JP7415342B2 - Photosensitive coloring composition, color filter and liquid crystal display device using the same - Google Patents

Description

The present invention relates to coloring compositions and photosensitive coloring compositions used for manufacturing color filters used in color liquid crystal display devices, color solid-state image sensors, organic EL display devices, quantum dot display devices, electronic paper, etc. The present invention also relates to a color filter and a liquid crystal display device including filter segments formed using the same.

Color filters are made by arranging two or more types of fine band-shaped filter segments (hereinafter also referred to as coating films) of different hues in parallel (in stripes) or across each other on a transparent substrate such as a glass substrate. Alternatively, two or more types of fine filter segments having different hues are arranged in order in each of the vertical and horizontal directions. The filter segments have small dimensions ranging from several microns to several hundred microns, and are neatly arranged in a predetermined arrangement for each hue.
Currently, the mainstream method for producing color filters is a method called a pigment dispersion method, which uses pigments with excellent light resistance, heat resistance, and other resistance as colorants. In addition, in the pigment dispersion method, a color filter is manufactured by the following method. First, a photosensitive coloring composition (pigment resist) made by dispersing a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass. After drying to remove the solvent from the coating, the coating is exposed in a pattern corresponding to the filter segments of a certain color. Next, the unexposed areas of this coating film are removed by development, and then, if necessary, a treatment such as heating is performed. As a result, a filter segment pattern of the first color is obtained. Then, by performing a similar operation to this, filter segment patterns of other colors are formed to complete a color filter.

When forming color filters, color resist patterns may change color (water stains) when exposed to an alkaline aqueous solution used as a developer. A method for use is disclosed. Furthermore, Patent Document 2 discloses a method for countering uneven development (water stains) using a polymerizable compound with a specific structure.

JP2016-102212A Japanese Patent Application Publication No. 2014-48556

The present invention aims to achieve the following objects.
That is, the object of the present invention is to obtain a coating film that has an excellent pattern shape when used as a pixel, and has reduced discoloration (less water stains) even when exposed to an alkaline solution, and has a good quality. It is an object of the present invention to provide a photosensitive coloring composition for a color filter that can form pixels, and also to provide a color filter formed using the same.

That is, the present invention is a photosensitive coloring composition containing a colorant (A), a binder resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and a thiol compound (E), The present invention relates to a photosensitive coloring composition characterized in that the thiol-based compound (E) contains a compound (E1) represented by the following general formula (1).

General formula (1)

(In general formula (1), R is an m-valent organic group, n represents 1 to 10, and m is an integer of 1 to 4.)

Furthermore, the present invention relates to the above-mentioned photosensitive coloring composition, which further contains a fluorosurfactant (F).

Further, the present invention provides that the fluorosurfactant (F) contains an ethylenically unsaturated monomer (FD1) containing a fluorinated alkyl group and/or a poly(perfluoroalkylene ether) chain, and another ethylenically unsaturated monomer (FD1) containing a fluorinated alkyl group and/or a poly(perfluoroalkylene ether) chain. The present invention relates to the above-mentioned photosensitive coloring composition characterized by comprising an unsaturated monomer (FD2) and a copolymer (FD).

Further, the present invention provides the above-mentioned photosensitive material, characterized in that the thiol compound (E1) represented by the general formula (1) is contained in an amount of 0.1 to 7.5% by mass based on the total nonvolatile content of the coloring composition. This invention relates to a coloring composition.

The present invention further relates to the photosensitive coloring composition described above, wherein the thiol compound (E) contains a thiol compound (E2) other than the thiol compound (E1).

The present invention also relates to a color filter comprising a base material and a filter segment formed using the photosensitive coloring composition.

The present invention also relates to a liquid crystal display device including the color filter described above.

By using the photosensitive coloring composition of the present invention, filter segments of each color without discoloration can be formed. Therefore, by using the photosensitive coloring composition of the present invention, a high quality color filter can be obtained.

FIG. 1 shows an example of the form of a color filter of the present invention.

Define terms used herein. When expressed as "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", unless otherwise specified, each , "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate" or "acrylamide and/or methacrylamide". "C.I." mentioned herein means color index (C.I.). Colorants include pigments and dyes.

<Colorant>
The photosensitive coloring composition of the present invention contains a pigment or a dye as a colorant.
As the pigment, organic or inorganic pigments can be used alone or in combination of two or more types. The pigment is preferably a pigment with high color development and high heat resistance, particularly a pigment with high heat decomposition resistance, and organic pigments are usually used. Specific examples of organic pigments that can be used in the coloring composition for color filters are shown below using color index numbers.

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, 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, 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 and the like. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, more preferably C.I. I. Pigment Red 177, 254, 291, 295, and 296.

The red colored composition also contains C. I. An orange pigment such as Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73 and/or a yellow pigment described below may be used in combination.

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, Examples include 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 heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6, more preferably C.I. I. Pigment Blue 15:6. The blue colored composition may also contain a purple pigment, which will be described later.

As the purple pigment, for example, 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, etc. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, etc., but is not particularly limited thereto. Among these, from the viewpoint of transmittance, C.I. I. pigment green 36, 58, 59, 62 or 63.
In addition, the green colored composition may also contain a yellow pigment described below.

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

The cyan coloring composition for forming the cyan filter segment includes, for example, C.I. I. Blue pigments such as Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, 16, and 81 can be used alone or in combination.

The magenta coloring composition for forming the magenta filter segment includes, for example, C.I. I. Pigment Violet 1, 19, C. I. Purple pigments and red pigments such as Pigment Red 144, 146, 177, 169, and 81 can be used alone or in combination. A yellow pigment can be used in combination with the magenta color composition.

Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron(III) oxide), cadmium red, ultramarine blue, deep blue, chromium oxide green, cobalt green, and amber. , synthetic iron black, etc. Inorganic pigments are used in combination with organic pigments in order to balance saturation and brightness while ensuring good coating properties, sensitivity, developability, etc.

<Refining of pigments>
When using an organic pigment as a coloring agent, it is preferable to perform a fine treatment and then mix it with other raw materials. Examples of the method for the micronization treatment include wet grinding, dry grinding, and solution precipitation. Among these, salt milling treatment using a kneader method, which is a type of wet milling, is preferred. The average primary particle diameter of the organic pigment after the micronization treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. Appropriate particle size further improves dispersibility and further improves the contrast ratio of the coating. Note that the average primary particle diameter is the average value of about 20 particles arbitrarily selected from an enlarged image of a TEM (transmission electron microscope). Note that if the particle has a vertical axis length and a horizontal axis length, the vertical axis length is used.

Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is milled using a batch method such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or planetary mixer. This is a process in which the mixture is mechanically kneaded using a continuous kneader while being heated, and then water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for salt milling pigments, it is possible to obtain pigments with very fine primary particle diameters, narrow distribution widths, and sharp particle size distributions.

Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. Among these, sodium chloride (salt) is preferred from the viewpoint of cost. The amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by weight, more preferably 300 to 1,000 parts by weight, based on 100 parts by weight of the pigment, from both treatment efficiency and production efficiency.

The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt. A water-soluble organic solvent is a compound that dissolves (mixes) in water and does not substantially dissolve the water-soluble inorganic salt. The water-soluble organic solvent is preferably a high boiling point solvent with a boiling point of 120° C. or higher, since it is difficult to volatilize due to the temperature increase during salt milling. Examples of water-soluble organic solvents 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, liquid polypropylene glycol, etc. Can be mentioned. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

Resin can be added as needed during the salt milling process. 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, insoluble in water, and more preferably partially soluble in a water-soluble organic solvent. The amount of resin used is preferably 5 to 200 parts by weight per 100 parts by weight of the pigment.

<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, and sulfur dyes. Also included are dye derivatives and lake pigments obtained by turning dyes into lakes.

In addition, dyes include acid dyes having acidic groups such as sulfonic acid and carboxylic acid; in the case of direct dyes, inorganic salts of acid dyes; acid dyes, quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, Or a salt-forming compound with a primary amine compound; a salt-forming compound such as a resin component having these amino groups and an acidic dye. A salt-forming compound of an acidic dye and a compound having an onium base is also preferable because it has excellent fastness. Note that the compound having an onium base is preferably a resin having a cationic group in the side chain.

Examples of the basic dye include salt-forming compounds with organic acids, perchloric acid, or metal salts thereof. Among the salt-forming compounds, salt-forming compounds of basic dyes are preferred because they have excellent resistance to various types and compatibility with pigments.

The chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, etc.). dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinone imine dyes (oxazine 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 Examples include dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and rhodamine dyes. 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. The specific structure of dyes can be found in the ``New Edition Dye Handbook'' (edited by the Organic Synthetic Chemistry Society; Maruzen, 1970), ``Color Index'' (The Society of Dyers and Colourists), and ``Pigment Handbook'' (edited by Okawara et al.; Kodansha, 1986). etc. are listed.

