Photosensitive coloring composition, color filter, and image display device

Abstract

To provide a photosensitive coloring composition which has good storage stability as a coloring composition and a photosensitive coloring composition, and enables dissolution of a display failure of a liquid crystal display device caused by zinc phthalocyanine, and a color filter and a liquid crystal display device formed using the photosensitive coloring composition.SOLUTION: A coloring composition is provided, including a zinc phthalocyanine pigment (A), an aluminum phthalocyanine pigment (B), a copper phthalocyanine pigment (C), a dispersion agent, a polymerizable compound, a photopolymerization initiator, and a binder resin.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a photosensitive coloring composition that can be used to form a color filter for use in a liquid crystal display device, an organic EL display device, a solid-state imaging device, or the like. [Background technology]

[0002] There are three operating modes for LCD devices: Twisted Nematic (TN), In Plane Switching (IPS), and Vertical Alignment (VA). Among these, the IPS mode is characterized by a wide viewing angle. Unlike other modes, the IPS mode does not have a common electrode formed on the second transparent substrate on which the color filters are formed. For this reason, IPS LCD devices are directly affected by the electrical characteristics of the color filter pixels, which can cause display defects.

[0003] Patent Documents 1 and 2 disclose photosensitive coloring compositions containing a zinc phthalocyanine pigment, a copper phthalocyanine pigment, and a specific dispersant. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2018-10210 A [Patent Document 2] JP 2018-45189 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, the zinc phthalocyanine pigment used in the conventional photosensitive coloring composition has good green coloring, but is an ionic substance and therefore photoconductive. Therefore, when a liquid crystal display device is used, if a horizontal electric field that drives liquid crystal molecules penetrates a color filter, photoelectric charges generated in the zinc phthalocyanine accumulate in the color layer and disturb the horizontal electric field, which has not been able to solve the problem of poor display.

[0006] An object of the present invention is to provide a photosensitive coloring composition which can produce a color filter which is less likely to cause display defects while using a zinc phthalocyanine pigment. [Means for solving the problem]

[0007] The photosensitive coloring composition of the present invention contains a zinc phthalocyanine pigment (A), an aluminum phthalocyanine pigment (B), a copper phthalocyanine pigment (C), a dispersant, a polymerizable compound, a photopolymerization initiator, and a binder resin. Effect of the Invention

[0008] According to the present invention described above, it is possible to provide a photosensitive coloring composition that uses zinc phthalocyanine and is capable of producing a color filter that is less likely to cause display defects, a color filter, and an image display device. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic cross-sectional view of a liquid crystal display device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The terms used in this specification are defined below. When "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" is written, it means "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively, unless otherwise specified. "CI" in this specification means Color Index (CI). Colorants include pigments and dyes. Polymerizable unsaturated groups are ethylenically unsaturated groups, such as vinyl groups and (meth)acryloyl groups. Monomers are compounds containing polymerizable unsaturated groups.

[0011] The photosensitive coloring composition of the present invention contains a zinc phthalocyanine pigment (A), an aluminum phthalocyanine pigment (B), a copper phthalocyanine pigment (C), a dispersant, a polymerizable compound, a photopolymerization initiator, and a binder resin. The photosensitive coloring composition is preferably used by applying it to a substrate to form a coating. The coating is preferably used as a green filter segment that constitutes a color filter by forming a pattern using a photolithography method.

[0012] The photosensitive coloring composition of the present invention is an ionic substance, and when the aluminum phthalocyanine pigment (B) and the copper phthalocyanine pigment (C) are used in combination with the zinc phthalocyanine pigment (A), which has a negative effect on electrical properties, the dielectric properties of the composition are improved, and the state in which the redness increases across the entire display screen can be improved. In addition, by using the copper phthalocyanine pigment (C), it is possible to reproduce colors in a color range that requires high coloring power, such as the Digital Cinema (DCI) standard and the Adobe standard, and coloring can be achieved in a wider color range. As a result, the coating formed from the photosensitive coloring composition can achieve both green coloring and display properties.

[0013] <Zinc phthalocyanine pigment (A)> Zinc phthalocyanine pigment (A) is a phthalocyanine pigment in which the central metal Q in the compound represented by the following general formula (1) is zinc (Zn).

[0014] General formula (1) [ka]

[0015] In the general formula (1), Q represents the central metal Zn, and X1 to X 16 each independently represents an atom of H, Cl, Br, or I.

[0016] The zinc phthalocyanine pigment (A) is preferably a halogenated compound represented by the following general formula (1), which improves the brightness and coloring power.

[0017] <Aluminum phthalocyanine pigment (B)> The aluminum phthalocyanine pigment (B) is a phthalocyanine pigment having an aluminum (Al) atom as the central metal. The aluminum phthalocyanine pigment (B) is preferably, for example, a pigment described in JP-A-2017-111398. When used, the display characteristics and brightness are improved.

[0018] The aluminum phthalocyanine pigment (B) is preferably a halogenated pigment as described in JP 2017-111398 A. This not only further improves the brightness but also improves the coloring power.

[0019] <Copper phthalocyanine pigment (C)> Copper phthalocyanine pigment (C) is a phthalocyanine pigment in which the central metal Q in the compound represented by the following general formula (2) is copper (Cu). The use of this pigment improves coloring strength.

[0020] General formula (2) [ka]

[0021] In the general formula (2), Q represents the central metal Cu, and X1 to X 16each independently represents an atom of H, Cl, Br, or I.)

[0022] The copper phthalocyanine pigment (C) is preferably a halogenated compound represented by the general formula (2), which improves the brightness.

[0023] The zinc phthalocyanine pigment (A), the copper phthalocyanine pigment (C) and the aluminum phthalocyanine pigment (B) can be used either alone or in combination of two or more kinds.

[0024] <Yellow pigment (D)> The photosensitive coloring composition may contain a yellow pigment (D). By containing a yellow pigment, the display properties can be improved, and the coloring power and brightness can also be improved.

[0025] Yellow pigments include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118 , 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, etc. Among these, CI Pigment Yellow 138, 139, 150, 185, 231, 233 are preferable.

[0026] <Other pigments> In this specification, other pigments can be used as colorants in addition to the above pigments. Examples of other pigments include the following organic pigments and inorganic pigments. The following organic pigments can be used as colorants for blue filter segments, red filter segments, etc., in addition to adjusting the color of the green filter segment. Specific examples of organic pigments are shown below with their color index numbers.

