JP7334525B2 - Photosensitive coloring composition, and color filter and liquid crystal display device using the same - Google Patents

Description

The present invention provides a color liquid crystal display device, a color solid-state imaging device, an organic EL display device, a quantum dot display device, and a photosensitive coloring composition used in the manufacture of color filters used in electronic paper and the like, and using the same The present invention relates to color filters and liquid crystal display devices.

The color filter is formed by arranging two or more fine band-shaped filter segments with different hues in parallel (stripe) or crossing each other on a transparent substrate such as a glass substrate, or are arranged so as to be arranged in order in each of the vertical and horizontal directions. The filter segments have small dimensions of several microns to several hundred microns, and are orderly arranged in a predetermined array for each hue.
Currently, the mainstream method for manufacturing color filters is a method called a pigment dispersion method, in which pigments having excellent resistance to light and heat are used as coloring agents. In addition, in the pigment dispersion method, a color filter is manufactured by the following method. First, a photosensitive coloring composition (pigment resist) obtained by dispersing a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass. After removing the solvent from the coating by drying, the coating is exposed with a pattern corresponding to filter segments of a certain color. Next, the unexposed portion of the coating film is removed by development, and then, if necessary, treatment such as heating is performed. As a result, a filter segment pattern for the first color is obtained. By performing the same operation, filter segment patterns of other colors are formed to complete the color filter.

When exposed to the alkaline developer used in the development process, there is a problem that a phenomenon (water staining) occurs in which the colored pattern (coating film) is discolored. Reference 1 discloses the use of certain surfactants. Patent Literature 2 discloses that a specific resin is used. Prior Document 3 discloses the use of a β-hydroxyalkylamide and a carboxyl group-containing oxetane compound. However, although the effect of alleviating water stains can be seen in any of these methods, it is not sufficient.

JP 2010-164965 A JP 2014-65865 A JP 2019-113614 A

An object of the present invention is to achieve the following objects.
That is, an object of the present invention is to provide a photosensitive composition for a color filter which does not cause water stains after development and can form pixels with good developability and contrast, and a color filter formed using the same. That's what it is.

That is, the present invention provides a photosensitive coloring composition containing a binder resin, a polymerizable compound, a photopolymerization initiator and a colorant, wherein the binder resin is a compound represented by the following general formula (I) (a ) and at least one binder resin (A) obtained by copolymerizing 36 to 60% by mass and 40 to 64% by mass of another compound (b) having an ethylenically unsaturated double bond. It relates to a photosensitive coloring composition.

general formula (I)

In general formula (I), R ₁ is hydrogen or CH ₃ , R ₂ is an alkylene group having 2 or 3 carbon atoms, R ₃ is hydrogen, or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, n is an integer from 1 to 15;

The present invention also relates to the photosensitive coloring composition, wherein the binder resin (A) has a weight average molecular weight of 32,000 to 45,000.

The present invention also relates to the photosensitive coloring composition, wherein the binder resin (A) has an ethylenic double bond in its side chain.

The present invention also relates to a color filter comprising a transparent substrate and a coloring material layer formed on the transparent substrate using the photosensitive coloring composition.

Moreover, this invention relates to the display apparatus provided with the said color filter.

The present invention provides a photosensitive coloring composition that does not cause water stains after development, has good developability, and has high contrast. According to the present invention, it is possible to form filter segments of each color that do not cause water stains after development. Therefore, the use of the photosensitive coloring composition of the present invention leads to good yield and reduction in production cost.

FIG. 1 shows a cross section of one embodiment of the display device of the present invention.

Terms used herein are defined. "(Meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" unless otherwise specified , “acryloyl and/or methacryloyl”, “acrylic and/or methacrylic”, “acrylic acid and/or methacrylic acid”, “acrylate and/or methacrylate”, or “acrylamide and/or methacrylamide”. References herein to "C.I." mean Color Index (C.I.). Colorants include pigments and dyes.

<Colorant>
The photosensitive coloring composition of the present invention contains a pigment or dye as a coloring agent.
As the pigment, organic or inorganic pigments can be used singly or in combination of two or more. As the pigment, a pigment having high color developability and high heat resistance, particularly a pigment having high heat decomposition resistance is preferable, and an organic pigment is usually used. Specific examples of organic pigments that can be used in the coloring composition for color filters are shown below by 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, 296.

Further, in the red colored composition, C.I. I. An orange pigment such as Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73 and/or a yellow pigment described later 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, 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. Moreover, you may use the below-mentioned purple pigment together with a blue coloring composition.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of 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 and the like, but are not particularly limited to these. Among these, from the viewpoint of transmittance, C.I. I. Pigment Green 36, 58, 59, 62 or 63.
Further, the green coloring composition may be used in combination with a yellow pigment described later.

Yellow pigments include, 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. I. Pigment Yellow 138, 139, 150, 185, 231, 233.

Cyan-colored compositions for forming cyan-colored filter segments include, 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 singly or in combination.

The magenta coloring composition for forming the magenta color filter segment includes, for example, C.I. I. Pigment Violet 1, 19, C.I. I. Purple pigments and red pigments such as Pigment Red 144, 146, 177, 169, 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 oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, and amber. , synthetic iron black, and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good applicability, sensitivity, developability, etc. while balancing chroma and lightness.

<Refinement of pigment>
When an organic pigment is used as a colorant, it is preferable to mix it with other raw materials after carrying out a refinement process. Examples of the method for the refinement treatment include wet grinding, dry grinding, dissolution precipitation, and the like. Among these, a salt milling treatment by a kneader method, which is one type of wet grinding, and the like are preferable. The average primary particle size of the organic pigment after refining is preferably 10 to 80 nm, more preferably 15 to 70 nm. Appropriate particle size improves the dispersibility and the contrast ratio of the film. The average primary particle size is the average value of approximately 20 particles arbitrarily selected from an enlarged image of a TEM (transmission electron microscope). When the particle has a vertical axis length and a horizontal axis length, the vertical axis length is used.

The salt milling treatment is a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent, for example, a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. batch type or In this treatment, the mixture is mechanically kneaded while being heated using a continuous kneader, and then washed with water to remove the water-soluble inorganic salt and the water-soluble organic solvent. The water-soluble inorganic salt functions 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 the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

Examples of water-soluble inorganic salts include sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like. Among these, sodium chloride (table salt) is preferable from the point of price. The amount of the water-soluble inorganic salt to be used is preferably 50 to 2000 parts by mass, more preferably 300 to 1000 parts by mass, based on 100 parts by mass of the pigment, from the viewpoint of both processing 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 (miscible in) water and does not substantially dissolve water-soluble inorganic salts. The water-soluble organic solvent is preferably a high boiling point solvent having a boiling point of 120° C. or higher because it is difficult to volatilize due to the temperature rise during salt milling. Water-soluble organic solvents include, for example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. mentioned. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.