<Dye derivative>
A pigment derivative can be used in the colored composition if necessary. A dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Dye derivatives include, for example, compounds having acidic substituents such as sulfo groups, carboxy groups, or phosphoric acid groups, as well as amine salts thereof, sulfonamide groups, or basic substituents such as tertiary amino groups at the terminals. Examples include compounds having a neutral substituent such as a phenyl group or a phthalimide alkyl 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, and benzoisomer pigments. Examples include indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

Specifically, diketopyrrolopyrrole dye derivatives include JP-A No. 2001-220520, WO 2009/081930 pamphlet, WO 2011/052617 pamphlet, WO 2012/102399 pamphlet, JP 2017-156397 pamphlet, and phthalocyanine-based dye derivatives. Pigment derivatives are disclosed in JP-A No. 2007-226161, WO2016/163351 pamphlet, JP-A-2017-165820, and Patent No. 5753266. Anthraquinone-based pigment derivatives are described in JP-A-63-264674 and JP-A-09-09. -272812, JP 10-245501, JP 10-265697, JP 2007-079094, WO2009/025325 pamphlet, quinacridone dye derivatives, JP 48-54128, JP-A-03-9961, JP-A 2000-273383, dioxazine dye derivatives, JP-A 2011-162662, thiazine indigo dye derivatives, JP-A 2007-314785, triazine dye derivatives are JP-A-61-246261, JP-A-11-199796, JP-A 2003-165922, JP-A 2003-168208, JP-A 2004-217842, and JP-A 2007-314681. , benzisoindole dye derivatives are disclosed in JP-A No. 2009-57478, and quinophthalone-based dye derivatives are described in JP-A Nos. 2003-167112, 2006-291194, 2008-31281, and 2012. -226110, naphthol dye derivatives, JP 2012-208329, JP 2014-5439, azo dye derivatives, JP 2001-172520, JP 2012-172092, acidic The substituent is described in JP-A No. 2004-307854, and the basic substituent is described in JP-A-2002-201377, JP-A 2003-171594, JP-A 2005-181383, and JP-A 2005-213404. Mention may be made of the dye derivatives described. Furthermore, in these documents, dye derivatives are sometimes described as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds; , a compound having a substituent such as a neutral group has the same meaning as a dye derivative.

These dye derivatives can be used alone or in combination of two or more.

The pigment derivative is preferably added in an amount of 1 to 100 parts by weight, more preferably 3 to 70 parts by weight, and even more preferably 5 to 50 parts by weight, per 100 parts by weight of the pigment.

By adding a dye derivative to a pigment and performing a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, and solvent salt milling, the dye derivative is adsorbed to the pigment surface, which is different from when no dye derivative is added. In comparison, the primary particles of the pigment can be made finer.

By adding a pigment derivative to the pigment and performing a dispersion process such as wet dispersion using two rolls, three rolls, or beads, the pigment derivative is adsorbed to the pigment surface, and the pigment surface becomes polar and adsorbs the resin-type dispersant. This promotes compatibility with pigments, dye derivatives, resin-type dispersants, solvents, and other additives, and improves dispersion stability and viscosity stability over time when used in colored compositions and colored curable compositions. do. In addition, due to improved compatibility, the coating film has excellent stability over time when the colored curable composition is applied to a glass substrate, etc., and the waiting time from application of the colored curable composition to exposure (PCD: Post Coating) The stability and characteristic dependence of the pattern shape on the waiting time from exposure to heat treatment (PED: Post Exposure Delay) and the line width sensitivity stability are improved. Furthermore, since the surface of the pigment is adsorbed and coated with the pigment derivative and the resin-type dispersant, it is possible to suppress crystal precipitation due to aggregation and sublimation of the pigment when the coating film is heated and baked. Furthermore, variations in development time and development residues are also suppressed.

<Resin type dispersant>
Known resin-type dispersants can be used in the photosensitive coloring composition of the present invention. The resin-type dispersant has a colorant affinity site that has the property of adsorbing to the added colorant and a site that is compatible with the colorant carrier, and has a colorant affinity site that has the property of adsorbing to the added colorant and a site that is compatible with the colorant carrier. Any substance may be used as long as it has the function of stabilizing it, and specifically, urethane dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amines, etc. salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, poly(lower alkyleneimine) and free carboxyl groups. Oil-based dispersants such as amides and their salts formed by reaction with polyesters having Water-soluble resins such as acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphate esters, etc. are used, and these These can be used alone or in combination of two or more.
Examples of polymeric dispersants having basic functional groups include nitrogen atom-containing graft copolymers and nitrogen atom-containing polymers having functional groups such as tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocycles in their side chains. Examples include acrylic block copolymers and urethane polymer dispersants.

The resin type dispersant is preferably used in an amount of about 3 to 200% by mass based on the total amount of the colorant, and more preferably in an amount of about 5 to 100% by mass from the viewpoint of film-forming properties.

<Binder resin (B)>
The coloring composition herein includes a binder resin. The binder resin is a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm. Note that the transmittance is preferably 95% or more. In terms of curability, the binder resin includes, for example, thermoplastic resin, thermosetting resin, active energy ray curable resin, and the like. Note that the active energy ray-curable resin may be a thermoplastic resin or a thermosetting resin that has an active energy ray-reactive functional group. In terms of physical properties, the binder resin is preferably an alkali-soluble resin from the viewpoint of developability. Alkali solubility is for imparting development solubility in the alkaline development step during color filter production, and an acidic group is required.

Binder resins can be used alone or in combination of two or more types.

The content of the binder resin is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, per 100 parts by mass of the colorant. When contained in an appropriate amount, a film can be easily formed and good color properties can be easily obtained.

<Thermoplastic resin>
Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, Examples include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.
Examples of thermoplastic resins having alkali solubility include resins having acidic groups such as carboxyl groups and sulfone groups. Examples of thermoplastic resins having alkali solubility include acrylic resins having acidic groups, α-olefin/(anhydrous) maleic acid copolymers, styrene/styrene sulfonic acid copolymers, and ethylene/(meth)acrylic acid copolymers. , or isobutylene/(anhydrous) maleic acid copolymer. Among these, acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers are preferred in view of improving developability, heat resistance, and transparency.

<Active energy ray-curable alkali-soluble resin>
The active energy ray-curable alkali-soluble resin preferably has an ethylenically unsaturated double bond. Ethylenically unsaturated double bonds can be introduced, for example, by methods (i) and (ii) shown below. The resin is three-dimensionally crosslinked due to the effect of the active energy rays, thereby increasing the crosslinking density and improving chemical resistance.

[Method (i)]
In method (i), for example, an ethylenically unsaturated monomer having an epoxy group is added to the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer with another monomer. The carboxyl group of an unsaturated monobasic acid having a heavy bond is subjected to an addition reaction. Next, the generated hydroxyl group is reacted with a polybasic acid anhydride, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

Ethylenically unsaturated monomers having an epoxy group include, for example, glycidyl (meth)acrylate, methylglycidyl (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 with unsaturated monobasic acids.

Unsaturated monobasic acids include monobasic acids such as (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and α-haloalkyl, alkoxyl, halogen, nitro, and cyano substituted products of (meth)acrylic acid. Examples include carboxylic acids.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. In addition, if necessary, such as increasing the number of carboxyl groups, use a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to reduce the remaining amount. It is also possible to hydrolyze the anhydride group.

As a method similar to method (i), for example, a part of the side chain carboxyl groups of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another monomer may be used. , is a method in which an ethylenically unsaturated monomer having an epoxy group is subjected to an addition reaction to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
Method (ii) involves adding an ethylenically unsaturated monomer having an isocyanate group to the side chain hydroxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer. This is a method in which the isocyanate groups of monomers are reacted.

The ethylenically unsaturated monomer having a hydroxyl group is, for example, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, Examples include hydroxyalkyl methacrylates such as glycerol mono(meth)acrylate and cyclohexanedimethanol mono(meth)acrylate. In addition, polyether mono(meth)acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to hydroxyalkyl (meth)acrylate, polyγ-valerolactone, polyε-caprolactone, and/or polyester Also included are polyester mono(meth)acrylates to which 12-hydroxystearic acid and the like are added. From the viewpoint of suppressing coating film foreign matter, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferable, and from the viewpoint of sensitivity, it is preferable to use one having 2 to 6 hydroxyl groups. Among them, glycerol mono(meth)acrylate is more preferable.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloyl ethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate. It will be done.

Other monomers that can constitute the alkali-soluble resin include, in addition to the other ethylenically unsaturated monomers already explained, N-substituted maleimides, alkyleneoxy group-containing monomers, and phosphoric acid ester group-containing ethylenically unsaturated monomers. monomers, carboxyl group-containing ethylenically unsaturated monomers, and the like.
N-substituted maleimides include, for example, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidehexane, 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-phenylene dimaleimide, N, N'-1,4-phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitro phenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, Examples include N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine, and the like. Examples of the alkyleneoxy group-containing monomer include EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, and paracumylphenol. Examples include EO or propylene oxide (PO) modified (meth)acrylate, nonylphenol EO modified (meth)acrylate, nonylphenol PO modified (meth)acrylate, and the like.

