obtained by salting an anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye. It is more preferable.

  Moreover, when it has a polymerizable unsaturated group in a pigment | dye frame | skeleton, it can be set as the dye excellent in tolerance, and it is preferable.

  Examples of the chemical structure of the dye include azo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthraquinones) Pyridone dyes), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes Dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes Indigo dyes, mention may be made thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and a dye structure derived from a dye selected from those metal complex dyes.

  Among these pigment structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium from the viewpoint of color characteristics such as hue, color separation, and color unevenness Preferred are dye structures derived from dyes selected from dyes, quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, phthalocyanine A pigment structure derived from a pigment selected from the system dyes is more preferable. For specific pigment compounds that can form a pigment structure, “New Edition Dye Handbook” (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), “Color Index” (The Society of Dyers and Colorists), “Dye Handbook” (Okawara et al.) Ed; Kodansha, 1986).

[Xanthene dyes]
The xanthene dyes that can be preferably used in the present invention are red and purple, and preferably have any form of an oil-soluble dye, an acid dye, a direct dye, and a basic dye. Moreover, it may be in the form of a lake pigment obtained by lacquering these dyes.
Among these, it is preferable to use a xanthene oil-soluble dye and a xanthene acid dye because of excellent hue.

A red or purple color means C.I. I. Solvent Red, C.I. Oil soluble dyes such as I. solvent violet, C.I. I. Basic Red, C.I. Basic dyes such as I. basic violet, C.I. I. Acid Red, C.I. Acid dyes such as I. acid violet, C.I. I. Direct Red, C.I. I. Direct dyes such as direct violet, and the like.
Here, the direct dye has a sulfonic acid group (—SO ₃ H, —SO ₃ Na) in the structure, and in the present invention, the direct dye is regarded as an acid dye.

Further, the xanthene basic dye is preferably used after being salted using an organic acid or perchloric acid. As the organic acid, organic sulfonic acid or organic carboxylic acid is preferably used. Of these, naphthalenesulfonic acid such as tobias acid and perchloric acid are preferably used in terms of resistance.
In addition, xanthene-based acid dyes are used as salt-forming compounds by salt formation using quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc., and resin components having these functional groups. In view of resistance, it is preferable to use it as a sulfonamide compound after sulfonamidation.

  Among these, a salt component of a xanthene acid dye and / or a sulfonic acid amide compound of a xanthene acid dye is preferable because of excellent hue and resistance, and further, a counter component that functions as a counter ion. It is more preferable to use a compound prepared by using a quaternary ammonium salt compound and a sulfonic acid amide compound obtained by sulfonamidating a xanthene acid dye.

  Among xanthene dyes, rhodamine dyes are preferable because they are excellent in color developability and resistance.

Hereinafter, the form of the xanthene dye used in the present invention will be specifically described in detail.

[Xanthene oil-soluble dye]
Xanthene oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, and C.I. I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solven Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet 10 and the like.
Among them, CI solvent red 35, CI solvent red 36, CI solvent red 49, CI solvent red 109, CI solvent red, which are rhodamine-based oil-soluble dyes having high color development Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferable.

[Xanthene basic dye]
Examples of xanthene basic dyes include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B) and the like. Among these, C.I. I. Basic Red 1, C.I. I. Basic violet 10 is preferably used.

[Xanthene acid dyes]
Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or rhodamine acid dye C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

These acidic dyes are preferably salt-forming compounds of acidic dyes and nitrogen-containing compounds, such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc., and their functionalities. It is preferable to form a salt using a resin component having a group to form a salt forming compound of a xanthene-based acidic dye because high heat resistance, light resistance, and solvent resistance can be imparted.
Further, it may be a salt-forming compound of an acid dye and a compound having an onium base, and among them, the compound having an onium base is a resin having a cationic group in the side chain, thereby reducing the lightness and resistance. It can be set as the outstanding coloring composition.

  Primary amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine), tridodecylamine, tetra Examples include aliphatic unsaturated primary amines such as decylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, beef tallow alkylamine, cured tallow alkylamine, allylamine, aniline, and benzylamine. .

  Secondary amine compounds include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkyl. Amine, di-cured tallow alkylamine, distearylamine, etc.

  Examples of the tertiary amine compound include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine and the like.

  The quaternary ammonium salt compounds include tetramethylammonium chloride, tetraethylammonium chloride, monostearyltrimethylammonium chloride, distearyldimethylammonium chloride, tristearylmonomethylammonium chloride, cetyltrimethylammonium chloride, trioctylmethylammonium chloride, dioctyldimethylammonium chloride. , Monolauryltrimethylammonium chloride, dilauryldimethylammonium chloride, trilaurylmethylammonium chloride, triamylbenzylammonium chloride, trihexylbenzylammonium chloride, trioctylbenzylammonium chloride, trilaurylbenzylammonium chloride Id, benzyl dimethyl stearyl ammonium chloride, and benzyl dimethyl octyl ammonium chloride, dialkyl (alkyl C14 -C18) dimethyl ammonium chloride (hydrogenated tallow), and the like.

  Specific examples of the quaternary ammonium salt compound products include, for example, Cotamin 24P, Cotamin 86P Conk, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50 manufactured by Kao Corporation, and Lion Corporation's Arcade 210- 80E, 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75, 2HP flakes, and the like. Among them, Cotamine D86P (distearyldimethylammonium chloride), Arcard 2HT-75 (dialkyl (alkyl is C14- C18) dimethylammonium chloride).

(Resin having a cationic group in the side chain)
The resin having a cationic group in the side chain will be described. The resin having a cationic group in the side chain for obtaining a salt-forming compound is not particularly limited as long as it has at least one onium base in the side chain, but a suitable onium salt structure is available. From the viewpoint of the above, ammonium salts, iodonium salts, sulfonium salts, diazonium salts, and phosphonium salts are preferable, and in consideration of storage stability (thermal stability), they are ammonium salts, iodonium salts, and sulfonium salts. It is more preferable. More preferred is an ammonium salt.

  The resin having a cationic group in the side chain is an alkali resin containing a structural unit represented by the following general formula (50), and the cationic group in the general formula (50) is an anionic group of the xanthene acid dye. A salt-forming compound can be obtained by forming a salt.

General formula (50)

[In the general formula (50), R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ^{52 to} R ⁵⁴ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R ^{52 to} R ⁵⁴ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ⁵⁵ —, —COO—R ⁵⁵ —, and R ⁵⁵ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

(Salt formation)
A salt-forming compound of an acid dye and a nitrogen-containing compound or a resin having a cationic group in the side chain can be produced by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 11-72969.
For example, a xanthene acid dye may be used, and after the xanthene acid dye is dissolved in water, a quaternary ammonium salt compound may be added and subjected to chlorination while stirring. Here, the sulfonic acid group (—SO ₃ H) and sodium sulfonate group (—SO ₃ Na) in the xanthene acid dye and the ammonium group (NH ₄ ⁺ ) part of the quaternary ammonium salt compound are combined. A salt compound is obtained. In addition, instead of water, methanol and ethanol are also solvents that can be used for the chlorination.

Further, the salt-forming compound used in the present invention is prepared by stirring or vibrating an aqueous solution in which a resin having a cationic group in the side chain represented by the general formula (50) and an acidic dye are dissolved, or the general formula (50 It can be easily obtained by mixing an aqueous solution of a resin having a cationic group in the side chain represented by (4) and an aqueous solution of an acidic dye under stirring or vibration. In the aqueous solution, the ammonium group of the resin and the anionic group of the acidic dye are ionized and these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, the salt composed of the counter anion of the resin and the counter cation of the acidic dye is water-soluble and can be removed by washing or the like. As for the resin having a cationic group in the side chain to be used and the acid dye, only a single type or a plurality of types having different structures may be used.
In addition, with other acidic dyes, a salt-forming compound with a nitrogen-containing compound or a resin having a cationic group in the side chain can be obtained in the same manner as the xanthene dye.

(Sulphonic acid amide compound)
The acidic dye used in the present invention may be a sulfonic acid amide compound obtained by reacting a sulfonic acid amide compound with an anionic dye.
The sulfonic acid amide compound of an acid dye that can be preferably used for the acid dye of the present invention is obtained by chlorinating an acid dye having —SO ₃ H and —SO ₃ Na by a conventional method, and converting —SO ₃ H into —SO ₂ Cl. This compound can be produced by reacting with an amine having a —NH ₂ group.
Specific examples of amine compounds that can be preferably used in sulfonamidation include 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, and 3-ethoxypropyl. It is preferable to use amine, cyclohexylamine or the like.
An example using a xanthene acid dye is C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 289 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 289.
In addition, C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 52 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 52 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 52.
Moreover, also in other acidic dyes, a sulfonic acid amide compound can be obtained in the same manner as xanthene dyes.

  Examples of such xanthene dyes include JP2010-032999A, JP2011-138094A, JP2011-227313A, JP2011-242752A, JP2012-107192A, No. 2013-033194, Japanese Patent Application No. 2011-71888, Japanese Patent Application No. 2013-72263, Japanese Patent Application No. 2013-81209, Japanese Patent Application Laid-Open No. 2014-173064, Japanese Patent Application No. 2013-53028, Japanese Patent Application No. 2013. No. -52186, JP 2014-196392 A, JP 2014-196393 A, JP 2014-201714 A, JP 2014-201715 A, JP 2013-050693 A, JP 2013-178478 A. Publication, JP2013-203356 Distribution, it is possible to use a known technique described in WO 2013/011687 pamphlet or the like.

[Dipyrromethene dye]
The dipyrromethene dye is a dye having a partial structure derived from a dipyrromethene dye as a partial structure of the dye part, and preferably a dipyrromethene compound and a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound. However, a metal complex compound in which the structure represented by the general formula (I) is coordinated to a metal atom or a metal compound (hereinafter, appropriately referred to as “dipyrromethene metal complex compound”) is preferable.

[Dipyrromethene metal complex compound]
The metal complex compound (dipyrromethene metal complex compound) in which the structure represented by the general formula (I) is coordinated to a metal atom or a metal compound will be described.

In general formula (I), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Represents.
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or 2 Valent metal chlorides are included. Examples of the metal or metal compound include ZnCl, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, and B, as well as AlCl3, InCl3, FeCl3, and TiCl2. Further, metal chlorides such as SnCl2, SiCl2, and GeCl2, metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) 2 are also included.
Among these, as a metal or a metal compound, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, and the like from the viewpoint of stability of the complex, spectral characteristics, heat resistance, light resistance, manufacturing suitability, and the like. Ni, Co, TiO, B, or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO is most preferred.

  Examples of such dipyrromethene dyes include JP-A-2008-292970, JP-A-2010-85758, JP-A-2010-84009, Japanese Patent Application No. 2010-43530, JP-A-2013-080010, Known techniques described in Japanese Unexamined Patent Publication No. 2013-210596 and International Publication No. 2013/141156 can be used.

[Triphenylmethane dye]
Examples of the triphenylmethane dye skeleton include a diaminotriphenylmethane dye skeleton, a triaminotriphenylmethane dye skeleton, and a rosic acid dye skeleton having an OH group.
Triaminotriphenylmethane-based dye skeletons are preferable in that they are excellent in color tone and more excellent in fastness to sunlight than others. Among them, a diphenylnaphthylmethane dye skeleton that is a basic dye is particularly preferable.