[0027] Red pigments include, for example, CI 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, 179 , 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, No. 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844. Among these, from the viewpoints of heat resistance, light fastness, and transmittance of the filter segment, preferred are CI Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6,368,844, and more preferred are CI Pigment Red 177, 254, 291, 295, 296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6,368,844.

[0028] The red pigment may be used in combination with an orange pigment such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73, or a red pigment, green pigment, blue pigment, or yellow pigment. A yellow pigment may be used in combination.

[0029] Examples of blue pigments include CI Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, 16, and 81. Red pigments, orange pigments, green pigments, purple pigments, and yellow pigments can be used in combination.

[0030] Examples of purple pigments and red pigments include CI Pigment Violet 1, 19, and 23. The purple pigment can be used in combination with a red pigment, an orange pigment, a green pigment, a blue pigment, and a yellow pigment.

[0031] <Mixing pigments> In the present invention, the organic pigment is preferably mixed with other raw materials after being subjected to a micronization treatment. Examples of the method of the micronization treatment include wet grinding, dry grinding, and dissolution precipitation. Among these, salt milling treatment using a kneader method, which is a type of wet grinding, is preferable. The average primary particle size of the organic pigment after the micronization treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. A moderate particle size improves dispersibility and the contrast ratio of the coating. The average primary particle size is the average value of about 20 particles arbitrarily selected from an enlarged image of a TEM (transmission electron microscope). When the particle has a vertical axis length and a horizontal axis length, the vertical axis length is used.

[0032] The salt milling process is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded under heating using a batch or continuous kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or a planetary mixer, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed during salt milling by utilizing the high hardness of the inorganic salt. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

[0033] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. Among these, sodium chloride (table salt) is preferred from the viewpoint of cost. The amount of the water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, and more preferably 300 to 1000 parts by mass, per 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

[0034] The water-soluble organic solvent moistens the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound that dissolves (is mixed) in water and does not substantially dissolve the water-soluble inorganic salt. The water-soluble organic solvent is preferably a high-boiling solvent having a boiling point of 120°C or more, in that it is less likely to volatilize due to the temperature rise during salt milling. Examples of the water-soluble organic solvent include 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, and liquid polypropylene glycol. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, relative to 100 parts by mass of the pigment.

[0035] During the salt milling treatment, a resin can be added as necessary. Examples of the resin include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in a water-soluble organic solvent. The amount of the resin used is preferably 5 to 200 parts by mass relative to 100 parts by mass of the pigment.

[0036] Examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black.

[0037] <dye> Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Also included are dye derivatives and lake pigments obtained by converting dyes into lakes.

[0038] The dye is preferably used as a salt-forming compound. Examples of the salt-forming compound include a salt-forming compound of an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound; a salt-forming compound of a resin component having an amino group and an acid dye; a salt-forming compound of an acid dye and a compound having an onium base; a salt-forming compound of a basic dye and an organic acid, perchloric acid, or a metal salt thereof. Among these, the salt-forming compound of a basic dye is preferred because it has excellent resistance to various types of substances and compatibility with pigments. The compound having an onium base is preferably a resin having a cationic group in the side chain.

[0039] The chemical structure of the dye may be, for example, an azo dye, a disazo dye, an azomethine dye (such as an indoaniline dye or an indophenol dye), a dipyrromethene dye, a quinone dye (such as a benzoquinone dye, a naphthoquinone dye, anthraquinone dye, or anthrapyridone dye), a carbonium dye (such as a diphenylmethane dye, a triphenylmethane dye, a xanthene dye, or an acridine dye), a quinoneimine dye (such as an oxazine dye), or a quinoneimine dye (such as an oxazine dye). dyes, thiazine dyes, etc.), azine dyes, polymethine 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, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, etc. Among these, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred. Specific structures of dyes are described in "New Edition Dye Handbook" (edited by Organic Synthesis Chemistry Association; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), "Dye Handbook" (edited by Okawara et al.; Kodansha, 1986), and the like.

[0040] <Dye derivatives> In this specification, a dye derivative can be used as necessary. The dye derivative is adsorbed to the surface of the organic pigment, which gives the surface of the organic pigment polarity and makes it easier to have affinity with the dispersant, thereby further improving the dispersibility of the organic pigment. The dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in the organic dye residue. Examples of the dye derivative include compounds having acidic substituents such as a sulfo group, a carboxy group, or a phosphate group, as well as amine salts thereof, sulfonamide groups, or compounds having basic substituents such as a tertiary amino group at the terminal, and compounds having neutral substituents such as a phenyl group or a phthalimidoalkyl group. Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0041] The dye derivatives can be used alone or in combination of two or more kinds.

[0042] The content of the dye derivative is preferably from 1 to 100 parts by mass, more preferably from 3 to 70 parts by mass, and even more preferably from 5 to 50 parts by mass, relative to 100 parts by mass of the organic pigment.

[0043] By adding a dye derivative to a pigment and carrying out a micronization treatment such as acid pasting, acid slurry, dry milling, salt milling, or solvent salt milling, the dye derivative is adsorbed onto the pigment surface, and the primary particles of the pigment can be made finer than when the dye derivative is not added.

[0044] The micronization treatment may be, for example, wet dispersion using a two-roll mill, a three-roll mill, beads, or the like.

[0045] <Dispersant> The dispersant may be a low molecular weight dispersant or a resin type dispersant, with the resin type dispersant being preferred. The resin type dispersant has a colorant affinity site that adsorbs to the organic pigment and a relaxation site that has high affinity with components other than the colorant and causes steric repulsion between dispersed particles. Resin-type dispersants, in terms of resin type, include, for example, urethane-based dispersants such as polyurethane, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylates, and modified products thereof, oil-based dispersants such as amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphates.

[0046] In terms of the type of functional group, examples of the resin-type dispersant include an acidic functional group-containing resin-type dispersant and a basic functional group-containing resin-type dispersant. The acidic functional group-containing resin-type dispersant is preferably, for example, a resin-type dispersant having an aromatic carboxylic acid structure, and is described, for example, in WO2008 / 007776, JP2008-029901A, JP2009-155406A, JP2010-185934A, JP2011-157416A, JP2009-251481A, JP2007-23195A, JP1996-143651A, and the like.