A resin can be added as needed during the salt milling process. Resins include, for example, natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in water-soluble organic solvents. The amount of the resin used is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.
<Dye>
Dyes include, for example, acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. In addition, dye derivatives and lake pigments obtained by converting dyes into lakes are also included.

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

Examples of basic dyes include organic acids, perchloric acid, and salt-forming compounds with these metal salts. Among salt-forming compounds, salt-forming compounds of basic dyes are preferable because they are excellent in various resistances and compatibility with pigments.

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.), quinoneimine 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 dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and the like; Among these, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, Quinophthalone dyes, phthalocyanine dyes and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes and phthalocyanine dyes are more preferred. Specific structures of dyes are described in "Handbook of Dyes" (edited by Synthetic Organic Chemistry Society; Maruzen, 1970), "Color Index" (The Society of Dyers and Colorists), and "Dye Handbook" (edited by Okawara et al.; Kodansha, 1986). etc.

<Dye derivative>
A pigment derivative can be used in the coloring composition as needed. A dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. Dye derivatives include, for example, compounds having acidic substituents such as sulfo, carboxy, or phosphate groups, and amine salts thereof, sulfonamide groups, or terminally basic substituents such as tertiary amino groups. compounds, and compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups.
Organic dyes include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, benzoiso Indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo and polyazo.

Specifically, diketopyrrolopyrrole-based dye derivatives, JP 2001-220520, WO2009/081930, WO2011/052617, WO2012/102399, JP 2017-156397, phthalocyanine Dye derivatives, JP-A-2007-226161, WO2016/163351 pamphlet, JP-A-2017-165820, Japanese Patent No. 5753266, anthraquinone-based dye derivatives, JP-A-63-264674, JP-A-09 -272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325, quinacridone dye derivatives, JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383, dioxazine-based dye derivatives, JP-A-2011-162662, thiazineindigo-based dye derivatives, JP-A-2007-314785, triazine-based dye derivatives , JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681 , JP-A-2009-57478 for benzoisoindole-based dye derivatives, JP-A-2003-167112 for quinophthalone-based dye derivatives, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012 -226110, naphthol dye derivatives, JP 2012-208329, JP 2014-5439, azo dye derivatives, JP 2001-172520, JP 2012-172092, acidic Substituents, JP-A-2004-307854, basic substituents, JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404 The dye derivatives described are mentioned. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound. A compound having a substituent such as a neutral group is synonymous with a dye derivative.

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

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

By adding a pigment derivative to the pigment and performing pigmentation treatments such as acid pasting, acid slurry, dry milling, salt milling, and solvent salt milling, the pigment derivative is adsorbed on the surface of the pigment. In comparison, the primary particles of the pigment can be made finer.

By adding a dye derivative to the pigment and performing a dispersion treatment such as wet dispersion using two rolls, three rolls, or beads, the dye derivative is adsorbed on the pigment surface, and the pigment surface becomes polar and the resin-type dispersant is adsorbed. is promoted, the compatibility with pigments, dye derivatives, resin-type dispersants, solvents, and other additives is improved, and the dispersion stability and viscosity stability over time when used as a colored composition or colored curable composition are improved. do. In addition, by improving the compatibility, the coating film has excellent temporal stability when the colored curable composition is applied to a glass substrate or the like, 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 and the like on the waiting time (PED: Post Exposure Delay) from exposure to heat treatment, and the line width sensitivity stability are improved. In addition, since the surface of the pigment is adsorbed and coated with the pigment derivative and the resin-type dispersant, it is possible to suppress the precipitation of crystals due to aggregation and sublimation of the pigment when the coating film is heated and baked. Further, variation in development time and development residue are suppressed.

<Resin Dispersant>

A known resin-type dispersant can be used in the photosensitive coloring composition of the present invention. The resin-type dispersant has a colorant affinity site having a property of adsorbing to the added colorant and a site compatible with the colorant carrier, and adsorbs to the added colorant to disperse in the colorant carrier. Specifically, urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amines 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, phosphoric acid esters and the like are used. 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 containing tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. in 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, more preferably in an amount of about 5 to 100% by mass, based on the total amount of the coloring agent.

<Binder resin>
The coloring composition herein contains a binder resin. The binder resin is a resin having a transmittance of 80% or more in the entire wavelength range of 400-700 nm. Note that the transmittance is preferably 95% or more. In terms of curing properties, binder resins include, for example, thermoplastic resins, thermosetting resins, active energy ray-curable resins, and the like. In addition, the active energy ray-curable resin may have an active energy ray-reactive functional group in a thermoplastic resin or a thermosetting resin. 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 alkali development step in producing a color filter, and an acidic group is required.

Binder resin can be used individually or in combination of 2 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, with respect to 100 parts by mass of the colorant containing the red pigment. When contained in an appropriate amount, a film can be easily formed, and good color characteristics can be easily obtained.

<Thermoplastic resin>
Thermoplastic resins include, for example, acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, Examples include polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.
Alkali-soluble thermoplastic resins include, for example, resins having acidic groups such as carboxyl groups and sulfone groups. Alkali-soluble thermoplastic resins include, for example, acrylic resins having acidic groups, α-olefin/(anhydride) maleic acid copolymers, styrene/styrenesulfonic acid copolymers, and ethylene/(meth)acrylic acid copolymers. , or isobutylene/(anhydride) maleic acid copolymer. Among these, an acrylic resin having an acidic group and a styrene/styrenesulfonic acid copolymer are preferred from the standpoint of improving developability, heat resistance and transparency.
Therefore, it is more preferable to use a resin having an ethylenically unsaturated double bond.

<Active energy ray-curable alkali-soluble resin>
An 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 by the effect of the active energy ray, thereby increasing the crosslink density and improving chemical resistance.

[Method (i)]
Method (i) is, for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with another monomer, and adding an ethylenically unsaturated divalent A carboxyl group of unsaturated monobasic acid having a double bond is subjected to an addition reaction. Then, the produced hydroxyl group is reacted with a polybasic acid anhydride to introduce 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 acid.

Unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and α-position haloalkyl, alkoxyl, halogen, nitro, and cyano substituted products of (meth)acrylic acid. Carboxylic acid etc. are mentioned.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. If necessary, such as increasing the number of carboxyl groups, using a tricarboxylic anhydride such as trimellitic anhydride or using a tetracarboxylic dianhydride such as pyromellitic dianhydride, the remaining It is also possible to hydrolyze the anhydride group.

As a method similar to method (i), for example, an ethylenically unsaturated monomer having a carboxyl group and a part of the side chain carboxyl group of a copolymer obtained by copolymerizing another monomer 2) is a method of subjecting an ethylenically unsaturated monomer having an epoxy group to an addition reaction to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
Method (ii) is obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer, and adding an ethylenically unsaturated monomer having an isocyanate group to the side chain hydroxyl group of the copolymer. This is a method of reacting the isocyanate group of the monomer.

Ethylenically unsaturated monomers having a hydroxyl group are, for example, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, Hydroxyalkyl methacrylates such as glycerol mono(meth)acrylate or cyclohexanedimethanol mono(meth)acrylate can be mentioned. In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to hydroxyalkyl (meth)acrylate, poly γ-valerolactone, poly ε-caprolactone, and/or poly Polyester mono(meth)acrylates to which 12-hydroxystearic acid or the like is added are also included. 2-Hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred from the viewpoint of suppressing foreign matter on the coating film, and from the viewpoint of sensitivity, it is preferable to use one having 2 to 6 hydroxyl groups. is preferred, and glycerol mono(meth)acrylate is more preferred.

Examples of ethylenically unsaturated monomers having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate, and the like. be done.

Other monomers that can constitute the alkali-soluble resin include, in addition to the other ethylenically unsaturated monomers already described, N-substituted maleimides, alkyleneoxy group-containing monomers, and phosphate 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-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy- 4-methyl-3-maleimidocoumarin, 4,4′-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N′-1,3-phenylenedimaleimide, N, N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitro phenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine and the like. Examples of alkyleneoxy group-containing monomers 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)acrylates, nonylphenol EO-modified (meth)acrylates, nonylphenol PO-modified (meth)acrylates, and the like.

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

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

<Alkali-soluble resin having no ethylenically unsaturated double bond>
The coloring composition herein can contain an alkali-soluble resin having no ethylenically unsaturated double bonds in order to adjust the degree of cure 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 30,000 or less, and 4,000, in order to impart alkali developing solubility. More than 20,000 or less is more preferable. Also, the value of Mw/Mn is preferably 10 or less. If the weight-average molecular weight (Mw) is less than 2,000, the adhesiveness to the substrate is lowered and the exposure pattern is less likely to remain. If it exceeds 40,000, the solubility in alkali development will be lowered, and a residue will be generated to deteriorate the linearity of the pattern.
The acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg/g) for imparting alkali 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 alkali development is lowered, and residues are generated, resulting in poor pattern linearity. If it exceeds 200, the adhesion to the substrate will be lowered, and the exposure pattern will be difficult to remain.

<Binder resin (A)>
36 to 60% by mass of the compound (a) represented by the general formula (I) and 40 to 64% by mass of another compound (b) having an ethylenically unsaturated double bond as the binder resin, as the resin described above Water staining after development can be suppressed by using at least one resin (A) obtained by copolymerizing the above.

general formula (I)

In general formula (I), R ₁ is hydrogen or CH ₃ , R ₂ is an alkylene group having 2 or 3 carbon atoms, R ₃ is hydrogen, or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, n is an integer from 1 to 15;

Examples of the compound (a) include ethylene oxide (EO)-modified (meth)acrylates of phenol, EO- or propylene oxide (PO)-modified (meth)acrylates of paracumylphenol, EO-modified (meth)acrylates of nonylphenol, and PO-modified nonylphenols. (Meth)acrylate and the like.

Other compounds (b) having ethylenically unsaturated double bonds include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso) butyl ( meth)acrylate, (iso)pentyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl (meth)acrylate, isobornyl (meth)acrylate, acid phosphooxyethyl (meth)acrylate, acid phosphooxypropyl (meth)acrylate, 3-chloro-2-acid phosphooxyethyl (meth)acrylate, acid phosphooxypolyethylene glycol mono(meth)acrylate, etc. However, there is no particular limitation other than compound (a). From the viewpoint of developability, it is preferable to contain a carboxyl group.

The proportion of the compound (a) in the binder resin (A) is preferably 36-60% by mass. More preferably 40 to 60% by mass, still more preferably 45 to 60% by mass. If the proportion of compound (a) is less than 36% by mass, the effect of suppressing water staining is small. If it is more than 60% by mass, the contrast ratio of the formed coating film will be lowered.

The weight average molecular weight of the binder resin (A) is preferably 32,000 to 45,000. More preferably 40,000 to 45,000. When the weight average molecular weight is less than 32,000, the effect of suppressing water staining is small. If it is more than 45,000, the developability will deteriorate.

The binder resin (A) is preferably an active energy ray-curable resin having an ethylenic double bond in the side chain by the method (i) or (ii) described above.

<Thermosetting compound>
In the present invention, a thermosetting compound can be used in combination with the thermoplastic resin as the binder resin. When producing a color filter using the photosensitive coloring composition of the present invention, by including a thermosetting compound, it reacts during baking of the filter segment and increases the crosslink density of the coating film, so the heat resistance of the filter segment is improved. However, the effect of suppressing pigment aggregation during baking of the filter segment and improving the contrast ratio can be obtained.

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 phenolic compounds, but the present invention is limited thereto. not to be Epoxy compounds and oxetane compounds are preferably used in the photosensitive coloring composition of the present invention.

<Polymerizable compound>
The photosensitive coloring composition of the present invention contains a coloring composition, a polymerizable compound, and a photopolymerization initiator. Polymerizable compounds include monomers or oligomers that are cured by ultraviolet rays, heat, or the like to form transparent resins.

Polymerizable compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) Acrylates, 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, methylolated Various acrylic and methacrylic esters such as melamine (meth)acrylate, epoxy (meth)acrylate, urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile and the like.

(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 an acid group include, for example, polyhydric alcohols and (meth)acrylic acid esters of free hydroxyl group-containing poly(meth)acrylates and dicarboxylic acids; Examples thereof 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. , malonic acid, succinic acid, glutaric acid, free carboxyl group-containing monoesters with dicarboxylic acids such as 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, 2-hydroxyethyl acrylate, 2-hydroxy Monohydroxy monoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates, and the like can be mentioned.