[Triphenylmethane basic dye]
The triphenylmethane-based basic dye develops color when the NH ₂ or OH group located in the para position with respect to the central carbon takes a quinone structure by oxidation.
Depending on the number of NH ₂ and OH groups, it can be divided into the following three types. Among them, a triaminoarylmethane-based basic dye is preferable in terms of good blue, red and green coloring.
a) Diaminotriphenylmethane basic dye b) Triaminotriphenylmethane basic dye c) Rosolic acid basic dye having OH group Triaminotriphenylmethane basic dye, diaminotriphenylmethane basic dye The dye has a clear color tone and is excellent in sunlight fastness than the other dyes and is preferable.

  Since the blue triphenylmethane basic dye has a spectral characteristic having a high transmittance at 400 to 440 nm, it can have high brightness, particularly when used for forming a blue filter segment. This is preferable because it is possible.

Specific examples of triphenylmethane basic dyes include C.I. I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 26 (Victoria Blue B conc.), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green) and the like.
Above all, from the point of brightness, C.I. I. Basic Blue 7 is preferably used.

  Further, in the case of a triphenyl basic dye, it can be used after being salted using an organic acid, perchloric acid or a metal salt thereof. Among them, a salt forming compound of a basic dye is preferable because of its resistance and excellent compatibility with pigments, and further, a basic dye and organic sulfonic acid, organic sulfuric acid, fluorine group-containing phosphorus, which are counter components that function as counter ions. It is possible to use a salt-forming compound obtained by salting an anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye. It is more preferable.

  Specifically, organic acids such as heteropoly acids, organic sulfonic acids such as aliphatic sulfonic acids and aromatic sulfonic acids, organic sulfuric acids such as aliphatic sulfuric acids and aromatic sulfuric acids, organic carboxylic acids such as aromatic carboxylic acids and fatty acids, Or it has the form of an acid dye. Alternatively, a metal salt thereof may be used. A salt-forming compound with a resin having an acid group is also preferable.

(Salt formation)
These salt forming compounds of a basic dye and an anionic counter can be synthesized by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 2003-215850.
For example, after the triarylmethane basic dye is dissolved in water, an organic sulfonic acid or (sodium organic sulfonate) solution is added, and the chlorination treatment may be performed while stirring. Here, a salt-forming compound is obtained in which the amino group (—NHC ₂ H ₅ ) portion in the triarylmethane basic dye and the sulfonic acid group (—SO ₃ H) portion of the organic sulfonic acid are bonded.
Here, the organic sulfonic acid can be dissolved in an alkali solution such as sodium hydroxide before the salt-forming treatment and used as a form of sodium sulfonate (—SO ₃ Na). In the present invention, a sulfonic acid group (—SO ₃ H) and a functional group (—SO ₃ Na) which is sodium sulfonate are also synonymous.

  Examples of such triphenylmethane dyes include JP-A No. 2002-014222, JP-A No. 2003-246935, JP-A No. 2003-246935, JP-A No. 2008-304766, and JP-A No. 2010-256598. Japanese Patent Application No. 2011-200560, Japanese Unexamined Patent Application Publication No. 2011-186043, Japanese Unexamined Patent Application Publication No. 2012-173399, Japanese Unexamined Patent Application Publication No. 2012-233303, Japanese Unexamined Patent Application Publication No. 2012-098522, Japanese Patent Application No. 2012-288970, Known techniques described in Japanese Patent Application No. 2012-200469, Japanese Patent Application Laid-Open No. 2014-196262, International Publication No. 2010/123071, Pamphlet of International Publication No. 2011/162217, International Publication No. 2013/108591, etc. Use It can be.

[Cyanine dyes]
Any cyanine dye can be used without limitation as long as it is a compound having a dye moiety containing a cyanine skeleton in the molecule.
Examples of cyanine dyes include C.I. I. Basic Yellow 11, 12, 13, 14, 21, 22, 23, 24, 28, 29, 33, 35, 40, 43, 44, 45, 48, 49, 51, 52, 53, C.I. I. Basic Red 12, 13, 14, 15, 27, 35, 36, 37, 45, 48, 49, 52, 53, 66, 68, C.I. I. Basic violet 7, 15, 16, 20, 21, 39, 40, C.I. I. Basic orange 27, 42, 44, 46, C.I. I. Basic blue 62, 63, etc. may be mentioned.
In addition, cyanine dyes described in JP2014-224970A, JP2013-261614A, and the like can also be used.

[Anthraquinone dyes]
An anthraquinone dye is a dye having an anthraquinone skeleton in the molecule.
Examples of the anthraquinone dye include C.I. I. Solvent Yellow 117, 163, 1
67, 189, C.I. I. Solvent Orange 77, 86, C.I. I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, C.I. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, C.I. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, C.I. I. Solvent Green 3, 28, 29, 32, 33, C.I. I. Acid Red 80, C.I. I. Acid Green 25, 27, 28, 41, C.I. I. Acid Violet 34, C.I. I. Acid Blue 25, 27, 40, 45, 78, 80, 112, C.I. I. Disperse Yellow 51, C.I. I. Disperse violet 26, 27, C.I. I. Disperse Blue 1, 14, 56, 60, C.I. I. Direct Blue 40, C.I. I. Modern Red 3, 11, C.I. I. Modern Blue 8 etc. are mentioned. Further, anthraquinone dyes described in JP-A-9-291237, WO2003 / 080734, WO2006 / 024617, JP2011-174987, JP2013-53273, and the like are used. It can be used as a known technique. The anthraquinone dye is preferably soluble in an organic solvent, and more preferably a blue, violet or red anthraquinone dye. As an anthraquinone dye, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 45, C.I. I. Acid Blue 80, C.I. I. Solvent Blue 104, and C.I. I. Solvent blue 122 is preferable from the viewpoint of brightness and contrast.

<Dispersant>
The dispersant of the present invention is characterized by containing a dispersant (X).
The dispersant (X) is an acid anhydride group in one or more acid anhydrides (b) selected from a tetracarboxylic acid anhydride (b1) and a tricarboxylic acid anhydride (b2) and a hydroxyl group-containing compound (a). A polyester portion X1 ′ having a carboxyl group obtained by reacting with a hydroxyl group;
A vinyl polymer portion X2 ′ formed by radical polymerization of an ethylenically unsaturated monomer (c) and having any one selected from the group consisting of structural units represented by the following general formulas (1) to (4): It is a dispersing agent.

In general, a dispersant has a structure of a site that adsorbs to a colorant and a site that has a high affinity for a colorant carrier and a solvent that is a dispersion medium, and the performance of the dispersant is determined by the balance between these two sites.
That is, in order to develop dispersibility, both the ability of the dispersant to adsorb to the colorant and the affinity to the colorant carrier and the solvent as the dispersion medium are very important. The colorant carrier referred to here comprises a resin and its precursor or a mixture thereof obtained by removing the colorant component and the dispersant from the solid content.

<< Dispersant (X) >>
The dispersant (X) is an acid anhydride group in one or more acid anhydrides (b) selected from a tetracarboxylic acid anhydride (b1) and a tricarboxylic acid anhydride (b2) and a hydroxyl group-containing compound (a). A polyester portion X1 ′ having a carboxyl group obtained by reacting with a hydroxyl group;
A dispersant having a vinyl polymer portion X2 ′ obtained by radical polymerization of an ethylenically unsaturated monomer (c), wherein the vinyl polymer portion is a structural unit represented by general formulas (1) to (4) It has any one chosen from the group which consists of.

  Here, the polyester portion X1 ′ of the main chain acts as a colorant adsorbing group and the vinyl polymer portion X2 ′ of the side chain acts as a colorant carrier affinity group, thereby suppressing aggregation of the colorant and improving stability. An excellent dispersion can be obtained. In addition, the vinyl polymer portion X2 ′ in the side chain in the dispersant (X) has any one selected from the group consisting of structural units represented by the general formulas (1) to (4). The coloring composition contained together with the agent (X) and the epoxy compound is not only dispersibility, contrast ratio, brightness, heat resistance, solvent resistance, but also developability, and a color filter coloring composition. It can be.

  The content of the dispersant (X) is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 60 parts by weight, and still more preferably 5 to 40 parts by weight with respect to 100 parts by weight of the colorant. When content of dispersing agent (X) exists in this range, it can be made more excellent by a dispersibility and tolerance.

  The weight average molecular weight of the dispersant (X) is preferably 2,000 to 35,000, more preferably 4,000 to 30,000, and still more preferably 6,000 to 20,000. When the weight average molecular weight is 2,000 or more, the stability of the coloring composition can be excellent, and when it is 35,000, the fluidity can be excellent.

  The acid value of the dispersant (X) is preferably 7 to 200 mgKOH / g. More preferably, it is 10-150 mgKOH / g, More preferably, it is 15-130 mgKOH / g. When the acid value is 7 mgKOH / g or more, the pigment adsorbing ability is good and the pigment dispersibility is excellent, and when the acid value is 200 mgKOH / g or less, the viscosity of the colored composition is low and the brightness is high.

[Structural units represented by general formulas (1) to (4)]
The structural units represented by the general formulas (1) to (4) will be described respectively.
[Structural unit represented by general formula (1)]
General formula (1)

[In general formula (1), n1 represents an integer of 1 to 4, R ₁ represents hydrogen or a methyl group, X represents a direct bond, or —CR ₆ R ₇ —Z—, and Z represents a direct bond or -CR ₈ R ₉ - is represented by,
R _{2 to} R ₉ are a hydrogen atom, a halogen atom, a phthalimide group, —CH ₂ CH ₂ COOH, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and —CH ₂ — contained in these groups may be substituted with —O—, —CO— or —OCO—,
R ₂ and R ₄ may be directly bonded to form an unsaturated double bond, R ₂ and R ₃ and / or R ₄ and R ₅ may be combined to form ═CH ₂ , R ₂ and R ₆ and R ₄ and R ₈ may be combined with the carbon atom to which they are bonded to form a ring having 6 to 10 carbon atoms, and “*” indicates a bond. ]

Examples of the substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms represented by R _{2 to} R _{9 in} the general formula (1) include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclohexenyl group, Propenyl group, 4-pentenyl group, 5-hexenyl group, 1-methyl-vinyl group, 2-methyl-vinyl group, n-2-propenyl group, 1,2-dimethyl-vinyl group, 1-methyl-propenyl group, Examples include 2-methyl-propenyl group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-octenyl group, 3-dodecenyl group, vinyl group, allyl group, 2- A methyl-propenyl group, 2-octenyl group, and 3-dodecenyl group are particularly preferable.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R _{2 to} R _{9 in} the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and the like, and a methyl group is particularly preferable.

Examples of the substituted or unsubstituted aryl group having 6 to 10 carbon atoms of R _{2 to} R _{9 in} the general formula (1) include a phenyl group and a naphthyl group, and a phenyl group is particularly preferable.

In the general formula (1), X is a direct _{bond, -CH 2 -, - CR 6} R 7 -CR 8 R 9 - _preferably, R 2 to R ₅ is a hydrogen atom, the number of carbon atoms of the substituted or unsubstituted 1 to 20 An alkyl group, a halogen atom, or a phthalimide group, or R ₂ and R _6, and R ₄ and R ₈ may form a ring having 6 to 10 carbon atoms together with the carbon atom to which they are bonded. preferable.