[0047] Examples of the basic functional group-containing resin type dispersant include nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups in the side chains including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. Note that an acidic functional group-containing resin type dispersant and a basic functional group-containing resin type dispersant can also be used in combination.

[0048] The dispersants can be used alone or in combination of two or more kinds.

[0049] The content of the dispersant is preferably from 3 to 200 parts by mass, and more preferably from 5 to 100 parts by mass, relative to 100 parts by mass of the organic pigment.

[0050] <Binder resin> The binder resin is preferably a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm when a coating having a thickness of 2 μm is formed. The transmittance is preferably 95% or more. The binder resin is preferably a thermoplastic resin or a photosensitive resin. The binder resin is preferably alkali-soluble. This allows the coating formed from the photosensitive coloring composition to be patterned by a photolithography method. The photosensitive resin not having alkali solubility and the alkali-soluble resin can have a thermosetting group. Examples of the thermosetting group include an epoxy group and an oxetanyl group.

[0051] The binder resins can be used alone or in combination of two or more kinds.

[0052] The content of the binder resin is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, per 100 parts by mass of the organic pigment. When an appropriate amount is contained, a coating can be easily formed and good color characteristics can be easily obtained.

[0053] Examples of the alkali-soluble resin include resins having an acidic group such as a carboxyl group or a sulfonic group. Examples of the alkali-soluble thermoplastic resin include acrylic resins having an acidic group, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers. Among these, acrylic resins having an acidic group and styrene / styrene sulfonic acid copolymers are preferred in terms of improving developability, heat resistance, and transparency.

[0054] <Thermoplastic resin> Thermoplastic resins are resins that are not alkali-soluble. Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylenes (HDPE, LDPE), polybutadiene, and polyimide resins.

[0055] <Alkali-soluble photosensitive resin> The alkali-soluble photosensitive resin has photosensitivity because it has a polymerizable unsaturated group. Any known resin can be used as the alkali-soluble photosensitive resin as long as it is alkali-soluble and photosensitive, but resins synthesized by the following method (i) or (ii) are preferred. When an alkali-soluble photosensitive resin is used, it is three-dimensionally crosslinked by light irradiation, increasing the crosslink density, improving the chemical resistance of the coating.

[0056] [Method (i)] Method (i) is, for example, a method in which a polymer of an epoxy group-containing monomer and other monomers is first synthesized. Next, a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain an alkali-soluble photosensitive resin. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

[0057] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0058] Examples of the monocarboxyl group-containing monomer include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position.

[0059] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. The polybasic acid anhydride may have a carboxyl group that does not form an acid anhydride.

[0060] Examples of other monomers include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate; Further examples include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

[0061] Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide N-substituted maleimides such as N-phenylenediamine benzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide and 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0062] In the method (ii), for example, a hydroxyl group-containing monomer, a monocarboxyl group-containing monomer, and other monomers are polymerized to prepare a polymer, and then the hydroxyl group of the polymer is reacted with an isocyanate group of an isocyanate group-containing monomer to synthesize an alkali-soluble photosensitive resin.

[0063] Examples of the hydroxyl group-containing monomer include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, and glycerol mono(meth)acrylate is more preferred.

[0064] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0065] The other monomers include, in addition to the other monomers exemplified in the above method (i), a phosphate group-containing monomer and the like.

[0066] The phosphate group-containing monomer is, for example, a compound obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0067] The above-mentioned raw materials for the binder resin can be used alone or in combination of two or more kinds. The binder resin can be used alone or in combination of two or more kinds.

[0068] The content of the binder resin is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, relative to 100 parts by mass of the colorant. In order to obtain good film-forming properties and various resistances, the content is preferably 20 parts by mass or more, and in order to obtain a high colorant concentration and to obtain good color characteristics, the content is preferably 400 parts by mass or less.

[0069] The weight average molecular weight (Mw) of the binder resin is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and even more preferably from 4,000 to 20,000. The value of Mw / Mn is preferably not more than 10. Here, Mn is the number average molecular weight.

[0070] The acid value of the alkali-soluble resin is preferably 50 to 200 mgKOH / g, more preferably 70 to 180 mgKOH / g, and even more preferably 90 to 170 mgKOH / g. A suitable acid value allows a high level of balance to be achieved among alkali solubility, adhesion, and residue suppression.

[0071] <Polymerizable compound> Examples of the polymerizable compound include an acid group-containing monomer, a urethane bond-containing monomer, and other monomers.

[0072] Examples of the acid group of the acid group-containing monomer include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

[0073] Examples of the acid group-containing monomer include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates; and the like. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates, such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, with dicarboxylic acids, such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and free carboxyl group-containing oligoesters of tricarboxylic acids, such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid, with monohydroxy monoacrylates or monohydroxy monomethacrylates, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0074] (Urethane bond-containing monomer) Examples of the urethane bond-containing monomer include polyfunctional urethane acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting the alcohol with a (meth)acrylate having a hydroxyl group.

[0075] Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol propylene oxide modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0076] Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

[0077] Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 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, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, trimethylolpropane EO modified tri(meth)acrylate, isocyanuric acid EO modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, Examples of the acrylic acid esters and methacrylic acid esters include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid ester of methylolated melamine, epoxy (meth)acrylate, and urethane acrylate, as well as (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

[0078] The polymerizable compounds can be used alone or in combination of two or more kinds.

[0079] The blending amount of the polymerizable compound is preferably 1 to 50 mass %, more preferably 2 to 40 mass %, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is blended, the curability and developability are further improved.

[0080] <Photopolymerization initiator> The photopolymerization initiator may be, for example, 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)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylamino)phenyl]-2-methyl-1-butanone. acetophenone compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzil dimethyl ketal; benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t-butanone) benzophenone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, triazine-based compounds such as 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Examples of suitable oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. Among these, oxime ester compounds are preferred.

[0081] (Oxime ester compounds) In oxime ester compounds, the NO bond of the oxime is cleaved by absorbing ultraviolet light, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, allowing patterns to be formed with a small amount of exposure. When the colorant concentration of a photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may decrease, resulting in a low degree of curing of the coating film. However, oxime ester compounds are preferably used because they have high quantum efficiency.