As the carboxyl group-containing ethylenically unsaturated monomer, the monomers already described can be used.

The phosphoric acid ester group-containing ethylenically unsaturated monomer is, for example, a compound obtained by reacting a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid with the hydroxyl group of the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer. be.

<Alkali-soluble resin without ethylenically unsaturated double bonds>
The coloring composition of the present specification can contain an alkali-soluble resin having no ethylenically unsaturated double bonds in order to adjust the degree of curing of the coating.

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 or more and 40,000 or less, preferably 3,000 or more and 300,00 or less, and 4,000 or more, in order to impart alkaline development solubility. More preferably, it is 20,000 or less. Moreover, it is preferable that the value of Mw/Mn is 10 or less. If the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate will decrease, making it difficult for the exposed pattern to remain. If it exceeds 40,000, the solubility in alkaline development will decrease, a residue will be generated, and the linearity of the pattern will deteriorate.
The acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg/g) in order to impart alkaline development solubility, preferably 70 or more and 180 or less, more preferably 90 or more and 170 or less. range. If the acid value is less than 50, the solubility in alkaline development will decrease, a residue will be generated, and the linearity of the pattern will deteriorate. When it exceeds 200, the adhesion to the substrate decreases, making it difficult for the exposed pattern to remain.

Each raw material used in the synthesis of the binder resin can be used alone or in combination of two or more.

<Thermosetting compound>
In the present invention, the binder resin can be used in combination with a thermoplastic resin and may further contain a thermosetting compound. When producing a color filter using the coloring composition for color filters of the present invention, by including a thermosetting compound, it reacts during baking of the filter segments and increases the crosslinking density of the coating film, thereby improving the heat resistance of the filter segments. The effect of this is that pigment aggregation during filter segment firing is suppressed and the contrast ratio is improved.

The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of thermosetting compounds include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds, but the present invention is not limited thereto. It is not something that will be done. Epoxy compounds and oxetane compounds are preferably used in the coloring composition for color filters of the present invention.

<Polymerizable compound (C)>
The photosensitive coloring composition of the present invention contains a polymerizable compound (C). Polymerizable compounds include monomers or oligomers that can be cured by ultraviolet rays, heat, etc. to produce transparent resins.

Examples of the polymerizable compound include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and β-carboxyethyl (meth)acrylate. 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, phenoxytetra Ethylene 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, 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, methylolation Various acrylic esters and methacrylic esters such as (meth)acrylic ester of melamine, epoxy (meth)acrylate, urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol Examples include trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile.

(Polymerizable compound having acid group)
The polymerizable compound can contain a photopolymerizable monomer having an acid group. Examples of acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups.

Photopolymerizable monomers having acid groups include, for example, esterification products of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohol and (meth)acrylic acid, and dicarboxylic acids; Examples include esterified products with hydroxyalkyl (meth)acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. , free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 2-hydroxyethyl acrylate, 2-hydroxy Examples include free carboxyl group-containing oligoesters with monohydroxy monoacrylates or monohydroxy monomethacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

(Polymerizable compound with urethane bond)
The polymerizable compound can contain a monomer having an ethylenically unsaturated bond and a urethane bond. The monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting a (meth)acrylate having a hydroxyl group. Examples include polyfunctional urethane acrylates obtained by

(Meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. ) 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 carboxy(meth)acrylate, a hydroxyl group-containing polyol polyacrylate, and the like.

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

The polymerizable compound (C) can be used alone or in combination of two or more types.

The amount of the polymerizable compound (C) is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight based on 100 parts by weight of nonvolatile content of the photosensitive coloring composition. When blended in an appropriate amount, curability and developability are further improved.

<Photopolymerization initiator (D)>
The photoinitiator (D) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1- one, 1-hydroxycyclohexyl phenylketone, 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-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1- Acetophenone compounds such as butanone; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, Benzophenone compounds such as acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2 - Thioxanthone compounds such as methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloro methyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s- Triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl) -6-triazine or triazine compounds such as 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2- (O-benzoyloxime)], or oxime esters such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) Compounds: Phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone Examples include quinone compounds such as; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds. Among these, oxime ester compounds are preferred.

The photopolymerization initiator (D) can be used alone or in combination of two or more types.

(oxime ester compound)
When an oxime ester compound absorbs ultraviolet light, the N—O bond of the oxime is cleaved to generate iminyl radicals and alkyloxy radicals. Since these radicals generate highly active radicals by further decomposition, a pattern can be formed with a small amount of exposure. If the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the degree of curing of the coating film may be low, but oxime ester compounds are preferably used because they have high quantum efficiency. Ru.

Oxime ester compounds include oximes described in JP-A No. 2007-210991, JP-A 2009-179619, JP-A 2010-037223, JP-A 2010-215575, JP-A 2011-020998, etc. Examples include ester photopolymerization initiators.

The content of the photopolymerization initiator is preferably 2 to 50 parts by weight, more preferably 2 to 30 parts by weight, based on 100 parts by weight of the colorant. When incorporated in an appropriate amount, photocurability and developability are further improved.

<Sensitizer>
Furthermore, the photosensitive coloring composition of the present invention can contain a sensitizer.
Examples of the sensitizer (H) include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone derivatives. , anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as 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, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyl Porphyrazine 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, or Michler ketone derivatives, α- Acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4, Examples include 4'-tetra(t-butylperoxycarbonyl)benzophenone and 4,4'-bis(diethylamino)benzophenone.

Among the above-mentioned sensitizers, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are mentioned as sensitizers that can particularly suitably sensitize. 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 and the like are used.

More specifically, there are "Pigment Handbook" (edited by Makoto Okawara et al., 1986, Kodansha), "Chemistry of Functional Pigments" (edited by Makoto Okawara et al., 1981, CMC), "Dye Handbook" (edited by Shin Okawara et al., 1981, CMC), and " Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (CMC, 1986). In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region may also be included.

The sensitizers can be used alone or in combination of two or more.

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

<Thiol compound (E)>
The photosensitive coloring composition of the present invention contains a thiol compound (E1) represented by formula (1).
Thiol compounds (E) are also used as curing agents for epoxy resins, chain transfer agents, photocurable monomers, crosslinking agents, adhesion improvers, etc., but they are not effective in reducing water stains, which is the objective of the present invention. It is important to include a thiol-based compound (E1) that exhibits the desired performance, and other thiol-based compounds (E2) may also have other properties.

<Thiol compound (E1)>
General formula (1)

(In general formula (1), R is an m-valent organic group, n represents 1 to 10, and m is an integer of 1 to 4.)
Examples of m-valent organic groups for R include monovalent to tetravalent groups corresponding to alkyl groups having 1 to 20 carbon atoms, monovalent to tetravalent groups corresponding to aryl groups having 6 to 20 carbon atoms, and 5 to 4 valent groups corresponding to aryl groups having 6 to 20 carbon atoms. A monovalent to tetravalent group corresponding to a heteroaryl group having 20 atoms, a monovalent to tetravalent group corresponding to a heteroaryl group having from 5 to 20 atoms, and a monovalent to tetravalent group corresponding to an alkyl group having from 1 to 20 carbon atoms. Examples include groups that are a combination of groups. n is preferably 2 to 4.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, benzyl group, tolyl group, and o-xylyl group. Examples of the heteroaryl group having 5 to 20 atoms include a pyrazole group, an imidazole group, a tetrazole group, a triazine group, an isocyanuric group, and the like.

Preferable examples of the thiol compound (E1) include trimethylolpropane dipropanethiol, pentaerythritol dipropanethiol, pentaerythritol tripropanethiol, and pentaerythritol tetrapropanethiol. These can be used alone or in combination of two or more.

The thiol compound (E1) represented by the general formula (1) is preferably contained in an amount of 0.1 to 7.5% by mass based on the total nonvolatile content of the coloring composition.

<Thiol compound (E2)>
A thiol compound (E2) other than the thiol compound (E1) can be used in combination with the photosensitive coloring composition of the present invention. Examples of the thiol compound (E2) include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthioglycolate. Thiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionate tris(2-hydroxyethyl)isocyanurate , 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, 1,4-bis(3 -mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylol Propane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), etc. are mentioned, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakis thiopropionate. pionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H ,3H,5H)-trione, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate),
Examples include mercapto compounds such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

<Polymerization inhibitor>
The photosensitive coloring composition can contain a polymerization inhibitor. This makes it possible to suppress exposure due to diffracted light from the mask during exposure using photolithography, making it easier to obtain a pattern with a desired shape.

Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, and 2-ethylcatechol. Propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4- Alkylcatechol compounds such as tert-butylcatechol and 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propyl Alkylresorcinol compounds such as resorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, Alkylhydroquinone compounds such as 2,5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide, etc. Examples include phosphine oxide compounds, phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite, pyrogallol, and phloroglucin.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass based on 100% by mass of nonvolatile content of the photosensitive coloring composition. In this range, the effect of the polymerization inhibitor becomes large, and the linearity of the taper, the wrinkles of the coating film, the pattern resolution, etc. become good.

<Ultraviolet absorber>
The photosensitive coloring composition of the invention may also contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorption function, and examples thereof include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds. .

The content of the ultraviolet absorber is preferably 5 to 70% by weight based on the total 100% by weight of the photopolymerization initiator and the ultraviolet absorber. When contained in an appropriate amount, the resolution after development is further improved.

Further, 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 contained in an appropriate amount, the adhesion between the substrate and the coating is further improved, and good resolution can be obtained.

Examples of benzotriazole compounds include 2-(5methyl-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, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethyl ethyl)-4-hydroxy, a mixture of C7-9 side chain 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-( Reaction product of 2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300, 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, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro- 2H-benzotriazol-2-yl)phenyl]propionate is mentioned. Other oligomer type and polymer type compounds having a benzotriazole structure can also be used.

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-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl) )-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester reaction product, 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-(hexyl oxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris Examples include (2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. Other oligomer type and polymer type compounds having a triazine structure can also be used.

Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-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, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like. Other oligomer type and polymer type compounds having a benzophenone structure can also be used.

Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. Other oligomer type and polymer type compounds having a salicylic acid ester structure can also be used.

<Antioxidant>
The photosensitive coloring composition of the present invention can contain an antioxidant. Antioxidants reduce the transmittance of the coating film in order to prevent the photopolymerization initiators and thermosetting compounds contained in the photosensitive coloring composition from oxidizing and yellowing due to heat curing and thermal processes during ITO annealing. You can improve. In particular, when the concentration of the colorant in the coloring composition is high, the amount of crosslinking component in the coating film decreases, and measures such as using a highly sensitive crosslinking component and increasing the amount of photopolymerization initiator are taken, resulting in stronger yellowing during the heat process. can be seen. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and obtain a high transmittance of the coating film.

Examples of antioxidants include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In this specification, the antioxidant is preferably a compound that does not contain a halogen atom.

Among these, hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferred from the viewpoint of achieving both transmittance and sensitivity of the coating film.

Antioxidants can be used alone or in combination of two or more.

Further, the content of the antioxidant is preferably 0.5 to 5.0% by mass based on 100% by mass of the solid content of the coloring composition because transmittance, spectral characteristics, and sensitivity are good.

<Fluorine surfactant (F)>
The photosensitive coloring composition of the present invention preferably contains a fluorosurfactant (F), which further reduces water stains, provides a more preferable taper angle between the base material and the pattern, and allows the black matrix and each color pixel to be There will be no light leakage between the Examples of the fluorine-based surfactant (F) include surfactants having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain, and side chain, and among them, for example, JP-A No. 2018-25687 An ethylenically unsaturated monomer (FD1) containing a fluorinated alkyl group and/or a poly(perfluoroalkylene ether) chain and another ethylenically unsaturated monomer (FD2) described in the publication, It is more preferable to include a copolymer (FD) of Moreover, it is preferable that the other ethylenically unsaturated monomer (FD2) has an adamantyl group.

Examples of the method for producing the compound (FD) include a method of polymerizing it in an organic solvent using a polymerization initiator. The organic solvent used here is preferably ketones, esters, amides, sulfoxides, ethers, and hydrocarbons, and specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability. Examples of the polymerization initiator include peroxides such as benzoyl peroxide, and azo compounds such as azobisisobutyronitrile. Furthermore, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid, etc. can be used if necessary.

As the ethylenically unsaturated monomer (FD1) containing a fluorinated alkyl group constituting the compound (FD), for example, those represented by the following general formula (L1) can be preferably exemplified.
General formula (L1)

[In the above general formula (L1), R represents a hydrogen atom or a methyl group, L represents any one of the following formulas (L-1) to (L-10), and Rf represents the following formula (Rf -1) to (Rf-7). ]

(n in the above formulas (L-1), (L-3) to (L-7) represents an integer of 1 to 8. m in the above formulas (L-8) to (L-10) is 1 represents an integer from 0 to 8, and n represents an integer from 0 to 8.
Rf'' in the above formulas (L-6) and (L-7) represents any one of the following formulas (Rf-1) to (Rf-7). )

n in the above formulas (Rf-1) to (Rf-4) is, for example, an integer of 1 to 6, preferably an integer of 4 to 6. m in the above formula (Rf-5) is, for example, an integer of 1 to 18, n is an integer of 0 to 5, and the sum of m and n is 1 to 23. Preferably, m is an integer from 1 to 5, n is an integer from 0 to 4, and the sum of m and n is from 4 to 5. m in the above formula (Rf-6) is, for example, an integer of 1 to 6, n is an integer of 1 to 3, l is an integer of 1 to 20, p is an integer of 0 to 5, In addition, the sum of the products of m, p, and n and l is 2 to 71. Preferably, m is an integer from 1 to 3, n is an integer from 1 to 3, l is an integer from 1 to 6, p is an integer from 0 to 2, and m, p and n The sum of the products of and l is 2 to 23.

Among the ethylenically unsaturated monomers (FD1) containing a fluorinated alkyl group, a fluorine-containing thermally decomposable resin exhibiting excellent smoothness can be obtained. A monomer having a fluorinated alkyl group having 1 to 6 carbon atoms is preferred, and a monomer having a fluorinated alkyl group having 4 to 6 carbon atoms to which a fluorine atom is directly bonded is more preferred.

The ethylenically unsaturated monomer (FD1) containing a poly(perfluoroalkylene ether) chain constituting the compound (FD) has a divalent fluorocarbon group having 1 to 3 carbon atoms and an oxygen atom. Examples include those having an alternately connected structure.

Further, it is preferable that the other ethylenically unsaturated monomer (FD2) constituting the compound (FD) is a monomer having an adamantyl group, and further suppression of water stains can be expected.

When the photosensitive coloring composition of the present invention contains a fluorine surfactant, the amount of the fluorine surfactant added is 0.001 to 2.0 mass based on the total solid content of the composition of the present invention. %, more preferably 0.005 to 1.0% by mass. Within this range, the coating properties of the coloring composition, pattern adhesion, and transmittance will be well balanced. The photosensitive coloring composition of the present invention may contain two or more types including other non-fluorine surfactants. When two or more types are included, it is preferable that the total amount falls within the above range.

Silicone surfactants can be used as non-fluorinated surfactants, and nonionic surfactants, cationic surfactants, and anionic surfactants are classified according to their properties, including non-fluorinated surfactants. Various surfactants can be used, such as surfactants.

<Storage stabilizer>
The colored composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Storage stabilizers include, for example, quaternary ammonium chloride such as benzyl trimethyl chloride and diethyl hydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples include organic phosphines and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of colorant (100% by weight).

<Adhesion improver>
The photosensitive coloring composition of the present invention may contain an adhesion improver such as a silane coupling agent in order to improve adhesion to the substrate. By improving the adhesion by the adhesion improver, the reproducibility of fine lines becomes better and the resolution improves.

Examples of adhesion improvers include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane. (Meth)acrylic silanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxy Silane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl- butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, aminosilanes such as hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, p-styryltrimethoxysilane Examples include silane coupling agents such as styryls such as, ureidos such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanates such as 3-isocyanatepropyltriethoxysilane. It will be done. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the colorant in the coloring composition. It is more preferable within this range because the effect is large and the balance between adhesion, resolution, and sensitivity is good.

<Method for producing photosensitive coloring composition>
The photosensitive coloring composition included in the present invention contains a colorant in a colorant carrier such as a dispersant and a binder resin and/or a solvent, preferably together with a dispersion aid (dye derivative or surfactant). It can be produced by finely dispersing it using various dispersion means such as a kneader, two-roll mill, three-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or attritor (colorant dispersion). . At this time, two or more types of colorants may be simultaneously dispersed in the colorant carrier, or they may be separately dispersed in the colorant carrier and mixed. If the coloring agent, such as a dye, has high solubility, specifically, if it is highly soluble in the solvent used, dissolved by stirring, and no foreign matter is detected, it is manufactured by finely dispersing it as described above. There's no need.

When used as a photosensitive coloring composition (resist material) for color filters, it can be prepared as a solvent-developable or alkali-developable coloring composition. A solvent-developable or alkaline-developable coloring composition comprises the colorant dispersion, a photopolymerizable monomer and/or a photopolymerization initiator, and, if necessary, a solvent, other dispersion aids, 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 to the prepared colored composition later.