Examples of the precursor of the structural unit represented by the general formula (1) include 2-methacryloyloxyethyl succinic acid and 2-acryloyloxyethyl succinic acid.
Or, as described later, the structural unit represented by the general formula (1) by reacting the hydroxyl group in the ethylenically unsaturated monomer or vinyl polymer with the acid anhydride represented by the general formula (6) It can also be used as a dispersant having

[Structural unit represented by general formula (2)]
General formula (2)

[In General Formula (2), n2 is an integer of 1 to 4, W1 represents —CR ₁₁ or a nitrogen atom, W2 represents —CR ₁₄ or a nitrogen atom, Y represents —COOH, —SO ₃ H, R ₁₀ Represents hydrogen or a methyl group, and R _{11 to} R ₁₄ are a hydrogen atom, a halogen atom, a nitro group, an ethynyl group, —SO ₃ H, —COOH, —COCl, —NHCOCH ₃ , a substituted or unsubstituted carbon number of 1 Represents an alkyl group of ˜20, and R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₁₃ and R ₁₄ may form a ring having 6 to 10 carbon atoms together with the carbon atom to which they are bonded. Often, “*” indicates a bond. ]

The general formula (2) halogen atom R ₁₁ to R ₁₄ in, fluorine atom, chlorine atom, bromine atom, an iodine atom, a bromine atom, a chlorine atom are particularly preferred.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R _{11 to} R _{14 in} the general formula (2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, decyl group, tetradecyl group, octadecyl group, hexadecyl group and the like, and methyl group, n-butyl group, octyl group Particularly preferred.

In General Formula (2), R _{11 to} R ₁₄ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a halogen atom.

  As will be described later, the structural unit represented by the general formula (2) is obtained by reacting the hydroxyl group in the ethylenically unsaturated monomer or vinyl polymer with the acid anhydride represented by the general formula (7). It can be a dispersant.

[Structural unit represented by general formula (3)]
General formula (3)

[In General Formula (3), n3 represents an integer of 1 to 3, R ₁₅ represents hydrogen or a methyl group, and R _{16 to} R ₂₅ represent a hydrogen atom, a substituent, or an unsubstituted alkyl group having 1 to 20 carbon atoms. R ₁₇ and R ₁₉ and / or R ₂₃ and R ₂₅ may be directly bonded to form an unsaturated double bond, and R ₁₇ and R ₂₃ may be combined with the carbon atom to which they are bonded. To form a ring, and “*” indicates a bond. ]

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R _{16 to} R _{25 in} the general formula (3) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and the like, and methyl group and tert-butyl group are particularly preferable.

Examples of the precursor of the structural unit represented by the general formula (3) include 2-methacryloyloxyethyl hexahydrophthalic acid and 2-acryloyloxyethyl hexahydrophthalic acid.
Alternatively, as described later, the structural unit represented by the general formula (3) is obtained by reacting the hydroxyl group in the ethylenically unsaturated monomer or vinyl polymer with the acid anhydride represented by the general formula (8). It can also be used as a dispersant having

[Structural unit represented by general formula (4)]
General formula (4)

[In General Formula (4), n4 is an integer of 1 to 3, R ₂₆ represents hydrogen or a methyl group, R ₃₁ represents a hydrogen atom or a methyl group, R _{27 to} R ₃₀ represent a hydrogen atom, a halogen atom, A nitro group, —COOH, a substituent or an unsubstituted alkyl group having 1 to 20 carbon atoms is represented, and “*” represents a bond. ]

As a halogen atom of R < ₂₇ > -R < ₃₀ > in General formula (4), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, A bromine atom and a chlorine atom are especially preferable.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R _{27 to} R _{30 in} the general formula (4) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and the like, and a methyl group is particularly preferable.

  As will be described later, the structural unit represented by the general formula (4) is obtained by reacting the hydroxyl group in the ethylenically unsaturated monomer or vinyl polymer with the acid anhydride represented by the general formula (9). It can be a dispersant.

When the dispersant (X) has a structural unit in which R _{2 to} R ₅ in the general formula (1) are hydrogen atoms, or a structural unit in which R _{11 to} R _{14 in} the general formula (2) are hydrogen atoms, development is performed. From the viewpoint of property and brightness. More preferably, R _{2 to} R ₅ in the general formula (1) have a structural unit that is a hydrogen atom.

[Synthesis Method of Dispersant (X)]
Examples of the synthesis method of the dispersant (X) include, but are not limited to, the following synthesis methods (1) to (3).

[Synthesis Method (1)]
In the presence of the compound (a1) having two hydroxyl groups and one thiol group in the molecule,
Radical polymerization of an ethylenically unsaturated monomer (c) including an ethylenically unsaturated monomer (c1) having any one selected from the group consisting of structural units represented by general formulas (1) to (4) A hydroxyl group in a vinyl polymer having two hydroxyl groups in one end region,
The vinyl polymer portion X2 ′ is generally treated by reacting with an acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2). Dispersant (X) having any one selected from the group consisting of structural units represented by formulas (1) to (4) is obtained.

  In the case of the synthesis method (1), when an ethylenically unsaturated monomer having a hydroxyl group is used as the ethylenically unsaturated monomer (c), the acid anhydride group in the acid anhydride (b) is Since it also reacts with the hydroxyl group of the ethylenically unsaturated monomer having a hydroxyl group, the purpose of reacting with the hydroxyl group at one end of the vinyl polymer cannot be achieved, and the target structure may not be obtained. It is not preferable.

[Synthesis method (2)]
One or more acid anhydrides (b) selected from a hydroxyl group in the compound (a1) having two hydroxyl groups and one thiol group in the molecule, and a tetracarboxylic acid anhydride (b1) and a tricarboxylic acid anhydride (b2) In the presence of a compound formed by reacting an acid anhydride group in
Radical polymerization of ethylenically unsaturated monomer (c) including ethylenically unsaturated monomer (c1) having any one selected from the group consisting of structural units represented by general formulas (1) to (4) Thus, the dispersant (X) having any selected from the group consisting of the structural units represented by the general formulas (1) to (4) in the vinyl polymer portion X2 ′ can be obtained.

[Synthesis Method (3)]
One or more acid anhydrides (b) selected from a hydroxyl group in the compound (a1) having two hydroxyl groups and one thiol group in the molecule, and a tetracarboxylic acid anhydride (b1) and a tricarboxylic acid anhydride (b2) In the presence of a compound formed by reacting an acid anhydride group in
By reacting a hydroxyl group in a hydroxyl group-containing compound obtained by radical polymerization of an ethylenically unsaturated monomer (c) containing an ethylenically unsaturated monomer having a hydroxyl group with an acid anhydride (d), vinyl is obtained. Dispersant (X) having any one selected from the group consisting of structural units represented by general formulas (1) to (4) in polymer portion X2 ′ can be obtained.

  The acid anhydride (d) is preferably an acid anhydride represented by the general formulas (6) to (9).

  Moreover, when it synthesize | combines by the synthesis method (1) or the synthesis method (2), the group which consists of a structural unit represented by General formula (1)-(4) as an ethylenically unsaturated monomer (c). In addition to obtaining the dispersant (X) using the ethylenically unsaturated monomer (c1) having any one selected from the above, the ethylenically unsaturated monomer having a hydroxyl group and the general formulas (6) to (6)-( It is also possible to use an ethylenically unsaturated monomer obtained by reacting with any of the acid anhydrides (d) represented by 9).

Subsequently, each component of the dispersant (X) will be described.
[Hydroxyl-containing compound (a)]
The hydroxyl group-containing compound is not particularly limited as long as it has a hydroxyl group in the molecule, but is preferably a polyol having two or more hydroxyl groups in the molecule, and in particular, two hydroxyl groups and one in the molecule. It is preferable that it is a compound (a1) which has a thiol group.

[Compound having two hydroxyl groups and one thiol group in the molecule (a1)]
Examples of the compound (a1) having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1, 2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, Examples include 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[Other polyols (a2)]
As other polyols (a2) that can be used, there are those belonging to the following groups (1) to (7) as long as only typical ones are exemplified. By using these polyol compounds in combination, it becomes easy to adjust the density of the carboxylic acid group and the ratio of the solvent-dissolving part.

  (1) ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1, 4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, or Polyhydric alcohols such as hexanetriol;

  (2) Various polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol Kind;

  (3) Various polyhydric alcohols as described above, and (cyclic) ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, or allyl glycidyl ether; Modified polyether polyols obtained by ring-opening polymerization of

  (4) Polyester polyols obtained by co-condensation with one or more of the various polyhydric alcohols described above and polycarboxylic acids, wherein the polycarboxylic acids are succinic acid, adipic acid, sebacic acid, Azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1 , 2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, etc. Resulting polyols;

  (5) Lactone obtained by polycondensation reaction of one or more of the various polyhydric alcohols described above with various lactones such as ε-caprolactone, δ-valerolactone, or 3-methyl-δ-valerolactone. Lactone-based polyester polyols, or lactone-modified polyester polyols obtained by polycondensation reaction of various polyhydric alcohols, polycarboxylic acids, and various lactones;

  (6) Epoxy compounds such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and / or polyhydric alcohols, or glycidyl esters of monobasic acids and / or polybasic acids, Epoxy-modified polyester polyols obtained by combining one or more of the polyester polyols during synthesis; or

  (7) Polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative, hydroxyl group-containing acrylic copolymer, hydroxyl group-containing fluorine-containing compound, or hydroxyl group-containing silicon resin And other polymer polyols.

  The other polyol (a2) optionally added shown in (1) to (7) may be used alone or in combination of two or more, but the weight average molecular weight is From the viewpoint of solubility and dispersion stability, it is preferably 40 to 10,000, more preferably 100 to 2,000, and still more preferably 100 to 1,000. When the weight average molecular weight is less than 40, the effect of improving the compatibility and dispersion stability is small, and when the weight average molecular weight is 10,000 or more, the compatibility may be deteriorated.

  The number of hydroxyl groups in one molecule of the other polyol (a2) is not particularly limited as long as the intended dispersant can be synthesized, but a diol is preferable. In particular, by reacting with tetracarboxylic dianhydride (b1), carboxyl groups serving as pigment adsorbing groups can be regularly arranged in the main chain, which is advantageous for pigment dispersion. When many polyols having more than two hydroxyl groups are used, the main chain of the polyester may be branched and complicated and bulky, and it may be difficult to obtain a dispersion effect. For the purpose of adjusting the molecular weight of the polyester (X) and adjusting the viscosity of the dispersion, it should be minimized from the viewpoint of design.

[Acid anhydride (b)]
The acid anhydride (b) of the present invention contains one or more selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2).
The two anhydride groups of the tetracarboxylic dianhydride (b1) react with the hydroxyl groups of the hydroxyl group-containing compound (a), thereby regularly forming carboxyl groups that serve as pigment adsorption groups on the main chain of the dispersant (X). This is advantageous for pigment dispersion.
When tricarboxylic anhydride (b2) is used, it can react with a hydroxyl group to form an ester bond, leaving a carboxyl group.

  In addition, polycarboxylic acid anhydrides other than tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2), dicarboxylic acid anhydrides, and anhydrides of compounds having 5 or more carboxylic acids can be used in combination. .

[Tetracarboxylic acid anhydride (b1)]
As tetracarboxylic dianhydride (b1) used in the present invention,
1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo Aliphatic tetracarboxylic dianhydrides such as [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, ethylene glycol Dimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4 4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4 , 4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride Anhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4, 4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis ( Triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid)- 4,4′-diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxy) Enoxy) phenyl] fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, or 3,4-dicarboxy-1,2,3,4 -Aromatic tetracarboxylic dianhydrides such as tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

  The tetracarboxylic dianhydride used in the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. These may be used alone or in combination. Since tetracarboxylic dianhydride forms a dispersant having two carboxyl groups in one unit of polyester by reaction with a polyol, the constitution of the dispersant (X) of the present invention from the viewpoint of pigment adsorptivity. Preferred as an element.