[0082] Examples of the oxime ester compound include oxime ester photopolymerization initiators described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, and the like.

[0083] The photopolymerization initiators can be used alone or in combination of two or more kinds.

[0084] The content of the photopolymerization initiator is preferably 2 to 50 parts by mass, and more preferably 2 to 30 parts by mass, based on 100 parts by mass of the colorant. When an appropriate amount is added, the photocurability and developability are further improved.

[0085] <Sensitizer> Examples of the sensitizer include polymethine dyes such as chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil 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, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. , phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc. Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred. 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, and the like are more preferred.

[0086] The sensitizers can be used alone or in combination of two or more kinds.

[0087] The content of the sensitizer is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator. When an appropriate amount is contained, the curability and developability are further improved.

[0088] <Thiol-based chain transfer agents> The photosensitive coloring composition can contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. When the thiol-based chain transfer agent is used in combination with a photopolymerization initiator, a thiyl radical that is not easily inhibited by oxygen during radical polymerization after irradiation with light is generated, and the sensitivity of the photosensitive coloring composition is improved.

[0089] The thiol chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol chain transfer agent has four or more SH groups. As the number of functional groups increases, the coating becomes easier to photocure from the surface to the deepest part.

[0090] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, and ethylene glycol bisthiopropionate. Examples of the thiopropionate include erythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and the like. Preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0091] The thiol chain transfer agents can be used alone or in combination of two or more kinds.

[0092] The content of the thiol chain transfer agent is preferably 0.1 to 10 mass%, more preferably 0.1 to 3 mass%, based on 100 mass% of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the photosensitivity and taper shape are improved, and wrinkles are less likely to occur on the coating surface.

[0093] <Polymerization inhibitor> The photosensitive coloring composition may contain a polymerization inhibitor, which can suppress photosensitivity due to diffracted light from a mask during exposure in a photolithography method, making it easier to obtain a pattern of a desired shape.

[0094] Examples of the polymerization inhibitor include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, and 2-n-butyl catechol. Examples of the alkyl resorcinol include alkyl resorcinol compounds such as ethylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucinone.

[0095] The content of the polymerization inhibitor is preferably 0.01 to 0.4% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. Within this range, the effect of the polymerization inhibitor is increased, and the linearity of the taper, wrinkles in the coating, pattern resolution, etc. are improved.

[0096] <Ultraviolet absorbing agent> The photosensitive coloring composition may contain an ultraviolet absorbing agent. Examples of the ultraviolet absorbing agent include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds. The ultraviolet absorbing agent may be an oligomer or a polymer.

[0097] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α, α-Dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, a mixture of 5 parts of 2-methoxy-1-methylethyl acetate and 95 parts of benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300 reaction products, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t- Butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0098] Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of the compound include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0099] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3H2O, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0100] Examples of the salicylate ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0101] The content of the ultraviolet absorber is preferably 5 to 70% by mass relative to 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When an appropriate amount is contained, the resolution after development is further improved.

[0102] The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the adhesion between the substrate and the coating is further improved, and good resolution can be obtained.

[0103] <Thermosetting compound (E)> The photosensitive coloring composition can contain a thermosetting compound (E). During the post-baking process when a color filter is produced using the photosensitive coloring composition, the thermosetting compound (E) is thermally cured to increase the crosslinking density of the coating, thereby improving heat resistance. This suppresses pigment aggregation during the post-baking process, improving the contrast ratio.

[0104] The thermosetting compound (E) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (E) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0105] The content of the thermosetting compound (E) is preferably 1 to 10 parts by mass relative to 100 parts by mass of the binder resin. When an appropriate amount is contained, the crosslink density of the coating is increased, and the heat resistance is further improved.

[0106] (hardening agent) The photosensitive coloring composition may contain a curing agent (curing accelerator). The curing agent assists the curing of the thermosetting compound (E). Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Examples of the curing agent include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.).

[0107] The curing agents can be used alone or in combination of two or more kinds.

[0108] The amount of the curing agent used is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the thermosetting compound (E).

[0109] <Antioxidants> The photosensitive coloring composition can contain an antioxidant. The antioxidant can prevent the coating film formed from the photosensitive coloring composition from yellowing due to oxidation during the thermal process of heat curing or ITO annealing, and suppress the decrease in the transmittance of the coating film. In particular, when the colorant concentration of the photosensitive coloring composition is high, the content of the polymerizable compound is relatively reduced, so that the coating film is likely to yellow when the amount of the photopolymerization initiator is increased or a thermosetting compound is added. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and the decrease in the transmittance of the coating film can be suppressed.

[0110] The antioxidant is a compound having a radical scavenging function or a peroxide decomposition function. Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, and hydroxylamine compounds. The antioxidant is preferably a compound that does not contain a halogen atom. Among these, from the viewpoint of achieving both the transmittance and sensitivity of the coating, hindered phenol compounds, hindered amine compounds, phosphorus compounds, and sulfur compounds are preferred.

[0111] The antioxidants can be used alone or in combination of two or more kinds.

[0112] The content of the antioxidant is preferably 0.5 to 5.0% by mass in 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0113] <Leveling agent> The photosensitive coloring composition can contain a leveling agent. This improves the wettability of the transparent substrate during film formation and the drying property of the film. Examples of the leveling agent include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

[0114] The surfactants can be used alone or in combination of two or more.

[0115] The content of the surfactant is preferably 0.001 to 2.0 parts by mass, more preferably 0.005 to 1.0 parts by mass, based on the non-volatile content of the photosensitive coloring composition. By being within this range, the balance between the coatability, pattern adhesion, and transmittance of the photosensitive coloring composition is further improved.

[0116] <Storage stabilizer> The photosensitive coloring composition can contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites.

[0117] The content of the storage stabilizer is preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the colorant.

[0118] <Adhesion improver> The photosensitive coloring composition can contain an adhesion improver. This improves the adhesion between the coating and the substrate. In addition, it becomes easier to form a narrow pattern by photolithography. Examples of the adhesion improver include a silane coupling agent.

[0119] Examples of the silane coupling agent include vinyl silanes such as vinyl trimethoxy silane and vinyl triethoxy silane, (meth)acrylic silanes such as 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, 3-methacryloxypropyl triethoxy silane and 3-acryloxypropyl trimethoxy silane, epoxy silanes such as 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl methyl diethoxy silane and 3-glycidoxypropyl triethoxy silane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxy silane, N-2-( aminosilanes such as N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane.