(Polymerizable compound having 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 polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, or reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth)acrylate having a hydroxyl group. and 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, 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, hydroxyl group-containing polyol polyacrylate, and the like.

Polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate and the like.

A polymerizable compound can be used individually or in combination of 2 or more types.

The blending amount of the polymerizable compound is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on 100% by mass of the non-volatile matter of the photosensitive coloring composition. Curability and developability are further improved when blended in an appropriate amount.

<Photoinitiator>
Photoinitiators include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1 -hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl] -2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, etc. Acetophenone compounds; 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, acrylated benzophenone , 4-benzoyl-4'-methyldiphenyl sulfide, or benzophenone compounds such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone , isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)- s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 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 ester compounds such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); Phosphine compounds such as (2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Quinones such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. Among these, oxime ester compounds are preferred.

A photoinitiator can be used individually or in combination of 2 or more types.

(Oxime ester compound)
In oxime ester-based compounds, the absorption of ultraviolet light causes cleavage of the NO bond of the oxime to produce iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When 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. However, oxime ester compounds are preferably used because they have high quantum efficiency. be.

Oxime ester compounds are oximes described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. Ester-based photopolymerization initiators can be mentioned.

The content of the photopolymerization initiator is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass, with respect to 100 parts by mass of the colorant. When blended in an appropriate amount, the photocurability and developability are further improved.

<Sensitizer>
Furthermore, the photosensitive coloring composition of the present invention can contain a sensitizer.
Sensitizers (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, tetraquinoxalylo porphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α- acyloxyester, acylphosphine oxide, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4, 4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone and the like.

Among the above sensitizers, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives can be mentioned as sensitizers capable of particularly suitable sensitization. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

More specifically, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al. Special Functional Materials" (1986, CMC), but are not limited to these. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be included.

A sensitizer can be used alone or in combination of two or more.

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

<Thiol chain transfer agent>
The photosensitive coloring composition of the present invention preferably contains a thiol chain transfer agent as a chain transfer agent. By using a thiol together with a photopolymerization initiator, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen, so the resulting colored composition has high sensitivity. .

Moreover, polyfunctional aliphatic thiols bonded to aliphatic groups such as methylene and ethylene groups having two or more thiol groups are preferred. More preferred are polyfunctional aliphatic thiols having 4 or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and it is possible to cure from the surface of the pattern to the vicinity of the substrate.

Polyfunctional thiols include, for example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropio trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s- Examples include triazines, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

A thiol-based chain transfer agent can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on 100% by mass of the nonvolatile matter of the photosensitive coloring composition. When contained in an appropriate amount, the photosensitivity and tapered shape are improved, and wrinkles are less likely to occur on the coating surface.

<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 photolithographic exposure, making it easier to obtain a pattern of a desired shape.

Examples of polymerization inhibitors include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2- 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 and tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide, etc. phosphine oxide compounds, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, phloroglucine and the like.

The content of the polymerization inhibitor is preferably 0.01 to 0.4% by mass based on 100% by mass of non-volatile matter in the photosensitive coloring composition. Within this range, the effect of the polymerization inhibitor is increased, and the straightness of the taper, the wrinkles of the coating film, the pattern resolution, etc. are improved.

<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 includes benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based 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.

Moreover, 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 non-volatile matter of the photosensitive coloring composition. When contained in an appropriate amount, the adhesion between the substrate and the film is further improved, and good resolution can be obtained.

Benzotriazole compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5 -bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl-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-( 2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 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. In addition, oligomer type and polymer type compounds having a benzotriazole structure can also be used.

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)-glycidate 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 (2-Hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine and the like. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.

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. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

Salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tertbutylphenyl salicylate. In addition, oligomer type and polymer type compounds having a salicylic acid ester structure can also be used.

<Antioxidant>
The photosensitive coloring composition of the invention may contain an antioxidant. Antioxidants prevent the photopolymerization initiators and thermosetting compounds contained in the photosensitive coloring composition from oxidizing and yellowing due to thermal curing and thermal processes during ITO annealing. can improve. In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film cross-linking component is reduced, so measures such as using a highly sensitive cross-linking component and increasing the amount of the photopolymerization initiator will increase the yellowing of the thermal process. can be seen. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and to obtain a high transmittance of the coating film.

Antioxidants include, for example, hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In this specification, the antioxidant is preferably a compound containing no halogen atom.

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

An antioxidant can be used individually or in combination of 2 or more types.

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

<Leveling agent>
A leveling agent is preferably added to the photosensitive coloring composition of the present invention for the purpose of improving the coating properties of the composition on a transparent substrate and the drying properties of the colored film. Various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants and anionic surfactants can be used as the leveling agent.

When a surfactant is contained in the photosensitive coloring composition of the present invention, the amount of surfactant added is 0.001 to 2.0% by mass with respect to the total solid content of the photosensitive coloring composition of the present invention. is preferred, and more preferably 0.005 to 1.0% by mass. Within this range, the coating properties of the coloring composition, the pattern adhesion, and the transmittance are well balanced.
The photosensitive coloring composition of the present invention may contain only one type of surfactant, or may contain two or more types of surfactants. When two or more types are included, the total amount is preferably within the above range.

<Storage stabilizer>
The photosensitive coloring 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, benzyltrimethyl chloride, quaternary ammonium chloride such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. organic phosphines, phosphites, and the like. The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the coloring agent (100% by mass).

<Adhesion improver>
The photosensitive coloring composition of the present invention can contain an adhesion improver such as a silane coupling agent in order to improve adhesion to the substrate. By improving the adhesion with the adhesion improving agent, the reproducibility of fine lines is improved and the resolution is improved.

Examples of adhesion improvers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- (Meth)acrylsilanes 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-aminopropylmethyldimethoxysilane 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, 3-mercaptopropylmethyldimethoxy mercaptos such as silane, 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureides such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide and silane coupling agents such as isocyanates such as , 3-isocyanatopropyltriethoxysilane. 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, per 100 parts by weight of the colorant in the coloring composition. Within this range, the effect is enhanced and the balance between adhesion, resolution, and sensitivity is good, which is more preferable.