  Furthermore, what is preferably used in the present invention is an aromatic tetracarboxylic dianhydride from the viewpoint of adsorptivity to a colorant, and more preferably a tetracarboxylic dianhydride having two or more aromatic rings. It is a thing. Aromatic carboxylic acids have higher pigment adsorption capacity than aliphatic carboxylic acids, and carboxylic acids having two or more aromatic rings are skeletons suitable for pigment adsorption and have high heat resistance.

  Specific examples include aromatic tetracarboxylic dianhydrides represented by the following general formula (11) or general formula (12).

Formula (11)

[In General Formula (11), k is 1 or 2. ]

Formula (12)

[In General Formula (12), Q ₁ is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, General Formula (13) :

Or a group represented by the general formula (14):

It is group represented by these. ]

[Tricarboxylic anhydride (b2)]
Examples of the tricarboxylic acid anhydride (b2) include aliphatic tricarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides.

  Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid- 1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride, etc. are mentioned.

  Examples of the aromatic tricarboxylic acid include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzenetricarboxylic acid anhydride], etc.), naphthalenetricarboxylic acid, and the like. Acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalenetricarboxylic acid anhydride 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride, 2,3,2 ′ -Biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, or 3,4,4'-biphenyl Sulfonic tricarboxylic acid anhydride and the like. Of these, aromatic tricarboxylic acid anhydrides are preferably used in the present invention from the viewpoint of adsorptivity to pigments.

The ratio of the acid anhydride group in one or more acid anhydrides (b) selected from the tetracarboxylic acid anhydride (b1) and the tricarboxylic acid anhydride (b2) to the hydroxyl group in the hydroxyl group-containing compound (a) is:
The acid anhydride group / hydroxyl group is preferably 0.5 to 1.5.
When it is smaller than 0.5 or larger than 1.5, there are many portions that do not react, and the intended dispersant is often not obtained.

[Ethylenically unsaturated monomer (c)]
The dispersant (X) of the present invention has a vinyl polymer site X2 ′ formed by radical polymerization of the ethylenically unsaturated monomer (c).
When synthesized by the synthesis method (1) or the synthesis method (2), the ethylenically unsaturated monomer (c) is selected from the group consisting of structural units represented by the general formulas (1) to (4). The dispersant (X) can be obtained using the ethylenically unsaturated monomer (c1) having any of the above. Further, the ethylenically unsaturated monomer (c1) is obtained by reacting an ethylenically unsaturated monomer having a hydroxyl group with any of the acid anhydrides (d) represented by the general formulas (6) to (9). Can also be obtained.

[Ethylenically unsaturated monomer (c1)]
As the ethylenically unsaturated monomer (c1), any ethylenically unsaturated monomer having any one selected from the group consisting of the structural units represented by the general formulas (1) to (4) can be used without limitation. However, it is preferably a (meth) acrylate monomer, such as 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth). Examples include acryloyloxyethylphthalic acid. 2- (Meth) acryloyloxyethyl succinic acid is preferable because it is more excellent in developability and brightness.

  Such an ethylenically unsaturated monomer (c1) reacts an ethylenically unsaturated monomer having a hydroxyl group with any of the acid anhydrides (d) represented by the general formulas (6) to (9). It can also be obtained.

  Further, in 100% by weight of the total ethylenically unsaturated monomer (c), the content of the ethylenically unsaturated monomer (c1) is preferably 2 to 50% by weight, more preferably 5 to 30% by weight. %. When it is 2% by weight or more, the developability becomes better, and when it is 50% by weight or less, the dispersibility becomes better.

(Ethylenically unsaturated monomer having a hydroxyl group)
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 methacrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate. Preferred are 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, and 2- or 3- or 4-hydroxybutyl (meth) acrylate.

(Acid anhydride (d))
Examples of the acid anhydride (d) include carboxylic acid anhydrides and sulfonic acid anhydrides. Preferably, it is any of acid anhydrides represented by general formulas (6) to (9).
Here, the same acid anhydride as the acid anhydride (b) can be used as the acid anhydride (d).
The acid anhydride (d) is an ethylenically unsaturated monomer having a hydroxyl group and an acid anhydride (d) represented by the general formulas (6) to (9) in the synthesis method (1) or (2). Or an ethylenically unsaturated monomer (c1) containing an ethylenically unsaturated monomer having a hydroxyl group in the synthesis method (3). ) In a hydroxyl group-containing compound obtained by radical polymerization to obtain a dispersant (X).

[Acid anhydride represented by the general formula (6)]
By using the acid anhydride represented by the general formula (6), a dispersant having the structural unit represented by the general formula (1) can be obtained.
General formula (6):

[In formula (6), X is a direct bond or is _represented by -CR ₆ R 7 -Z-, Z is a direct bond or _-CR 8 _{R 9} - is represented by,
R _{2 to} R ₉ are a hydrogen atom, a halogen atom, a phthalimide group, —CH ₂ CH ₂ COOH, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and —CH ₂ — contained in these groups may be substituted with —O—, —CO— or —OCO—,
R ₂ and R ₄ may be directly bonded to form an unsaturated double bond, R ₂ and R ₃ and / or R ₄ and R ₅ may be combined to form ═CH ₂ , R ₂ and R ₆ and R ₄ and R ₈ may be combined with the carbon atom to which they are bonded to form a ring having 6 to 10 carbon atoms. ]

R _{2 to} R ₉ in the general formula (6) are the same as those in the general formula (1). X is preferably a direct bond, —CH ₂ —, —CR ₆ R ₇ —CR ₈ R ₉ —, wherein R _{2 to} R ₅ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a halogen atom It is preferably an atom or a phthalimide group, and R ₂ and R ₆ and R ₄ and R ₈ are preferably combined with the carbon atom to which they are bonded to form a ring having 6 to 10 carbon atoms.

  Specific examples of the acid anhydride represented by the general formula (6) include acid anhydrides (d-1, 2, 10, 11, 12, 15, 18) shown in Table 1 described later.

[Acid anhydride represented by general formula (7)]
By using an acid anhydride represented by the general formula (7), a dispersant having a structural unit represented by the general formula (2) can be obtained.
General formula (7)

[In General Formula (7), W 1 represents —CR ₁₁ or a nitrogen atom, W 2 represents —CR ₁₄ or a nitrogen atom, and R _{11 to} R ₁₄ represent a hydrogen atom, a halogen atom, a nitro group, an ethynyl group, — SO ₃ H, —COOH, —COCl, —NHCOCH ₃ , a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₁₃ and R ₁₄ are A ring having 6 to 10 carbon atoms may be formed integrally with the carbon atom to which is bonded. ]

_R 11 in the general formula (7) _{to R 14} are the same as _R 11 _{to R 14} in the general formula (2). R _{11 to} R ₁₄ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a halogen atom.

  Specific examples of the acid anhydride represented by the general formula (7) include acid anhydrides (d-3, 4, 5, 6, 7, 8, 16, 17) shown in Table 1 described later.

[Acid anhydride represented by the general formula (8)]
By using an acid anhydride represented by the general formula (8), a dispersant having a structural unit represented by the general formula (3) can be obtained.
General formula (8)

[In General Formula (8), R _{16 to} R ₂₅ represent a hydrogen atom, a substituent, or an unsubstituted alkyl group having 1 to 20 carbon atoms, and R ₁₇ and R ₁₉ and / or R ₂₃ and R ₂₅ May be directly bonded to form an unsaturated double bond, and R ₁₇ and R ₂₃ may be combined with the carbon atom to which they are bonded to form a ring. ]

_R 16 in the general formula (8) _{to R 25} are the same as _R 16 _{to R 25} in the general formula (3).

  Specific examples of the acid anhydride represented by the general formula (8) include acid anhydrides (d-13 and 14) shown in Table 1 described later.

[Acid anhydride represented by the general formula (9)]
By using an acid anhydride represented by the general formula (9), a dispersant having a structural unit represented by the general formula (3) can be obtained.
General formula (9)

[In General Formula (9), R ₃₁ represents a hydrogen atom or a methyl group, and R _{27 to} R ₃₀ represent a hydrogen atom, a halogen atom, a nitro group, —COOH, a substituent, or an unsubstituted C 1-20. Represents an alkyl group. ]

R < ₂₇ > -R < ₃₁ > in General formula (9) is the same as R < ₂₇ > -R < ₃₁ > in General formula (4).

  Specific examples of the acid anhydride represented by the general formula (9) include an acid anhydride (d-9) shown in Table 1 described later.

As preferred examples of the acid anhydride (d), the following compounds can be exemplified.

  The acid anhydride (d) is preferably an acid anhydride represented by the general formula (6) or the general formula (7), and among them, the acid anhydride (d-1, 3, 15, 16, or 18) is preferable from the viewpoint of developability.

[Other ethylenically unsaturated monomers]
Examples of the ethylenically unsaturated monomer other than the ethylenically unsaturated monomer (c1) include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, and fumaric acid diesters. Itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like.

Specific examples of such an ethylenically unsaturated monomer include the following compounds.
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (Meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, iso Linear or branched alkyl (meth) acrylates such as myristyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate;
Cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, tertiarybutylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate;
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;
(Meth) acrylates having an aromatic ring of benzyl (meth) acrylate and phenoxyethyl (meth) acrylate;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl Ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol Monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (Meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, polyethylene glycol monostearyl ether (meth) acrylate, and octoxypolyethylene glycol-polypropylene glycol (meth) acrylate, (Poly) alkylene glycol monoalkyl ether (meth) acrylates;
Phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, parac Milphenoxyethylene glycol (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, and nonylphenoxypoly (ethylene glycol-propylene glycol) (meth) ) Having an aromatic ring such as acrylate (poly) Ruki glycol (meth) acrylates;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
N-substituted (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholine;
Nitriles such as (meth) acrylonitrile are exemplified.
Styrenes such as styrene and α-methylstyrene;
Macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate and vinyl propionate;

  Furthermore, a carboxyl group-containing ethylenically unsaturated monomer can be used in combination. Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, (meth) acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, β-carboxyethyl (meth) acrylate, and ω- Examples include carboxypolycaprolactone (meth) acrylate.

  Moreover, although the ethylenically unsaturated monomer which has the hydroxyl group mentioned above can also be used, in this case, since it may react with an acid anhydride (b) during a synthesis | combination, synthesis method (2) Is preferably selected.

  These ethylenically unsaturated monomers can be used as a mixture of two or more at any ratio as required.

Among the other ethylenically unsaturated monomers, it is preferable to use methyl (meth) acrylate, and 40% to 80% by weight of methyl (meth) acrylate in 100% by weight of the total ethylenically unsaturated monomer (c). % Is preferable from the viewpoints of heat resistance and developability. More preferably, it is 50 to 80% by weight. By being 40% by weight or more, the solvent resistance and heat resistance are excellent, and when it is 80% by weight or less, the viscosity stability can be further improved.
Since methyl (meth) acrylate has a high glass transition temperature of about 105 ° C., the glass transition temperature Tg of the vinyl polymer portion X2 ′ is increased, and as a result, the heat resistance is improved. In general, when Tg is high, developability may be lowered. However, the colored composition of the present invention can have both heat resistance and developability by having a specific acidic site.