[0120] The content of the adhesion improver is preferably from 0.01 to 10 parts by mass, and more preferably from 0.05 to 5 parts by mass, based on 100 parts by mass of the organic pigment.

[0121] <Method for producing photosensitive coloring composition> The photosensitive coloring composition is prepared by dispersing an organic pigment, a dispersant, a solvent, and the like to prepare a pigment dispersion. When a dispersing aid such as a dye derivative is used in the dispersion process, the organic pigment can be dispersed more finely. Also, when the organic pigment has high solubility in the solvent, the dispersion process may not be necessary. When two or more types of pigments are used in combination, a pigment dispersion can be prepared for each type of pigment and then mixed. Also, a pigment dispersion can be prepared by using multiple pigments at once. Next, the polymerizable compound, the photopolymerization initiator, and the binder resin are blended and mixed with the pigment dispersion to obtain a photosensitive coloring composition. It goes without saying that the timing of blending each material is arbitrary.

[0122] The dispersion treatment can be carried out using a dispersion device such as a kneader, 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.

[0123] <Solvent> The photosensitive coloring composition can contain a solvent. This makes it easier to adjust the viscosity of the photosensitive coloring composition, making it easier to form a coating with a smooth surface. The solvent may be appropriately selected according to the purpose of use, and may be contained in an appropriate amount.

[0124] Examples of the solvent include ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- or -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0125] Among these, in terms of coatability and drying property, solvents having a boiling point of 120° C. or more and 180° C. or less at 1 atm are preferred. For example, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are more preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are even more preferred.

[0126] The solvents can be used alone or in combination of two or more.

[0127] <Removal of large particles> The photosensitive coloring composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or membrane filter, etc. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

[0128] <Color filters> In this specification, the color filter comprises a base material (also referred to as a substrate) and a filter segment formed from a photosensitive coloring composition. The color filter preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of colorant (A) used. The color filter may further have a magenta filter segment, a cyan filter segment, and a yellow filter segment as the color filter segments. Examples of the substrate include a transparent substrate and a reflective substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[0129] <Manufacturing method for color filters> It is preferable to form a color filter by first forming a black matrix on a substrate and then forming filter segments. It is also possible to form a thin film transistor (TFT) on the substrate before forming the black matrix. Examples of the black matrix include a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, and a resin film with a light-shielding agent dispersed therein.

[0130] The filter segments can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, etc. In this specification, the most preferred method is the photolithography method.

[0131] In the photolithography method, for example, a photosensitive coloring composition containing a colorant of a certain color tone is applied onto a transparent substrate so that the dry film thickness is about 0.2 to 5 μm to form a coating. The obtained coating (hereinafter referred to as the first coating) is exposed (irradiated with light) through a mask having a predetermined pattern. Then, the coating is developed by immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like, and the uncured parts are removed to obtain a desired pattern. This process can be similarly carried out using a photosensitive coloring composition containing a colorant of another color tone to produce a color filter having filter segments of each color. In addition, a second coating (oxygen barrier film) can be formed on the first coating before exposure using polyvinyl alcohol or a water-soluble acrylic resin. This prevents the first coating from coming into contact with oxygen, thereby further improving the exposure sensitivity. In addition, the color filter can be heated to cure the uncured photopolymerizable compound in the filter segment.

[0132] Examples of the coating device include a spray coater, a spin coater, a slit coater, and a roll coater. A drying step can be carried out during coating. Examples of the drying device include a hot air oven and an infrared heater.

[0133] The developer may be an alkaline developer, for example, an inorganic alkali such as sodium carbonate or sodium hydroxide, or an organic alkali such as dimethylbenzylamine or triethanolamine. A defoaming agent or a surfactant may be added to the developer.

[0134] The color filter is attached to the opposing substrate using a sealant, liquid crystal is injected through the injection port provided in the seal, the injection port is sealed, and a polarizing film or retardation film is attached to the outside of the substrate as necessary to manufacture a liquid crystal display device. This liquid crystal display device is preferably used in a liquid crystal display mode that uses color filters such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertically aligned (VA), and optically convencive bend (OCB).

[0135] The color filter in this specification can be used for applications such as solid-state imaging devices, organic EL displays, quantum dot displays, electronic paper, and head-mounted displays, in addition to liquid crystal displays.

[0136] <Image display device> The image display device of this specification includes a color filter. The image display device preferably further includes a light source. A liquid crystal display device will be described as an example of the image display device. The liquid crystal display device includes a color filter and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED, but in the present invention, it is preferable to use a white LED because it widens the red reproduction range. Fig. 1 is a schematic cross-sectional view of a liquid crystal display device 10 including a color filter of the present invention. The device 10 shown in Fig. 1 includes a pair of transparent substrates 11 and 21 arranged to face each other with a space therebetween, and a liquid crystal LC is sealed between them.

[0137] The liquid crystal LC is aligned according to a driving mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence), etc. A TFT (Thin Film Transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. In addition, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0138] On the other hand, a color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. Red, green and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0139] A transparent protective film (not shown) is formed as necessary to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of the transparent protective film. An alignment layer 24 is provided to cover the transparent electrode layer 23.

[0140] In addition, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Below the polarizing plate 25, a backlight unit 30 is provided.

[0141] The white LED light source may be one in which a fluorescent filter is formed on the surface of a blue LED, or one in which a fluorescent material is contained in the resin package of a blue LED, and has a wavelength (λ3) in the range of 430 nm to 485 nm at which the emission intensity is maximized, a wavelength (λ4) in the range of 530 nm to 580 nm at which the emission intensity is maximized, and a wavelength (λ5) in the range of 600 nm to 650 nm at which the emission intensity is maximized, and the ratio (I4 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less. In particular, a white LED light source (LED1) having spectral characteristics in which the ratio (I5 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less, or a white LED light source (LED2) having a wavelength (λ1) at which the emission intensity is maximum within the range of 430 nm to 485 nm, a peak wavelength (λ2) of the second emission intensity within the range of 530 nm to 580 nm, and a ratio (I2 / I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 is 0.2 or more and 0.7 or less is preferred.

[0142] Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.).