<Method for producing photosensitive composition>
The photosensitive coloring composition included in the present invention contains a coloring agent in a coloring agent carrier such as a dispersant or a binder resin and/or a solvent, preferably together with a dispersing aid (dye derivative or surfactant), It can be manufactured by finely dispersing using various dispersing 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 kinds of coloring agents and the like may be dispersed in the coloring agent carrier at the same time, or may be mixed separately dispersed in the coloring agent carrier. If the colorant such as dye has high solubility, specifically, if it has high solubility in the solvent to be used, and if it is dissolved by stirring and no foreign matter is confirmed, it is manufactured by finely dispersing as described above. No need.

When used as a photosensitive coloring composition (resist material) for color filters, it can be prepared as a solvent-developing or alkali-developing coloring composition. The solvent-developable or alkali-developable colored composition comprises the above-mentioned colorant dispersion, a photopolymerizable monomer and/or a photopolymerization initiator, and optionally a solvent, other dispersing aids, and additives. etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Solvent>
The photosensitive coloring 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 applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

As the solvent, a solvent commonly used in the field can be used. Considering the performance such as boiling point, SP value, evaporation rate, viscosity, etc., it can be used alone or as appropriate according to the coating conditions (speed, drying conditions, etc.). used in combination.

Solvents used include, for example, ester solvents (solvents containing -COO- in the molecule but not containing -O-), ether solvents (solvents containing -O- in the molecule but not containing -COO-) , ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule but not containing -COO-), alcohol solvents (solvents containing OH in the molecule solvents that do not contain -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

Among the above solvents, it is preferable to include an organic solvent having a boiling point of 120° C. or higher and 180° C. or lower 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 is filtered by means of centrifugation, filtration with a sintered filter or a membrane filter, etc., to obtain coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more. Removal of particles and entrained dust is preferred. Thus, the coloring composition preferably does not substantially contain particles of 0.5 μm or larger. 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 comprises a red filter segment, a green filter segment and a blue filter segment. Also, the color filter may further comprise a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment.

<Manufacturing method of color filter>
A color filter is preferably formed by first forming a black matrix on a substrate and then forming filter segments. In addition, the black matrix can be formed after thin film transistors (TFTs) are formed on the substrate in advance.
The black matrix includes, for example, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed.

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.
In the printing method, a pattern can be formed only by repeating printing and drying of a photosensitive coloring composition prepared as a printing ink, and therefore, as a method for producing a color filter, it is low cost and excellent in mass productivity. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to have a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, it is also important to control the fluidity of the ink on the printing press, and it is also possible to adjust the viscosity of the ink using a dispersant or an extender.

In the electrodeposition method, a transparent conductive film formed on a transparent substrate is used to fabricate a color filter by electrodepositing filter segments of each color on the transparent conductive film by electrophoresis of colloidal particles. In the transfer method, filter segments are formed on the release-treated surface of the release sheet. Next, this filter segment is transferred to a transparent substrate to produce.

In the photolithography method, for example, a photosensitive coloring composition containing a coloring agent of a certain tone is applied onto a transparent substrate so that the dry film thickness is about 0.2 to 5 μm to form a film. The obtained coating (hereinafter referred to as the first coating) is exposed (light irradiation) through a mask having a predetermined pattern. Next, the film is developed by immersing it in a solvent or an alkaline developer or by spraying the developer to remove uncured portions to obtain a desired pattern. A color filter having filter segments of each color can be produced by performing this step in the same manner using a photosensitive coloring composition having a colorant of another color tone. Also, a second coating (oxygen blocking film) can be formed on the first coating before exposure using polyvinyl alcohol or a water-soluble acrylic resin. As a result, the first film does not come into contact with oxygen, thereby further improving the exposure sensitivity. Also, the color filters can be heated to cure uncured photopolymerizable compounds in the filter segments. The photolithography method is preferable because a color filter with higher precision can be produced than the printing method.

Coating devices include, for example, spray coating, spin coating, slit coating, and roll coating. A drying process can be performed in the case of coating. Examples of the drying device include hot air ovens, infrared heaters, and the like.

Examples of the developer include inorganic alkalis such as sodium carbonate and sodium hydroxide; and organic alkalis such as dimethylbenzylamine and triethanolamine. Also, the developer can contain an antifoaming agent and a surfactant.

The color filter of the present invention is laminated with a counter substrate using a sealing agent, liquid crystal is injected from an injection port provided in the sealing portion, the injection port is sealed, and if necessary, a polarizing film or a retardation film is attached to the substrate. A color liquid crystal display device is manufactured by laminating the film to the outside of the film. This color liquid crystal display device has Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertically Aligned (VA), Optically Convened Bend (OCB). ) can be used in a liquid crystal display mode in which coloration is performed using a color filter.

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

<Liquid crystal display device>
A liquid crystal display device having the color filter of the present invention will be described.
A liquid crystal display device of the present invention comprises the color filter of the present invention and a light source. As a light source, a cold cathode fluorescent lamp (CCFL) and a white LED can be used. In the present invention, it is preferable to use a white LED in terms of widening the reproduction range of red. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 having a color filter of the present invention. The device 10 shown in FIG. 1 comprises a pair of transparent substrates 11 and 21 spaced and opposed to each other, with a liquid crystal LC 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). 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 ITO, for example, is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13 . 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 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 filters 22, and a transparent electrode layer 23 made of, for example, ITO is formed thereon. is provided.

A polarizing plate 25 is formed on the outer surface of the transparent substrate 21 . 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 phosphor is contained in a resin package of a blue LED. 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 of 600 nm to 650 nm, and has a wavelength The ratio (I4/I3) of the emission intensity I3 at λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 (I5/I3 ) has a spectral characteristic of 0.1 to 1.3, and a wavelength (λ1) at which the emission intensity is maximized in the range of 430 nm to 485 nm, and the range of 530 nm to 580 nm has a second emission intensity peak wavelength (λ2) within, and the ratio (I2/I1) of the emission intensity I1 at the wavelength λ1 to the emission intensity I2 at the wavelength λ2 is 0.2 or more and 0.7 or less A white LED light source (LED2) with a is preferred.

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

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

The following examples illustrate the invention. "Parts" and "%" in the examples represent "parts by mass" and "% by mass", respectively.
In addition, Example 1, Example 2, and Example 5 are reference examples.

PGMAc represents propylene glycol monomethyl ether acetate.

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

(Average molecular weight of resin)
The number average molecular weight (Mn) and weight 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 an apparatus, two separation columns were connected in series, and "TSK-GEL SUPER HZM-N" was used as both packing materials, and the oven temperature was 40. °C, a THF solution was used as an eluent, and the flow rate was 0.35 ml/min. The sample was dissolved in a solvent consisting of 1 wt % of the above eluent and injected in 20 microliters. 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 and stir to dissolve uniformly. ) 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.