<Solvent>
The colored composition of the present invention contains a solvent in order to facilitate the formation of a colored film by coating it on a substrate such as glass to a dry film thickness of 0.2 to 5 μm. The solvent is selected in consideration of good coating properties of the coloring composition, solubility of each component of the coloring composition, and safety.

As the solvent, any solvent commonly used in the field can be used, and it can be used alone or as appropriate depending on the application conditions (speed, drying conditions, etc.), taking into consideration performance such as boiling point, SP value, evaporation rate, and viscosity. used in combination.

Examples of the solvents used include ester solvents (solvents containing -COO- in the molecule but not containing -O-), 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 -COO- in the molecule), Examples include solvents containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

Among the above-mentioned solvents, it is preferable to include an organic solvent having a boiling point of 120° C. or more and 180° C. or less at 1 atm from the viewpoint of coating properties and drying properties. Among them, 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 and the like are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are more preferred.

<Removal of coarse particles>
The photosensitive coloring composition of the present invention can be produced into coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, filtration with a sintered filter or membrane filter, etc. It is preferable to remove particles and mixed dust. As described above, it is preferable that the colored composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be explained.
The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment. Further, the color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

<Production method of color filter>
It is preferable to form a color filter by first forming a black matrix on a base material, and then forming filter segments. Note that the black matrix can be formed after forming a thin film transistor (TFT) on the base material in advance.
Examples of the black matrix include chromium, a multilayer film of chromium/chromium oxide, an inorganic film such as titanium nitride, and a resin film in which a light shielding agent is dispersed.

The filter segments can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, or the like.
The printing method allows pattern formation by simply repeating printing and drying of a photosensitive coloring composition prepared as a printing ink, so it is a low-cost and excellent method for producing color filters in mass production. Furthermore, advances in printing technology have made it possible to print fine patterns with high dimensional accuracy and smoothness. In order to perform printing, it is preferable to use a composition that prevents the ink from drying or solidifying on the printing plate or blanket. It is also important to control the fluidity of the ink on the printing press, and the viscosity of the ink can also be adjusted using a dispersant or extender pigment.

In the electrodeposition method, a color filter is produced by using a transparent conductive film formed on a transparent substrate and electrodepositing filter segments of each color on the transparent conductive film by electrophoresis of colloidal particles. Furthermore, in the transfer method, filter segments are formed on the release-treated surface of the release sheet. This filter segment is then transferred to a transparent substrate to produce it.

In the photolithography method, for example, a photosensitive coloring composition containing a coloring agent of a certain color is applied onto a transparent substrate to form a film with a dry film thickness of about 0.2 to 5 μm. The obtained film (hereinafter referred to as the first film) is exposed (light irradiated) through a mask having a predetermined pattern. Next, development is performed by immersing in a solvent or alkaline developer or spraying a developer, and uncured portions are removed to obtain a desired pattern. By similarly performing this step using photosensitive coloring compositions having colorants of other colors, color filters having filter segments of each color can be manufactured. Furthermore, a second film (oxygen barrier film) can be formed on the first film before exposure using polyvinyl alcohol or a water-soluble acrylic resin. As a result, the first film does not come into contact with oxygen, so that the exposure sensitivity is further improved. Additionally, the color filter can be heated to cure uncured photopolymerizable compounds in the filter segments. Note that the photolithography method is preferable because a color filter can be manufactured with higher precision than the printing method.

Examples of the coating device include spray coating, spin coating, slit coating, and roll coating. A drying process can be performed during coating. Examples of the drying device include a hot air oven and an infrared heater.

Examples of the alkaline developer include inorganic alkalis such as sodium carbonate and sodium hydroxide; and organic alkalis such as dimethylbenzylamine and triethanolamine. Furthermore, an antifoaming agent and a surfactant can be added to the developer.

The color filter of the present invention is attached to a counter substrate using a sealant, liquid crystal is injected through an injection port provided in the sealing part, the injection port is sealed, and a polarizing film or a retardation film is attached to the substrate as necessary. A color liquid crystal display device is manufactured by pasting it on the outside. This color liquid crystal display device supports twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convensed bend (OCB). ) can be used in a liquid crystal display mode that performs colorization using color filters.

In this specification, the color filter can be used in applications other than liquid crystal display devices, such as solid-state image sensors, organic EL display devices, quantum dot display devices, electronic paper, and head-mounted displays.

<Liquid crystal display device>
A liquid crystal display device equipped with a color filter of the present invention will be explained.
The liquid crystal display device of the present invention includes the color filter of the present invention 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 the red reproduction area is expanded. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with a color filter of the present invention. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 that are spaced apart and facing each other, and a liquid crystal LC is sealed between them.

The liquid crystal LC is aligned according to a drive mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence), or the like. 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. Furthermore, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments that make up the color filter 22 are separated by a black matrix (not shown).

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

Furthermore, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED, and those in which a blue LED resin package contains a phosphor. λ3), has a wavelength (λ4) at which the emission intensity is maximum within the range of 530 nm to 580 nm, has a wavelength (λ5) at which the emission intensity is maximum within the range from 600 nm to 650 nm, and has a wavelength The ratio (I4/I3) of the emission intensity I3 at wavelength λ3 and the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio (I5/I3) of the emission intensity I3 at wavelength λ3 and the emission intensity I5 at wavelength λ5 is ) is 0.1 or more and 1.3 or less, or a white LED light source (LED1) that has a wavelength (λ1) with maximum emission intensity in the range of 430nm to 485nm and in the range of 530nm to 580nm. spectral characteristics having a second peak wavelength of emission intensity (λ2) within the range, and a ratio (I2/I1) of emission intensity I1 at wavelength λ1 to emission intensity I2 at wavelength λ2 of 0.2 or more and 0.7 or less. It is preferable to use a white LED light source (LED2).

Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Chemicals) and NSSW304D-HG-V1 (manufactured by Nichia Chemicals).

Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemicals) and NSSW304D (manufactured by Nichia Chemicals).

The present invention will be explained below with reference to Examples. In addition, "parts" and "%" in Examples represent "parts by mass" and "% by mass", respectively.

Prior to Examples, a calculation method for measuring the weight average molecular weight of the resin and the acid value of the resin will be explained.

(Average molecular weight of resin)
The number average molecular weight (Mn) and mass average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the equipment, two separation columns were connected in series, and the packing material for both was "TSK-GEL SUPER HZM-N" connected in two series, and the oven temperature was 40. The measurement was performed at a flow rate of 0.35 ml/min using a THF solution as an eluent. The sample was dissolved in a solvent consisting of 1 wt % of the above eluent, and 20 microliters of the sample was injected. All molecular weights are polystyrene equivalent values.

(acid value of resin)
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the resin solution, stir to dissolve uniformly, and use an automatic titration device ("COM-555" manufactured by Hiranuma Sangyo) using 0.1 mol/L KOH aqueous solution as the titrant. ) to measure the acid value (mgKOH/g) of the resin solution. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

(Ammonium salt value of resin having cationic group in side chain)
The ammonium salt value of a resin having a cationic group in the side chain is determined by titration with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and is then converted to the equivalent amount of potassium hydroxide. , indicates the ammonium salt value of non-volatile matter.

<Manufacture of finely divided pigment>
(Finely divided pigments A-1 to 5)
Finely divided aluminum phthalocyanine pigments (A-1 to A-5) having the following formulas 2 to 6 were produced according to Examples of JP-A-2017-111398. The structure is shown below.

(Finely divided aluminum phthalocyanine pigment A-1)
Formula (2)

(Finely divided aluminum phthalocyanine pigment A-2)
Formula (3)

(Finely refined aluminum phthalocyanine pigment A-3)
Formula (4)

(Finely refined aluminum phthalocyanine pigment A-4)
Formula (5)

(Finely divided aluminum phthalocyanine pigment A-5)
Formula (6)

(Finely divided pigment (A-6))
Phthalocyanine pigment C. I. 100 parts of Pigment Green 58 ("FASTGEN GREEN A110" manufactured by DIC Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 6 hours. This kneaded material was poured into 3,000 parts of warm water, heated to 70°C and stirred for 1 hour to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight and finely divided. A pigment (A-6) was obtained.