[0143] Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D (manufactured by Nichia Chemical Industries, Ltd.).

[0144] The image display device according to the present specification can be used for applications such as solid-state imaging devices, organic EL display devices, quantum dot display devices, electronic paper, and head-mounted displays, in addition to liquid crystal display devices. EXAMPLES

[0145] The present invention will be described below based on examples, but the present invention is not limited thereto. Note that "parts" means "parts by mass" and "%" means "% by mass". In addition, the blending amounts in the tables are in principle parts by mass.

[0146] Each measurement method is explained below.

[0147] (Average primary particle size of pigment) A solvent (methoxypropyl acetate) is added to the pigment powder, a small amount of a dispersant (Disperbyk-161: manufactured by BYK-Chemie) is added, and the measurement sample is treated with ultrasound for 1 minute. Next, three photographs (three fields of view) in which more than 100 primary particles of the pigment are confirmed are taken using a transmission electron microscope (TEM), and the size of 100 primary particles is measured in order from the top left of each photograph. Specifically, the minor axis diameter and major axis diameter of each primary particle of the pigment are measured in nm units, and the average is taken as the primary particle diameter of the pigment particle. A total of 20 distributions are created in 5 nm increments, and the median value of the 5 nm increments (e.g., 8 nm for 6 nm to 10 nm) is approximated as the particle diameter of the particles, and the number-average particle diameter is calculated based on the particle diameter and the number of each particle.

[0148] (Acid value of resin) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of the resin solution, and the solution was stirred to dissolve uniformly. The solution was titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 mol / L KOH aqueous solution as the titrant, and the acid value (mgKOH / g) of the resin solution was measured. The acid value per unit of non-volatile content of the resin was calculated from the acid value of the resin solution and the concentration of non-volatile content of the resin solution.

[0149] (Weight average molecular weight of resin (Mw)) The weight average molecular weight (Mw) of the resin is the polystyrene-equivalent weight average molecular weight (Mw) measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, using THF as the developing solvent.

[0150] (Resin double bond equivalent) The double bond equivalent was calculated as the mass of the resin per 1 mol of double bonds.

[0151] <Method of manufacturing colorant> [Zinc phthalocyanine colorant (A-1)] 100 parts of zinc phthalocyanine pigment (A), CI Pigment Green 58 (DIC "FASTOGEN GREEN A110"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 6 hours at 80° C. This mixture was added to 2000 parts of warm water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which was filtered and washed repeatedly to remove salt and solvent, and then dried at 80° C. overnight to obtain 96 parts of zinc phthalocyanine colorant (A-1).

[0152] [Aluminum phthalocyanine colorant (B-1)] The same procedure as for the production of the zinc phthalocyanine colorant (A-1) was carried out, except that CI Pigment Green 58 (DIC Corporation's "FASTOGEN GREEN A110") was changed to the aluminum phthalocyanine pigment (B)1 having the following structure, which was produced according to the examples of JP2017-111398A, to obtain 96 parts of an aluminum phthalocyanine colorant (B-1).

[0153] (Aluminum phthalocyanine pigment (B)1) According to the examples of JP 2017-111398 A, an aluminum phthalocyanine pigment (B)1 of the following formula (1) was produced. The structure is shown below. Formula (1)

[0154] [ka]

[0155] [Aluminum phthalocyanine colorant (B-2)] Except for changing CI Pigment Green 58 (DIC Corporation's "FASTOGEN GREEN A110") to aluminum phthalocyanine pigment (B)2 having the following structure produced according to the examples of JP2017-111398A, the same production method as that for zinc phthalocyanine colorant (A-1) was carried out to obtain 96 parts of aluminum phthalocyanine colorant (B-2).

[0156] (Aluminum phthalocyanine pigment (B)2) According to the examples of JP 2017-111398 A, aluminum phthalocyanine pigment (B) 2 of the following formula (2) was produced. The structure is shown below. Formula (2)

[0157] [ka]

[0158] [Aluminum phthalocyanine colorant (B-3)] The same procedure as for the production of the zinc phthalocyanine colorant (A-1) was carried out, except that CI Pigment Green 58 (DIC Corporation's "FASTOGEN GREEN A110") was changed to the aluminum phthalocyanine pigment (B) 3 having the following structure, which was produced according to the examples of JP2017-111398A, to obtain 96 parts of an aluminum phthalocyanine colorant (B-3).

[0159] (Aluminum phthalocyanine pigment (B)3) According to the example of JP 2017-111398 A, an aluminum phthalocyanine pigment (B)3 of the following formula (3) was produced. The structure is shown below. Formula (3)

[0160] [ka]

[0161] [Aluminum phthalocyanine coloring agent (B-4)] The same procedure as for the production of the zinc phthalocyanine colorant (A-1) was carried out, except that CI Pigment Green 58 (DIC Corporation's "FASTOGEN GREEN A110") was changed to the aluminum phthalocyanine pigment (B) 4 having the following structure, which was produced according to the examples of JP2017-111398A, to obtain 96 parts of an aluminum phthalocyanine colorant (B-4).

[0162] (Aluminum phthalocyanine pigment (B)4) According to the example of JP 2017-111398 A, an aluminum phthalocyanine pigment (B) 4 of the following formula (4) was produced. The structure is shown below. Formula (4)

[0163] [ka]

[0164] [Aluminum phthalocyanine coloring agent (B-5)] Except for changing CI Pigment Green 58 (DIC Corporation's "FASTOGEN GREEN A110") to aluminum phthalocyanine pigment (B) 5 having the following structure produced according to the examples of JP2017-111398A, the same production as that of zinc phthalocyanine colorant (A-1) was carried out to obtain 96 parts of aluminum phthalocyanine colorant (B-5).

[0165] (Aluminum phthalocyanine pigment (B)5) According to the examples of JP 2017-111398 A, aluminum phthalocyanine pigment (B) 5 of the following formula (5) was produced. The structure is shown below. Formula (5)

[0166] [ka]

[0167] [Copper phthalocyanine colorant (C-1)] The same procedure as for the production of zinc phthalocyanine colorant (A-1) was carried out, except that CI Pigment Green 58 (DIC Corporation's "FASTOGEN GREEN A110") was changed to CI Pigment Green 36 (TOYO COLOR Corporation's "LIONOL GREEN 6YK") of the copper phthalocyanine pigment (C), to obtain 96 parts of copper phthalocyanine colorant (C-1). [Copper phthalocyanine colorant (C-2)] The same procedure as for the production of zinc phthalocyanine colorant (A-1) was carried out, except that CI Pigment Green 58 (DIC Corporation's "FASTOGEN GREEN A110") was changed to CI Pigment Blue 15:3 (TOYO COLOR Co., Ltd.'s "Lionol Blue FG-7351") of copper phthalocyanine pigment (C), to obtain 96 parts of copper phthalocyanine colorant (C-2).