[Synthesis of polyester part X1 ′]
The synthesis of the polyester portion X1 ′ is carried out in the acid anhydride group and the hydroxyl group-containing compound (a) in one or more acid anhydrides (b) selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2). This is a step of reacting with the hydroxyl group.

As the catalyst used for the production of the polyester part X1 ′ of the present invention, known catalysts can be used. As a catalyst, for example,
Triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, or 1,5-diazabicyclo- [4.3.0] A tertiary amine compound such as -5-nonene, or mono-n-butyltin (IV) oxide may be used.

  In the production of the polyester part X1 ′ of the present invention, it is possible to produce only with the raw materials listed so far, but a solvent is used in order to avoid problems such as high viscosity and non-uniform reaction. Is preferred. There is no limitation in particular as a solvent used, A well-known thing can be used. Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, toluene, xylene, or acetonitrile. After completion of the reaction, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step or as part of a product.

  The reaction temperature for the synthesis of the polyester part X1 'is 50 ° C to 180 ° C, preferably 80 ° C to 140 ° C. When the reaction temperature is 50 ° C. or lower, the reaction rate is slow, and when the reaction temperature is 180 ° C. or higher, the carboxyl group and the hydroxyl group may undergo an esterification reaction, resulting in a decrease in acid value or gelation. Ideally, the reaction is stopped until the absorption of the acid anhydride is eliminated by infrared absorption, but the reaction may be stopped when 97% or more of the acid anhydride is half-esterified by acid value measurement.

[Synthesis of vinyl polymer portion X2 ′]
The vinyl polymer part X2 ′ which is a side chain of the dispersant is obtained by changing the compound (a1) having two hydroxyl groups and one thiol group in the molecule according to the molecular weight of the target vinyl polymer part X2 ′. It can be obtained by mixing and heating the ethylenically unsaturated monomer (c) and optionally a polymerization initiator. )
Alternatively, the hydroxyl group in the compound (a1) having two hydroxyl groups and one thiol group in the molecule, and the acid anhydride group in the tricarboxylic acid anhydride (b1) and / or the tetracarboxylic acid dianhydride (b2) Is obtained by mixing and heating the ethylenically unsaturated monomer (c) and, optionally, a polymerization initiator in accordance with the molecular weight of the target vinyl polymer portion X2 ′. be able to.

  The hydroxyl group-containing compound (a) is a bulk polymerization or solution using 0.5 to 10 parts by weight based on 100 parts by weight of the total weight of the total amount of the ethylenically unsaturated monomer (c). Polymerization is preferably performed, and more preferably 0.8 to 6 parts by weight. When the molecular weight is less than 0.5 parts by weight, the molecular weight of the vinyl polymer portion X2 ′ is too high, and the absolute amount increases as an affinity site for the pigment carrier and the solvent, and the dispersibility effect itself decreases. When the amount exceeds 10 parts by weight, the molecular weight of the vinyl polymer portion X2 ′ is too low, and the steric repulsion effect is lost as an affinity site for the pigment carrier and the solvent, and it is difficult to suppress the aggregation of the pigment. It may become. Further, since the glass transition temperature Tg of the vinyl polymer portion X2 'is also lowered, the heat resistance is insufficient, so that the recently required physical properties cannot be satisfied.

  The acid value of the vinyl polymer portion X2 'is preferably 10 to 100 mgKOH / g. When the acid value is 10 mgKOH / g or more, the developability is excellent even when the vinyl polymer portion X2 'has a high molecular weight and a high Tg in order to increase heat resistance. Less than 100 mgKOH / g is preferable because it is excellent in dispersibility, brightness, and CR. From the said viewpoint, More preferably, it is 25-70 mgKOH / g.

  The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C. When the temperature is lower than 40 ° C., the polymerization does not proceed sufficiently, and when the temperature is higher than 150 ° C., the molecular weight may be difficult to control.

  The weight average molecular weight of the vinyl polymer portion X2 'is preferably 2,000 to 40,000, more preferably 2000 to 30,000, and still more preferably 2,200 to 25,000. This site becomes an affinity site for the pigment carrier and the solvent. When the weight average molecular weight of the vinyl polymer portion X2 'is less than 2,000, the steric repulsion effect is lost as an affinity site for the pigment carrier and the solvent, and it may be difficult to suppress pigment aggregation. Further, since the glass transition temperature Tg of the vinyl polymer portion X2 'is also lowered, the heat resistance is insufficient, so that the recently required physical properties cannot be satisfied. Moreover, when it exceeds 40,000, the absolute amount will increase as an affinity site | part with respect to a pigment carrier and a solvent, and the dispersibility effect itself may fall. Further, the viscosity of the dispersion may increase. The vinyl polymer portion X2 'can be easily adjusted in molecular weight to the above range, and has good affinity for the solvent.

  In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the total monomer weight of the total weight of the ethylenically unsaturated monomer (c). . As the polymerization initiator, an azo compound and an organic peroxide can be used.

Examples of azo compounds include
2,2′-azobisisobutyronitrile, 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), 2,2′-azobis [2- (2-imidazolin-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) peroxydicarbonate, t-butylperoxyneo Examples include decanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide.

  These polymerization initiators can be used alone or in combination of two or more.

  In the case of solution polymerization, the polymerization solvents are ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol mono Ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used, but is not particularly limited thereto. These polymerization solvents may be used as a mixture of two or more. After completion of the reaction, the solvent used in the polymerization reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step or as part of a product.

《Other dispersants》
The coloring composition for a color filter of the present invention may be used in combination with other dispersants.
Specific examples of other dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) and polyesters having free carboxyl groups, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified polymer Acrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, it can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554 1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

<Binder resin>
The binder resin disperses, dyes, or penetrates the colorant, and examples thereof include a thermoplastic resin. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading (deterioration of spectral characteristics) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. 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 binder resin is used as a photosensitive coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin is preferably used in an amount of 20 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 1000 parts by weight or less.

  Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

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

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

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

  Examples of the unsaturated ethylenic 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 also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

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

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

  Examples of unsaturated ethylenic monomers 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 unsaturated ethylenic 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.

<Thermosetting compound>
The colored composition of the present invention includes an epoxy compound as a thermosetting compound, and includes an epoxy compound and a dispersing agent (X), thereby being excellent in chemical resistance and solvent resistance after curing the colored composition. Further, it is possible to suppress a decrease in brightness of adjacent color filters.

<< Epoxy compound >>
The epoxy compound in the present invention is not particularly limited as long as it has an epoxy group, and may be a low molecular compound or a high molecular weight compound such as a resin, but a polyfunctional epoxy resin is particularly preferable.
A colored film having a high crosslinking density can be obtained by thermally crosslinking the epoxy group of the epoxy compound with the carboxyl group and the hydroxyl group of the binder resin or the dispersing agent during baking in the color filter manufacturing process.

  In the case of an epoxy resin, the preferred weight average molecular weight is preferably 200 or more and 100,000 or less. A more preferable molecular weight is 300 or more and 10,000 or less, and further preferably 500 or more and 5000 or less.

  As for content of the epoxy compound in solid content of the coloring composition for color filters, 5 to 20 weight% is preferable. When the content is 5% by weight or more, the effect of improving the solvent resistance is enhanced. can do.

The total content of the epoxy compound and the dispersant (X) is preferably 30 to 200 parts with respect to 100 parts by weight of the colorant, and the total content of the epoxy compound and the dispersant (X) is the solid content of the color composition. Among them, 10 to 50% by weight is preferable.
Moreover, it is preferable that content of an epoxy compound is 25-150 weight part with respect to 100 weight part of dispersing agents (X). More preferably, it is 35-120 weight part.
By setting it as such a range, it can be set as the coloring composition excellent not only in the brightness and contrast ratio but in tolerance.

As the epoxy resin that can be used in the present invention, any of bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, and the like can be used.
Preferred are novolak type epoxy resins and alicyclic epoxy resins, and particularly preferred are alicyclic epoxy resins.
The number of functional groups is preferably bifunctional or higher, and more preferably trifunctional or higher because of excellent thermal crosslinkability and good solvent resistance.

  As the bifunctional epoxy compound, EPICLON 830, 840, 850, 860, 1050, 2050, 3050, 4050, 7050, HM-091, 101 manufactured by DIC, Denacol EX-211, 212, 252, 711 manufactured by Nagase ChemteX, 721 etc. are mentioned.

  Examples of the polyfunctional epoxy compound having 3 or more functional groups that can be used in the present invention include novolak type epoxy resin, EHPE3150 (manufactured by Daicel Chemical Industries), which is a polymer alicyclic main chain epoxy resin.

  The novolac type epoxy resin is a compound represented by the following general formula (15), and is classified into a phenol novolac type epoxy resin and a cresol novolac type epoxy resin.

General formula (15)

  R101 is each independently a methyl group or a hydrogen atom, and q is an integer of 2 to 100.

  Specific examples of the novolak type epoxy resin include EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-4500, EOCN-4600, XD-1000, XD-1000-L, and XD-1000-. 2L, NC-3000, NC-3000-H (Nippon Kayaku Co., Ltd.), YDPN-638, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN -700-10, YDCN-704, YDCN-704A (manufactured by Nippon Steel Chemical Co., Ltd.), N-660, N-665, N-670, N-673, N-680, N-690, N-695 N-665-EXP, N-672-EXP, N-655-EXP-S, N-662-EXP-S (manufactured by DIC). And the like.

EHPE3150 (manufactured by Daicel Chemical Industries), which is a polymer alicyclic main chain epoxy resin, is a compound represented by the following general formula (16), and the number of functional groups is about 15.
Formula (16)

R is undisclosed and n is about 15.

Other polyfunctional epoxy compounds having 3 or more functional groups include techmore VG3101 (made by Printec Co., Ltd.) which is a trifunctional epoxy resin, TETRAD-C and TETRAD-X (which are Mitsubishi Gas Chemical Co., Ltd.) which are tetrafunctional epoxy resins. Etc.).
Moreover, Nagase ChemteX Denacol EX-313,314,321,411,421,512,521,611,612,614,614B, 622, etc. are mentioned.
Moreover, Mitsubishi Chemical JER1031S, 1302H60, 604, 630, 630LSD etc. are mentioned.

<< Other thermosetting compounds >>
Examples of other thermosetting compounds include thermosetting compounds such as benzoguanamine compounds / resins, rosin-modified maleic resins, rosin-modified fumaric resins, melamine compounds / resins, urea resins, and phenol resins, and these thermosetting compounds. Monomers and oligomers before heat polymerization of the functional resin can also be used.

<Solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

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-butylal 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 Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Recall monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol 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 Tons, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  A solvent can be used in the quantity of 100-10000 weight part with respect to 100 weight part of coloring agents in a coloring composition, Preferably it is 500-5000 weight part.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy 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, tricyclodeca Nyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate, methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The content of the photopolymerizable monomer is preferably 5 to 500 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 400 parts by weight from the viewpoint of photocurability and developability. .

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether Or a benzoin compound such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p- Toxiphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis ( Trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl Triazine compounds such as-(4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoylo Shim)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 5 to 400 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.
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.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

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 content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<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.

Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3- Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate) ), Dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s- Examples include triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine.
These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

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 colorant.
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.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 1.0 part by weight with respect to 100 parts by weight of the total weight of the coloring composition.