(Finely divided pigment (A-7))
In a stainless steel reaction vessel equipped with a reflux tube, under a nitrogen atmosphere, 200 parts of tert-amyl alcohol dehydrated with a molecular sieve and 140 parts of sodium-tert-amyl alkoxide were added, and the mixture was heated to 100°C with stirring to dissolve the alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and heated to 90° C. with stirring to dissolve them, thereby preparing a solution of the mixture thereof. The heated solution of this mixture was slowly dropped into the alcoholate solution heated to 100° C. at a constant rate over 2 hours while stirring vigorously. After completion of the dropwise addition, heating and stirring were continued at 90° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Furthermore, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to a glass jacketed reaction vessel, and the mixture was cooled to -10°C. This cooled mixture was cooled to 75°C using a high-speed stirring disperser while rotating a shear disk with a diameter of 8 cm at 4000 rpm.The alkali metal salt of the previously obtained diketopyrrolopyrrole compound The solution was added in portions. At this time, the alkali metal salt of the diketopyrrolopyrrole compound is added at a rate of 75°C while cooling so that the temperature of the mixture consisting of methanol, acetic acid, and water is always kept below -5°C. It was added in small portions over approximately 120 minutes while adjusting the amount. After addition of the alkali metal salt, red crystals precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5° C. and then filtered to obtain a red paste. This paste was redispersed in 3,500 parts of methanol cooled to 0°C to form a suspension with a methanol concentration of approximately 90%, and stirred at 5°C for 3 hours to perform particle sizing and washing accompanied by crystal transition. Subsequently, the water paste of diketopyrrolopyrrole compound obtained by filtering with an ultrafilter was dried at 80° C. for 24 hours and pulverized to obtain diketopyrrolopyrrole pigment 1.
Next, 100 parts of diketopyrrolopyrrole pigment 1, 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 10 hours. Next, the kneaded mixture was poured into warm water, heated to about 80°C and stirred for 1 hour to form a slurry, filtered and washed with water to remove salt and diethylene glycol, dried at 80°C overnight, and pulverized. A finely divided pigment (A-7) having a diketopyrrolopyrrole pigment was obtained by

(Finely divided pigment (A-8))
Copper phthalocyanine blue pigment C. I. 100 parts of Pigment Blue 15:6 ("Lionor Blue ES" manufactured by Toyo Color Co., Ltd.), 1000 parts of crushed common salt, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50°C for 12 hours. did. This mixture was poured into 3000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then heated to 80°C for 24 hours. It was dried to obtain a finely divided pigment (A-8).

(Finely divided pigment (A-9 to 11))
Finely divided quinophthalone pigments (A-9 to A-11) having the following formulas (7) to (9) were prepared according to Examples of JP-A No. 2012-226110. The structure is shown below.

(Finely divided quinophthalone yellow pigment A-9)
Formula (7)

(Finely divided quinophthalone yellow pigment A-10)
Formula (8)

(Finely divided quinophthalone yellow pigment A-11)
Formula (9)

(Finely divided pigment (A-12))
C. I. 100 parts of Pigment Yellow 138 (PY138) (PALIOTOL YELLOW K0960-HD manufactured by BASF), 700 parts of sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and heated at 80°C for 6 hours. Kneaded. This mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80°C to form a slurry. After repeated filtration and water washing to remove salt and solvent, it was dried at 80°C overnight to form a finely divided pigment ( A-12) was obtained.

(Finely divided pigment (A-13))
Isoindoline yellow pigment C. I. 100 parts of pigment yellow 139 ("Irgafore Yellow 2R-CF" manufactured by BASF), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader and kneaded at 60° C. for 10 hours. Next, this mixture was poured into 3 liters of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, and after repeated filtration and water washing to remove sodium chloride and solvent, It was dried at ℃ for one day and night to obtain a finely divided pigment (A-13).

(Finely divided pigment (A-14))
100 parts of a metal complex yellow pigment (C.I. pigment yellow 150, "Yellow Pigment E4GN" manufactured by Lanxess Corporation), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.). The mixture was kneaded at 60°C for 10 hours. Next, this mixture was poured into 3 liters of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, and after repeated filtration and water washing to remove sodium chloride and solvent, It was dried at ℃ for one day and night to obtain a finely divided pigment (A-14).

(Finely divided pigment (A-15))
Yellow pigment C. I. Pigment Yellow 185 ("Paliotol Yellow D1155" manufactured by BASF): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were placed in a stainless steel 1-gallon kneader and kneaded at 120° C. for 8 hours. Next, this kneaded material was poured into 5 liters of warm water, heated to 70°C and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C overnight. , a finely divided pigment (A-15) was obtained.

<Dye manufacturing method>
(Resin 1 having a cationic group in the side chain)
67.3 parts of methyl ethyl ketone was charged into a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised 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 homogenized, then charged into a dropping funnel, attached to a four-neck separable flask, and added dropwise over 2 hours. Two hours after completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more based on nonvolatile components and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50°C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added and reacted at 50°C for 2 hours, heated to 80°C over 1 hour, and further reacted for 2 hours. In this way, a resin 1 was obtained in which the resin component had 47% by mass of ammonium groups and a cationic group in the side chain. The ammonium salt value of the obtained resin was 34 mgKOH/g.

(Dye 01 (AR52-JK))
C. by following the steps below. I. Dye 01 (AR52-JK), which is a salt-forming compound consisting of Acid Red 52 and Resin 1 having a cationic group in its side chain, was produced.
30 parts (calculated as non-volatile content) of Resin 1 having a cationic group in the side chain were added to 2000 parts of water, thoroughly stirred and mixed, and then heated to 60°C. Meanwhile, 10 parts of C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the resin solution. After the dropwise addition, the mixture was stirred at 60° C. for 120 minutes to fully react. To confirm the end point of the reaction, the reaction solution was dropped onto a filter paper, and the end point was determined to be the end point when there was no bleeding, and it was determined that a salt-forming compound had been obtained. After cooling to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water in a drier, and 32 parts of C.I. I. Dye 01 (AR52-JK), which is a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in its side chain, was obtained. At this time, C.I. in Dye 01 (AR52-JK) I. The content of the effective pigment component derived from Acid Red 52 was 25% by mass.

<Method for producing dye solution>
(Dye solution (DS-01))
The following mixture was stirred and mixed to be uniform, and then filtered through a filter with a pore size of 5.0 μm to prepare a dye solution (DS-01).
Dye 01: 16.0 parts Propylene glycol monomethyl ether acetate: 84.0 parts

<Dye derivative (a1)>
Mix equal amounts of dye derivative (a1-1) and dye derivative (a1-2) as shown below,
It was used.
Pigment derivative (a1-1)
Pc represents a phthalocyanine skeleton.

Pigment derivative (a1-2)

(Manufacture of dispersant (a2) solution)
A reaction vessel equipped with a gas inlet tube, temperature, condenser, and stirrer was charged with 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 PGMAc, and the mixture was purged with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50°C, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a reaction was carried out for 7 hours while adding a solution of 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of PGMAc. It was confirmed by solid content measurement that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 100°C for 7 hours. . After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the reaction was terminated, and the mixture was diluted with PGMAc so that the solid content was 30% by measuring the solid content, and the acid value was 70 mgKOH/g. A dispersant (a2) solution having a weight average molecular weight of 8,500 was obtained.

<Example of manufacturing binder resin (B) liquid>
<Production of binder resin (B1-M: non-photosensitive resin) mixed liquid>
(Preparation of binder resin (B1-1) liquid)
196 parts of propylene glycol monomethyl ether acetate was placed in a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device. After that, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) were added from the dropping tube. A mixture of 20.7 parts of 2,2'-azobisisobutyronitrile 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 an additional 3 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content.Propylene glycol monomethyl ether was added to the previously synthesized resin solution so that the nonvolatile content was 20%. Acetate was added to prepare a binder resin (B1-1) solution. The mass average molecular weight (Mw) was 26,000.

(Preparation of binder resin (B1-2) liquid)
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube was placed in a nitrogen atmosphere, and 210 parts of propylene glycol monomethyl ether acetate was added thereto, and the temperature was raised to 100° C. with stirring. Next, 106 parts of benzyl methacrylate, 22 parts of acrylic acid, and 22 parts of dicyclopentanyl methacrylate (FA-513M, manufactured by Hitachi Chemical) were dissolved in 215 parts of propylene glycol monomethyl ether acetate, and further 2,2'-azobisisobutyl A solution prepared by dissolving 3.6 parts of ronitrile was added dropwise into the flask, and stirring was continued at 100° C. for 5 hours to obtain a solution of acrylic resin. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content.Propylene glycol monomethyl ether was added to the previously synthesized resin solution so that the nonvolatile content was 20%. A binder resin was prepared by adding acetate to obtain a resin (B1-2) solution having a mass average molecular weight (Mw) of 10,000.

<Solvent (N)>
(N-1) Cyclohexanone 20 parts (N-2) Ethyl 3-ethoxypropionate 20 parts (N-3) Propylene glycol monomethyl ether 20 parts (N-4) Cyclohexanol acetate 20 parts (N-5) Dipropylene glycol 20 parts (N-1) to (N-5) of methyl ether acetate were mixed in the above mass parts to prepare a solvent (N).