[0168] [Yellow colorant (D-1)] The same procedure as for the production of zinc phthalocyanine colorant (A-1) was carried out, except that CI Pigment Green 58 (DIC Corporation's "FASTOGEN GREEN A110") was used instead of CI Pigment Yellow 138 (BASF Japan Ltd.'s "Paliotol Yellow K0961HD"), to obtain 96 parts of a yellow colorant (D-1).

[0169] <Dispersant manufacturing example> (Preparation of Dispersant Solution 1) In a reaction vessel equipped with a gas inlet tube, a temperature control, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAC) were charged and replaced with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile and 90 parts of PGMAC was added and reacted for 7 hours. It was confirmed that 95% or more had reacted by measuring the non-volatile content. Next, 19 parts of pyromellitic anhydride, 50 parts of PGMAC, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 100°C for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. Next, PGMAC was added to dilute the mixture to a non-volatile content of 40 parts, and dispersant solution 1 with an acid value of 70 mgKOH / g and a weight average molecular weight (Mw) of 8,500 was obtained.

[0170] <Production example of binder resin> (Preparation of binder resin solution 1) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 196 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C. The atmosphere in the reaction vessel was replaced with nitrogen, and a mixture of 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. Next, PGMAC was added so that the non-volatile content was 20 parts, and a binder resin solution 1 with a weight average molecular weight (Mw) of 26,000 was obtained.

[0171] (Preparation of binder resin solution 2) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 207 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C and substituted with nitrogen in the reaction vessel. From the dropping tube, a mixture of 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a resin solution. Next, the nitrogen gas was stopped and dry air was injected for 1 hour while stirring the entire resin solution obtained. After cooling to room temperature, a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karens MOI manufactured by Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70°C over 3 hours. After the dropwise addition was completed, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, cyclohexanone was added so that the non-volatile content was 20 parts, and a binder resin solution 2 with a weight average molecular weight (Mw) of 18,000 was obtained.

[0172] (Preparation of binder resin solution 3) A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube was charged with 182 g of PGMAC, and the atmosphere in the flask was changed from air to nitrogen. After that, the temperature was raised to 100°C, and a solution of 3.6 g of azobisisobutyronitrile added to a mixture of 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of tricyclodecane-based monomethacrylate (FA-513M, Hitachi Chemical Co., Ltd.), and 136 g of PGMAC was dropped into the flask from the dropping funnel over a period of 2 hours, and stirring was continued at 100°C for a further 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g [0.25 mol, (50 mol parts relative to the carboxyl group of the methacrylic acid used in this reaction)] of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone were added to the flask, and the reaction was continued for 6 hours at 110°C, after which the reaction was terminated. Next, cyclohexanone was added so that the nonvolatile content became 20 parts, and a binder resin solution 3 having a weight average molecular weight (Mw) of 13,000 was obtained.

[0173] (Preparation of binder resin solution 4) 100 parts of PGMAC was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable 4-neck flask, and heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction. Next, the inside of the flask was purged with air, and 17.0 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added, and the reaction was continued for 5 hours at 120°C, and terminated when the non-volatile acid value reached 0.8. Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added, and the reaction was terminated for 4 hours at 120°C. Next, PGMAC was added so that the non-volatile content became 20 parts, and binder resin solution 4 with a weight average molecular weight (Mw) of 12,000 was obtained.

[0174] <Method of producing colorant dispersion> [Zinc phthalocyanine colorant dispersion (P-1)] The mixture below was stirred and mixed until homogenous, and then dispersed in an Eiger mill (Eiger Japan, "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 5 hours. The mixture was then filtered through a 5.0 μm filter to prepare a colorant dispersion (P-1). Zinc phthalocyanine colorant (A-1): 12.0 parts Dispersant solution 1: 10.0 parts Binder resin solution 1: 25.0 parts PGMAC: 53.0 copies

[0175] [Aluminum phthalocyanine colorant dispersion (P-2)] The mixture below was stirred and mixed until homogeneous, and then dispersed in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") for 5 hours using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a 5.0 μm filter to produce a colorant dispersion (P-2). Aluminum phthalocyanine colorant (B-1): 12.0 parts Dispersant solution 1: 10.0 parts Binder resin solution 1: 25.0 parts PGMAC: 53.0 copies

[0176] [Aluminum phthalocyanine colorant dispersions (P-3 to P-6)] Hereinafter, colorant dispersions (P-3 to P-6) were prepared in the same manner as colorant dispersion (P-2), except that the aluminum phthalocyanine colorants shown in Table 1 were used instead.

[0177] [Table 1]

[0178] [Copper phthalocyanine colorant dispersion (P-7)] The mixture below was stirred and mixed until homogeneous, and then dispersed in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") for 5 hours using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a 5.0 μm filter to produce a colorant dispersion (P-7). Copper phthalocyanine colorant (C-1): 12.0 parts Dispersant solution 1: 10.0 parts Binder resin solution 1: 25.0 parts PGMAC: 53.0 copies

[0179] [Copper phthalocyanine colorant dispersion (P-8)] The mixture below was stirred and mixed until homogeneous, and then dispersed in an Eiger mill (Eiger Japan, "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 5 hours. The mixture was then filtered through a 5.0 μm filter to prepare a colorant dispersion (P-8). Copper phthalocyanine colorant (C-2): 12.0 parts Dispersant solution 1: 10.0 parts Binder resin solution 1: 25.0 parts PGMAC: 53.0 copies