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

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

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

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

<Ultraviolet 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].
These ultraviolet absorbers can be used singly or in combination of two or more at any ratio as required.

Examples of the polymerization inhibitor include hydroquinone such as methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol. Derivatives and phenolic compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. And manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine Nitroso compounds and their ammonium salts or aluminum salts and the like.
These polymerization inhibitors can be used singly or as a mixture of two or more at any ratio as required.

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 colorant 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.

<Antioxidant>
The colored composition for a color filter of the present invention can contain an antioxidant in order to increase the transmittance of the coating film. Antioxidants prevent the photopolymerization initiator contained in the color filter coloring composition from being oxidized and yellowed by the thermal process during thermal curing and ITO annealing, and thus increase the transmittance of the coating film. it can. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

Preferable examples of the antioxidant include hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfide antioxidants. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.
These antioxidants can be used singly or in combination of two or more at any ratio as required.

  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.

  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 and ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl).

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

The content of 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.

<Other ingredients>
The coloring composition for a color filter of the present invention contains an adhesion improver such as a silane coupling agent or an amine compound that has a function of reducing dissolved oxygen in order to improve adhesion to a transparent substrate. Can be made.

  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 colorant in the coloring composition.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -2-ethylhexyl dimethylaminobenzoate, N, N-dimethyl paratoluidine, etc. are mentioned.

<Method for producing colored composition for color filter>
The coloring composition for a color filter of the present invention comprises a kneader, a coloring agent in a coloring agent carrier such as a resin and / or a solvent, if necessary, together with a dispersing aid, using a dispersing agent (X). It can be produced by finely dispersing using various dispersing means such as a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed.
The epoxy compound may be added at the stage of preparing the colorant dispersion, and the same effect can be obtained even if it is added later to the prepared colorant dispersion.
When the solubility of the colorant such as a dye is high, specifically, it is highly soluble in the solvent to be used, and if it is dissolved and no foreign matter is confirmed by stirring, it is finely dispersed as described above. There is no need. In this case, the dispersant (X) can be used by simply adding and mixing it with a colorant solution in which a dye or the like is dissolved.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, not only the dispersant but also a dispersion aid such as a pigment derivative and a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more.

  The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

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

  When the surfactant is added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the content of the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion may be affected by an excessive dispersant. .

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

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention preferably includes a red filter segment, a green filter segment, and a blue filter segment on a substrate, and further includes a magenta filter segment, a cyan filter segment, or a yellow filter segment. The at least 1 filter segment may be formed from the coloring composition of this invention.

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

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

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

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

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like 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 this filter segment is transferred to a desired substrate.

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

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as

  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.

  If the black matrix is formed in advance before forming the filter segment on the transparent substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, chromium, a chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used. A black matrix formed from is preferable. A thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment and / or the black matrix on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  Formation of each color filter segment and black matrix by photolithography is performed by the following method. That is, the color composition for color filter prepared as a color composition for solvent development type or alkali development type color filter is dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It is applied so that the film thickness is 0.2 to 10 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.

  Thereafter, the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove uncured portions and forming a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment and the black matrix formed by development, heating can be performed as necessary. According to the photolithography method, it is possible to form a filter segment and a black matrix with higher accuracy than the printing method.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase UV exposure sensitivity, after applying and drying the above color filter coloring composition, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. Ultraviolet exposure can also be performed after forming a film.

  An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. “PGMAc” means propylene glycol monomethyl ether acetate.

  The number average molecular weight (Mn) of the resin and the dispersant, the acid value of the resin and the dispersant, the ammonium salt value of the resin having a cationic group in the side chain, and the average primary particle size of the pigment are as follows. It is.

(Number average molecular weight of resin and dispersant (Mn))
The number average molecular weight (Mn) of the resin is a polystyrene equivalent measured by using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. Number average molecular weight (Mn).

(Acid value of resin and dispersant (mgKOH / g))
The acid value of the resin is a value obtained by converting the measured acid value (mgKOH / g) into a solid content according to the potentiometric titration method of JIS K 0070.

(Ammonium salt value of a resin having a cationic group in the side chain)
The ammonium salt value of the resin having a cationic group in the chain is a value converted to an equivalent of potassium hydroxide after being obtained by titration with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, The ammonium salt value of solid content is shown.

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

  Subsequently, production of acrylic resin solutions, dispersants, pigment derivatives, resins having a cationic group in the side chain, fine pigments, dyes, pigment dispersions, dye solutions, and green resist materials used in Examples and Comparative Examples A method will be described.

<Method for producing acrylic resin solution>
(Preparation of acrylic resin 1)
A reactor equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer was charged with 70.0 parts of PGMAc, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 2 , 2′-Azobisisobutyronitrile (0.4 parts) was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain a solution of acrylic resin 1 having a number average molecular weight (Mn) of 13000. 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 PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20 wt%. Acrylic resin 1 was prepared.

<Method for producing dispersant>
(Dispersant (X-1))
[First step]
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 4.0 parts of 3-mercapto-1,2-propanediol, 24.4 parts of PGMac, 6.46 parts of pyromellitic anhydride, as a catalyst After adding 0.005 part of monobutyltin (IV) oxide and replacing with nitrogen gas, the mixture was reacted at 130 ° C. for 2 hours and at 100 ° C. for 2 hours. (First step) It was confirmed by titration that 90% or more of the acid anhydride was half-esterified, and cooled to room temperature.
[Second step]
Methyl methacrylate 50 parts, t-butyl acrylate 6.1 parts, cyclohexyl acrylate 6.1 parts, 2-methoxyethyl acrylate 6.1 parts, n-butyl methacrylate 6.1 parts, t-butyl methacrylate 6.1 parts, benzyl The reaction vessel was further charged with 6.1 parts of methacrylate, 7.6 parts of 2-hydroxyethyl methacrylate, and 44 parts of PGMAc, and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and 0.3 part of 2,2′-azobisisobutyronitrile dissolved in 24 parts of PGMAc was added in 20 portions every 30 minutes. It reacted for time, and it was confirmed that 95% reacted by solid content measurement.
[Third step]
Next, 5.8 parts of succinic anhydride and 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 2 hours and at 80 ° C. for 5 hours. I let you. It was confirmed by titration that 90% or more of the acid anhydride was half-esterified, and a dispersant (X-1) having an acid value of 60 mgKOH / g and a number average molecular weight (Mn) of 8,100 per solid content was obtained. .
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20 wt%. Thus, a dispersant (X-1) solution was obtained.

(Dispersant (X-2 to 30))
Dispersants (X-2 to 30) were obtained in the same manner as the dispersant (X-1) except that the raw material types and the blending amounts (parts by weight) shown in Tables 2 to 4 were changed.

(Dispersant (X-31))
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade and a thermometer, 50 parts of methyl methacrylate, 6.1 parts of t-butyl acrylate, 6.1 parts of cyclohexyl acrylate, 6.1 parts of methoxyethyl acrylate, n- 6.1 parts of butyl methacrylate, 6.1 parts of t-butyl methacrylate, 6.1 parts of benzyl methacrylate, 13.37 of 2-methacryloyloxyethyl succinic acid, and 44 parts of PGMAc were charged and replaced with nitrogen gas. Heat the reaction vessel to 80 ° C, add 4.0 parts of 3-mercapto-1,2-propanediol, then dissolve 0.3 parts of 2,2'-azobisisobutyronitrile in 24 parts of PGMAc. This was added in 20 portions every 30 minutes, reacted for 12 hours at 80 ° C., and 95% was confirmed by solid content measurement. Next, 6.46 parts of pyromellitic anhydride and 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added, and 5 hours at 80 ° C. for 2 hours at 120 ° C. Reacted for hours. It was confirmed by titration that 90% or more of the acid anhydride was half-esterified, and a dispersant (X-31) having an acid value of 60 mgKOH / g and a number average molecular weight (Mn) of 8,100 per solid content was obtained. . After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Dispersant (X-31) was obtained.

(Dispersant (X-32-40, XC-1, 2))
Dispersants (X-32 to 39, XC-1 and 2) were obtained in the same manner as the dispersant (X-31) except that the raw material types and the blending amounts (parts by weight) shown in Table 3 were changed. .

The abbreviations in Tables 2 to 5 are as follows.
* Methyl (meth) acrylate content (wt%)
= Methyl (meth) acrylate content in 100% by weight of ethylenically unsaturated monomer (c) << ethylenically unsaturated monomer (c) >>
MMA: methyl methacrylate t-BA: t-butyl acrylate CHA: cyclohexyl acrylate 2-MTA: 2-methoxyethyl acrylate n-BMA: n-butyl methacrylate t-BMA: t-butyl methacrylate BzMA: benzyl acrylate HEMA: 2-hydroxy Ethyl methacrylate HPMA: 2-hydroxypropyl methacrylate HBMA: 2-hydroxybutyl methacrylate HEA: 2-hydroxyethyl acrylate HPA: 2-hydroxypropyl acrylate HBA: 2-hydroxybutyl acrylate MAA: methacrylic acid (ethylenically unsaturated monomer ( c1))
HOMS: 2-methacryloyloxyethyl succinic acid HOA: 2-acryloyloxyethyl succinic acid MMS: 2-methacryloyloxyethyl hexahydrophthalic acid MOA: 2-acryloyloxyethyl hexahydrophthalic acid

<< Acid anhydride (b) >>
PMA: pyromellitic dianhydride (Daicel Chemical Industries, Ltd.)
TMA: Trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd.)
<< Acid anhydride (d) >>
Acid anhydrides (d-1) to (d-18) shown in Table 1

BTO: monobutyltin (IV) oxide AIBN: 2,2′-azobisisobutyronitrile DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene

(Dispersant (X-41))
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, under air, 0.3 part of hydroquinone, 44 parts of PGMAc, 5.8 parts of succinic anhydride, 7.6 parts of 2-hydroxyethyl methacrylate, As a catalyst, 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene was added and reacted at 120 ° C. for 2 hours and at 80 ° C. for 5 hours. It was confirmed by titration that 90% or more of the acid anhydride was half-esterified, allowed to cool to room temperature, and further 50 parts of methyl methacrylate, 6.1 parts of t-butyl acrylate, 6.1 parts of cyclohexyl acrylate, methoxyethyl A reaction vessel was charged with 6.1 parts of acrylate, 6.1 parts of n-butyl methacrylate, 6.1 parts of t-butyl methacrylate, and 6.1 parts of benzyl methacrylate and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and 0.3 part of 2,2′-azobisisobutyronitrile dissolved in 24 parts of methoxypropyl acetate was added in 20 portions every 30 minutes. It was confirmed that 95% had reacted by solid content measurement, and the dispersant (X-40) having an acid value of 40 mgKOH / g and a number average molecular weight (Mn) of 8,100 per solid content was measured. Obtained. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20 wt%. Dispersant (X-41) was obtained.

<Method for producing pigment derivative>
(Dye derivative 1)
After 50 parts of copper phthalocyanine as a dye component was chlorosulfonated, it was reacted with 14 parts of N, N-dimethylaminopropylamine as an amine component to obtain a dye derivative 1 having a basic group.
Dye derivative 1

CuPc represents a copper phthalocyanine residue.