<Preparation of colored composition>
(Manufacture of colored composition)
[Manufacture example 1]
The following mixture was stirred and mixed until it was homogeneous, and then dispersed for 3 hours using an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) using zirconia beads with a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to produce a colored composition (X-1) containing 20% by mass of non-volatile components.
Pigment (A-1) 15.0 parts Pigment (A-9) 5.0 parts Pigment derivative (a1) 1.5 parts Dispersant (a2: non-volatile content 30% liquid) 5.0 parts Binder resin (B1-M : Non-volatile content 20.0% liquid) 20.0 parts Solvent (N) 53.5 parts

[Production Examples 2 to 14]
(Production of colored compositions (X-2 to 14))
Colored compositions (X-2 to X-14) were prepared in the same manner as colored composition (X-1) except that the compositions were changed to those shown in Table 1.

(Preparation of binder resin (B1-M) liquid)
A binder resin (B1-M) mixed solution was prepared by mixing and stirring equal amounts of a binder resin (B1-1) solution and a binder resin (B1-2) solution.

<Example of manufacturing binder resin (B2: photosensitive resin) mixed liquid>
(Preparation of binder resin (B2-1) liquid)
207 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 80°C, and the inside of the reaction vessel was replaced with nitrogen. After that, from the dropping tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110, manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2 A mixture of 1.33 parts of '-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain a copolymer resin solution. Next, the entire amount of the obtained copolymer solution was stirred while stopping nitrogen gas and injecting dry air for 1 hour. After cooling to room temperature, 2-methacryloyloxyethyl isocyanate (Karens A mixture of 6.5 parts of MOI), 0.08 parts of dibutyltin laurate, and 26 parts of propylene glycol monomethyl ether acetate was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether was added to the previously synthesized resin solution so that the nonvolatile content was 20%. A binder resin (B2-1) was prepared by adding acetate. The mass average molecular weight (Mw) was 18,000.

(Preparation of binder resin (B2-2) liquid)
333 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and after changing the atmosphere inside the flask from air to nitrogen, the temperature was raised to 100 ° C. 70.5 g (0.40 mol) of benzyl methacrylate, 71.1 g (0.50 mol) of glycidyl methacrylate, 22.0 g (0.10 mol) of tricyclodecane skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical), and A solution prepared by adding 3.6 g of azobisisobutyronitrile to a mixture of 164 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel to the flask over 2 hours, and the mixture was further stirred at 100° C. for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 43.0 g of methacrylic acid [0.5 mol, (100 mol % based on the glycidyl group of glycidyl methacrylate used in this reaction)] and 0.0 g of trisdimethylaminomethylphenol were added. 9 g and 0.145 g of hydroquinone were placed in a flask, and the reaction was continued at 110°C for 6 hours, and the reaction was terminated when the nonvolatile acid value reached 1 mgKOH/g. Next, 60.9 g (0.40 mol) of tetrahydrophthalic anhydride and 0.8 g of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain a photosensitive transparent resin solution with an acid value of 80 mg KOH/g. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content, and the nonvolatile content was 20% by mass in the photosensitive transparent resin solution synthesized earlier. A binder resin (B2-2) solution was prepared by adding propylene glycol monomethyl ether acetate. The mass average molecular weight (Mw) was 12,000.

(Adjustment of binder resin (B2-3) liquid)
182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and after changing the atmosphere inside the flask from air to nitrogen, the temperature was raised to 100 ° C. 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 skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical), and A solution prepared by adding 3.6 g of azobisisobutyronitrile to a mixture of 136 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel to the flask over 2 hours, and the mixture was further stirred at 100° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g [0.25 mol, (50 mol % based on the carboxyl group of methacrylic acid used in this reaction)] of glycidyl methacrylate and 0.0 g of trisdimethylaminomethylphenol were added. 9 g and 0.145 g of hydroquinone were put into a flask, and the reaction was continued at 110° C. for 6 hours to obtain a photosensitive transparent resin solution with an acid value of 79 mg KOH/g. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content, and the nonvolatile content was 20% by mass in the photosensitive transparent resin solution synthesized earlier. A binder resin (B2-3) solution was prepared by adding propylene glycol monomethyl ether acetate. The mass average molecular weight (Mw) was 13,000.

(Preparation of binder resin (B2-4) liquid)
A separable flask equipped with a cooling tube was prepared as a reaction tank, and on the other hand, as a monomer dropping tank, 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, Prepare a well-stirred mixture of 120 parts of methyl methacrylate, 4 parts of t-butyl peroxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation), and 40 parts of propylene glycol monomethyl ether acetate, and add a chain transfer agent. A dropping tank was prepared in which 8 parts of n-dodecanethiol and 32 parts of propylene glycol monomethyl ether acetate were thoroughly stirred and mixed.
A reaction tank was charged with 395 parts of propylene glycol monomethyl ether acetate, the atmosphere was replaced with nitrogen, and the temperature of the reaction tank was raised to 90° C. by heating in an oil bath while stirring. After the temperature of the reaction tank stabilized at 90°C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. Each dropwise addition took 135 minutes while maintaining the temperature at 90°C. 60 minutes after the dropwise addition was completed, the temperature of the reaction tank was raised to 110°C. After maintaining the temperature at 110° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen = 5/95 (volume ratio) was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were placed in a reaction tank, and the mixture was allowed to react at 110°C for 12 hours. Ta. After that, 150 parts of propylene glycol monomethyl ether acetate was added and cooled to room temperature. Approximately 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether acetate was added to the mixture at a concentration of 20% by mass to obtain a binder resin (B2-4) liquid. The mass average molecular weight (Mw) of the resin was 18,000, and the acid value per nonvolatile content was 2 mgKOH/g.

(Preparation of binder resin (B2-M) mixed solution)
A binder resin (B2-M) mixed solution was prepared by mixing and stirring equal amounts of four types of binder resin (B2-1) to (B2-4) solutions.

<Thermosetting compound (BE)>
・Epoxy compound (BE-1)
(BE-1-1) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol
[EHPE-3150 (manufactured by Daicel)],
(BE-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase ChemteX Corporation)],
(BE-1-3) Triglycidyl isocyanurate (BE-1-1) to (BE-1-3) were mixed in equal amounts to prepare an epoxy compound (BE-1).
・Oxetane compound (BE-2):
3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane
[Aron oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

<Polymerizable compound (C)>
(C-1) Trimethylolpropane triacrylate
[Aronix M309 (manufactured by Toagosei Co., Ltd.)]
(C-2) Dipentaerythritol penta and hexaacrylate
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]
(C-3) Polybasic acidic acrylic oligomer
[Aronix M520 (manufactured by Toagosei Co., Ltd.)]
(C-4) Caprolactone modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]

(C-5) Polyfunctional urethane acrylate as shown below Pentaerythritol triacrylate (432 g and hexamethylene diisocyanate 84 g) were charged into a 5-necked reaction vessel with a content of 1 liter, and reacted at 60°C for 8 hours to form a (meth)acryloyl group. A product containing a polyfunctional urethane acrylate (C-5) having It was confirmed by IR analysis that no isocyanate groups were present in the reaction product.

(C-6) Bifunctional bisphenol A type (meth)acrylate
[ABE-300 (manufactured by Shin Nakamura Chemical Co., Ltd.)]
(C-7) Ethoxylated isocyanuric acid triacrylate
[A-9300 (manufactured by Shin Nakamura Chemical Co., Ltd.)]
As described above, (C-1) to (C-7) were mixed in the same amount to obtain a polymerizable compound (C).

<Photopolymerization initiator (D)>
(D-1) 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one
[Omnirad 907 (manufactured by IGM Resins)]
(D-2) 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone
[Omnirad 379EG (manufactured by IGM Resins)]
(D-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
[Omnirad TPO (manufactured by IGM Resins)]
(D-4) 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole
[Biimidazole (manufactured by Kurogane Kasei Co., Ltd.)]
(D-5) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine Co., Ltd.)]
(D-6) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan)]
(D-7) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one
[Omnirad 2959 (manufactured by IGM Resins)]
(D-8) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide
[Omnirad 819 (manufactured by IGM Resins)]
The above (D-1) to (D-8) were mixed in the same amount to prepare a photopolymerization initiator (D).