(Amine value of basic resin type dispersant)
The amine value of the basic resin-type dispersant is a value obtained by converting the total amine value (mgKOH/g) measured according to the method of ASTM D 2074 into the non-volatile content.

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

<Production of micronized pigment>
(Refined pigment (P-1))
copper phthalocyanine blue pigment C.I. I. 100 parts of Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyocolor Co., Ltd.), 1000 parts of crushed 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 is put 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, which is repeatedly filtered and washed with water to remove salt and solvent, then heated to 80°C for 24 hours. After drying, a finely divided pigment (P-1) was obtained.

(Refined pigment (P-2))
200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium-tert-amyl alkoxide are added to a stainless steel reaction vessel equipped with a reflux tube under a nitrogen atmosphere, and heated to 100° C. with stirring to form an 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 dissolved by heating to 90° C. with stirring to prepare a solution of their mixture. A heated solution of this mixture was slowly added dropwise at a constant rate over 2 hours into the alcoholate solution heated to 100° C. while being vigorously stirred. After the dropwise addition was completed, heating and stirring were continued at 90° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to a jacketed glass reaction vessel and cooled to -10°C. This cooled mixture was cooled to 75° C. while rotating a shear disk with a diameter of 8 cm at 4000 rpm using a high-speed stirring disperser. The solution was added in small portions. At this time, the rate of adding the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid, and water is always kept at -5 ° C. or less. was added in portions over approximately 120 minutes, adjusting the . After addition of the alkali metal salt, red crystals precipitated to form a red suspension. Subsequently, the resulting red suspension was washed with an ultrafiltration device at 5° C. and filtered to obtain a red paste. This paste was re-dispersed in 3500 parts of methanol cooled to 0° C. to form a suspension having a methanol concentration of about 90%, stirred at 5° C. for 3 hours, and subjected to particle sizing and washing accompanied by crystal transition. Subsequently, the water paste of the diketopyrrolopyrrole compound obtained by filtration with an ultrafilter was dried at 80° C. for 24 hours and pulverized to obtain a diketopyrrolopyrrole pigment 1.
Next, 100 parts of the diketopyrrolopyrrole pigment 1, 1000 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 10 hours. Next, the kneaded mixture is put into hot water, stirred for 1 hour while heating to about 80°C to form a slurry, filtered and washed with water to remove salt and diethylene glycol, dried at 80°C for a day and night, and pulverized. Thus, a finely divided pigment (P-2) having a diketopyrrolopyrrole pigment was obtained.

(Refined pigment P-3 to 7)
Finely divided aluminum phthalocyanine pigments (P-3 to 7) of the following formulas 2 to 6 were produced according to the examples of JP-A-2017-111398. The structure is shown below.

(Micronized aluminum phthalocyanine pigment P-3)
formula (2)

(Micronized aluminum phthalocyanine pigment P-4)
Formula (3)

(Micronized aluminum phthalocyanine pigment P-5)
Formula (4)

(Micronized aluminum phthalocyanine pigment P-6)
Formula (5)

(Micronized aluminum phthalocyanine pigment P-7)
Formula (6)

(Refined pigment (P-8))
phthalocyanine pigment C.I. I. 100 parts of Pigment Green 58 ("FASTGEN GREEN A110" manufactured by DIC), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 6 hours. This kneaded product is put into 3000 parts of hot water and stirred for 1 hour while heating to 70° C. to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. A modified pigment (P-8) was obtained.

(Refined pigment (P-9 to 11))
Finely divided quinophthalone pigments (P-9 to 11) of the following formulas (7) to (9) were prepared according to the examples of JP-A-2012-226110. Its structure is shown below.

(Micronized quinophthalone yellow pigment P-9)
Formula (7)

(Micronized quinophthalone yellow pigment P-10)
Formula (8)

(Micronized quinophthalone yellow pigment P-11)
formula (9)

(Refined pigment (P-12))
C. I. Pigment Yellow 138 (PY138) (BASF "Pariotol Yellow K0960-HD") 100 parts, sodium chloride 700 parts, and diethylene glycol 180 parts are charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and heated at 80 ° C. for 6 hours. Kneaded. This mixture is poured into 2000 parts of hot water and stirred for 1 hour while heating to 80°C to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent. P-12) was obtained.

(Refined pigment (P-13))
isoindoline yellow pigment C.I. I. 100 parts of pigment yellow 139 (“Irgafor 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 is poured into 3 liters of hot water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which is filtered and washed repeatedly to remove sodium chloride and the solvent. C. for one day to obtain a finely divided pigment (P-13).

(Refined pigment (P-14))
Metal complex yellow pigment (CI pigment yellow 150, Lanxess "Yellow Pigment E4GN") 100 parts, 1600 parts of sodium chloride, and 190 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), The mixture was kneaded at 60°C for 10 hours. Next, this mixture is poured into 3 liters of hot water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which is filtered and washed repeatedly to remove sodium chloride and the solvent. C. for one day to obtain a finely divided pigment (P-14).

(Refined pigment (P-15))
yellow pigment C.I. I. Pigment Yellow 185 (“Pariotol 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 product is put into 5 liters of hot water, stirred for 1 hour while heating to 70° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a day and night. , to obtain a finely divided pigment (P-15).

<Method for producing dye>
(Resin 1 having a cationic group in the side chain)
A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2'-azobis(2,4-dimethylvaleronitrile ) and 25.1 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and added dropwise over 2 hours. After 2 hours from the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the non-volatile matter and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50°C. 3.2 parts of methyl chloride and 22.0 parts of ethanol were added thereto, and the mixture was reacted at 50° C. for 2 hours, then heated to 80° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 1 having a cationic group in a side chain containing 47% by mass of ammonium group as a resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH/g.

(Dye 01 (AR52-JK))
The C.I. I. Dye 01 (AR52-JK), which is a salt-forming compound consisting of Acid Red 52 and Resin 1 having a cationic group in the side chain, was produced.
To 2000 parts of water was added 30 parts of Resin 1 having a cationic group on its side chain in terms of non-volatile content, and the mixture was sufficiently stirred and mixed, and then heated to 60°C. On the other hand, 10 parts of C.I. I. An aqueous solution was prepared by dissolving Acid Red 52, and was added dropwise to the previous resin solution. After dropping, the mixture was stirred at 60° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, the reaction solution was added dropwise to a filter paper, and the point at which no bleeding occurred was regarded as the end point, and it was determined that a salt-forming compound was obtained. After allowing to cool 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 moisture with a dryer. I. Dye 01 (AR52-JK), which is a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in the side chain, was obtained. At this time, C.I. I. The content of the active coloring component derived from Acid Red 52 was 25% by mass.