(Dye derivative 2)
By using diphenyl diketopyrrolopyrrole as a dye component and N-aminopropylmorpholine as an amine component, a dye derivative 2 having a basic group was obtained in the same manner as in the preparation of dye derivative 1.
Dye derivative 2

(Dye derivatives 3, 4)
Synthesis was performed as described in JP-A-2007-156395 and JP-A-2007-79094 to obtain dye derivatives 3 and 4.
Dye derivative 3

Dye derivative 4

<Method for producing resin having cationic group in side chain>
(Resin 1 having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2′-azobis (2,4-dimethylvaleronitrile) ) And 25.1 parts of methyl ethyl ketone were made uniform, charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the number average molecular weight (Mn) was 3400, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 1 having a cationic group in the side chain having 47% by weight of an ammonium group as the resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

<Method for producing fine pigments>
(Fine refined pigment (PB-1))
C. I. 100 parts of Pigment Blue 15: 6 (PB15: 6) (“Rionol Blue ES” manufactured by Toyocolor Co., Ltd.), 800 parts of crushed salt, and 100 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho), 70 The mixture was kneaded for 12 hours. The mixture was added to 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 98 parts fine Pigmented pigment (PB-1) was obtained. The average primary particle size was 28.3 nm.

(Refined pigment (PR-1))
C. I. 200 parts of Pigment Red 254 ("B-CF" manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , 190 parts of refined pigment (PR-1) was obtained. The average primary particle size was 27.6 nm.

(Refined pigment (PR-2))
C. I. 100 parts of Pigment Red 177 (PR177) (“chromophthaled red A2B” manufactured by BASF), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. Then, salt milling was performed. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of (refined pigment PR-2) were obtained. The average primary particle size was 33 nm.

(Refinement pigment (PR-3))
C. I. 200 parts of Pigment Red 269 (“Toner Magenta F8B” manufactured by Clariant), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , 190 parts of refined pigment (PR-3) was obtained. The average primary particle size was 39.6 nm.

(Fine refined pigment (PG-1))
Phthalocyanine green pigment C.I. I. 120 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyochem Co., Ltd.), 1600 parts of sodium chloride, and 270 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 12 hours. The mixture was added to 5000 parts of warm water, stirred for 1 hour while heating to about 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 117 parts of A fine pigment (PG-1) was obtained. The average primary particle size was 32.6 nm.

(Fine refined pigment (PG-2))
Phthalocyanine green pigment C.I. I. 100 parts of Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product is poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 97 parts of a modified pigment (PG-1) were obtained. The average primary particle size was 28.2 nm.

(Fine refined pigment (PY-1))
C. I. 100 parts of Pigment Yellow 138 (PY138) (“Pariotor Yellow K0960-HD” manufactured by BASF), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C. for 6 hours. Kneaded. The mixture was poured into 2000 parts of warm water, stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 95 parts fine. Pigmented pigment (PY-1) was obtained. The average primary particle size was 40.2 nm.

<Dye production method>
(Dye 1)
In the following procedure, C.I. I. Dye 1, which is a salt-forming compound comprising Acid Red 52 and Resin 1 having a cationic group in the side chain, was produced.
The resin 1 having a cationic group in a side chain of 30 parts in terms of solid content was added to 2000 parts of water, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the previous resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. Dye 1 which is a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in the side chain was obtained. At this time, C.I. I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

(Dye 2)
In the following procedure, C.I. I. Dye 2, which is a salt-forming compound composed of Acid Red 289 and Resin 1 having a cationic group in the side chain, was produced.
The resin 1 having a cationic group in a side chain of 30 parts in terms of solid content was added to 2000 parts of water, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 289 was dissolved was prepared and added dropwise little by little to the resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. Dye 2 which is a salt-forming compound of Acid Red 289 and Resin 1 having a cationic group in the side chain was obtained. At this time, C.I. I. The content of the effective pigment component derived from Acid Red 289 was 27% by weight.

(Dye 3)
In the following procedure, C.I. I. Dye 3 which is a salt-forming compound composed of Acid Red 52 and distearyldimethylammonium chloride (Coatamine D86P) (cation part has a molecular weight of 550) was prepared.
In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 52 is dissolved, sufficiently mixed and stirred, heated to 70 to 90 ° C., and then Cotamine D86P is added dropwise little by little. Coatamine D86P may be dissolved in water and used as an aqueous solution. After adding Cotamine D86P dropwise, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. Dye 3 which is a salt-forming compound of Acid Red 52 and distearyldimethylammonium chloride was obtained.

(Dye 4-6)
Based on the description in JP-A-2013-203956, dyes 4 to 6 as the following xanthene sulfonic acid amide compounds were obtained.
In addition,

It is.

Dye 4

Dye 5

Dye 6

(Dye 7)
Dipyrromethene dye Exemplified compound I-1 described in JP 2008-292970 A was obtained, and this was designated as Dye 7. (See paragraph 0107)

(Dye 8, 9)
Cyanine dyes Fluorescent pigment (A-11) and fluorescent pigment (A-17) described in Examples of JP-A-2015-18208 were obtained, and these were designated as dyes 8 and 9, respectively. (See paragraph 0318)

(Dye 10, 11)
Anthraquinone dyes Salt-forming compounds (A-1) and salt-forming compounds (A-11) described in Examples of JP2011-174987A were obtained, and these were designated as Dye 10 and Dye 11, respectively.
(See paragraphs 0142 and 0152)

(Dye 12)
2,8-Diamino-1-naphthol-5,7-disulfonic acid (molecular weight 334) is dissolved in a 7-15 mol% sodium hydroxide solution and sufficiently mixed and stirred to obtain its sodium salt. This 2,8-diamino-1-naphthol-5,7-disulfonic acid sodium salt aqueous solution is heated to 70 to 90 ° C., and then Victoria Pure Blue dye (CI Basic Blue 7) is added dropwise little by little. . The Victoria Pure Blue dye may be dissolved in water and used as an aqueous solution. After dripping Victoria pure blue dye, it stirs at 70-90 degreeC for 40-60 minutes, and fully reacts. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. The mixture is allowed to cool to room temperature with stirring, and then suction filtered and washed with water. After washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and salted with Victoria Pure Blue dye and 2,8-diamino-1-naphthol-5,7-disulfonic acid. The dye 12 which is a compound and a triarylmethane salt forming compound was obtained.

(Dye 13)
In a 1 L stainless steel reaction vessel equipped with a reflux tube, C.I. I. 5.0 parts of basic violet 10 (BV10: manufactured by Taoka Chemical Co., Ltd .: Rhodamine B) and 1.6 parts of hydroxyethyl methacrylate (HEMA) are dissolved in 40 ml of dichloromethane, and 1- (3-dimethylaminopropyl) -3-ethyl is dissolved. Carbodiimide hydrochloride (2.2 parts) and dimethylaminopyridine (0.25 part) were added, and the mixture was stirred at room temperature for 24 hours. The obtained dichloromethane solution was washed with water and dried under reduced pressure, and then purified on a silica gel column to obtain Dye 13. The yield was 51.6%.

BV10 Dye 13

<Method for producing pigment dispersion>
(Pigment dispersion (DP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a blue pigment dispersion (DP-1) was obtained.
The pigment dispersion was adjusted to have a solid content of 20% by weight with PGMAc.

Hereinafter, solid content weight is shown.
Fine pigment (PB-1): 11.0 parts Pigment Blue 15: 6
Dye derivative 1: 1.0 part Dispersant (X-1): 8.0 parts

(Pigment dispersion (DP-2 to 53))
Pigment dispersions (DP-2 to 53) were obtained in the same manner as the pigment dispersion (DP-1) except that the composition was changed to the composition shown in Table 2.
In addition, about the pigment dispersion (DP-2 to 41), the dispersing agent (X-2 to 41) was used, respectively.
Further, for the pigment dispersion (DP-52, 53), two kinds of finer pigments (PG-1) (PG36) and finer pigments (PY-1) (PY138) are used, and (PG-1) / (PY-1) = 7/3.

<Method for producing dye solution>
(Dye solution (DA-1))
The following mixture was stirred and mixed to be uniform and then filtered through a 5.0 μm filter to prepare a dye solution (DA-1).

Dye 1: 16.0 parts PGMAc: 84.0 parts

  Dye solutions (DA-2 to 13) were obtained in the same manner as the dye solution (DA-1) except that the dye was changed to the composition shown in Table 7.

<Green resist material manufacturing method> +
(Alkali developable green resist material (E1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a green pigment dispersion (DPE-1) was obtained.
The pigment dispersion was adjusted to have a solid content of 20% by weight with PGMAc.

Hereinafter, solid content weight is shown.
Refined pigment (PG-2): 6.0 parts Pigment Green 58
EFKA4300 (manufactured by BASF): 4.0 parts

Next, the following raw materials are mixed and stirred so that the solid content becomes the following blending amount (part by weight), PGMac is added to adjust the nonvolatile content to 16% by weight, and the mixture is filtered through a 1.0 μm filter. An alkali development type green resist material (E1) was obtained.

Green pigment dispersion (DPE-1): 66.7 parts Acrylic resin 1: 13.3 parts Aronix M402 (manufactured by Toa Gosei): 10.0 parts Irgacure 907 (manufactured by BASF): 10.0 parts

[Example 1]
(Alkali development type blue resist material (RB-1))
Using the pigment dispersion (DP-1) and the dye solution (DA-1), the following raw materials are mixed and stirred so that the solid content becomes the following blending amount, and PGMac is added to add a non-volatile content of 16 weight. % And filtered through a 1.0 μm filter to obtain an alkali development type blue resist material (RB-1).

Hereinafter, solid content weight is shown.
Pigment dispersion (DP-1): 33.3 parts Dye 1: 5.0 parts Acrylic resin 1: 11.7 parts Epoxy compound: 10.0 parts (Neopentyl glycol diglycidyl ether (2 functional groups)),
"EX-211" manufactured by Nagase ChemteX Corporation)
Photopolymerizable monomer: 30.0 parts (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator: 10.0 parts ("Irgacure 907" manufactured by BASF)

[Examples 2 to 60, Comparative Examples 1 to 12]
(Alkali development type blue resist material (RB-2 to 72))
Mix so as to have the composition and blending amount (solid part by weight) shown in Tables 8 and 9 and adjust the non-volatile content to 16% by weight using PGMAc, similarly to the alkali developing type blue resist material (RB-1). (Alkaline development type blue resist material (RB-2 to 72)) was obtained.

[Example 61]
(Alkali development type red resist material (RR-1))
Using the pigment dispersion (DP-45) and the dye solution (DA-13), the following raw materials are mixed and stirred so that the solid content becomes the following blending amount, and PGMAc is added, and the non-volatile content is 16 wt. % And filtered through a 1.0 μm filter to obtain an alkali developing type red resist material (RR-1).

Hereinafter, solid content weight is shown.
Pigment dispersion (DP-45): 53.3 parts Dye 13: 8.0 parts Acrylic resin 1: 3.7 parts Epoxy compound: 10.0 parts (of 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct (functional group number 15),
“EHPE3150” manufactured by Daicel Chemical Industries, Ltd.)
Photopolymerizable monomer: 15.0 parts (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator: 10.0 parts ("Irgacure 907" manufactured by BASF)

[Examples 62 to 66, Comparative Examples 13 to 16]
(Alkali development type blue resist material (RR-2 to 10))
Mix so as to have the composition and blending amount (solid part by weight) described in Tables 6 and 7 and adjust the non-volatile content to 16% by weight using PGMAc, similarly to the alkali developing type red resist material (RR-1). Thus, (alkaline development type red resist material (RR-2 to 10)) was obtained.