[0180] [Example 1] (Photosensitive coloring composition (L-1)) The following mixture was stirred and mixed to be homogeneous, filtered through a 5.0 μm filter, and mixed to prepare a photosensitive coloring composition (L-1). Zinc phthalocyanine colorant dispersion (P-1): 28.93 parts Aluminum phthalocyanine colorant dispersion (P-2): 16.88 parts Copper phthalocyanine colorant dispersion (P-7): 2.41 parts Binder resin solution 2: 2.24 parts Binder resin solution 3: 2.20 parts Binder resin solution 4: 2.13 parts Polymerizable compound 1 ("KAYARAD DPCA-30" manufactured by Nippon Kayaku Co., Ltd.): 2.25 parts Photopolymerization initiator 1 (BASF Japan "Irgacure OXE-01") : 0.15 parts Photopolymerization initiator 2 (BASF Japan "Irgacure OXE-04") : 0.15 parts Thiol Chain Transfer Agent 1 (Pentaerythritol Tetrakisthiopropionate) : 0.05 part Antioxidant 1 (ADEKA "Adeka STAB AO-80"): 0.05 parts UV absorber 1 (ADEKA "ADEKA STAB LA-29"): 0.05 parts Adhesion improver 1 (Shin-Etsu Silicone "KBM-403"): 0.50 parts Leveling agent 1 (a mixed solution of 1 part of BYK-330 manufactured by BYK Chemie dissolved in 100 parts of PGMAC): 1.00 parts PGMAC: 41.03 copies

[0181] [Examples 2 to 24, Comparative Examples 1 to 4] (Photosensitive coloring composition (L-2~L-28)) As shown in Table 2-1 below, photosensitive coloring compositions (L-2 to 28) were obtained in the same manner as the photosensitive coloring composition (L-1), except that the types and amounts (parts by weight) of the colorant dispersion (P) and the thermosetting compound (E) were changed. 1~19 is a reference example.

[0182] <Thermosetting compound (E)> Thermosetting compound 1 (E-1) A solution of Daicel's "EHPE3150" dissolved in PGMAC to a non-volatile content of 20% by mass

[0183] [Table 2-1]

[0184] [Table 2-2]

[0185] <Evaluation of Photosensitive Coloring Composition> The obtained colored compositions (L-1 to L-28) were subjected to tests for storage stability, contrast ratio, and dielectric loss tangent by the following methods. The test results are shown in Table 3. The meaning of the evaluation rank is as follows: ◎: Very good 〇: Good △: Practical ×: Not suitable for practical use

[0186] (Dielectric tangent) The photosensitive coloring composition was applied using a spin coater onto a glass substrate with a length of 100 mm, width of 100 mm, and thickness of 0.7 mm, on which aluminum had been evaporated for use as an electrode, so that the film thickness after drying would be 2.0 μm. Next, after drying under reduced pressure, the composition was exposed to ultraviolet light using an ultra-high pressure mercury lamp at an integrated light quantity of 300 mJ and an illuminance of 30 mW to obtain a coated substrate. The coated substrate was then heated at 230°C for 1 hour, allowed to cool, and then a 3.464×10 -4 m 2 Aluminum for the electrodes was vapor-deposited, and a sample was prepared by sandwiching the cured film between the aluminum electrodes. The capacitance of the obtained sample was measured from 10 Hz to 1 MHz using an impedance analyzer ("Model 1260" manufactured by Solartron) at an applied voltage of 100 mV, and the dielectric tangent at 20 Hz was calculated and evaluated according to the following criteria.

[0187] (Dielectric tangent) ◎: Less than 0.015 ○: 0.015 or more and less than 0.020 ×: 0.020 or more

[0188] (Storage stability) The storage stability of the obtained photosensitive coloring composition was evaluated by the following method. The initial viscosity of the photosensitive coloring composition on the day after preparation and the viscosity over time after aging at 40° C. for one week were measured using an E-type viscometer (TOKI SANGYO Co., Ltd.'s "ELD type viscometer") at 25° C. and a rotation speed of 50 rpm. From the initial viscosity and the viscosity over time values, the viscosity change rate over time was calculated using the following formula, and the storage stability was evaluated in two stages. [Change rate of viscosity over time] = |([Initial viscosity] - [Viscosity over time]) / [Initial viscosity]| x 100 ○: Viscosity change rate is less than 5% ×: Viscosity change rate is 5% or more

[0189] (Contrast ratio) The coloring composition was applied to a glass substrate of 100 mm x 100 mm and 1.1 mm thick using a spin coater, and heated at 230 ° C for 20 minutes to obtain a coating. At this time, the coating was applied by changing the application conditions (spin coater rotation speed, time) as appropriate so that the thickness of the coating was y = 0.645 under C light source after heat treatment at 230 ° C. A color luminance meter (Topcon Corporation "BM-5A") was used as the luminance meter, and a polarizing plate (Nitto Denko Corporation "NPF-G1220DUN") was used as the polarizing plate. During the measurement, a black mask with a 1 cm square hole was used to measure the transmitted light as the luminance on the polarizing plate, and the ratio of the luminance when the polarizing plates were parallel to the luminance when they were perpendicular was calculated as the contrast ratio. (Contrast ratio) = (Luminance when parallel) / (Luminance when perpendicular) The judging criteria are as follows: ◎: 5500 or more ○: 5000 to less than 5500 △: 4500 or more but less than 5000 ×: Less than 4500

[0190] [Table 3] [Explanation of symbols]

[0191] 10 LCD display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color Filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing Plate 30 Backlight unit 31 White LED light source LC Liquid Crystal

Claims

1. A photosensitive coloring composition comprising a zinc phthalocyanine pigment (A), an aluminum phthalocyanine pigment (B), a copper phthalocyanine pigment (C), a thermosetting compound (E), a dispersant, a polymerizable compound, a photopolymerization initiator, and a binder resin, In a total of 100 mass% of the zinc phthalocyanine pigment (A), the aluminum phthalocyanine pigment (B), and the copper phthalocyanine pigment (C), The pigment comprises 40 to 90% by mass of a zinc phthalocyanine pigment (A), 5 to 59% by mass of an aluminum phthalocyanine pigment (B), and 1 to 10% by mass (excluding 10% by mass) of a copper phthalocyanine pigment (C); The photosensitive coloring composition contains an oxime ester compound as the photopolymerization initiator.

2. The photosensitive coloring composition according to claim 1 , further comprising a yellow pigment (D).

3. A color filter comprising a substrate and filter segments formed from the photosensitive coloring composition according to claim 1 or 2.

4. An image display device comprising the color filter according to claim 3 .

Images