<Method for producing dye solution>
(Dye solution (DS-01))
After the following mixture was uniformly stirred and mixed, the mixture was 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)>
A mixture of equal amounts of dye derivative (a1-1) and dye derivative (a1-2) as described below was used.
Dye derivative (a1-1)
Pc represents a phthalocyanine skeleton.

Dye derivative (a1-2)

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

<Production example of binder resin (B) liquid>
<Production of binder resin (B1-M: non-photosensitive resin) (B1-1) (B1-2) mixture>
(Preparation of binder resin (B1-1) liquid)
196 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80°C, and the inside of the reaction vessel was replaced with nitrogen. After that, from the dropping tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) A mixture of 20.7 parts and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 more hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. A binder resin (B1-1) liquid was prepared by adding acetate. The weight average molecular weight (Mw) was 26,000.

(Preparation of binder resin (B1-2) liquid)
Put 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a separable four-necked flask, a thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer, and heat the vessel to 120°C while injecting nitrogen gas. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 parts of azobisisobutyronitrile was added dropwise from a dropping tube over 2.5 hours to polymerize. reacted.
Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120°C for 5 hours. The reaction was terminated when the molecular weight reached 0.8 to obtain a resin solution having a weight average molecular weight of about 12,000 (measured by GPC).
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added and reacted at 120° C. for 4 hours. A solution was prepared.

(Preparation of binder resin (B1-M) liquid)
Equal amounts of binder resin (B1-1) liquid and binder resin (B1-2) liquid were mixed and stirred to prepare a binder resin (B1-M) mixed liquid.

<Solvent (N)>
(N-1) 20 parts of cyclohexanone (N-2) 20 parts of ethyl 3-ethoxypropionate (N-3) 20 parts of propylene glycol monomethyl ether (N-4) 20 parts of cyclohexanol acetate (N-5) dipropylene glycol 20 parts of methyl ether acetate (N-1) to (N-5) were mixed in the above parts by mass to obtain a solvent (N).

<Preparation of colored composition>
(Production of coloring composition (X-1))
After stirring and mixing the following mixture uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), the pore size is 5.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (X-1) having a nonvolatile content of 20% by mass.
Pigment (P-1) 19.4 parts Dye 01 5.0 parts Pigment derivative (a1) 1.5 parts Dispersant (a2) solution 5.0 parts Binder resin (B1-M) liquid 19.0 parts Solvent (N ) 50.1 parts

(Production of colored compositions (X-2 to 14))
Coloring compositions (X-2 to 14) were prepared in the same manner as the coloring composition (X-1) except that the compositions shown in Table 1 were changed.

<Production example of binder resin (A)>
(Preparation of binder resin (A-1) liquid)
A separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirring device was charged with 70.0 parts of cyclohexanone, heated to 80°C, and after replacing the inside of the flask with nitrogen, the contents were passed through the dropping tube. , n-butyl methacrylate (BMA) 10.8 parts, 2-hydroxyethyl methacrylate (HEMA) 3.9 parts, methacrylic acid (MAA) 3.6 parts, paracumylphenol ethylene oxide modified acrylate (M110: manufactured by Toagosei Co., Ltd. A mixture of 10.8 parts of Aronix M110), 0.9 parts of benzyl methacrylate (BzMA) and 0.9 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 hours to obtain the desired binder resin (A-1) solution having a solid content of 30%. The weight average molecular weight of this binder resin (A-1) was 40,000.

(Production of binder resins (A-2) to (A-11) and (A-14) solutions)
Synthesized and adjusted in the same manner as the binder resin (A-1) solution, except that the material type, mass, and molecular weight were changed as described in Table 2, and the binder resins (A-2) to (A-11), ( A-14) A solution was obtained.

(Preparation of binder resin (A-12) liquid)
A separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirring device was charged with 65.0 parts of cyclohexanone, heated to 80°C, and after replacing the inside of the flask with nitrogen, the contents were passed through the dropping tube. , n-butyl methacrylate (BMA) 9.3 parts, glycerol methacrylate (GLM) 1.1 parts, methacrylic acid (MAA) 3.0 parts, paracumylphenol ethylene oxide modified acrylate (M110: Aronix M110 manufactured by Toagosei Co., Ltd.) A mixture of 13.5 parts, 0.9 parts of benzyl methacrylate (BzMA) and 0.9 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and the total amount of the copolymer solution obtained was stirred while injecting dry air for 1 hour, and then cooled to room temperature. A mixture of 2.2 parts of MOI), 0.03 parts of dibutyltin laurate and 5 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for 1 hour to obtain the desired binder resin (A-12) solution having a solid content of 30%. The weight average molecular weight of this binder resin (A-12) was 40,000.

(Preparation of binder resin (A-13) liquid)
A separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirring device was charged with 65.0 parts of cyclohexanone, heated to 80°C, and after replacing the inside of the flask with nitrogen, the contents were passed through the dropping tube. , n-butyl methacrylate (BMA) 9.3 parts, 2-hydroxyethyl methacrylate (HEMA) 1.5 parts, methacrylic acid (MAA) 3.0 parts, paracumylphenol ethylene oxide modified acrylate (M110: manufactured by Toagosei Co., Ltd. A mixture of 13.5 parts of Aronix M110), 0.9 parts of benzyl methacrylate (BzMA) and 0.9 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and the total amount of the copolymer solution obtained was stirred while injecting dry air for 1 hour, and then cooled to room temperature. A mixture of 1.8 parts of MOI, 0.03 parts of dibutyl tin laurate and 5 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for 1 hour to obtain the desired binder resin (A-13) solution having a solid content of 30%. The weight average molecular weight of this binder resin (A-13) was 40,000.

M111 in Table 2 represents Aronix M111 manufactured by Toagosei Co., Ltd. GLM-MOI represents a structural unit obtained by reacting glycerol methacrylate and 2-methacryloyloxyethyl isocyanate. HEMA-MOI represents a structural unit obtained by reacting 2-hydroxyethyl methacrylate and 2-methacryloyloxyethyl isocyanate.