<Thiol compound (E)>
(E1-1: PEPT) Pentaerythritol tripropanethiol (E1-2: TMPT) Trimethylolpropane dipropanethiol (E1-3: PETT) Pentaerythritol tetrapropanethiol (E2-1: PEMP) Trimethylolpropane tris(3 -Mercaptopropionate)
(E2-2:PEMB) Pentaerythritol tetrakis (3-mercaptobutyrate)

<Production of leveling agent (F) liquid>
(Manufacture of leveling agent (FD-1-1) liquid)
In a reaction vessel purged with nitrogen, 117 parts by mass of methyl ethyl ketone, 50 parts by mass of 2-propanol, 4.69 parts by mass of 2,2'-bipyridyl, and 1.49 parts by mass of cuprous chloride were charged, and the mixture was stirred at 20°C for 30 minutes. . Thereafter, 78.1 parts by mass of 2-hydroxyethyl methacrylate and 2.93 parts by mass of ethyl 2-bromoisobutyrate were added, and the mixture was reacted at 20° C. for 16 hours under a nitrogen stream. Next, 45.8 parts by mass of methyl ethyl ketone, 19.5 parts by mass of 2-propanol, and 40 parts by mass of 2-(nonafluorobutyl)ethyl methacrylate represented by the following formula were added, and the mixture was heated to 60°C and reacted for 8 hours. Ta. Further, 91.6 parts by mass of methyl ethyl ketone, 39 parts by mass of 2-propanol, and 80 parts by mass of 2-(nonafluorobutyl)ethyl methacrylate were added and reacted for 26 hours. This reaction mixture was dissolved in methanol and purified by reprecipitation with water/methanol to obtain a block polymer. 60 parts by mass of this block polymer was dissolved in 80 parts by mass of methyl ethyl ketone, 10 parts by mass of tin 2-ethylhexanoate solution (0.2% by mass methyl ethyl ketone solution), and 0.1 mass parts of polymerization inhibitor (p-methoxyphenol). 1 part was added and the temperature was raised to 60°C. While introducing dry air into the liquid, 44.1 parts by mass of a 50% by mass solution of 2-acryloyloxyethyl isocyanate in methyl ethyl ketone was added dropwise, reacted for 1 hour, and further reacted at 80°C for 3 hours to obtain a fluorine content of 20% by mass. % of a fluorine-containing radically polymerizable copolymer which is a block copolymer was obtained. Further, propylene glycol monomethyl ether acetate was added to the obtained polymer solution to obtain a solution containing 20% by mass of the fluorine radical polymerizable copolymer.

(Production of leveling agent (FD-2-1 to FD-2-12) liquid)
Using methyl isobutyl ketone as a solvent and t-butylperoxy-2-ethylhexalate as a polymerization initiator, polymerization was carried out at the side chain or poly(perfluoroalkylene ether) chain having a fluorinated alkyl group listed in Table 2 and its terminal. A polymerization reaction was carried out using a compound having a sexually unsaturated group and a polymerizable unsaturated monomer having an adamantyl group having a reactive functional group to obtain a fluororesin solution.
After cooling to room temperature, about 2 g of the fluororesin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content.Propylene glycol monomethyl ether was added to the fluororesin solution so that the nonvolatile content was 20% by weight. Acetate was added to obtain FD-2-1 to FD-2-12 listed in Table 2.

FD1 and FD2 in Table 2 are shown below.

"-PFPE-" in the following formula represents a poly(perfluoroalkylene ether) chain.

<Sensitizer (G)>
(G-1) 2,4-diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(G-2) 4,4'-bis(diethylamino)benzophenone [CHEMARK DEABP (manufactured by Chemark Chemical)]
As described above, (G-1) and (G-2) were mixed in the same amount to prepare a sensitizer (G).

<Polymerization inhibitor (H)>
(H-1) 3-methylcatechol (H-2) Methylhydroquinone (H-3) tert-butylhydroquinone Above, (H-1) to (H-3) are mixed in equal amounts, and a polymerization inhibitor is added. (H).

<Ultraviolet absorber (I)>
(I-1) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine [TINUVIN400 (manufactured by BASF Japan)]
(I-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN900 (manufactured by BASF Japan)]
The above (I-1) and (I-2) were mixed in the same amount to prepare an ultraviolet absorbent (I).

<Antioxidant (J)>
(J-1) Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (J-2) Dioctadecyl 3,3'-thiodipropanoate (J-3) Tris[2 , 4-di-(tert)-butylphenyl]phosphine (J-4) bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (J-5) p-octylphenyl salicylate, (J -1) to (J-5) were mixed in the same amount to prepare an antioxidant (J).

<Storage stabilizer>
(L-1) 2,6-bis(1,1-dimethylethyl)-4-methylphenol (“BHT” manufactured by Honshu Chemical Industry Co., Ltd.)
(L-2) Triphenylphosphine (“TPP” manufactured by Hokuko Chemical Industry Co., Ltd.)
As described above, (L-1) and (L-2) were mixed in the same amount to prepare a storage stabilizer.

<Adhesion improver>
(M-1) 3-glycidoxypropyltriethoxysilane [Shin-Etsu silicone silane coupling agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-2) 3-methacryloxypropyltriethoxysilane [Shin-Etsu silicone silane coupling agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-3) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu silicone silane coupling agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-4) 3-mercaptopropyltrimethoxysilane [Shin-Etsu silicone silane coupling agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
The above (M-1) to (M-4) were mixed in the same amount to prepare an adhesion improver.

<Method for producing photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition (Y-1))
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y-1).
Coloring composition (X-1: nonvolatile content 27.0%): 50.0 parts Binder resin (B2-M: nonvolatile content 20.0%): 15.0 parts Thermosetting compound (BE-1): 1 .0 part Thermosetting compound (BE-2): 1.0 part Polymerizable compound (C): 3.0 parts Photopolymerization initiator (D): 1.8 parts Thiol compound (E1-1): 0 .4 parts Fluorine surfactant (FD-2-1: non-volatile content 3%): 1.0 part Sensitizer (G): 0.2 part Polymerization inhibitor (H): 0.1 part Ultraviolet absorber (I): 0.1 part Antioxidant (J): 0.1 part Storage stabilizer (L): 0.1 part Silane coupling agent (M): 0.2 part Solvent (N): 26.0 Department

[Examples 2 to 52, Comparative Examples 1 to 4]
(Preparation of photosensitive coloring composition (Y-2 to 56))
Photosensitive coloring compositions (Y-2 to 56) were prepared in the same manner as in Example 1, except that the types of the coloring composition and binder resin solution in Example 1 were changed as shown in Table 3. In this specification, Examples 1 to 30, 33 to 49, and 52 are reference examples. In addition, each raw material is as described above.

<Evaluation of photosensitive coloring composition>
Each test was conducted in the following manner. The results of the test are shown in Table 4.
The meaning of the evaluation rank is as follows.
◎: Very good 〇: Good △: Possible for practical use ×: Not suitable for practical use

(Pattern shape evaluation)
The obtained photosensitive coloring composition was coated on a 100 mm x 100 mm, 0.7 mm glass substrate to a film thickness of 3.4 μm, and then passed through a mask having a stripe pattern of 100 μm width under conditions of 40 mJ/cm ^{2 .} UV exposure was performed. Thereafter, the pattern was obtained by immersing it in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 23°C for 40 seconds, and washing with pure water. Ta. The resulting coating film was subjected to a heat treatment (post-bake) for 20 minutes in an oven at 230° C., and the pattern shape was confirmed using a scanning electron microscope (“S-3000H” manufactured by Hitachi High Tech). For evaluation, a SEM image of a cross section of a striped pattern with a width of 100 μm was captured, and the taper angle between the base material and the end of the pattern cross section was evaluated using a protractor as follows.

◎: Taper angle of 50 degrees or more and less than 90 degrees 〇: 40 to less than 50 degrees △: 30 to less than 40 degrees
×: Less than 30 degrees

(Water stain evaluation)
In the same manner as the pattern shape evaluation described above, a substrate having both a patterned part and a non-patterned part was prepared, and water stains in the solid painted part without a pattern were observed using a magnifying glass. The evaluation criteria are as follows.
◎: There was no water stain.
○: Water stains were less than 10% of the solid area.
Δ: Water stains were present in 10% or more to less than 30% of the solid area.
×: Water stains were present in 30% or more of the solid area.

10 Liquid crystal 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 (6)

A photosensitive coloring composition containing a colorant (A) (excluding xanthene dyes), a binder resin (B), a polymerizable compound (C), a photopolymerization initiator (D) and a thiol compound (E). hand,
The colorant (A) contains an aluminum phthalocyanine pigment,
A photosensitive coloring composition characterized in that the thiol compound (E) contains a compound (E1) represented by the following general formula (1) and a thiol compound (E2) other than the thiol compound (E1).
General formula (1)

(In general formula (1), R is an m-valent organic group, n represents 1 to 10, and m is an integer of 1 to 4.) The photosensitive coloring composition according to claim 1, further comprising a fluorosurfactant (F). The fluorosurfactant (F) contains an ethylenically unsaturated monomer (FD1) containing a fluorinated alkyl group and/or a poly(perfluoroalkylene ether) chain, and another ethylenically unsaturated monomer ( 3. The photosensitive coloring composition according to claim 2, comprising a copolymer (FD) of (FD2) and (FD2). Any one of claims 1 to 3, characterized in that the thiol compound (E1) represented by general formula (1) is contained in an amount of 0.1 to 7.5% by mass based on the total nonvolatile content of the coloring composition. photosensitive coloring composition. A color filter comprising a base material and a filter segment formed using the photosensitive coloring composition according to any one of claims 1 to 4. A liquid crystal display device comprising the color filter according to claim 5.