[Example 67]
(Alkali development type green resist material (RG-1))
Using the pigment dispersion (DP-52), the following raw materials are mixed and stirred so that the solid content becomes the following blending amount, and PGMac is added to adjust the non-volatile content to 16% by weight. Filtration through a filter gave an alkali development type green resist material (RG-1).

Hereinafter, solid content weight is shown.
Pigment dispersion (DP-52): 66.7 parts Acrylic resin 1: 3.3 parts Epoxy compound: 10.0 parts (1,2-epoxy-4 of 2,2-bis (hydroxymethyl) -1-butanol -(2-oxiranyl) cyclohexane adduct (functional group number 15),
“EHPE3150” manufactured by Daicel Chemical Industries, Ltd.)
Photopolymerizable monomer: 10.0 parts (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator: 10.0 parts ("Irgacure 907" manufactured by BASF)

[Comparative Example 17]
(Alkali development type green resist material (RG-2))
Mixed so as to have the composition and blending amount (solid weight part) described in Table 8, adjusted to 16% by weight of non-volatile content using PGMAc, and similar to the alkali developing type green resist material (RG-1), (Alkali development type green resist material (RG-2)) was obtained.

Abbreviations in Tables 8 to 11 are described below.
Epoxy content * 1 (in the composition)
Content (% by weight) of epoxy compound in solid content of coloring composition for color filter
* 2 (for dispersant (X))
Content of epoxy compound with respect to 100 parts by weight of dispersant (X) (parts by weight)

<Epoxy compound>
EX-211: Neopentyl glycol diglycidyl ether (functional group number 2)
"EX-211" manufactured by Nagase ChemteX Corporation
EX-314: Glycerol polyglycidyl ether (functional group number 3)
“EX-314” manufactured by Nagase ChemteX Corporation
-EOCN-1020:

Nippon Kayaku "EOCN-1020" (functional group number 5-8)
EHPE3150:


R is undisclosed and n is about 15.
“EHPE3150” manufactured by Daicel Chemical Industries, Ltd. (number of functional groups: about 15)
<Photopolymerizable unsaturated monomer>
M402: “Aronix M402” manufactured by Toa Gosei Co., Ltd.
<Photopolymerization initiator>
IRG907: “Irgacure 907” manufactured by BASF

<Evaluation of coloring composition for color filter>
The viscosity stability, NMP resistance, and coating film heat resistance of the colored compositions obtained in Examples and Comparative Examples were evaluated by the following methods. Tables 12 to 15 show the evaluation results.
In addition, the film thickness of the coating film was measured using Dektak 3030 (made by Nippon Vacuum Technology Co., Ltd.).
Also, ◎ is a practically good level, ◯ is a practical level, and x is a level not suitable for practical use.

(Evaluation of viscosity)
The viscosity of the pigment composition was adjusted to the initial viscosity η ₁ and kept at a constant temperature of 40 ° C. for one week, and the viscosity after aging was set to η ₂ , and the E-type viscometer “ELD viscometer” ( Using Toki Sangyo Co., Ltd.) under the conditions of 25 ° C. and rotation speed 20 rpm. A lower initial viscosity means higher dispersion stability. Regarding the viscosity stability, the difference between the initial viscosity and the viscosity with time was within ± 10%, and the difference between ± 10% and over was ± 10%.

(Developability evaluation)
A substrate obtained by applying the obtained photosensitive coloring composition onto a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater at a rotation speed at which the film thickness after drying becomes 2 μm was obtained at 70 ° C. for 20 After partial drying, spray development was performed using an aqueous sodium carbonate solution at 23 ° C., and developability was evaluated in four stages. The alkali developer was 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao Corporation), and 90% by weight of water. The thing which consists of was used.
The developability evaluation was determined according to the following criteria.

◎: Can be completely removed within 15 seconds ○: Over 15 seconds but can be completely removed within 20 seconds △: Over 20 seconds but completely removed within 30 seconds ×: Over 30 seconds Can not be completely removed

(Evaluation of NMP resistance)
After applying the resist material obtained so that the dry coating film becomes about 2.5 μm on the transparent substrate, and exposing to ultraviolet rays through the mask having the above-mentioned stripe pattern, the alkali developer is sprayed by spraying. The uncured part was removed to form a stripe pattern. Thereafter, it was baked in an oven at 230 ° C. for 20 minutes. Here, after measuring the chromaticity (L * (1), a * (1), b * (1)) with C light source, it was immersed in NMP (N-methylpyrrolidone) for 30 minutes, and further with C light source. Was measured (L * (2), a * (2), b * (2)).
Using the color difference values before and after NMP immersion, the color difference ΔE * ab was calculated according to the following formula, and the heat resistance of the coating film was evaluated in the following three stages.

ΔE * ab = [[L * (2) −L * (1)] ² + [a * (2) −a * (1)] ² + [b * (2) −b * (1)] ² ] ^1/2

ΔE * ab is 3 or more: ×
ΔE * ab is greater than 1 and less than 3:
ΔE * ab is 1 or less: ◎

(Evaluation of heat resistance of coating film)
After applying the resist material obtained so that the dry coating film becomes about 2.5 μm on the transparent substrate, and exposing to ultraviolet rays through the mask having the above-mentioned stripe pattern, the alkali developer is sprayed by spraying. The uncured part was removed to form a stripe pattern. Thereafter, it was baked in an oven at 230 ° C. for 20 minutes. Thereafter, an ITO (indium tin oxide) film was formed by sputtering so as to have an average film thickness of 1500 angstroms. Using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.), the chromaticity 1 (L * (1), a * (1), b * (1)) of the obtained coating film with a C light source Measured. Further, as a heat resistance test, the sample was heated in an oven at 230 ° C. for 3 hours, and chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source was measured.
Using the measured color difference value, the color difference ΔE * ab was calculated according to the following formula, and the heat resistance of the coating film was evaluated.

ΔE * ab = [[L * (2) −L * (1)] ² + [a * (2) −a * (1)] ² + [b * (2) −b * (1)] ² ] ^1/2

ΔE * ab is 3 or more: ×
ΔE * ab is greater than 1 and less than 3:
ΔE * ab is 1 or less: ◎
As judged.

  From the results of Tables 12 to 15, the colored composition containing the dispersant (X) and the epoxy compound, which is the invention of the present application, has excellent dispersibility and stability over time even when a finer pigment or dye is used as the colorant. It was confirmed that the color filter coloring composition had chemical resistance and heat resistance, and also had excellent developability for an aqueous alkali solution.

<Manufacture of color filters>
A red resist material (RR-1) was coated on a 100 mm × 100 mm glass substrate with a die coater to a thickness of about 2.5 μm, and the solvent was removed and dried in an oven at 70 ° C. for 20 minutes. Subsequently, stripe pattern exposure was performed with ultraviolet rays using an exposure apparatus. The exposure amount was 100 mJ / cm ² . Further, spray development is performed with a developer composed of an aqueous sodium carbonate solution to remove unexposed portions, and then the substrate is washed with ion-exchanged water. The substrate is heated at 230 ° C. for 20 minutes to form a red filter segment having a line width of about 50 μm. did. Next, in the same manner, a green filter segment is formed using the resist material E1 next to the red filter segment, and then a blue filter segment is formed using the blue resist material (RB-3). Three colors are formed on the same glass substrate. A color filter having the following filter segments was obtained.

  When the color filter resist material of the present invention was used, a color filter having good solvent resistance in a wide chromaticity range, high brightness, and high contrast ratio could be obtained.

Claims (8)

A color filter coloring composition containing a colorant, a dispersant, a binder resin, a thermosetting compound, and a solvent,
Dispersing agent
An acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2) is reacted with a hydroxyl group in the hydroxyl group-containing compound (a). Polyester part X1 ′ having a carboxyl group;
A vinyl polymer portion X2 ′ formed by radical polymerization of an ethylenically unsaturated monomer (c) and having any one selected from the group consisting of structural units represented by the following general formulas (1) to (4): Containing a dispersant (X) having,
A coloring composition for a color filter, wherein the thermosetting compound contains an epoxy compound.
General formula (1)

[In general formula (1), n1 represents an integer of 1 to 4, R ₁ represents hydrogen or a methyl group, X represents a direct bond, or —CR ₆ R ₇ —Z—, and Z represents a direct bond or -CR ₈ R ₉ - is represented by,
R _{2 to} R ₉ are a hydrogen atom, a halogen atom, a phthalimide group, —CH ₂ CH ₂ COOH, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and —CH ₂ — contained in these groups may be substituted with —O—, —CO— or —OCO—,
R ₂ and R ₄ may be directly bonded to form an unsaturated double bond, R ₂ and R ₃ and / or R ₄ and R ₅ may be combined to form ═CH ₂ , R ₂ and R ₆ and R ₄ and R ₈ may be combined with the carbon atom to which they are bonded to form a ring having 6 to 10 carbon atoms, and “*” indicates a bond. ]
General formula (2)

[In General Formula (2), n2 represents an integer of 1 to 4, W ₁ represents —CR ₁₁ or a nitrogen atom, W ₂ represents —CR ₁₄ or a nitrogen atom, Y represents —COOH, —SO ₃ H, R ₁₀ represents hydrogen or a methyl group, and R _{11 to} R ₁₄ represent a hydrogen atom, a halogen atom, a nitro group, an ethynyl group, —SO ₃ H, —COOH, —COCl, —NHCOCH ₃ , substituted or unsubstituted carbon. Represents an alkyl group of 1 to 20, R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₁₃ and R ₁₄ together with the carbon atom to which they are bonded form a ring of 6 to 10 carbon atoms. “*” Indicates a bond. ]
General formula (3)

[In General Formula (3), n3 represents an integer of 1 to 3, R ₁₅ represents hydrogen or a methyl group, and R _{16 to} R ₂₅ represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. R ₁₇ and R ₁₉ and / or R ₂₃ and R ₂₅ may be directly bonded to form an unsaturated double bond, and R ₁₇ and R ₂₃ may be combined with the carbon atom to which they are bonded. May form a ring, and “*” indicates a bond. ]
General formula (4)

[In General Formula (4), n4 is an integer of 1 to 3, R ₂₆ represents hydrogen or a methyl group, R ₃₁ represents a hydrogen atom or a methyl group, R _{27 to} R ₃₀ represent a hydrogen atom, a halogen atom, A nitro group, —COOH, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and “*” represents a bond. ]   The coloring composition for a color filter according to claim 1, wherein the colorant contains a dye.   The coloring composition for a color filter according to claim 1 or 2, wherein the number of functional groups of the epoxy compound is 3 or more.   The coloring composition for a color filter according to any one of claims 1 to 3, wherein the acid value of the dispersant (X) is 6 to 100 mgKOH / g.   The coloring composition for a color filter according to any one of claims 1 to 4, wherein methyl (meth) acrylate is 40 to 80% by weight in 100% by weight of the ethylenically unsaturated monomer (c). . The dispersant (X) has a structural unit in which R _{2 to} R ₅ in the general formula (1) are hydrogen atoms, or a structural unit in which R _{11 to} R _{14 in} the general formula (2) are hydrogen atoms. The coloring composition for color filters according to any one of claims 1 to 5.   Furthermore, a photoinitiator is contained, The coloring composition for color filters of any one of Claims 1-6 characterized by the above-mentioned.   A color filter comprising a filter segment formed from the coloring composition for a color filter according to claim 1 on a substrate.