<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 Corporation)],
(BE-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase ChemteX Corporation)],
(BE-1-3) Equal amounts of triglycidyl isocyanurate (BE-1-1) to (BE-1-3) were mixed to obtain 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 according to the following Pentaerythritol triacrylate (432 g, hexamethylene diisocyanate 84 g) was charged in a 1-liter, 5-necked reaction vessel, reacted at 60 ° C. for 8 hours, and (meth) acryloyl group In the product, the ratio of the polyfunctional urethane acrylate (C-5) is 70% by mass, and the remainder is other photopolymerizable It was confirmed by IR analysis that no isocyanate group was 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.)]
The above (C-1) to (C-7) were mixed in equal amounts to obtain a polymerizable compound (C).

<Photoinitiator (D)>
(D-1) 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one
[Omnirad 907 (manufactured by IGM Resins)]
(D-2) 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1
[Omnirad 369 (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)]
(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 equal amounts to obtain a photopolymerization initiator (D).

<Thiol chain transfer agent (E)>
(E-1) trimethylolethane tris (3-mercaptobutyrate)
[TEMB (manufactured by Showa Denko)]
(E-2) Trimethylolpropane tris (3-mercaptobutyrate)
[TPMB (manufactured by Showa Denko)]
(E-3) Pentaerythritol tetrakis (3-mercaptopropionate)
[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(E-4) trimethylolpropane tris (3-mercaptopropionate)
[TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(E-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate
[TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
The above (E-1) to (E-5) were mixed in equal amounts to obtain a thiol-based chain transfer agent (E).

<Leveling agent (F)>
"BYK-330" manufactured by Big Chemie Co., Ltd. 1 copy,
A mixed solution prepared by dissolving 1 part of "Megafac F-551" manufactured by DIC and 1 part of "EMULGEN 103" manufactured by Kao in 97 parts of PGMAc.

<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 Chemmark Chemical)]
The above (G-1) and (G-2) were mixed in equal amounts to obtain a sensitizer (G).

<Polymerization inhibitor (H)>
(H-1) 3-methylcatechol (H-2) methylhydroquinone (H-3) tert-butylhydroquinone and 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 the UV absorber (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 equal amounts to obtain 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 Hokko Chemical Industry Co., Ltd.)
Equal amounts of (L-1) and (L-2) were mixed to obtain 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 equal amounts to prepare an adhesion improver.

<Method for producing a 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: non-volatile content 27.0%): 20.0 parts binder resin (A-1: non-volatile content 30.0%): 6.5 parts thermosetting compound (BE-1): 0 .3 parts Thermosetting compound (BE-2): 0.2 parts Polymerizable compound (C): 6.0 parts Photopolymerization initiator (D): 0.8 parts Thiol compound (E): 0.3 Part Leveling agent (F: 3% non-volatile): 0.4 part Sensitizer (G): 0.2 part Polymerization inhibitor (H): 0.01 part Ultraviolet absorber (I): 0.01 part Oxidation Inhibitor (J): 0.02 parts Storage stabilizer (L): 0.01 parts Silane coupling agent (M): 0.2 parts Solvent (N): 65.05 parts

[Examples 2 to 25, Comparative Examples 1 to 2]
(Preparation of photosensitive coloring composition (Y-2 to 27))
Photosensitive coloring compositions (Y-2 to 27) were prepared in the same manner as in Example 1 except that the types of the coloring composition and binder resin solution of Example 1 were changed as shown in Table 3.
In addition, each raw material is as described above.

<Evaluation of photosensitive coloring composition>
Each test was performed by the following method. Table 4 shows the results of the test.
The meaning of the evaluation rank is as follows.
◎: Excellent 〇: Good △: Practical ×: Not suitable for practical use

(Water stain evaluation)
The resulting photosensitive coloring composition was applied to a 100 mm×100 mm, 0.7 mm glass substrate to a film thickness of 3.4 μm, and exposed through a mask having a stripe pattern of 100 μm width at 40 mJ/cm ² UV exposure was performed at . After that, it is developed by being immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C. for 40 seconds, and washed with pure water to obtain a pattern. Ta. A magnifying glass was used to observe water stains on the non-patterned solid coated portion. The evaluation criteria are as follows.
A: There was no water stain.
Good: Water stains were less than 10% of the solid portion.
Δ: Water stains were 10% or more and less than 30% of the solid portion.
x: Water stains were 30% or more of the solid portion.

(Contrast ratio evaluation after post-baking)
The obtained photosensitive coloring composition was applied onto a glass substrate of 100 mm×100 mm and 0.7 mm, and heat-treated (post-baked) at 240° C. for 20 minutes. A cured film having a thickness of 0 μm was obtained. The contrast ratio of the obtained cured film was measured. Evaluation criteria are as follows.
◎: 15000 or more ○: 13500 or more and less than 15000 △: 12000 or more and less than 13500 ×: less than 12000

(Developability)
The resulting colored composition for color filters was spin-coated on a glass substrate using a spin coater so that the dry film thickness would be 2.4 μm, and dried in vacuum. The coating film was developed by spraying with a 2% by mass potassium hydroxide aqueous solution, and the time until the coating thickness was dissolved was measured to evaluate the development speed of the colored composition. The rank of evaluation is as follows.
◎: Less than 20 seconds ○: 20 seconds or more and less than 40 seconds △: 40 seconds or more and less than 60 seconds ×: 60 seconds or more

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 (4)

A photosensitive coloring composition containing a binder resin, a polymerizable compound, a photopolymerization initiator , a coloring agent , and a dispersant ,
The binder resin is obtained by copolymerizing 45 to 60% by mass of a compound (a) represented by the following general formula (I) and 40 to 55 % by mass of another compound (b) having an ethylenically unsaturated double bond. contains at least one binder resin (A) formed by
The compound (b) having another ethylenically unsaturated double bond contains methacrylic acid,
A photosensitive coloring composition , wherein the binder resin (A) has a weight average molecular weight of 32,000 to 45,000 .
general formula (I)
In general formula (I), R ₁ is hydrogen or CH ₃ , R ₂ is an alkylene group having 2 or 3 carbon atoms, R ₃ is hydrogen, or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, n is an integer from 1 to 15; 2. The photosensitive coloring composition according to claim 1 , wherein the binder resin (A) has an ethylenic double bond in its side chain. A color filter comprising a transparent substrate and a colorant layer formed on the transparent substrate using the photosensitive coloring composition according to claim 1 or 2 . A display device comprising the color filter according to claim 3 .